Post-curing treatment for anti-fouling coatings

Abstract

The present invention relates to a post-curing treatment method for an antifouling paint coating, comprising the following steps: a. A step of applying an emulsifying composition onto the surface of the antifouling paint coating; b. The step of keeping the emulsified composition in contact with the surface of the antifouling paint coating for at least 2 hours; Includes, The present invention relates to a method wherein the emulsifying composition comprises a liquid continuous phase containing water and a liquid dispersion phase containing one or more poly(oxyalkylene)-modified silicone oils. The present invention further relates to the use of a post-curing treatment to impart antifouling properties to an antifouling paint coating. The present invention further relates to a structure, preferably a marine structure, having an antifouling topcoat on its outer surface that has been subjected to a post-curing treatment.

Description

[Technical Field] 【0001】 The present invention relates to a post-cure treatment method for antifouling coatings. The present invention further relates to the use of a post-cure treatment to impart antifouling properties to an antifouling paint coating. The present invention further relates to a structure, preferably a marine structure, having an antifouling topcoat on its outer surface that has been post-treated. [Background technology] 【0002】 Water structures, particularly submersible marine structures that come into contact with water, especially seawater, tend to be contaminated by marine organisms. Antifouling coatings are widely used on such structures, such as ships, buoys, and ship structures, to suppress or facilitate the removal of such marine organisms. 【0003】 Antifouling coating systems for steel structures, such as marine structures, typically consist of three main layers: a rust-preventive layer applied to the steel plate substrate, an antifouling layer, and an intermediate layer, often called a "tie coat," to establish strong adhesion between the rust-preventive and antifouling layers. The antifouling layer is often composed of a polysiloxane-based binder matrix. 【0004】 Polysiloxane-based coatings are widely used as antifouling coatings for marine structures. Known principles for improving the antifouling effect of polysiloxane-based coatings involve incorporating hydrophilic modified oils and, in most cases, active ingredients such as biocides and enzymes. For example, WO2011 / 076856 discloses an antifouling coating composition comprising a polysiloxane-based binder system, a biocide, and a hydrophilic modified silicone oil, and WO2016 / 004961 discloses an antifouling coating composition comprising a polysiloxane-based binder system, a biocide, and a poly(oxyalkylene)-modified alcohol. 【0005】 All of these disclosures describe adding poly(oxyalkylene) modified oils such as silicone oil, long-chain alcohols, and hydrophilic modified oils such as acrylic acid oil to the coating composition before curing. That is, the hydrophilic modified oil is included in the (wet) coating composition before being applied to the substrate surface. 【0006】 The antifouling properties of the above coatings are determined by the presence of these oils contained in the coating. The concentration of the oil has been observed to decrease over time due to various mechanisms such as degradation, diffusion, and leaching (Camos etal., Progressin Organic Coatings(2017), 112:101-108). The loss of hydrophilic oil can lead to fouling, and generally, it is desirable to renew the coating system before the hydrophilic modified oil is completely depleted. The conventional method of restoring antifouling performance is to apply a completely new coating layer or coating system. Applying either a complete antifouling coating system or just the antifouling layer alone is time-consuming and costly and requires a large amount of coating material. 【0007】 The addition of hydrophobic silicone oil after curing has recently been disclosed by Kolle et al. (Scientific Reports, Nature(2022) 12:11799: On the mechanism of marine fouling-prevention performance of oil-containing silicone elastomers). According to this post-curing method, it is necessary to completely immerse the coated object, and thus the hull, in (hydrophobic) silicone oil to allow the oil to be incorporated into the coat, which is a cumbersome method and requires a large amount of silicone oil. Furthermore, the polysiloxane-based coat absorbs silicone oil in an amount of 45 - 50 wt% of the polydimethylsiloxane coat, causing the coat to swell up to 50% (from 100 μm to 150 μm). This is thought to potentially have an adverse effect on the mechanical properties or long-term properties of the film. 【0008】 Other documents in this technical field include WO2019 / 233985 and CN114761496, etc. 【0009】 A simple and inexpensive method for extending and / or improving the antifouling properties of an antifouling coating is considered beneficial. 【Summary of the Invention】 【0010】 The present invention is a method for post-cure treatment of an antifouling paint coating, comprising the following steps: a. Applying an emulsion composition onto the surface of the antifouling paint coating; b. Allowing the emulsion composition to remain in contact with the surface of the antifouling paint coating for at least 2 hours; comprising providing a method wherein the emulsion composition comprises a liquid continuous phase containing water and a liquid dispersed phase containing one or more poly(oxyalkylene) modified silicone oils. 【0011】 In one aspect, the present invention relates to the use of the method of the present invention for improving the antifouling properties of an antifouling paint coating. 【0012】 In one aspect, the present invention relates to an antifouling paint coating, preferably a non-erosive paint coating, treated by the method of the present invention. 【0013】 Further details of the present invention are described in the dependent claims and the following description. 【Embodiments for Carrying out the Invention】 【0014】 The present invention relates to a post-curing treatment method for an antifouling paint coating. The terms "antifouling paint coating" and "antifouling coating" are used interchangeably and refer to a coating obtained from a coating composition that provides a fouling-releasing surface from which marine organisms cannot adhere or which are released from the coating as water moves along the surface. The antifouling paint coating is preferably a non-erosive paint coating, and more preferably a polysiloxane-based paint coating. 【0015】 The inventors have found a simple and effective post-curing treatment for antifouling coatings that can improve and / or extend the antifouling properties of the antifouling coating. Unexpectedly, the inventors have found that poly(oxyalkylene) modified silicone oil (hydrophilic or amphiphilic) can be incorporated into the (hydrophobic) antifouling coating simply by applying an emulsified composition to the surface of the antifouling coating. 【0016】 Therefore, in one embodiment, the present invention simply relates to a method for incorporating one or more poly(oxyalkylene)-modified silicone oils into a polysiloxane-based paint coating. 【0017】 In the context of the present invention, the term "emulsified composition" refers to a multiphase system comprising at least a liquid continuous phase and a liquid dispersed phase. In the context of the present invention, the continuous phase comprises water, and the dispersed phase comprises one or more poly(oxyalkylene)-modified silicone oils. 【0018】 Therefore, the method involves the following steps: a. The step of applying an emulsifying composition to the surface of the antifouling paint coating; and b. The step of keeping the emulsified composition in contact with the surface of the antifouling paint coating for at least 2 hours; Includes, The emulsifying composition comprises a liquid continuous phase containing water and a liquid dispersion phase containing one or more poly(oxyalkylene)-modified silicone oils. 【0019】 In one embodiment, the total amount of water constitutes 40 to 99% by weight of the emulsified composition. The total amount of poly(oxyalkylene)-modified silicone oil constitutes 1 to 40% by weight of the emulsified composition. 【0020】 In one embodiment, the total amount of water is 40-99 or 40-95, 40-90, 40-85, or 40-80 or 40-75 or 40-70% by weight of the emulsified composition, for example 45-99 or 45-95 or 45-90 or 45-85, or 45-80 or 45-75 or 45-70% by weight of the emulsified composition, for example 50-99 or 50-95 or 50-90 or 50-85, or 50-80 or 50-75 or 50-70% by weight, for example 55-99 or 55-95 or 55-90 or 55-85, or 55-80 or 55-75 or 55-70% by weight, for example 60-99 or It consists of 60-95 or 60-90 or 60-85 or 60-80 or 60-75 or 60-70% by weight, for example 63-99 or 63-95 or 63-92% by weight, for example 65-99 or 65-95 or 65-90 or 65-85% by weight, or 65-80 or 65-75 or 65-70% by weight, for example 70-99 or 70-95 or 70-90 or 70-85% by weight, or 70-80 or 70-75% by weight, for example 75-99 or 70-95 or 70-90 or 70-85 or 70-80% by weight, for example 80-99 or 80-95 or 80-90 or 80-85% by weight. In a preferred embodiment, the total amount of water constitutes 50 to 90% by weight, more preferably 50 to 80% by weight, for example, 50 to 70% by weight, of the emulsifying composition. 