JP5993451B2 - Biocidal fouling removal coating system - Google Patents

Description

  The present invention relates to the use of a fouling removal coating to control biocide leaching from a coating system comprising a fouling removal coating and a biocidal underlayer coating. The invention further relates to such a coating system, its use for preventing fouling on a substrate, and a substrate coated with the coating system.

  Man-made marine structures that are immersed in water, such as ships and boat hulls, buoys, drilling bases, dry dock equipment, oil-producing rigs and pipes are fouled by aquatic organisms such as green and brown algae, barnacles, mussels Tend to. Such structures are generally made of metal, but may include other structural materials such as concrete. This fouling is annoying for the hull of the boat. This is because, due to fouling, the frictional resistance due to water increases during movement, resulting in a decrease in speed and an increase in fuel costs. Fouling is annoying for static structures such as drilling bases and oil production rig legs. First, the resistance of a thick layer of fouling to waves and flows can cause unexpected and potentially dangerous stresses in the structure, and second, fouling can cause defects such as stress cracks and This is to make it difficult to investigate the structure for corrosion. Fouling is annoying for pipes such as cooling water intakes and discharges. This is because the effective cross-sectional area decreases due to fouling, and as a result, the flow velocity decreases.

  Fouling has traditionally been prevented by antifouling paints containing biocides. This biocide is gradually leached from the paint. The most commercially successful antifouling method involves the use of antifouling coatings containing materials that are toxic to aquatic animals, such as triorganotin compounds. However, such coatings are increasingly being repelled due to the detrimental effects that some such toxins can have when released into the aquatic environment under certain circumstances. It is.

  For many years, certain coatings such as elastomers such as silicones, for example as disclosed in British Patent 1,307,001 and US Pat. No. 3,702,778. It is known that rubber is resistant to fouling by aquatic organisms. Such coatings are believed to be non-biocidal and generally hydrophobic, providing a surface that physically prevents colonization and / or a surface to which the organism cannot be easily attached. For this reason, the coating can be said to be an antifouling coating rather than an antifouling coating. The decontamination property can be characterized by barnacle adhesion measurements, such as ASTM D5618-94. By this method, barnacle adhesion values of the following: silicone 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) are obtained. (JC Lewthwaite, AF Molland and KW Thomas, “An Investigation into the variation of ship skin fictional resistance with fouling”, Trans. RINA, Vol. 127, pp. 269-284, London (1984)) Literature 1)). As an indicator when a coating is considered for decontamination, the decontamination coating typically has an average barnacle adhesion value of less than 0.4 MPa.

  Silicone rubbers and silicone compounds are generally very low toxic. The disadvantage of this decontamination system is that, when applied to the hull of a boat, the accumulation of fouling organisms is reduced, but a relatively high boat speed is required to remove all fouling species. is there. For this reason, in some instances it has been shown that it is necessary to navigate at a speed of at least 10 knots in order to sufficiently remove fouling from a hull treated with such a coating. For this reason, silicone rubber has so far obtained only limited commercial success.

  It has long been known that the adhesion of a silicone antifouling coating to an anticorrosion coating is generally poor if a suitable tie coat or link coat is used and sufficient adhesion is not ensured. Such tie coats often include silicone. Examples of silicone-containing tie coats are described in European Patent No. 521983 (Patent Document 3) and European Patent No. 1832630 (Patent Document 4).

  A combination of a suitable tie coat and second coating layer may be referred to as a “double” fouling removal system. To date, the compositions described in the prior art for use as tie coats in such duplex systems generally do not contain added biocides. WO 2008/013825 clearly teaches avoiding the use of biocides as part of these systems.

  British Patent No. 1409048 discloses a marine polyurethane topcoat composition that can be applied over a biocidal antifouling coating and that can absorb 30 to 300% of its own weight of seawater. Yes. The polyurethane topcoat of GB 1409048 is not a fouling removal coating within the context of the present invention (see: “Redefining antifouling coatings”, Journal of Protective Coatings and Linings, September 1999, pages 26-35). 2) The same document discloses that polyurethane has extremely high barnacle adhesion strength compared to silicone). The subsequent antifouling coating layer is not disclosed or suggested in British Patent No. 1409048.

  European Patent No. 0313233 (Patent Document 7) includes a primary layer of an antifouling and anticorrosive marine paint containing a toxic substance against marine organisms, and a second layer of a porous organic polymer film adhered to the primary layer. Antifouling marine coatings are described. The porous organic polymer film is preferably polytetrafluoroethylene (EPTFE). A porous organic polymer film is not a coating in the context of the present invention because it is applied as a liquid mixture and then dried or cured to form a dry, continuous film. Furthermore, polytetrafluoroethylene is an unsuitable material for use as a decontamination surface (see: “Redefining antifouling coatings” above, which shows high barnacle adhesion strength). The subsequent use of the antifouling coating layer is neither disclosed nor suggested in EP 0313233.

  U.S. Pat. No. 4,129,610 describes a water-soluble coating composition for ship bottoms comprising a vinyl copolymer and a water-soluble epoxy compound. The water-soluble coating composition is applied on a primer coating layer having a toxic substance. The water-soluble coating composition of US Pat. No. 4,129,610 is not considered an antifouling coating within the context of the present invention (see: “Redefining antifouling coatings”, supra, in which the epoxy coating barnacles It has been reported that the adhesion strength is extremely high.) There is no disclosure or suggestion of the use of a secondary fouling removal coating layer.

  French Patent No. 2636958 (Patent Document 9) describes a chlorinated adhesion primer for silicone elastomer. Based on this publication, triorganotin oxide or halide biocide or copper oxide may be added to the primer. Tributyltin oxide or fluoride and copper oxide are mentioned only as suitable biocide additives for such systems and there is no illustration or further description of a primer containing any biocide. This document makes no mention of biocide leaching and there is no possible teaching on a decontamination system with a primer containing any biocide.

  WO 95/32862 discloses a double fouling removal system that can be used on a substrate to combat fouling by marine organisms. The duplex system comprises a tie layer and a release layer, and 3-isothiazolone biocide is embedded in either the tie layer or the release layer. The literature shows that 3-isothiazolone should be used as a biocide, and that the leaching rate of biocide from the tie layer is inversely proportional to the square root of time, other than the biocide solubility in water. There is an exclusive teaching that there is no other factor to control the leaching rate. Therefore, the biocide leaching is hardly controlled in such a system and is not suitable as a biocidal fouling removal coating system with a controlled biocide leaching rate within the framework of the present invention. Immediately after immersion of the substrate in seawater, the substrate coated with a system such as that disclosed in WO 95/32862, wherein the biocide leaching rate from the tie layer is inversely proportional to the square root of time, It has been found that it remains substantially free of fouling and exhibits superior performance compared to a substrate coated with a fouling removal coating system that does not contain biocides. However, the superior performance is not sustained and the coated substrate is gradually covered with biofouling, and within 4-6 months, the system of WO 95/32862 contains a biocide. Exhibits as severe fouling as a substrate coated with a nonfouling removal coating system.

