Method for establishing a fouling release coating system

Abstract

To provide a method of establishing a fouling release coating system on a surface of a base material, and a fouling release coating system itself.SOLUTION: A method is used in which a fouling release coating composition includes one or more types of steric hindrance amines, in particular, a 2,2,6,6-tetra alkyl piperidine derivative.SELECTED DRAWING: None

Description

[Technical Field]

[0001] A method for establishing a fouling-release coating system on a surface of a substrate as well as a fouling-release coating system are provided. [Background technology]

[0002] Aquatic structures, particularly submerged marine structures that come into contact with water, especially seawater, have a tendency to be fouled by marine organisms. To inhibit the settlement of such organisms or to promote their release, antifouling and fouling release coating systems are extensively used on structures such as ships, buoys, ship structures, and the like.

[0003] Fouling release coating systems for steel structures typically include three main layers: a corrosion protection layer applied to the steel substrate, a fouling release layer, and an intermediate layer, often called a "tie-coat," which establishes a strong bond between the often incompatible corrosion protection and fouling release layers.

[0004] Silicone-based fouling release coatings and coating systems for marine applications are typically considered to be relatively stable systems against various types of degradation, thus, for example, light stabilizers are not required for polysiloxane-based fouling release coatings due to the inherent UV stability of the polysiloxane / silicone polymer molecules.

[0005] Examples of modern types of such fouling release coatings are those described in WO 2011 / 076856, WO 2013 / 000479, WO 2014 / 117786 and WO 2016 / 004961. Other references in this field include WO 2016 / 088630, U.S. Patent Application Publication No. 2003232910, JP 2010280852, WO 2013000478 and WO 9800017. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2011 / 076856 [Patent Document 2] International Publication No. 2013 / 000479 [Patent Document 3] International Publication No. 2014 / 117786 [Patent Document 4] International Publication No. 2016 / 004961 [Patent Document 5] International Publication No. 2016 / 088630 [Patent Document 6] US Patent Application Publication No. 2003232910 [Patent Document 7] Japanese Patent Application Laid-Open No. 2010280852 [Patent Document 8] International Publication No. 2013000478 [Patent Document 9] International Publication No. 9800017 Summary of the Invention [Problem to be solved by the invention]

[0007] The present inventors have now determined that the combination of hindered amines, particularly piperidine derivatives (such as those known as hindered amine light stabilizers), and poly(oxyalkylene) components in polysiloxane-based marine fouling release coatings significantly improves the antifouling performance of such coatings. Surprisingly, this effect is evident even when the coatings are immersed in seawater and thereby hidden from sunlight. [Means for solving the problem]

[0008] There is thus provided a method for establishing a fouling release coating system on a surface of a substrate, the method comprising the following successive steps: a. optionally applying one or more layers of a primer composition onto the surface of the substrate and curing the layers, thereby forming a primed substrate; b. applying one or more layers of a liquid silicone-containing tie coat composition onto the primed substrate or surface of the substrate and curing the layer, thereby forming a cured tie coat layer; c. applying one or more layers of a fouling release coating composition over the cured tie coat layer, wherein the fouling release coating composition comprises a condensation-curable polysiloxane-based binder matrix comprising at least 40% by dry weight of the coating composition, the polysiloxane portion of the binder matrix being greater than 65% by weight, and curing the fouling release coating composition; wherein the tie coat composition and / or the fouling release coating composition comprises a component having a poly(oxyalkylene) chain; and Wherein, the tie coat composition and / or the fouling release coating composition further comprises one or more sterically hindered amines, in particular 2,2,6,6-tetraalkylpiperidine derivatives.

[0009] A fouling release coating system obtained by this method is also provided. a. Base material, b. Optionally, one or more primer layers; c. at least one silicone-containing tie coat layer d. A fouling release layer comprising a condensation-curable polysiloxane-based binder matrix constituting at least 40% by dry weight of its coating, said binder matrix being represented by more than 65% by weight of polysiloxane moieties, and said coating comprising a component having a poly(oxyalkylene) chain; 1. A fouling release coating system comprising: A fouling release coating system is also provided, wherein the tie coat layer and / or the fouling release layer further comprises one or more sterically hindered amines, particularly 2,2,6,6-tetraalkylpiperidine derivatives.

[0010] Further details of the invention are set out in the dependent claims and the following description.

[0011] <Detailed disclosure> In a first aspect, a method is provided for establishing a fouling release coating system on a surface of a substrate.

[0012] The term "substrate" is intended to mean a solid material onto which a coating composition can be applied. The substrate typically comprises a metal, such as steel, iron, aluminum, or fiberglass. In the most interesting embodiment, the substrate is a metal substrate, particularly a steel substrate. In an alternative embodiment, the substrate is a fiberglass substrate.

[0013] The term "surface" is used in its ordinary sense to refer to the outer boundary of an object to which the fouling release coating system of the present invention is applied. Thus, the surface of the substrate may be any "native" surface (e.g., a steel surface). Typically, however, the substrate is coated with, for example, an anticorrosion coating, and such coating constitutes the surface of the substrate. Alternatively, the substrate may have a painted coating, e.g., a worn antifouling coating, or the like. When present, the anticorrosion coating is typically applied to a total dry film thickness of 100 to 600 μm, e.g., 150 to 450 μm, e.g., 200 to 400 μm.

[0014] Specific examples of surfaces suitable for coating in accordance with the present invention are the surfaces of all types of structures and objects, such as ships (including, but not limited to, boats, yachts, motor boats, motor launches, ships, tugboats, tankers, container ships and other cargo vessels, submarines, and naval vessels of all types), pipes, onshore and offshore machinery, bridge piers, pilings, bridge substructures, hydraulic equipment and structures, underwater oil well structures, nets and other aquaculture equipment, and buoys.

[0015] <Primer coating> In a first optional step, the method includes applying one or more layers of a primer composition onto the surface of the substrate and curing the layers, thereby forming a primed substrate. The primed substrate thus constitutes a substrate coated with a cured primer layer.

[0016] The primer composition is typically an epoxy-based primer composition. Suitable epoxy-based coatings are commercially available products such as Hempel Light Primer 45557, Hempadur 17634 and Hempadur 15570.

[0017] The term "epoxy-based composition" should be interpreted as a combination of one or more epoxy resins, one or more curing agents, any reactive epoxy diluents, and any reactive acrylic modifiers.

[0018] An "epoxy-based composition" comprises one or more epoxy resins selected from aromatic or non-aromatic epoxy resins (e.g., hydrogenated epoxy resins) containing two or more epoxy groups per molecule, arranged in an internal, terminal, or cyclic structure, together with one or more suitable curing agents acting as crosslinkers. To reduce viscosity and improve application and physical properties, the composition may contain a combination of a reactive diluent selected from monofunctional glycidyl ethers or esters of aliphatic, alicyclic, or aromatic compounds.

[0019] Suitable epoxy-based compositions are believed to include epoxies and modified epoxy resins selected from bisphenol A, bisphenol F, novolac epoxies, non-aromatic epoxies, cycloaliphatic epoxies, epoxidized polysulfides, glycidyl esters, and epoxy-functional acrylic resins, or any combination thereof.

[0020] The epoxy-based primer composition also includes one or more curing agents selected from compounds or polymers containing at least two reactive hydrogen atoms attached to nitrogen.

[0021] Suitable curing agents include amines or amino-functional polymers selected from aliphatic amines and polyamines (e.g., cycloaliphatic amines and polyamines), polyamidoamines, polyoxyalkyleneamines (e.g., polyoxyalkylenediamines), aminated polyalkoxyethers (e.g., those commercially available as "Jeffamine"), alkyleneamines (e.g., alkylenediamines), aralkylamines, aromatic amines, Mannich bases (e.g., those commercially available as "Phenalkamine"), and amino-functional silanes, as well as their epoxy adducts and derivatives. Those skilled in the art will recognize that epoxy adducts are the substoichiometric reaction products of epoxies with one or more amines containing active hydrogen atoms attached to the nitrogen atom, as described in Kurt Weigel, "Epoxy Resin Varnishes," 1965, Wissenschaftliche Verlagsgesellschaft MBH, Stuttgart, pp. 203-210.

[0022] The primer composition is typically applied and cured to a dry film thickness of from 20 to 900 μm, for example from 20 to 750 μm, such as from 50 to 600 μm.

[0023] The term "applying" with respect to any layer / composition is used in its usual sense in the coatings industry. Thus, "applying" is by any conventional means, e.g., brush, roller, spray, dipping, etc. The most commercially interesting technique of "applying" a coating composition is by spraying. Spraying is effected by conventional spraying equipment known to those skilled in the art.

[0024] <Tie coat> In a second step, the method includes applying one or more layers of a liquid silicone-containing tie coat composition onto the primed substrate or the surface of the substrate and curing the layers, thereby forming a cured tie coat layer.

[0025] Commonly suitable tie coat compositions are those coatings found in the patent documents WO 2014 / 166492, WO 2010 / 018164 and WO 2005 / 033219.

[0026] The tie coat composition is silicone-containing and therefore preferably comprises one or more crosslinkable polysiloxanes, preferably selected from hydroxy-functional polysiloxanes, C1-C4 alkoxy-functional polysiloxanes, amino-functional polysiloxanes, and epoxy-functional polysiloxanes.

[0027] Suitably, the tie coat composition comprises 3 to 90%, preferably 10 to 80%, more preferably 20 to 60%, by wet weight of the total tie coat composition, of one or more of the above crosslinkable polysiloxanes. Even more preferably, the tie coat composition comprises 3 to 15% or greater than 40%, by wet weight of the total tie coat composition, of one or more of the above crosslinkable polysiloxanes.

[0028] The tie coat composition may further comprise one or more hydrolyzable silanes having two or more hydrolyzable groups, and the tie coat composition preferably comprises up to 30% of the one or more hydrolyzable silanes having two or more hydrolyzable groups, by wet weight of the total tie coat composition.

[0029] The tie coat composition may contain one or more epoxy- or isocyanate-functional polymers. In this way, good compatibility with the underlying epoxy primer layer can be achieved. The epoxy-functional polymer in the tie coat composition is preferably crosslinkable with the crosslinkable polysiloxane. Any of the epoxy resins described above for the primer composition may be suitable as the epoxy-functional polymer in the tie coat composition.

[0030] The tie coat composition may further comprise a condensation catalyst to promote crosslinking. Examples of suitable catalysts include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin-2-ethylhexanoate, dioctyltin dilaurate, dioctyltin diacetate, dioctyltin dioctoate, dioctyltin-2-ethylhexanoate, dioctyltin neodecanoate, tin naphthenate, tin butyrate, tin oleate, tin caprylate, iron 2-ethylhexanoate, lead 2-ethyloctoate, cobalt 2-ethylhexanoate, manganese 2-ethylhexanoate, zinc 2-ethylhexanoate, and zinc 2-ethylhexanoate. Organometallic and metal salts of organic carboxylic acids such as zinc phthenate, zinc stearate, cobalt naphthenate and titanium naphthenate; catalysts containing tertiary amines such as guanidine derivatives, such as 1,2-dicyclohexyl-3-(1-piperidyl)guanidine (FR 2930778); 1-butyl-2,3-dicyclohexyl-1,3-dimethylguanidine (WO 2010149869), and further tertiary amines such as 1,4-ethylenepiperazine (DABCO) and 2,4,6-tris(dimethylaminomethyl)phenol.

[0031] The catalyst may be used alone or in combination of two or more catalysts. The amount of catalyst used depends on the reactivity of the catalyst and crosslinker, and the desired recoating interval between subsequent coating / drying times. In a preferred embodiment, the catalyst concentration is 0.01 to 10% by weight, e.g., 0.01 to 4%, e.g., 0.005 to 2%, and particularly 0.001 to 1% of the total formulation of the epoxy binder system and curing agent.

[0032] The tie coat composition may further comprise a solvent and additives.

[0033] Examples of solvents are alcohols such as methanol, ethanol, propanol and butanol, aliphatic, cycloaliphatic and aromatic hydrocarbons such as white spirit, cyclohexane, toluene, xylene and naphtha solvent, esters such as methoxypropyl acetate, n-butyl acetate and 2-ethoxyethyl acetate; octamethyltrisiloxane and mixtures thereof.

[0034] When solvent is present, it typically comprises 5-50% by volume of the tie coat composition.

[0035] Examples of additives include: (i) Non-reactive fluids such as organopolysiloxanes; e.g., polydimethylsiloxane, methylphenylpolysiloxane; petroleum oils and combinations thereof; (ii) surfactants such as derivatives of propylene oxide or ethylene oxide, e.g., alkylphenol ethylene oxide condensates (alkylphenol ethoxylates); ethoxylated monoethanolamides of unsaturated fatty acids, such as ethoxylated monoethanolamide of linoleic acid; sodium dodecyl sulfate; and soybean lecithin; (iii) Wetting agents and dispersing agents such as those described in M. Ash and I. Ash, Paint and Coatings Materials Handbook, Vol. 1, 1996, Gower Publishing Ltd, UK, pp. 821-823 and 849-851; (iv) thickening and anti-settling agents such as colloidal silica, hydrous aluminum silicate (bentonite), aluminum tristearate, aluminum monostearate, xanthan gum, chrysotile, pyrogenic silica, hydrous castor oil, organically modified clays, polyamide waxes, and polyethylene waxes; and (v) Dyes such as 1,4-bis(butylamino)anthraquinone and other anthraquinone derivatives; toluidine dyes, etc.

[0036] Any additive typically comprises 0 to 30% by dry weight of the tie coat composition, for example 0 to 15%.

[0037] Additionally, the tie coat composition may include pigments and fillers.

[0038] Pigments and fillers are considered in this invention as ingredients that can be added to the tie coat composition that are not significantly related to adhesive performance. "Pigments" are typically characterized as rendering the final tie coat composition non-transparent and non-translucent, while "fillers" are typically characterized as not rendering the tie coat composition non-translucent and not significantly contributing to hiding any material beneath the coated composition.

[0039] Examples of pigments are titanium dioxide, red iron oxide, zinc oxide, carbon black, graphite, yellow iron oxide, red molybdate, yellow molybdate, zinc sulfide, antimony oxide, sodium aluminum sulfate, quinacridone, phthalocyanine blue, phthalocyanine green, black iron oxide, indanthrone blue, aluminum cobalt oxide, carbazole dioxazine, chromium oxide, isoindoline orange, bis-acetoacet-o-tridiol, benzimidazolone, quinaphthalone yellow, isoindoline yellow, tetrachloroisoindolinone, and quinophthalone yellow grades.

[0040] Examples of fillers are calcite, dolomite, talc, mica, feldspar, barium sulfate, kaolin, nepheline, silica, perlite, magnesium oxide, and calcium carbonate, such as quartz flour. Aside from the filler examples mentioned above, the tie coat composition may also include fibers, such as those generally and specifically described in WO 00 / 77102, which is incorporated herein by reference, since fillers (and pigments) can also be added in the form of nanotubes or fibers.

[0041] Any pigments and / or fillers typically comprise 0-60% by dry weight of the tie coat composition, such as 0-50%, preferably 5-45%, such as 5-40% or 5-35%.

[0042] To facilitate convenient application of the tie coat composition (e.g., by spray, brush, or roller application techniques), the tie coat composition typically has a viscosity in the range of 25 to 25,000 mPa·s, e.g., 150 to 15,000 mPa·s, and particularly 200 to 4,000 mPa·s.

[0043] In some embodiments, the tie coat of the present invention is applied over an old epoxy-based coating such as: Old epoxy coatings that have been cleaned to remove contaminants, or Old epoxy coating that has been cleaned to remove contaminants and roughened by sanding, sweeping, etc.

[0044] In certain embodiments, the tie coat comprises one or more poly(oxyalkylene)-modified polysiloxane oils as described herein.

[0045] In another particular embodiment, the tie coat comprises one or more sterically hindered amine moieties, as described herein, and the hindered amine moieties, particularly 2,2,6,6-tetraalkylpiperidine moieties, are preferably present in an amount of 0.003 to 0.5 mol / kg per coating layer.

[0046] In a particularly preferred form, the tie coat may comprise both one or more poly(oxyalkylene)-modified polysiloxane oils and one or more sterically hindered amines, as described herein.

[0047] <Fouling Release Coating Composition> In a third step, the method includes applying one or more layers of a fouling release coating composition onto the cured tie coat layer and curing the fouling release coating composition, thereby establishing a fouling release coating system.

[0048] The expression "fouling release" (as well as "fouling control") should be understood to relate to any kind of biological fouling (i.e., colonization of surfaces by living organisms) of surfaces exposed to an aqueous environment or aqueous liquids (e.g., inside tanks, pipes, etc.). However, the coatings defined herein are considered to be particularly relevant for avoiding or reducing marine biofouling, i.e., biofouling that occurs in connection with exposure of surfaces to a marine environment, in particular seawater.

[0049] The fouling release coating composition comprises at least 40% by dry weight of a condensation-curable polysiloxane-based binder matrix comprising said coating composition, and is represented by a polysiloxane portion of greater than 65% by weight of the condensation-curable polysiloxane-based binder matrix.

[0050] <Polysiloxane binder matrix> The polysiloxane-based binder matrix should be understood to be composed of reactive polysiloxane binder components, such as functional organopolysiloxanes (such as polydialkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, or combinations thereof), crosslinkers, silicates (e.g., ethyl silicate), etc. Thus, the reaction between such components is believed to result in a binder matrix typically in the form of a three-dimensional, covalently interconnected network. Thus, the polysiloxane-based binder matrix is crosslinked.

[0051] The fouling release composition is cured by polymerization / crosslinking through the formation of siloxane bonds via a condensation reaction, which provides a binder matrix whose backbone consists solely of Si-O-Si repeating units.

[0052] The polysiloxane binder matrix is prepared from a polysiloxane binder, which is a functional organopolysiloxane having terminal and / or pendant functionality. Terminal functionality is preferred. The functionality can be a hydrolyzable group, such as an alkoxy group or a ketoxime group, or the functionality can be a silanol group. A minimum of two reactive groups per molecule is preferred. If the molecule contains only two reactive groups, such as silanol groups, it may be necessary to use an additional reactant, a crosslinker, to achieve the desired crosslink density. The crosslinker can be an alkoxysilane, such as methyltrimethoxysilane, although a wide range of useful silanes is available, as described below. The silane can be used as is or as its hydrolysis-condensation product.

