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    • 专利摘要:
    COMPOSITIONS OF INCLUDING CONTROL COATING. The present invention relates to an inlay control coating composition comprising a binder system based on polysiloxane, 0.01-20% dry weight of one or more hydrophilic modified polysiloxanes, and one or more biocides. The hydrophilic modified polysiloxane can be a polysiloxane modified by poly (oxyalkyl), for example a polysiloxane having grafted poly (oxyalkylene) chains and / or having incorporated into the main chain of the same poly (oxyalkylene) chains. Poly (oxyalkylene) can for example be selected from polyoxyethylene, polyoxypropylene and poly (oxyethylene-co-oxy-propylene) (polyethylene glycols / polypropylene glycols). The application describes a marine structure comprising at least part of the outer surface thereof an external coating prepared from the coating composition. In addition, the application describes the use of the combination of non-reactive hydrophilic modified polysiloxanes and biocides, where the weight ratio between hydrophilic modified polysiloxanes and biocides is in the range 1: 0.2 to 1: 6, to improve properties anti-fouling of a polysiloxane based coating composition.
    公开号:BR112012015153A2
    申请号:R112012015153-3
    申请日:2010-12-22
    公开日:2020-09-15
    发明作者:Peter Christian Weinrich Thorlaksen；Anders Blom；Ulrik Bork
    申请人:Hempel A/S；
    IPC主号:
    专利说明:

    Invention Patent Descriptive Report for "COMPOSITION OF INCRUSTATION CONTROL COATING, MARINE STRUCTURE AND USE OF COMBINATION OF NON-REACTIVE HYDROPHYLIC HYDROPHYLIC AND BIOCIDED COMBINATIONS TO IMPROVE THE ANTI-INCREDIBLE PROPERTIES"
    FIELD OF THE INVENTION The present invention relates to new fouling control coating compositions.
    BACKGROUND OF THE INVENTION Traditionally, silicone formulations rely on physical media, this being primarily a factor of modulus of elasticity and surface tension to create a low-scale surface. Traditional polydimethylsiloxane coatings (PDMS) have shown difficulty in resisting sludge scale over time, thereby reducing the drag reduction advantage.
    Consequently, there is a need for polysiloxane based coating compositions for fouling control combining the benefits of conventional polysiloxane based fouling release compositions with the benefits of antifouling coating compositions with biocidal base.
    WO 2007/053163 describes an anti-fouling material which may include one or more of several suitable copolymers (e.g., block copolymers, graft copolymers, etc.) that provide biocidal and / or fouling release characteristics. Copolymers can include a polysiloxane backbone with one or more polymers grafted onto the polysiloxane backbone. Such grafted polymers can carry biocidal groups.
    WO 2008/132195 describes an anti-fouling coating composition comprising a curable polymer (for example, a polymer containing organosiloxane) and an organosilicone polymer.
    WO 2008/132196 describes a method for physically detaining
    1a / 33 marine inlay whose method involves forming on the substrate a coating composition comprising curable polyorganosiloxane, polyoxyalkylene block copolymer, organosilicon crosslinking agent and / or catalyst.
    The polyoxyalkylene is reacted to the silicone binder by addition reaction (vinyl / hybrid) to form a block copolymer of polyoxyalkylene and polysiloxane. The copolymer can subsequently be finished with vinyltrimethoxysilane to form a moisture-curable binder.
    US 2004/006190 describes a room temperature curable organopolysiloxane composition, which includes (A) an organo-polysiloxane with the terminals blocked with a hydroxyl group, a hydrolyzable group, or both of these types of groups, and (B ) an organo-silicon compound containing a hydrolyzable group, a condensation product by 1st partial hydrolysis thereof, or a mixture of the two, and (C) a polysiloxane with at least one oxyalkylene group attached to a silicon atom by means of - of, for example, a CC-Si connection. WO 2002/088043 describes a process for coating a siliceous substrate with a layer containing silicon, in which in a first step a layer comprising a biocide is applied. US 2002/0197490 A1 describes a composition based on curable anti-fouling polysiloxane comprising hydrophobic silica possibly in combination with hydrophilic silica. In some embodiments, the composition also comprises a silicone oil, for example, oils comprising polyethylene glycol or polypropylene glycol moieties. It is also considered that anti-fouling agents can be used, in particular copper and inorganic copper compounds. EP 2 103 655 A1 describes a composition based on curable anti-fouling polysiloxane comprising a reaction curable silicone rubber and a particularly designated organo-polysiloxane mixture. In some embodiments, the composition also comprises a silicone oil, for example, a polyether modified silicone oil. It is also considered that anti-fouling agents can be used, in particular copper and inorganic copper compounds. US 6,313,193 B1 a.i. describes a composition comprising a silanol-terminated polydimethyl siloxane, a dimethylethoxy-terminated polydimethyl siloxane, polydiethoxy siloxane, and benzalkonium chloride.
    The polydietoxy siloxane reacts with the polydimethyl siloxanes so that the polydietoxy siloxane becomes an integral part of the binder network.
    JP 2006 052283 A discovers a coating composition comprising a polyether modified silicone oil having polyoxyalkylene side chains, an acrylic type binder system based on a polysiloxane macropolymer and an antifouling.
    JP 2006 299132 A describes an anti-fouling coating composition that is based on a vinyl-polymer-binder system that includes polysiloxane side chains, and which is modified with certain reactive silanes, and which also comprises , for example, . a polysiloxane modified by poly (oxyalkylene). The composition can likewise include an anti-fouling agent.
    - Silicon based fouling release coatings have shown an advantage over conventional anti-fouling coatings showing significantly lower drag resistance, therefore - - often reduced fuel consumption from marine vessels. The difference is especially obvious as long as the silicone coating is * free of marine scale including sludge scale. Many conventional silicone coatings have so far only been able to maintain a sludge-free surface for a shorter period.
    Some traditional biocide containing anti-fouling coatings has demonstrated greater resistance to marine fouling compared to silicone-based fouling release coatings under, for example, static conditions. The surface characteristics of such a coating will, however, lead to increased drag resistance compared to silicone coatings even when the surface is free of scale.
    The logic behind the present invention was to extend the sludge-free period of a silicone-based coating by combining the biocidal components of the anti-fouling coatings with a silicone-based fouling release coating. This provides a coating with low drag resistance that will remain fouling free for a longer time than conventional silicone based fouling release coatings.
    SUMMARY OF THE INVENTION Due to the needs mentioned above, the present inventors have now developed fouling control coating compositions that comprise biocides and one or more modified hydrophilic polysiloxanes that facilitate and control the leaching of the biocides. In this way, the advantages of silicone fouling release are combined with those of traditional anti-fouling coatings, thereby gaining a low friction, fouling free surface with the use of - a relatively small amount of biocide. The present inventors have realized that the use of certain hydrophilic modified polysiloxanes, in particular polyoxyalkylene modified polysiloxanes), (see also below) makes it possible to obtain an average for biocidal water transport through a cross-linked polysiloxane film , in particular a film of a coating composition based on polysiloxane. The rate of leaching of the biocide can be controlled * among others by the amount and hydrophilicity / hydrophilic portions of the added polysiloxane (s).
    Thus, in a first aspect the present invention relates to a fouling control coating composition comprising a binder system based on polysiloxane, 0.01-20% dry weight of one or more polysiloxanes hydrophilic, and one or more biocides.
    A second aspect of the invention relates to a marine structure comprising at least a part of the outer surface of the same external coating prepared from a coating composition as defined herein.
    In currently preferred embodiments of the foregoing aspects, the weight ratio between one or more hydrophilic modified polysiloxanes and one or more biocides is in the range 1: 0.2 to 1: 6.
