Hardenable composition based on polysiloxanes
Patent Information
- Application Number
- DE502018016177
- Authority / Receiving Office
- DE · DE
- Patent Type
- Patents
- Current Assignee / Owner
- Priority Date
- 2017-09-28
- Filing Date
- 2018-09-12
- Publication Date
- 2025-11-13
- Estimated Expiration
- 2038-09-12
Description
[0001] The invention relates to a hardenable composition based on polysiloxanes, its manufacturing process and its use.
[0002] In a wide variety of application areas, surface coatings are sought that prevent or at least reduce the adhesion of dirt of various kinds.
[0003] Particularly on structures exposed to permanent water exposure, such as ship hulls, buoys, fishing nets, cooling ducts and discharge pipes, offshore drilling rigs, or water tanks exposed to seawater and / or freshwater, the adhesion and growth of organisms (biofouling) causes considerable economic losses. In the case of ships, these losses result, for example, from increased friction and the associated increase in fuel consumption. Surfaces of static structures also suffer mechanical damage due to increased resistance to waves or currents, leading to shorter maintenance cycles and thus reduced operating time.
[0004] For facade paints, coatings are also being sought that prevent or delay the growth of microorganisms / algae.
[0005] Surface coatings with self-polishing properties are known from the prior art. This self-polishing property can be achieved, among other things, through the use of degradable polymer coatings, which continuously renew the surface due to their degradation behavior. Such a polymer property can lead to the removal of various types of soiling, thus keeping the surface clean. Effects of this kind can be used in anti-graffiti, anti-icing, easy-to-clean, and anti-dirt-pickup coatings, as well as for the prevention of biofouling.
[0006] Polymers that degrade upon contact with water are well-known in the field of antifouling coatings. Acrylate esters / silylated acrylates are primarily used. A special class of materials are poly(esters). Here, the degradation property is determined by the choice of monomers, the polymer architecture, and the molar mass.
[0007] Anti-fouling paint compositions are known from the prior art in which the polymer of the binder system is a trialkyltin derivative of a polymer with carboxylic acid groups in the monomer segments. They form a coating film that dissolves slowly in seawater, thus preventing the adhesion of biofouling through the secretion of the organotin compound. However, their use has been subject to legal restrictions in recent years due to problems of marine pollution and the highly neurotoxic properties of organotin compounds.
[0008] DE102015202278 A1 discloses aqueous dispersions of organosilicon compounds containing, among other components, silyl-terminated polyethers, polysiloxanes with alkoxysilyl or silanol groups, and catalysts. These dispersions are used in coatings.
[0009] Therefore, there is a need for a suitable binder system for the production of coatings capable of preventing the adhesion of microorganisms / algae in order to prevent or delay biogrowth by them.
[0010] Surprisingly, it was found that a hardenable composition containing as Component A at least one polysiloxane, component B at least one silyl group-bearing polyether and / or reaction products of a silyl group-bearing polyether with one or more isocyanate-containing compounds according to formula (I) with a = 1 to 100, preferably 1 to 10, particularly preferably 2 to 5, b = 1 to 500, preferably 1 to 400, particularly preferably 1 to 300, c = 0 to 500, preferably 1 to 400, particularly preferably 1 to 300, f = 0 to 2, g = 1 to 3, wherein g + f = 3, h = 1 to 10, preferably 1 to 6, particularly preferably 1 to 3, n = 1 to 10, preferably 1 to 5, particularly preferably 1 to 3, wherein the fragments with the indices a, b and c are freely permutable over the molecular chain and the sum of a, b and c is greater than 3, and wherein R1 is a saturated or unsaturated, linear or branched organic hydrocarbon residue, which is considered The hydrocarbon residue may contain heteroatoms O, S and / or N, preferably containing 1 to 400 carbon atoms, preferably 1 to 200 carbon atoms, particularly preferably 1 to 20 carbon atoms, R 1< * = hydrogen, is a saturated or unsaturated, linear or branched organic hydrocarbon residue.which may contain O, S and / or N as heteroatoms, preferably the hydrocarbon residue contains 1 to 400 carbon atoms, preferably 1 to 200 carbon atoms, particularly preferably 1 to 20 carbon atoms, R 2< = independently an alkyl group with 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, R 3< = independently an alkyl group with 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, R 4< = independently a hydrogen radical, a linear, branched or cyclic alkyl or chloroalkyl group with 1 to 20 carbon atoms, R 5< = independently a hydrogen radical or a linear, branched or cyclic alkyl or chloroalkyl group with 1 to 20 carbon atoms, an aryl or alkaryl group, and / or reaction products of a silyl group-bearing polyether according to formula (I) with one or more isocyanate-containing Compounds, where R 1< * is preferably a hydrogen, are involved,provided that component B has a higher proportion of repeating units (b) than repeating units (a) and / or (c) and component C has at least one catalyst , a coating can be produced that has such a property.
[0011] Surprisingly, it was found that the composition according to the invention, by combining hydrophilic and hydrophobic components, could produce a coating that has a surface with amphiphilic properties and can therefore counteract bio-growth.
[0012] If chemical (sum) formulas are used in the present invention, the indicated indices can represent both absolute numbers and average values.
[0013] For polymeric compounds, the indices preferably represent mean values.
[0014] Unless otherwise stated, percentages are given as weight percentages.
[0015] If measured values are given below, these measurements were carried out under standard conditions (25 °C and 1013 mbar), unless otherwise stated.
[0016] Unless otherwise stated, where average values are given below, they are weight averages.
[0017] Preferably, the composition according to the invention comprises silyl group-bearing polyethers with various repeating units, which are produced by reaction with one or more alkylene oxides, glycidyl ethers, carbon dioxide, cyclic anhydrides, isocyanates, caprolactones or cyclic carbonates or mixtures thereof.
[0018] The repeating units can preferably have a statistical distribution and / or a block-like distribution and / or a gradient distribution.
[0019] Preferably, the silyl group-bearing polyether has one or more terminal and / or one or more side-lying alkoxysilyl residues.
[0020] Silyl group-bearing polyethers are produced according to a process in accordance with EP 2 093 244 B1, EP 2 289 972 B1 or EP 2 289 961 A1.
[0021] It is well known to those skilled in the art which method can be used to produce silyl group-bearing polyethers.
[0022] Indices a, b, and c represent the preferred repeating units. Further repeating units d, e, f, etc., resulting, for example, from reactions with carbon dioxide, cyclic anhydrides, isocyanates, caprolactones, or cyclic carbonates, or mixtures thereof, are also conceivable.