[0053] In some embodiments, the fouling release coating composition (i.e., the composition for the preparation of the fouling release coating) comprising the polysiloxane-based binder system may be a condensation-curable composition, as will be apparent to those skilled in the art.

[0054] Examples are two-component condensation-curable compositions based on silanol-reactive polydiorganosiloxanes and silanes with hydrolyzable groups, or one-component condensation-curable compositions based on alkoxy or other hydrolyzable-reactive polydiorganosiloxanes.

[0055] In some embodiments, the binder phase comprises (i) a binder and (ii) a crosslinker, which should contain hydrolyzable or other reactive groups for the binder (i) to participate in the formation of a matrix.

[0056] The binder (i) typically comprises 40 to 90% by dry weight of the coating composition (which also corresponds to the dry weight of the coating).

[0057] The crosslinker (ii) preferably constitutes 0 to 10% by dry weight of the coating composition (also by dry weight of the coating) and is, for example, an organosilicon compound represented by the following general formula (2), its partial hydrolysis-condensation product, or a mixture of the two:

[0058] [ka]

[0059] In the formula, each R independently represents an unsubstituted or substituted monovalent hydrocarbon group or hydrolyzable group of 1 to 6 carbon atoms, each X independently represents a hydrolyzable group, and a represents an integer of 0 to 2, such as 0 to 1.

[0060] In the art of polymer chemistry, the term "partial hydrolysis-condensation product" is well known to refer to compounds that have been allowed to react with themselves in a condensation reaction to produce an oligomer or polymer, but which still retain the reactive / hydrolyzable groups used in the crosslinking reaction.

[0061] The compound represented by formula (2) acts as a crosslinker for binder (i). By combining binder (i) and crosslinker (ii), the composition can be formulated as a single curable RTV (room temperature vulcanizable) component. If the reactivity on the terminal silicon groups of binder (i) consists of easily hydrolyzable groups such as dimethoxy or trimethoxy, a separate crosslinker is usually not required to cure the film. The technology behind the curing mechanism and examples of crosslinkers are described in U.S. Patent Application Publication No. 2004 / 006190.

[0062] In one embodiment, R represents a hydrophilic group such as a poly(oxyalkylene) group, in which case there is a C bond between the silicon atom and the poly(oxyalkylene) group. 2~5 Preferably, the organopolysiloxane has an -alkyl spacer, and therefore the organopolysiloxane may have an oxyalkylene domain.

[0063] Preferred crosslinking agents are selected from tetramethoxysilane, tetraethoxysilane; tetrapropoxysilane; tetra-n-butoxysilane; vinyltris(methylethyloximino)silane; vinyltris(acetoxime)silane; methyltris(methylethyloximino)silane; methyltris(acetoxime)silane; vinyltrimethoxysilane; methyltrimethoxysilane; vinyltris(isopropenoxy)silane; tetraacetoxysilane; methyltriacetoxysilane; ethyltriacetoxysilane; vinyltriacetoxysilane; di-t-butoxy-diacetoxysilane; methyltris(ethyllactate)silane and vinyltris(ethyllactate)silane and their hydrolysis-condensation products.

[0064] More preferred crosslinkers are tetraethoxysilane; vinyltris(methylethyloximino)silane; methyltris(methylethyloximino)silane; vinyltrimethoxysilane; methyltris-(methylethyloximino)silane; methyltris(ethyllactate)silane; vinyltris(ethyllactate)silane and their hydrolysis-condensation products.

[0065] More preferred crosslinkers are tetraethoxysilane, vinyltrimethoxysilane, methyltris(ethyllactate)silane, vinyltris(ethyllactate)silane, and hydrolysis-condensation products thereof. In a specific embodiment, the crosslinker is tetraethoxysilane or a hydrolysis-condensation product thereof. In another specific embodiment, the crosslinker is vinyltrimethoxysilane or a hydrolysis-condensation product thereof. In yet another specific embodiment, the crosslinker is methyltris(ethyllactate)silane or a hydrolysis-condensation product thereof. In yet another specific embodiment, the crosslinker is vinyltris(ethyllactate)silane or a hydrolysis-condensation product thereof. In yet another embodiment, the crosslinker is a hydrolysis-condensation product thereof. In another embodiment, the crosslinker is not a hydrolysis-condensation product.

[0066] Other interesting crosslinkers are those selected from vinyltriethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane, tetraisopropoxysilane, tetrabutoxysilane and their hydrolysis-condensation products.

[0067] In some interesting embodiments, the polysiloxane-based binder comprises a polydimethylsiloxane-based binder.

[0068] In other interesting embodiments, the binder may comprise a fluoro-modified, for example, fluoroalkyl-modified polysiloxane binder such as silanol-terminated poly(trifluoropropyl-methylsiloxane).

[0069] The polysiloxane binder matrix typically constitutes at least 40% by dry weight of the coating composition or (optionally) cured coating, at least 50% by dry weight, preferably at least 60% by dry weight, such as at least 70% by dry weight, in particular 50-90% by dry weight, or 50-98% by dry weight, for example 50-96% by dry weight, in particular 60-95% by dry weight, or 50-95% by dry weight, or 60-94% by dry weight, or 70-96% by dry weight, or even 70-94% by dry weight, or 75-93% by dry weight, or 75-92% by dry weight.

[0070] The binder is in the form of a crosslinked matrix that incorporates other ingredients, such as additives, pigments, fillers, biocides, etc., as well as any poly(oxyalkylene) modified alcohols (see below), any poly(oxyalkylene) modified polysiloxane oils (see below), sterically hindered amines (e.g., 2,2,6,6-tetraalkylpiperidine derivatives), into the fouling release coating.

[0071] In some embodiments, the polysiloxane-based binder matrix may include, as part of the binder matrix, terminal and / or pendant poly(oxyalkylene) chains, e.g., poly(oxyalkylene) chains selected from polyoxyethylene, polyoxypropylene, and poly(oxyethylene-co-oxypropylene) (see also below), as disclosed, for example, in WO 2013 / 000478.

[0072] The term "polysiloxane-based binder matrix" is intended to mean that the binder matrix is predominantly composed of polysiloxane moieties, i.e., represented by more than 65 wt. %, preferably more than 70 wt. %, e.g., more than 75 wt. % of the binder matrix. Preferably, the polysiloxane moieties constitute 65-100 wt. %, e.g., 65-99.9 wt. %, in particular 70-100 wt. %, or 70-99 wt. %, or 70-98 wt. %, or 75-97 wt. %, or even 75-99 wt. %, or 80-98 wt. %, or 90-97 wt. % of the binder matrix (i.e., binder components and any crosslinkers). The remainder of the binder matrix may be made up, for example, of any poly(oxyalkylene) chains and any (non-polysiloxane) crosslinkers, if present. In some important embodiments, the polysiloxane-based binder matrix consists solely of polysiloxane moieties and residues of any non-polysiloxane crosslinker. Importantly, the term "polysiloxane-based binder matrix" should be understood in its conventional sense, i.e., the binder matrix has a backbone structure of polysiloxane moieties. The term "polysiloxane" is well known to refer to polymers having a backbone with alternating silicon and oxygen atoms and lacking carbon atoms (see New Encyclopedia Britannica, Vol. 30; Micropedia, Vol. IX, 1975, defining polysiloxane with reference to silicones). Similarly, the term polyorganosiloxane is intended to mean a polysiloxane backbone with organic (i.e., carbon-based) substituents on the silicon atoms.

[0073] When calculating the respective amounts of polysiloxane moieties and any other moieties for a given starting material (or adduct), it is typically fairly easy to distinguish between the two. However, to eliminate any doubt about any linker between the two, it should be understood that any poly(oxyalkylene) chain (mentioned here only as an example) includes all atoms up to, but not including, the silicon atom to which the moiety is covalently bonded to the polysiloxane moiety. For example, in a structure of the type [polysiloxane-O]-Si(Me)-CHCHCHCH-[poly(oxyalkylene)], the [polysiloxane-O]-Si(Me) moiety is described as the silicone moiety, while CHCHCH-[poly(oxyalkylene)] is described as the poly(oxyalkylene) chain.

[0074] <Catalyst> The coating composition used to form the fouling release coating may further comprise a condensation catalyst to promote crosslinking. Examples of suitable catalysts include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin-2-ethylhexanoate, dioctyltin dilaurate, dioctyltin diacetate, dioctyltin dioctoate, dioctyltin-2-ethylhexanoate, dioctyltin dineodecanoate, tin naphthenate, tin butyrate, tin oleate, tin caprylate, bismuth-2-ethylhexanoate, bismuth octanoate, bismuth neodecanoate, iron 2-ethylhexanoate, lead 2-ethyloctoate, cobalt 2-ethylhexanoate, manganese 2-ethylhexanoate, Organometallic and metal salts of organic carboxylic acids such as zinc 2-ethylhexanoate, zinc naphthenate, zinc stearate, cobalt naphthenate, and titanium naphthenate; titanate and zirconate esters such as tetrabutyl titanate, tetrakis(2-ethylhexyl) titanate, triethanolamine titanate, tetra(isopropenoxy)titanate, titanium tetrabutanolate, titanium tetrapropanolate; titanium tetraisopropanolate, zirconium tetrapropanolate, zirconium tetrabutanolate; and chelated titanates such as diisopropylbis(acetylacetonyl)titanate. Additional catalysts include tertiary amines such as triethylamine, tetramethylethylenediamine, pentamethyldiethylenetriamine, and 1,4-ethyleneepiperazine. Further examples include guanidine-based catalysts. Further examples of condensation catalysts are described in WO 2008 / 132196 and US 2004 / 006190.

[0075] The catalyst may be used alone or in combination of two or more catalysts. In one embodiment, the catalyst is selected from the group consisting of tin and titanium dioxide (titanium dioxide) hydrate. In a specific embodiment, the catalyst is tin-based. In one embodiment, a tin-free catalyst is included. In another embodiment, the catalyst includes one or more titanium dioxide (titanium dioxide) hydrates. The amount of catalyst used depends on the reactivity of the catalyst and the crosslinker and the desired drying time. In a preferred embodiment, the catalyst concentration is 0.01 to 10 wt %, for example, 0.01 to 3.0 wt %, or 5.0 to 10 wt %, or 0.1 to 4.0 wt %, or 1.0 to 6.0 wt %, of the total weight of the binder (i) and crosslinker (ii).

[0076] In some embodiments, no catalyst is included.

[0077] <Solvents, additives, pigments and fillers> The coating composition used to form the fouling release coating may further include solvents and additives.

[0078] Examples of solvents are aliphatic, cycloaliphatic and aromatic hydrocarbons such as white spirit, cyclohexane, toluene, xylene and naphtha solvents, esters such as methoxypropyl acetate, n-butyl acetate and 2-ethoxyethyl acetate; octamethyltrisiloxane and mixtures thereof. Alternatively, the solvent system may contain water or be aqueous (>50% water in the solvent system).

[0079] In one embodiment, the solvent is selected from aliphatic, cycloaliphatic and aromatic hydrocarbons such as white spirit, cyclohexane, toluene, xylene and naphtha solvents, esters such as methoxypropyl acetate, n-butyl acetate and 2-ethoxyethyl acetate; octamethyltrisiloxane and mixtures thereof, preferably those solvents having a boiling point of 110° C. or higher.

[0080] When solvent is present, it typically comprises 5-50% by volume of the coating composition, it being understood that such components evaporate during drying / curing of the coating, so that the final coating is substantially free of any solvent.

[0081] Examples of additives include: (i) Non-reactive fluids such as organopolysiloxanes; e.g., polydimethylsiloxane, methylphenylpolysiloxane; petroleum oils and combinations thereof; (ii) surfactants such as ethoxylated monoethanolamides of unsaturated fatty acids, e.g., ethoxylated monoethanolamide of linoleic acid; sodium dodecyl sulfate; and soybean lecithin; (iii) Wetting agents and dispersing agents such as those described in M. Ash and I. Ash, Paint and Coatings Materials Handbook, Vol. 1, 1996, Gower Publishing, UK, pp. 821-823 and 849-851; (iv) thickening and anti-settling agents (e.g., thixotropic agents) such as colloidal silica, hydrous aluminum silicate (bentonite), aluminum tristearate, aluminum monostearate, xanthan gum, chrysotile, pyrogenic silica, hydrous castor oil, organically modified clays, polyamide waxes, and polyethylene waxes; (v) dyes such as 1,4-bis(butylamino)anthraquinone and other anthraquinone derivatives; toluidine dyes, etc.; and (vi) Antioxidants such as bis(tert-butyl)hydroquinone, 2,6-bis(tert-butyl)phenol, resorcinol, 4-tert-butylcatechol, tris(2,4-di-tert-butylphenyl)phosphite, and pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate salt).

[0082] Any additive will typically constitute 0-30% by dry weight of the coating composition or cured coating (as the case may be), for example 0-15%.

[0083] Preferably, the coating composition comprises one or more thickeners and / or anti-settling agents (e.g. thixotropic agents), preferably in an amount of 0.2 to 10% by dry weight of the coating composition or (optionally) the cured coating, such as 0.5 to 5% by dry weight, for example 0.6 to 4% by dry weight.

[0084] Additionally, the coating composition used to form the fouling release coating may include pigments and fillers.

[0085] Pigments and fillers are considered in this invention as ingredients that can be added to a coating composition that are not significantly related to adhesive performance. A "pigment" is typically characterized as making the final paint coating non-transparent and non-translucent, while a "filler" is typically characterized as not making the paint non-translucent and not significantly contributing to hiding any material underneath the coating.

[0086] Examples of pigments are grades of titanium dioxide, red iron oxide, zinc oxide, carbon black, graphite, yellow iron oxide, red molybdate, yellow molybdate, zinc sulfide, antimony oxide, sodium aluminum sulfate, quinacridone, phthalocyanine blue, phthalocyanine green, black iron oxide, indanthrone blue, aluminum cobalt oxide, carbazole dioxazine, chromium oxide, isoindoline orange, bis-acetoacet-o-tridiol, benzimidazolone, quinaphthalone yellow, isoindoline yellow, tetrachloroisoindolinone, and quinophthalone yellow.

[0087] Examples of fillers are calcite, dolomite, talc, mica, feldspar, barium sulfate, kaolin, nepheline, silica, perlite, magnesium oxide, and calcium carbonate such as quartz flour. Apart from the above-mentioned examples of fillers, the coating composition may also comprise fibers, such as those generally and specifically described in WO 00 / 77102, which is incorporated herein by reference, since fillers (and pigments) can also be added in the form of nanotubes or fibers.

[0088] Any pigments and / or fillers typically constitute 0 to 60% by dry weight of the coating composition or (as the case may be) cured coating, such as 0 to 50% by dry weight, preferably 5 to 45% by dry weight, such as 5 to 40% by dry weight, or 5 to 35% by dry weight, or 0.5 to 25% by dry weight, or 1 to 20% by dry weight. Taking into account the density of any pigments and / or fillers, such ingredients typically constitute 0.2 to 20% by dry weight, such as 0.5 to 15% by dry weight, of the solids of the coating composition or (as the case may be) cured coating.

[0089] To facilitate convenient application of the coating composition (e.g., by spray, brush, or roller application techniques), the coating composition typically has a viscosity in the range of 25 to 25,000 mPa·s, for example in the range of 150 to 15,000 mPa·s, and particularly in the range of 200 to 4,000 mPa·s.

[0090] <Poly(oxyalkylene) chain> The fouling release coatings and tie coats (and corresponding coating compositions) include components having poly(oxyalkylene) chains. The nature of such poly(oxyalkylene) chains can be rather diverse, in that the components having such poly(oxyalkylene) chains can be discrete molecules in which the poly(oxyalkylene) chains comprise one or more moieties, or the poly(oxyalkylene) chains can be covalently incorporated into a binder matrix, for example, as pendant or terminal groups.

[0091] In components having a poly(oxyalkylene) chain, it should be understood that the poly(oxyalkylene) chain includes all atoms up to, but not including, the oxygen atom to which it is connected (or the heteroatom to which it is connected). As an example, in a structure of the type [polysiloxane-O]-Si(Me)-CHCHCH-[poly(oxyalkylene)] (similar to the poly(oxyalkylene)-modified polysiloxane and poly(oxyalkylene)-modified binder matrix described in detail below), the [polysiloxane-O]-Si(Me)- portion is described as the silicone portion, while the -CHCHCH-[poly(oxyalkylene)] is described as the poly(oxyalkylene) chain. As another example, (poly(oxyalkylene)-O-) X -R-(-O-FA) Y In structures of the type (similar to poly(oxyalkylene) modified alcohols described in detail below), -(-O-) X -R-(-O-FA) Y The moiety is described as an alcohol moiety and the poly(oxyalkylene) is described as a poly(oxyalkylene) chain.

[0092] Preferably, each of the poly(oxyalkylene) chains contains at least three repeating units, for example, at least five repeating units. In many interesting embodiments, the chains contain 3 to 1,000 repeating units, such as 3 to 200, or 5 to 150, or 5 to 100 repeating units. In other interesting embodiments, the chains contain 3 to 30 repeating units, for example, 3 to 20 repeating units, for example, 3 to 15, or even 4 to 12 repeating units. In yet other interesting embodiments, the chains contain 6 to 20 repeating units, for example, 8 to 15 repeating units.

[0093] In the most interesting embodiments, the poly(oxyalkylene) chains have a number average molecular weight (Mn) in the range of 100 to 50,000 g / mol, for example in the range of 100 to 30,000 g / mol, and in particular in the range of 200 to 20,000 g / mol, or in the range of 200 to 10,000 g / mol. In other interesting embodiments, the poly(oxyalkylene) chains have a number average molecular weight (Mn) in the range of 200 to 5,000 g / mol, for example in the range of 200 to 2,500 g / mol, or even in the range of 300 to 1,000 g / mol.