    A third aspect of the invention relates to the use of the combination of one or more non-reactive hydrophilic modified polysiloxanes and one or more biocides, wherein the weight ratio between the one or more hydrophilic modified polysiloxanes and one or more biocides is in the range 1: 0.2 to 1: 6, to improve the anti-fouling properties of a coating composition based on polysiloxane.
    DETAILED DESCRIPTION OF THE INVENTION The coating composition As mentioned above, the present invention provides a fouling control coating composition comprising a binder system based on 0.01-20% polysiloxane, for example, - 0.05-10 %, by dry weight, of one or more hydrophilic modified polysiloxanes, and one or more biocides. Hydrophilic modified polysiloxane Hydrophilic modified polysiloxanes are widely used as surfactants and emulsifiers due to the content of both hydrophilic and lipophilic groups in the same molecule. Means for obtaining the hydrophilic character include modification of the main polysiloxane chain by the addition of oligomeric or nonionic polymeric groups that can be polarized by charge and / or capable of hydrogen bonding, enhancing their interaction with polar solvents, in particular with water, or with other polar oligomeric or polymeric groups. Examples of these groups include, amides (for example, poly (vinyl pyrrolidone), polylN- (2-hydroxypropyl) methacrylamide], poly (N, N-dimethacrylamide)), acids (for example poly (acrylic) acid), alcohols (eg poly (glycerol!), poly-HEMA, polysaccharides), ketones (polyketones), aldehydes (eg poly (aldehyde) glulonate, amines (eg polyvinylamine), esters (eg polycaprolactones, poly acetate (vinyl), polyacrylates), ethers (for example polyoxyalkylenes such as polyethylene glycol, polypropylene glycol), imides (for example poly (2-methyl-2-oxazoline)), etc., including copolymers from the above. obtained by modification with polyoxyalkylene groups.
    It should be clear that it is understood that the hydrophilic oligomers / polymers with which the polysiloxane component (s) are modified are of non-silicone origin.
    Preferably, the "oligomers" and "polymers" mentioned above include at least 3 repeat units, as well as at least 5 repeat units.
    In many interesting embodiments, oligomers or polymers include 5-1,000 repeat units, such as 5-200, or 8- 150, or 10-100 repeat units.
    In some preferred embodiments, hydrophilic groups (i.e., oligomeric or polymeric groups) have an average numerical molecular weight (Mn) in the range of 100-50,000 g / mol, such as in the range of 200-30,000 - g / mol , in particular in the range of 300-20,000 g / mol, or in the range of 400-10,000 gi / mol. —— In the present description with claims, the term "modified hydrophilic" in the context of "modified hydrophilic polysiloxane" is intended to mean that the oligomeric or polymeric groups with which the polysiloxane - is modified, itself (ie as discrete molecules) have a solubility of at least 1% (w / w) in demineralized water at 25ºC.
    Ú Of particular interest are those hydrophilic modified polysiloxanes where the relative weight of the hydrophilic moieties is 1% or more of the total weight (for example, 1-90%), such as 5% or more (for example, 5-80%) , in particular 10% or more (e.g. 10-70%) of the total weight of the hydrophilic modified polysiloxane.
    The function of the hydrophilic modified polysiloxane is to facilitate the dissolution and transport of the biocide to the surface.
    Potentially, the hydrated layer formed in the coating-water interface in the same way will help in retaining the biocide on the surface, consequently allowing the coating to show its incrustation preventing activity during extended exposure intervals.
    The hydrophilic modified polysiloxane does not - contain groups that can react with the binder or crosslinker (if present), therefore the hydrophilic modified polysiloxane is intended to be non-reactive, in particular with respect to the binder components.
    Ways to control the leaching rate include the hydrophilic modified polysiloxane molecule size, hydrophilicity and miscibility with the binder. A very small molecule tends to allow a high rate of leaching of the biocide, a very large molecule may not allow the leaching of the biocide to be of the desired rate. It is further hypothesized that the ability of hydrophilic polysiloxanes to form a hydrated layer in the coating-water interface is also important for this invention. In this respect, the diffusion rates of hydrophilic polysiloxanes in the ink matrix, their relative division between —polysiloxane and water matrix, the hydrophilic / hydrophobic balance, their interaction with the chosen biocides (s), and the hydration capacity of hydrophilic substituents influence the final performance.
    Consequently, in a preferred embodiment, the hydrophilic modified polysiloxane has an average numerical molecular weight (Mr) in the range of 100-100,000 g / mol, as in the range of 250-75,000 g / mol, particularly in the 500-50,000 g / mol range.
    - It is also preferred if the modified hydrophilic polysiloxane has a viscosity in the range of 10-20,000 mPa-s, as in the range * of 20-10,000 mPa's, in particular in the range of 40-5,000 mPars.
    Likewise, high hydrophilicity, for example, due to a high concentration of hydrophilic groups such as polyethylene oxide in the molecule, could lead to an early depletion of the biocide (s) due to a high rate leaching. A combination of modified hydrophilic polysiloxanes with different molecular weights and / or hydrophilicity can be used to control leaching of the biocide.
    The hydrophilic modified polysiloxanes are devoid of any reactive silicone groups such as Si-OH groups, hydrolyzable groups such as Si-OR (alkoxy) groups, etc., to avoid reaction with components of the binder system based on polysiloxane. Otherwise, the modified hydrophilic polysiloxane can be completely integrated into the polysiloxane binder network, which is undesirable for purposes of obtaining the technical effect on which the present invention relies.
    In a currently preferred embodiment, the modified hydrophilic polysiloxane is a polysiloxane modified by poly (oxyalkylene). In a variant of this, polysiloxane modified by poly-lifoxyalkylene) is a polysiloxane having grafted to it poly-lifoxy alkylene chains). An illustrative example of the structure of such hydrophilic modified polysiloxanes is formula (A): Rº Rº R Rº Rdo s o do da ds | | * x y: Rº
    Í is), = fo]
    ES. the Y (A) ”in which each R 'is independently selected from C.5-alkyl (including straight or branched hydrocarbon groups) and aryl (for example, phenyl -CsHs), in particular methyl; each R is independently selected from -H, C, i, 4-alkyl (for example -CH3, -CH2CH3, -CH2CH2CH3, CH (CH3) ,, CH2CH2xCH2CH; 3), phenyl (CsHs), and C14-alkylcarbonyl (for example - C (= 0) CHz3, -C (= 0) CHxCH; 3 and C (= 0) CHxCH2CH; 3), in particular -H and methyl; each R is independently selected from C> .5-alkylene (for example -CH2CH72-, -CHCH (CH3) -, CHCH2CH27, CHICH2CH; CH> -, CH2CH (CH2CH3) -), arylene (for example 1,4-phenylene) and C2.5-alkylene substituted with aryl (for example, 1-phenyl ethylene), in particular C2.5-alkylene such as -CH2CH7- and -CHCH (CH3) -); x is 0-2000, y is 1-100 and x + y is 1-2000; and n is 0-50, m is 0-50 and m + n is 1-50. Commercially available hydrophilic modified polysiloxanes of this type are DC5103 (Dow Corning), DC Q2-5097 (Dow Corning), and DC193 (Dow Corning).
