KR101980220B1 - Biocidal foul release coating systems - Google Patents

Abstract

A structure coated with a biocidal fountain release coating system,
a. Providing a substrate,
b. Coating the first coating layer on the substrate,
c. Applying one or more subsequent coating layers over the first coating layer,
Wherein the first coating layer comprises a biocide,
Wherein the subsequent coating layer (s) comprises less biocidal agent than the first coating layer, does not include or substantially does not include a biocide,
Wherein the first coating and the subsequent coating layer (s) form a biocidal fountain release coating system that exhibits an adjustable leakage of biocide.

Description

{BIOCIDAL FOUL RELEASE COATING SYSTEMS}

The present invention relates to the use of a fountain release coating to control the release of biocidal agents from a coating system comprising a foul release coating and a biocidal underlying coating. The present invention also relates to such a coating system, its use for inhibiting fouling on a substrate, and a substrate coated with the coating system.

Water-borne ships and boats Artificial offshore structures such as hulls, buoys, drilling platforms, dry dock facilities, oil production excavators and pipes are prone to aquatic organisms such as green algae and brown algae, barnacles and mussels. These structures are usually metal, but may also include other structural materials such as concrete. Such fouling in the boat hull is problematic because it increases the frictional resistance during movement in water, which reduces speed and increases fuel cost. First, the resistance of thick fouling layers to waves and algae can cause unexpected and potentially dangerous stresses on the structure, and second, fouling interferes with structural testing for defects such as stress cracking and corrosion , It is also a headache for fixed structures such as drilling platforms and bridges of oil production drilling rigs. Even in pipes such as cooling water withdrawals and drains, this is a nuisance because the effective cross-sectional area is reduced by fouling to reduce the flow rate.

Fouling has traditionally been prevented by antifouling paints containing biocides, which gradually release biocides from the paint. The most commercially successful fouling inhibition method is to use an antifouling coating containing a toxic substance, for example, a triorganotin compound, on aquatic life forms. However, due to the adverse effects that may occur when certain toxins are released into the aquatic environment under certain conditions, such coatings are being considered for less use.

For example, some coatings, for example, elastomers such as silicone rubber coatings, as disclosed in British Patent 1,307,001 and U.S. Patent 3,702,778, have long been known to exhibit resistance to fouling by aquatic organisms . Since such coatings are considered non-biocidal, generally hydrophobic, physically non-fixable and / or provide a surface on which the organism is not readily adhered, the coating is more of a fountain release coating than an antifouling coating . The foul release characteristics can be specified by a barnacle attachment measurement, for example, ASTM D 5618-94. In this way, the following numerical values of the opener attachment were recorded: silicon surface (0.05 MPa), polypropylene surface (0.85 MPa), polycarbonate surface (0.96 MPa), epoxy surface (1.52 MPa) and urethane surface (1.53 MPa) JC Lewthwaite, AF Molland and KW Thomas, "An Investigation into the Variation of Ship Skin Resistance with Fouling", Trans. RINA, Vol. 127, pp. 269-284, London (1984). As a criterion as to whether the coating can be regarded as a foul release type, the fountain release coating usually has an average tack coat adhesion value of less than 0.4 MPa.

Silicone rubber and silicone compounds generally exhibit very low toxicity. The disadvantage of such a foul release system when applied to a boat hull is that relatively high ship speeds are required to remove all fouling species, even if the accumulation of foul organisms is reduced. Thus, in some cases, it has been shown that such a coating requires a speed of at least 10 knots to remove fouling to a satisfactory level from the treated hull. For this reason, silicon rubber has achieved some limited commercial success so far.

It has also long been known that attachment of a silicone foul release coating to a rust-preventive coating is generally not satisfactory, unless proper adhesion is achieved using a tie-coat or a link coat. Such tie coats often contain silicon. Examples of silicone-containing tie coats are described in EP521983 and EP1832630.

A combination of a suitable tie coat and a second coating layer is sometimes referred to as a " duplex " foul release system. Until now, compositions disclosed in the prior art for use as tie coats in such duplex systems are generally free of biocides and WO2008 / 013825 is far from using biocides as part of such systems Are explicitly described.

GB1409048 discloses a marine polyurethane topcoat composition that is applied over a biocidal antifouling coating and is capable of absorbing 30% to 300% of its own weight of seawater. The polyurethane topcoat of GB1409048 is not a foul release coating according to the context of the present invention (see Redefining antifouling coatings, Journal of Protective Coatings and Linings, September 1999, pages 26-35, It is disclosed that the barnacle attachment strength is much higher than that of the barn. No mention is made of GB 1409048 for subsequent foulard coatings.

EP 0 313 233 describes a first layer of antifouling paint containing a substance harmful to marine organisms and a second layer of polytetrafluoroethylene (EPTFE) which is a porous organic polymer film deposited on the first layer A marine antifouling coating composition is disclosed. The porous organic polymer film is not a content-based coating agent of the present invention since it is not applied as a liquid mixture and dried or cured to form a dried continuous film. Moreover, polytetrafluoroethylene is a material unsuitable for use as a fountain release surface (see Redefining antifouling coatings described above, which describes the high strength of the barnacle attachment). The use of subsequent fountain coatings is not mentioned or suggested in EP 0 313 233.

US 4,129,610 discloses a waterborne coating composition for marine flooring comprising a vinyl copolymer and a water-soluble epoxy compound. This water-soluble coating composition is applied onto a primer coating layer containing a toxic substance. The water-soluble coating compositions of US 4,129,610 are not considered foul release coatings according to the teachings of the present invention (see Redefining antifouling coatings described above, which are described as having high opener adhesion strength of epoxy coatings). The use of subsequent fountain coatings is not mentioned or suggested.

FR2636958 discloses chlorinated adhesive primers for silicone elastomers. According to this document, a triorganotin oxide or halide biocide or copper oxide may be added to the primer. Tributyltin oxides or fluorides and copper oxides are only suitable biocidal additives mentioned in the above systems, but are not illustrated or further described for primers containing any biocidal agent. This publication does not mention biocide leaks at all and teaching to foul release systems with primers containing random biocides is not possible.

WO 95/32862 discloses a duplex foul release system that can be used on substrates to prevent fouling by marine organisms. This duplex system consists of a binding layer and an emissive layer, wherein the 3-isothiazolone biocide is impregnated in either the binding layer or the emissive layer. This document only shows that 3-isothiazolone should be used as a biocide and that the rate of leakage of biocidal agents from the bond layer is inversely proportional to the square root of time, except for potential biocide solubility Other factors do not control the leak rate. Thus, leakage of biocides is not considered to be a biocidal fountain release coating system with controlled release rate of biocidal agents included in the framework of the present invention, as it is scarcely controlled in this system. A substrate coated with a system such as the system disclosed in WO 95/32862 wherein the rate of leakage of biocide in the bonding layer is inversely proportional to the square root of time is such that the substrate does not contain a biocide immediately after the substrate is immersed in seawater, Substantially non-fouled and thus superior to the comparative substrate coated with the biocide-free oil release coating system. However, due to poor performance, the coated substrate is gradually covered with biological deposits, and within 4-6 months the system of WO 95/32862 has the same effect as a substrate coated with a biocide-free oil release coating system Indicates severe fouling.