[0094] The poly(oxyalkylene) chain is typically selected from poly(ethylene glycol) chains, poly(propylene glycol) chains, and poly(ethylene glycol-co-propylene glycol) chains. Examples of the latter are poly(ethylene glycol)-block-poly(propylene glycol), poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol), poly(propylene glycol)-block-poly(ethylene glycol), poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol), and poly(ethylene glycol-random-propylene glycol).

[0095] <Poly(oxyalkylene) modified polysiloxane oil> In some embodiments, the component having a poly(oxyalkylene) chain is selected from non-reactive poly(oxyalkylene)-modified polysiloxane oils. Examples of such poly(oxyalkylene)-modified polysiloxane oils of formula (A), (B), or (C) are disclosed in WO 2014 / 117786 (see in particular pages 33-37 thereof).

[0096] Such poly(oxyalkylene)-modified polysiloxane oils are widely used as surfactants and emulsifiers due to the content of both hydrophilic and lipophilic groups in the same molecule. The poly(oxyalkylene)-modified polysiloxane oil is non-reactive, i.e., the oil is selected so as not to contain groups that can react with the binder or any individual binder component. Therefore, the poly(oxyalkylene)-modified silicone oil is intended to be particularly non-reactive with the binder component so that the poly(oxyalkylene)-modified silicone oil is not covalently bonded to the binder, but instead is freely embedded in the binder film, where, in principle, such silicone oil can move more or less freely. In particular, the poly(oxyalkylene)-modified silicone oil lacks reactive groups with the polysiloxane binder component (or any crosslinker), as further illustrated in the following examples of silicone oils (A), (B), and (C). It is accepted that silicone oils may have "functional" groups, such as C-OH groups, so long as they do not undergo any significant chemical reaction with the ambient air at room temperature or with any binder components or any additives contained in the coating composition.

[0097] Of particular interest are poly(oxyalkylene)-modified polysiloxane oils in which the relative weight of the poly(oxyalkylene) chains is 1% or more (e.g., 1 to 90%) of the total weight, for example, 5% or more (e.g., 5 to 80%), and especially 10% or more (e.g., 10 to 70%) of the total weight of the poly(oxyalkylene)-modified polysiloxane oil. In one embodiment, the relative weight of the poly(oxyalkylene) chains is in the range of 25 to 60%, for example, 30 to 50%, of the total weight of the poly(oxyalkylene)-modified polysiloxane oil.

[0098] In a preferred embodiment, the poly(oxyalkylene)-modified polysiloxane oil has a number average molecular weight (Mn) in the range of 100 to 100,000 g / mol, for example in the range of 250 to 75,000 g / mol, particularly in the range of 500 to 50,000 g / mol, or in the range of 500 to 30,000 g / mol.

[0099] In another preferred embodiment, the poly(oxyalkylene)-modified polysiloxane oil has a number average molecular weight (Mn) in the range of 500 to 20,000 g / mol, for example 1,000 to 10,000 g / mol, or 1,000 to 7,500 g / mol, or even 1,500 to 5,000 g / mol.

[0100] It is also preferred if the poly(oxyalkylene)-modified polysiloxane oil (if present) has a viscosity in the range of 10 to 20,000 mPa·s, for example 20 to 10,000 mPa·s, especially 40 to 5,000 mPa·s.

[0101] In one variation of the present invention, the poly(oxyalkylene)-modified polysiloxane oil is a polysiloxane grafted to a poly(oxyalkylene) chain. An illustrative example of the structure of such a poly(oxyalkylene)-modified silicone oil is formula (A):

[0102] [ka]

[0103] During the ceremony, Each R 1 is C 1~5 - independently selected from alkyl (including linear or branched hydrocarbon groups) and aryl (e.g., phenyl (-C6H5)), in particular methyl; Each R 2 -H,C 1~4 -Alkyl (e.g., -CH3, -CH2CH3, -CH2CH2CH3, CH(CH3)2, CH2CH2CH2CH3), phenyl (-C6H5), and C 1~4- independently selected from alkylcarbonyl (e.g., -C(=O)CH3, -C(=O)CH2CH3 and -C(=O)CH2CH2CH3), in particular -H and methyl; Each R 3 is independently selected from -CH2CH2- and -CH2CH(CH3)-; Each R 4 Ha-(CH2) 2~6 - selected from; x is 0-2500, y is 1-100, and x+y is 1-2000; and n is 0 to 50, m is 0 to 50, and m+n is 1 to 70.

[0104] In some embodiments of formula (A) herein above, n+m comprises 3 to 60 repeat units, for example 3 to 50 repeat units, for example 3 to 30 or even 4 to 20 repeat units. In further or alternatively interesting embodiments, n+m comprises 6 to 40 repeat units, for example 8 to 30 or 10 to 25 repeat units.

[0105] In certain specific embodiments of formula (A) herein above, x + y is less than 50, for example less than 30, or less than 20. In another specific embodiment, x + y comprises 3 to 50 repeating units, for example 3 to 30 repeating units, for example 8 to 30, or for example 15 to 45, or for example 3 to 15, or even 4 to 12 repeating units. In yet another interesting embodiment, x + y comprises 6 to 20 repeating units, for example 8 to 15 repeating units.

[0106] In another variant of the present invention, the poly(oxyalkylene)-modified polysiloxane oil is a polysiloxane incorporated into the backbone of a poly(oxyalkylene) chain. An illustrative example of the structure of such a poly(oxyalkylene)-modified silicone oil is represented by the formula (B):

[0107] [ka]

[0108] During the ceremony Each R 1 is C 1~5 - independently selected from alkyl (including linear or branched hydrocarbon groups) and aryl (e.g., phenyl (-C6H5)), in particular methyl; Each R 2 -H, C 1~4 -Alkyl (e.g., -CH3, -CH2CH3, -CH2CH2CH3, CH(CH3)2, CH2CH2CH2CH3), phenyl (-C6H5), and C 1~4 - independently selected from alkylcarbonyl (e.g., -C(=O)CH3, -C(=O)CH2CH3 and -C(=O)CH2CH2CH3), in particular -H and methyl; Each R 3 is independently selected from -CH2CH2- and -CH2CH(CH3)-; Each R 4 is -(CH2) 2~6 - selected from; x is 1 to 2500; and n is 0 to 50, m is 0 to 50, and m+n is 1 to 70.

[0109] In some embodiments of formula (B) herein above, n+m comprises 3 to 60 repeat units, for example 3 to 50 repeat units, for example 3 to 30 or even 4 to 20 repeat units. In yet another interesting embodiment, n+m comprises 6 to 40 repeat units, for example 8 to 30 or 10 to 25 repeat units.

[0110] In some embodiments of formula (B) herein above, x comprises 3 to 1000 repeating units, for example 3 to 200, or 5 to 150, or 5 to 100 repeating units, for example 5 to 50 repeating units. In another interesting embodiment, x comprises 3 to 30 repeating units, for example 3 to 20 repeating units, for example 3 to 15 or even 4 to 12 repeating units. In yet another interesting embodiment, x comprises 6 to 20 repeating units, for example 8 to 15 repeating units, or 8 to 50, or 10 to 45, or 20 to 40 repeating units.

[0111] In some embodiments of formula (B) herein above, n+m+x comprises 3 to 120 repeat units, for example 3 to 100 repeat units, for example 3 to 80 or even 4 to 50 repeat units. In yet another interesting embodiment, n+m+x comprises 6 to 40 repeat units, for example 8 to 35 repeat units, for example 8 to 30 repeat units.

[0112] In some embodiments of formula (B) herein above, n+m+x comprises 3 to 30 repeat units, for example 3 to 20 repeat units, for example 3 to 15, or even 4 to 12 repeat units. In yet another interesting embodiment, n+m+x comprises 6 to 20 repeat units, for example 8 to 25 repeat units, for example 8 to 15 repeat units.

[0113] In yet another variation of this, the poly(oxyalkylene)-modified polysiloxane oil is a polysiloxane incorporated into the backbone of a poly(oxyalkylene) chain and grafted to the poly(oxyalkylene) chain. An illustrative example of the structure of such a poly(oxyalkylene)-modified silicone oil is formula (C):

[0114] [ka]

[0115] During the ceremony, Each R 1 is C 1~5 - independently selected from alkyl (including linear or branched hydrocarbon groups) and aryl (e.g., phenyl (-C6H5)), in particular methyl; Each R 2 -H, C 1~4 -Alkyl (e.g., -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2CH3), phenyl (-C6H5), and C 1~4 - alkylcarbonyl (e.g., -C(=O)CH3, -C(=O)CH2CH3 and -C(=O)CH2CH2CH3), in particular independently selected from -H and methyl; Each R 3 is independently selected from -CH2CH2- and -CH2CH(CH3)-; Each R 4 Ha-(CH2) 2~6 - selected from; x is 0-2500, y is 1-100, and x+y is 1-2000; k is 0 to 50, l is 0 to 50, and k+l is 1 to 50; and n is 0 to 50, m is 0 to 50, and m+n is 1 to 50.

[0116] In some embodiments of formula (C) herein above, n+m comprises 3 to 60 repeat units, for example 3 to 50 repeat units, for example 3 to 30 or even 4 to 20 repeat units. In yet other interesting embodiments, n+m comprises 6 to 40 repeat units, for example 8 to 30 or 10 to 25 repeat units.

[0117] In some embodiments of formula (C) herein above, k+l comprises 3 to 60 repeating units, for example 3 to 50 repeating units, for example 3 to 30 or even 4 to 20 repeating units. In yet another interesting embodiment, k+l comprises 6 to 40 repeating units, for example 8 to 30 or 10 to 25 repeating units.

[0118] In some embodiments of formula (C) herein above, x+y is less than 50, for example, less than 30, or less than 20. In another specific embodiment, x+y comprises 3 to 50 repeating units, for example, 3 to 30 repeating units, for example, 8 to 30, or for example, 15 to 45, or for example, 3 to 15, or even 4 to 12 repeating units. In yet another interesting embodiment, x+y comprises 6 to 20 repeating units, for example, 8 to 15 repeating units.

[0119] In the above structural formulas (A), (B), and (C), the groups -CHCH(CH)-, -CHCH(CHCH)-, etc., can be present in either of two possible orientations. Similarly, it should be understood that the segments present x and y times are typically distributed randomly or in blocks within the polysiloxane structure.

[0120] In these embodiments and variations, the poly(oxyalkylene) is preferably selected from polyoxyethylene, polyoxypropylene, and poly(oxyethylene-co-oxypropylene), which may also be referred to as poly(ethylene glycol), poly(propylene glycol), and poly(ethylene glycol-co-propylene glycol). Thus, in the above structural formulas (A), (B), and (C), each R linking two oxygen atoms 3 is preferably selected from -CH2CH2- and -CH2CH(CH3)-, while each R3 connecting the silicon atom and the oxygen atom is 2~5 -alkyl.

[0121] Preferably, the non-reactive poly(oxylalkylene)-modified polysiloxane oil is devoid of aromatic substituents.

[0122] It should be understood that the one or more non-reactive poly(oxylalkylene)-modified polysiloxane oils, if present, can be of different types, such as two or more types described above.

[0123] Commercially available non-reactive poly(oxyalkylene) modified silicone oils of interest are OFX-5103, OFX-190, OFX 5211, OFX-5247, OFX-3667, and OFX-193 (all from Xiameter), BYK-331, DBE-621 from BYK, CMS-222 from Gelest, CoatOSil 3501, Silwet 7280, CoatOSil 7210, CoatOSil 7200, CoatOSil 7602, CoatOSil 1220 (all from Momentive), TEGO Glide 410 and TEGO Glide 435 from Evonik Industries, and KF 945 from Shin-Etsu.

[0124] When present, the one or more poly(oxyalkylene)-modified polysiloxane oils are typically included in the coating composition (and in the cured coating) in an amount of 0.01 to 20% by dry weight, e.g., 0.05 to 10% by dry weight. In certain embodiments, the one or more poly(oxyalkylene)-modified polysiloxane oils constitute 0.05 to 7% by dry weight, e.g., 0.1 to 5% by dry weight, and particularly 0.5 to 3% by dry weight, of the coating composition / cured coating. In certain other embodiments, the one or more poly(oxyalkylene)-modified polysiloxane oils constitute 1 to 10% by dry weight, e.g., 2 to 9% by dry weight, and particularly 2 to 7% by dry weight, or 3 to 7% by dry weight, or 3 to 5% by dry weight, or 4 to 8% by dry weight, of the coating composition / cured coating.

[0125] When poly(oxyalkylene)-modified polysiloxane oils are present in the coating composition (and cured coating), the poly(oxyalkylene) chains typically comprise 0.005 to 10% by dry weight, e.g., 0.025 to 5% by dry weight. In certain embodiments, the poly(oxyalkylene) chains comprise 0.025 to 3.5% by dry weight, e.g., 0.05 to 2.5% by dry weight, and particularly 0.25 to 1.5% by dry weight, of the coating composition / cured coating. In certain other embodiments, the poly(oxyalkylene) chains comprise 0.5 to 5% by dry weight, e.g., 1 to 4.5% by dry weight, and particularly 1 to 3.5% by dry weight, or 1.5 to 3.5% by dry weight, or 1.5 to 2.5% by dry weight, or 2 to 4% by dry weight, of the coating composition / cured coating.

[0126] <Poly(oxyalkylene) denatured alcohol> In other embodiments, the component having a poly(oxyalkylene) chain is selected from poly(oxyalkylene) modified alcohols of general formula (I):

[0127] [ka]

[0128] During the ceremony, each POA represents a poly(oxyalkylene) moiety; Each FA is C 8~30 represents a fatty acyl moiety of R is the alcohol R(OH) X+Y wherein the organic residue has 2 to 50 carbon atoms; and X is 1 to 5, Y is 0 to 10, and X+Y is 1 to 12.

[0129] In the above formula (I), the -O- in relation to POA-O- represents the ether oxygen covalently bonded to the organic residues of the poly(oxyalkylene) and alcohol. The fatty acid acyl moiety FA is a long-chain acyl moiety that forms an ester bond (-OC(=O)-) together with the -O- in -O-FA.

[0130] The organic residue is typically of pure hydrocarbon origin, i.e., consisting of linear, branched, cyclic, unsaturated, and / or aromatic moieties, except that it may contain one to five ether linkages (-COC-) that are part of or directly attached to a ring structure. In some embodiments, the organic residue is of pure hydrocarbon origin.

[0131] In one embodiment, the alcohol R(OH) X+Y The organic residue R has 2 to 50 carbon atoms, for example 3 to 50 carbon atoms, and has only linear, branched and / or unsaturated moieties.

[0132] In another embodiment, the alcohol R(OH) X+Y The organic residue R has 2 to 50 carbon atoms, for example 3 to 50 carbon atoms, and is selected from substituted phenols, sorbitans, or sterols.

[0133] The organic residue R as in the above embodiment typically has 2 to 50 carbon atoms, for example 3 to 50 carbon atoms, or 6 to 50 carbon atoms, for example 8 to 45 carbon atoms, for example 9 to 40 carbon atoms, or 10 to 35 carbon atoms.

[0134] In embodiments where X+Y is 1, the organic residue typically has from 6 to 50 carbon atoms.

[0135] Typically, the poly(oxyalkylene) moieties POA each have a structure such that R 1 O-[R 2 -O]nR 3 -represents a moiety, where R 1 is hydrogen, C 1~4 -Alkyl-C(=O)- and C 1~4 -alkyl; each R 2 and R 3 is selected from ethyl-1,2-ene and propyl-1,2-ene; and n is an integer from 1 to 150.

[0136] The poly(oxyalkylene) moiety POA is typically a poly(oxyalkylene) moiety selected from polyoxyethylene, polyoxypropylene and poly(oxyethylene-co-oxypropylene).

[0137] In some interesting embodiments, n is in the range of 4-150, for example 5-100, for example 6-75, in particular 6-30.

[0138] In one embodiment, the poly(oxyalkylene) is selected from polyoxyethylene and poly(oxyethylene-co-oxypropylene), preferably poly(oxyalkylene), for example, having a number average molecular weight of 100 to 20,000 g / mol, for example, 200 to 20,000 g / mol, in particular 300 to 5,000 g / mol.

[0139] In one variation of the invention, the poly(oxyalkylene) is selected from polyoxyethylene, illustrative examples of which are PEG-30 and PEG-75.

[0140] In another variation of the invention, the poly(oxyalkylene) is selected from poly(oxyethylene-co-oxypropylene), illustrative examples of which are PEG-5 / PPG-5 and PEG-10 / PPG-3.5.

[0141] Alcohol R(OH) X+Y The fatty acid that gives rise to the fatty acyl moiety FA by partial esterification of C 8~30 fatty acids, e.g., C 10~24 In some variations, the fatty acid may contain one or more unsaturated bonds. Examples of fatty acids are stearic acid, lauric acid, and oleic acid.

[0142] In formula (I), (POA-O-) X -R-(-O-FA) YIn some embodiments, X is 1 to 5, Y is 0 to 10, and X+Y is 1 to 12. In some embodiments, X is 1 to 5 and Y is 0. In other embodiments, X is 1 and Y is 1 to 10. In still other embodiments, X is 1 to 3 and Y is 1 to 5.

[0143] In some embodiments, the one or more poly(oxyalkylene) modified alcohols have a melting point of 0 to 60°C, for example 0 to 45°C, particularly 0 to 30°C.

[0144] In a further embodiment, the one or more poly(oxyalkylene) denatured alcohols have a surface tension above the critical micelle concentration in water of 20 to 55 mN / m, e.g., 25 to 50 mN / m, e.g., 25 to 45 mN / m, or 30 to 50 mN / m, preferably 30 to 45 mN / m. The surface tension is determined as described in the Examples section.

[0145] In one embodiment, the coating comprises 1 to 10% by dry weight, such as 2 to 8% by dry weight, especially 3 to 7% by dry weight, of one or more of the above poly(oxyalkylene) modified alcohols.

[0146] In another embodiment, the coating comprises 1 to 10%, such as 2 to 8%, especially 3 to 7%, by solids of one or more of the above poly(oxyalkylene) modified alcohols.