    In another variant of this, polysiloxane modified by polyoxyalkylene) is a polysiloxane having incorporated into the main chain of the same poly (oxyalkylene) chains. An illustrative example of the structure of such hydrophilic modified polysiloxanes is formula (B): R R Rº 2 3 ad L A) 3 2 | R o-Fr or ve HA Ro qo R x (B) - where each R 'is independently selected from C, .5-alkyl (including linear or branched hydrocarbon groups) and aryl (for example phenyl ( CgHs)), in particular methyl; each Rº is independently selected from -H, Ci, -alkyl * (for example -CH3, -CH2CH3, -CHCH2CH3, CH (CH3) ,, CHXCH2CH2C0Hs3), phenyl (CsHs), and Ci4-alkylcarbonyl (for example - C (= 0) CH3, -C (= O0) CH2CH; 3 and C (= O) CH2CH2CH3), in particular -H and methyl; each R is independently selected from C2.5-alkylene (for example -CH2CH72-, -CH2CH (CH3) -, -CH2CH2CH7-, -CHxCHCH2C0Ha-, -CH2CH (CH2CH3) -), arylene (for example 1,4-phenylene) and C72.5-alkylene substituted with aryl (for example 1-phenylethylene), in particular C7.5-someoneylene such as -CH2CH> 7- and -CHCH (CH3) -); x is 0-2500; and n is 0-50, m is 0-50 and m + n is 1-50. Commercially available hydrophilic modified polysiloxanes of this type are DC 2-8692 (Dow Corning, DC Q4-3669 (Dow Corning), and DC Q4-3667 (Dow Corning). In yet another variant of this, polysiloxane modified by polyoxyalkoxyalkylene ) is a polysiloxane having incorporated into the main chain of the same polyoxyalkylene chains and having polyoxyalkylene chains
    to this. An illustrative example of the structure of such hydrophilic modified polysiloxanes is formula (C):
    PIRATES 2 3 3 L L "1 3 3 2 bo Ae x e y
    W Rº | o [e] - Only | where each R 'is independently selected from C; .5-alkyl (including straight or branched hydrocarbon groups) and aryl (for example, phenyl (CgHs)), in particular methyl; . each Rº is independently selected from -H, C;, - alkyl (for example -CH3, -CH2CH3, -CHCH2CH3, -CH (CH3) s, -CHCH2CH2C Ha), - - phenyl (CsHs), and Ci4-alkylcarbonyl ( for example, -C (= 0) CHz3, -C (= 0) CH2CH3 eCc (= 0) CH.CHxCH3), in particular -H and methyl; each Rº is independently selected from C> .5-alkylene (for example, -CH2CH2-, -CH2CH (CH3) -, -CH2CH2CH72-, -CH2CH2CH2C0Ha-, -CH2CH (CH2CH3) -), arylene (for example, 1, 4-phenylene) and C2.5-alkylene substituted with aryl (for example, 1-phenyl ethylene), in particular C> .5-alkylene such as -CH2CH72- and -CHCH (CH3) -); x is 0-2000, y is 1-100 and x + y is 1-2000; k is 0-50, | is 0-50 and k + Hl is 1-50, n is 0-50, m is 0-50 and m + n is 1-50. In the previous structures (A), (B) and (C), the groups -CHxCH (CH3) -, CH; CH (CH; CH; 3) -, etc. they can be present in any of the two possible orientations. Similarly, it should be understood that the present x and y segments are sometimes typically randomly
    polysiloxane structure.
    In these modalities and variants, poly (oxyalkylene) is preferably selected from polyoxyethylene, polyoxypropylene and poly (oxy-ethylene-co-oxypropylene), which are sometimes referred to as polyethylene glycol, polypropylene glycol and poly (ethylene glycol- co-propylene glycol). Consequently, in the structures above (A), (B) and (C), each Rº bonds two oxygen atoms is preferably selected from -CH2CH72- and -CHCH (CH3) -, since each Rº it binds a silicon atom and an oxygen atom is preferably selected from C> .5-alkyl. In some modalities of the previous structures (A), (B) and i (C), R it is preferably not hydrogen. Other examples of hydrophilic modified polysiloxanes are polysiloxanes modified with carbinol groups or N-pyrrolidone carboxylate or polyglycerin copolymers. It should be understood that one or more hydrophilic modified polysiloxanes can be different types, for example, two or more of the types described above. Commercially available examples of modified hydrophilic polysiloxanes are CMS-222 and YBD-125, also ex. Gelest, USA, and KF-6100 and KF-6104, also ex. Shin-Etsu, Japan. ] In some interesting embodiments, the modified hydrophilic polysiloxane is a hydrophilic polysiloxane.
    The term "hydrophilic polysiloxane" is intended to mean that the polysiloxane has been designed to be relatively more hydrophilic than a straight chain methyl terminated polysiloxane (i.e., polydimethylsiloxane; PDMS) having the same number of silicone atoms. The relative hydrophilicity is preferably determined according to the Hydrophilicity Test described in the Experimental section.
    The one or more modified hydrophilic polysiloxanes in the coating composition in an amount of 0.01-20%, for example, 0.05-10%, in dry weight. In certain embodiments, the one or more hydrophilic modified polysiloxanes constitutes 0.05-7% dry weight, for example, 0.1-5% dry weight, in particular 0.5-3% dry weight, of the composition of coating. In certain other embodiments, the one or more hydrophilic modified polysiloxanes constitutes 1-10% by dry weight, for example, 2-9% by dry weight, in particular 2-7% by dry weight, or 3-7% by dry weight , or 3-5% by dry weight, or 4-8% by dry weight, of the coating composition.
    Biocides The coating composition likewise includes a biocide.
    In the present context, the term "biocide" is intended to mean an active substance intended to destroy, deter, render harmless, prevent the action of, or otherwise exert a control effect on any harmful organism by chemical or biological means. . Illustrative examples of biocides are those selected from metallo-dithiocarbamates such as bis (dimethyldithiocarbamate) zinc, ethylene-2 bis (dithiocarbamate) zinc, ethylene-bis (dithiocarbamate) manganese, and complexes among them; bis (1-hydroxy-2 (1H) -pyridinethionate-O, S) -copper; copper acrylate; bis (1-hydroxy-2 (1H) -pyridinethionate-O, S) -zinc; phenyl dihydrochloride (bispyridyl) - + - bismuth; metal biocides such as copper (1) oxide, cuprous oxide, metallic copper, copper metal alloys such as copper-nickel alloys; salts of "- —metals such as cuprous thiocyanate, basic copper carbonate, copper hydroxide, barium metaborate, and copper sulfide; heterocyclic nitrogen compounds such as 3a, 4,7,7a-tetrahydro-2 - (( trichloromethyl) -thio) -1H-isoindole-1,3 (2H) -dione, pyridine-triphenylborane, 1- (2,4,6-trichlorophenyl) -1H-pyrrole-2,5-dione, 2,3,5 , 6-tetrachlor-4- (methylsulfonyl) -pyridine, 2-methylthio-4-tert-butylamino-6-cyclopropylamine-s-triazine, and quinoline derivatives; heterocyclic sulfur compounds such as 2- (4 -thiazolyl) benzimidazole, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-octyl-3 (2H) -isothiazoline (Sea-Nineº -21 1N), 1,2-benzisothiazolin-3-one, and 2- (thiocyanatomethylthio) -benzothiazole; urea derivatives such as N- (1,3-bis (hydroxymethyl) -2,5-dioxo-4-imidazolidinyl ) -N, N'-bis (hydroxymethyl) urea, and N- (3,4-dichlorophenyl) -N N-dimethylurea, N, N-dimethylchlorophenylurea; ouimides of carboxylic acids; sulfonic acids and sulfenic acids such as 2,4,6-triclo rofenyl maleimide, 1,1-dichloro-N - ((dimethylamino) sulfonyl) -1-fluoro-N- (4-methylphenyl) -netanesulfenamide, 2,2-dibromo-3-nitrile-propio-
    namide, N- (fluorodichloromethylthio) -phthalimide, N, N-dimethyl-N'-phenyl-N '- (fluorodichloromethylthio) -sulfamide, and N-methylol formamide; salts or esters of carboxylic acids such as 2 - ((3-iodo-2-propynyl) oxy) -ethanol phenylcarbamate and N, N-didecyl-N-methyl-poly (oxyethyl) ammonium propionate; amines such as dehydro-biethylamines and cocodimethylamine; substituted methane such as di (2-hydroxyethoxy) methane, 5,5'-dichloro-2,2'-dihydroxydiphenylmethane, and methylene-bysiocyanate; substituted benzene such as 2,4,5,6-tetrachloro-1,3-benzenodicarbonitrile, 1,1-dichloro-N - ((dimethylamino) -sulfonyl) -1-fluoro-N-phenylmethanesulfenamide, and 1 - ((di - iodomethyl) sulfonyl) -4-methyl-benzene; tetraalkyl phosphonium halides such as tri-n-butyltetradecyl phosphonium chloride; guanidine derivatives such as n-dodecylguanidine hydrochloride; disulfides such as bis- (dimethylthiocarba- - moil) -disulfide, tetramethylthiuram disulfide; imidazole-containing compound, such as medetomidine; 2- (p-chlorophenyl) -3-cyano-4-bromo-5S-trifluoromethyl pyrrole and mixtures thereof.