【0021】 In one embodiment, the total amount of poly(oxyalkylene)-modified silicone oil constitutes 1 to 40, 1 to 35, 1 to 30, or 1 to 25% by weight of the emulsified composition, for example, 2 to 40, 2 to 35, 2 to 30, or 2 to 25% by weight, for example, 5 to 40, 1 to 35, 5 to 30, or 5 to 25% by weight, for example, 10 to 40, 10 to 35, 10 to 30, or 10 to 25% by weight, for example, 15 to 40, 15 to 35, 15 to 30, or 15 to 25% by weight. In a preferred embodiment, the total amount of poly(oxyalkylene)-modified silicone oil constitutes 5 to 30% by weight of the emulsified composition, more preferably 10 to 30% by weight, for example, 15 to 25% by weight. 【0022】 The inventors unexpectedly discovered that poly(oxyalkylene)-modified silicone oil can be effectively incorporated into the antifouling coating simply by applying the emulsified composition to the surface of the antifouling coating. The emulsified composition can be applied directly to the surface of the antifouling coating by means of a brush, spray, roller, etc. The composition can also be applied to vertical surfaces such as the sides of the hull. From the method disclosed by Kolle et al. in Scientific Reports, Nature (2022) 12:11799, it is known that hydrophobic silicone oil can be incorporated into the antifouling coating by immersing the entire object to be coated (i.e., the hull) in oil for a certain period of time. In contrast to the method of the present invention, the method proposed by Kolle et al. is very cumbersome and requires a large amount of oil. 【0023】 The post-curing treatment of the present invention can extend the antifouling properties of aged antifouling coatings. This method offers many advantages. For example, replacing a coating or simply applying a new antifouling coating to a ship usually requires a longer period of dry docking. The method of the present invention significantly reduces dry docking time by simply replenishing aged or worn antifouling coatings with poly(oxyalkylene) modified silicone oil. The terms "aged coating" and "worn coating" refer to coatings that have been applied and used for a certain period of time, for example, at least 6 months, for example, at least 1 year, for example, at least 2 years. In the case of aged antifouling coatings, this means that the coating has been immersed in water for at least that period. In one embodiment, the aged coating is an antifouling paint coating originally prepared from an antifouling coating composition containing a hydrophilic modified oil in the wet stage. The post-curing treatment of the present invention is performed after the hydrophilic modified oil has been partially or completely released from the coating. That is, this treatment serves as a replenishment of the hydrophilic modified oil to the coating. 【0024】 The method of the present invention can also be used to improve the antifouling properties of a coating immediately after application, prepared from a coating composition that does not yet contain poly(oxyalkylene) modified silicone oil. That is, the poly(oxyalkylene) modified silicone oil is not included in the coating composition but is simply incorporated after curing. The term "immediately applied coating" refers to a coating that has not yet been used for its intended purpose. In one embodiment, the emulsion composition is applied to the surface of the coating within three months after application, for example, within two months after application, for example, within four weeks, three weeks, two weeks, or just one week after application. In a further embodiment, the immediately applied coating has not been immersed in water. The immediately applied coating is one that has been cured before the emulsion composition is applied. That is, the term "immediately applied coating" refers to a coating that is cured before the emulsion composition is applied. In one embodiment, the coating immediately after application is cured for at least 3 hours, for example, at least 4 hours, for example, at least 5 hours, preferably at least 6 hours, for example, at least 8 hours, for example, at least 10 hours, for example, at least 12 hours, 16 hours, 20 hours, or 24 hours before the application of the emulsifying composition. 【0025】 A further advantage is that the emulsified composition of the present invention can be prepared and transported on-site at a concentration that can be further diluted with water before application, thus reducing the amount of material to be transported. Furthermore, since the emulsified composition can be prepared without any volatile organic compounds (VOCs), it provides a safe and environmentally friendly alternative to overcoating or replacing antifouling coatings. 【0026】 The emulsified composition may optionally further contain one or more light stabilizers, such as hindered amine light stabilizers (HALS), and / or radical scavengers, and / or one or more ultraviolet absorbers. Although not preferred, the emulsified composition may also contain one or more biocides. 【0027】 The emulsified composition may also include additives, which are further described below. 【0028】 The emulsified composition is applied to the surface of an antifouling coating. The antifouling coating is preferably a non-erosive coating, and more preferably a polysiloxane-based coating prepared from a coating composition comprising a polysiloxane-based binder system. The polysiloxane-based binder system preferably comprises more than 50% by weight, for example more than 55% by weight, for example more than 60% by weight, or more than 65% by weight, preferably more than 70% by weight, for example more than 75% by weight, or more than 80% by weight, or more than 85% by weight, or more than 90% by weight, or more than 95% by weight, based on the total binder system weight. Antifouling coatings comprising a polysiloxane-based binder system are known to those skilled in the art and are described, for example, in WO2011 / 079856, WO2013 / 000477, and WO2014 / 117786. 【0029】 The emulsified composition is prepared from a first composition and a second composition. The first composition comprises a liquid carrier for a continuous phase containing water, and the second composition comprises one or more poly(oxyalkylene)-modified silicone oils. The liquid carrier may optionally contain one or more additional liquids having suitable properties in addition to water. The first and second compositions may also contain further components such as hindered amine-based light stabilizers, ultraviolet absorbers, and additives, as described later. 【0030】 In the context of this invention, when "emulsified composition" is referred to, it means a mixed composition that is ready to be applied onto an antifouling coating. 【0031】 Poly(oxyalkylene) modified silicone oil According to the present invention, the emulsified composition comprises a dispersed phase containing one or more poly(oxyalkylene)-modified silicone oils. 【0032】 Poly(oxyalkylene)-modified silicone oils are widely used as surfactants and emulsifiers because they contain both hydrophilic and lipophilic groups within the same molecule. "Poly(oxyalkylene)-modified silicone oil" typically refers to hydrophobic silicone oils modified with poly(oxyalkylene) moieties, such as in the internal side chains and / or terminals. Poly(oxyalkylene) refers to a repeating unit of oxygen and alkylene, typically ethylene and propylene. 【0033】 Of particular interest are poly(oxyalkylene) modified silicone oils in which the relative weight of poly(oxyalkylene) chains is 1% or more (e.g., 1-90%), 5% or more (e.g., 5-80%), and especially 10% or more (e.g., 10-70%) of the total weight of the poly(oxyalkylene) modified silicone oil. In one embodiment, the relative weight of poly(oxyalkylene) chains is in the range of 25-60%, for example, 30-50%, of the total weight of the poly(oxyalkylene) modified silicone oil. In another embodiment, the relative weight of poly(oxyalkylene) chains is in the range of 15-50%, for example, 20-40%. 【0034】 When calculating the amount of the poly(oxyalkylene) portion in a given poly(oxyalkylene) modified silicone oil, it is usually fairly easy to distinguish between the silicone portion and the poly(oxyalkylene) portion. However, in order to eliminate any suspicion that there is some kind of linking group between the two, it is necessary to understand that the poly(oxyalkylene) portion includes all atoms up to the silicon atom adjacent to the poly(oxyalkylene) portion (but does not include the silicon atom itself). As an example, in a structure like the following formula (I), the residue in formula (i) corresponds to the poly(oxyalkylene) portion (hydrophilic portion). 