British Patent 1,307,001 US Pat. No. 3,702,778 European Patent No. 521983 EP 1832630 International Publication No. 2008/013825 British Patent No. 1409048 European Patent No. 0313233 US Pat. No. 4,129,610 French Patent Invention No. 2636958 Specification International Publication No. 95/32862

J.C. Lewthwaite, A.F. Molland and K. W. Thomas, `` An Investigation into the variation of ship skin fictional resistance with fouling '', Trans. R.I.N.A., Vol. 127, pp. 269-284, London (1984) `` Redefining antifouling coatings '', Journal of Protective Coatings and Linings, September 1999, pages 26-35

  Surprisingly, it has been found that structures coated with a biocidal fouling removal coating system exhibiting controlled leaching of biocides can be produced.

In accordance with the present invention, such a structure is
a. Providing a substrate,
b. Coating the substrate with a primary coating layer; and c. The primary coating layer may be obtained by applying at least one secondary coating layer on the top surface, wherein the primary coating layer and the secondary coating layer form a biocidal fouling removal coating system, The layer comprises biocides, the secondary coating layer has less biocides than the primary coating layer, and the secondary coating layer is free or substantially free of biocides.

  The biocidal fouling removal coating system as defined in this application exhibits biocide controlled leaching.

The controlled leaching of the biocide is indicated by the biocide release rate (R ₅ ) from the fouling removal coating system of the present invention 5 days after application of the coating and 30 days after application of the coating. The ratio R ₅ / R ₃₀ to the biocide release rate (R ₃₀ ) is 1.5 or less (≦ 1.5), preferably ≦ 1.33, more preferably ≦ 1.11. means.

  The biocidal fouling removal coating system of the present invention exhibits excellent fouling resistance both short and long after the substrate is immersed in seawater.

  Within the framework of the present invention, the biocidal fouling removal coating system physically prevents settlement and / or has a surface to which aquatic / marine organisms cannot easily attach and the biocide is from the coating system. The coating system to be released.

  A tie coat or adhesion promoting layer may be present between the substrate and the first coating layer to improve the adhesion of the first primary coating layer to the substrate. In order to improve the corrosion resistance of the substrate, there may be an anti-corrosion coating applied on the substrate before the primary coating layer is applied. More generally, one or more layers may be present on the substrate before the primary coating layer comprising the biocide is applied to the substrate.

  To prepare the coating layer, the coating composition is applied as a liquid mixture to the surface (eg, a substrate or another coating layer). The coating composition is then dried or cured to form a dry continuous coating film / layer on the surface.

  We realize that the leaching rate of biocides from a biocidal fouling removal coating system can be controlled by applying one or more secondary coating layers on top of the primary coating layer. did. Here, the primary coating layer includes biocide, and the secondary coating layer has less biocide than the primary coating layer, and does not include or substantially does not include biocide. The advantage of this is that the biocide leaching rate can be adjusted, the dependence on time can be reduced, and in fact a more linear correlation with time can be maintained. Thus, a desired more constant rate of biocide leaching can be achieved. This is advantageous to provide extended performance life, more efficient use of the biocide, and reduced environmental impact. Furthermore, biocide leaching can be controlled such that the ability of the antifouling coating system to prevent fouling under slow or stationary conditions is particularly improved.

  In the context of the present invention, biocide leaching (sometimes known as biocide release) and biocide leaching rate (biocide release rate) should be clearly distinguished from fouling removal. The leaching rate is the rate at which the biocide is released into the surrounding water by the coating system, and is typically expressed as the amount of biocide per unit area, unit time. Fouling removal relates to the prevention of fouling and / or the ease of removal by non-biocidal means from the surface of a soaked substrate. For example, the defouling properties can be characterized by a barnacle adhesion measurement, which can be performed using ASTM D5618-94, which is a standard test method or related method for measuring barnacle adhesion strength in shear. . Both complement the mechanisms to control fouling but are independent of each other.

  More specifically, the inventors have realized that the leaching rate can be controlled by changing the composition of the secondary coating layer. The primary coating layer behaves as a biocide reservoir that contains an immediate supply of biocide to be released. The leaching rate of the biocide can be controlled by changing certain properties of the primary and secondary coating layers. These properties include, but are not limited to, pigment volume concentration, crosslink density, pigment size and shape, polymer molecular weight, presence and amount of incompatible fluid, crosslink chemical properties and film thickness of the secondary coating layer. can give.

  The biocide reservoir combined with a secondary coating layer control mechanism can adjust the biocide leaching rate for the final application.

Within the framework of the present invention, a coating system showing controlled release of biocide has a biocide release rate (R ₃₀ ) of 30 days after immersion in water and a release rate (R ₃₀ ) of 5 days after immersion in water. ₅ ) which is at least 67% of the system. That is, the coating system showing biocide controlled leaching is a system in which R ₅ / R ₃₀ is 1.5 or less.

In one embodiment of the invention, R ₅ / R ₃₀ is 1.5 or less. In a further embodiment of the invention R ₅ / R ₃₀ is 1.33 or less. In yet a further embodiment of the invention, R ₅ / R ₃₀ is 1.11 or less.

In WO 95/32862, a double decontamination system has a biocide leaching rate from the tie layer that is inversely proportional to the square root of time, and potential other than biocide solubility in water. Describes that there are no other factors controlling the leaching rate. In this system, the release rate of the biocide is described as ^{F (t) ~36 / t 0.5} , F is the leaching rate of [mu] g / cm ² / day (μgcm ^-2 days ^-1), t is the time of day. For this system, R ₅ / R ₃₀ = F (5) / F (30) = 30 ^0.5 / 5 ^0.5 = 2.45. WO 95/32862 discloses a biocidal fouling removal coating in which the substrate is first coated with a coating layer comprising biocides and then overcoated with a secondary layer substantially free of biocides. It is not taught that the system will provide a more gradual and more sustained release profile of the biocide from the antifouling coating surface.

  According to the present invention, the secondary coating layer applied to the upper surface of the primary coating layer has fewer biocides than the primary coating layer. Furthermore, the secondary coating layer is free or substantially free of biocide. Substantially free of biocides means that the secondary coating layer contains less than 1.0 wt% biocides (based on the total weight of the coating composition). Preferably, the secondary coating layer comprises less than 0.5 wt% biocide, more preferably less than 0.1 wt%. For the avoidance of doubt, weight percent (wt%) is weight percent based on the total weight of the coating composition.

  In one embodiment, the secondary coating layer further comprises an incompatible fluid.

  The incompatible fluid in the secondary coating layer helps to achieve improved fouling removal performance. Without being bound by theory, it is believed that the fluid may have an impact on the transport of the biocide.

  In further embodiments, the biocide is encapsulated, adsorbed or supported or bound, either partially or wholly.

  The biocide encapsulation, adsorption, support or binding may provide a second mechanism for biocide leaching from the coating system to achieve even more gradual release and longer lasting effects.

The present invention relates to (i) a biocidal fouling removal coating system and (ii) a structure coated with the biocidal fouling removal coating system, wherein the biocidal fouling removal coating system comprises:
a. Base material,
b. Primary coating layer,
c. Including at least one secondary coating layer on an upper surface of the primary coating layer;
The primary coating layer includes biocide, the secondary coating layer includes less biocide than the primary coating layer, and the secondary coating layer does not include or substantially includes biocide. Absent. The biocidal fouling removal coating system exhibits controlled leaching of the biocide.

  One embodiment of the present invention is a structure coated with a biocidal fouling removal coating system as defined above.

Primary Coating Layer Containing Biocide The composition of the primary coating layer is not particularly limited, but preferably, the composition of the primary coating layer includes a polymer. The polymer preferably forms an elastomer. More preferably it is a polyorganosiloxane. Even more preferably, this is polydimethylsiloxane. Furthermore, the polyorganosiloxane may comprise two or more different viscosity polyorganosiloxanes.