[0023] Organic alkoxysilane compounds such as 3-glycidyloxypropyltrimethoxy- or -triethoxysilane, which are available, for example, under the trade names DYNASYLAN® < GLYMO or DYNASYLAN® < GLYEO (trademarks of Evonik Degussa GmbH), are used in the manufacture of preferred component B. Isocyanato-functional alkoxysilane compounds can also be used; For example, 3-isocyanatopropyltrimethoxysilane is available under the trade names Geniosil® < GF 40 (Wacker Chemie) or Silquest® < A-Link 35, Silquest* Y-5187 (Momentive), and 3-isocyanatopropyltriethoxysilane VESTANAT® < EP-IPMS (Evonik Industries AG), KBE-9007 (ShinEtsu), or Silquest® < A-1310 / A-Link 25 (Momentive). These represent the repeating units (a).
[0024] In general, all alkylene oxides known to a person skilled in the art can be used to generate the repeating units (b) and / or (c). Preferably, for example, ethylene oxide (EO), propylene oxide (PO), 1,2-epoxy-2-methylpropane (isobutylene oxide), epichlorohydrin, 2,3-epoxy-1-propanol, 1,2-epoxybutane (butylene oxide, hereinafter also abbreviated as BO), 2,3-epoxybutane, 2,3-dimethyl-2,3-epoxybutane, 1,2-epoxypentane, 1,2-epoxy-3-methylpentane, 1,2-epoxyhexane, 1,2-epoxycyclohexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxynonane, 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, styrene oxide (hereinafter also abbreviated as SO), 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, vinylcyclohexene oxide, (2,3-epoxypropyl)benzene, vinyloxirane, 3-phenoxy-1,2-epoxypropane, 2,3-epoxymethyl ether, 2,3-epoxyethyl ether, 2,3-epoxylisopropyl ether, (3,4-epoxybutyl) stearate, 4,5-Epoxypentyl acetate, 2,3-Epoxylpropane methacrylate, 2,3-Epoxypropane acrylate, Glycidyl butyrate, Methyl glycidate, Ethyl 2,3-epoxybutanoate,4-(Trimethylsilyl)butane-1,2-epoxide, 4-(Triethylsilyl)butane-1,2-epoxide, 3-(Perfluoromethyl)-1,2-epoxypropane, 3-(Perfluoroethyl)-1,2-epoxypropane, 3-(Perfluorobutyl)-1,2-epoxypropane, 3-(Perfluorohexyl)-1,2-epoxypropane, 4-(2,3-Epoxypropyl)morpholine, 1-(Oxiran-2-ylmethyl)pyrrolidin-2-one are used.
[0025] All of the alkylene oxides mentioned can be used individually or in any mixtures.
[0026] Ethylene oxide and / or propylene oxide are particularly preferred.
[0027] Preferably, the silyl group-bearing polyether has a ratio of repeating units (b) to (a) of > 5:1, particularly preferably > 8:1, most preferably > 10:1, and especially a ratio of b to a between 11:1 and 20:1. It is assumed that a high proportion of repeating units (b) after hydration causes and / or promotes the formation of a hydrogel. It is presumed that this "masks" the substrate surface (ship hulls, buoys, fishing nets, etc.) so that microorganisms do not perceive it as a surface.
[0028] Preferably, the process for producing the silyl group-bearing polyether is carried out such that the silyl group-bearing polyether has an NCO value of < than 0.1 wt.%.
[0029] Preferably, the isocyanate-containing compounds are mono-, di- and / or trifunctional isocyanates selected from the group consisting of methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, other linear or branched or cyclic C4-C20 alkyl monoisocyanates, in particular lauryl isocyanate, stearyl isocyanate, toluene-2,4-diisocyanate (TDI), diphenylmethane diisocyanate or methylenediphenyl diisocyanate (MDI), hexamethylene diisocyanate (HMDI), 2,2,4-trimethylhexane-1,6-diisocyanate (TMDI), polymeric diphenylmethane diisocyanate (PMDI), isophorone diisocyanate (IPDI), 4,4'-diisocyanatodicyclohexylmethane (H12MDI), isophorone diisocyanate (IPDI), triphenylmethane triisocyanate, 1,3,5-benzene triisocyanate and 2,4,6-toluene triisocyanate.
[0030] The urethanization of the silyl group-bearing polyether is known to the skilled person according to US 9,035,011 (EP2 636 696) or US 8,993,706, US 9,441,145 (EP2 289 972).
[0031] Preferably, the polysiloxane is a linear, simply or multiply branched Si-OH or SiOR 3< functional polysiloxane.
[0032] Hydroxyfunctional siloxanes are available from Evonik Industries under the trade name Polymer OH, but also, for example, from Dow Corning under the product names DOW CORNING ®< 3-3602, XIAMETER ®< OHX-4081, DOW CORNING ®< 5-0299, XIAMETER ®< OHX-4000 POLYMER 2000CS, XIAMETER ®< OHX-4081, XIAMETER ®< PMX-0156 SILANOL FLUID.
[0033] Alkoxy-functional methyl and methyl / phenyl siloxane oligomers are available from ShinEtsu, for example, KC-89S, KR-500, X 40-9225, X 40-9246, X 40-9250, KR-401N, X-40-9227, KR-510, KR-9218, and KR-213. Hybrids are also available that incorporate additional functionality, such as epoxy functionality, like X-41-1053, X-41-1059A, X-24-9590, and KR-516.
[0034] Methoxy-functional methyl and methyl / phenyl siloxanes are available from Dow Corning under the trade names Dow Corning® US-CF 2403 Resin, US-CF 2405 Resin, 3037 Intermediate, 3074 Intermediate, and RSN-5314 Intermediate. Silanol-functional methyl / phenyl resins are marketed under the trade names RSN-0409 HS Resin, RSN-0431 HS Resin, RSN-0804 Resin, RSN-0805 Resin, RSN-0806 Resin, RSN-0808 Resin, and RSN-0840 Resin.
[0035] Epoxy-functional siloxanes are available on the market from, among others, Evonik Industries under the trade name TEGOMER® < E-Si 2330 or from ShinEtsu under the trade names KF-105, X22-163 a, X22-163 b, X22-163 c, X22-169 As, X22-169 B or Dow Corning Toray AY 42-119, BY 16-760, BY 16-839, BY 16-869, BY 16-870, BY 16-877. Epoxy compounds are available on the market from, among others, Momentive / Hexion under the trade names Epon, Eponex, Epalloy and Ipox Chemicals under the trade names ipox ER, ipox CL and ipox RD.
[0036] Alkoxy-functional methyl / phenyl and methyl silicone resins, which are also offered partially hydrolyzed to the corresponding silanol, are available under the trade name SILRES® from Wacker Chemie, such as REN 50, REN 60, REN 80, KX, HK 46, MSE 100 or SY 300, IC 836, REN 168, SY 409, IC 232, SY 231, IC 368, IC 678.