【0035】 In a preferred embodiment, the number-average molecular weight (Mn) of the poly(oxyalkylene)-modified silicone oil is in the range of 100 to 100,000 g / mol, for example, in the range of 250 to 75,000 g / mol, particularly in the range of 500 to 50,000 g / mol, or in the range of 500 to 30,000 g / mol. 【0036】 In another preferred embodiment, the poly(oxyalkylene)-modified silicone oil has a number-average molecular weight (Mn) in the range of 500 to 20,000 g / mol, for example, 1,000 to 10,000 g / mol, or 1,000 to 7,500 g / mol, or even 1,500 to 5,000 g / mol. 【0037】 In a preferred embodiment, the poly(oxyalkylene)-modified silicone oil has a structure according to the following formula (I). 【0038】 [ka] During the ceremony, Each R 1 The group is independently selected from C1-C5 alkyl groups (including linear or branched hydrocarbon groups) and aryl groups (e.g., phenyl(-C6H5)), preferably methyl; R 5 and R 6 Each is independently R 1 , and residues represented by the following formula (i): 【0039】 [ka] Selected from; Each R 2 These are independently selected from -H, C1-C4 alkyl (e.g., -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2CH3), phenyl (-C6H5), and C1-C4 alkylcarbonyl (e.g., -C(=O)CH3, -C(=O)CH2CH3, and -C(=O)CH2CH2CH3), and in particular -H, methyl, and -C(=O)CH3; Each R3 is independently selected from C2-C5 alkylene (e.g., -CH2CH2-, -CH2CH(CH3)-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH(CH2CH3)-), arylene (e.g., 1,4-phenylene), and C2-C5 alkylene substituted with aryl (e.g., 1-phenylethylene), and is particularly selected from C2-C5 alkylene such as -CH2CH2- and -CH2CH(CH3)-; each R 4 is -(CH2) 2-6 -; x is an integer from 0 to 2500, y is an integer from 0 to 100, provided that x + y is 1 or more; n is from 1 to 70; provided that at least one of R 6 or R 5 is a residue according to formula (i). 【0040】 In particular, there are three variations in the structure of formula (I). These are polysiloxanes grafted with poly(oxyalkylene) chains, polysiloxanes in which poly(oxyalkylene) chains are incorporated into the backbone, and combinations of these two variations. 【0041】 Graft chain In one embodiment, the poly(oxyalkylene) modified silicone oil comprises a polysiloxane grafted with poly(oxyalkylene) chains. 【0042】 Specific examples of the structure of such poly(oxyalkylene) modified silicone oils include R 5 are both R 1 ; R 6 is a residue represented by formula (i); x is an integer from 0 to 2500, y is an integer from 1 to 100; R 1 , R 2 , R 3 , R 4Examples include compounds of formula (I) where n is as defined above. 【0043】 Chains incorporated into the skeleton In one embodiment, the poly(oxyalkylene)-modified silicone oil constitutes a polysiloxane in which poly(oxyalkylene) chains are incorporated into its backbone. 【0044】 A specific example of such a poly(oxyalkylene) modified silicone oil structure is: R 5 At least one of them is a residue according to formula (i); X is an integer between 1 and 2500, and y is 0; R 1 , R 2 , R 3 , R 4 Examples of compounds of formula (I) are as defined above. In this particular embodiment, R 5 Both are residues according to formula (i). 【0045】 Combination of incorporated chains and grafted chains In one embodiment, the poly(oxyalkylene)-modified silicone oil incorporates poly(oxyalkylene) chains into its skeleton, and simultaneously constitutes a polysiloxane in which poly(oxyalkylene) chains are grafted onto the skeleton. 【0046】 A specific example of such a poly(oxyalkylene) modified silicone oil structure is: R 6 and R 5 At least one of these constitutes a residue according to formula (i); X is an integer between 1 and 2500, and y is an integer between 1 and 100; R 1 , R 2 , R 3 , R 4 Examples include compounds of formula (I) where n is as defined above. 【0047】 In this particular embodiment, R 6 and R 5 Both constitute the residues according to formula (i). 【0048】 It should be understood that the one or more non-reactive poly(oxyalkylene) modified silicone oils may be of different types, for example, two or more of the above types. 【0049】 In formula (I), which includes the three variations described above, groups such as -CH2CH(CH3)- and -CH2CH(CH2CH3)- can exist in either of two possible orientations. Similarly, it should be understood that fragments present x and y times are usually distributed randomly or in a block-like manner within the polysiloxane structure. 【0050】 In these embodiments and their variations, poly(oxyalkylene) is preferably selected from polyoxyethylene, polyoxypropylene, and poly(oxyethylene-co-oxypropylene), which may also be called poly(ethylene glycol), poly(propylene glycol), and poly(ethylene glycol-co-propylene glycol). Therefore, in formula (I) above, each R linking the two oxygen atoms 3 The R atoms are preferably selected from -CH2CH2- and -CH2CH(CH3)-, while each R atom connects the silicon atom and the oxygen atom. 4 The alkyl group is preferably selected from C2 to C5 alkyl groups. 【0051】 Preferably, the non-reactive poly(oxyalkylene) modified silicone oil does not contain aromatic substituents. 【0052】 The following embodiments relate to the compound of formula (I) itself and the three variations described above. 【0053】 In a preferred embodiment, n is 3 to 60, for example 3 to 50, for example 3 to 40, for example 4 to 20. In a further embodiment, n is 6 to 40, for example 6 to 30, 6 to 25, or 6 to 20. 【0054】 In a preferred embodiment, x is 3 to 1000, for example 3 to 500, for example 3 to 200, for example 3 to 150, for example 3 to 100, for example 3 to 50, for example 3 to 30, for example 3 to 20, for example 3 to 15 or 4 to 12. In a further embodiment, x is 6 to 200, for example 6 to 100, for example 6 to 50, for example 6 to 20. In another embodiment, x is 10 to 200, for example 10 to 100, for example 10 to 50, for example 10 to 20. In yet another embodiment, x is 20 to 200, for example 20 to 100, for example 20 to 50. 【0055】 In a preferred embodiment, n+x is 3 to 1000, for example 3 to 500, for example 3 to 200, for example 3 to 150, for example 3 to 100, for example 3 to 50. In a further embodiment, n+x is 6 to 100, for example 6 to 50, for example 6 to 40 or 6 to 30. 【0056】 In a preferred embodiment, x+y is 3 to 1000, for example 3 to 500, for example 3 to 200, for example 3 to 150, for example 3 to 100, for example 3 to 50, for example 3 to 30, for example 8 to 30, or x+y is 3 to 15, for example 4 to 12, or x+y is 6 to 20, for example 8 to 15. 【0057】 Some interesting commercially available non-reactive poly(oxyalkylene) modified silicone oils include DOWSIL 2-8692 from DOW; OFX-5103, OFX-190, OFX-5211, OFX-5220, OFX-5247, OFX-5329, OFX-5330, OFX-3667, OFX-193 (all from Xiameter); BYK-331, BYK-378, BYK-Silclean3701, BYK-Silclean3710, BYK-3760, BYK-377 (all from BYK); Gelest's DBE-621, CMS-222; CoatOSil 3501, Silwet 7280, CoatOSil 7210, CoatOSil 7200, CoatOSil 7602, CoatOSil 1220 (all from Momentive); TEGO Glide 410 and TEGO Glide 435 from Evonik Industries; Borchi Gol LA200 (from Borchers); and KF352A, KF353, KF945, KF6012, KF-6015, KF6017, KF-6020, and KF-6701 from Shin-Etsu Chemical Co., Ltd. In the context of the present invention, poly(oxyalkylene) modified silicone oils preferably have an HLB (hydrophilic-lipophilic balance) of 1.5 to 14, for example 1.5 to 14, preferably 1.5 to 12, more preferably 1.5 to 10, for example 1.5 to 8 or 2 to 10, which, as specified herein, is typically measured according to the Griffin model using the formula “weight % of hydrophilic groups” / 5 (Reference: Griffin, WC Calculation of HLB values ​​of non-ionic Surfaces, J. Soc. Cosmet. Chem. 1954, 5, 249-256). The HLB parameter is an established method for characterizing nonionic surfactants. 【0058】 Poly(oxyalkylene) modified silicone oils are also described further in, for example, WO2011 / 076856 and WO2014 / 117786. 【0059】 Typically, the total amount of poly(oxyalkylene) modified silicone oil constitutes 1 to 40, 1 to 35, 1 to 30, or 1 to 25% by weight of the emulsified composition, for example, 2 to 40, 2 to 35, 2 to 30, or 2 to 25% by weight, for example, 5 to 40, 1 to 35, 5 to 30, or 5 to 25% by weight, for example, 10 to 40, 10 to 35, 10 to 30, or 10 to 25% by weight, for example, 15 to 40, 15 to 35, 15 to 30, or 15 to 25% by weight. Preferably, the total amount of poly(oxyalkylene) modified silicone oil constitutes 5 to 30% by weight of the emulsified composition, more preferably 10 to 30% by weight, for example, 15 to 25% by weight. 【0060】 Further ingredients The emulsified composition may contain further components, if present, which are typically those included in the first or second composition before mixing. 【0061】 The aforementioned further components may be selected from a non-limiting list of hindered amine light stabilizers, UV absorbers, and additives, as further described below. 