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

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

  Preferably, the polymer is crosslinkable. Depending on the type of crosslinkable polymer, the coating composition may require a crosslinker. The need for the presence of a cross-linking agent depends on the type and number of functional groups present in the polymer. If the polymer contains alkoxy-silyl groups, generally a small amount of water and optionally the presence of a condensation catalyst is sufficient to achieve complete curing of the coating after application. For these compositions, atmospheric moisture is generally sufficient to induce curing, and usually it is not necessary to heat the coating composition after application.

  The present crosslinker optionally present may be a functional silane and / or a crosslinker comprising one or more of any acetoxy, alkoxy, amide, alkenoxy and oxime groups. Such crosslinking agents are shown, for example, in International Publication No. 99/33927, page 19, line 9 to page 21, line 17. Mixtures of different crosslinkers can also be used.

  Preferably, the crosslinker is present in an amount of 0.1% to 20 wt%, based on the total weight of the coating composition.

  The primary coating layer includes biocide. “Contains / containing” means that the biocide is present in the body of the coating layer (meaning that the biocide is mixed into the coating composition prior to curing / drying).

  The biocide of the present invention can be one or more inorganic, organometallic, metal-organic or organic biocides for marine or freshwater organisms. Inorganic biocides include, for example, copper salts such as copper oxide, copper thiocyanate, copper powder, copper carbonate, copper chloride, copper nickel alloys, and silver salts such as silver chloride or nitrate. Can be given. Organic metal and metal-organic biocides include pyrithione zinc (zinc salt of 2-pyridinethiol-1-oxide), pyrithione copper, bis (N-cyclohexyl-diazeniumdioxy) copper, ethylene-bis (dithiocarbamine) ) Zinc (ie, dinebu), zinc dimethyldithiocarbamate (ziram), and ethylene-bis (dithiocarbamate) manganese (ie, manzeb) complexed with a zinc salt. Organic biocides include formaldehyde, dodecylguanidine hydrochloride, thiabendazole, N-trihalomethylthiophthalimide, trihalomethylthiosulfamide, N-arylmaleimide, such as N- (2,4,6-trichlorophenyl) maleimide, 3- (3,4-dichlorophenyl) -1,1-dimethylurea (diuron), 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 2-methylthio-4-butylamino-6-cyclopropyl Amino (cyclopopylamine) -s-triazine, 3-benzo [b] thien-yl-5,6-dihydro-1,4,2-oxathiazine 4-oxide, 4,5-dichloro-2- (n-octyl)- 3 (2H) -isothiazolone, 2,4,5,6-tetrachloroisophthalonitrile, Rilfluanide, diclofluuride, diiodomethyl-p-tosylsulfone, capsaicin, N-cyclopropyl-N ′-(1,1-dimethylethyl) -6- (methylthio) -1,3,5-triazine-2,4- Diamine, 3-iodo-2-propynylbutylcarbamate, medetomidine, 1,4-dithiaanthraquinone-2,3-dicarbonitrile (dithianon), borane, such as pyridine triphenylborane, 5-position and optionally 1 Substituted 2-trihalogenomethyl-3-halogeno-4-cyanopyrrole derivatives such as 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (tralopyryl), and , Furanones such as 3-butyl-5- (dibromomethylidene) -2 (5H) -fur Ranones, and mixtures thereof, macrocyclic lactones such as avermectins such as avermectin B1, ivermectin, doramectin, abamectin, amectin and selamectin and quaternary ammonium salts such as didecyldimethylammonium chloride and alkyldimethylbenzylammonium chloride Things are given. In one embodiment, the biocide may be 3-isothiazolone. However, it has been found in the present invention that this biocide should preferably be in an encapsulated, adsorbed or bound form. In another embodiment, the biocide is not 3-isothiazolone.

  Preferably, the biocide is organic or metal-organic. Without being bound by theory, it is believed that biocide leaching is related to the physical diffusion of the biocide by a passive transport process from the primary coating layer through the secondary coating layer. Thus, biocide flow from the coating system will be controlled, in part, by biocide diffusion through the secondary coating layer and compatibility with the secondary coating layer. As expected for organometallic biocides, such as organotin, if diffusion or compatibility is inherently high, the resulting leaching rate is inherently high and difficult to control, reducing the life of the coating and undesirable Environmental impact may occur. As expected for inorganic biocides, such as the inorganic salt of copper, if the diffusion or compatibility is essentially low, the leaching rate is also inherently low and fouling may occur. In general, when using organic or metallic organic biocides, the use of the coating system of the present invention makes it possible to properly control the leaching rate and prevent unacceptable environmental damage. It becomes possible.

  In the context of the present invention, an inorganic biocide is a biocide that contains metal atoms and no carbon atoms in its chemical structure. An organometallic biocide is a biocide that contains metal atoms, carbon atoms and metal-carbon bonds in its chemical structure. The metal-organic biocide is a biocide that contains a metal atom and a carbon atom in its chemical structure and does not contain a metal-carbon bond. An organic biocide is a biocide that contains carbon atoms in its chemical structure and no metal atoms.

  Preferably, for superior antifouling properties, the biocide is one or more 2-trihalogenomethyl-3-halogeno-4-cyanopyrrole derivatives substituted at the 5-position and optionally at the 1-position, For example, tralopyryl, 1,4-dithiaanthraquinone-2,3-carbonitrile (dithianon), pyrithione copper, pyrithione zinc, tolyl fluoride, dichlorofuranide and N-cyclopropyl-N ′-(1,1-dimethyl) Ethyl) -6- (methylthio) -1,3,5-triazine-2,4-diamine.

  Preferably, the biocide is in the primary coating layer composition 0.05 to 50 wt%, more preferably 3 to 30 wt%, most preferably 10 to 20 wt% based on the total weight in the composition of the primary coating layer. Present in the amount of. In any case, the amount of biocide present in the primary coating layer must be greater than the amount of biocide in at least one secondary coating layer when the coating layer is applied to the substrate. .

  Furthermore, the biocide may optionally be wholly, partially or encapsulated, adsorbed or supported or bound. Certain biocides are difficult or dangerous to handle and are advantageously used in capsule-filled or adsorbed or supported or bound form. Furthermore, the capsule filling, adsorption or support or binding of the biocide provides a second mechanism for controlling the biocide leaching rate from the coating system to achieve even more gradual release and long lasting effects. obtain.

  The method of encapsulating, adsorbing or supporting or binding the biocide is not particularly limited with respect to the present invention. Encapsulated biocides for use in the present invention can be prepared, for example, as described in European Patent No. 1791424, with amino-formaldehyde or hydrolyzed monolayer and double-layer walls Examples include polyvinyl acetate-phenol resin capsules or microcapsules. Suitable encapsulated biocides are, for example, encapsulated 4,5-dichloro-2- (n-octyl) -3 (2H, commercially available from Dow Microbiological Control as Sea-Nine CR2 marine antifouling agent. ) -Isothiazolone.

  Methods by which an adsorbed or supported or bound biocide can be prepared include, for example, host-guest complexes, such as chelates described in EP 0709358, phenolic resins described in EP 0880892, carbon-based absorption The use of agents such as those described in EP 1142477 or inorganic microporous carriers such as amorphous silica, amorphous alumina, pseudoboehmite or zeolites described in EP 1115282 may be mentioned.