    Currently, it is preferred that the biocide does not comprise tin. Currently preferred biocides are those selected from - - from the group consisting of 2,4,5,6-tetrachloroisophthalonitrile (chlorothhalonyl), copper thiocyanate (cuprous sulfocyanate), N-dichloro-fluoromethylthio-N ', N'-dimethyl -N- - phenylsulfamide (Diclofluanide), 3- (3,4-dichlorophenyl) -1,1-dimethylurea (Diuron), 4- - bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole -3-carbonitrile, (2- (p-chlorophenyl) - 3-cyano-4-bromo-5-trifluoromethyl pyrrole; Tralopyril), Nº-ferc-butyl-N-cyclopropyl-6-methylthio-1,3,5- triazine-2,4-diamine (Cybutrin), (RS) -4- [1- (2,3-dimethylphenyl) etill-3H-imidazole (Medetomidine), 4,5-dichloro-2-n-octyl-4- isothiazolin-3-one (DCOIT, Mar-Nineº 211N), dichlor-N - ((dimethylamino) sulfonyl) fluorine-N- (p-tolyl) metansulphenamide (Tolitfluanide), 2- (thiocyanomethylthio) -1 thiocyanate, 3-benzothiazole ((2-benzothiazolylthio) methyl; TCMTB), triphenylborane pyridine (TPBP); bis (1-hydroxy- 2 (1H) -pyridinationate-O, S) - (T-4) zinc (zinc pyridination; Zinc pyrithione), bis (1-hydroxy-2 (1H) -pyridinationate-O, S) - T-4) copper (copper pyridinationa; Copper Pyrithione), zinc ethylene-1,2-bis-dithiocarbamate (zinc-ethylene-N-N'-dithiocarbamate; Zineb) and diiodomethyl-p-tolylsulfone; Amical 48. Preferably, at least one biocide is selected from the list above. In a particularly preferred embodiment, biocides are preferably selected from biocides that are effective in soft encrustation such as sludge and algae.
    Examples of such biocides are 3- (3,4-dichlorophenyl) -1,1-dimethylurea (Diuron), Nº-tert-butyl-Nº-cyclopropyl-S-methylthio-1,3,5-tri- azine- 2,4-diamine (Cybutrin), 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT, —Mar-Nineº 211N), bis (1-hydroxy-2 (1H) -pyridinationate -O, S) - (T-4) zinc (zinc pyridine; Zinc Pyrithione), bis (1-hydroxy-2 (1H) -pyridinationate-O, S) -T-4) copper (copper pyridination) ; Copper Pyrithione) and zinc ethylene-1,2-bis-dithiocarbamate (zinc-ethylene-N-N'-dithiocarbamate; Zineb). In another particularly preferred embodiment, the biocide is an organic biocide, such as a pyrithione complex, such as zinc pyrithione.
    Organic biocides are those that are completely or partly of - organic origin.
    As detailed in US 7,377,968, in those examples where the biocide is quickly emptied from the film due to, for example, a high water solubility or a high level of immiscibility with the matrix composition, it may be advantageous to add one or more of the biocide (s) in form - —encapsulated as a means of controlling biocide dosage and extending effective film life.
    Encapsulated biocides can be added * if the free biocide alters the properties of the polysiloxane matrix in a way that is detrimental to its use as anti-fouling coatings (eg, mechanical integrity, drying times, etc.). In a particularly preferred embodiment, the biocide is encapsulated 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT, Mar-Nineº CR ). In another particularly preferred embodiment, the biocide is selected from zinc pyrithione, copper pyrithione, and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT, Mar-Nineº 211N ). The biocide has a solubility preferably in the range of 0-20 mg / L, such as 0.00001-20 mg / L, in water at 25 ° C.
    The biocide typically constitutes 0.1-10% dry weight, for example, 0.5-8% dry weight, in particular 1-8% dry weight, of the coating composition.
    The relative weight ratio between one or more polysiloxanes
    hydrophilic and one or more biocides is typically in the range of 1: 0.05 to 1: 1000, for example 1: 0.1 to 1: 120, such as 1: 0.1 to 1:10, or 1: 0, 15 to 1: 8, in particular 1: 0.2 to 1: 6, or 1: 0.2 to 1: 5, or 1: 0.25 to 1: 4, especially 1: 0.3 to 1: 3. Polysiloxane-based binder system The fouling control coating composition of the invention included here a polysiloxane-based binder system.
    The binder system forms a cross-linked matrix that includes the biocide (s) and the modified hydrophilic polysiloxane as well as other components such as solvents, additives, pigments, fillers, etc.
    The polysiloxane-based binder is an organopolysil-. functional xane, with terminal and / or pendant functionality.
    Terminal functionality is preferred.
    The functionality can be hydrolyzable groups, such as for example, alkoxy groups, ketoxime groups or silanol groups.
    A minimum of two reactive groups per molecule is preferred.
    If the molecule contains only two reactive groups, for example, silanol groups, it may be necessary to use an additional reagent, a crosslinker, to obtain the desired crosslinking density.
    The crosslinker can for example be a silicate alkoxide such as methyltrimethoxysilane, however a wide range of useful silanes is available as will be described later.
    Silane can be used as is or as condensation products for hydrolyzing them.
    Although condensation cure is very preferred, the functionality of organopolysiloxane is not limited to a condensation cure.
    In this way, other types of curing can be used, for example, amine / epoxy alone or in combination with a condensation reaction.
    In such cases, the organo-polysiloxane can have terminal groups of epoxy or amine and pending hydrolyzable groups, for example, with alkoxy functionality.
    In some embodiments, the fouling coating composition including the polysiloxane-based binder system may be a reaction-curable composition or a moisture-curable composition as will be apparent to the person skilled in the art.
    Examples of this are a two-component condensation cure composition based on a hydroxyl-retaining polydiorganosiloxane and a silane with hydrolyzable groups, or a moisture-curable composition of a component based on an alkoxy or poly-diorganosiloxane. other hydrolyzable activity.
    In one embodiment, the binder phase comprises (i) a binder and (ii) crosslinking agent of which the binder (i) should include hydrolyzable groups or other reactive groups to participate in the formation of the matrix.