【0062】 Hindered amine light stabilizers (HALS) In one embodiment, the emulsified composition further comprises one or more hindered amine light stabilizers (HALS) containing a sterically hindered amine moiety, which may be selected from, for example, 2,2,6,6-tetraalkylpiperidine derivatives. Such sterically hindered amine moieties have been demonstrated to improve the antifouling performance of polysiloxane-based antifouling coatings when used in combination with components containing poly(oxyalkylene) chains (WO2019 / 233985). 【0063】 The presence of a sterically hindered amine moiety (e.g., a 2,2,6,6-tetraalkylpiperidine motif) appears to play an important role in the functionality of hindered amine light stabilizers. Otherwise, a wide range of derivatives, from those existing as standalone molecules to those constituting part of oligomeric or polymer structures, would be applicable. 【0064】 In one embodiment, the hindered amine light stabilizer contains the hindered amine portion of general formula I. 【0065】 [ka] During the ceremony, Each R1 is independently selected from C1-C4 alkyl groups, preferably methyl; R2 may be substituted with C1~C 30 Alkyl, C2-C may be substituted. 30 Alkenyl, aryl (may be substituted), C1-C (may be substituted) 30 Alkoxy, C1-C may be substituted. 30 Alkenyloxy, aryloxy (may be substituted), C1-C (may be substituted) 30 Alkylcarbonyl, C1-C may be substituted. 30 Alkenylcarbonyls, and optionally substituted arylcarbonyls, -H and -OH(NO · Selected from a list consisting of (equivalent to); R3 is a divalent group that may be substituted, forming an N-heterocyclic 5-membered, 6-membered, or 7-membered ring together with the intervening -C(R1)2-N(R2)-C(R1)2- group; R2 and / or R3 having the aforementioned meanings may each be independently linked to 1 to 200, for example 1 to 150, for example 1 to 100, preferably 1 to 50, for example 1 to 40, or 1 to 30, or 1 to 20, or 1 to 10 hindered amine moieties having general formula I. 【0066】 In some embodiments, R2 may be replaced by C1~C 30 Alkyl, C1-C may be substituted. 30The following are selected: alkenyl, optionally substituted aryl, optionally substituted C1-C8 alkoxy, optionally substituted C1-C8 alkenyloxy, optionally substituted aryloxy, optionally substituted C1-C8 alkylcarbonyl, optionally substituted C1-C8 alkenylcarbonyl, and optionally substituted arylcarbonyl. 【0067】 In one embodiment, R2 is selected from C1-C4 alkyl, C1-C4 alkoxy, and C1-C4 alkylcarbonyl. 【0068】 In some embodiments, R3 is selected from -CH2-C(~)-CH2- (corresponding to piperidine) and -CH2-N(~)-CH2- (corresponding to piperazine), particularly -CH2-C(~)-CH2-, where "~" indicates a hydrogen atom and / or a bonding site such as a substituent, linking group, scaffold, dendrimer, or polymer. 【0069】 In certain embodiments, R3 is selected from -CH2-C(R4)-CH2- (corresponding to piperidine) and -CH2-N(R4)-CH2- (corresponding to piperazine), in particular -CH2-C(R4)-CH2-, where R4 is defined (general and specifically) below for general formula II. 【0070】 In some embodiments, the hindered amine light stabilizer is a single molecule containing only one hindered amine moiety, particularly the piperidine moiety of general formula II (shown below). 【0071】 In other embodiments, the hindered amine light stabilizer is an oligomer containing, for example, 2 to 200 hindered amine moieties, particularly the piperidine moiety of general formula II below. In these variations, these moieties are linked to one another. 【0072】 In a preferred embodiment, the hindered amine light stabilizer is selected from 2,2,6,6-tetraalkylpiperidine derivatives. That is, the hindered amine moiety is the 2,2,6,6-tetraalkylpiperidine moiety of general formula II. 【0073】 [ka] In the formula, R1 and R2 are defined as above, and R4 represents a hydrogen atom and / or a bond point in the polymer. 【0074】 In some embodiments, R4 represents zero (the 4th position of piperidine is not substituted). 【0075】 In some embodiments, R4 is C1~C 30 Alkyl, C1-C 30 Alkenyl, aryl, hydroxy, C1-C 30 Alkoxy, C1-C 30 Alkenyloxy, aryloxy, C1-C 30 Alkylcarbonyl, C1~C 30 Alkenylcarbonyl, arylcarbonyl, C1-C 30 Alkylcarbonyloxy, C1~C 30 Each substituent R4, which represents one or two substituents selected from alkenylcarbonyloxy and arylcarbonyloxy and has the meaning described above, may be independently linked to 1 to 200 hindered amine moieties having general formula II. 【0076】 In some embodiments, R4 represents one or two substituents selected from C1-C8 alkoxys, C1-C8 alkenyloxys, aryloxys, C1-C8 alkylcarbonyloxys, C1-C8 alkenylcarbonyloxys, and arylcarbonyloxys. 【0077】 In other embodiments, R4 represents two substituents that form a spiro structure, such as a heterocyclic spiro structure. 【0078】 A wide variety of hindered amine-based light stabilizers, such as 2,2,6,6-tetraalkylpiperidine derivatives, exist in the literature and commercially available products. Preferred ones are N-C1~C 30 Alkylpiperidine derivatives, N-C1~C 30 Alkenylpiperidine derivatives, N-arylpiperidine derivatives, N-C1~C 30 Alkoxypiperidine derivatives, N-C1~C 30 Alkenyloxypiperidine derivatives, N-aryloxypiperidine derivatives, N-C1~C 30 Alkylcarbonylpiperidine derivatives, N-C1~C 30 - These are alkenylcarbonylpiperidine derivatives and N-arylcarbonylpiperidine derivatives. 【0079】 In some embodiments, the following types are used: N-C1~C 30 Alkylpiperidine derivatives, N-C1~C 30 Alkenylpiperidine derivatives and N-arylpiperidine derivatives, particularly N-C1~C 30 Alkylpiperidine derivatives are more preferred. 【0080】 In other embodiments, the following types are used: N-C1~C 30 Alkoxypiperidine derivatives, NC1-C 30 Alkenyloxypiperidine derivatives, and N-aryloxypiperidine derivatives, particularly N-C1~C 30 Alkoxypiperidine derivatives are more preferred. 【0081】 In yet another embodiment, the following types: N-C1~C 30 Alkylcarbonylpiperidine derivatives, N-C1~C 30 Alkenylcarbonylpiperidine derivatives, and N-arylcarbonylpiperidine derivatives, particularly N-C1~C 30 - Alkylcarbonylpiperidine derivatives are more preferred. 【0082】 While not bound by any particular theory, it is considered preferable that the pKa value of the 2,2,6,6-tetraalkylpiperidine derivative be less than 8.5. Therefore, it is preferable that N is substituted (i.e., not NH). More preferably, the pKa is less than 8.0, for example less than 7.0, for example less than 6.0, or less than 5.0. 【0083】 Furthermore, it is preferable that the 2,2,6,6-tetraalkylpiperidine derivative (and generally sterically hindered amines) in the overall structure of formula I or II does not contain either primary or secondary amines. Moreover, it is preferable that the structure of formula I or II does not contain sterically unhindered tertiary amines. 【0084】 In the context of the present invention, the alkylene moiety and the alkenylene moiety include both linear and branched portions. For example, C1-C 30 Alkyl groups include linear and branched C1-C groups. 30 Alkyl groups are included. When it is stated that the R groups (especially R1, R2, R3, and R4) "may be substituted," this means that they may be substituted with halogens (-F, -Cl, -Br, or -I), -C1-C4 alkyl groups, or -OH groups at any preferred position. The term "spiro" has its usual meaning in organic chemistry, i.e., it means two or more rings sharing a common atom. 【0085】 The hindered amine light stabilizer moiety, such as a derivative of formula I or II, can exist in the emulsion composition as a single molecule and / or as part of an oligomeric or polymer structure. In one embodiment, the sterically hindered amine moiety, such as a derivative of formula I or II, exists in the emulsion composition as a single molecule. In another embodiment, the sterically hindered amine moiety exists in the emulsion composition as part of an oligomeric or polymer structure. 【0086】 Examples of hindered amine light stabilizers, particularly 2,2,6,6-tetraalkylpiperidine derivatives, are further described in WO2019 / 233985 and WO2016 / 105974, which are incorporated herein by reference. 【0087】 Specific examples of commercially available 2,2,6,6-tetramethylpiperidine type hindered amine light stabilizers include Sabostab UV65 (N-CH3), Sabostab UV40 (NH), Sabostab UV79 (NH) from Sabo SpA; Hostavin 3058 (N-acyl), Hostavin 3070 (oligomer), Hostavin 3050 from Clariant; Tinuvin 622 (oligomer), Tinuvin 144 (N-CH3), Flamestab NOR 116 (NOR), Chimassorb 944 (NH), Tinuvin 249 (NOR), Tinuvin 440 (N-acyl), Tinuvin 152 (NOR), Tinuvin 123 (NOR), Uvinul 4050 H (NH), and Lignostab from BASF. These include 1198 (NO·, monomer), Uvinul 5050 H (NH, polymer); ADK STAB LA-52 (N-CH3), ADK STAB LA-68 (NH), ADK STAB LA-82 (N-CH3) from Adeka Palmarole; and UBS-0822 (NH, siloxane) and UBS-0541 (NH, siloxane) from Gelest, with Tinuvin 123 (NOR), Hostavin 3050, and Tinuvin 292 being preferred. 