  The polymer of the biocidal primary coating layer composition is crosslinkable. The composition optionally includes a catalyst. Suitable catalysts are, for example, carboxylates of various metals such as tin, zinc, iron, lead, barium and zirconium. Said salts are preferably salts of long-chain carboxylic acids, such as dibutyltin dilaurate, dibutyltin dioctoate, iron stearate, tin (II) octoate and lead octoate. Further examples of suitable catalysts include organobismuth and organotitanium compounds, and organophosphoric acids such as bis (2-ethyl-hexyl) hydrogen phosphate. Other possible catalysts include chelates such as dibutyltin acetoacetonate. Furthermore, the catalyst is a halogenation having at least one halogen substituent on the carbon atom in the α-position to the acid group and / or at least one halogen substituent on the carbon atom in the β-position to the acid group. Organic acids or hydrolyzable derivatives may be included to form such acids under the conditions of the condensation reaction.

  Alternatively, the catalysts may include International Publication Nos. WO 2008/223325, JP 2008055855, JP 2009106717, 2009106718, 2009106719, 2009106720, 20091067221, 2009106722, 2009106723. No. 2009106724, No. 2009103894, No. 20090091307, No. 2009009184, No. 2009009185, No. 200956608, and No. 200956609.

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

  Preferably, the biocidal primary coating layer composition according to the present invention also comprises one or more fillers, pigments, further catalysts and / or solvents. Suitable fillers are, for example, barium sulfate, calcium sulfate, calcium carbonate, silica or silicates (eg talc, feldspar and kaolin), aluminum paste / flakes, bentonite or other clays. Some fillers, such as fumed silica, may have a thixotropic effect in the coating composition. The proportion of the filler may range from 0 to 25 wt% based on the total weight of the coating composition. Preferably, the clay is present in an amount of 0 to 1 wt%, preferably the thixotropic agent is present in an amount of 0 to 5 wt% based on the total weight of the coating composition.

  Suitable pigments include, for example, iron black, red pepper, iron yellow, titanium dioxide, zinc oxide, carbon black, graphite, molybdenum red, bismuth vanadate yellow, molybdenum yellow, zinc sulfide, antimony oxide, cobalt / zinc titanium oxide green, Zinc / tin titanate orange, lanthanide sulfide orange and red, manganese pyrophosphate purple, sodium aluminum sulfonate, quinacridone, phthalocyanine blue, phthalocyanine green, iron black, indanthrone blue, cobalt aluminum oxide, carbazole dioxazine, chromium oxide ( III), isoindoline orange, bis-acetoaceto-tridiol, benzimidazolone, quinaphthalone yellow, isoindoline yellow, tetrachloroisoindolinone and quinophthalone yellow. The pigment proportion may range from 0 to 10 wt% based on the total weight of the coating composition. Suitable solvents include aromatic hydrocarbons, alcohols, ketones, esters and mixtures of the above, or aliphatic hydrocarbons. Preferred solvents include methyl isoamyl ketone and / or xylene. Preferably, the solvent is present in an amount of 10 to 40 wt% based on the total weight of the composition.

The composition optionally includes an adhesion promoting material, typically in an amount of 0.01-0.5 wt%, based on the total weight of the composition. Suitable adhesion promoters include, for example, silanes such as amino silanes, epoxy silanes, methacryloyloxypropyl silanes and mercapto silanes.
Preferably, the adhesion promoter is
^{_{(RO) x R 3-x}} SiR 1 N (R 2) 2
This type of aminosilane.

In the aminosilane, each R is independently C1-8 alkyl (eg, methyl, ethyl, hexyl, octyl, etc.), C1-4 alkyl, O, C2-4 alkyl; aryl (eg, phenyl) and aryl C1— Selected from 4 alkyl (eg, 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 or aryl groups or (CH ₂ ) _2-4- NH ₂ .

Alternatively, the adhesion promoter is
(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
These are “bipodal” silanes described in WO2010018164.
In said “bipodal” silane, R ¹ , R ² and R ⁵ are independently a C1-C5 alkylene group, and R ³ and R ⁴ are independently selected from methyl or ethyl .

Alternatively, the adhesion promoter is
A-Si (R) _a (OR) _(3-a)
Types of epoxy silanes.
In the epoxy silane, A is an epoxide substituted with a monovalent hydrocarbon group having 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; selected from aryl (eg phenyl) and aryl C1-4 alkyl (eg benzyl); a is 0 or 1 is there.
The group A in the epoxy silane is preferably a glycidoxy-substituted alkyl group, for example 3-glycidoxypropyl. Examples of the epoxy silane include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldiethoxymethoxysilane, 2-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxy-4-methylcyclohexyl) -ethyltrimethoxysilane, 5,6-epoxy-hexyltrimethoxysilane; or oligomers thereof.

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

Secondary Coating Layer, Fouling Removal Layer The composition of the secondary coating layer is not particularly limited, but the composition preferably contains a polymer. Preferably, the polymer forms an elastomer. More preferably it is a polyorganosiloxane. Even more preferably, this is polydimethylsiloxane. Furthermore, the polyorganosiloxane may comprise two or more different viscosity polyorganosiloxanes.

  Said polyorganosiloxane has one or more, preferably two or more reactive functional groups, for example hydroxyl, alkoxy, acetoxy, carboxyl, hydrosilyl, amine, epoxy, vinyl or oxime functional groups.

  Alternatively, the polymer may be as described in WO2000081196. The polymer is a polyorganosiloxane polyoxyalkylene block copolymer of formula PS- (A-PO-A-PS) n. In the formula, PS represents a polyorganosiloxane block, PO represents a polyoxyalkylene block, A represents a divalent moiety, and n has a value of 1 or 2 or more.

  The polymer may optionally be cross-linked with another organosilicone crosslinker comprising two or more groups Y reactive with the group X, the presence or absence of a catalyst (as defined herein above). Below, there are two or three reactive groups X on the polyorganosiloxane block per molecule that can self-condense and crosslink.

  Preferably, the polyorganosiloxane polymer is present in an amount of 30 to 90 wt%, based on the total weight of the coating composition.

  Preferably, the polymer is crosslinkable. Depending on the type of crosslinkable polymer, the coating composition may require a crosslinker. The presence of the cross-linking agent is only necessary if the curable polymer cannot be cured by condensation. This will depend on the type and number of functional groups present in the polymer. If the polymer contains alkoxy-silyl groups, a small amount of water and optionally the presence of a condensation catalyst is generally sufficient to achieve complete curing of the coating after application. For these compositions, atmospheric moisture is generally sufficient to induce curing and generally it will not be necessary to heat the coating composition after application.

  The optionally present crosslinker can be a functional silane and / or a crosslinker comprising one or more optional acetoxy, alkoxy, amide, alkenoxy and oxime groups. Such crosslinking agents are shown, for example, in International Publication No. 99/33927, page 19, line 9 to page 21, line 17. Mixtures of different crosslinkers can also be used.