[0037] The production of such silicone resins has long been known in the literature (see W. Noll - Chemie und Technologie der Silicone, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 1960) and is also described in the German patent DE 34 12 648.
[0038] Preferably, the polysiloxane is an alkoxypolysiloxane.
[0039] The composition preferably comprises at least one epoxy-functional compound and one amino-functional compound as further components.
[0040] Preferably, the epoxy-functional compound is an epoxy-functional silane or siloxane, or an aromatic or aliphatic glycidyl ether, or their condensates or mixtures thereof.
[0041] Preferred epoxy functional compounds are the epichlorohydrin-derived glycidyl ethers, glycidyl esters, and glycidylamines, more preferably bisphenol A diglycidyl ethers, bisphenol F diglycidyl ethers, glycidyl ethers of novolaks (epoxy novolak resins), hydrogenated bisphenol A diglycidyl ethers, hydrogenated bisphenol F diglycidyl ethers, phenyl glycidyl ethers, cresyl glycidyl ethers, tert-butyl glycidyl ethers, diglycidylaniline, tetraglycidylmethylenedianiline, triglycidylaminophenol, 1,6-hexane diglycidyl ethers, 1,4-butane diglycidyl ethers, cyclohexanedimethyl diglycidyl ethers, alkyl glycidyl ethers, benzyl glycidyl ethers, trimethylolpropane triglycidyl ethers, pentaerythritol tetraglycidyl ethers, and brominated glycidyl ethers such as tetrabromobisphenol A. Diglycidyl ethers, alkyl glycidyl esters, triglycidyl isocyanurate, allyl glycidyl ethers, poly(alkylene glycol) diglycidyl ethers, and epoxide compounds of unsaturated hydrocarbons and unsaturated fats or fatty acids.Oligomeric and polymeric epoxy compounds selected from epoxy-bearing polyolefins and siloxanes, or epoxy compounds formed by chain extension, preferably from diglycidyl ethers with OH-functional compounds, are also preferred. Epoxy compounds with two or more than two epoxy groups per molecule are particularly preferred.
[0042] Preferably, the amino-functional compound is an amino-functional alkoxysilane, more preferably an amino-functional di- or trialkoxysilane. Such amino-functional di- or trialkoxysilanes are available on the market, for example under the trade names Dynasylan® (Evonik Industries AG), Silquest® (Momentive), KBE903, KBM903, KBM603, KBE603, KBM602 (ShinEtsu), Geniosil® (Wacker Chemie), or Z-6011, AZ-720, Z-6610, Z-6015, Z-6020Z, Z-6094, Z-6021, 1-6436Z-6023, AY43-009 (Dow Corning).
[0043] Preferably, the stoichiometric ratio of epoxy function to amino function is in the range of 5 : 0.1 to 0.1 : 5, preferably 1 : 1.5, particularly preferably 1 : 1.
[0044] Preferably, the composition according to the invention comprises at least one crosslinking agent, according to formula (II) R 6< d Si(OR 7< ) e formula (II) with the stipulation 0 ≤ d ≤ 2, 0 ≤ e ≤ 4 and d + e = 4, R 6< = independently an alkyl group or cycloalkyl group with 1 to 8 carbon atoms or an aromatic group with 6 to 20 carbon atoms, R 7< = independently an alkyl group with 1 to 8 carbon atoms, preferably a methyl, ethyl, propyl or isopropyl group.
[0045] Alkyl groups can be, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, or t-butyl groups. An aromatic group can be, for example, a phenyl group. Preferred substituents R are methyl or phenyl, or mixtures of methyl and phenyl, where the Ph:Me ratio can range from 0:1 to 1:0.
[0046] Catalysts selected from the group of catalysts promoting the hydrolysis-condensation mechanism, such as organotin catalysts, titanates or zirconates, organometallic compounds of aluminum, iron, calcium, magnesium, zinc or bismuth, Lewis acids or organic acids / bases, linear or cyclic amidines, guanidines or amines or a mixture thereof, are preferably used.
[0047] Preferred catalysts are the hydrolysis / condensation catalysts for alkoxysilanes known to those skilled in the art. Preferably, organic tin compounds are used as hardening catalysts, such as dibutyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin diacetate, dibutyltin dioctoate, or dioctyltin dilaurate, dioctyltin diacetylacetonate, dioctyltin diketanoate, dioctylstannoxane, dioctyltin dicarboxylate, dioctyltin oxide, preferably dioctyltin diacetylacetonate, dioctyltin dilaurate, dioctyltin diketanoate, dioctylstannoxane, dioctyltin dicarboxylate, dioctyltin oxide, and particularly preferably dioctyltin diacetylacetonate and dioctyltin dilaurate. Furthermore, zinc salts such as zinc octoate, zinc acetylacetonate and zinc 2-ethylcaproate, or tetraalkylammonium compounds such as N,N,N-trimethyl-N-2-hydroxypropyl-ammonium hydroxide, N,N,N-trimethyl-N-2-hydroxypropylammonium-2-ethylhexanoate or choline 2-ethylhexanoate can also be used.The use of zinc octoate (zinc 2-ethylhexanoate) and tetraalkylammonium compounds is preferred, especially that of zinc octoate. Further preferred are bismuth catalysts, e.g., TIB Kat (TIB Mannheim) or Borchi® catalysts, titanates, e.g., titanium(IV) isopropylate, iron(III) compounds, e.g., iron(III) acetylacetonate, aluminum compounds, such as aluminum triisopropylate, aluminum trisec-butoxide and other alcoholates as well as aluminum acetylacetonate, calcium compounds, such as calcium disodium ethylenediamine tetraacetate or calcium diacetylacetonate, or also amines, e.g., triethylamine, tributylamine, 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, N,N-bis-(N,N-dimethyl-2-aminoethyl)-methylamine, N,N-dimethylcyclohexylamine, N,N-dimethylphenylamine. N-Ethylmorpholine etc..Organic or inorganic Brønsted acids such as acetic acid, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid, or benzoyl chloride, hydrochloric acid, phosphoric acid, and their mono- and / or diesters, such as butyl phosphate, (iso)propyl phosphate, dibutyl phosphate, etc., are also preferred as catalysts. Organic compounds containing guanidine groups and organosilicon compounds are also preferred. Combinations of several catalysts can, of course, be used. Furthermore, photolatent bases, as described in WO 2005 / 100482, can also be used as catalysts.
[0048] The hardening catalyst is used in amounts of 0.1 to 5.0 wt.%, preferably 0.2 to 4.0 wt.% and particularly preferably 0.5 to 3 wt.% based on the mass sum of component (A), compound (b1) and the optional alkoxysilane compounds.
[0049] Preferably, the composition according to the invention contains further additives selected from the group consisting of plasticizers, fillers, solvents, adhesion promoters, rheology additives, stabilizers, catalysts, solvents and drying agents, in particular chemical moisture-drying agents.