【0088】 If hindered amine light stabilizers are present in the emulsified composition, they are usually present in amounts of up to 10% by weight of the emulsified composition, for example, up to 5% by weight, 4% by weight, 3% by weight, or 2% by weight or 1% by weight of the emulsified composition, preferably 0.01 to 10% by weight of the emulsified composition, for example, 0.1 to 5% by weight of the emulsified composition, for example, 0.1 to 4% by weight, or 0.1 to 3% by weight, or 0.1 to 2% by weight, or 0.1 to 1% by weight of the emulsified composition. 【0089】 The hindered amine light stabilizer contained in the composition is usually included in the second composition before the first composition is mixed with the second composition. 【0090】 UV absorber The emulsified composition may further contain one or more UV absorbers. UV absorbers are light stabilizers that absorb harmful ultraviolet rays and protect polymers from UV degradation due to their high UV absorption capacity, and dissipate the absorbed UV energy as heat without changing the properties of the polymer. This mechanism is complementary to the free radical scavenging mechanism of hindered amine light stabilizers, and consequently, UV absorbers may be used alone, or higher performance can be achieved by using them in combination with hindered amine light stabilizers. 【0091】 However, in one embodiment, as described above, the UV absorber is present without the simultaneous presence of the hindered amine light stabilizer. 【0092】 Examples of UV absorbers include benzotriazoles, benzoates, benzophenones, cyanoacrylates, oxanilides, and triazines. 【0093】 Preferred UV absorbers are benzotriazoles or triazines. 【0094】 Some interesting commercially available UV absorbers include Tinuvin 99-2, Tinuvin 326, Tinuvin 900, Tinuvin 1130, ADK STAB LA-29, ADK STAB LA-46, and ADK STAB 1413. 【0095】 If present, the total amount of UV absorbers typically constitutes up to 10% by weight of the emulsified composition, for example, up to 5% by weight, 4% by weight, 3% by weight, 2% by weight, or 1% by weight of the emulsified composition, preferably 0.01 to 10% by weight of the emulsified composition, for example, 0.1 to 5% by weight of the emulsified composition, for example, 0.1 to 4% by weight, 0.1 to 3% by weight, 0.1 to 2% by weight, or 0.1 to 1% by weight of the emulsified composition, or 0.01 to 4% by weight of the emulsified composition, for example, 0.01 to 3% by weight, 0.01 to 2% by weight, or 0.01 to 1% by weight. 【0096】 The ultraviolet absorber contained in the composition is typically added to the second composition before mixing the first composition with the second composition. 【0097】 biocides The claimed post-curing treatment provides an effective antifouling effect without including a biocide in the emulsified composition. Therefore, in a preferred embodiment, the emulsified composition contains no biocides for the purpose of imparting the antifouling effect. While the inclusion of biocides is undesirable, the emulsified composition may contain a biocide. Biocides relevant to antifouling systems are well known to those skilled in the art and can be selected, for example, from those listed in WO2023 / 036923. 【0098】 additives The emulsified composition and / or the first composition may contain additives such as rheological modifiers (including thixotropic agents, thickeners, and anti-settling agents), dispersants, wetting agents, surfactants, binders, plasticizers, and dyes. Examples of rheological modifiers include colloidal silica, hydrated aluminum silicate (bentonite), aluminum tristearate, aluminum monostearate, xanthan gum, chrysotile, calcined silica, hydrogenated castor oil, hydroxyethylcellulose, organically modified clay, polyamide wax, and polyethylene wax. The additives are typically added to the first composition before mixing the first and second compositions. The rheological modifier is typically present in the emulsified composition in an amount of 0 to 10% by weight, more preferably 0.1 to 5.0% by weight, and even more preferably 0.1 to 2.0% by weight. 【0099】 Since the claimed composition is aqueous, antifungal components known to those skilled in the art may be included as further additives to improve the shelf life. 【0100】 Preparation of emulsified compositions The emulsified composition is prepared from a first composition and a second composition. The first composition contains a liquid carrier for the continuous phase (typically water), and the second composition contains one or more poly(oxyalkylene)-modified silicone oils. The first and second compositions may also contain further components such as hindered amine-based light stabilizers, ultraviolet absorbers, and additives, as described later. 【0101】 The emulsified composition can be prepared by first preparing the first composition containing water and optional additives, then separately preparing the second composition containing the poly(oxyalkylene) modified silicone oil and optionally a hindered amine-based light stabilizer and an ultraviolet absorber, and then mixing the first and second compositions. An example of a method for preparing the emulsified composition is shown below. 【0102】 All components of the first composition can be mixed at 3500 rpm for at least 15 minutes in a high-speed dissolving machine equipped with an impeller disc. The components of the second composition can be mixed manually for at least 2 minutes. Then, the first and second compositions can be mixed at 3500 rpm for at least 15 minutes using a high-speed dissolving machine equipped with an impeller disc immediately before application. Those skilled in the art can utilize methods similar to and modified from those described herein. 【0103】 It is important to understand that when we refer to an "emulsified composition," it means a mixed composition that contains the components of the continuous phase and dispersed phase in the desired amounts and is ready to be applied to an antifouling coating. 【0104】 Application of emulsified composition The emulsified composition according to the present invention is applied to an antifouling coating, preferably a polysiloxane-based coating. 【0105】 The term "coating" is used in the common sense of the paint industry. Therefore, "coating" is carried out by any conventional means, such as brushes, rollers, or sprays. The most commercially interesting methods of "coating" an emulsion composition are by roller or spray. Therefore, the emulsion composition is preferably sprayable. Spraying is carried out by conventional spraying equipment known to those skilled in the art. The emulsion composition is typically coated with a wet film thickness of 30-400 μm, e.g., 50-400 μm, e.g., 75-300 μm, or 75-200 μm, e.g., about 100 μm. 【0106】 Typically, the emulsified composition is applied in an amount of 0.03 to 0.4 liters per square meter, for example, 0.05 to 0.4 liters per square meter, or for example, 0.075 to 0.3 liters per square meter. 【0107】 After contact with the surface for at least two hours, any residual emulsified composition remaining on the surface can be removed directly or by dissolving it during navigation. The composition is typically removed with water, for example, by rinsing the surface with water, cleaning with a brush or sponge, or by air blowing. The water may contain soap, which is optionally removed by subsequent rinsing with water. Another method for removing excess composition is by abrasion, for example, by polishing with a cloth. In one embodiment, excess composition remains on the surface without being removed. 【0108】 The phrase "at least a portion of the surface of the substrate" means that the emulsified composition can be applied to any portion of the surface. The emulsified composition is applied to at least a portion of a substrate (e.g., an antifouling coating) whose surface can come into contact with water (e.g., seawater). 【0109】 The term "base coat" refers to the top layer of an antifouling coating. Typical base coats include polysiloxane-based coatings. Alternative base coats, such as acrylate coatings and other non-corrosive coatings, may also be included. 【0110】 The term "surface" is used in its ordinary sense and refers to the external boundary of an object. In the context of the present invention, the emulsion composition is applied to the surface of an antifouling coating. The antifouling coating to which the emulsion composition is applied is typically found on the surface of marine structures such as ships (including, but not limited to, all kinds of boats, yachts, motorboats, engine boats, ocean liners, tugboats, tankers, container ships and other cargo ships, submarines, and naval vessels). In one embodiment, the antifouling coating is found on structures such as pipes, coastal and offshore machinery, piers, piles, and bridge foundations, hydroelectric power plants and structures, and subsea oil well structures. 【0111】 In one embodiment, the emulsified composition is applied on a freshly applied antifouling paint coat, as described above. In another embodiment, the emulsified composition is applied on an aged coat, such as a worn antifouling paint coat. 