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

  When the polymer of the secondary coating layer composition is crosslinkable, the composition may optionally include a catalyst. Suitable catalysts are, for example, carboxylates of various metals such as tin, zinc, iron, lead, barium and zirconium. Said salts are preferably salts of long-chain carboxylic acids such as dibutyltin dilaurate, dibutyltin dioctoate, iron stearate, tin (II) octoate and lead octoate. Further examples of suitable catalysts include organobismuth and organotitanium compounds, and organophosphates such as hydrogen bis (2-ethyl-hexyl) phosphate. Other possible catalysts include chelates such as dibutyltin acetoacetonate. Further, the catalyst has at least one halogen substituent at the [alpha] -position relative to the acid group, and / or at least at the carbon atom [beta] -position relative to the acid group. Halogenated organic acids having one halogen substituent or hydrolyzable derivatives may be included to form such acids under the conditions of the condensation reaction.

  Alternatively, the catalysts may include International Publication Nos. WO 2008/223325, JP 2008055855, JP 2009106717, 2009106718, 2009106719, 2009106720, 20091067221, 2009106722, 2009106723. No. 2009106724, No. 2009103894, No. 20090091307, No. 2009009184, No. 2009009185, No. 200956608, and No. 200956609.

Preferably, the catalyst is present in an amount of 0.05 to 4 wt%, based on the total weight of the coating composition.
Preferably, the secondary coating layer composition of the present invention also includes one or more fillers, pigments, catalysts and / or solvents. Suitable fillers are, for example, barium sulfate, calcium sulfate, calcium carbonate, silica or silicates (eg talc, feldspar and kaolin), aluminum paste / flakes, bentonite or other clays. Some fillers, such as fumed silica, may have a thixotropic effect in the coating composition. The proportion of the filler may range from 0 to 25 wt% based on the total weight of the coating composition. Preferably, the clay is present in an amount of 0 to 1 wt%, preferably the thixotropic agent is present in an amount of 0 to 5 wt%, based on the total weight of the coating composition.

  Suitable pigments are, for example, iron black, brown, iron yellow, titanium dioxide, zinc oxide, carbon black, graphite, molybdenum red, molybdenum yellow, zinc sulfide, antimony oxide, sodium aluminum sulfonate, quinacridone, phthalocyanine blue, phthalocyanine green , Iron black, indanthrone blue, cobalt aluminum oxide, carbazole dioxazine, chromium oxide, isoindoline orange, bis-acetoaceto-tridiol, benzimidazolone, quinaphthalone yellow, isoindoline yellow, tetrachloroisoindolinone and quinophthalone yellow is there. The pigment ratio may range from 0 to 25 wt% based on the total weight of the coating composition. Suitable solvents include aromatic hydrocarbons, alcohols, ketones, esters and mixtures of the above, or aliphatic hydrocarbons. Preferred solvents include methyl isoamyl ketone and / or xylene. Preferably, the solvent is present in an amount of 0 to 40 wt%, based on the total weight of the composition.

  The fouling removal properties of the coating system in the present invention are generally improved when the secondary coating layer composition generally forms a hydrophobic or amphiphilic fouling removal coat when dried or cured. . The majority of the secondary coating layer and the hydrophobicity of the surface can be characterized by various means such as seawater uptake measurements or surface contact angle measurements. Preferably, the seawater uptake of the secondary coating layer is less than 30% by weight, more preferably less than 25% by weight. Preferably, the equilibrium water contact angle of the secondary coating layer is greater than 30 degrees at 23 ° C.

  In a preferred embodiment, the secondary coating layer composition comprises an incompatible fluid or grease. In the context of the present invention, an incompatible fluid is a silicone, organic or inorganic molecule or polymer, usually insoluble (either in whole or in part) in the secondary coating layer (elastomer network). Means a liquid, but optionally an organic soluble grease or wax. Once the primary and secondary coating layers are cured, the fluid will be concentrated at the surface of the secondary coating layer to reinforce its antifouling properties. An example of an incompatible fluid is provided in WO 2007/10274. In WO 2007/10274, the incompatible fluid is a fluorinated polymer or oligomer in a polysiloxane coating. The method of concentrating the fluorinated polymer / oligomer on the surface of the cured polysiloxane coating layer is performed thermodynamically due to the difference in surface energy. The low surface energy provided by the fluorinated polymer or oligomer combined with the elastic properties provided by the cured polysiloxane improves the fouling removal properties of the coating.

Suitable fluids are for example:
a) Linear and trifluoromethyl branched fluorinated end-capped perfluoropolyethers (eg Fomblin Y®, Krytox K® fluid or Demnum S® oil);
b) linear diorgano (OH) end-capped perfluoropolyether (eg Fomblin Z DOL®, Fluorolink®);
c) Low MW polychlorotrifluoroethylene (eg, 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 diorgano-functional end-capped fluorinated alkyl- or alkoxy-containing polymers or oligomers can also be used (eg, carboxy-, ester-functional fluorinated alkyl- or alkoxy-containing polymers or oligomers).

Alternatively, the fluid may be, for example, a formula:
Q ₃ Si—O— (SiQ ₂ —O—) _n SiQ ₃
Of silicone oil.
In the formula, each group Q represents a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer such that the silicone oil has a viscosity of 20 to 5000 mPas. At least 10% of the groups Q are generally methyl groups and at least 2% of the groups Q are phenyl groups. Most preferably, at least 10% of the —SiQ ₂ —O— units are methyl-phenylsiloxane units. Most preferably, the silicone oil is methyl-terminated poly (methylphenylsiloxane). The oil preferably has a viscosity of 20 to 1000 mPas. Suitable silicone oils are sold, for example, under the trademarks Rhodorsil Huile 510V100 and Rhodorsil Huile 550 by Bluestar Silicones. The silicone oil improves the resistance of the coating system to aquatic fouling.

に示されるような有機シリコーンでもよい。
前記有機シリコーン中、
Ｒ１は、同一でも異なってもよく、場合により、アミン基で置換されたアルキル、アリールおよびアルケニルの基、式ＯＲ５の酸素含有基から選択され、Ｒ５は、水素またはＣ１〜６アルキルおよび式（Ｉ）：
Ｒ６−Ｎ（Ｒ７）−Ｃ（Ｏ）−Ｒ８−Ｃ（Ｏ）−ＸＲ３
に基づく官能基である。
式（Ｉ）中、
Ｒ６は、１から１２個の炭素原子のアルキル、ヒドロキシアルキル、カルボキシアルキル、および、１０個以下の炭素原子のポリオキシアルキレンから選択され；
Ｒ７は、水素、１から６個の炭素原子のアルキル、ヒドロキシアルキル、カルボキシアルキル、１から１０個の炭素原子のポリオキシアルキレンから選択され；Ｒ７は、Ｒ８に結合されて、環を形成し得る；
Ｒ８は、１〜２０個の炭素原子を有するアルキル基である；
Ｒ９は、水素または、場合により、酸素または窒素含有基で置換された、１〜１０個の炭素原子を有するアルキル基であり；
Ｘは、Ｏ、ＳおよびＮＨから選択され；
前記有機シリコーンポリマー中の少なくとも１つのＲ１基が、上記式（Ｉ）またはその塩誘導体に基づく官能基であるという条件であり；
Ｒ２は、同一でも異なってもよく、アルキル、アリールおよびアルケニルから選択され；
Ｒ３およびＲ４は、同一でも異なってもよく、アルキル、アリール、末端化または非末端化ポリオキシアルキレン、アルカリル、アラルキレンおよびアルケニルから選択され；
ａは、０から５０，０００の整数であり；
ｂは、０から１００の整数であり；ならびに、
ａ＋ｂは、少なくとも２５である。 The fluid is