Surprisingly, it has been found that a structure coated with a biocidal fountain release coating system can be fabricated to exhibit controlled release of biocidal agents.

In the present invention,

a. Providing a substrate

b. Coating the first coating layer on the substrate,

c. And applying one or more subsequent coating layers over the first coating layer,

Wherein the first coating layer and the subsequent coating layer form a biocidal fountain release coating system wherein the first coating layer contains a biocidal agent and the subsequent coating layer (s) , Or the subsequent coating layer (s) does not contain a biocidal agent or does not contain or does not substantially contain a biocidal agent.

The biocidal fountain release coating system as defined in the present invention represents a controlled release of biocidal agents.

The controlled release of the biocide is determined by the ratio of the leakage rate of the biocide from the foul release coating system of the present invention at 5 days (R ₅ ) after coating application and 30 days (R ₃₀ ) after coating application , And R ₅ / R ₃₀ is (≤) 1.5 or less, preferably ≤ 1.33, and more preferably ≤ 1.11.

The biocidal fountain release coating system of the present invention exhibits excellent antifouling properties for both short term and long term after the substrate is immersed in seawater.

In the framework of the present invention, the biocompatible fountain release coating system is a coating system in which the biocide is released from the coating system, which is physically immobilized and / or has a surface to which the aquatic / marine organism can not readily adhere.

In order to improve the adhesion of the first coating layer to the substrate, there may be a tie coat or adhesion promoter between the substrate and the first coating layer. To improve the corrosion resistance of the substrate, a rust preventive coating may be applied to the substrate before applying the first coating layer. More generally, there may be one or more coating layer (s) on the substrate prior to applying the first coating layer comprising the biocide to the substrate.

To build a coating layer, the coating composition is applied to the surface (e.g., to a substrate or other coating layer) as a liquid mixture; The coating composition is then dried or cured to form a dry continuous coating film / layer on the surface.

The present inventors have found that the biocide leakage rate of the biocidal fountain release coating system is lower than that of the first coating layer on the first coating layer containing the biocide, Or by applying subsequent coatings or subsequent coatings that do not include, or substantially do not include, additives. The advantage of this is that the rate of biocide leakage can be controlled, the time dependence can be low, and a more linear correlation with the actual time can be maintained. Thus, a preferred and more constant rate of biocide release can be realized. This is advantageous in that it achieves long-term performance life, more effective use of biocides, and reduced environmental impact. In addition, biocidal leaks can be adjusted to enhance the anti-fouling power of the fountain release coating system, particularly at low speeds or at rest.

In the present invention, biocide leakage (sometimes referred to as biocide release) and biocide release rate (biocide release rate) should be clearly distinguished from foul releases. The rate of release is the rate at which the biocide is released into the surrounding water by the coating system, typically expressed as biocidal weight / unit area / unit time. The foul release is associated with preventing fouling and / or ease of fouling from the surface of the immersed substrate using non-biocidal agents. For example, the foul release characteristic may be specified by a barnacle attachment measurement or related method that can be performed using ASTM D 5618-94, a standard inspection method for measuring the barnacle attachment strength at the front end. Both of these are complementary mechanisms for controlling fouling, but they are independent of each other.

More specifically, the present inventors have realized that the leak rate can be controlled through the compositional diversification of the subsequent coating layer (s). The first coating layer serves as a biocide reservoir containing biocidal agents that can be immediately supplied for release. The rate of leakage of the biocidal agent can be adjusted to diversify some properties of the first coating layer and the subsequent coating layer (s). These attributes include, by way of non-limiting example, the pigment volume concentration, the cross-link density, the presence and amount of non-affinity fluid, the cross-linking chemistry of the subsequent coating layer (s), and the thickness of the film.

The reservoir of biocidal agent, in combination with the regulatory mechanism of the subsequent coating (s), can tailor biocide leakage rates to the end user.

In the framework of the present invention, the coating system exhibiting controlled release of biocides is characterized in that the release rate (R ₃₀ ) of the biocide after 30 days of water immersion is at least 67% of the release rate (R ₅ ) System. In other words, a coating system exhibiting controlled release of biocides is a system with R ₅ / R ₃₀ ≤ 1.5.

In one embodiment of the invention, R ₅ / R ₃₀ is ≤ 1.5. In another embodiment, R ₅ / R ₃₀ is ≤ 1.33. In another embodiment of the present invention, R ₅ / R ₃₀ is ≤ 1.11.

In WO 95/32862, a duplex fountain release system is described in which the rate of biocide leakage in the binding layer is inversely proportional to the time square root, and other factors do not regulate the rate of leakage other than the solubility of potentially anhydrous biocides. In this system, the rate of release of the biocide is described as F (t) ~36 / t ^0.5 , where F is the leakage rate expressed in g / cm ² / day (cm cm ^-2 day ^-1 ) And t is the time in day. The R ₅ / R ₃₀ of this system is F (5) / F (30) = 30 ^0.5 / 5 ^0.5 = 2,45. WO 95/32862 discloses a biocidal fountain release coating system in which a substrate is first coated with a coating containing a biocidal agent and then a subsequent layer (s) substantially free of biocidal agent is coated thereon, Did not teach that it would achieve a more gradual and sustained release profile of the biocide from the coated surface.

According to the present invention, the subsequent coating layer (s) applied over the first coating layer contains less biocidal agents than the first coating layer. Furthermore, there is no or substantially no biocide in the subsequent coating layer (s). Substantial absence of biocidal agent means that the subsequent coating layer (s) contains less than 1.0 wt.% (Based on the total amount of coating composition) biocide. Preferably, the subsequent coating layer (s) comprises less than 0.5 wt% biogenic agent, more preferably less than 0.1 wt%. To avoid chaos, wt% (wt%) is wt% based on the total amount of coating composition.

In one embodiment, the subsequent coating layer (s) further comprises a non-affinity fluid.

The non-affinity fluid helps achieve improved foul release performance in the subsequent coating layer (s). Without wishing to be bound by theory, it is believed that the fluid can act on the movement of biocides.

In a further embodiment, the biocide is encapsulated, adsorbed, supported, or partially or wholly bound.

The encapsulation, adsorption, support, or binding of the biocide can provide a second mechanism for controlling the release of the biocide from the coating system to achieve a much more gradual release and a long lasting effect.

The present invention relates to a structure coated with (i) a biocidal fountain release coating system, and (ii) a biocidal fountain release coating system, wherein the biocidal fountain release coating system comprises:

a. materials,

b. The first coating layer,

c. And at least one subsequent coating layer present on the first coating layer,

Wherein the first coating layer contains a biocide and the subsequent coating layer (s) has a lower biocide content than the first coating layer, and wherein the subsequent coating layer does not include or substantially contain a biocidal agent. I never do that. The biocidal fountain release coating system represents a controlled release of biocidal agents.

One embodiment of the present invention is a structure coated with the aforementioned biocidal fountain release coating system.