[0050] It can be advantageous if the curable mixture according to the invention includes a drying agent, e.g., for binding water or moisture introduced by formulation components or subsequently introduced during the filling process or storage. In principle, all drying agents known from the prior art can be used as drying agents in the curable mixtures according to the invention.Preferred chemical drying agents include vinyltrimethoxysilane (Dynasylan® < VTMO, Evonik or Geniosil® < XL 10, Wacker), vinyltriethoxysilane (Dynasylan® < VTEO, Evonik or Geniosil® < GF 56, Wacker), N-trimethoxysilylmethyl-O-methylcarbamate (Geniosil® < XL 63, Wacker), N-dimethoxy(methyl)silylmethyl-O-methylcarbamate, N-methyl[3-(trimethoxysilyl)-propyl]carbamate (Geniosil® < GF 60, Wacker), vinyldimethoxymethylsilane (Geniosil® < XL 12, Wacker), vinyltris(2-methoxyethoxy)silane (Geniosil® < GF 58, Wacker), and bis(3-triethoxysilylpropyl)amine (Dynasylan® < 1122, Evonik), Bis(3-trimethoxysilylpropyl)amine (Dynasylan ®< 1124), N-Dimethoxy(methyl)silylmethyl-O-methyl-carbamate (Geniosil ®< XL 65, Wacker) or oligomeric vinylsilanes such as Dynasylan ®< 6490 and Dynasylan ®< 6498 (both available from Evonik) alone or mixtures thereof.Preferably, the drying agents are selected from vinyltrimethoxysilane (Dynasylan® < VTMO, Evonik or Geniosil® < XL 10, Wacker AG) or vinyltriethoxysilane (Dynasylan® < VTEO, Evonik or Geniosil® < GF 56, Wacker). Furthermore, it may be advantageous to use a physical drying agent, preferably zeolite, molecular sieve, anhydrous sodium sulfate or anhydrous magnesium sulfate, in addition to or as an alternative to chemical drying.
[0051] The proportion of drying agents in the curable compositions according to the invention is preferably greater than 0 to 5 wt.%, preferably 0.2 to 3 wt.% based on the amount of alkoxysilyl group-bearing polymers used.
[0052] The use of solvents can also be advantageous. For example, solvents can reduce the viscosity of the uncrosslinked binder or facilitate its application to the surface. In principle, all solvents and solvent mixtures are suitable. A suitable solvent can be selected from the group of alkanes, alkenes, alkynes, benzene, and aromatics with aliphatic and aromatic substituents, carboxylic acid esters, linear and cyclic ethers, and, at high pressures, also carbon dioxide, halogenated aliphatic or aromatic hydrocarbons, ketones or aldehydes, lactones (γ-butyrolactone), lactams (e.g., γ-butyrolactone).N-methyl-2-pyrrolidone), nitriles, nitro compounds, tertiary carboxylic acid amides (dimethylformamide), urea derivatives such as tetramethylurea or dimethylpropyleneurea (DMPU), sulfoxides such as dimethyl sulfoxide (DMSO), sulfones such as sulfolane, carbonic acid esters such as dimethyl carbonate or ethylene carbonate. Also included are protic solvents such as water, methanol, ethanol, n- and isopropanol and other alcohols, primary and secondary amines, carboxylic acids and their esters, as well as anhydrides, primary and secondary amides such as formamide. Preferred solvents in coating applications include ethers, e.g., tert-butyl methyl ether, esters such as ethyl acetate or n-butyl acetate, tert-butyl acetate or diethyl carbonate, and alcohols such as ethanol and the various regioisomers of propanol and butanol. Furthermore, preferred solvents are aromatic and / or aliphatic solvents such as benzene, toluene or naphtha fractions.
[0053] If required, the curable mixtures according to the invention may also contain one or more substances selected from the group comprising co-crosslinkers, flame retardants, deaerators, curing accelerators for the amine-epoxide reaction, antimicrobial and preservative substances, dyes, colorants and pigments, antifreeze, fungicides and / or reactive diluents, as well as complexing agents, spray aids, wetting agents, perfumes, light stabilizers, radical scavengers, UV absorbers and stabilizers, in particular stabilizers against thermal and / or chemical stresses and / or stresses from ultraviolet and visible light.
[0054] UV stabilizers are preferably known products based on hindered phenolic systems or benzotriazoles. For example, so-called HALS amines can be used as light stabilizers. For example, products or product combinations known to those skilled in the art, such as Tinuvin® stabilizers (BASF), such as Tinuvin® 1130, Tinuvin® 292, or Tinuvin® 400, preferably Tinuvin® 1130 in combination with Tinuvin® 292, can be used as stabilizers. The amount used depends on the degree of stabilization required.
[0055] Inorganic pigments such as metal oxides or spinel pigments are particularly suitable for coloring coating systems. Typical corrosion protection pigments, such as zinc phosphate, are also used to improve corrosion protection.
[0056] Preferred fillers include precipitated or ground chalk, inorganic carbonates in general, precipitated or ground silicates, precipitated or pyrogenic silicas, glass powder, hollow glass spheres (so-called bubbles), metal oxides such as TiO₂, Al₂O₃, natural or precipitated barium sulfates, quartz flour, sand, aluminum trihydrate, talc, mica, cristobalite flour, reinforcing fibers such as glass fibers or carbon fibers, long or short-fiber wollastonites, cork, carbon black, or graphite. Hydrophobic fillers can be advantageously used, as these products exhibit lower water absorption and improve the storage stability of the formulations.
[0057] Preferably the composition according to the invention contains 1 wt.% to 85 wt.%, preferably 5 wt.% to 75 wt.%, particularly preferably 20 wt.% to 60 wt.% component A, 1 wt.% to 50 wt.%, preferably 10 wt.% to 40 wt.%, particularly preferably 15 wt.% to 35 wt.% component B, 0.01 wt.% to 5 wt.%, preferably 0.05 wt.% to 3 wt.%, particularly preferably 0.1 wt.% to 2 wt.% component C based on 100% by weight of the composition.
[0058] Preferably, it can contain 0.1 wt.% to 40 wt.%, preferably 10.0 wt.% to 35 wt.%, particularly preferably 20.0 wt.% to 30.0 wt.% component D consisting of at least one epoxy-functional compound and one amino-functional compound based on the total composition.
[0059] Preferably, component D consists of 30 wt.% to 95 wt.%, preferably 40 wt.% to 90 wt.%, particularly preferably 65 wt.% to 85 wt.% of the epoxy functional compound and of 0.1 wt.% to 50 wt.%, preferably 5 wt.% to 40 wt.%, particularly preferably 10 wt.% to 30 wt.% of the amino functional compound based on the total composition.