An organic silicone as shown in FIG.
In the organic silicone,
R 1 may be the same or different and is optionally selected from alkyl, aryl and alkenyl groups substituted with amine groups, oxygen-containing groups of formula OR 5, R 5 is hydrogen or C 1-6 alkyl and formula (I ):
R6-N (R7) -C (O) -R8-C (O) -XR3
Is a functional group based on
In formula (I),
R6 is selected from alkyl of 1 to 12 carbon atoms, hydroxyalkyl, carboxyalkyl, and polyoxyalkylene of up to 10 carbon atoms;
R7 is selected from hydrogen, alkyl of 1 to 6 carbon atoms, hydroxyalkyl, carboxyalkyl, polyoxyalkylene of 1 to 10 carbon atoms; R7 can be bonded to R8 to form a ring. ;
R8 is an alkyl group having 1 to 20 carbon atoms;
R9 is hydrogen or an alkyl group having 1 to 10 carbon atoms, optionally substituted with an oxygen or nitrogen containing group;
X is selected from O, S and NH;
Provided that at least one R1 group in the organosilicone polymer is a functional group based on the 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 may be the same or different and are selected from alkyl, aryl, terminated or unterminated 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 at least 25.

In one embodiment,
R2, R3 and R4 are independently selected from methyl and phenyl, more preferably methyl.
R6 is an alkyl group having 1 to 12, more preferably 2 to 5 carbon atoms.
R7 is hydrogen or an alkyl group having 1 to 4 carbon atoms.
R8 is an alkyl group having 2 to 10 carbon atoms.
R9 is hydrogen or an alkyl group having 1 to 5 carbon atoms.
X is an oxygen atom.
a + b is in the range of 100 to 300.

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

Method for controlling the release rate of biocide Based on the present invention, a method for controlling the release rate of biocide from a fouling removal coating system comprising: The ratio R ₅ / R ₃₀ between the release rate of the biocide (R ₅ ) and the release rate (R ₃₀ ) 30 days after application of the coating is 1.5 or less,
a. Providing a substrate,
b. Coating the substrate with a primary coating layer;
c. Applying at least one secondary coating layer on top of the primary coating layer;
A method is provided wherein the primary coating layer comprises a biocide, and the secondary coating layer has less biocide and no or substantially no biocide than the primary coating layer.

In one embodiment, the method of the present invention is such that the ratio R ₅ / R ₃₀ is 1.33 or less (≦ 1.33), and preferably 1.11 or less (≦ 1.11). It is possible to control the release rate of the biocide from the fouling removal coating system.

  Suitably, the primary coating layer and / or the secondary coating layer comprises an elastomeric polymer. The elastomeric polymer is as described in all previous paragraphs.

  Suitably, the primary coating layer and / or the secondary coating layer comprises a polyorganosiloxane. The secondary coating layer is as described in all of the previous paragraphs.

  Suitably, the substrate is coated with an anticorrosion coating and the primary coating layer used as a tie coat over the anticorrosion coating.

  Suitably, the biocide in the primary coating layer is an organic or metal-organic biocide. The biocide is as described in all previous paragraphs.

  Suitably the biocide is any one or more of the aforementioned biocides, most suitably 2-trihalogenomethyl-3-halogeno-4 substituted at the 5-position and optionally at the 1-position. -A cyanopyrrole derivative or 1,4-dithiaanthraquinone-2,3-carbonitrile.

  Suitably, the secondary coating layer comprises a non-compatible fluid that is insoluble in the secondary coating layer, such as silicone, organic or inorganic molecules or polymers.

Applications The coating system according to the invention can be applied to the substrate by conventional techniques such as brushing, roller coating, dipping or spraying (airless and conventional).

  After the secondary coating layer is cured, it can be immediately immersed to provide instant antifouling and antifouling protection. The resulting coating system has very good antifouling and antifouling properties. This makes the coating system according to the invention very suitable for use in preventing fouling in marine and freshwater applications. The coating system can be submerged in water, in whole or in part, for both dynamic and static structures, such as hulls, boat hulls, buoys, drilling bases, oil rigs, floating production storage shipments. It can be used for facilities (FPSO), pipes, power plant cooling water intakes, fishing nets, fish rods, and other aquaculture and marine facilities / structures, etc. The coating system can be applied to any substrate used for these structures, for example, metals such as iron, aluminum, concrete, wood, plastic or fiber reinforced resin.

In addition to the coating system according to the invention having a controlled release of biocide from the decontamination coating system, the biocide release rate (R) from the decontamination coating system 5 days after application of said coating. ₅ ) and the ratio R ₅ / R ₃₀ of the biocide release rate (R ₃₀ ) 30 days after application of the coating is 1.5 or less (≦ 1.5) (preferably 1.33 or less) For a wide range of fouling types, including (i) sludge fouling, (ii) seaweed fouling, (iii) soft fouling and (iv) hard fouling, specifically low speed navigating surface ships It has been found to be effective compared to systems that do not contain a biocide or antifouling coating layer.

  The coating system may be applied directly to an untreated substrate. Alternatively, the coating system of the present invention may be applied to a substrate on which a surface treatment or other coating layer has been previously applied. Examples of such surface treatment and other coating layers include an anticorrosion coating, a biocidal antifouling coating, a seal coat, a tie coat, and an adhesion promoting layer.

  For new ship and boat hull application, the system will typically be applied directly onto a substrate having one or more anticorrosive coatings. During maintenance and repair or recoating, the formulation is typically optionally over the existing coating formulation (including any link coats) or removed from the existing coating formulation. After recoating the anticorrosion coating, it will be applied directly onto the substrate.

  The base material in which the fouling is prevented is not particularly limited, and examples thereof include arbitrary iron, plastic, concrete, wood, fiber reinforced resin, and aluminum.

  In typical situations, for coating ship and boat hulls, the primary coating layer will be applied, resulting in a dry film thickness in the range of 100-200 μm. The secondary coating layer will be applied to provide a dry film thickness in the range of 100-200 μm. When a thicker dry film thickness is required, the required film thickness can be produced by continuous coating, each having a dry film thickness of 100-200 μm. On the other substrate, the primary coating layer is applied to provide a dry film thickness in the range of 50 to 500 μm, and the secondary coating layer is applied to dry in the range of 50 to 500 μm. A film thickness will be provided.

  The present invention will now be described with reference to the following examples. They are intended to illustrate the invention, but are not to be construed as limiting its scope in any way.

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

The biocide leaching rate for each coating system was determined experimentally. In summary, two panels coated with each coating system were immersed in a synthetic seawater storage tank. The panel was periodically transferred to a new synthetic seawater leaching rate measuring vessel and slowly shaken for a certain period. At the end of this period, the panel was returned to the storage tank and the amount of biocide leached into the container was measured by chemical analysis. From the determined amount of leached biocide, the exposed surface area of the coated panel, and the knowledge of the immersing period in the leaching rate measuring vessel, the leaching rate of the biocide is determined as μg cm ⁻² d ⁻¹ Can be represented.

Artificial seawater Artificial seawater was prepared by mixing 33 g of salt per liter of deionized water using a commercially available Instant Ocean Sea Salt.