[0147] In yet another embodiment, the coating (or corresponding coating system) has a density of 1 to 20, for example 2 to 18, in particular 3 to 16 g / m 2 The poly(oxyalkylene) modified alcohols may include one or more of the above poly(oxyalkylene) modified alcohols.

[0148] In one particular embodiment, the coating comprises one or more poly(oxyalkylene) modified alcohols that comprise or consist of one or more poly(oxyalkylene) modified sterols.

[0149] Sterols are compounds derived from terpenes and share the general structural formula (II).

[0150] [ka]

[0151] where position 3 (of the A ring) is a hydroxy functional group and position 17 (similar to cholesterol) is typically a (C 20 ~C 27 (The chain is provided as the most typical configuration.) Other positions, such as the 4th and 1st positions, may also have substituents (typically methyl groups), just as the structure may contain an ethylenically unsaturated double bond, for example, between carbons 5 and 6, as in cholesterol, or between carbons 8 and 9, as in lanosterol. Sterols may also have one or more hydroxyl groups other than the hydroxyl group at position 3.

[0152] In some embodiments, the sterol represents the alcohol R—OH, and therefore X+Y is 1.

[0153] The hydroxy group at the 3-position is available for functionalization, for example ether modification, such as with poly(oxyalkylene), to give poly(oxyalkylene)-modified sterols.

[0154] Poly(oxyalkylene)-modified sterols can be prepared by reacting a sterol alcohol with an alkylene oxide, thereby polymerizing the polyalkylene oxide through an alcohol-initiated ring-opening polymerization. Typical sources of such sterols are Aqualose by Croda, Generol by BASF, and Lipolan by Lipo Chemicals. Functionalizing the 3-hydroxy group of sterols with poly(oxyalkylenes) has been found to provide compounds particularly useful in fouling release coatings in combination with biocides, particularly organic biocides such as zinc pyrithione, copper pyrithione, and zineb.

[0155] In the present invention, "poly(oxyalkylene)-modified sterol" is to be understood as a product consisting of a sterol of general structural formula (II) that is ether-functionalized mainly with poly(oxyalkylene) at the 3-position (i.e., -OH at the 3-position is replaced by POA-O-).

[0156] In the present invention, the term "consisting essentially of" means that at least 75% by weight of the solids of the "poly(oxyalkylene)-modified sterol" consists of sterols of general structure (II) ether-functionalized at the 3-position with poly(oxyalkylene). Preferably, at least 80%, e.g., at least 85% or at least 90% by weight of the solids of the "poly(oxyalkylene)-modified sterol" consists of such sterols. The content of ether-functionalized sterols of general structure (II) being less than 100% is due to the fact that many commercially available qualities of "sterols" contain small amounts of impurities.

[0157] Examples of poly(oxyalkylene) modified sterols are Aqualose L30 and Polychol 20 (eg, Croda), PEG75 flakes (eg, NK Chemical).

[0158] In another particular embodiment, the alcohol R(OH) X+Y is selected from phenols.

[0159] Phenols are compounds of the general structural formula (III):

[0160] [ka]

[0161] wherein the 1-position is a hydroxyl functional group, and the hydrogens at the 2-, 3-, 4-, 5-, or 6-positions may be replaced with linear, branched, cyclic, unsaturated, and / or aromatic moieties, and may further have a fatty acyl moiety of the formula -O-FA as described above. In one interesting variant, the phenyl is substituted, particularly at the 2-, 4-, and 6-positions, respectively, with, for example, styryl, nonyl, and / or butyl groups. Thus, in the latter case, the alcohol may be selected from tristyrylphenol, nonylphenol, and tributylphenol.

[0162] The hydroxy group at the 1-position is available for further functionalization with poly(oxyalkylene) as described above to give poly(oxyalkylene)-modified phenols.

[0163] Examples of phenolic compounds are Sapogenat T080 (eg Clarian) and Serdox NSP14 (eg Croda).

[0164] In yet another particular embodiment, the alcohol R(OH) X+Y is sorbitan. Sorbitan is a compound of general structural formula (IV):

[0165] [ka]

[0166] It corresponds to an alcohol of the general formula R(OH)4. Sorbitan can be modified by partial esterification of up to three of its four OH groups with fatty acids, leaving one or more unmodified OH groups available for poly(oxyalkylene) modification. Formula (I) (POA-O-) X -R-(-O-FA) Y In some embodiments of the formula, X is 1-3, Y is 1-3, and X+Y is 4, for example, where X is 1-2, Y is 2-3, and X+Y is 4.

[0167] In a specific embodiment, the poly(oxyalkylene)-modified sorbitan is based on sorbitan trioleate, with the poly(oxyalkylene) leaving only one —OH group available for further functionalization as described above to give poly(oxyalkylene)-modified sorbitan trioleate, i.e., X is 1 and Y is 3.

[0168] In yet another particular embodiment, the alcohol is a C 1 alcohol, such as a saturated straight chain primary alcohol and a saturated branched chain secondary or tertiary alcohol. 6~30 The hydroxyl groups are available for functionalization, e.g., ether modification with poly(oxyalkylene), and poly(oxyalkylene)-modified C 6~30 Alcohols, such as linear primary alcohols and poly(oxyalkylene)-modified branched secondary and / or tertiary alcohols, are provided. In some embodiments, such alcohols have 8 to 30 carbon atoms, e.g., 10 to 24 carbon atoms.

[0169] Specific examples of the above alcohols include C 10~15 Saturated linear primary alcohol, branched C 13 C such as alcohol, oleyl alcohol 8~30 It is an alkyl alcohol.

[0170] An example of such an alcohol is e.g. Croda Tween 85.

[0171] It should be understood that the above embodiments can be viewed independently or in combination, and thus, one or more poly(oxyalkylene) modified alcohols may be represented by different ones of the above-identified types or by several variations within the same type.

[0172] When present, the one or more poly(oxyalkylene) denatured alcohols are typically included in the coating composition (and cured coating) in an amount of 0.01 to 20% by dry weight, e.g., 0.05 to 10% by dry weight. In certain embodiments, the one or more poly(oxyalkylene) denatured alcohols comprise 0.05 to 7% by dry weight, e.g., 0.1 to 5% by dry weight, and particularly 0.5 to 3% by dry weight of the coating composition / cured coating. In certain other embodiments, the one or more poly(oxyalkylene) denatured alcohols comprise 1 to 10% by dry weight, e.g., 2 to 9% by dry weight, and particularly 2 to 7% by dry weight, or 3 to 7% by dry weight, or 3 to 5% by dry weight, or 4 to 8% by dry weight of the coating composition / cured coating.

[0173] When poly(oxyalkylene) denatured alcohol is present in the coating composition (and cured coating), the poly(oxyalkylene) chain typically comprises 0.005 to 10% by dry weight, e.g., 0.025 to 5%. In certain embodiments, the poly(oxyalkylene) chain comprises 0.025 to 3.5% by dry weight, e.g., 0.05 to 2.5% by dry weight, and particularly 0.25 to 1.5% by dry weight, of the coating composition / cured coating. In certain other embodiments, the poly(oxyalkylene) chain comprises 0.5 to 5% by dry weight, e.g., 1 to 4.5% by dry weight, and particularly 1 to 3.5% by dry weight, or 1.5 to 3.5% by dry weight, or 1.5 to 2.5% by dry weight, or 2 to 4% by dry weight, of the coating composition / cured coating.

[0174] <Poly(oxyalkylene) modification of binder matrix> In one variation, the binder matrix includes covalently bonded poly(oxyalkylene) chains as part thereof, and when present, such poly(oxyalkylene) chains preferably constitute 1 to 30% by weight of the binder matrix, such as 2 to 20% by weight, e.g., 1 to 10% by weight.

[0175] It should be understood that the poly(oxyalkylene) chains contained in the polysiloxane-based binder matrix are, of course, not silicon-based.

[0176] In one embodiment, the binder comprises a curable diorganopolysiloxane represented by the following general formula (1):

[0177] [ka]

[0178] In the formula, each A 1 are independently selected from hydroxyl groups, hydrolyzable groups, and other functional groups such as amines or epoxies; each A 2 are independently selected from alkyl, aryl, alkenyl, and hydrolyzable groups; each A 3 and A 4 are independently selected from alkyl, arylalkenyl, and poly(oxyalkylene) groups, 3 and / or A 4 When is a poly(oxyalkylene) group, such group may be 2~5 - may be attached to the silicon atom via an alkylene linker; a=1 to 25000, b=1 to 2500 and a+b is at least 5.

[0179] In an alternative embodiment, the binder comprises a curable diorganopolysiloxane represented by the general formula (1x):

[0180] [ka]

[0181] In the formula, each A 1 , A 2 , A 3 , A 4 , a and b are as defined above for formula (1), and in the formula, each A 5 are independently selected from oxygen or alkyl groups having 2 to 5 carbon atoms.

[0182] In another embodiment, polysiloxane binders having poly(oxyalkylene) chains grafted as side chains (pendant groups) can be prepared by a hydrosilylation reaction between a hydrogen-functionalized polysiloxane and a poly(oxyalkylene) component containing unsaturated groups (-CH=CH), such as allyl or vinyl groups, in the presence of a hydrosilylation catalyst such as platinum, according to Equation (1c). An example of a poly(oxyalkylene) compound is allyl-terminated poly(ethylene glycol). This synthesis is carried out at elevated temperatures, such as 60-150°C. To cure the polymer, it must be functionalized with hydrolyzable groups or other reactive groups, such as vinyltrimethoxysilane. The reaction follows the same principles as grafting poly(oxyalkylene) chains onto polysiloxanes, as outlined in Equation (1b). Functionalization can be carried out prior to the attachment of the poly(oxyalkylene) groups, but is not required.

[0183] The binder resulting from reaction (1b) is further modified with poly(ethylene glycol) monoallyl ether to yield a curable polysiloxane modified with poly(oxyalkylene) chains, as outlined in formula (1c).

[0184] [ka]

[0185] [ka]

[0186] The resulting binder can be used as is or in combination with a curable diorganosiloxane (of the general type shown in Formula 1).

[0187] It is possible to graft the poly(oxyalkylene) chains onto the polysiloxane before grafting the hydrolyzable silane onto the polysiloxane (i.e., in the reverse order of the synthesis described in equations (1b) and (1c)).

[0188] Therefore, in one interesting embodiment, a cured paint coating comprising a polysiloxane-based binder matrix includes pendant poly(oxyalkylene) chains as part thereof.

[0189] The term "pendant" means that the poly(oxyalkylene) chains are attached to the polysiloxane backbone at non-terminal positions, such that such positions are attached at only one end, forming a "graft" on the polysiloxane backbone (matrix). This may be referred to as a "branched chain."

[0190] The pendant poly(oxyalkylene) chains typically have functional groups (non-reactive functionalities) at their free ends that exhibit, for example, biocidal activity. However, in most embodiments, the poly(oxyalkylene) chains do not have such functional groups but are in the form of native poly(oxyalkylene) forms, which may be end-capped, as with alkyl groups, or terminated with hydroxyl or methoxy groups.

[0191] Another binder variation is an ABA copolymer of a polysiloxane (A) and a poly(oxyalkylene) polymer (B). An example of the polymer structure is shown in formula (1d). In this variation, poly(oxyalkylene) polymer units are introduced into the polysiloxane backbone to form an alternating block copolymer. Introducing poly(oxyalkylene) groups into the binder can increase the hydrophilicity of the binder, as described in reference WO 2008 / 132196. The binders can be used alone or in combination, and the copolymer structure can be ABA or BAB. In the case of BAB, the end groups of the silicone moiety are capped by poly(oxyalkylene) chains, so pendant curable functionality is required.

[0192] [ka]

[0193] In yet another variation, the poly(oxyalkylene) chain is obtained by hydrosilylation of a poly(oxyalkylene) compound containing at least one unsaturated group (-CH=CH), such as an allyl or vinyl group, with a silane bearing a hydride group, e.g., an HSi(R*) group, where each R* is a C 1~4 -alkyl and C 1~4 -alkoxy (e.g., methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, and butoxy), where at least one is C, such as, for example, trimethoxysilane, triethoxysilane, or methyldimethoxysilane. 1~4 -alkoxy, which, in the presence of a hydrosilylation catalyst, such as platinum, results in a curable poly(oxyalkylene). The reaction is carried out at elevated temperatures, such as 60-150°C. The synthesis is outlined in Equation (1e). The polymer must be used in combination with, for example, component (i) (Equation 1). Further examples of useful silanes include, but are not limited to, triethoxysilane, tripropoxysilane, and tert-butyldiethoxysilane.

[0194] [ka]

[0195] In one variation, hydrophilicity can be achieved using poly(oxyalkylene)silanes such as those of the general type represented by formula (2a) (or by incorporating poly(oxyalkylene) chains into binder (i) as outlined in the previous section). The poly(oxyalkylene)silanes react with silanols or poly(oxyalkylene) chains in the binder component (formula (1) or (1e)), thereby incorporating the poly(oxyalkylene) chains.

[0196] [ka]

[0197] During the ceremony, Each R independently represents an unsubstituted or substituted monovalent hydrocarbon group of 1 to 6 carbon atoms or a hydrolyzable group. Each X independently represents a hydrolyzable group. Each R 2 -H, C 1~4 -Alkyl (e.g., -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2CH3), phenyl (-C6H5), and C 1~4 - alkylcarbonyl (e.g., -C(=O)CH3, -C(=O)CH2CH3 and -C(=O)CH2CH2CH3), in particular independently selected from -H and methyl; Each R 3 is C 2~5 -C substituted with alkylene (e.g., -CH2CH2-, -CH2CH(CH3)-, CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH(CH2CH3)-), arylene (e.g., 1,4-phenylene), and aryl (e.g., 1-phenylethylene) 2~5 -Alkylene, especially C 2~5 - alkylene, independently selected from, for example, -CH2CH2- and -CH2CH(CH3)-; p is 3 to 50; a is 0 to 2; z is 1 to 3.

[0198] The introduction of oxyalkylene units into the organopolysiloxane increases the hydrophilicity of the binder, especially when the ethylene oxide type -[CH2CH2-O]- is used.

[0199] In a further aspect, the poly(oxyalkylene) modification of the binder consists of both ABA modifications (as described above) and pendant poly(oxyalkylene) chains.

[0200] It should be understood that the coating in which the poly(oxyalkylene) chains form part of the polysiloxane-based binder matrix, i.e., the moieties, are covalently incorporated into the binder matrix. It should also be understood that the covalent bonds formed are preferably non-hydrolyzable.

[0201] It should be understood that the poly(oxyalkylene) chains contained in the polysiloxane-based binder matrix are, of course, not silicon-based.

[0202] The incorporation of the poly(oxyalkylene) chain into the polysiloxane polymer backbone is typically achieved via a linking group. A linking group is understood to be the product of the reaction of two mutually reactive functional groups: one functional group on the polysiloxane backbone and one functional group on the poly(oxyalkylene) chain. For example, an amine linking group is the result of, for example, but not limited to, the reaction of a glycidyl ether with a primary or secondary amine. Examples of useful linking groups between the poly(oxyalkylene) chain and the polysiloxane backbone include: amine groups, ether groups, amide groups, 1, 2, 3 triazoles, CC bonds, CC double bonds, CC triple bonds, Si-C bonds, C-S bonds, S-S bonds, urethane groups, and urea groups. The most preferred linking group is an Si-C bond prepared by a platinum-catalyzed hydrosilylation reaction, in which the functional group on the polysiloxane backbone is a hydride and the functional group on the poly(oxyalkylene) chain is an allyl group.

[0203] In some embodiments, the poly(oxyalkylene) chain preferably imparts a permanent hydrophilic character to the binder matrix. Therefore, in such embodiments, the poly(oxyalkylene) chain preferably does not contain any bonds that are hydrolyzable in seawater. Therefore, the poly(oxyalkylene) chain preferably does not contain ester or acid anhydride bonds.

[0204] When the polysiloxane-based binder system described above is characterized by including one or more polysiloxane components modified with poly(oxyalkylene) chains as part of the binder matrix, such polysiloxane components react with other polysiloxane components, and a crosslinker provides hydrophilic properties to the binder system. Alternatively, poly(oxyalkylene) chains or poly(oxyalkylene) chains functionalized with reactive silanes that react with the polysiloxane binder or poly(oxyalkylene) chains to form non-hydrolyzable bonds can also be used.

[0205] The polysiloxane component must contain silicon reactive groups such as Si-OH groups, hydrolyzable groups such as Si-OR groups (e.g., alkoxy, oxime, acetoxy, etc.) to facilitate reaction with other components of the polysiloxane-based binder system.

[0206] When the poly(oxyalkylene)-modified chains are present in the coating composition (and cured coating) covalently attached to the binder matrix, the poly(oxyalkylene) chains typically comprise 1 to 30% by dry weight, e.g., 2 to 25%. In certain embodiments, the poly(oxyalkylene) chains comprise 3 to 20% by dry weight, e.g., 5 to 20% by dry weight, and particularly 6 to 17% by dry weight, of the coating composition / cured coating. In certain other embodiments, the poly(oxyalkylene) chains comprise 3 to 15% by dry weight, e.g., 4 to 12% by dry weight, and particularly 3 to 10% by dry weight, or 4 to 9% by dry weight, or 5 to 10% by dry weight, or 7 to 12% by dry weight, of the coating composition / cured coating.

[0207] <Sterically hindered amine> An essential component of the fouling release coating and / or tie coat (and corresponding coating composition) is one or more sterically hindered amines (e.g., 2,2,6,6-tetraalkylpiperidine derivatives). The inventors have discovered that the hindered amine moiety (e.g., 2,2,6,6-tetraalkylpiperidine moiety) of such sterically hindered amines, when used in combination with a component containing a poly(oxyalkylene) chain, improves the antifouling performance of immersed polysiloxane-based fouling release coating / system.

[0208] In one embodiment, the sterically hindered amine is present in the tie coat composition and coating. In another embodiment, the sterically hindered amine is present in the fouling release composition and coating.

[0209] The presence of a sterically hindered amine motif (e.g., a 2,2,6,6-tetraalkylpiperidine motif) is believed to play a key role due to the sterically hindered amine functionality. Otherwise, it is understood that a wide range of derivatives are applicable, including those present as individual molecules, those that are part of oligomeric or polymeric structures, and those that are covalently incorporated into binder matrices.