[0060] Preferably, component D has more epoxy-functional compound than amino-functional compound.
[0061] Preferably, the composition according to the invention has a water content of <1000 ppm, preferably <200 ppm, particularly preferably <50 ppm.
[0062] By adding drying agents, the water content can be reduced to 0 ppm.
[0063] Advantageously, the composition according to the invention has a sufficient quantity of drying agents to increase the storage stability of the composition, particularly in 1K systems.
[0064] Depending on the storage location, storage method and other additives, the expert can determine the sufficient amount of desiccant.
[0065] It is also conceivable to provide the composition according to the invention as a 2K system. In this case, component A and component B are provided separately from component C. The provision of the composition according to the invention can be adapted to the existing manufacturing process of the respective coating.
[0066] Another variant of the 2K systems is the composition according to the invention in the presence of a component D. Here, the proportion of epoxy-functional compound is provided together with component A and component B, but component C should be provided separately and the amine-functional compound of component D should optionally also be provided separately from the other components.
[0067] Those skilled in the art are aware that other variations in composition are possible. Each must be adapted to the specific process conditions during production and use.
[0068] Another object of the invention is coatings, varnishes and paints containing a curable composition according to the invention.
[0069] Another invention is the use of the curable composition for the production of coatings, varnishes and paints, preferably for the prevention or reduction of biofouling.
[0070] The coating system according to the invention, applied to the substrate, cures upon exposure to atmospheric moisture through a catalyzed hydrolysis-condensation crosslinking process. A combined forced drying at elevated temperature and simultaneous chemical crosslinking through hydrolysis-condensation, with sufficient moisture introduced into the oven, are not mutually exclusive and depend significantly on the substrate to be coated.
[0071] The objects according to the invention are described below by way of example, without the invention being limited to these exemplary embodiments. Methods: Drying time measurements
[0072] To assess the catalytic activity of catalysts in a binder, the drying time can be determined using a drying recorder. ASTM D5895 describes such a test procedure. Following this method, drying time measurements were performed using a BK3 type drying recorder (The Mickle Laboratory Engineering Co. Ltd., Goose Green, Gomshall, Guildford, Surrey GU5 9LJ, UK). Binder films were applied to standard glass strips (30 x 2.5 cm x 2 mm) using a box doctor blade (Erichsen Model 360, wet film thickness 100 µm). The standard glass strips were first cleaned of dust, dirt, and grease with acetone and subsequently with an ethanol / deionized water mixture. The slider was then moved to the left into the starting position using a lever on the back. The scoring pins were then folded down onto the sample glass plates. The test duration was set to 24 hours and the measurement was started.After 24 hours, if necessary, the stylus was repositioned at the starting point to obtain a 48-hour reading. Once the test period had elapsed, the scoring styluses were flipped up and the glass plates removed for evaluation. The drying times were read from the attached time scale. Inert working mode
[0073] "Inert" conditions mean that the gas space within the apparatus is filled with an inert gas, such as nitrogen or argon. This is achieved by flooding the apparatus, with a subsequent low-level inert gas flow ensuring continuous inerting. application
[0074] The binder composition is generally applied by spraying, but can also be applied using other techniques such as brushing, rolling, flooding, dipping, wiping, or pouring. Suitable substrates include metallic surfaces such as steel, cast steel, stainless steel, aluminum, cast aluminum, or hot-dip galvanized steel. For improved adhesion, the substrate can be roughened by sandblasting or grinding. Non-metallic substrates such as glass, plastics, or inorganic substrates such as ceramics, stoneware, concrete, etc., can also be used.
[0075] The binder composition according to the invention, applied to the substrate, then hardens upon exposure to atmospheric moisture through a catalyzed hydrolysis-condensation crosslinking process. A combined forced drying at elevated temperature and simultaneous chemical crosslinking through hydrolysis-condensation, with sufficient moisture introduced into the oven, are not mutually exclusive.
[0076] Another advantage of hydrolysis-condensation coating systems with a catalyst is that they are not subject to pot life issues when used in closed containers, as curing only occurs in the presence of water from the ambient humidity. Unlike conventional, purely physical-curing coating systems, such as those based on silicone resins, which require baking at least 30 minutes at 250 °C to achieve full mechanical and chemical resistance, the energy required for oven drying can be completely eliminated here. viscosity
[0077] The viscosity was determined as a function of shear rate at 25 °C using the Anton Parr MCR301 rheometer in a plate-plate setup with a gap width of 1 mm. The diameter of the upper plate was 40 mm. The viscosity at a shear rate of < 10 s⁻¹ was recorded and is shown in Tables 2 and 3.
[0078] GPC measurements to determine polydispersity and mean molar masses were performed under the following measurement conditions: column combination SDV 1000 / 10000 Å (length 65 cm), temperature 30 °C, THF as mobile phase, flow rate 1 ml / min, sample concentration 10 g / l, RI detector, evaluation against polypropylene glycol standard (6000 g / mol). NCO content
[0079] The NCO content in percent was determined by back titration with 0.1 molar hydrochloric acid after reaction with dibutylamine according to DIN EN ISO 11909. Further conditions
[0080] Unless otherwise stated, percentages given in the context of the present invention are expressed as percentages by weight. For compositions, percentages refer to the total composition unless otherwise stated. Where average values are given below, they are numerical averages unless otherwise stated. Where measured values are given below, these were determined at a pressure of 101,325 Pa, a temperature of 23 °C, and an ambient relative humidity of approximately 40% unless otherwise stated. Materials and equipment:
[0081] Glass plates, manufacturer: Gläserei Glänzer, dimensions: 90 x 150 x 5 mm; PVC sheets, material no.: 4364002858, KVG Kunststoff Betriebs GmbH; 300 µm box squeegee, manufacturer: Simex; 300 µm cube squeegee, manufacturer: TQC GmbH, Dispermat, VMA Getzmann with Teflon disc; wide-mouth glass bottles Chemicals and raw materials used: Component A (Polysiloxane)
[0082] Four polysiloxanes were used. Table 1: Polysiloxane Type and company Phenyl-methyl ratio (Ph:Me) Methoxy value (wt%) Molecular weight (Mw = kg / mol) A1 US-CF 2405, Dow Corning 1:0 28 ~4 A2 3037 Intermediate, Dow Corning 0,25:1 15-18 ∼1 A3 3074 Intermediate, Dow Corning 1:1 15-18 ~1.3 A4 Polymer OH 20, Evonik CAS No. 70131-67-8 Component B (reaction products with silyl group-bearing polyether)
[0083] Three components B1 to B3 were used, with B1 and B2 having no repeating unit (b).