【0112】 Numbered Embodiments Embodiments of the present invention are disclosed below. It should be understood that the various aspects, embodiments, practices, and features of the present invention described herein may be claimed individually or in any combination. 【0113】 E1. A post-curing treatment method for an antifouling paint coating, comprising the following steps: a. A step of applying an emulsifying composition onto the surface of the antifouling paint coating; b. The step of keeping the emulsified composition in contact with the surface of the antifouling paint coating for at least two hours; Includes, A method wherein the emulsifying composition comprises a liquid continuous phase containing water and a liquid dispersion phase containing one or more poly(oxyalkylene)-modified silicone oils. 【0114】 E2. The total amount of water is 40-99 or 40-95, 40-90, 40-85, or 40-80 or 40-75 or 40-70% by weight of the emulsified composition, for example 45-99 or 45-95 or 45-90 or 45-85, or 45-80 or 45-75 or 45-70% by weight of the weight of the emulsified composition, for example 50-99 or 50-95 or 50-90 or 50-85, or 50-80 or 50-75 or 50-70% by weight, for example 55-99 or 55-95 or 55-90 or 55-85, or 55-80 or 55-75 or 55-70% by weight, for example 60-99 or 60-95 A method according to Embodiment E1, comprising 60-90 or 60-85 or 60-80 or 60-75 or 60-70% by weight, for example 63-99 or 63-95 or 63-92% by weight, for example 65-99 or 65-95 or 65-90 or 65-85 or 65-80 or 65-75 or 65-70% by weight, for example 70-99 or 70-95 or 70-90 or 70-85 or 70-80 or 70-75% by weight, for example 75-99 or 70-95 or 70-90 or 70-85 or 70-80% by weight, for example 80-99 or 80-95 or 80-90 or 80-85% by weight. 【0115】 E3. A method according to any of Embodiments E1 to E2, wherein the total amount of poly(oxyalkylene) modified silicone oil constitutes 1 to 40 or 1 to 35 or 1 to 30 or 1 to 25% by weight of the emulsified composition, for example 2 to 40 or 2 to 35 or 2 to 30 or 2 to 25% by weight, for example 5 to 40 or 1 to 35 or 5 to 30 or 5 to 25% by weight, for example 10 to 40 or 10 to 35 or 10 to 30 or 10 to 25% by weight, for example 15 to 40 or 15 to 35 or 15 to 30 or 15 to 25% by weight. 【0116】 E4. The total amount of water is 40-99 or 40-95, 40-90, 40-85 or 40-80 or 40-75 or 40-70% by weight of the emulsified composition, for example 45-99 or 45-95 or 45-90 or 45-85 or 45-80 or 45-75 or 45-70% by weight of the emulsified composition, for example 50-99 or 50-95 or 50-90 or 50-85 or 50-80 or 50-75 or 50-70% by weight, for example 55-99 or 55-95 or 55-90 or 55-85 or 55-80 or 55-75 or 55-70% by weight, for example 60-99 or 6 Consists of 0-95 or 60-90 or 60-85 or 60-80 or 60-75 or 60-70% by weight, for example 63-99 or 63-95 or 63-92% by weight, for example 65-99 or 65-95 or 65-90 or 65-85 or 65-80 or 65-75 or 65-70% by weight, for example 70-99 or 70-95 or 70-90 or 70-85 or 70-80 or 70-75% by weight, for example 75-99 or 70-95 or 70-90 or 70-85 or 70-80% by weight, for example 80-99 or 80-95 or 80-90 or 80-85% by weight, A method according to any of Embodiments E1 to E3, wherein the total amount of poly(oxyalkylene) modified silicone oil constitutes 1 to 40 or 1 to 35 or 1 to 30 or 1 to 25% by weight of the emulsified composition, for example, 2 to 40 or 2 to 35 or 2 to 30 or 2 to 25% by weight, for example, 5 to 40 or 1 to 35 or 5 to 30 or 5 to 25% by weight, for example, 10 to 40 or 10 to 35 or 10 to 30 or 10 to 25% by weight, for example, 15 to 40 or 15 to 35 or 15 to 30 or 15 to 25% by weight. 【0117】 E5. A method according to any of embodiments E1 to E4, wherein the emulsified composition is kept in contact with the surface of the antifouling paint coating for at least 3 hours, preferably at least 4 or 5 hours, more preferably at least 6, 7, 8, 9 or 10 hours, for example, at least 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23 or 24 hours. 【0118】 E6. A method according to any of embodiments E1 to E5, wherein the emulsified composition is kept in contact with the surface of the antifouling paint coating for 4 to 48 hours, for example 4 to 40 hours, 4 to 36 hours, 4 to 32 hours, 4 to 28 hours, or 4 to 24 hours, or 6 to 48 hours, for example 6 to 40 hours, 6 to 36 hours, 6 to 32 hours, 6 to 28 hours, or 6 to 24 hours. 【0119】 E7. A method according to any of embodiments E1 to E6, wherein the emulsifying composition is prepared from a first composition containing water and a second composition containing poly(oxyalkylene) modified silicone oil. 【0120】 E8. The method according to Embodiment E7, wherein the first composition comprises at least 70% by weight, for example at least 80% by weight, for example at least 90% by weight, preferably at least 95% by weight, for example at least 99% by weight of water, and the second composition comprises at least 1% by weight, for example at least 5% by weight, for example at least 10% by weight, for example at least 15% by weight, for example at least 20% by weight of poly(oxyalkylene) modified silicone oil. 【0121】 E9. Follow these steps: c. After step b, a step to remove excess emulsifying composition from the surface of the antifouling paint coating, Includes, A method according to any of embodiments E1 to E8, wherein the removal is performed by washing the surface with water or by cleaning it with a brush or sponge. 【0122】 E10. A method according to embodiment E9, wherein the removal is further carried out by washing the surface with soap and then rinsing it with water. 【0123】 E11. A method according to any one of embodiments E1 to E10, characterized in that the poly(oxyalkylene) modified silicone oil has an HLB value in the range of 1.5 to 14, for example 1.5 to 14, preferably 1.5 to 12, more preferably 1.5 to 10, for example 1.5 to 8 or 2 to 10. 【0124】 E12. A method according to any of embodiments E1 to E11, wherein the poly(oxyalkylene) portion of the poly(oxyalkylene)-modified silicone oil is selected from polyoxyethylene; polyoxypropylene and / or poly(oxyethylene-co-oxypropylene), preferably polyoxyethylene. 【0125】 E13. A method according to any of Embodiments E1 to E12, wherein the emulsified composition is applied to a wet film thickness of 30 to 400 μm, for example 50 to 400 μm, for example 75 to 300 μm, or 75 to 200 μm, for example about 100 μm. 【0126】 E14. The emulsified composition and / or the second composition may further i) One or more hindered amine light stabilizers; and / or ii) One or more UV absorbers; A method according to any of embodiments E1 to E13, including the above. 【0127】 E15. The method according to Embodiment E14, wherein one or more hindered amine light stabilizers are selected from 2,2,6,6-tetraalkylpiperidine derivatives. 【0128】 E16. A method according to any one of embodiments E14 to E15, wherein the one or more hindered amine light stabilizers are present in an amount of up to 10% by weight of the emulsified composition, for example, up to 5% by weight, 4% by weight, 3% by weight, 2% by weight, or 1% by weight of the emulsified composition. 【0129】 E17. A method according to any of embodiments E14 to E16, wherein the one or more hindered amine-based light stabilizers are present in an amount of 0.01 to 10% by weight of the emulsion composition, for example, 0.1 to 5% by weight, for example, 0.1 to 4% by weight or 0.1 to 3% by weight or 0.1 to 2% by weight or 0.1 to 1% by weight, or 0.01 to 4% by weight of the emulsion composition, for example, 0.01 to 3% by weight or 0.01 to 2% by weight or 0.01 to 1% by weight. 【0130】 E18. A method according to any of embodiments E14 to E17, wherein one or more ultraviolet absorbers are selected from a list consisting of benzotriazoles, benzoates, benzophenones, and triazines. 【0131】 E19. A method according to any of embodiments E14 to E18, wherein the one or more ultraviolet absorbers are present in an amount of up to 10% by weight of the emulsified composition, for example, up to 5% by weight, up to 4% by weight, up to 3% by weight, up to 2% by weight, or up to 1% by weight of the emulsified composition. 【0132】 E20. A method according to any of embodiments E14 to E19, wherein the one or more ultraviolet absorbers are present in an amount of 0.01 to 5% by weight of the emulsified composition, for example, 0.1 to 5% by weight of the emulsified composition, for example, 0.1 to 4% by weight or 0.1 to 3% by weight or 0.1 to 2% by weight or 0.1 to 1% by weight of the emulsified composition, or in an amount of 0.01 to 4% by weight of the emulsified composition, for example, 0.01 to 3% by weight or 0.01 to 2% by weight or 0.01 to 1% by weight of the emulsified composition. 【0133】 E21. A method according to any of Embodiments E1 to E21, wherein the emulsifying composition and / or the first composition further comprises one or more additives such as one or more rheological modifiers such as a thixotropic agent, a thickener and / or an anti-settling agent. 