[0210] In certain embodiments, the sterically hindered amine comprises a hindered amine moiety of general formula I:

[0211] [ka]

[0212] During the ceremony, each R1 is independently a straight or branched chain C1-C4 alkyl, preferably methyl;

[0213] R2 is -H, optionally substituted straight or branched chain C 1~30 Alkyl, optionally substituted straight or branched chain C 2~30 Alkenyl, optionally substituted aryl, -OH(NO · ), optionally substituted linear or branched C 1~30 Alkoxy, optionally substituted straight or branched chain C 1~30 Alkenyloxy, optionally substituted aryloxy, optionally substituted straight or branched chain C 1~30 Alkylcarbonyl, optionally substituted straight or branched chain C 1~30 -alkenylcarbonyl, and optionally substituted arylcarbonyl.

[0214] R3 is an optionally substituted divalent group which, together with the intervening -C(R1)2-N(R2)-C(R1)2- groups, forms a 5-, 6- or 7-membered N-heterocyclic ring.

[0215] and wherein R2 and / or R3, having the above meanings, can each independently lead to one or more hindered amine moieties having general formula I:

[0216] Preferably, R1 is methyl.

[0217] In some embodiments, R2 is an optionally substituted C 1~30 Alkyl, optionally substituted C 1~30 Alkenyl, optionally substituted aryl, -OH, optionally substituted C 1~30 Alkoxy, optionally substituted C 1~30 Alkenyloxy, optionally substituted aryloxy, optionally substituted C 1~30 Alkylcarbonyl, optionally substituted C 1~30 -alkenylcarbonyl and optionally substituted arylcarbonyl, especially optionally substituted C 1~30 Alkyl, optionally substituted C 1~30 Alkenyl, optionally substituted aryl, optionally substituted C 1~8 Alkoxy, optionally substituted C 1~8 Alkenyloxy, optionally substituted aryloxy, optionally substituted C 1~8 Alkylcarbonyl, optionally substituted C 1~8 -alkenylcarbonyl, and optionally substituted arylcarbonyl.

[0218] In another embodiment, R2 is C 1~4 -Alkyl, C 1~4 -alkoxy, C 1~4 -alkylcarbonyl.

[0219] In some embodiments, R3 is selected from -CH2-C(~)-CH2- (corresponding to piperidine) and -CH2-N(~)-CH2- (corresponding to piperazine), particularly -CH2-C(~)-CH2-, where "~" indicates a hydrogen atom and / or a point of attachment to a substituent, linker, scaffold, dendrimer, polymer, or the like.

[0220] In a particular embodiment, R3 is selected from -CH2-C(R4)-CH2- (corresponding to piperidine) and -CH2-N(R4)-CH2- (corresponding to piperazine), in particular -CH2-C(R4)-CH2-, where R4 is (generally and specifically) as defined in general formula II below.

[0221] It is presently preferred that R2 is not -H, since the presence of secondary amines in the fouling release / tie coat compositions, which lead to fouling release coatings, can have a detrimental effect on the formation of the polysiloxane binder matrix.

[0222] It is also believed that R2 should preferably not be selected from -H and -OH.

[0223] In some embodiments, the sterically hindered amine is a discrete molecule containing only one hindered amine moiety, particularly a piperidine moiety of general formula II (below).

[0224] In other embodiments, the sterically hindered amine is an oligomer comprising, for example, 2 to 20 hindered amine moieties, particularly piperidine moieties of general formula II (below). In a variation herein, the moieties are linked to each other.

[0225] In yet another embodiment, the sterically hindered amine is a polymeric oligomer containing, for example, 5 to 200 hindered amine moieties, particularly piperidine moieties of general formula II (below), as repeating backbone or repeating grafting sites in the polymer structure.

[0226] In a variation of the above, the sterically hindered amine is immobilized in a polysiloxane-based binder matrix.

[0227] More particularly, the sterically hindered amine is selected from 2,2,6,6-tetraalkylpiperidine derivatives, i.e., the hindered amine moiety is a 2,2,6,6-tetraalkylpiperidine moiety of general formula II:

[0228] [ka]

[0229] wherein R1 and R2 are defined as above; R4 represents a hydrogen atom and / or a point of attachment to the polymer.

[0230] In some variations, the substituents for R4 are selected from those substituents further defined below as substituents for heterocycles.

[0231] In one embodiment, R4 is 0 (if the 4-position of the piperidine is not substituted), C 1~30 -Alkyl, C 1~30 -Alkenyl, aryl, hydroxy, C 1~30 -alkoxy, C 1~30 -Alkenyloxy, aryloxy, C 1~30 -Alkylcarbonyl, C 1~30 -Alkenylcarbonyl, arylcarbonyl, C 1~30 -Alkylcarbonyloxy, C 1~30 -represents one or two substituents selected from alkenylcarbonyloxy, and arylcarbonyloxy, wherein the substituents R4 as defined above may each independently be connected to one or more hindered amine moieties having the general formula II.

[0232] In some embodiments, R4 is C 1~30 -Alkyl, C 1~30 -Alkenyl, aryl, C 1~30 -alkoxy, C 1~30 -Alkenyloxy, aryloxy, C 1~30 -Alkylcarbonyl, C 1~30 -Alkenylcarbonyl, arylcarbonyl, C 1~30 -Alkylcarbonyloxy, C 1~30 -alkenylcarbonyloxy and arylcarbonyloxy, in particular C 1~8 -alkoxy, C 1~8-Alkenyloxy, aryloxy, C 1~8 -Alkylcarbonyloxy, C 1~8 -alkenylcarbonyloxy, and arylcarbonyloxy.

[0233] In other embodiments, R4 represents two substituents forming a spiro structure, e.g., a heterocyclic spiro structure. The term "spiro" has its usual meaning in organic chemistry, i.e., two or more rings sharing a common atom.

[0234] Variations of sterically hindered amines, such as 2,2,6,6-tetraalkylpiperidine derivatives, are abundant in the literature and in commercial sources. For example, due to the fact that 2,2,6,6-tetraalkylpiperidines as individual molecules are readily mobile in polysiloxane-based coatings, it may be desirable to modify their tendency to migrate by structural derivatization, such as modifying water solubility, and / or by increasing molecular weight (reducing mobility), or by covalent immobilization of the sterically hindered amine moiety (e.g., piperidine moiety).

[0235] In certain embodiments, the sterically hindered amine moieties are present within separate molecules.

[0236] In another embodiment, the sterically hindered amine moiety is present as part of an oligomeric or polymeric structure.

[0237] In yet another embodiment, the sterically hindered amine moieties are present immobilized in a binder matrix.

[0238] Therefore, for illustrative purposes, various examples of 2,2,6,6-tetraalkylpiperidine derivatives are presented below.

[0239] In some embodiments, the piperidine derivatives exist as separate molecules.

[0240] In other embodiments, the piperidine derivative is part of an oligomeric or polymeric structure.

[0241] In one variant, such oligomeric / polymeric piperidine derivatives are of the nature of (meth)acrylates, as disclosed, for example, in WO 2016 / 105974, and have the formula (R b ) m -R a -NH-C(=O)-LX,

[0242] X is:

[0243] [ka]

[0244] R 1 , R 2 , R 7 and R 8 is C 1~4 - independently selected from alkyl, preferably methyl; R 3 , R 4 , R 5 and R 6 is hydrogen and C 1~4 - independently selected from alkyl, preferably hydrogen; A is R as defined above for general formula I and general formula II. 3 is selected as, preferably not NH; L is selected from -O- and a single bond, preferably -O-; m is an integer from 1 to 6; R a is the m+1 valence, preferably C 1~6 - a linking group having an alkylene or polyhydrocarbon group; R b is the formula OC(=O)-C(R d )=CH2, where R d is a methyl or hydrogen (alkyl)acryloyloxy functional group.

[0245] In another variation, the piperidine derivatives are independently selected from polymers comprising the following segments:

[0246] [ka]

[0247] In the formula, n represents an integer of 3 to 100.

[0248] Illustrative examples of commercially available sterically hindered amines of the 2,2,6,6-tetramethylpiperidine type are Sabostab UV65 (N-CH), Sabostab UV40 (NH), Sabostab UV79 (NH) from Sabo SpA; Hostavin (N-Acyl), Hostavin 3070 (Oligomeric) from Clariant; Tinuvin 622 (Oligomer), Tinuvin 144 (N-CH), Flamestavin (N-Oligomeric) from BASF. ) NOR116 (NOR), Chimassocib 944 (NH), Tinuvin 249 (NOR), Tinuvin 440 (N-Acyl), Tinuvin 152 (NOR), Tinuvin 123 (NOR), Uvinul 4050H (NH), Lignostab 1198 (NO·monomer), Uvinul 5050H (NH, polymer); Adeka Palmarol Palmarole ADK STAB LA-52 (N-CH3), ADK STAB LA-68 (NH), ADK STAB LA-82 (N-CH3); and Gelest UBS-0822 (NH, siloxane) and UBS-0541 (NH, siloxane).

[0249] Typically, the sterically hindered amine, such as a piperidine derivative, is present in a total amount of 0.05 to 10% by dry weight of the coating (or coating composition), such as 0.08 to 8%, or for example 0.1 to 7%, such as 0.12 to 5%, especially 0.15 to 3%.

[0250] Since the sterically hindered amine motif, e.g., the 2,2,6,6-tetraalkylpiperidine motif, is believed to be at least partly responsible for the improved performance, it is believed that the hindered amine moiety, in particular the 2,2,6,6-tetraalkylpiperidine moiety, should preferably be present in an amount of 0.003 to 0.5, e.g., 0.005 to 0.2, for example, 0.008 to 0.2, in particular 0.01 to 0.1 mol / kg of the coating.

[0251] In another embodiment, the sterically hindered amine moiety, such as a 2,2,6,6-tetraalkylpiperidine moiety, is present in the coating in an amount of 0.015 to 100, such as 0.04 to 100, especially 0.08 to 15, mol / kg of poly(oxyalkylene) chain.

[0252] In certain embodiments where the poly(oxyalkylene) chains are present in individual molecules of the coating (i.e., not immobilized), the coating typically has a mass of 0.3 to 12, e.g., 0.4 to 8, especially 0.5 to 6 g / m 2 and 0.1 to 20, for example 0.2 to 10, particularly 0.3 to 6 g / m 2 and one or more of the above sterically hindered amines, in particular 2,2,6,6-tetraalkylpiperidine derivatives.

[0253] In another embodiment in which the poly(oxyalkylene) chains are present in individual molecules of the coating (i.e., not immobilized), the coating comprises 0.3 to 6 dry weight %, for example 0.4 to 4 dry weight %, in particular 0.5 to 3 dry weight % of one or more of the above-mentioned poly(oxyalkylene) chains, and 0.1 to 10 dry weight %, for example 0.2 to 5 dry weight %, in particular 0.3 to 3 dry weight % of one or more of the above-mentioned sterically hindered amines, in particular 2,2,6,6-tetraalkylpiperidine derivatives.

[0254] In yet another embodiment in which the poly(oxyalkylene) chains are fixed to a binder, the coating is typically from 1 to 60, e.g., from 2 to 40, especially from 3 to 30 g / m 2and 0.1 to 20, for example 0.2 to 10, particularly 0.3 to 6 g / m 2 and one or more of the above sterically hindered amines, in particular 2,2,6,6-tetraalkylpiperidine derivatives.

[0255] In another embodiment, in which the poly(oxyalkylene) chains are present in individual molecules of the coating (i.e., not immobilized), the coating comprises 1 to 30% by dry weight, for example 2 to 20% by dry weight, in particular 3 to 15% by dry weight, of one or more of the above-mentioned poly(oxyalkylene) chains and 0.1 to 10% by dry weight, for example 0.2 to 5% by dry weight, in particular 0.3 to 3% by dry weight, of one or more of the above-mentioned sterically hindered amines, in particular 2,2,6,6-tetraalkylpiperidine derivatives.

[0256] When the sterically hindered amine is of general formula II, the 2,2,6,6-tetraalkylpiperidine derivative is typically selected from the following classes: NH piperidine derivatives, NC 1~30 Alkylpiperidine derivatives, NC 1~30 Alkenylpiperidine derivatives, N-arylpiperidine derivatives, N-hydroxypiperidine derivatives, NC 1~30 Alkoxypiperidine derivatives, NC 1~30 Alkenyloxypiperidine derivatives, N-aryloxypiperidine derivatives, NC 1~30 Alkylcarbonylpiperidine derivatives, NC 1~30 -alkenylcarbonylpiperidine derivatives, and N-arylcarbonylpiperidine derivatives, where the N substituent may be substituted as defined for R3 above.

[0257] Preferred are the following types: NC 1~30 -Alkylpiperidine derivatives, NC 1~30 -Alkenylpiperidine derivatives, N-arylpiperidine derivatives, NC 1~30 -Alkoxypiperidine derivatives, NC 1~30 -Alkenyloxypiperidine derivatives, N-aryloxypiperidine derivatives, NC 1~30-Alkylcarbonylpiperidine derivatives, NC 1~30 -alkenylcarbonylpiperidine derivatives, and N-arylcarbonylpiperidine derivatives.

[0258] In some embodiments, the following types are more preferred: NC 1~30 Alkylpiperidine derivatives, NC 1~30 Alkenylpiperidine derivatives and N-arylpiperidine derivatives, especially NC 1~30 Alkylpiperidine derivatives.

[0259] In other embodiments, the following types are more preferred: NC 1~30 Alkoxypiperidine derivatives, NC 1~30 Alkenyloxypiperidine derivatives and N-aryloxypiperidine derivatives, especially NC 1~30 Alkoxypiperidine derivatives.

[0260] In yet other embodiments, the following types are more preferred: NC 1~30 Alkylcarbonylpiperidine derivatives, NC 1~30 -Alkenylcarbonylpiperidine derivatives and N-arylcarbonylpiperidine derivatives, especially NC 1~30 Alkylcarbonylpiperidine derivatives.

[0261] The type of substituent (or its absence) on the N atom of the 2,2,6,6-tetraalkylpiperidine moiety affects the pKa value of the piperidine derivative, which in turn can affect the efficiency of the stabilizing effect on the poly(oxyalkylene) chain.

[0262] For example, the pKa values (and pKb values) of the above exemplary group classes are as follows:

[0263] [Table 1]

[0264] Without being bound by any particular theory, it is understood that the pKa value of the 2,2,6,6-tetraalkylpiperidine derivative should preferably be less than 8.5. Therefore, it is preferred that N is substituted (i.e., not NH). More preferably, the pKa is less than 8.0, for example, less than 7.0, for example, less than 6.0 or even less than 5.0.

[0265] Moreover, the 2,2,6,6-tetraalkylpiperidine derivatives (and generally sterically hindered amines) in the overall structure of formula I or II preferably do not contain any primary or secondary amines. Moreover, the structure of formula I or II preferably does not contain any non-bulky tertiary amines.

[0266] It should be understood that the above embodiments can be viewed independently or in combination.

[0267] In some embodiments, such 2,2,6,6-tetraalkylpiperidine derivatives are in liquid form at 20°C.

[0268] In some embodiments, the sterically hindered amine, in particular the 2,2,6,6-tetraalkylpiperidine derivative, has a solubility in water at 20°C of up to 0.1% by weight, preferably less than 0.01% by weight, more preferably less than 0.001% by weight, and even more preferably less than 0.0001% by weight.

[0269] In some embodiments, the component having a poly(oxyalkylene) chain is selected from poly(oxyalkylene)-modified polysiloxane oils and poly(oxyalkylene)-modified alcohols (see the "Poly(oxyalkylene)-modified polysiloxane oils" and "Poly(oxyalkylene)-modified alcohols" sections above).

[0270] In another embodiment, the component having a poly(oxyalkylene) chain is selected from poly(oxyalkylene) modifications of the binder matrix (see above under "Poly(oxyalkylene) Modification of the Binder Matrix").

[0271] When any R group (particularly R, R, R, and R) is described as "optionally substituted," this means that it can be substituted at any suitable position with halogen (-F, -Cl, -Br, or -I), -C1-C4 alkyl, or OH.

[0272] <Biocides> It should be understood that the coating may, although not necessarily, include one or more biocides.

[0273] In the present invention, the term "biocide" is intended to mean an active substance intended to destroy, deter, neutralize, prevent the action of, or otherwise exert a control effect on, any harmful organism by chemical or biological means.