[0084] B1 is a trimethoxysilyl group-terminated polyurethane produced according to a process according to EP1 093 482 (US 6884852) which has a viscosity of 35,000 mPas. Production of B2
[0085] In a 5-liter autoclave, 400 g of polypropylene glycol with an average molar mass of 2000 g / mol were placed and treated with 150 ppm (based on the total volume) of a zinc hexacyanocobaltate double metal cyanide catalyst. For inerting, the reactor was pressurized with nitrogen up to 3 bar and then depressurized to atmospheric pressure. This process was repeated twice more. While stirring, the reactor contents were heated to 130 °C and evacuated to approximately 20 mbar to remove volatile components. After 30 minutes, 80 g of propylene oxide were added to the evacuated reactor to activate the catalyst. The internal pressure initially rose to approximately 0.8 bar. After about 6 minutes, the reaction started, which was indicated by a drop in the reactor's internal pressure. A mixture of 2352 g propylene oxide and 166.8 g Dynasylan ®< GLYEO (Evonik company) was then continuously added over approximately 180 minutes at 90-110 °C.After a one-hour post-reaction, the mixture was deodorized at <100 mbar to remove any remaining unreacted alkylene oxide. Subsequently, 500 ppm of Irganox® < 1135 (BASF) was stirred in for 15 minutes. A colorless, viscous prepolymer (16,500 mPas at 25 °C) was obtained, containing an average of 3 mol of triethyoxysilyl groups and 2 OH groups per molecule, with a polydispersity Mw / Mn of 2.3. The weight fraction of EO in the prepolymer was 0%.
[0086] At 60 °C, 97.7 g of isophorone diisocyanate were added, the mixture was stirred for five minutes, and then 0.08 g of TIB Kat 216 (dioctyltin dilaurate) was added. The mixture was stirred for 45 minutes, heated to 80 °C, and then 216 g of a polyether of the general formula C₄H₉O[CH₂CH(CH₃)O]₅H₆ was added. The mixture was then stirred for a further 3 hours.
[0087] The finished product B2 had a viscosity of 67,000 mPas at 25 °C and a polydispersity M w / M n of 5.2. The NCO content was <0.1%. Production of B3
[0088] In a 5-liter autoclave, 400 g of polypropylene glycol with an average molar mass of 2000 g / mol were placed and treated with 150 ppm (based on the total volume) of a zinc hexacyanocobaltate double metal cyanide catalyst. For inerting, the reactor was pressurized with nitrogen up to 3 bar and then depressurized to atmospheric pressure. This process was repeated twice more. While stirring, the reactor contents were heated to 130 °C and evacuated to approximately 20 mbar to remove volatile components. After 30 minutes, 80 g of propylene oxide were added to the evacuated reactor to activate the catalyst. The internal pressure initially rose to approximately 0.8 bar. After about 6 minutes, the reaction started, which was indicated by a drop in the reactor's internal pressure. A mixture of 1847 g propylene oxide, 449 g ethylene oxide and 222.4 g Dynasylan ®< GLYEO (Evonik company) was then continuously added over approximately 180 minutes at 90-110 °C.After a one-hour post-reaction, the mixture was deodorized at <100 mbar to remove any remaining unreacted alkylene oxide. Subsequently, 500 ppm of Irganox® < 1135 (BASF) was stirred in for 15 minutes. A colorless, viscous prepolymer (14,000 mPas at 25 °C) was obtained, containing an average of 4 mol of triethyoxysilyl groups and 2 OH groups per molecule, with a polydispersity Mw / Mn of 2.5. The weight fraction of EO in the prepolymer was 15.0%.
[0089] At 60 °C, 107 g of isophorone diisocyanate were added, the mixture was stirred for five minutes, and then 0.08 g of TIB Kat 216 (dioctyltin dilaurate) was added. The mixture was stirred for 45 minutes, heated to 80 °C, and then 224 g of a polyether of the general formula C₄H₉O[CH₂CH(CH₃)O]₅H₆ was added. The mixture was then stirred for a further 3 hours.
[0090] The finished product B3 had a viscosity of 56,000 mPas at 25 °C and a polydispersity Mw / Mn of 5.0. The NCO content was <0.1%. Component C (catalyst.)
[0091] The catalyst used was the product TibKat 318 (DBTL) from TIB Mannheim with CAS No. 68299-15-0. Component D
[0092] Epoxy-functional and amino-functional compounds are commercially available products. Table 2: Epoxy-functional and amino-functional compounds Epoxy-functional / amino-functional compound company Product name Characteristic D1 a,w-epoxypropoxypropyl-functional polydimethylsiloxane Read DMS-E12, CAS No. 102782-97-8 Epoxy 1.7 Eq / kg (=588 g / eq) D2 epoxy resin Hexion Eponex Resin 1510 Epoxy 4.717 Eq / kg (=212 g / eq) D3 Aminopropyltriethoxysilane Evonik Dynasylan AMEO, CAS no. 919-30-2 solvent
[0093] Xyol, isomer mixture (Aldrich, CAS No. 1330-20-7) Isopropanol (Aldrich, article number 59300-M) 1. Preparation of the composition and application for determining the coating quality, drying behavior and antifouling properties
[0094] The compositions Z1-Z12 according to the invention and the comparative compositions VZ1-VZ36 were prepared as follows, according to the information in Tables 3-6: Component A was placed in nitrogen-inertized wide-mouth bottles (250 ml) and overlaid with component B. The mixture was then homogenized for 2 minutes at 2000 rpm using a disperser with an attached Teflon disc (VMA Getzmann). The epoxy-functional component D1 or D2 was then added and homogenized, followed by the calculated amount of the amino-functional catalyst D3. After repeated homogenization for 2 minutes at 2000 rpm, catalyst C was added and homogenized again. For curable compositions without component D, component C was added directly after component B, and homogenization was carried out analogously.All mixing processes at the dispersant were carried out in such a way as to keep gas ingress into the composition to a minimum. An inert gas cover ensured the gas volume above the binder phase.