A first coating layer containing a biocidal agent

The composition of the first coating layer is not particularly limited, but preferably, the first coating layer composition comprises a polymer. The polymer preferably forms an elastic body. More preferably, it is a polyorganosiloxane. Even more preferably, it is a polydimethylsiloxane. In addition, the polyorganosiloxane may also comprise two or more polyorganosiloxanes having different viscosities.

Preferably, the polyorganosiloxane has at least one, more preferably at least two, reactive functional groups such as hydroxyl, alkoxy, acetoxy, carboxyl, hydrosilyl, amine, epoxy, vinyl or oxime functional groups.

Preferably, the polymer is present in an amount of from 5 to 50 wt%, based on the total amount of the coating composition. More preferably, the polymer is present in an amount of from 8 to 20 wt%.

Preferably, the polymer is crosslinkable. Depending on the type of crosslinkable polymer, the coating composition may require a crosslinking agent. The need for the presence of a crosslinking agent will be determined by the type and number of functional groups present in the polymer. When the polymer comprises an alkoxy-silyl group, the presence of a small amount of water and, optionally, a condensation catalyst is generally sufficient to achieve complete coating cure after application. For these compositions, atmospheric humidity is generally sufficient to induce curing, and generally there will be no need to apply heat to the coating composition after application.

The optionally present crosslinking agent may be a crosslinking agent comprising any one or more of functional silane and / or acetoxy, alkoxy, amido, alkenoxy and oxime groups. Examples of such cross-linking agents are described in WO 99/33927, page 19, line 9, page 21, line 17. Mixtures of various cross-linking agents may also be used.

Preferably, the crosslinking agent is present in an amount of from 0.1% to 20% by weight, based on the total amount of the coating composition.

The first coating layer comprises a biocide. &Quot; Containing / containing " means that the biocidal agent is present in the coating layer body (i.e., it is mixed into the coating composition before curing / drying).

The biocide of the present invention may be one or more of an inorganic, organometallic, metal-organic or organic biocide for marine or freshwater organisms. Examples of the inorganic biocidal agent include copper salts such as copper oxide, copper thiocyanate, copper bronze, copper carbonate, copper chloride and copper nickel alloy, and silver salts such as silver chloride or nitric acid silver; Organometallic and metal-organic biocides include zinc pyrithione (the zinc salt of 2-paradinethiol-1-oxide), copper pyrithione, bis (N-cyclohexyldiazeniumdioxy) copper, zinc ethylenebis (I.e., zineb), zinc dimethyldithiocarbamate (ziram), and complexes of zinc salts with manganese ethylene-bis (dithiocarbamate) (i.e., mancozeb); Organic biocides include, but are not limited to, formaldehyde, dodecylguanidine monohydrochloride, thiabendazole, N-trihalomethyl thiophthalimide, trihalomethyl thiosulfamide, N-aryl maleimide, (2,4,6-trichlorophenyl) maleimide, 3- (3,4-dichlorophenyl) -1,1-dimethylurea, 2,3,5,6-tetrachloro- (Methylsulfonyl) pyridine, 2-methylthio-4-butylamino-6-cyclopropylamino-s-triazine, 3-benzo [b] thien -yl-5,6-dihydro- -Oxathiazine 4-oxide, 4,5-dichloro-2- (n-octyl) -3 (2H) -isothiazolone, 2,4,5,6-tetrachloroisophthalonitrile, tolylfluanid, dichlofluanid, diiodomethyl-p-tolylsulfone, capsciacin, N-cyclopropyl-N '- (1,1-dimethylethyl) -6- Thio) -1,3,5-triazine-2,4-diamine, 3-iodo-2-propynyl butylcarbazole Dithian anthraquinone-2,3-dicarbonitrile (dithianon), borane such as pyridine triphenylborane, optionally in combination with 5, Trihalogeno-4-cyanopyrrole derivatives substituted at the 1-position, for example 2- (p-chlorophenyl) -3-cyano- -Trifluoromethylpyrrole (tralopyril), and furanones such as 3-butyl-5- (dibromomethylidene) -2 (5H) -furanone, and mixtures thereof, Such as avermectin, such as avermectin B1, ivermectin, doramectin, abamectin, amamectin and selamectin, and the like, Quaternary ammonium salts such as, for example, undecyldimethylammonium chloride and alkyldimethylbenzylammonium chloride. In one embodiment, the biocide may be 3-isothiazolone, but the inventors have found that such biocides should preferably be in an encapsulated, adsorbed or bound form. In another embodiment, the biocide is not a 3-isothiazolone.

Preferably, the biocide is organic or metal-organic. Without wishing to be bound by theory, it is believed that the leakage of biocidal agents involves physical diffusion from the first coating layer to the subsequent coating (layer) by a passive migration process of the biocide. The flowability of the biocide from the coating system will thus be controlled, in part, by diffusion of the biocidal agent into the entire subsequent coating layer (s) and compatibility with the subsequent coating layer (s). If the diffusion or affinity is intrinsically high, as is the case in organometallic biocides such as organotin, etc., the leak rate formed will also be inherently high and will be difficult to control, thus reducing the lifetime of the coating and having an adverse environmental impact . As in inorganic inorganic biocides such as copper and the like, if the diffusion or affinity is essentially low, the leak rate will be inherently low and fouling can occur. In general, the use of organic biocides or metal-organic biocides can adequately control the rate of leakage through the use of the coating system of the present invention and prevent unacceptable environmental damage.

In the context of the present invention, an inorganic biocide is a biocide that contains a metal atom in its chemical structure and is free of carbon atoms; The organometallic biocide is a biocide comprising a metal atom, a carbon atom and a metal-carbon bond in its chemical structure; Metal-organic biocides are biocides containing metal atoms and carbon atoms in their chemical structure and no metal-carbon bonds; Organic biocides are biocidal agents that contain carbon atoms in the chemical structure but no metal atoms.

Preferably, for good antifouling properties, the biocide is one of the 2-trihalogenomethyl-3-halogeno-4-cyanopyrrole derivatives substituted at position 5 and optionally at position 1, (Dithianon), copper pyrithione, zinc pyrithione, tolyl fluoride, dichlorofluanide, and N-tert-butylanthraquinone-2,3-dicarbonitrile Cyclopropyl-N '- (1,1-dimethylethyl) -6- (methylthio) -1,3,5-triazine-2,4-diamine.

Preferably, the biocide (s) is present in the first coating layer in an amount of from 0.05 to 50 wt%, more preferably from 3 to 30 wt%, and most preferably from 10 to 20 wt%, based on the total amount of the first coating layer composition Lt; / RTI > In some cases, the amount of biocide present in the first coating layer must be greater than the amount of biocide in one or more subsequent coating layer (s) at the time the coating layer is applied to the substrate.

In addition, the biocide may optionally be encapsulated, adsorbed, supported, or otherwise bonded wholly or partially. Some biocides are difficult to handle or toxic, and are advantageously used in encapsulation, adsorption, support, or combined form. Additionally, the encapsulation, adsorption, support or binding of the biocidal agent may provide a secondary mechanism for controlling the rate of leakage of the biocide from the coating system to achieve a much more gradual release and long-lasting effect have.