【0134】 E22. A method according to Embodiment E21, wherein the rheological modifier is selected from colloidal silica, hydrated aluminum silicate (bentonite), aluminum tristearate, aluminum monostearate, xanthan gum, chrysotile, calcined silica, hydrogenated castor oil, hydroxyethylcellulose, organically modified clay, polyamide wax, and polyethylene wax. 【0135】 E23. A method according to any of embodiments E21 to E22, wherein the rheological modifier is present in an amount of 0 to 10% by weight, more preferably 0.1 to 5.0% by weight, and even more preferably 0.1 to 2.0% by weight. 【0136】 E24. A method according to any of Embodiments E1 to E23, wherein the emulsified composition is applied by brush, roller, or spray application, preferably by spray application. 【0137】 E25. A method according to any of embodiments E1 to E24, wherein the antifouling coating is applied to the outer surface of the substrate, and the substrate is a substrate for immersion in water, such as a ship. 【0138】 E26. A method according to any of embodiments E1 to E25, comprising an initial step of confirming that the substrate has the antifouling coating on its outer surface. 【0139】 E27. A method according to any of embodiments E1 to E26, wherein the antifouling coating is a non-erosive coating, preferably a polysiloxane-based coating. 【0140】 E28. A method according to any of embodiments E1 to E27, wherein the antifouling coating is a coating applied immediately after application. 【0141】 E29. A method according to any of embodiments E1 to E28, wherein the antifouling coating is an aged coating such as a worn coating. 【0142】 E30. A method according to any of embodiments E1 to E29, wherein the antifouling paint coating constitutes the outermost layer of an antifouling system further comprising a primer and / or tie coat. 【0143】 E31. The emulsifying composition is the following or substantially the following: • Continuous liquid phase containing water, • A liquid dispersion phase containing one or more poly(oxyalkylene) modified silicone oils. Optionally, one or more hindered amine light stabilizers, preferably 2,2,6,6-tetraalkylpiperidine derivatives, Optionally, one or more UV absorbers, and • 1 or more, preferably 2 or more rheological modifiers, A method according to any one of embodiments E1 to E30, comprising: A method according to any of embodiments E1 to E30. 【0144】 E32. The emulsified composition is as follows: • A liquid continuous phase containing at least 60% by weight of water in the emulsified composition, • 1 to 25% by weight of one or more poly(oxyalkylene) modified silicone oils in the emulsified composition. • 1 to 10% by weight of the emulsified composition, one or more hindered amine light stabilizers, preferably 2,2,6,6-tetraalkylpiperidine derivatives. • Two or more rheological modifiers in an amount of 0.1 to 10% by weight (total) of the emulsified composition. The method according to any one of embodiments E1 to E31, which includes or comprises the same. 【0145】 E33. Use of any of the methods according to embodiments E1 to E32 for improving the antifouling properties of an antifouling paint coating. 【0146】 E34. A non-erosive coating, such as an antifouling coating or polysiloxane-based coating, treated by any of the methods according to Embodiments E1 to E32. 【0147】 E35. An antifouling coating according to Embodiment E32, wherein at least a portion of the outer surface, i) One or more cured primer layers; ii) One or more cured tie coat layers; and iii) One or more additional layers of hardened antifouling coating Includes, An antifouling coating, wherein the antifouling coating is treated by a method according to any of embodiments E1 to E32. 【0148】 All documents cited herein, including publications, patent applications, and patents, are incorporated by reference, individually and specifically, and in whole, to the same extent as they are described herein (to the maximum extent permitted by law), regardless of any other instances elsewhere in this specification where specific documents are incorporated by reference. 【0149】 In the context describing the present invention, terms such as “a,” “an,” and “the,” and similar references, should be interpreted as including both singular and plural forms unless otherwise specified herein or unless the context clearly contradicts this interpretation. For example, the phrase “(the composition)” should be understood, unless otherwise specified, to refer to the various “compositions” of the present invention or any particular described embodiment. 【0150】 In this specification, any description of an aspect of the invention that uses terms such as “comprising,” “having,” “including,” or “containing” with respect to an element is intended to provide support for similar aspects of the invention that “consists of,” “consists essentially of,” or “substantially comprises” that particular element, unless otherwise stated or unless the context clearly contradicts it (for example, a composition described in this specification as containing a particular element should be understood to also describe a composition consisting of that element, unless otherwise stated or unless the context clearly contradicts it). 【0151】 Any use of examples or exemplary language (such as "for instance," "for example," "eg," "such as," etc.) herein is intended solely to provide a clearer description of the invention and, unless otherwise stated, does not limit the scope of the invention. 【0152】 Headings and subheadings are used herein for convenience only and should not be construed as limiting the invention in any way. Any use of examples or exemplary language herein (such as "for instance," "for example," "eg," "such as") is intended solely to clarify the invention and, unless otherwise stated, does not limit the scope of the invention. References and incorporations of patent documents herein are for convenience only and do not reflect any views on the validity, patentability, and / or applicability of such patent documents. 【0153】 It should be understood that the various aspects, embodiments, practices, and features of the present invention referred to herein may be claimed individually or in any combination. [Examples] 【0154】 experiment The present invention will be illustrated by the following non-limiting embodiments. 【0155】 Antifouling performance (raft performance) test A static immersion test was conducted using a 150mm x 200mm acrylic plate. The emulsified composition was applied to the polysiloxane-based coating using an airless spray, doctor blade applicator, brush, or roller. After a predetermined time, the emulsified solution was removed for approximately 1 minute using tap water and a sponge. The remaining emulsified composition was removed using soap. Further rinsing with water removed any soap residue. 【0156】 When the polysiloxane coating was applied, it was applied to a suitable tie coat according to the specifications of the polysiloxane coating, and then cured for at least 6 hours so that the coating was touch-dry before application of the emulsion composition. The polysiloxane coating was applied to a dry film thickness (dft) of approximately 66–200 μm. In most cases, the dft was 200 μm. 【0157】 The antifouling performance test was conducted using panels in Vilanova i la Geltru, northeastern Spain. At this test site, the panels were immersed in seawater with an average temperature of 17-18°C and a salinity of 37-38 ppt (parts per thousand). 【0158】 The panel was examined every 4 to 12 weeks and evaluated according to the following criteria. 【0159】 [Table 1] 【0160】 Extraction and quantification of poly(oxyalkylene) modified silicone oil using GPC Samples of the silicone substrate coating were cut with a scalpel and added to 0.5-1 mL of tetrahydrofuran (THF) containing a polystyrene internal standard (C=0.554 μmol / L, Mw=130 kg / mol). After extracting the samples in a shaker for 2 hours, they were transferred to 1 mL vials using the tilt method. 【0161】 The content of polyoxyalkylene-modified silicone oil absorbed into the polysiloxane-based coating was quantified using gel permeation chromatography (GPC). The GPC system consisted of two PLgel 5μm Mixed D (300×7.5mm) tubes and one PLgel 5μm Mixed C tube. O The system consisted of three columns (300 × 7.5 mm). GPC curves were recorded using an ELS detector and a mixed eluent of tetrahydrofuran and 5% triethylamine at a flow rate of 1 mL / min. To quantify the amount of poly(oxyalkylene)-modified silicone oil extracted from the coating, a calibration curve was created by adding poly(oxyalkylene)-modified silicone oil to a liquid poly(siloxane) coating mixture before application. A calibration curve was created (using BYK-3764 as the poly(oxyalkylene)-modified silicone oil), and this was used to calibrate all poly(oxyalkylene)-modified silicone oils. 【0162】 material 【0163】 [Table 2] 【0164】 [Table 3] 【0165】 The polysiloxane coating (SC) was prepared by mixing all the components of Part I in a pearl mill at 75°C for 30 minutes, and then filtering through a sieve. The components of Part II were mixed manually for 2 minutes. 