[0095] After a short resting period of 5 minutes, the compositions according to the invention, as well as comparison compositions for evaluating the film properties, were applied at room temperature to glass plates (Glänzer Glassworks, dimensions: 90 x 150 x 5 mm) cleaned with isopropanol using a 300 µm box doctor blade (300 µm box doctor blade, Simex) and dried at room temperature. To determine the drying time, they were applied to standard glass strips (30 x 2.5 cm x 2 mm) using a box doctor blade (Erichsen Model 360, wet film thickness 100 µm). In addition, PVC panels (PVC sheets, 200 x 400 x 5 mm, item no. 4364002858, KVG Kunststoff Betriebs GmbH), which had previously been pretreated with a commercially available primer for improved adhesion, were coated by spray application. To achieve the required spray viscosities, these were adjusted by dilution with xylene (isomer mixture). Drying was then carried out for 24 hours in designated drying ovens at room temperature. Table 3: Compositions with component A1 VZ1 VZ2 VZ3 Z1 VZ4 VZ5 VZ6 Z2 VZ7 VZ8 VZ9 Z3 Component A A1 70 70 70 70 70 70 70 70 70 70 70 70 Component B B1 30 30 30 B2 30 30 30 B3 30 30 30 Component C Catalyst* 2 2 2 2 2 2 2 2 2 2 2 2 Component D D1 30 30 30 30 D2 30 30 30 30 D3** 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1
[0096] The figures are given in parts of weight, whereby *Component C is given in wt% based on the total composition and **the amount of component D3 is calculated using the ratio of D1 or D2 according to the specified mole ratio. Table 4: Compositions with component A2 VZ10 VZ1 1 VZ12 Z4 VZ13 VZ14 VZ15 Z5 VZ16 VZ17 VZ18 Z6 Component A A2 70 70 70 70 70 70 70 70 70 70 70 70 Component B B1 30 30 30 B2 30 30 30 B3 30 30 30 Component C Catalyst* 2 2 2 2 2 2 2 2 2 2 2 2 Component D D1 30 30 30 30 D2 30 30 30 30 D3** 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1
[0097] The figures are given in parts of weight, whereby *Component C is given in wt% based on the total composition and **the amount of component D3 is calculated according to the ratio of D1 or D2 as specified in the mole ratio. Table 5: Compositions with component A3 VZ19 VZ20 VZ21 Z7 VZ22 VZ23 VZ24 Z8 VZ25 VZ26 VZ27 Z9 Component A A3 70 70 70 70 70 70 70 70 70 70 70 70 Component B B1 30 30 30 B2 30 30 30 B3 30 30 30 Component C Catalyst* 2 2 2 2 2 2 2 2 2 2 2 2 Component D D1 30 30 30 30 D2 30 30 30 30 D3** 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1
[0098] The figures are given in parts of weight, whereby *Component C is given in wt% based on the total composition and **the amount of component D3 is calculated according to the ratio of D1 or D2 as specified in the mole ratio. Table 6: Compositions with component A4 VZ28 VZ29 VZ30 Z10 VZ31 VZ32 VZ33 Z11 VZ34 VZ35 VZ36 Z12 Component A A4 70 70 70 70 70 70 70 70 70 70 70 70 Component B B1 30 30 30 B2 30 30 30 B3 30 30 30 Component C Catalyst* 2 2 2 2 2 2 2 2 2 2 2 2 Component D D1 30 30 30 30 D2 30 30 30 30 D3** 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1
[0099] The figures are given in parts of weight, whereby *Component C is given in wt% based on the total composition and **the amount of component D3 is calculated according to the ratio of D1 or D2 as specified in the mole ratio. 2. Assessment of the applied compositions
[0100] Table 7: Drying time and appearance Drying time [h] Look Drying time [h] Look VZ1 <12 2 VZ19 < 24 2 VZ2 <24 2 VZ20 < 24 2 VZ3 <24 2 VZ21 < 24 2 Z1 <24 1 Z7 < 12 1 VZ4 < 24 2 VZ22 < 12 1 VZ5 < 24 2 VZ23 < 12 1 VZ6 < 24 2 VZ24 < 12 2 Z2 < 24 1 Z8 < 12 1 VZ7 < 24 2 VZ25 < 12 2 VZ8 < 24 2 VZ26 < 12 2 VZ9 < 24 2 VZ27 < 12 1 Z3 < 24 1 Z9 < 12 1 VZ10 < 24 2 VZ28 < 48 2 VZ11 < 24 3 VZ29 < 48 2 VZ12 < 24 3 VZ30 < 48 2 Z4 < 24 1 Z10 < 36 1 VZ13 < 24 2 VZ31 < 48 2 VZ14 < 24 2 VZ32 < 36 2 VZ15 < 24 2 VZ33 < 36 2 Z5 < 24 1 Z11 < 24 1 VZ16 < 24 2 VZ34 < 36 2 VZ17 < 24 2 VZ35 < 36 2 VZ18 < 24 2 VZ36 < 36 2 Z6 < 24 1 Z12 < 24 1
[0101] Visual assessment of the coating: 1 = very good, even lift, no defects, clear; 2 = good, even lift, mostly no defects, clear or cloudy; 3 = not OK, uneven lift, many defects 3. Determination of the antifouling properties
[0102] To test the compositions regarding their effectiveness in preventing biofouling, the compositions produced under point 1 were applied to PVC panels, analogous to the above description, which were then placed in the North Sea (Hooksiel or Norderney) for static immersion experiments.
[0103] The coated PVC test panels (coatings according to the invention B1 - B12, comparison coatings VB1 - VB36) measuring 20 x 40 cm were submerged at a depth of 20 cm below the water surface between March and October 2015. Every two months, the test panels were visually inspected and assessed for fouling. Furthermore, a 10 cm strip in the lower area of the test panel was wiped with a standard rubber squeegee (window rubber blade) without applying pressure, once from right to left and then from left to right, to determine the ease of removal of the fouling.
[0104] The overall assessment was carried out using a scale as follows: 0 = no growth 1 = minimal growth, very easy to remove 2 = light growth, very easy to remove 3 = moderate growth, noticeable residue 4 = heavy growth, heavy residue 5 = very heavy growth, cannot be removed Table 8: coating 0 months 2 months 4 months 6 months 8 months VB1 0 2 4 5 5 VB2 0 2 4 5 5 VB3 0 2 4 5 5 B1 0 1 1 2 3 VB4 0 1 3 4 5 VB5 0 1 2 4 5 VB6 0 1 2 3 5 B2 0 0 1 1 3 VB7 0 1 2 4 5 VB8 0 1 3 4 5 VB9 0 2 3 3 5 B3 0 0 1 1 3 VB10 0 1 3 5 5 VB11 0 2 3 5 5 VB12 0 1 3 5 5 B4 0 1 1 2 3 VB13 0 1 3 5 5 VB14 0 1 2 4 5 VB15 0 1 2 3 5 B5 0 0 1 1 2 VB16 0 1 2 4 5 VB17 0 1 3 4 5 VB18 0 2 3 3 5 B6 0 0 1 2 2 VB19 0 2 4 4 5 VB20 0 2 5 5 5 VB21 0 2 4 5 5 B7 0 1 1 1 2 VB22 0 1 3 4 5 VB23 0 1 2 4 5 VB24 0 1 2 3 5 B8 0 0 0 0 1 VB25 0 1 2 4 5 VB26 0 1 3 4 5 VB27 0 2 3 3 5 B9 0 0 0 0 1 VB28 0 2 2 3 4 VB29 0 2 3 5 5 VB30 0 2 4 5 5 B10 0 1 1 1 2 VB31 0 1 2 4 5 VB32 0 1 2 4 5 VB33 0 1 2 3 5 B11 0 0 0 1 1 VB34 0 1 2 4 4 VB35 0 1 2 3 4 VB36 0 2 3 3 4 B12 0 0 0 1 1
[0105] The coatings with the compositions B1 - B12 according to the invention showed minimal to slight fouling after 8 months, which was very easy to remove.