The method of encapsulating, adsorbing, supporting or binding a biocidal agent is not particularly limited in the present invention. Examples of methods by which encapsulated biocides can be prepared for use in the present invention include single- or double-walled amino-formaldehyde or hydrolyzed polyvinyl acetate-phenolic resin capsules or microcapsules as described in EP 1791424 . An example of a suitable encapsulated biocide is a 4,5-dichloro-2- (n-octyl) -3 (2H) -isothiazolone capsule marketed by Dow Microbial Control as a antifouling agent for Sea- have.

Examples of methods by which adsorbed, supported or bound biocides can be prepared include host-guest complexes such as inclusion compounds as described in EP0709358, phenolic resins as described in EP0880892, carbon-based compounds as described in EP1142477 Adsorbents, or inorganic microporous supports such as amorphous silica, amorphous alumina, pseudoboehmite or zeolite described in EP 1115282.

When the polymer of the biocidal first coating layer composition is crosslinkable, the composition may optionally comprise a catalyst. Examples of suitable catalysts include the carboxylates of various metals such as tin, zinc, iron, lead, barium and zirconium. These salts are preferably long-chain carboxylic acid salts, for example, dibutyltin dilaurate, dibutyltin dioctoate, iron stearate, tin (II) octoate and lead octoate. Other examples for suitable catalysts include organic bismuth, organic titanium compounds and organic-phosphates, such as bis (2-ethyl-hexyl) hydrogen phosphate. Other possible catalysts include chelates such as dibutyltin acetoacetonate. Further, the catalyst may be a halogenated (meth) acrylate having at least one halogen substituent on the carbon atom in the [alpha] - position relative to the acid group and / or one or more halogen substituents on the carbon atom in the [beta] Organic acids, or derivatives capable of hydrolyzing to form acids under condensation reaction conditions.

In other embodiments, the catalyst may be one described in any document of WO2007122325A1, WO2008055985A1, WO2009106717A2, WO2009106718A2, WO2009106719A1, WO2009106720A1, WO2009106721A1, WO2009106722A1, WO2009106723A1, WO2009106724A1, WO2009103894A1, WO2009118307A1, WO2009133084A1, WO2009133085A1, WO2009156608A2, and WO2009156609A2.

The catalyst of the biocidal first coating layer composition is preferably present in an amount of from 0.01 to 4 wt%, based on the total amount of the coating composition.

Preferably, the biocidal first coating layer composition according to the present invention further comprises one or more fillers, pigments, additional catalysts and / or solvents. Examples of suitable fillers are barium sulfate, calcium sulfate, calcium carbonate, silica or silicates (e.g. talc, feldspar and china clay), aluminum pastes / flakes, bentonites or other clays. Some fillers, such as fumed silica, may have a thixotropic effect on the coating composition. The proportion of filler may range from 0 to 25 wt% based on the total amount of coating composition. Preferably, the clay is present in an amount of 0 - 1 wt% based on the total amount of the coating composition and the thixotrope is present in an amount of 0 - 5 wt%.

Examples of suitable pigments include black iron oxide, red iron oxide, yellow iron oxide, titanium dioxide, zinc oxide, carbon black, graphite, red molybdate, bismuth vanadate yellow, yellow molybdate, zinc sulfide, antimony oxide, cobalt oxide / Zinc titanate green, zinc titanate / tin orange, lanthanide sulfide orange and red, manganese pyrophosphate violet, sodium aluminum sulfosilicate, quinacridone, phthalocyanine blue, phthalocyanine green, black iron oxide, indanthrone blue, cobalt aluminum oxide, (III) chromium, isoindoline orange, bis-acetoaceto-tolidiole, benzimidazolone, quinaphthalone yellow, isoindoline yellow, tetrachloroisoindolinone, and Quinophthalone Yellow. The proportion of the pigment may range from 0 to 10 wt% based on the total amount of the coating composition. Suitable solvents include aromatic hydrocarbons, alcohols, ketones, esters and mixtures of these materials with each other or mixtures of these materials with aliphatic hydrocarbons. Preferred solvents include methyl isoamyl ketone and / or xylene. Preferably, the solvent is present in an amount of from 10 to 40 wt%, based on the total amount of the composition.

The composition optionally comprises an adhesion promoting material in an amount typically from 0.01 to 0.5 wt%, based on the total amount of the composition. Examples of suitable adhesion promoters include silanes such as aminosilanes, epoxysilanes, methacryloyloxypropylsilanes and mercaptosilanes.

Preferably, the adhesion promoter is an aminosilane of the following type:

_{(RO) x R 3-x} SiR 1 N (R 2) 2

Each R is independently selected from the group consisting of C1-8 alkyl (e.g., methyl, ethyl, hexyl, octyl, etc.), C1-4 alkyl, O, C2-4 alkyl; Aryl (e.g., phenyl), and arylC1-4alkyl (e.g., benzyl); R ¹ is selected from (CH ₂ ) _1-4 , methyl-substituted trimethylene and (CH 2) _2-3 , O, (CH ₂ ) _2-3 ; R ² is selected from hydrogen, alkyl, cycloalkyl, aralkyl, aryl or (CH ₂ ) _2-4 -NH ₂ .

In another embodiment, the adhesion promoter is a " dipodal " silane of the following type, as described in WO2010018164:

(R ³ O) ₃ SiR ¹ NHR ² Si (OR ⁴ ) ₃ or (R ³ O) ₃ SiR ¹ NHR ⁵ NHR ² Si (OR ⁴ ) ₃

R ¹ , R ² and R ⁵ are independently C1 - And C5 alkylene group, R ³ and R ⁴ are selected from methyl or ethyl independently.

In another example, the adhesion promoter is an epoxy silane of the following type:

A-Si (R) _a (OR) _(3-a)

A is an epoxy-substituted monovalent hydrocarbon radical of 2 to 12 carbon atoms; Each R is independently C1-8 alkyl (e.g., methyl, ethyl, hexyl, octyl, etc.), C1-4-alkyl-, O-, C2-4-alkyl; Aryl (e.g., phenyl), and arylC1-4alkyl (e.g., benzyl); a is 0 or 1;

The A group in the epoxy silane is preferably a glycidoxy-substituted alkyl group, for example, 3-glycidoxypropyl. Epoxysilanes include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldiethoxymethoxysilane, 2-glycidoxypropyl tri Methoxysilane, 2- (3,4-epoxy-4-methylcyclohexyl) -ethyltrimethoxysilane, 5,6-epoxy-hexyltriethoxysilane; Or oligomers thereof.

More preferably, the adhesion promoter is N-2-aminoethyl-3-aminopropyltrimethoxysilane. Additional optional additives include dispersants such as unsaturated polyamide acid ester salts.

Subsequent coating layer (s), fountain release layer

The composition of the subsequent coating layer (s) is not particularly limited, but the composition preferably comprises a polymer. Preferably, the polymer forms an elastic body. More preferably, it is a poly-free siloxane. Even more preferably, it is a polydimethylsiloxane. In addition, the polyorganosiloxane may also include two or more polyorganosiloxanes having different viscosities.