Panel manufacture A 15 × 10 cm polycarbonate panel was masked to a known surface area (typically about 100 cm ² ). 125μm dry film thickness of 2-pack epoxy anticorrosion paint (Intershield 300, International Paint) was applied using a drawdown bar, and then the biocide-containing coating layer was applied to a 100μm dry film thickness with a drawdown bar. Used and coated. After drying, the final “finish” coat was applied to the thin film with a draw down bar at a dry film thickness of 15 μm (except for Example 5 using a dry film thickness of 100 μm). The masking tape was removed and the edges of the coated panel were sealed with a two pack epoxy anticorrosive paint (Intershield 300, International Paint) using a brush. Each coat was cured under atmospheric conditions before applying the secondary coating layer and before immersing in the storage tank.

Storage tank The panel was completely immersed in 40 liters of artificial seawater in a strictly clean glass tank. The water was constantly circulated through an activated carbon filter to prevent an increase in biocide or its degradation products. The temperature of the storage tank was maintained around 22-23 ° C. All panels were left immersed in the storage tank for the duration of the experiment, except during leaching rate measurement using the leaching rate measuring vessel on a predetermined measurement day.

Leaching rate measuring vessel Individually clean polypropylene containers with lids (15 x 8 x 8 cm, l x w x h) containing 100 ml artificial seawater at a temperature of around 22-23 ° C on a given measurement day The panel was moved to. The container was shaken slowly for 2 hours using an orbital mixer, and then the panel was returned to the storage tank.

を使用して、浸出速度Ｒを決定するのに使用し得る。
式中、Ｃは、前記浸出速度測定容器中のバイオサイドの当量濃度であり、Ｖは、前記浸出速度測定容器中の人工海水の体積（リットル）であり、ｔは、前記浸出速度測定容器中での前記パネルの浸漬期間（時間）であり、Ａは、前記パネル上の前記コーティング系の曝された表面積（ｃｍ^２）である。 Determination of leaching rate—Overview The concentration of biocide in the leaching rate measuring vessel can be determined using standard analytical methods known to those skilled in the art, for example, high performance liquid chromatography (HPLC). Next, the concentration of biocide in the leaching rate measuring container is expressed by the following formula:

Can be used to determine the leaching rate R.
In the formula, C is the equivalent concentration of biocide in the leaching rate measuring container, V is the volume (liter) of artificial seawater in the leaching rate measuring container, and t is in the leaching rate measuring container. Is the immersion period (hours) of the panel at A, and A is the exposed surface area (cm ² ) of the coating system on the panel.

Example 1-8 leaching rate determination-tralopyril Approximately 12 ml of artificial seawater from each leaching rate measuring vessel was transferred to a glass vial at the end of the shaking period. Quantitative conversion of leached tralopyril to 3-bromo-5- (4-chlorophenyl) -4-cyano-1H-pyrrole-3-carboxylic acid (BCPCCA) by holding the vial at 45 ° C. overnight It was confirmed.

  The BCCCCA concentration in the treated sample was determined using an Agilent 1100 HPLC system equipped with a Pursuit UPS 2.4 μm C18 column (50 × 3 mm) at a ratio of 50: 49.95: 0.05 parts by volume as the mobile phase. Measured by high performance liquid chromatography (HPLC) with direct injection using a mixture of acetonitrile, water and orthophosphoric acid.

A minimum of six calibration standards covering the range of 10 to 500 μg liter ⁻¹ were prepared fresh daily by appropriately diluting a stock solution of 1000 μg liter ⁻¹ BCCPCA in tetrahydrofuran with artificial seawater. Artificial seawater blanks were analyzed before and after the reference set and after each sample set. Inspection standards were performed after every 5 samples to check the reproducibility of the analytical method. At each time point, the analytical method proved reproducible.

に基づいて算出する。
式中、Ｃ_{ｔｒａｌｏｐｙｒｉｌ}は、前記浸出速度測定容器中のトラロピリルの当量濃度であり、Ｖは、前記浸出速度測定容器中の人工海水の体積（リットル）であり、ｔは、前記浸出速度測定容器中での前記パネルの浸漬期間（時間）であり、Ａは、前記パネル上の前記コーティング系の曝された表面積（ｃｍ^２）である。 At the end of the shaking period, the equivalent concentration of tralopyril in the leaching rate measuring vessel is calculated by multiplying the relative molar mass of tralopyril and BCCCCA and the BCCCCA concentration determined by the leaching rate of tralopyril. To do. Then, R is represented by the following formula:

Calculate based on
In the formula, C _tyropyril is the equivalent concentration of tralopyril in the leaching rate measuring vessel, V is the volume (liter) of artificial seawater in the leaching rate measuring vessel, and t is in the leaching rate measuring vessel. Is the immersion period (hours) of the panel at A, and A is the exposed surface area (cm ² ) of the coating system on the panel.

Table 3 shows the leaching rate results collected for the 5 day (R ₅ ) and 30 day (R ₃₀ ) measurements, as well as R ₅ / R ₃₀ . In any case, the result is an average of the results of two panels for each coating system.

  As shown in the table, each coating system exhibits controlled leaching as defined within the framework of the present invention. The uncoated one exhibits biocide leaching rate behavior corresponding to the biocide leaching rate proportional to the square root of time. Furthermore, by changing certain parameters of the secondary coating layer, the control can exhibit a reduction, improvement or behavior of biocide leaching rate that remains essentially constant over time.

^＊国際公開第２００８／１３２２３６号の実施例１２に対応

^１）：浸漬後５日のバイオサイドの放出速度
^２）：浸漬後３０日のバイオサイドの放出速度
In addition, various average rates of biocide leaching can be achieved. By varying certain parameters of the secondary coating layer, the biocide leaching rate can be controlled such that higher or lower biocide leaching rates can be obtained at any given time.

^* Corresponds to Example 12 of International Publication No. 2008/132236

¹⁾ : Biocide release rate 5 days after immersion
²⁾ : Biocide release rate 30 days after immersion

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

  Test panels were fabricated to determine the performance of each coating system that controlled biocide leaching from the primary coating layer and prevented fouling. The coating systems of Examples 9 to 12 were applied to 60 × 60 cm marine plywood panels with rollers to dry film thicknesses for the primary and secondary coating layers of about 100 and 150 μm, respectively. The plate was pre-primed with one coat of 2-pack epoxy anticorrosive paint (Intershield 300, International Paint) containing about 125 μm DFT per coat. Half of each panel (left hand side) is coated with a coating system corresponding to one of the coating systems of Examples 9 to 12, and as a control, the other half of the panel (right hand side) is a commercially available antifouling tie coat. (Intersleek 737, International Paint). Both sides then had a standard antifouling finish coat applied (Intersleek 757, International Paint). Prior to application of the secondary coating layer and the start of the test, each coat was fully cured under atmospheric conditions.

  The test panel was simultaneously immersed in natural tropical marine water at a depth of 0.5 to 1.0 m in Changi, Singapore, known for the severe increase in fouling. The panel was periodically removed from the water and photographed and the increase in fouling on the coating system was evaluated before re-immersing the panel.

  The coating system comprising tralopyril (Example 9) and dithianone (Example 10) remained substantially free of fouling even after 8 months of immersion. The coating system comprising pyrithione copper (Example 11) and pyrithione zinc (Example 12) showed a greater increase in fouling after 8 months than Examples 9 and 10, but less fouling than the control coating. Showed an increase.

  In all cases, the coating systems of Examples 9 to 12 were free of bubbles and cracks after 8 months of immersion.