    The binder (i) typically constitutes 20-90% dry weight of the coating composition, and is, for example, a curable di-organopolysiloxane represented by a general formula (1) shown below: A THE A A "phone oba 0) ER E) E ab 'where each A' is independently selected from a hydroxy group, a hydrolyzable group and another functional group, such as amine or epoxy; each A 'is independently selected from alkyl , aryl, alkenyl and a hydrolyzable group; each A and Aº is independently selected from alkyl and aryl alkenyl; a = 1-25,000, b = 1-2,500 and a + b is at least 30; Binders can be used alone or in combination In a preferred embodiment, only one generic type of binder is used.
    The cross-linking agent (ii) preferably constitutes 0-10% dry weight of the coating composition and is, for example, an organosilicon compound represented by the general formula (2) shown below, a condensation product by partial hydrolysis thereof, or a mixture of the two:
    Ra-Si — Xs4a (2) where, each R independently represents a substituted or unsubstituted monovalent hydrocarbon group of 1 to 6 carbon atoms, each X independently represents a hydrolyzable group, and a represents a number integer from 0 to 2, such as from 0 to
    1.
    The compound outlined in formula (2) acts as a crosslinker for the binder (i). The composition can be formulated as a curable RTV component (vulcanizable at room temperature) by mixing the binder (i) and the crosslinking agent (ii). If the reactivity in the Si terminal group of the binder (i) consists of easily hydrolyzable groups, such as dimethoxy or trimethoxy, a separate crosslinker is not normally necessary to cure the film.
    Preferred crosslinkers are those selected from tetraethoxysilane; vinyltris (methyl ethyloxime) silane; methyltris (methyl ethyloxime) silane; vinyltrimethoxysilane; methyltrimethoxysilane and vinyltrisopropenoxysilane; as well as condensation products by hydrolysis thereof.
    In some interesting embodiments, the polysiloxane-based binder comprises a polydimethylsiloxane-based binder.
    The polysiloxane-based binder system typically constitutes at least 40% dry weight, in particular 50-90% dry weight, of the coating composition.
    Catalyst The coating composition can also comprise a condensation catalyst to accelerate crosslinking. Examples of suitable catalysts include organometal - and metal salts of organic carboxy acids, such as dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin dioctoate, dibutyl tin 2-ethyloxide, dioctyl tin diylate , tin dioctyl diacetate, dioctyl dioctoate is
    tin, dioctyl tin 2-ethyloxate, dioctyltin di neodecanoate, tin naphthenate, tin butyrate, tin oleate, tin caprilate, iron 2-ethyloxate, lead 2-ethyloctoate, cobalt-2- ethyloxate, manganese 2-ethyloxate, zinc 2-ethyloxate, zinc naphthenate, zinc stearate, cobalt naphthenate and titanium naphthenate; titanate and zirconate esters such as tetrabutyl titanate, tetracis (2-ethylexyl) titanate, triethanolamine titanate, tetra (isopropenyloxy) titanate, titanium tetrabutanolate, titanium tepropanotate; titanium tetraisopropanolate, zirconium tetrapropanolate, zirconium tetrabutanolate; chelated titanates such as bis (diisopropyl acetylacetonylititanate).
    Other condensation catalysts are described in WO 2008/132196 and US 2004/006190. . The catalyst can be used alone or as a combination of two or more catalysts.
    The amount of catalyst to be used is dependent on the reactivity of the catalyst and the desired crosslinker (s) and drying time.
    In a preferred embodiment, the catalyst concentration is between 0.01-10% by weight of the total combined amount of the binder (n) (i) and crosslinking agent (ii). Solvents, additives, pigments and fillers The coating composition can also comprise solvents and additives.
    Examples of solvents are aliphatic, cycloaliphatic and aromatic hydrocarbons such as white alcohol, cyclohexane, toluene, xylene and solvent naphtha, esters such as methoxypropyl acetate, n-butyl acetate and 2-ethoxy ethyl acetate; octamethyltrisiloxane, and mixtures thereof.
    Solvents, if any, typically make up 5-50% by volume of the coating composition.
    Examples of additives are: (i) non-reactive fluids such as organo-polysiloxanes; for example, polydimethylsiloxane, methylphenyl polysiloxane; petroleum oils and combinations thereof; (ii) surfactants such as propylene oxide or ethylene oxide derivatives such as alkylphenol ethylene oxide condensates (ethoxy-
    alkylphenol sides); ethoxylated monoethanolamides of unsaturated fatty acids such as ethoxylated monoethanolamides of linoleic acid; dodecyl sulfate sodium; and soy lecithin; (iii) wetting and dispersing agents such as those described in M Ashel. Ash, "Handbook of Paint and Coating Raw Materials, Vol. 1", 1996, Gower Publ. Ltd., Great Britain, pp 821-823 and 849-851; (iv) thickening and anti-sedimentation agents such as colloidal silica, hydrated aluminum silicate (bentonite), aluminum tristearate, aluminum monostearate, xanthan gum, chrysotile, fumed silica, hydrogenated dericin oil, organomodified clays, polyamide waxes and polyethylene stocks; and . (v) dyes such as 1,4-bis (butylamino) anthraquinone and other anthraquinone derivatives; toluidine dyes, etc. Any additives typically make up 0-30%, such as 0-15%, by dry weight of the coating composition. In addition, the coating composition may comprise .- - pigments and fillers. Pigments and fillers are in the present context seen in conjunction - as components that can be added to the coating composition with only limited implications for adhesion properties. "Pigments" are usually characterized by the fact that they make the final paint coating opaque and non-translucent, whereas "fillers" are usually characterized by the fact that they do not make the paint non-translucent and therefore do not contribute significantly the skin any material below the coating.
    Examples of pigments are degrees of titanium dioxide, red iron oxide, zinc oxide, carbon black, graphite, yellow iron oxide, red molybdate, yellow molybdate, zinc sulfide, antimony oxide, sulfosilicates of sodium aluminum, quinacridones, phthalocyanine, green phthalocyanine, black iron oxide, indanthrene blue, cobalt aluminum oxide, carbazol dioxazin, chromium oxide, orange isoindoline, bisacetoacet-o-tolidiola, benzimidazolone, yellow quinaphthalone , yellow isoindoline, tetrachloroisoindolinone, quinophthalone yellow.
    Examples of fillers are calcium carbonate such as dolomite, talc, mica, feldspar, barium sulfate, kaolin, nepheline, silica, perlite, magnesium oxide, and quartz flour, etc. Fillers (and pigments) can likewise be added in the form of nanotubes or fibers, thus, apart from the examples mentioned above fillers, the coating composition can likewise comprise fibers, for example those generally and specifically described in WO 00 / 77102 which are incorporated herein by reference.
    Any pigments and / or fillers typically constitute 0-60%, such as 0-50%, preferably 5-45%, such as 5-40% or 5-35%, by dry weight R of the coating composition. In order to facilitate easy application of the coating composition (for example, by spray, brush or roller application techniques), the coating composition typically has a viscosity in the range of 25-25,000 mPa-: s, such as as in the range of 150-15,000 mPa's, in particular in. range200-4000 mPa's. Preparation of the coating composition: The coating composition can be prepared by any suitable technique that is generally used within the field of ink production. In this way, the various components can be mixed together using a mixer, a high speed disperser, a ball mill, a pearl mill, a binder, a three-roller mill, etc. The coating compositions are typically prepared and transported with two or three component systems that should be combined and thoroughly mixed immediately before use. The paints according to the invention can be filtered using bag filters, protective filters, wire opening filters, wedge wire filters, metal end filters, turnoclean EGLM filters (eg Cuno), DELTA strain filters (eg Cuno), and Jenag Strainer filters (eg Jenag), or by vibration filtration. An example of a suitable preparation method is described in the Examples.
    The coating composition to be used in the method of the invention is typically prepared by mixing two or more components, for example, two premixes, a premix comprising the one or more reactive polysiloxane binders and a premix comprising o one or more crosslinking agents.