[0274] Illustrative examples of biocides are metal-dithiocarbamates such as bis(dimethyldithiocarbamate)zinc, ethylene-bis-(dithio-carbamate)zinc, ethylene-bis-(dithio-carbamate)-manganese, dimethyldithiocarbamate zinc, and complexes therebetween; bis(1-hydroxy-2(1H)-pyridine-thionato O,S)-copper; copper acrylate; bis(1-hydroxy-2(1H)-pyridine-thionato O,S)-zinc; phenyl -(Bispyridyl)-bismuth dichloride; metal biocides such as copper metal alloys like copper-nickel alloys resembling copper powder; metal salts such as copper thiocyanate, basic copper carbonate, copper hydroxide, barium metaborate, copper chloride, silver chloride, silver nitrate and copper sulfide; 3a,4,7,7a-tetrahydro-2-((trichloromethyl)-thio)-1H-isoindule-1,3(2H)-dione, pyridine-triphenylborane, 1-(2,4,6-trichlorophenyl)-1H-pyrrole Heterocyclic nitrogen compounds such as 2,5-thiazolyl-2,5-dione, 2,3,5,6-tetrachloro-4-(methyl-sulfonyl)-pyridine, 2-methyl-thio-4-tert-butyl-amino-6-cyclopropyl-amine-s-triazine, quinoline derivatives; 2-(4-thiazolyl)-benzimidazole, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-octyl-3(2H)-isothiazoline (Sea-Nine®) -211N), 1,2-benz-iso-thiazolin-3-one, and 2-(thiocyanatomethyl-thio)-benzo-thiazole; urea derivatives such as N-(1,3-bis(hydroxylmethyl)-2,5-dioxo-4-imidazolidinyl)-N,N'-bis(hydroxymethyl)-urea, and N-(3,4-dichloro-phenyl)-N,N-dimethylurea, N,N-dimethyl-chlorophenylurea; amides or imides of carboxylic acids;Sulfonic acids and sulfenic acids such as 2,4,6-trichlorophenylmaleimide, 1,1-dichloro-N-((dimethyl-amino)-sulfonyl)-1-fluoro-N(4-methyl-phenyl)-methane-sulfenamide, 2,2-dibromo-3-nitrilo-propionamide, N-(fluorodichloro-methyl-thio)-phthalimide, N,N-dimethyl-N'-phenyl-N'-(fluorodichloro-methyl-thio)-sulfamide, and N-methylolformamide; 2-((3-iodo-2-propynyl)oxy)- Salts or esters of carboxylic acids such as N,N-didecyl-N-methyl-poly(oxy-ethyl)-ammonium propionate; amines such as dihydroabietylamine and coco-dimethylamine; substituted methanes such as di(2-hydroxy-ethoxy)methane, 5,5'-dichloro-2,2'-dihydroxy-diphenylmethane, and methylene-bisthiocyanate; 2,4,5,6-tetrachloro-1,3-benzenedicarbonitrile, 1,1-dichloro-N-((dimethyl-amino) )-sulfonyl)-1-fluoro-N-phenylmethanesulfenamide, and substituted benzenes such as 1-((diiodomethyl)sulfonyl)-4-methyl-benzene; tetraalkylphosphonium halide compounds such as tri-n-butyl-tetradecylphosphonium chloride; guanidine derivatives such as n-dodecylguanidine hydrochloride; disulfides such as bis-(dimethylthiocarbamoyl)-disulfide, tetramethylthiuram disulfide; imidazole-containing compounds such as medetomidine; 2-(p-chlorophenyl)- 3-cyano-4-bromo-5-trifluoromethylpyrrole; bis(N-cyclohexyl-diazeniumdioxy)copper, thiabendazole, N-trihalomethylthiophthalimide, trihalomethylthiosulfamide, capsaicin, 3-iodo-2-propynyl butylcarbamate, 1,4-dithiaanthraquinone-2,3-dicarbonitrile (dithianon), furanones such as 3-butyl-5-(dibromomethylidene)-2(5H)-furanone, macrocyclic lactones such as avermectins, and mixtures thereof.

[0275] Currently, it is preferred that the biocide (if present) be tin-free.

[0276] Currently, the preferred biocides are 2,4,5,6-tetrachloroisophthalonitrile (chlorothalonil), copper thiocyanate (copper sulfocyanate), N-dichloro-fluoromethylthio-N',N'-dimethyl-N-phenylsulfamide (dichlfluanid), 3-(3,4-dichloro-phenyl)-1,1-dimethylurea (diuron), N 2 -tert-Butyl-N 4 -cyclopropyl-6-methylthio-1,3,5-triazine-2,4-diamine (sibutrin), 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole 3-carbonitrile (2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole; tralopyril), N 2 -tert-Butyl-N 4-Cyclopropyl-6-methylthio-1,3,5-triazine-2,4-diamine (Sibutrin), (RS)4-[1-(2,3-dimethylphenyl)ethyl]-3H-imidazole (Medetomidine), 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT, Sheenaine(R)211N), dichloro-N-((dimethylamino)sulfonyl)fluoro-N-(p-tolyl)methane-sulfenamide (tolylfluanid), 2-(thiocyanomethylthio)-1,3-benzothiazole ((2-benzothiazolylthio)-methylthiocyanate; TCMTB), triphenylborane and diisopropylparaben (TPBP); bis(1-hydroxy-2(1H)-pyridine-thionato O,S)-(T-4)zinc (zinc pyridinethione; zinc pyrithione), bis(1-hydroxy-2(1H)-pyridine-thionato O,S)-T-4)copper (copper pyridinethione; copper pyrithione), ethylene-1,2-bis-dithiocarbamate zinc (ethylene-N-N'-dithiocarbamate zinc; zineb), copper(I) oxide, copper metal, 3-(3,4-dichlorophenyl)-1,1-dimethylurea (diuron), and diiodomethyl-p-tolylsulfone; Amical 48. Preferably, at least one biocide is selected from the above list.

[0277] In a preferred embodiment (of the variants containing one or more biocides), the biocide is preferably selected from among biocides that are effective against soft soils such as slime and algae. Examples of such biocides are N 2 -tert-Butyl-N 4-cyclopropyl-6-methylthio-1,3,5-triazine-2,4-diamine (sibutrin), 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT, Sheenaine(R) 211N), bis(1-hydroxy-2(1H)-pyridinethionate O,S)-(T-4)zinc (pyridinethione zinc; zinc pyrithione), bis(1-hydroxy-2(1H)-pyridinethionate O,S)-(T-4)zinc (pyridinethione zinc; zinc pyrithione), (O,S)-T-4)copper (copper pyridinethione; copper pyrithione; copper omadine) and ethylene-1,2-bis-dithiocarbamate zinc (ethylene-N-N'-dithiocarbamate zinc; zineb), copper(I) oxide, metallic copper, copper thiocyanate, (copper sulfocyanate), bis(1-hydroxy-2(1H)-pyridinethionate O,S)-T-4)copper (copper pyridinethione; copper pyrithione; copper omadine).

[0278] In some embodiments, at least one biocide is an organic biocide. In more particularly preferred embodiments, the one or more biocides are organic biocides, such as pyrithione complexes, such as zinc pyrithione or copper pyrithione. The organic biocide is of completely or partially organic origin.

[0279] In certain important embodiments, the one or more biocides include at least one of bis(1-hydroxy-2(1H)-pyridinethionato O,S)-(T-4) zinc (zinc pyridinethione; zinc pyrithione), bis(1-hydroxy-2(1H)-pyridinethionato O,S)-(T-4) copper (copper pyridinethione; copper pyrithione), and ethylene-1,2-bis-dithiocarbamate zinc (ethylene-N-N'-dithiocarbamate zinc; zineb).

[0280] As described in U.S. Patent Application Publication No. 7,377,968, it may be advantageous to add one or more biocides in encapsulated form as a means of controlling the biocide dosage and extending its useful life in the film if the biocide is rapidly depleted from the film, for example, due to high water solubility or high immiscibility with the matrix composition. Encapsulated biocides may also be added if the free biocide alters the performance of the polysiloxane matrix in a manner detrimental to its use as an antifouling coating (e.g., mechanical integrity, drying time, etc.).

[0281] In one embodiment, the biocide is encapsulated with 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (Sea-Nine CR2).

[0282] The biocide preferably has a solubility in water at 25° C. in the range of 0 to 20 mg / L, for example 0.00001 to 20 mg / L.

[0283] In one embodiment, the coating comprises 2 to 20% by dry weight, such as 4 to 16% by dry weight, especially 5 to 13% by dry weight, of one or more of the above biocides.

[0284] In another embodiment, the coating comprises 1 to 13%, such as 2 to 10%, especially 3 to 8%, of the solids of one or more of the above biocides.

[0285] In yet another embodiment, the coating comprises from 2 to 35, for example from 3 to 30, in particular from 4 to 25 g / m of one or more of the above biocides. 2 Includes:

[0286] It should be understood that the above embodiments may be applied independently or in combination.

[0287] In some embodiments, no biocides are included.

[0288] Specific Embodiments of the Invention In certain embodiments, the fouling release composition comprises:

[0289] 40 to 98% by dry weight, for example 60 to 95% by dry weight, of a polysiloxane-based binder matrix, wherein the binder matrix is represented by a polysiloxane portion of more than 65% by weight of the binder matrix; 0.1 to 20% by dry weight, for example 1 to 10% by dry weight, of one or more additives, 0 to 25% by dry weight, for example 0.1 to 15% by dry weight, of one or more pigments and fillers, 0.5 to 10% by dry weight, for example 0.7 to 8% by dry weight, in particular 1 to 6% by dry weight, of one or more poly(oxyalkylene) chains, and 0.05 to 10% by dry weight, for example 0.1 to 7% by dry weight, in particular 0.15 to 5% by dry weight, of one or more piperidine derivatives.

[0290] In another embodiment, the fouling release composition comprises:

[0291] 50-90% by dry weight of a polysiloxane-based binder matrix, in which more than 60%, in particular 60-99.5%, or even 70-99%, or 90-97% of the binder matrix is represented by polysiloxane moieties, the remainder of the binder matrix being preferably made up of hydrophilic oligomeric / polymeric moieties and any crosslinking agent, preferably comprising 1-30% by weight, for example 2-20% by weight, for example 1-10% by weight of the binder matrix, 0.1 to 20% by dry weight, for example 1 to 10% by dry weight, of one or more additives, 0 to 25% by dry weight, for example 0.1 to 15% by dry weight, of one or more pigments and fillers, and 0.05 to 10% by dry weight, for example 0.1 to 7% by dry weight, in particular 0.15 to 5% by dry weight, of one or more piperidine derivatives.

[0292] In another embodiment, the fouling release composition comprises:

[0293] 50-90% by dry weight of a polysiloxane-based binder matrix, in which more than 60% by weight of the binder matrix, in particular 60-99.5%, or even 70-99%, or 90-97%, is represented by polysiloxane moieties, the remainder of the binder matrix being preferably made up of hydrophilic oligomeric / polymeric moieties and any crosslinking agent, preferably comprising 1-30% by weight, for example 2-20% by weight, for example 1-10% by weight of the binder matrix, 1 to 10% by dry weight of one or more poly(oxyalkylene)-modified polysiloxane oils; 0.1 to 20% by dry weight, for example 1 to 10% by dry weight, of one or more additives, 0 to 25% by dry weight, for example 0.1 to 15% by dry weight, of one or more pigments and fillers, and 0.05 to 10% by dry weight, for example 0.1 to 7% by dry weight, in particular 0.15 to 5% by dry weight, of one or more piperidine derivatives.

[0294] In another embodiment, the fouling release composition comprises:

[0295] a polysiloxane-based binder matrix of 40 to 98%, for example 60 to 95%, by solid volume, which binder matrix is represented by a polysiloxane portion of more than 65% by weight of the binder matrix; 0.1% to 20%, e.g., 0.1% to 15%, by solid volume of one or more additives; 1 to 10%, e.g., 2 to 8%, by solid volume of one or more pigments and fillers; 1 to 30%, for example 2 to 20%, especially 3 to 15%, by solid volume of one or more poly(oxyalkylene) chains; and 0.05 to 10%, for example 0.1 to 7%, particularly 0.15 to 5%, by solid volume of one or more of the above piperidine derivatives.

[0296] In a more specific embodiment, the fouling release coating (and corresponding coating composition) described above comprises, as a poly(oxyalkylene chain)-containing component, 1 to 15%, for example 1 to 12%, in particular 2 to 9%, by solid volume, of one or more poly(oxyalkylene)-modified polysiloxane oils, in particular with a molecular weight of 600 to 30,000, for example 800 to 20,000 or 1,000 to 10,000, more specifically 1,400 to 10,000 or 1,400 to 7,000 g / mol, and an HLB of 4 to 16, for example 5 to 15 or 6 to 14, in particular 7 to 13.

[0297] In a more specific embodiment, the fouling release coating (and corresponding coating composition) described above comprises, as a poly(oxyalkylene chain)-containing component, 1 to 15%, for example 1 to 12%, in particular 2 to 9%, by solid volume, of one or more poly(oxyalkylene) modified alcohols as defined herein above, with a molecular weight of 500 to 5,000, for example 600 to 4,000 or 600 to 3,000 g / mol and an HLB of 6 to 16, for example 7 to 16 or 8 to 16, in particular 9 to 15.

[0298] In a variation of the above embodiment, the sterically hindered amine is selected from 2,2,6,6-tetraalkylpiperidine derivatives (general formula II).

[0299] In one embodiment, the weight ratio between the total amount of one or more poly(oxyalkylene) chains and one or more sterically hindered amines, such as 2,2,6,6-tetraalkylpiperidine derivatives, is in the range of 1:0.01 to 1:3, for example 1:0.02 to 1:2, particularly 1:0.04 to 1:1.5.

[0300] In a variation of the above embodiment, the sterically hindered amine, such as a piperidine derivative, is present in a total amount of 0.05 to 10% by dry weight of the coating (or coating composition), such as 0.08 to 8% by dry weight, or for example 0.1 to 7% by dry weight, such as 0.12 to 5% by dry weight, in particular 0.15 to 3% by dry weight.

[0301] In one embodiment, the tie coat composition comprises:

[0302] 3 to 90%, preferably 10 to 80%, more preferably 20 to 60%, by wet weight of the total tie coat composition, of one or more of the above crosslinkable polysiloxanes; 0.1 to 20% by dry weight, for example 1 to 10% by dry weight, of one or more additives, 0 to 25% by dry weight, for example 0.1 to 15% by dry weight, of one or more pigments and fillers, 0.5 to 10% by dry weight, for example 0.7 to 8% by dry weight, in particular 1 to 6% by dry weight, of one or more poly(oxyalkylene) chains, and 0.05 to 10% by dry weight, for example 0.1 to 7% by dry weight, in particular 0.15 to 5% by dry weight, of one or more piperidine derivatives.

[0303] In another embodiment, the tie coat composition comprises:

[0304] 3 to 90%, preferably 10 to 80%, more preferably 20 to 60%, by wet weight of the total tie coat composition, of one or more of the above crosslinkable polysiloxanes. Preferably, the hydrophilic oligomer / polymer moiety constitutes 1 to 30% by weight of the binder matrix, for example 2 to 20% by weight, for example 1 to 10% by weight, 0.1 to 20% by dry weight, for example 1 to 10% by dry weight, of one or more additives, 0 to 25% by dry weight, for example 0.1 to 15% by dry weight, of one or more pigments and fillers, and 0.05 to 10% by dry weight, for example 0.1 to 7% by dry weight, in particular 0.15 to 5% by dry weight, of one or more piperidine derivatives.

[0305] In another embodiment, the tie coat composition comprises:

[0306] 3-90%, preferably 10-80%, more preferably 20-60% by wet weight of the total tie coat composition of one or more of the above crosslinkable polysiloxanes, preferably 1-30% by weight of the binder matrix, e.g., 2-20% by weight, e.g., 1-10% by weight of the hydrophilic oligomeric / polymeric moiety; 1 to 10% by dry weight of one or more poly(oxyalkylene)-modified polysiloxane oils; 0.1 to 20% by dry weight, for example 1 to 10% by dry weight, of one or more additives, 0 to 25% by dry weight, for example 0.1 to 15% by dry weight, of one or more pigments and fillers, and 0.05 to 10% by dry weight, for example 0.1 to 7% by dry weight, in particular 0.15 to 5% by dry weight, of one or more piperidine derivatives.

[0307] In another embodiment, the tie coat composition comprises: 3 to 90 wt. %, preferably 10 to 80 wt. %, more preferably 20 to 60 wt. %, by wet weight of the total tie coat composition, of one or more of the above crosslinkable polysiloxanes, wherein the crosslinkable polysiloxane is represented by greater than 65 wt. % of the polysiloxane portion of the binder matrix; 1 to 30%, for example 2 to 20%, especially 3 to 15%, by solid volume of one or more poly(oxyalkylene) chains; and 0.05 to 10%, for example 0.1 to 7%, particularly 0.15 to 5%, by solid volume of one or more of the above piperidine derivatives.

[0308] In one embodiment, the tie coat composition comprises:

[0309] 3 to 15% by wet weight of the total tie coat composition of one or more of the above crosslinkable polysiloxanes, 0.1 to 20% by dry weight, for example 1 to 10% by dry weight, of one or more additives, 0 to 25% by dry weight, for example 0.1 to 15% by dry weight, of one or more pigments and fillers, 0.5 to 10% by dry weight, for example 0.7 to 8% by dry weight, in particular 1 to 6% by dry weight, of one or more poly(oxyalkylene) chains, and 0.05 to 10% by dry weight, for example 0.1 to 7% by dry weight, in particular 0.15 to 5% by dry weight, of one or more piperidine derivatives.

[0310] In another embodiment, the tie coat composition comprises:

[0311] 3 to 15 percent by wet weight of the total tie coat composition of one or more of the above crosslinkable polysiloxanes. The hydrophilic oligomer / polymer moiety preferably constitutes 1 to 30% by weight of the binder matrix, for example 2 to 20% by weight, for example 1 to 10% by weight. 0.1 to 20% by dry weight, for example 1 to 10% by dry weight, of one or more additives, 0 to 25% by dry weight, for example 0.1 to 15% by dry weight, of one or more pigments and fillers, and 0.05 to 10% by dry weight, for example 0.1 to 7% by dry weight, in particular 0.15 to 5% by dry weight, of one or more piperidine derivatives.

[0312] In another embodiment, the tie coat composition comprises:

[0313] By wet weight of the total tie coat composition, 3-15% of one or more of the above crosslinkable polysiloxanes. The hydrophilic oligomeric / polymeric moieties preferably comprise 1-30% by weight of the binder matrix, e.g., 2-20% by weight, e.g., 1-10% by weight. 1 to 10% by dry weight of one or more poly(oxyalkylene)-modified polysiloxane oils; 0.1 to 20% by dry weight, for example 1 to 10% by dry weight, of one or more additives, 0 to 25% by dry weight, for example 0.1 to 15% by dry weight, of one or more pigments and fillers, and 0.05 to 10% by dry weight, for example 0.1 to 7% by dry weight, in particular 0.15 to 5% by dry weight, of one or more piperidine derivatives.

[0314] In another embodiment, the tie coat composition comprises:

[0315] 3-15% by wet weight of the total tie coat composition of one or more of the above crosslinkable polysiloxanes, with greater than 65% by weight of the binder matrix being represented by the polysiloxane moiety; 1 to 30%, for example 2 to 20%, especially 3 to 15%, by solid volume of one or more poly(oxyalkylene) chains; and 0.05 to 10%, for example 0.1 to 7%, particularly 0.15 to 5%, by solid volume of one or more of the above piperidine derivatives.