The polyorganosiloxane has at least one, preferably at least two reactive functional groups such as hydroxyl, alkoxy, acetoxy, carboxyl, hydrosilyl, amine, epoxy, vinyl or oxime functional groups.

In another example, the polymer is a polyorganosiloxane polyoxyalkylene block copolymer wherein the polymer is a PS- (A-PO-A-PS) n type wherein the PS is a polyorganosiloxane block and the PO is a polyoxyalkylene block , A is a divalent moiety, and n is a value greater than or equal to 1, as described in WO2008132196.

The polymer may be a mixture of other organosilicon crosslinkers with two or more Y groups that are capable of self-condensing and crosslinking in the presence or absence of a catalyst (as described herein before) And two or three reactive groups X in the polyorganosiloxane block per molecule,

Preferably, the polyorganosiloxane (s) polymer (s) are present in an amount of from 30 to 90 wt%, based on the total amount of the coating composition.

Preferably, the polymer is crosslinkable. Depending on the type of crosslinkable polymer, the coating composition may require a crosslinking agent. The presence of the crosslinking agent is essential only when the curable polymer can not be cured by condensation. This will depend on the type and number of functional groups present in the polymer. When the polymer comprises an alkoxy-silyl group, the presence of a small amount of water and, optionally, a condensation catalyst is generally sufficient to achieve complete cure of the coating after application of these compositions. For these compositions, atmospheric humidity is generally sufficient to induce curing, so it is generally not necessary to apply heat to the coating composition after application.

The optionally present crosslinking agent may be a crosslinking agent comprising any one or more of functional silane and / or acetoxy, alkoxy, amido, alkenoxy and oxime groups. Examples of such cross-linking agents are described in WO 99/33927, page 19, line 9, page 21, line 17. Mixtures of various cross-linking agents may also be used.

Preferably, the crosslinking agent is present in an amount of from 1% to 25 wt%, based on the total amount of the coating composition.

When the polymer of the subsequent coating layer composition is crosslinkable, the composition optionally comprises a catalyst. Examples of suitable catalysts include the carboxylates of various metals such as tin, zinc, iron, lead, barium and zirconium. These salts are preferably long-chain carboxylic acid salts, for example, dibutyltin dilaurate, dibutyltin dioctoate, iron stearate, tin (II) octoate and lead octoate. Other examples for suitable catalysts include organic bismuth, organic titanium compounds and organic-phosphates, such as bis (2-ethyl-hexyl) hydrogen phosphate. Other possible catalysts include chelates such as dibutyltin acetoacetonate. Further, the catalyst may be a halogenated (meth) acrylate having at least one halogen substituent on the carbon atom in the [alpha] - position relative to the acid group and / or one or more halogen substituents on the carbon atom in the [beta] Organic acids, or derivatives capable of hydrolyzing to form acids under condensation reaction conditions.

In other embodiments, the catalyst may be one described in any document of WO2007122325A1, WO2008055985A1, WO2009106717A2, WO2009106718A2, WO2009106719A1, WO2009106720A1, WO2009106721A1, WO2009106722A1, WO2009106723A1, WO2009106724A1, WO2009103894A1, WO2009118307A1, WO2009133084A1, WO2009133085A1, WO2009156608A2, and WO2009156609A2.

Preferably, the catalyst is present in an amount of 0.05 to 4 wt%, based on the total amount of the coating composition.

Preferably, the subsequent coating layer composition according to the present invention further comprises one or more fillers, pigments, catalysts and / or solvents. Examples of suitable fillers are barium sulfate, calcium sulfate, calcium carbonate, silica or silicates (e.g. talc, feldspar and china clay), aluminum pastes / flakes, bentonites or other clays. Some fillers, such as dry silica, may have a thixotropic effect on the coating composition. The proportion of filler may range from 0 to 25 wt% based on the total amount of coating composition. Preferably, the clay is present in an amount of 0 - 1 wt%, based on the total amount of the coating composition, and preferably the thixotropic agent is present in an amount of 0 - 5 wt%.

Examples of suitable pigments are black iron oxide, red iron oxide, yellow iron oxide, titanium dioxide, zinc oxide, carbon black, graphite, red molybdate, yellow molybdate, zinc sulfide, antimony oxide, sodium aluminum sulfosilicate, Wherein the colorant is at least one selected from the group consisting of phthalocyanine blue, phthalocyanine green, black iron oxide, indanthrone blue, cobalt aluminum oxide, carbazado dye, chromium oxide, isoindoline orange, bis-acetoacetato-tolyldiol, benzimidazolone, quinaphthalone yellow, Reddish yellow, tetrachloroisoindolinone, and quinophthalone yellow. The proportion of the pigment may range from 0 to 25 wt% based on the total amount of the coating composition. Suitable solvents include aromatic hydrocarbons, alcohols, ketones, esters and mixtures of these materials with each other or mixtures of these materials with aliphatic hydrocarbons. Preferred solvents include methyl isoamyl ketone and / or xylene. Preferably, the solvent is present in an amount of from 0 to 40 wt%, based on the total amount of the composition.

The fountain release characteristics of coating systems according to the present invention are generally improved when the subsequent coating layer (s) composition forms an overall hydrophobic or amphiphilic fountain release coat when dried or cured. The bulk and surface hydrophobicity of the subsequent coating layer (s) can be specified by various means, for example, by seawater uptake measurement or surface contact angle measurement. Preferably, the seawater absorption of the subsequent coating layer (s) is less than 30 wt%, more preferably less than 25 wt%. Preferably, the balloon contact angle of the subsequent coating layer (s) is greater than 30 degrees at 23 占 폚.

In a preferred embodiment, the subsequent coating layer (s) composition comprises an incompatible fluid or grease. In the context of the present invention, an incompatible fluid means a silicone, organic or inorganic molecule or polymer, usually a liquid, and optionally a (fully or partially) ) Non-miscible, organosoluble grease or wax. Once the first and subsequent coatings are cured, the fluid will be concentrated on the surface of the subsequent coating layer (s), increasing its fountain release properties. Examples of non-affinity fluids are given in WO2007 / 10274. In WO 2007/10274, the non-affinity fluid is a fluorinated polymer or oligomer in the polysiloxane coating; The process of thickening the fluorinated polymer / oligomer on the surface of the cured polysiloxane coating layer is thermodynamically driven due to the difference in surface energy. The low surface energy provided by the fluorinated polymer or oligomer improves the fountain release properties of the coating in combination with the elastic properties provided by the cured polysiloxane.

Examples of suitable fluids are:

a) linear and trifluoromethyl branched fluorine end-capped perfluoropolyethers (e.g., Fomblin Y ^® , Krytox K ^® fluid or Demnum S ^® oil);

b) Linear di-organo (OH) end-capped perfluoropolyethers (eg Fomblin Z DOL ^® , Fluorolink E ^® );

c) a poly ethylene chlorotrifluoroethylene with a low molecular weight (for example, Daifloil CTFE ^® Fluid)

In all cases, the fluorinated alkyl- or alkoxy containing polymer or oligomer does not participate in virtually any crosslinking reaction. Other mono- and di-organofunctional end-capped fluorinated alkyl- or alkoxy-containing polymers or oligomers may be used (e.g., carboxy-, ester-functional- fluorinated alkyl- or alkoxy- containing polymers or oligomers ).