    It should be understood that when reference is made to the coating composition, it is the mixed coating composition ready to be applied.
    In addition, all amounts declared as% dry weight of the coating composition should be understood as% dry weight of the mixed paint composition ready to be applied, that is, the weight apart from the solvents (if any). ] Specific modalities of the coating composition - In a preferred embodiment, the top coating comprises: o. (1) 40-70% by weight of the total topcoat composition of a silanol-terminated polydiorganosiloxane and a crosslinker; (ii) 0.1-10%, such as 0.5-8%, by wet weight of the composition of. - full top coat of one or more biocides, preferably selected from organic biocides; and '(iii) 0.1-10%, such as 0.5-8%, by wet weight of the total topcoat composition of one or more hydrophilic modified polysiloxanes selected from polysiloxanes modified by polyoxyalkylene. ) (as corresponding to the structures shown here above). In another preferred embodiment, the topcoat comprises (1) 40-70% wet weight of the total topcoat composition of a silanol-terminated polydiorganosiloxane and a crosslinker; (ii) 0.5-8% by wet weight of the total topcoat composition of one or more organic biocides; and (iii) 0.5-8%, by wet weight, of the total topcoat composition of one or more hydrophilic modified polysiloxanes selected from the poly (oxyalkylene) modified polysiloxanes (such as cor-
    corresponding to the structures presented above), in which the weight ratio between the one or more hydrophilic modified polysiloxanes and one or more biocides is in the range 1: 0.2 to 1: 6. In yet another preferred embodiment, the binder in the preferred embodiments mentioned above, was pre-reacted in a moisture-free environment to form a single component formulation by mixing 100 parts by weight of silanol-terminated polydiorganosiloxane with 0, 5-30 parts by weight hydrolyzable crosslinker, such as vinyltrimethoxysilane.
    Application of the coating composition The coating composition of the invention is typically applied to at least part of the surface of a substrate. . The term "apply" is used in its normal meaning within the paint industry. In this way, "applying" is carried out by means of any conventional means, for example, by brush, roller, spray, immersion, etc. The most commercially interesting way to "apply" the coating composition is by spraying. Spraying is carried out by. —Means of conventional spray equipment known to the person skilled in the art. The coating is typically applied to a dry film thickness of 50-600 µm, such as 50-500 µm, for example 75-400 µm. The term "at least part of a substrate surface" refers to the fact that the coating composition can be applied to any fraction of the surface. For many applications, the coating composition is at least applied to the part of the substrate (eg a container) where the surface (eg the ship's shell) can come in contact with water, eg sea water.
    The term "substrate" is intended to mean a solid material on 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 embodiments, the substrate is a metal substrate, in particular a steel substrate. In an alternative fashion, the substrate is a fiberglass-reinforced polyester substrate. In some embodiments, the substrate is at least part of the outer surface of a marine structure.
    The term "surface" is used in its normal sense, and refers to the outer limit of an object. Particular examples of such surfaces are the surface of marine structures, such as containers (including but not limited to boats, yachts, motorboats, jib engines, ocean liners, tugs, tankers, container ships and other cargo ships. , submarines, and naval containers of all types), tubes, shore and offshore machinery, buildings and objects of all kinds such as piers, pilasters, bridge substructures, hydroelectric installations and structures, 'wellhead structures underwater oil, nets and other facilities of BR aquatic culture, and buoys, etc. The surface of the substrate can be the "native" surface (for example, the steel surface). However, the substrate is typically coated, for example, with an anti-corrosion coating and / or a fixing coating, so that the surface of the substrate is made up of such a re. —Vestment. When present, the (anticorrosive and / or fixing) coating is typically applied on a total dry film thickness of 100-600 µm, such as 150-450 µm, for example, 200-400 µm. Alternatively, the substrate may carry an ink coating, for example, a worn scale control paint coating, or the like.
    In an important embodiment, the substrate is a metal substrate (for example a steel substrate) coated with an anti-corrosion coating such as an anti-corrosion epoxy based coating, for example cured epoxy based coating, or a shop-primer, for example. example a shop-primer rich in zinc. In another relevant embodiment, the substrate is a fiberglass-coated polyester substrate coated with an epoxy primer coating.
    A Marine Structure The present invention likewise provides a marine structure comprising at least part of the outer surface with an external fouling control coating prepared from a coating composition as defined herein above. In particular, at least as part of the outer surface carrying the outer coating is a submerged part of said structure.
    The coating composition, the method of establishing the coating on the substrate surface, and the coating characteristics follow the directions determined here above.
    In one embodiment, the fouling control coating system of the marine structure can consist of an anti-corrosion layer, a fixation coating and the fouling control coating as described here. 'In a particular embodiment of the above marine structure, a. anti-corrosion layer has a total dry film thickness of 100-600 µm, such as 150-450 µm, for example, 200-400 µm; the fixing coating has a total dry film thickness of 50-500 µm, such as 50-400 µm, for example 75-350 µm or 75-300 µm or 75-250 µm; and the fouling control coating has a total dry film thickness. —Of 20-500 um, such as 20-400 um, for example 50-300 um. Another modality of the marine structure is that where at least * - a part of the outer surface of said structure is coated with a paint system comprising a total dry film thickness of 150-400 µm of an anti-corrosion layer of an epoxy based coating established by application of 1-4, such as 2-4, layers; a total dry film thickness of 20-400 µm of the fixation liner established by applying 1-2 layers; and a total dry film thickness of 20-400 µm of the scale control coating established by applying 1-2 layers.
    In another modality of the marine structure above, the fouling control coating is applied directly to the anticorrosive layer without the use of a fixation coating. Use to improve the anti-fouling properties of a polysiloxane based coating composition The invention also relates to the use of the combination of one or more non-reactive hydrophilic modified polysiloxanes and one or more bio-acids, in which the weight ratio between the one or more modified hydrophilic polysiloxanes and one or more biocides is in the range 1: 0.2 to 1: 6, to improve the anti-fouling properties of a coating composition based on polysiloxane. The combination is particularly relevant for improving the anti-fouling properties against sludge and algae.
    It should be understood that the types of modified non-reactive hydrophilic polysiloxanes, the biocides, and the types of binder systems based on suitable polysiloxane are as defined above, rightly. the quantities and relative proportions of the various ingredients are as defined also above. o General Remarks Although the present description and claims occasionally refer to a polysiloxane, etc., it should be understood that the composi-. —Coating sections defined here may comprise one, two or more types of the individual components. In such modalities, the total quantity * - each component should correspond to the quantity defined above for the individual component.
    The "(s)" in the expressions: compound (s), polysiloxane (s), agent (s), etc. indicate that one, two or more types of the individual components may be present.
    On the other hand, when the expression "one" is used, only one (1) respective component is present. EXAMPLE 1 RF-5000 materials, ex. Shin-Etsu - Japan, polydimethylsiloxane terminated in Xylene silanol from local supplier DC200, ex. Dow Corning - USA, DC5103 polydimethyl siloxane, ex. Dow Corning - USA, polysiloxane modified by polyether (siloxylated polyether) DC550, ex. Dow Corning - USA, non-reactive methylphenyl polysiloxane Zinc Omadine, ex. Arch Chemicals Inc. - Ireland,
    Zinc Pyrithione Copper Omadine, ex.
    Arch Chemical Inc. - Ireland, Silikat TES 40 WN Copper Pyridine, ex.
    Wacker Chemie - Germani, Neostann U-12 ethyl silicate, ex.
    Nitto Kasai - Japan, Dibutiltine Acetylaceton Dilaurate, ex.
    Wacker Chemie - Germani, 2,4-pentanedione DC190, ex.