Claims
1. Curable composition comprising, as - component A, at least one polysiloxane, - component B, at least one polyether bearing silyl groups and / or reaction products of a polyether bearing silyl groups with one or more isocyanate-containing compounds of formula (I): with a = 1 to 100, preferably 1 to 10, more preferably 2 to 5, b = 1 to 500, preferably 1 to 400, more preferably 1 to 300, c = 0 to 500, preferably 1 to 400, more preferably 1 to 300, f = 0 to 2, g = 1 to 3, with the proviso that g + f = 3, h = 1 to 10, preferably 1 to 6, more preferably 1 to 3, n = 1 to 10, preferably 1 to 5, more preferably 1 to 3, with the proviso that the fragments having the indices a, b and c are distributed over the molecule chain in a freely permutable manner and that the sum total of a, b and c is > 3, and where R1 = a saturated or unsaturated, linear or branched organic hydrocarbon radical which may contain O, S and / or N as heteroatoms, the hydrocarbon radical preferably containing 1 to 400 carbon atoms, preferably 1 to 200 carbon atoms, more preferably 1-20 carbon atoms, R1* = hydrogen, a saturated or unsaturated, linear or branched organic hydrocarbon radical which may contain O, S and / or N as heteroatoms, the hydrocarbon radical preferably containing 1 to 400 carbon atoms, preferably 1 to 200 carbon atoms, more preferably 1-20 carbon atoms, R2 = independently at each instance an alkyl group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, R3 = independently at each instance an alkyl group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, R4 = independently at each instance a hydrogen radical, a linear, branched or cyclic alkyl or chloroalkyl group having 1 to 20 carbon atoms, R5 = independently at each instance a hydrogen radical or a linear, branched or cyclic alkyl or chloroalkyl group having 1 to 20 carbon atoms, an aryl or alkaryl group, and / or reaction products of a polyether bearing silyl groups of the formula (I) with one or more isocyanate-containing compounds, where R1* is preferably a hydrogen, with the proviso that component B has a higher proportion of repeat units (b) than repeat units (a) and / or (c) and - component C, at least one catalyst.
2. Composition according to Claim 1, characterized in that the polyether bearing silyl groups has various repeat units that are prepared by reaction with one or more alkylene oxides, glycidyl ethers, carbon dioxide, cyclic anhydrides, isocyanates, caprolactones or cyclic carbonates or mixtures thereof.
3. Composition according to either of the preceding claims, characterized in that the polyether bearing silyl groups has one or more terminal and / or one or more pendant alkoxysilyl radicals.
4. Composition according to any of the preceding claims, characterized in that the polyether bearing silyl groups has a ratio of repeat units of b to a of > 5:1, more preferably > 8:1, even more preferably > 10:1, and especially a ratio of b to a between 11:1 and 20:1.
5. Composition according to Claim 1, characterized in that the polysiloxane is a linear or singly or multiply branched Si-OH- or SiOR3-functional polysiloxane.
6. Composition according to Claim 1, characterized in that the polysiloxane is an alkoxypolysiloxane.
7. Composition according to Claim 1, characterized in that the polysiloxane has at least one epoxy functionality and / or one alkoxy functionality.
8. Composition according to Claim 1, characterized in that it includes, as further constituents, at least one epoxy-functional compound and one amino-functional compound.
9. Composition according to Claim 8, characterized in that the stoichiometric ratio of epoxy function to amino function is in the range from 5:0.1 to 0.1:5, preferably 1:1.5, more preferably 1:1.
10. Composition according to Claim 8, characterized in that the epoxy-functional compound comprises epoxy-functional silanes or epoxy-functional siloxanes or aromatic or aliphatic glycidyl ethers or condensates thereof or mixtures thereof.
11. Composition according to Claim 8, characterized in that the amino-functional compound is an amino-functional alkoxysilane, preferably an amino-functional di- or trialkoxysilane.
12. Composition according to Claim 1, characterized in that it includes at least one crosslinker of the formula (II) R6dSi(OR7)e Formula (II) with the proviso that 0 ≤ d ≤ 2, 0 ≤ e ≤ 4 and d + e = 4, R6 = independently at each instance an alkyl group or cycloalkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 20 carbon atoms, R7 = independently at each instance an alkyl group having 1 to 8 carbon atoms, preferably a methyl, ethyl, propyl or isopropyl group.
13. Composition according to Claim 1, characterized in that the catalyst is selected from the group of the catalysts that promote the hydrolysis condensation mechanism, such as organotin catalysts, titanates or zirconates, organometallic compounds of aluminium, of iron, of calcium, of magnesium, of zinc or bismuth, Lewis acids or organic acids / bases, linear or branched or cyclic amidines, guanidines or amines, or a mixture thereof.
14. Composition according to any of the preceding claims, characterized in that further additives selected from the group of the plasticizers, fillers, adhesion promoters, rheology additives, stabilizers, catalysts, solvents and drying agents, especially chemical moisture drying agents, are present.
15. Composition according to any of the preceding claims, comprising - 1% by weight to 85% by weight, preferably 5% by weight to 75% by weight, more preferably 20% by weight to 60% by weight, of component A, - 1% by weight to 50% by weight, preferably 10% by weight to 40% by weight, more preferably from 15% by weight to 35% by weight, of component B, - 0.01% by weight to 5% by weight, preferably 0.05% by weight to 3% by weight, more preferably from 0.1% by weight to 2% by weight, of component C, based on 100% by weight of the composition.
16. Composition according to Claim 15, characterized in that it contains 0.1% by weight to 40% by weight, preferably 10.0% by weight to 35% by weight, more preferably from 20.0% by weight to 30.0% by weight, of component D consisting of at least one epoxy-functional compound and one amino-functional compound based on the overall composition.
17. Composition according to Claim 16, characterized in that component D is composed of 30% by weight to 95% by weight, preferably 40% by weight to 90% by weight, more preferably of 65% by weight to 85% by weight, of the epoxy-functional compound and of 0.1% by weight to 50% by weight, preferably 5% by weight to 40% by weight, more preferably of 10% by weight to 30% by weight, of the amino-functional compound based on the overall composition.
18. Coatings, paints and dyes comprising a curable composition according to any of the preceding claims.
19. Use of the curable composition according to Claim 1 for production of coatings, paints and dyes, preferably for prevention or reduction of biofouling.