[0316] In one embodiment, the tie coat composition comprises:

[0317] >40% by wet weight of the total tie coat composition of one or more of the above crosslinkable polysiloxanes; 0.1 to 20% by dry weight, for example 1 to 10% by dry weight, of one or more additives, 0 to 25% by dry weight, for example 0.1 to 15% by dry weight, of one or more pigments and fillers, 0.5 to 10% by dry weight, for example 0.7 to 8% by dry weight, in particular 1 to 6% by dry weight, of one or more poly(oxyalkylene) chains, and 0.05 to 10% by dry weight, for example 0.1 to 7% by dry weight, in particular 0.15 to 5% by dry weight, of one or more piperidine derivatives.

[0318] In another embodiment, the tie coat composition comprises:

[0319] By wet weight of the total tie coat composition, >40% of one or more of the above crosslinkable polysiloxanes. The hydrophilic oligomeric / polymeric moieties preferably comprise 1-30% by weight of the binder matrix, e.g., 2-20% by weight, e.g., 1-10% by weight. 0.1 to 20% by dry weight, for example 1 to 10% by dry weight, of one or more additives, 0 to 25% by dry weight, for example 0.1 to 15% by dry weight, of one or more pigments and fillers, and 0.05 to 10% by dry weight, for example 0.1 to 7% by dry weight, in particular 0.15 to 5% by dry weight, of one or more piperidine derivatives.

[0320] In another embodiment, the tie coat composition comprises:

[0321] >40% by wet weight of the total tie coat composition of one or more of the above crosslinkable polysiloxanes. The hydrophilic oligomer / polymer moiety preferably constitutes 1 to 30% by weight of the binder matrix, for example 2 to 20% by weight, for example 1 to 10% by weight. 1 to 10% by dry weight of one or more poly(oxyalkylene)-modified polysiloxane oils; 0.1 to 20% by dry weight, for example 1 to 10% by dry weight, of one or more additives, 0 to 25% by dry weight, for example 0.1 to 15% by dry weight, of one or more pigments and fillers, and 0.05 to 10% by dry weight, for example 0.1 to 7% by dry weight, in particular 0.15 to 5% by dry weight, of one or more piperidine derivatives.

[0322] In another embodiment, the tie coat composition comprises:

[0323] >40% by wet weight of the total tie coat composition of one or more of the above crosslinkable polysiloxanes, represented by more than 65% by weight of the polysiloxane portion of the binder matrix, and 1 to 30%, e.g., 2 to 20%, especially 3 to 15%, by solid volume of one or more poly(oxyalkylene) chains; and 0.05 to 10%, for example 0.1 to 7%, particularly 0.15 to 5% by solid volume of one or more of the above piperidine derivatives.

[0324] In a more specific embodiment, the tie coat composition comprises, as the poly(oxyalkylene chain)-containing component, 1 to 15%, e.g., 1 to 12%, and particularly 2 to 9%, by solid volume, of one or more poly(oxyalkylene)-modified polysiloxane oils, particularly having a molecular weight of 600 to 30,000, e.g., 800 to 20,000 or 1,000 to 10,000, more particularly 1,400 to 10,000 or 1,400 to 7,000 g / mol, and an HLB of 4 to 16, e.g., 5 to 15 or 6 to 14, and particularly 7 to 13.

[0325] In a more specific embodiment, the tie coat composition comprises, as the poly(oxyalkylene chain)-containing component, 1 to 15%, for example 1 to 12%, and in particular 2 to 9%, by solid volume, of one or more poly(oxyalkylene) modified alcohols as defined herein above, in particular with a molecular weight of 500 to 5,000, for example 600 to 4,000 or 600 to 3,000 g / mol, and an HLB of 6 to 16, for example 7 to 16 or 8 to 16, in particular 9 to 15.

[0326] In a variation of the above embodiment, the sterically hindered amine is selected from 2,2,6,6-tetraalkylpiperidine derivatives (general formula II).

[0327] In one embodiment, the weight ratio between the total amount of one or more poly(oxyalkylene) chains and one or more sterically hindered amines, such as 2,2,6,6-tetraalkylpiperidine derivatives, is in the range of 1:0.01 to 1:3, for example 1:0.02 to 1:2, particularly 1:0.04 to 1:1.5.

[0328] In a variation of the above embodiment, the sterically hindered amine, such as a piperidine derivative, is present in a total amount of 0.05 to 10% by dry weight of the coating (or coating composition), such as 0.08 to 8% by dry weight, or for example 0.1 to 7% by dry weight, such as 0.12 to 5% by dry weight, in particular 0.15 to 3% by dry weight.

[0329] <Fouling Release Coating System> In one aspect, there is provided a fouling release coating system obtainable by the method of the present invention. All details of all components and layers described herein for the method also relate to the fouling release system.

[0330] In a second aspect, there is provided a fouling release coating system comprising:

[0331] a. Base material, b. Optionally, one or more primer layers; c. at least one silicone-containing tie coat layer; d. a fouling release layer comprising a condensation-cured polysiloxane-based binder matrix constituting at least 40% by dry weight of said coating, said fouling release layer being represented by a polysiloxane portion of greater than 65% by weight of said binder matrix, said coating comprising a component having a poly(oxyalkylene) chain; Here, the tie coat layer and / or the fouling release layer further comprises one or more sterically hindered amines, particularly 2,2,6,6-tetraalkylpiperidine derivatives.

[0332] In one embodiment of such coating systems, the tie coat comprises one or more poly(oxyalkylene)-modified polysiloxane oils. In another embodiment, the tie coat comprises one or more sterically hindered amines, as defined herein. In another embodiment of such coating systems, the tie coat comprises both one or more poly(oxyalkylene)-modified polysiloxane oils and one or more sterically hindered amines, as defined herein.

[0333] The inclusion of a sterically hindered amine (such as a 2,2,6,6-tetraalkylpiperidine derivative) in the tie coat and a poly(oxyalkylene) chain in the fouling release coating is believed to improve the longevity of the fouling release performance of the fouling release coating system compared to systems in which the first coating does not contain a sterically hindered amine. Without being bound by any particular theory, it is believed that sterically hindered amines, such as a 2,2,6,6-tetraalkylpiperidine derivative, can migrate from the underlying coating to the silicone fouling release coating. This likely occurs to a greater extent when the underlying tie coat is of the soft variety compared to the underlying hard coating.

[0334] <Application of coating composition> The coating compositions of the present invention are typically applied to at least a portion of the surface of a substrate.

[0335] The term "applying" is used in its usual sense in the coatings industry. Thus, "applying" can be by any conventional means, e.g., brush, roller, spray, dipping, etc. The most commercially interesting technique for "applying" a coating composition is by spraying. Therefore, it is preferred that the coating composition be sprayable. Spraying can be achieved by conventional spraying equipment known to those skilled in the art. Coatings are typically applied at a dry film thickness of 50-600 μm, e.g., 50-500 μm, e.g., 75-400 μm, or 100-300 μm.

[0336] Furthermore, the coating composition preferably exhibits sagging resistance, with reference to ASTM D 4400-99 (i.e., relating to the ability to be applied at a suitable film thickness to a vertical surface without sagging), of at least 70 μm, e.g., at least 200 μm, e.g., at least 300 μm, preferably at least 400 μm, especially at least 600 μm.

[0337] The term "at least a portion of the surface of the substrate" refers to the fact that the coating composition can be applied to any fraction of the surface. In many applications, the coating composition is applied to at least a portion of a substrate (e.g., a ship) whose surface (e.g., a ship's hull) comes into contact with water, such as seawater.

[0338] The term "substrate" is intended to mean a solid material onto which the coating composition is applied. The substrate typically comprises a metal, such as steel, iron, aluminum, or fiberglass reinforced polyester. In the most interesting embodiment, the substrate is a metal substrate, particularly a steel substrate. In an alternative embodiment, the substrate is a fiberglass reinforced polyester substrate. In some embodiments, the substrate is at least a portion of the outermost surface of a marine structure.

[0339] The term "surface" is used in its ordinary sense to refer to the outer boundary of an object. Particular examples of such surfaces are the surfaces of marine structures such as ships (including but not limited to boats, yachts, motorboats, motor craft, mega ships, tugboats, tankers, container ships and other cargo vessels, submarines, and naval vessels of all kinds), pipes, onshore and offshore machinery, bridge piers, pilings, bridge substructures, flotation devices, hydraulic equipment and structures, underwater oil well structures, nets and other aquaculture equipment, buoys, and all kinds of structures and objects.

[0340] The surface of the substrate may be either a "native" surface (e.g., a steel surface). However, the substrate is typically coated with, for example, a corrosion protection coating and / or tie coat so that the surface of the substrate is comprised of such a coating. When present, the (corrosion protection and / or tie) coating is typically applied at a total dry film thickness of 50-600 μm, e.g., 150-450 μm, e.g., 200-400 μm, or 20-200 μm. Alternatively, the substrate may have a paint coating, e.g., a fouling release paint coating or the like.

[0341] In one important embodiment, the substrate is a metal substrate (e.g., a steel substrate) coated with a corrosion-protective coating, such as a cured epoxy-based coating or a shop primer, e.g., a zinc-rich shop primer. In another related embodiment, the substrate is a fiberglass-reinforced polyester substrate coated with an epoxy primer coating.

[0342] The coatings of the main aspects of the invention are typically applied as the outermost coating (also known as a topcoat), i.e., the coating is exposed to the environment, e.g., an aquatic environment. However, it should be understood that the coatings of the main aspects of the invention may alternatively be applied as a layered system in which the coating described in the main aspects of the invention is coated with one or more layers of one or more other coating compositions to obtain and improve control over the leaching rate of the leachable components in the coating.

[0343] Prior to application of the coating composition to the marine structure, the marine structure may first be coated with a primer system which may comprise several layers, and which may be any conventional primer system used in connection with the application of coating compositions to marine structures. Thus, the primer system may optionally include a layer of an adhesion-promoting primer followed by a corrosion-protective primer.

[0344] The present invention relates to a method for establishing a fouling release coating system on the surface of a substrate, comprising the following successive steps:

[0345] a) applying one or more layers of a primer composition onto the surface of the substrate, thereby forming a primed substrate;

[0346] b) applying one or more layers of a tie coat composition onto the surface of the primed substrate and curing the layers, thereby forming a cured tie coat; and

[0347] c) applying one or more layers of a fouling release coating composition as defined herein onto the surface of the cured tie coat and curing the layers, thereby forming a cured fouling release coating as defined herein above (main aspect).

[0348] In some currently less preferred variations of the above methods, the cured fouling release coating may be further coated with a topcoat, for example a PDMS-based topcoat.

[0349] The present invention now relates (according to another aspect) to a method for establishing a fouling release coating system on the surface of a substrate, comprising the following successive steps:

[0350] a) applying one or more layers of a fouling release coating composition as defined herein to the surface of said substrate, e.g., optionally either the original substrate or a substrate already bearing one or more coatings, and curing said layers, thereby forming, for alternative embodiments, a cured first coating as defined herein above; and

[0351] b) applying one or more layers of a fouling release coating composition as defined herein onto the surface of the cured first coating and curing the layers, thereby forming, for an alternative embodiment, a cured second coating as defined herein above.

[0352] The present invention also relates (according to another aspect) to a method for establishing a fouling release coating system on the surface of a substrate, comprising the following successive steps:

[0353] a) applying one or more layers of a primer composition onto a surface of the substrate and curing the layers, thereby forming a primed substrate;

[0354] b) optionally applying one or more layers of tie coat composition onto the surface of the primed substrate and curing the layers, thereby forming a cured tie coat;

[0355] c) applying one or more layers of a fouling release coating composition as defined herein onto the surface of said primed substrate or onto the surface of said tie coat, as the case may be, and curing said layers, thereby forming a cured first coating as defined herein above for alternative embodiments;

[0356] d) applying one or more layers of a fouling release coating composition as defined herein onto the surface of the cured first coating and curing the layers, thereby forming a cured second coating as defined herein above for the alternative embodiment.

[0357] The present invention further relates to a method for establishing a fouling release coating system on the surface of an old antifouling coating system, comprising the following successive steps:

[0358] a) applying one or more layers of a sealer / link coat composition onto the surface of the substrate and curing the layers, thereby forming a sealed substrate;

[0359] b) optionally applying one or more layers of tie coat composition onto the surface of the buried substrate and curing the layers, thereby forming a cured tie coat;

[0360] c) applying one or more layers of a fouling release coating composition as defined herein onto the surface of the primed substrate or onto the surface of the tie coat, as the case may be, and curing the layers, thereby forming a cured first coating as defined herein above for alternative embodiments; and

[0361] d) applying a fouling release coating composition as defined herein onto the surface of one or more layers of said cured first coating and curing said layers, thereby forming a cured second coating as defined herein above for the alternative embodiment.

[0362] The present invention further relates to a method for establishing a fouling release coating system on the surface of an old fouling release coating system, comprising the following successive steps:

[0363] a) optionally applying one or more layers of a tie coat composition onto the surface of the aged fouling release coating system and curing the layers, thereby forming a cured tie coat;

[0364] b) applying one or more layers of a fouling release coating composition as defined herein onto the surface of the primed substrate or onto the surface of the tie coat, as the case may be, and curing the layers, thereby forming a cured first coating as defined herein above for alternative embodiments; and

[0365] c) applying one or more layers of a fouling release coating composition as defined herein onto the surface of the cured first coating and curing the layers, thereby forming a cured second coating as defined herein above for the alternative embodiment.

[0366] <Marine structures> The present invention also provides marine structures comprising on at least a portion of their surface an outermost fouling release coating system (or coating) as defined herein above, in particular at least the portion of the exterior surface carrying the outermost coating being a submerged portion of said structure.

[0367] The coating composition, the method of establishing the coating on the substrate surface, and the properties of the coating are in accordance with the instructions given herein above.

[0368] In certain embodiments, a fouling release coating system for a marine structure may consist of a corrosion protection layer, a tie coat, and a fouling release coating system as described herein.

[0369] In an alternative embodiment, the fouling release coating composition is applied on top of a used fouling release coating system, for example on top of a used polysiloxane-based fouling release coating.

[0370] In certain embodiments of the marine structure, the corrosion protection layer has a total dry film thickness of 100 to 600 μm, e.g., 150 to 450 μm, e.g., 200 to 400 μm; the tie coat has a total dry film thickness of 50 to 500 μm, e.g., 50 to 400 μm, e.g., 75 to 350 μm, 75 to 300 μm, or 75 to 250 μm; and the fouling release coating has a total dry film thickness of 20 to 500 μm, e.g., 20 to 400 μm, e.g., 50 to 300 μm.

[0371] A further embodiment of the marine structure is one in which at least a portion of the outermost surface of said structure is coated with a fouling release coating system comprising:

[0372] Anticorrosion layer of epoxy-based coating established by applying 1-4 layers, e.g. 2-4 layers, with a total dry film thickness of 150-400 μm; A tie coat established by applying one to two layers with a total dry film thickness of 20 to 400 µm; and Fouling release coating established by application of 1-2 layers (according to the main aspect) with a total dry film thickness of 20-400 μm.

[0373] A further embodiment of the marine structure is one in which at least a portion of the outermost surface of said structure is coated with a fouling release coating system comprising (in alternative aspects):

[0374] Anticorrosion layer of epoxy-based coating established by applying 1-4 layers, e.g. 2-4 layers, with a total dry film thickness of 150-400 μm; Tie coats established by applying one to two layers to a total dry film thickness of 20 to 400 μm; Total dry film thickness of 20-400 μm established by applying 1-2 layers; a first coating of fouling release coating (see alternative embodiments); A second coat of fouling release coating established by applying one to two layers with a total dry film thickness of 20 to 400 μm (see alternative embodiments).

[0375] In another embodiment of the above marine structure, a fouling release coating is applied directly onto the corrosion protection layer without the use of a tie coat.

[0376] <General precautions> Although the present specification and claims may refer to polysiloxanes and the like, it should be understood that the coating compositions defined herein may include one or more individual components, and in such embodiments, the total amount of each component should correspond to the amounts listed above for the individual components.

[0377] References to compounds, polysiloxanes, drugs, etc. indicate that one or more of each individual component type may be present.

[0378] On the other hand, when the expression "one type" is used, there is only one type of each ingredient.

[0379] The expression "dry weight %" should be understood to mean, in some cases, the percentage of each component based on the dry weight of the coating or coating composition. For the most practical purposes (and thus, unless otherwise specified), "dry weight %" when referring to a cured coating is the same as the "dry weight %" of the coating composition.

Examples

[0380] <Viscosity> In the invention of the present application with claims, the viscosity is measured at 25 °C in accordance with ISO 2555:1989.

[0381] <Determination of pKa value> The pKa value of a sterically hindered amine such as a 2,2,6,6-tetraalkylpiperidine derivative is measured by non-aqueous titration. An organic standard substance with a known pKa value in water is titrated in a non-aqueous medium (1:1 acetonitrile:chloroform and 0.1 N perchloric acid / dioxane titration system) to generate a non-aqueous calibration plot of the half-neutralization point potential against pKa. Then, the "unknown" hindered amine is titrated to determine the half-neutralization point potential and extrapolated to obtain the corresponding pKa from this calibration plot.

[0382] <Determination of HLB value> The HLB (hydrophilic-lipophilic balance) value of a molecule modified with poly(oxyalkylene) is determined according to the method of Griffin. HLB value = 20 * M h / M where M h is the weight of the hydrophilic (e.g., poly(oxyalkylene)) groups in the molecule and M is the weight of the whole molecule.

[0383] <Method for preparing model coating> Part (i): Mix the binder, solvent, pigment, biocide (if applicable), sterically hindered amine (e.g., 2,2,6,6-tetraalkylpiperidine derivative), any poly(oxyalkylene)-modified silicone oil or alcohol, and additives in a Diaf dissolver equipped with a rotor disc (e.g., 70 mm diameter rotor disc in a 1 L can at 2000 rpm for 15 minutes).

[0384] Part (ii): Mix the curing agent, solvent, catalyst and 2,4-pentanedione in a Diaphragm Dissolver equipped with a rotor disk (e.g., a 70 mm diameter rotor disk in a 1 L can at 500 rpm for 2 minutes).