    Dow Corning-USA, DBE-621 polyether modified polysiloxane, ex.
    General - USA, Dimethylsiloxane - BYK331 ethylene oxide block copolymer, ex.
    BYK - Germani, YBD-125 polyether modified polydimethylsiloxane, ex.
    Gelest - USA, Dimethylsiloxane - N-pyrrolidone carboxylate copolymer CMS-222, ex.
    Gelest - USA, Carbinol functional PDOMS - 20% non-siloxane Sea-Nine 211N, ex.
    Dow Chemicals - USA, 4,5-dichloro-2-n-: octyl-4-isothiazolin-3-0 in Sea-Nine CR2, ex.
    Dow Chemicals - USA, 4,5- BR encapsulated Baiferrox 130M dichloro-2-n-octyl-4-isothiazolin-3-one, ex.
    Lanxess - Germani, Iron oxide Aerosil R8200, ex.
    Evonik Industries - Germani, 2 fumigated silica treated with hexamethyldisilazane Viscosity In the present claim with claims, viscosity is measured at. —25ºC according to ISO 2555: 1989. Hydrophilicity - Relating to a PDMS 'Polysiloxanes that are truly more hydrophilic than the corresponding polydimethylsiloxane (PDMS) can be identified by one or all of the following tests: A.
    Water Capture Due to its inherent hydrophobic properties, PDMS will not capture water.
    An experimental criterion for identifying hydrophilic polysiloxanes is that their hydrophilic content should allow them to capture at least 0.1% of their own weight when immersed in demineralized water.
    When 99.9 parts by weight of hydrophilic polysiloxane are vigorously mixed with 0.1 part by weight of demineralized water, the polysiloxane will dissolve, absorb or swell the water resulting in no fasevisible separation.
    Preparation method for Model Composition A, B, / C, D, E Paints:
    Part (i) (silanol-terminated polydimethylsiloxane), xylene, (poly-dimethylsiloxane), silica, (polyamide wax), red iron oxide, (polyether modified polysiloxane), (biocide) were mixed in a dissolve Diaf painter equipped with an impeller disc (70 mm in diameter) in a 1L canister for 15 minutes at 2000 rpm.
    Part (ii) (ethyl silicate, xylene, catalyst, 2,4-pentanedione, (methylphenyl polysiloxane)) were mixed in a Diaf dissolver equipped with an impeller disc (70 mm in diameter) in a 1 L can. for 2 minutes at 500 rpm.
    Before application, part (i) and part (ii) are mixed in one: homogeneous mixture 'Test Methods Bubble Box Test SS The Bubble Box test is used to determine the influence of hydrophilic modified polysiloxanes (silicone oils hydrophilic) on the stability of the PDMS coating to which they are added. . "Preparation of Panels Steel panels (150x75x15 mm) are coated with 100 um * (dry film thickness, DFT) of a commercial epoxy primer (HEMPADUR Quattro 17634) applied by muffled spray.
    After 12 - 48 hours of drying at room temperature, a silicone fixing coating (HEMPASIL Nexus 27302) is applied by a 300 µm release doctor blade.
    After 16-30 hours of drying the topcoat paint compositions are applied by 400 µm release Dr. Blade.
    The panels are dried for 24 hours before testing in the blister box.
    Test The surface of the panel with the coating system is exposed to 40ºC, saturated water vapor, at an angle of 15º / 60º to the horizontal.
    The reverse side of the panel is exposed at room temperature.
    At the selected inspection intervals during and after the exposure is completed, the action between fixing coating / top coating and condition generates!
    of the top coat are evaluated.
    Adhesion assessment between fixing coating and top coating is based on the classification below: Adhesion Classification Value LACK / POOR No adhesion / poor adhesion GOOD Acceptable adhesion Panels are exposed for two months and typically checked every week.
    Examples of adhesion between the PDMS top coat and Hempasil Nexus fixation coat after the addition of 5% w / w of hydrophilic modified polysiloxanes (polyether type) to the PDMS top coat (test results in Bubble Box after 3 weeks of exposure): (polyether type) Raft Test * - Preparation of Panels An acrylic panel (150x200 mm), sandblasted on one side to facilitate adhesion of the coating, is coated with 100 µm (DFT) of an epoxy commercial (HEMPEL Light Primer 45551) applied by air spraying.
    After 6 - 24 hours of drying at room temperature, a fixing coating is applied by a 300 µm release Dr. Blade.
    After 16-30 hours of drying the topcoat paint compositions are applied per 400 µm release Dr. Blade.
    The panels are dried for at least 72 hours before immersion in the raft.
    Test Panels are tested in two different locations; Spain and Cinapura.
    Test Site in Spain Located in Vilanova in north-eastern Spain.
    In this test site the panels are immersed in sea water with salinity in the range of 37-38 parts per thousand at an average temperature of 17-18ºC.
    Singapore Test Site In this test site the panels are immersed in seawater with salinity in the range of 29-31 parts per thousand at a temperature in the range of 29-31ºC.
    Fo) Panels are always inspected 4-12 weeks and evaluated according to the following scale: Niver Tpbescription = | Algae + Animals <10% 10% <algae + Animals <25% Algae + Animals> 25% Examples. All entries in the model paint chart are by weight unless otherwise stated. - - Model paints | Composition Composition Composition = = | top coating coating A top B top C art Polydimethylsiloxane finished 55.4 in Silane! (5000 cSt) 'Polydimethyl Siloxane 50 cSt Thickener AA Pigments gg Rg Hydrophilic modified polysiloxane: Polysiloxane modified by 4.8 4.8 polyether (DC5103; eae pv | Zinc pyrithione Rg Copper pyrithione vv Total part (Part I (Silicate ethylphenyl polysiloxane non-reactive Dibutyltin dilaurate 5 gg 2,4-pentanedione AA Total part (ii Total part (i) e (ii 100,0 100,0 100,0 Raft performance in EXCELLENT EXCELLENT EXCELLENT Spain (12 months ; Raft performance in EXCELLENT EXCELLENT EXCELLENT Singapore (12 months;
    Model Paints Composition of Composition of | Coating coating composition | top coating D top E top F reference reference reference Part A Finished polydimethylsiloxane Polidimethyl siloxane 50 cSt [Thickener 1 2a | 22 9 gg Pigments ag Hydrophilic modified polysiloxane: 51 polyether modified polysiloxane (DC5103; 'Braga) ame ro o) Copper AB pyrithione Total part (i are Reactive ethyl silicate' Dibutiltine dilaurate Pas 2,4-pentanodione Total part (ii Total part (i) e (ii 100.0 og * | Raft performance at REASONABLE REASONABLE REASONABLE Spain (12 months;. | Raft performance in POOR REASONABLE Singapore (12 months: Comments on results (composition AF)): Some biocides could be more effective against some fouling species than others.
    Because fouling species vary from place to place, performance of the topcoat composition can likewise vary.
    Results are therefore included from both raft sites.
    The performance of biocide topcoat compositions is dramatically increased when a hydrophilic modified polysiloxane such as a non-reactive polyether modified polysiloxane is added (composition A and B) as this ensures the transport of biocide through the PDMS coatings cross-linked to the surface .
    Biocides alone or biocides in combination with non-reactive hydrophobic polysiloxanes
    do not increase the performance of the top coating composition (composition D). It is also found that the use of a modified non-reactive hydrophilic polysiloxane not only provides the advantages of the combination of the modified non-reactive hydrophilic polysiloxane and the biocide.