【0166】 Stain-resistant performance The following compositions were prepared according to the formulations provided herein. Next, the emulsified compositions were applied to a newly applied coating layer using a doctor blade applicator with a gap size of 300 μm. After 96 hours, the emulsified compositions were removed from the substrate by gently washing with a sponge using warm water and detergent for approximately 1 minute. Residual soap was removed with warm water. The substrate was then air-dried vertically at room temperature. The treated panels were examined for their antifouling properties according to the formulations provided above. 【0167】 [Table 4] 【0168】 Table 3A shows that post-treatment of silicone coatings with emulsified compositions containing hydrophilic modified oils of various concentrations significantly improves antifouling performance compared to untreated coatings. Furthermore, it can be seen that the amount of polyoxyalkylene-modified silicone oil that can be extracted after treatment with the emulsified composition is equivalent to that obtained when up to 2% by weight of polyoxyalkylene-modified silicone oil is added to a liquid polysiloxane mixture before coating application. In Example 3A.4, the values ​​were below the detection limit of the extraction and quantification methods. 【0169】 [Table 5] 【0170】 Table 3B shows that post-treatment of a silicone coating with an emulsified composition containing hydrophilic modified oil at various concentrations significantly improves its antifouling performance compared to both the emulsified composition without hydrophilic modified oil and the untreated coating. 【0171】 [Table 6] 【0172】 Table 4 shows that the incorporation of poly(oxyalkylene) modified silicone oil increases with contact time, and that the antifouling performance improves with increasing contact time. Comparative Example 4.9, which was untreated, shows that its performance had already deteriorated after 4 weeks. 【0173】 [Table 7] 【0174】 Table 5 shows that all types of poly(oxyalkylene) modified silicone oils tested exhibited "good" or "excellent" raft performance after 20 weeks in Spanish seawater. Comparative Example 5.6 shows poor performance at both 20 and 36 weeks. 【0175】 [Table 8] 【0176】 Table 6 shows that raft performance after 29 weeks in Spanish seawater is "good" when HLB=10, but deteriorates when HLB increases to 14. 【0177】 [Table 9] 【0178】 Table 7 shows the methods using compositions with varying concentrations of poly(oxyalkylene) modified silicone oil and HALS. It can be seen that the performance of the treated panels is high at various concentrations. 【0179】 The examples in Tables 3A and 7 were investigated for their antifouling performance using the same test series. In other words, the blank coats (reference) in Tables 3A and 7 are the same. 【0180】 [Table 10] 【0181】 Table 8 demonstrates superior performance for substrates of different thicknesses. It also shows that more oil is absorbed as the film thickness increases. 【0182】 The examples in Tables 3A, 7, and 8 were investigated for their antifouling performance using the same test series. In other words, the blank coats (reference) in Tables 3A, 7, and 8 are the same. 【0183】 [Table 11] 【0184】 Table 9 shows the methods using compositions with varying concentrations of hindered amine-based light stabilizers and UV absorbers. It can be seen that the performance of the treated panels remains high even when the concentrations are changed.

Claims

[Claim 1] A post-curing treatment method for an antifouling paint coating, comprising the following steps: a. A step of applying an emulsified composition onto the surface of the antifouling paint coating; b. The step of keeping the emulsified composition in contact with the surface of the antifouling paint coating for at least two hours; Includes, A method wherein the emulsifying composition comprises a liquid continuous phase containing water and a liquid dispersion phase containing one or more poly(oxyalkylene)-modified silicone oils. [Claim 2] The total amount of water constitutes 40 to 99% by weight of the emulsified composition; and The method according to claim 1, wherein the total amount of poly(oxyalkylene) modified silicone oil constitutes 1 to 40% by weight of the emulsified composition. [Claim 3] The method according to claim 1 or 2, wherein the emulsified composition is kept in contact with the surface of the antifouling paint coating for at least 3 hours, preferably at least 4 or 5 hours, more preferably at least 6, 7, 8, 9 or 10 hours, for example, at least 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23 or 24 hours. [Claim 4] Furthermore, follow these steps: c. After step b, a step of removing excess emulsified composition from the surface of the antifouling paint coating, Includes, The method according to any one of claims 1 to 3, wherein the removal is performed by washing the surface with water or by cleaning it with a brush or sponge. [Claim 5] The method according to any one of claims 1 to 4, characterized in that the poly(oxyalkylene) modified silicone oil has an HLB value in the range of 1.5 to 14, for example 1.5 to 14, preferably 1.5 to 12, more preferably 1.5 to 10, for example 1.5 to 8 or 2 to 10. [Claim 6] The method according to any one of claims 1 to 5, wherein the antifouling coating is a non-erosive coating, preferably a polysiloxane-based coating. [Claim 7] The method according to any one of claims 1 to 6, wherein the emulsified composition is applied to a wet film thickness of 30 to 400 μm, for example 50 to 400 μm, for example 75 to 300 μm, or 75 to 200 μm, for example about 100 μm. [Claim 8] The method according to any one of claims 1 to 7, wherein the emulsifying composition is prepared from a first composition containing water and a second composition containing poly(oxyalkylene) modified silicone oil. [Claim 9] The emulsified composition and / or the second composition further i) One or more hindered amine light stabilizers; and / or ii) One or more UV absorbers The method according to any one of claims 1 to 8, including the method described in any one of claims 1 to 8. [Claim 10] The method according to claim 9, wherein the one or more hindered amine-based light stabilizers are present in an amount of 0.01 to 10% by weight of the emulsion composition, for example, 0.1 to 5% by weight, for example, 0.1 to 4% by weight, or 0.1 to 3% by weight, or 0.1 to 2% by weight, or 0.1 to 1% by weight, or 0.01 to 4% by weight of the emulsion composition, for example, 0.01 to 3% by weight, or 0.01 to 2% by weight, or 0.01 to 1% by weight. [Claim 11] The method according to any one of claims 1 to 10, wherein the poly(oxyalkylene) portion of the poly(oxyalkylene) modified silicone oil is selected from polyoxyethylene; polyoxypropylene and / or poly(oxyethylene-co-oxypropylene), and is preferably polyoxyethylene. [Claim 12] The method according to any one of claims 1 to 11, wherein the antifouling coating is a coating applied immediately after application. [Claim 13] The method according to any one of embodiments 1 to 11, wherein the antifouling coating is an aged coating such as a worn coating. [Claim 14] The method according to any one of claims 1 to 13, wherein the emulsifying composition and / or the first composition contains one or more additives, such as one or more (preferably two or more) rheological modifiers, such as a thixotropic agent, a thickener and / or a settling inhibitor. [Claim 15] The emulsifying composition is the following or substantially the following: • Continuous liquid phase containing water, - A liquid dispersion phase containing one or more poly(oxyalkylene) modified silicone oils, Optionally, one or more hindered amine light stabilizers, preferably 2,2,6,6-tetraalkylpiperidine derivatives, Optionally, one or more UV absorbers, and - One or more, preferably two or more rheological modifiers, The method according to any one of the above claims. [Claim 16] The emulsified composition is as follows: - A liquid continuous phase containing at least 60% by weight of water in the emulsified composition, - 1 to 25% by weight of one or more poly(oxyalkylene) modified silicone oils in the emulsified composition. - 1 to 10% by weight of the emulsified composition one or more hindered amine light stabilizers, preferably 2,2,6,6-tetraalkylpiperidine derivatives, - Two or more rheological modifiers in an amount of 0.1 to 10% by weight (total) of the emulsifying composition, The method according to any one of the claims, comprising or including the above. [Claim 17] Use of the method according to any one of claims 1 to 16 to improve the antifouling properties of an antifouling paint coating. [Claim 18] A non-erosive antifouling coating, such as an antifouling coating, preferably a polysiloxane-based coating, treated by the method described in any one of claims 1 to 16.

Images