In another embodiment, the fluid can be, for example, a silicone oil of the formula:

Q ₃ Si-O- (SiQ ₂ -O-) _n SiQ ₃

Wherein each Q group is a hydrocarbon radical of 1-10 carbon atoms and n is an integer which makes the silicone oil have a viscosity of 20-5000 m Pa s. At least 10% of Q groups are generally methyl groups, and at least 2% of Q groups are phenyl groups. Most preferably, at least 10% of the -SiQ ₂ -O- units are methyl-phenylsiloxane units. Most preferably, the silicone oil is a methyl-terminated poly (methylphenylsiloxane). The oil preferably has a viscosity of 20-1000 m Pa s. Examples of suitable silicone oils are sold under the trade names Rhodorsil Huile 510 V100 and Rhodorsil Huile 550 from Bluestar Silicones. Silicone oils improve the resistance of the coating system to aquatic fouling.

Further, the fluid may be an organosilicone represented as follows:

 In this formula,

R 1 may be the same or different and is selected from an alkyl, aryl and alkenyl group optionally substituted by an oxygen-containing group of formula OR 5 and an organic group according to formula (I) wherein R 5 is hydrogen or C 1-6 alkyl, Selected:

                 -R6-N (R7) -C (O) -R8-C (O)

In this formula,

R6 is selected from alkyl, hydroxyalkyl, carboxyalkyl of from 1 to 12 carbon atoms, and polyoxyalkylene of up to 10 carbon atoms;

R7 is selected from hydrogen, alkyl, hydroxyalkyl, carboxyalkyl of 1-6 carbon atoms, and polyoxyalkylene of 1-10 carbon atoms; R7 may be bonded to R8 to form a ring;

- R8 is an alkyl group having 1-20 carbon atoms;

R9 is hydrogen or an alkyl group having from 1 to 10 carbon atoms, optionally substituted with an oxygen-containing group or a nitrogen-containing group;

X is selected from O, S and NH;

Provided that at least one R1 group in the organosilicon polymer is a functional group according to formula (I) or a salt derivative thereof;

R2 may be the same or different and is selected from alkyl, aryl and alkenyl;

- R3 and R4, which may be the same or different, are selected from alkyl, aryl, capped or non-capped polyoxyalkylene, alkaryl, aralkylene and alkenyl;

- a is an integer from 0 to 50,000;

b is an integer from 0 to 100; And

- a + b is greater than 25.

In one embodiment,

- R2, R3 and R4 are independently selected from methyl and phenyl, more preferably methyl.

- R6 is an alkyl group having from 1 to 12 carbon atoms, preferably from 2 to 5 carbon atoms.

- R7 is hydrogen or an alkyl group having 1-4 carbons.

- R8 is an alkyl group having 2-10 carbon atoms.

- R9 is hydrogen or an alkyl group having 1-5 carbon atoms.

X is an oxygen atom.

- a + b is in the range of 100 - 300.

In one embodiment, the fluid is present from 0.01 to 10 wt%, based on the total amount of the coating composition. Most preferably, the fluid is present in the range of 2-7 wt%.

How to control the release rate of biocides

According to the invention, the ratio of the pawl release from the coating system, the coating is applied five days after biocide release rate (R ₅₎ and the coating is applied 30 days after the biocide release rate (R ₃₀₎ a, that is, R ₅ / R ₃₀ < / RTI > to < RTI ID = 0.0 > ≤ 1.5, < / RTI >

The method comprises:

a. Providing a substrate

b. Coating the first coating layer on the substrate,

c. Applying one or more subsequent coating layers over the first coating layer,

Wherein the first coating layer contains a biocidal agent and the subsequent coating layer (s) contains less biocidal agent than the first coating layer, and wherein the subsequent coating layer does not contain a biocide or substantially do not include.

In one embodiment, the inventive method can adjust the rate of release of the biocide from the fountain release coating system such that R ₅ / R ₃₀ is (≤) 1.33 or less, preferably (≤) 1.11 or less.

Suitably, the first coating layer and / or subsequent coating layer (s) comprise an elastomeric polymer. The elastomeric polymer is as described in the entire paragraphs above.

Suitably, the first coating layer and / or subsequent coating layer (s) comprise a polyorganosiloxane. The subsequent coating layer (s) are as described in the overall paragraphs above.

Suitably, the substrate is coated with a rust-inhibiting coating, and the first coating is used as a tie coat over the rust-inhibiting coating.

Suitably, the biocide in the first coating layer is an organic or metal-organic biocidal agent. Biocides are as described in the full paragraphs above.

Suitably, the biocide is one or more of any of the biocidal agents mentioned above and most suitably is a 2-trihalogenomethyl-3-halogeno-4 substituted at position 5 and optionally at position 1 -Cyanopyrrole derivatives or 1,4-dithian anthraquinone-2,3-dicarbonitrile.

Suitably, the subsequent coating layer (s) comprises a non-affinity fluid that is non-compatible with the subsequent coating layer (s), such as silicon, organic or inorganic molecules or polymers.

apply

The coating system according to the invention is brushing. Roller coating, dipping, or spraying (nonporous and conventional).

After the subsequent coating layer (s) is cured, it is immediately immersed and can provide immediate antifouling and fountain release protection. The obtained coating system has excellent antifouling and fountain release characteristics. This makes the coating system according to the invention very suitable for use in preventing fouling in marine and freshwater applications. Coating systems may be used in the manufacture of hulls, buoys, drilling platforms, oil production drilling rigs, floating production storage and offloading vessels (FPSOs), pipes, Can be used for both dynamic and static structures, such as cooling water withdrawal devices, fish nets, fish cages and other aquaculture devices and marine devices / structures. Coating systems can be applied to all substrates used in these structures, such as metals, e.g., steel, aluminum, concrete, wood, plastic or fiber-reinforced resins.

The coating system according to the invention is characterized by a ratio of release rate (R ₅ ) of biocide after 5 days of coating application to release rate (R ₃₀ ) of biocide from fountain release coating system after 30 days of coating application, That is, in addition to having a rate of release of the biocidal agent controlled from the fountain release coating system such that R ₅ / R ₃₀ is less than (≤) 1.5 (preferably ≤ 1.33), it does not include a biocide or fountain release coating (I) slime fouling, (ii) weed fouling, (iii) soft bodied fouling in aquatic vessels, And (iv) hard bodied fouling of hard tissue organisms.

The coating system can be applied directly to the untreated substrate. As another example, the coating system of the present invention can be applied to a substrate to which surface treatment or other coating layer has been previously applied. Examples of such coatings include anti-corrosive coatings, biocidal antifouling coatings, sealer coats, tie coats, adhesion promoting layers, and the like.

In applications for newbuilding on ships and boat hulls, the system will typically be applied directly onto a substrate having one or more rust-inhibiting coatings. Upon maintenance or repainting, the system may optionally be applied over an existing coating configuration (with an optional link coat), or after the existing coating configuration has been removed and one or more antifouling coatings have been applied again, .