    Model Paints Composition Composition Composition & Coating | top coating | ee topo G topo H reference are AI Finished polydimethylsiloxane Pigments ag A 2 - Hydrophilic modified polysiloxane: Polysiloxane modified by 28 polyether modified polysiloxane (DBE-621 'o eae Copper pyrithione A ineo Praline Total part (Part I Silicate of ethyl: Dibutyltin dilaurate oa oa | 2 4-pentanedione * [Total part (ii Total part (i) and (ii) 100.0 | 100 | 100.0 Rafting performance in EXCELLENT [so | POOR Spain 38 weeks 38 weeks Raft performance in EXCELLENT EXCELLENT POOR Singapore 38 weeks 38 weeks; 38 weeks, Comments for results (compositions Gl) Compositions G and H contain biocides, and show improved performance compared to the reference (composition |) that only contains the hydrophilic modified polysiloxane (type polyether).
    Model Paints Composition of Composition of Composition of coating | top coating coating J top K top L art reference in Silanol (5000 cSt) | BC thickener a [hydrophilic gases
    EEEEEERT CT fied polysiloxane (YBD-125;
    ESEC RR RAL carbinol (CMS-222 o eae + Pyrione de aineo arte O | Dibutifia ditaurate AA E oo oameme ee. | Spain Singapore 24 weeks; 24 weeks) 24 weeks Comments for results (compositions J Ke L) It is observed that the examples of PDMS compounds modified by hydrophilic non-PEG, used in compositions J and K (YBD-125 and CMS-222) show an improved performance compared to the biocide-free polysiloxane reference (composition L) after 24 weeks of immersion - are static in Singapore. top coat Top coat N (reference Part II Thickened finished polydimethylsiloxane Bag Modified polysiloxane | herotea and met |
    Continuation Model paints Coating composition | Top coat composition Top coat N (part reference Polysiloxane modified by 28 polyether (BYK-331 'Bays | 4,5-Dichloro-2-n-octyl-4-isothiazo- 4,6 lin-3- encapsulated one (-91% vw) 4.2 4,5-dichloro-2-n-octyl-14.0 solution 4-isothiazolin-3-0na (30% W 4.2 Total part (Gio Gio silicate part) ethyl Dibutyltin dilaurate 2,4-pentanedione 1 [og: Total part (ii Las 68: Total part (i) e (ii 100,0 100,0 Performance in raft in Spain. Performance in raft in Cin- EXCELLENT GOOD gapura 11 weeks; 11 weeks) Comments for results (compositions M and N): Compositions M and N have the same concentration as the solution of. 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one of biocide pure.
    It is seen that the encapsulated biocide has a better effect than the non-N encapsulated biocide. * Both compositions contained the same modified hydrophilic polysiloxane.
    权利要求:
    Claims (10)
    [1]
    1. Scale control coating composition, characterized by the fact that it comprises a binder system based on polysiloxane, 0.01-20% dry weight of one or more hydrophilic modified polysiloxanes, and one or more biocides, in which the weight ratio between the one or more hydrophilic modified polysiloxanes and the one or more biocides is in the range of 1: 0.2 to 1: 6, and in which the one or more hydrophilic modified polysiloxanes do not contain groups that can react with the binder or any crosslinker.
    [2]
    Coating composition according to claim 1, characterized in that the relative weight ratio between the one or more modified hydrophilic polysiloxanes and the one or more biocides is 1: 0.2 to 14.
    [3]
    Coating composition according to claim 10 or 2, characterized in that the one or more modified hydrophilic polysiloxanes constitute 2-7% by dry weight of the coating composition.
    [4]
    Coating composition according to any one of claims 1 to 3, characterized in that the one or more biocides constitutes 0.1-10% in dry weight of the coating composition, and in which the one or more most biocides are (are) a pyrithione complex.
    [5]
    Topcoat composition according to any one of claims 1 to 4, characterized in that it comprises: (1) 40-70% wet weight of the total topcoat composition of a silanol-terminated polydiorganosiloxane and a crosslinker; (ii) 0.1-10% by wet weight of the total top coat composition of one or more biocides, preferably selected from - organic biocides; and (iii) 0.1-10% by wet weight of the total topcoat composition of one or more hydrophilic modified polysiloxanes selected from the poly (oxyalkylene) modified polysiloxanes.
    [6]
    Coating composition according to any one of claims 1 to 5, characterized in that the polysiloxane-based binder system comprises (i) a binder and (ii) a cross-linking agent, wherein the binder (i) constitutes 20-90% dry weight of the coating composition and is a curable di-organopolysiloxane represented by the general formula (1): A a A A fot fotto-ts (1) EV BIN E), E where each A 'is independently selected from a hydroxy group, a hydrolyzable group, an amine group and an epoxy group; each A it is independently selected from alkyl, aryl, alkenyl and a hydrolyzable group; each Aº and Aº is independently selected from alkylaryl alkenyl; a = 1-25,000, b = 1-2,500 and a + b is at least 30; wherein said hydrolyzable groups are selected from alkoxy groups and ketoxime groups; and wherein the crosslinker is selected from tetraethoxysilane; vinyltris (methylethyloxime) silane; methyltris (methyl ethyloxime) silane; vinyltrimethoxysilane; methyltrimethoxysilane and vinyltrisopropenoxysilane; and condensation products by hydrolysis thereof.
    [7]
    Coating composition according to any one of claims 1 to 6, characterized in that the hydrophilic modified polysiloxane is a poly (oxyalkylene) modified polysiloxane, in which the poly (oxyalkylene) is selected from polyoxyethylene, polyoxypropylene and poly (oxyethylene-co-oxypropylene).
    [8]
    8. Marine structure, characterized by the fact that it comprises at least part of its outer surface with a
    outer layer prepared from a coating composition as defined in any one of claims 1 to 7.
    [9]
    9. Structure according to claim 8, characterized by the fact that at least as part of the outer surface carrying the outer covering is a submerged part of said structure.
    [10]
    10. Use of the combination of one or more non-reactive hydrophilic modified polysiloxanes and one or more biocides, where the weight ratio between the one or more hydrophilic modified polysiloxanes and the one or more biocides is in the range of 1: 0, 2 to 1: 6, and in which the one or more hydrophilic modified polysiloxanes do not contain groups that can react with the binder or any crosslinker, characterized by the fact that it is to improve the anti-fouling properties of a coating composition based on polysiloxane.
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    同族专利:
    公开号 | 公开日
    PL2516559T3|2015-04-30|
    EP2516559B1|2015-01-21|
    JP2013515122A|2013-05-02|
    CN105368311A|2016-03-02|
    CN102782057B|2016-04-13|
    KR20120125260A|2012-11-14|
    KR101798604B1|2017-11-16|
    US9534121B2|2017-01-03|
    JP2016191056A|2016-11-10|
    KR20170127071A|2017-11-20|
    HRP20150081T1|2015-05-08|
    ES2528606T3|2015-02-10|
    HRP20150081T8|2015-07-03|
    DK2516559T3|2015-02-02|
    JP6283060B2|2018-02-21|
    EP2516559A1|2012-10-31|
    WO2011076856A1|2011-06-30|
    CN102782057A|2012-11-14|
    PT2516559E|2015-02-06|
    KR102078783B1|2020-02-19|
    CN105368311B|2019-03-01|
    US20120264847A1|2012-10-18|
    SG181914A1|2012-07-30|
    JP5990462B2|2016-09-14|
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    法律状态:
    2020-09-29| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-10-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2021-01-12| B11B| Dismissal acc. art. 36, par 1 of ipl - no reply within 90 days to fullfil the necessary requirements|
    2021-11-23| B350| Update of information on the portal [chapter 15.35 patent gazette]|
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    EP09180360.1|2009-12-22|
    EP09180360|2009-12-22|
    PCT/EP2010/070509|WO2011076856A1|2009-12-22|2010-12-22|Novel fouling control coating compositions|
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