These results clearly show that the performance of the coating system according to the invention, which prevents fouling over a long period of time, is significantly improved over standard commercial fouling removal coating systems.
Specific examples of the present invention provided by the above disclosure include the following inventions.
[1] A structure coated with a biocidal fouling removal coating system,
a. Providing a substrate,
b. Coating the substrate with a primary coating layer;
c. Applying at least one secondary coating layer on the upper surface of the primary coating layer;
Obtained by
The primary coating layer includes a biocide, the secondary coating layer has fewer biocides than the primary coating layer, and is free or substantially free of biocides, the primary coating layer and the secondary A structure wherein the coating layer forms a biocidal fouling removal coating system that exhibits controlled leaching of the biocide.
[2] The biocide release rate (R ₅ ) from the fouling removal coating system 5 days after application of the coating and the biocide release rate (R ₃₀ ) 30 days after application of the coating . The structure according to [1], wherein the ratio R ₅ / R ₃₀ is 1.5 or less.
[3] The structure according to [2], wherein the ratio R ₅ / R ₃₀ is 1.33 or less.
[4] The structure according to any one of [1] to [3], wherein the primary coating layer and / or the secondary coating layer includes an elastic polymer.
[5] The structure according to any one of [1] to [4], wherein the primary coating layer and / or the secondary coating layer contains polyorganosiloxane.
[6] The structure according to any one of [1] to [5], wherein the base material is coated with an anticorrosion coating, and the primary coating layer is used as a tie coat covering the anticorrosion coating.
[7] The structure according to any one of [1] to [6], wherein the biocide in the primary coating layer is an organic or metal-organic biocide.
[8] 2-trihalogenomethyl-3-halogeno-4-cyanopyrrole derivative, or 1,4-dithiaanthraquinone-2, wherein the biocide is substituted at one or more of the 5-position and optionally the 1-position The structure according to any one of [1] to [7], which is 3-carbonitrile.
[9] The structure according to any one of [1] to [8], wherein the secondary coating layer includes an incompatible fluid.
[10] The base material is an offshore structure or aquaculture structure, for example, hull, boat hull, buoy, excavation base, oil rig, floating production storage shipping equipment (FPSO), pipe, cooling water for power plant The structure according to any one of [1] to [9], which is a water intake, a fishing net, or a fish rod.
[11] A method for controlling the release rate of biocide from a decontamination coating system, the biocide release rate (R ₅ ) from the decontamination coating system 5 days after the coating is applied, and The ratio R ₅ / R ₃₀ to the biocide release rate (R ₃₀ ) 30 days after coating is 1.5 or less,
a. Providing a substrate,
b. Coating the substrate with a primary coating layer;
c. Applying at least one secondary coating layer on the upper surface of the primary coating layer;
Wherein the primary coating layer comprises biocide, the secondary coating layer has less biocide than the primary coating layer, and is free or substantially free of biocide.

Claims (15)

A structure coated with a biocidal fouling removal coating system,
a. Providing a substrate that is an offshore structure or aquaculture structure ;
b. Coating the substrate with a primary coating layer;
c. Obtained by applying at least one secondary coating layer on the upper surface of the primary coating layer;
The primary coating layer is formed from a coating composition comprising biocide;
The secondary coating layer is formed from a coating composition that has less biocide and no or substantially no biocide than the coating composition that forms the primary coating layer;
The primary coating layer and the secondary coating layer form a biocidal fouling removal coating system;
The structure wherein the primary coating layer and the secondary coating layer comprise polyorganosiloxane and fumed silica. Ratio R ₅ between the biocide release rate (R ₅ ) from the fouling removal coating system 5 days after application of the coating and the biocide release rate (R ₃₀ ) 30 days after application of the coating. The structure according to claim 1, wherein / R ₃₀ is 1.5 or less. The structure according to claim 2, wherein the ratio R ₅ / R ₃₀ is 1.33 or less.   The structure according to any one of claims 1 to 3, wherein the substrate is coated with an anticorrosion coating, and the primary coating layer is used as a tie coat covering the anticorrosion coating.   The biocide is a 2-trihalogenomethyl-3-halogeno-4-cyanopyrrole derivative, 1,4-dithiaanthraquinone-2,3-dicarbo, substituted at the 5-position and optionally at the 1-position, such as tralopyryl. Nitrile (dithianone), pyrithione copper, pyrithione zinc, tolyl fluoride, diclofluuride, and N-cyclopropyl-N ′-(1,1-dimethylethyl) -6- (methylthio) -1,3,5- The structure according to any one of claims 1 to 4, which is one or more of triazine-2,4-diamine.   The structure according to any one of claims 1 to 5, wherein the biocide in the primary coating layer is an organic or metal-organic biocide.   Of the 2-trihalogenomethyl-3-halogeno-4-cyanopyrrole derivatives substituted at the 5-position and optionally the 1-position, or 1,4-dithiaanthraquinone-2,3-carbonitrile The structure according to any one of claims 1 to 6, wherein the structure is one or more.   8. A structure according to any one of the preceding claims, wherein the secondary coating layer comprises an incompatible fluid. Wherein the substrate, the hull, a boat hull, buoys, drilling platforms, oil rigs, floating production storage shipping facility (FPSO), pipe, cooling water intake of the plant, a fishing net or fish cage according to claim 1 The structure according to any one of 8.   The structure is a ship or a hull of a boat, and the primary coating layer is applied to provide a dry film thickness in the range of 100 to 200 μm, and the secondary coating layer is applied to dry in the range of 100 to 200 μm. The structure according to any one of claims 1 to 9, which provides a film thickness. A method for controlling the release rate of biocide from a decontamination coating system, the biocide release rate (R ₅ ) from the decontamination coating system 5 days after application of the coating, and the application of the coating The ratio R ₅ / R ₃₀ with the release rate (R ₃₀ ) of the biocide 30 days after the construction is 1.5 or less,
a. Providing a substrate that is an offshore structure or aquaculture structure ;
b. Coating the substrate with a primary coating layer;
c. Applying at least one secondary coating layer on top of the primary coating layer;
The primary coating layer is formed from a coating composition comprising biocide;
The secondary coating layer is formed from a coating composition that has less biocide and no or substantially no biocide than the coating composition that forms the primary coating layer;
The method wherein the primary coating layer and the secondary coating layer comprise polyorganosiloxane and fumed silica.   The method of claim 11, wherein the substrate is coated with an anti-corrosion coating and the primary coating layer is used as a tie coat over the anti-corrosion coating.   The biocide is a 2-trihalogenomethyl-3-halogeno-4-cyanopyrrole derivative, 1,4-dithiaanthraquinone-2,3-dicarbo, substituted at the 5-position and optionally at the 1-position, such as tralopyryl. Nitrile (dithianon), pyrithione copper, pyrithione zinc, tolyl fluoride, diclofluuride, N-cyclopropyl-N ′-(1,1-dimethylethyl) -6- (methylthio) -1,3,5-triazine The method according to claim 11 or 12, which is one or more of 2,4-diamine.   14. A method according to any one of claims 11 to 13, wherein the secondary coating layer comprises an incompatible fluid. Said substrate, hull, a boat hull, buoys, drilling platforms, oil rigs, floating production storage shipping facility (FPSO), pipe, cooling water intake of the plant, fishing nets or fish cage, or the whole or part 15. A method according to any one of claims 11 to 14 wherein the is aquaculture and offshore equipment or structures immersed in water.