The substrate to which fouling is to be inhibited is not particularly limited and includes any of steel, plastic, concrete, wood, fiber-reinforced resin and aluminum.

In a typical situation, in application to the hull of a boat and a boat, a first coating layer is applied to form a dry film thickness in the range of 100-200 microns, followed by the subsequent coating layer (s) Thereby forming a thickness. If the dry film thickness should be thicker, a desired film thickness can be formed by successively applying a dry film thickness of 100-200 [mu] m at a time. In the case of other substrates, a first coating layer is applied to form a dry film thickness in the range of 50-500 mu m and a subsequent coating layer (s) applied to form a dry film thickness in the range of 50-500 mu m.

The present invention will now be described with reference to the following embodiments. These embodiments are for the purpose of illustrating the invention and are not to be construed as limiting the scope in any way.

Examples

Examples 1-8

Eight coating systems (Examples 1-8) were prepared according to the present invention.

The biocide leakage rate of each coating system was measured through experiments. In short, a pair of panels coated with each coating system was immersed in a holding tank with synthetic seawater. These panels periodically moved to a vessel for measuring the leak rate of fresh synthetic sea water and gently shaken for a fixed period of time. At the end of this period, the panels were moved back to the holding tank and the amount of biocide leaking into the container was determined by chemical analysis. Measuring the amount of the leaked biocides, through the information about the period of immersion in the exposed surface area and for measuring the leak rate of the coated container panel, and can obtain the leak rate of the biocide, in ㎍ cm ^-2 d ^-1 .

Artificial seawater

Artificial seawater was prepared by mixing 33 g of salt per liter of deionized water using commercially available instant sea salt.

Panel preparation

A 15 x 10 cm polycarbonate panel was masked to have a defined surface area (typically about 100 cm ² ). A two pack epoxy rust-inhibiting paint (Intershield 300, International Paint) was applied through a draw down bar with a dry film thickness of 125 microns and then the biocide-containing coating layer was applied to the dry film thickness 100 Mu m. After drying, the final 'Finish' coat was applied to the film through a drawdown bar to a dry film thickness of 15 microns (in Example 5, applied with a dry film thickness of 100 microns). The masking tape was removed and the edges of the coated panel were brushed with a two-pack epoxy rust-preventive paint (Intershield 300, International Paint). Each coat was cured in the ambient atmosphere prior to application of the subsequent coating layer (s) and before immersion in the holding tank.

Holding tank

The panels were thoroughly soaked in 40 L of artificial seawater in a very clean glass tank and artificial seawater was continuously circulated through an activated charcoal filter to prevent build up of the biocide or its degradation products. The temperature of the holding tank was maintained at about 22-23 ° C. All panels were kept immersed in the holding tank during the entire run, except during the measurement of the leak rate performed using a leak rate measurement vessel on a predetermined measurement day.

Container for measuring leak rate

On a predetermined day of the measurement, the panels were placed in polypropylene containers (15 x 8 x 8 cm, l x w x h), each with a very clean lid, containing 100 ml of artificial seawater at about 22-23 ° C. These vessels were gently agitated for 2 hours using an orbital mixer, and then the panel was again placed in a holding tank.

Leak Rate Measurement - General

The concentration of the biocide in the container for the leak rate measurement can be measured using standard analytical methods known to those skilled in the art, for example, high performance liquid chromatography (HPLC). Then, using the concentration of the biocide in the container for measuring the leak rate, the leak rate R can be obtained by the following equation.

C is the equivalent concentration of the biocide in the container for measuring the leak rate, V is the volume (L) of artificial seawater in the container for measuring the leak rate, t is the volume (Hour), and A is the surface area of the panel exposed to the coating system (cm < ² >).

Leak Rate Measurement of Examples 1-8 - Tralopyril < RTI ID = 0.0 >

At the end of the agitation period, about 12 ml of artificial seawater was taken from each leak rate measuring vessel and placed in a glass vial. The vial was placed at 45 ° C overnight to allow the leaked tralopyryl to be quantitatively converted to 3-bromo-5- (4-chlorophenyl) -4-cyano-1H-pyrrole-3-carboxylic acid (BCCPCA) Respectively.

The BCCPCA concentration of the treated samples was determined using an acetonitrile, water and orthophosphoric acid mixture with a volume fraction of 50: 49.95: 0.05 as the mobile phase in an Agilent 1100 HPLC system equipped with a Pursuit UPS 2.4 占 퐉 C18 column (50 x 3 mm) By high performance liquid chromatography (HPLC).

A minimum of six standards covering a range of 10 - 500 μg L ^-1 were freshly prepared by appropriately diluting the BCCPCA stock solution in 1000 μg L ^-1 of the tetrahydrofuran with artificial seawater. The artificial seawater blanks were analyzed before and after the standard material and after each sample set. A check of the reference material was carried out after every 5 samples in order to examine the reproducibility of the analysis method. Every time the analysis method proved reproducible.

At the end of the stirring period, the equivalent concentration of tralopyryl in the vessel for measuring the leak rate is calculated by multiplying the BCCPCA measured concentration by the relative molar weight of tralopyril and BCCPCA, and then calculating the leak rate R of tralopyril according to the following equation do:

In the above equation, C _tralopyril is the equivalent concentration of _tralopyryl in the vessel for measuring the leak rate, V is the volume (L) of artificial seawater in the vessel for measuring the leak rate, t is the immersion of the panel in the vessel for measuring the leak rate Hour, and A is the surface area of the panel exposed to the coating system (cm ² ).

Table 3 shows R ₅ / R ₃₀ , the leak rate results obtained for 5 days (R ₅ ) and 30 days (R ₃₀ ) of the measurements. In each, the result is the average result of a pair of panels for each coating system.

As can be seen, each coating system represents a controlled release as defined in the framework of the present invention, and all of the coatings exhibit a biocide leak rate pattern in which the biocide leak rate is proportional to the time square root. In addition, by varying certain parameters of the subsequent coating layer, control over the biocide leak rate aspect can be practiced and can be reduced, increased, or essentially constant over time.

In addition, different biocide leak average rates can be obtained, and by making changes to specific parameters of the subsequent coating layer, biocide leak rates can be achieved at any given time, with higher or lower biocide leak rates being achieved .