[0385] Before application, parts (i) and (ii) are mixed together according to the composition given in the examples, and then the mixture is stirred to obtain homogeneity.

[0386] <Anti-fouling performance test> [Raft test]

[0387] <Panel preparation> Acrylic panels (150 x 200 mm), sandblasted on one side to facilitate coating adhesion, were coated with 100 μm (DFT) of a commercial epoxy (HEMPEL Light Primer 45551) by air spray. After drying at room temperature for 6 to 24 hours, a tie coat was applied with a doctor blade with a 300 μm clearance. After drying for 16 to 30 hours, a topcoat coating composition was applied with a doctor blade with a 400 μm clearance. The panels were allowed to dry for at least 72 hours before immersion in the raft.

[0388] <Test> The panels will be tested in two different locations: Spain and Singapore.

[0389] <Test site in Spain> Located in Vilanova in northeastern Spain, the test site involves immersing panels in seawater with salinities ranging from 37 to 38 ppm at an average temperature of 17 to 18 degrees Celsius.

[0390] <Singapore test site> In this test site, the panels are immersed in seawater with salinities ranging from 29 to 31 ppm at temperatures ranging from 29 to 31°C.

[0391] The panels are inspected every 4 to 12 weeks and rated according to the following scale:

[0392] [Table 2]

[0393] <Example> For testing antifouling performance, the following model coatings may be prepared: All items in the model coating table are listed by weight unless otherwise specified.

[0394] <Material>

[0395] [Table 3]

[0396] [Table 4]

[0397] Examples 1-4 demonstrate the improved antifouling performance of coatings containing poly(oxyalkylene)-modified siloxane oil and NOR hindered amine (at various levels) compared to a reference example containing only poly(oxyalkylene)-modified siloxane oil.

[0398] [Table 5]

[0399] Examples 5-8 demonstrate the improved antifouling performance of coatings containing poly(oxyalkylene)-modified siloxane oil and NOR hindered amine (at various levels) compared to a reference example containing only poly(oxyalkylene)-modified siloxane oil.

[0400] [Table 6]

[0401] Examples 9-12 demonstrate the improved antifouling performance of coatings containing poly(oxyalkylene)-modified siloxane oil and N-CH3 hindered amines (at various levels) compared to a reference example containing only poly(oxyalkylene)-modified siloxane oil.

[0402] [Table 7]

[0403] Examples 13-15 show other examples of the improved effect of antifouling performance of coatings containing poly(oxyalkylene)-modified siloxane oil and NOR hindered amine or silane-modified N-CH3 hindered amine in a poly(oxyalkylene) binder system different from Examples 1-12, compared to the reference example containing only poly(oxyalkylene)-modified siloxane oil.

[0404] [Table 8]

[0405] Examples 16 and 17 show the improved antifouling performance of coatings containing poly(oxyalkylene)-modified lanolin oil or poly(oxyalkylene)-modified siloxane oil and NOR hindered amine, and the equally good effectiveness of these two oils.

[0406] [Table 9]

[0407] Examples 18 and 19 demonstrate the improved antifouling effect of coatings containing poly(oxyalkylene) modified siloxane oil and / or silane modified poly(oxyalkylene) and NOR hindered amine.

[0408] [Table 10]

[0409] Examples 20-22 demonstrate the improved effectiveness of antifouling performance of coatings containing poly(oxyalkylene) modified siloxane oils and NH or N-CH3 hindered amines. The preferred embodiments of the present invention are as follows. [1] 1. A method for establishing a fouling release coating system on a surface of a substrate, comprising the following successive steps: a. optionally applying one or more layers of a primer composition onto the surface of said substrate and curing said layers, thereby forming a primed substrate; b. applying one or more layers of a liquid silicone-containing tie coat composition onto the primed substrate or surface of the substrate and curing the layer, thereby forming a cured tie coat layer; c. applying one or more layers of a fouling release coating composition onto the cured tie coat layer and curing the fouling release coating composition, wherein the fouling release coating composition is a coating composition At least 40g dry weight %of composition wherein greater than 65 wt.% of the binder matrix is represented by polysiloxane moieties; the tie coat composition and / or the fouling release coating composition comprises a component having a poly(oxyalkylene) chain; and the tie coat composition and / or the fouling release coating composition further comprises one or more sterically hindered amines, particularly 2,2,6,6-tetraalkylpiperidine derivatives. [2] The method of [1], wherein the sterically hindered amine is a hindered amine moiety of general formula I: [ka] During the ceremony, Each R1 is independently a straight or branched chain C 1 ~C 4 is alkyl; R2 is -H, optionally substituted straight or branched chain C 1~30 Alkyl, optionally substituted straight or branched chain C 2~30 Alkenyl, optionally substituted aryl, -OH, optionally substituted straight or branched chain C 1~30 Alkoxy, optionally substituted straight or branched chain C 1~30 Alkenyloxy, optionally substituted aryloxy, optionally substituted straight or branched chain C 1~30 Alkylcarbonyl, optionally substituted straight or branched chain C 1~30 -alkenylcarbonyl, and optionally substituted arylcarbonyl. R3 is between -C(R1) 2 -N(R2)-C(R1) 2 is an optionally substituted divalent group which together with the - group forms an N-heterocyclic 5-, 6- or 7-membered ring. [3] The fouling release coating according to [2], wherein the hindered amine moiety is selected from 2,2,6,6-tetraalkylpiperidine moieties of general formula II:

change

[10] 10. The method of any one of the preceding claims, wherein the tie coat composition comprises 3 to 90%, preferably 10 to 80%, more preferably 20 to 60%, even more preferably 3 to 15%, more preferably greater than 40%, of the one or more crosslinkable polysiloxanes, by wet weight of the total tie coat composition.

[11] 5. The method of any one of the preceding claims, wherein the tie coat composition further comprises one or more hydrolyzable silanes having two or more hydrolyzable groups.

[12] 11. The method of claim 10, wherein the tie coat composition comprises up to 30% by wet weight of the total tie coat composition of the one or more hydrolyzable silanes having two or more hydrolyzable groups.

[13] 10. The method of any one of the preceding claims, wherein the tie coat composition comprises one or more epoxy-functional polymers.

[14] Item 11. The method of any one of the preceding items, wherein the primer composition is an epoxy-based primer composition.

[15] 5. The method of any one of the preceding claims, wherein the sterically hindered amine, particularly a 2,2,6,6-tetraalkylpiperidine derivative, is present in a total amount of 0.05 to 10% by dry weight of the top coat composition.

[16] 10. A method according to any one of the preceding claims, wherein the sterically hindered amine, in particular a 2,2,6,6-tetraalkylpiperidine derivative, is immobilised, for example by covalent bonding, to a condensation-curable polysiloxane-based binder matrix or filler, for example silica.

[17] Item 11. The method of any one of the preceding items, wherein the poly(oxyalkylene) chains have a number average molecular weight (Mn) in the range of 200 to 50,000 g / mol.

[18] Item 11. The method of any one of the preceding items, wherein the component having a poly(oxyalkylene) chain is selected from poly(oxyalkylene)-modified polysiloxane oils.

[19] Item 11. The method of any one of the preceding items, wherein the poly(oxyalkylene) chains are covalently bonded to the polysiloxane-based binder matrix.

[20] 5. The method of any one of the preceding claims, wherein the tie coat comprises one or more poly(oxyalkylene)-modified polysiloxane oils.

[21] 5. The method of any one of the preceding claims, wherein the tie coat comprises one or more sterically hindered amines as defined in any one of [1] to [5].

[22] A fouling release coating system obtainable by the method according to any one of the preceding claims.

[23] a. Base material, b. Optionally, one or more primer layers; c. at least one silicone-containing tie coat layer; d. A fouling release layer comprising a condensation-cured polysiloxane-based binder matrix constituting at least 40% by dry weight of its coating, wherein greater than 65% by weight of the binder matrix is represented by polysiloxane moieties and the coating comprises a component having a poly(oxyalkylene) chain; 1. A fouling release coating system comprising: The fouling release coating system, wherein the tie coat layer and / or the fouling release layer further comprises one or more sterically hindered amines, particularly 2,2,6,6-tetraalkylpiperidine derivatives.

[24]

[23] The coating system according to

[23] , wherein the tie coat layer comprises one or more poly(oxyalkylene)-modified polysiloxane oils.

[25] The coating system according to any one of

[23] and

[24] , wherein the tie coat layer comprises one or more sterically hindered amines as defined in any one of [1] to [5].

[26] 25. The coating system of claim 24, wherein the hindered amine moieties, particularly 2,2,6,6-tetraalkylpiperidine moieties, are present in the tie coat layer in an amount of 0.003 to 0.5 mol / kg of layer.

Claims

1. 1. A method for establishing a fouling release coating system on a surface of a substrate, comprising the following successive steps: a. optionally applying one or more layers of a primer composition onto the surface of the substrate and curing the layers, thereby forming a primed substrate; b. applying one or more layers of a liquid silicone-containing tie coat composition onto the primed substrate or surface of the substrate and curing the layers, thereby forming a cured tie coat layer; c) applying one or more layers of a fouling release coating composition over the cured tie coat layer and curing the fouling release coating composition, wherein the fouling release coating composition comprises a condensation-curable polysiloxane-based binder matrix comprising at least 40% by dry weight of the coating composition, greater than 65% by weight of the binder matrix being represented by polysiloxane moieties, the tie coat composition and / or the fouling release coating composition comprises a component having a poly(oxyalkylene) chain, and the tie coat composition and / or the fouling release coating composition further comprises one or more sterically hindered amines; The sterically hindered amine has the general formula I: 【Chemical 1】 [In the formula, Each R1 is independently a straight or branched chain C １ ~C ４ is alkyl; R2 is —H, optionally substituted straight or branched chain C １～３０ Alkyl, optionally substituted straight or branched chain C ２～３０ Alkenyl, optionally substituted aryl, —OH, optionally substituted straight or branched chain C １～３０ Alkoxy, optionally substituted straight or branched chain C １～３０ Alkenyloxy, optionally substituted aryloxy, optionally substituted straight or branched chain C １～３０ Alkylcarbonyl, optionally substituted straight or branched chain C １～３０ - selected from alkenylcarbonyl, and optionally substituted arylcarbonyl; R3 is between -C(R1) ２ -N(R2)-C(R1) ２ - is an optionally substituted divalent group which together with the - group forms an N-heterocyclic 5-, 6-, or 7-membered ring, and each R3 may be independently linked to one or more additional sterically hindered amine moieties having the general formula I. is a sterically hindered amine moiety represented by The method wherein the sterically hindered amine is present in an amount of at least 0.05 dry weight percent based on the tie coat composition and / or the fouling release coating composition.

2. The sterically hindered amine moiety has the general formula II: 【Chemistry 2】 wherein R1 and R2 are as defined for general formula I; R4 represents a hydrogen atom or C １～３０ Alkyl, C １～３０ Alkenyl, aryl, C １～３０ Alkoxy, C １～３０ Alkenyloxy, aryloxy, C １～３０ Alkylcarbonyl, C １～３０ -Alkenylcarbonyl, arylcarbonyl, C １～３０ Alkylcarbonyloxy, C １～３０ -Alkenylcarbonyloxy and arylcarbonyloxy, especially C １～８ -alkoxy, C １～８ -Alkenyloxy, aryloxy, C １～８ -Alkylcarbonyloxy, C １～８ - one or two substituents selected from alkenylcarbonyloxy, and arylcarbonyloxy, and / or a point of attachment to a polymer, wherein two of said substituents for R4 may form a spiro structure, and R4 may each independently be linked to one or more additional sterically hindered amine moieties having general formula II. The method of claim 1, wherein the 2,2,6,6-tetraalkylpiperidine moiety is selected from the group consisting of:

3. 3. The method of claim 2, wherein R2 is not H and / or R2 is not —OH.

4. The sterically hindered amine comprises a 2,2,6,6-tetraalkylpiperidine moiety of general formula II, and the piperidine derivative is N—C １～３０ -Alkylpiperidine derivatives, N-C １～３０ -Alkenylpiperidine derivatives, N-arylpiperidine derivatives, N-C １～３０ -alkoxypiperidine derivatives, N—C １～３０ -Alkenyloxypiperidine derivatives, N-aryloxypiperidine derivatives, N—C １～３０ -Alkylcarbonylpiperidine derivatives, N-C １～３０ 4. The method according to claim 2, wherein the arylcarbonylpiperidine derivative is selected from the group consisting of N-alkenylcarbonylpiperidine derivatives and N-arylcarbonylpiperidine derivatives.

5. A method according to any one of claims 1 to 4, wherein the sterically hindered amine moieties are present in the coating in an amount of 0.003 to 0.5 mol / kg per coating layer.

6. The method of any one of claims 2 to 5, wherein the sterically hindered amine is in liquid form at 20°C.

7. The method according to any one of claims 1 to 6, wherein the component having a poly(oxyalkylene) chain is selected from poly(oxyalkylene)-modified alcohols represented by general formula (I): 【Chemistry 3】 [In the formula, each POA represents a poly(oxyalkylene) moiety; Each FA is ８～３０ represents a fatty acyl moiety, R is the alcohol R(OH) Ｘ＋Ｙ wherein the organic residue has 2 to 50 carbon atoms; and X is 1 to 5, Y is 0 to 10, and X+Y is 1 to 12.

8. 8. The method of any one of claims 1 to 7, wherein the tie coat composition comprises one or more crosslinkable polysiloxanes, preferably selected from hydroxy-functional polysiloxanes, C1-C4 alkoxy-functional polysiloxanes, amino-functional polysiloxanes, and epoxy-functional polysiloxanes.

9. 9. The method of any one of claims 1 to 8, wherein the tie coat composition comprises 3 to 90%, preferably 10 to 80%, more preferably 20 to 60%, even more preferably 3 to 15%, more preferably greater than 40%, of the one or more crosslinkable polysiloxanes by wet weight of the total tie coat composition.

10. The method of any one of claims 1 to 9, wherein the tie coat composition further comprises one or more hydrolyzable silanes having two or more hydrolyzable groups.

11. 11. The method of claim 10, wherein the tie coat composition comprises up to 30% by wet weight of the total tie coat composition of the one or more hydrolyzable silanes having two or more hydrolyzable groups.

12. The method of any one of claims 1 to 11, wherein the tie coat composition comprises one or more epoxy-functional polymers.

13. The method according to any one of claims 1 to 12, wherein the primer composition is an epoxy-based primer composition.

14. The method of any one of claims 1 to 13, wherein the sterically hindered amines are present in a total amount of 0.05 to 10% by dry weight based on the fouling release coating composition.

15. A method according to any one of claims 1 to 14, wherein the sterically hindered amine is immobilised, for example by covalent bonding, to a condensation-curable polysiloxane-based binder matrix or filler, for example silica.

16. 16. The method of any one of claims 1 to 15, wherein the poly(oxyalkylene) chains have a number average molecular weight (Mn) in the range of 200 to 50,000 g / mol.

17. The method according to any one of claims 1 to 16, wherein the component having a poly(oxyalkylene) chain is selected from poly(oxyalkylene)-modified polysiloxane oils.

18. The method of any one of claims 1 to 17, wherein the poly(oxyalkylene) chains are covalently bonded to the polysiloxane-based binder matrix.

19. The method of any one of claims 1 to 18, wherein the tie coat comprises one or more poly(oxyalkylene)-modified polysiloxane oils.

20. 20. The method of any one of claims 1 to 19, wherein the tie coat comprises one or more sterically hindered amines as defined in any one of claims 1 to 4.

21. 21. The method of any one of claims 1 to 20, wherein the component having a poly(oxyalkylene) chain is present in an amount of 0.5 to 10% based on the dry weight of the tie coat composition and / or the fouling-release coating composition.

22. a. base material, b. Optionally, one or more primer layers; c. at least one silicone-containing tie coat layer; d. A fouling release layer comprising a condensation-cured polysiloxane-based binder matrix constituting at least 40% by dry weight of the coating, wherein greater than 65% by weight of the binder matrix is ​​represented by polysiloxane moieties; 1. A fouling release coating system comprising: the fouling release layer comprises a component having a poly(oxyalkylene) chain, 1. A fouling release coating system, wherein the tie coat layer and / or the fouling release layer further comprises one or more sterically hindered amines, The sterically hindered amine has the general formula I: 【Chemistry 4】 [In the formula, Each R1 is independently a straight or branched chain C １ ~C ４ is alkyl; R2 is —H, optionally substituted straight or branched chain C １～３０ Alkyl, optionally substituted straight or branched chain C ２～３０ Alkenyl, optionally substituted aryl, —OH, optionally substituted straight or branched chain C １～３０ Alkoxy, optionally substituted straight or branched chain C １～３０ Alkenyloxy, optionally substituted aryloxy, optionally substituted straight or branched chain C １～３０ Alkylcarbonyl, optionally substituted straight or branched chain C １～３０ - selected from alkenylcarbonyl, and optionally substituted arylcarbonyl; R3 is between -C(R1) ２ -N(R2)-C(R1) ２ - is an optionally substituted divalent group which together with the - group forms an N-heterocyclic 5-, 6-, or 7-membered ring, and each R3 may be independently linked to one or more additional sterically hindered amine moieties having the general formula I. is a sterically hindered amine moiety represented by A fouling release coating system wherein the sterically hindered amine is present in an amount of at least 0.05 dry weight percent based on the tie coat composition and / or the fouling release coating composition.

23. 23. The coating system of claim 22, wherein the tie coat layer comprises one or more poly(oxyalkylene)-modified polysiloxane oils.

24. 24. The coating system of claim 22 or 23, wherein the tie coat layer comprises one or more sterically hindered amines as defined in any one of claims 1 to 4.

25. 25. The coating system of claim 24, wherein the sterically hindered amine moieties are present in the tie coat layer in an amount of 0.003 to 0.5 mol / kg of layer.

26. 25. The coating system of claim 24, wherein the sterically hindered amine is present in a total amount of 0.05 to 10% based on the dry weight of the topcoat composition.

27. 23. The coating system of claim 22, wherein the component having a poly(oxyalkylene) chain is present in an amount of 0.5 to 10% based on the dry weight of the tie coat composition and / or the fouling-release coating composition.

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