Table 1: Formulation of first coating layer-Examples 1-8

material weight% Polydimethylsiloxane 13.8 Long-chain unsaturated polyaminoamides and high molecular weight acid esters of salt-based surfactants 0.6 Tralorphyl 13.6 Titanium dioxide 6.7 Dry silica 0.6 Methyl isoamyl ketone 18.6 Oxime-cured silicone mastics 37.2 Xylene 7.8 Chlorinated polyolefin 0.8 N-2-aminoethyl-3-aminopropyltrimethoxysilane 0.2 Dioctyl tin dilaurate 0.1

Table 2: Detailed formulation of the second coating layer (ingredients are expressed as volume% relative to the total volume of the composition)

Constituent Example One 2 3 4 5 6 7 8 Short-chain polydimethylsiloxane (viscosity 7.5 Stoke) 59.5 Silicone polyether block copolymer * 78.6 Polydimethylsiloxane (viscosity 35 Stoke) 65.6 59.5 59.5 59.5 59.5 Dry silica (hydrophobic) 1.5 1.8 1.5 1.5 1.5 1.5 Red iron oxide 13.2 Mica iron oxide 7.9 Disparson 6500 amide (commercially available) 2 Titanium dioxide 6.5 6.5 6.5 6.5 Carbon black 1.4 1.4 1.4 1.4 Xylene 18.4 20.5 18.4 18.4 23.6 18.4 Tetra-ethyl orthosilicate 2.7 3 2.7 2.7 2.7 2.7 Polymethylphenylsiloxane oil 5.2 5.7 5.2 5.2 5.2 2,4-pentanedione 4.3 3.9 4.7 4.3 4.3 4.3 4.3 Dioctyl tin dilaurate 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Intersleek 970 commercial product 100

* Example 12 of WO 2008/132236

Table 3: Leak rate results - Examples 1-8

Example The primary variable (s) Average leak rate
(Cm cm ^-2  d ^-One ) R ₅ / R ₃₀ R ₅ ¹⁾ R ₃₀ ²⁾ One Crosslink density 8.4 8.4 1.00 2 Subsequent coating layer (s) chemistry 5.6 7.0 0.80 3 Pigment presence 9.7 7.3 1.32 4 Hydrophobicity of pigments 10.7 8.5 1.25 5 The thickness of the subsequent coating layer (s) 9.0 7.0 1.28 6 Fluid type 9.0 11.0 0.81 7 Existence of fluid 9.6 8.4 1.14 8 Pigment form 9.3 10.1 0.92

¹⁾ : Release rate of biocide at 5 days after immersion

²⁾ : Release rate of biocide at 30 days after immersion

Examples 9-12

As shown in Table 4, the additional coating systems according to the present invention (Examples 9-12) were prepared (all examples) in comparison with commercial biocide-free fountain release coating systems.

Table 4: Formulation of first coating layer of Examples 9-12

material weight% Polydimethylsiloxane 12.80 Long-chain unsaturated polyaminoamides and high molecular weight acid esters of salt-based surfactants 0.55 Biocide 20.00 Methyl isoamyl ketone 23.91 Oxime-cured silicone mastics 34.56 Xylene 6.07 Chlorinated polyolefin 1.88 N-2-aminoethyl-3-aminopropyltrimethoxysilane 0.16 Dioctyl tin dilaurate 0.03

Example Biocide 9 Tralopyril 10 Dithianon 11 Copper pyrithione (CPT) 12 Zinc pyrithione (ZPT)

A test panel was prepared to measure the ability of each coating system to control leakage of biocides from the first coating layer and inhibit fouling. The coating systems of Examples 9-12 were applied by rollers to a 60 x 60 cm marine plywood panel to form a first coating layer and a subsequent coating layer, respectively, at a dry film thickness of about 100 and 150 [mu] m. The board was pre-soaked with a one-coat, two pack epoxy rust-preventive paint (Intershield 300, International Paint), and the DFT per coat was about 125 μm. Half (left side) of each panel was coated with one coating system of Examples 9-12, and the other half (right side) of the panel as a control was coated with a commercial fountain release tie coat (Intersleek 737, International Paint). Then, a standard foul release finish coat (Intersleek 757, International paint) was applied to both sides. Prior to application of the subsequent coating layer (s) and prior to the start of the test, each coat was fully cured in the ambient atmosphere.

The test panels were simultaneously immersed in natural tropical marine water at depths of 0.5 - 1.0 m in the Singapore window, where fouling proliferation is known to be a serious problem. The panels were periodically taken out of the water, photographed, and evaluated for fouling proliferation on the coating system prior to panel re-immersion.

The coating system containing tralopyril (Example 9) and the coating system containing dithianone (Example 10) remained substantially free of fouling even after immersion for 8 months. Coating systems containing copper pyrithione (Example 11) and zinc pyrithione (Example 12) showed more severe foul ring growth after 8 months than Examples 9 and 10, The proliferation severity was less.

In all cases, the coating systems of Examples 9-12 did not have blisters and cracks when immersed for 8 months.

These results clearly show that the long term fouling inhibiting power of the coating system according to the present invention is significantly improved over the standard commercial fountain release coating system.

Claims (11)

A structure coated with a biocidal foul release coating system,
The structure,
a. Providing a substrate,
b. Coating the first coating layer on the substrate,
c. Applying one or more subsequent coating layers over the first coating layer,
Wherein the first coating layer is formed from a coating composition comprising a biocide,
The subsequent coating layer (s) are formed from the coating composition (s) that contain little or no biocides, or do not substantially contain biocides, than the coating composition that forms the first coating layer,
Wherein the first coating and the subsequent coating layer (s) form a biocidal fountain release coating system,
Wherein the first coating layer and / or the subsequent coating layer (s) comprises a polyorganosiloxane. The method according to claim 1,
Wherein the pawl release after the coating application of the coating system biocide release rate of the day 5 (R ₅₎ and the coating ratio, R ₅ / R ₃₀ of the 30 day biocide release rate (R ₃₀₎ of the then applied to 1.5 or less Characterized by. 3. The method of claim 2,
The ratio R ₅ / R ₃₀ is the structure, characterized in that not more than 1.33. 4. The method according to any one of claims 1 to 3,
Wherein the first coating layer and / or the subsequent coating layer (s) comprises an elastomeric polymer. 4. The method according to any one of claims 1 to 3,
The substrate is coated with an anticorrosion coating,
Wherein the first coating layer is used as a tie coat on the rust-inhibitive coating. 4. The method according to any one of claims 1 to 3,
Wherein the biocide in the first coating layer is an organic biocide or a metal-organic biocide. 4. The method according to any one of claims 1 to 3,
Wherein the biocide is selected from the group consisting of 2-trihalogenomethyl-3-halogeno-4-cyanopyrrole or 1,4-dithianthraquinone-2,3-dicarbonyl Tril. ≪ / RTI > 4. The method according to any one of claims 1 to 3,
Wherein the subsequent coating layer (s) comprises an incompatible fluid. 4. The method according to any one of claims 1 to 3,
Wherein said substrate is selected from the group consisting of marine structures, aquaculture structures, ship hulls, boat hulls, buoys, drilling platforms, oil production drilling rigs, floating production storage and offloading vessels (FPSO) Characterized in that it is a water intake, a fish net or a fish cage. CLAIMS 1. A method of regulating the rate of release of biocidal agents from a fountain release coating system,
R ₅ / R ₃₀ of the release rate (R ₅ ) of the biocide at 5 days after coating application and the release rate (R ₃₀ ) of biocide at 30 days after coating application of the foul release coating system is 1.5 or less ,
The method comprises:
a. Providing a substrate,
b. Coating the first coating layer on the substrate,
c. Applying one or more subsequent coating layers over the first coating layer,
Wherein the first coating layer is formed from a coating composition comprising a biocide,
The subsequent coating layer (s) may be formed from a coating composition (s) that contains little or no biocides, or that does not substantially contain biocides, than the coating composition that forms the first coating layer ≪ / RTI > delete