Post-cure treatment of antifouling coatings

Abstract

The present invention relates to a method for post-curing treatment of an anti-fouling paint coating comprising the steps of: a. Applying an emulsifying composition onto a surface of the anti-fouling paint coating, b. Keeping the emulsifying composition in contact with the surface of the anti-fouling paint coating for at least 2 hours; wherein the emulsified composition comprises a liquid continuous phase and a liquid dispersed phase, the liquid continuous phase comprising water, and the liquid dispersed phase comprising one or more poly (oxyalkylene) modified silicone oils. The invention also relates to the use of a post-cure treatment for providing anti-fouling properties to anti-fouling paint coatings. The invention also relates to a structure, preferably a marine structure, having an anti-fouling topcoat on the outer surface subjected to a post-cure treatment.

Description

Technical Field

[0001] This invention relates to a method for post-curing treatment of an antifouling coating. The invention also relates to the use of post-curing treatment to provide antifouling properties to an antifouling paint coating. Furthermore, the invention relates to structures having an antifouling surface coating that has undergone post-curing treatment on its outer surface, preferably marine structures. Background Technology

[0002] Aquatic structures that come into contact with water, especially seawater, particularly submerged marine structures, are prone to fouling by marine organisms. Antifouling coatings are widely used on such structures, such as ships, buoys, and vessel structures, to inhibit the attachment of these marine organisms or encourage their release.

[0003] Antifouling coating systems for steel structures (such as marine structures) typically consist of three main layers: an anti-corrosion layer applied to the steel structure, an antifouling layer, and an intermediate layer (often called an "adhesive layer") used to establish a strong bond between the anti-corrosion and antifouling layers. The antifouling layer is usually composed of a polysiloxane alkyl adhesive matrix.

[0004] Polysiloxane coatings are widely used in antifouling coatings for marine structures. Known principles for improving the antifouling effect of polysiloxane coatings include the inclusion of hydrophilically modified oils and, most commonly, biocides or enzymes. For example, WO2011 / 076856 discloses an antifouling coating composition comprising a polysiloxane binder system, a biocide, and a hydrophilically modified silicone oil; WO2016 / 004961 discloses an antifouling coating composition comprising a polysiloxane binder system, a biocide, and a poly(oxyalkylene) modified alcohol.

[0005] All of these disclosures describe the addition of hydrophilically modified oils, such as poly(oxyalkylene) modified oils, including silicone oils, long-chain alcohols, and acrylate oils, to pre-curing coating compositions, i.e., the hydrophilically modified oils are included in the (wet) coating composition before being applied to the surface of the substrate.

[0006] The antifouling performance of the coatings described above depends on the oils present in the coating. It has been observed that oil concentrations decrease over time due to various mechanisms, such as degradation, diffusion, and exudation (Camós et al., Progress in Organic Coatings (2017), 112: 101-108). Loss of hydrophilic oils can lead to contamination, and it is generally desirable to renew the coating system before the hydrophilically modified oils are completely depleted. The traditional way to renew antifouling properties is by applying a completely new coating or system. Applying a complete antifouling coating system, or even just an antifouling layer, is time-consuming, costly, and requires a large amount of coating material.

[0007] Recently, Kolle et al. disclosed a method of adding hydrophobic silicone oil after curing (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, the coated object and therefore the hull must be completely immersed in the (hydrophobic) silicone oil to introduce the oil into the coating, which is a cumbersome method and requires a large amount of silicone oil. Furthermore, the polysiloxane coating absorbs silicone oil at a rate of 45-50 wt% of the polydimethylsiloxane coating, causing the coating to swell by up to 50% (100-150 µm). This can have adverse effects on the mechanical properties or long-term performance of the film.

[0008] Other documents in this technical field include WO2019 / 233985 and CN114761496.

[0009] A simple and inexpensive method to extend and / or improve the antifouling performance of an antifouling coating would be beneficial. Invention Overview

[0011] This invention provides a method for post-curing treatment of an antifouling paint coating, comprising the following steps:

[0012] a. Apply the emulsified composition to the surface of the antifouling paint coating;

[0013] b. Keep the emulsified composition in contact with the surface of the antifouling coating for at least 2 hours;

[0014] The emulsified composition comprises a continuous liquid phase and a dispersed liquid phase, the continuous liquid phase comprising water, and the dispersed liquid phase comprising one or more poly(oxyalkylene) modified silicone oils.

[0015] In one aspect, the present invention relates to the use of the method of the present invention for improving the antifouling performance of antifouling paint coatings.

[0016] In one aspect, the present invention relates to an antifouling paint coating that has been treated by the method of the present invention, preferably a paint coating that is not easily corroded.

[0017] Further details of the invention are set forth in the dependent claims and the following description. Invention Details

[0019] This invention relates to a method for post-curing treatment of an antifouling paint coating. The terms "antifouling paint coating" and "antifouling coating" are used interchangeably, referring to a coating obtained from a coating composition that provides a surface from which marine organisms cannot adhere or release dirt when water moves along the surface. The antifouling paint coating is preferably a paint coating that is not easily corroded, and more preferably a polysiloxane-based paint coating.

[0020] The inventors have discovered a simple and effective post-curing treatment for antifouling paint coatings that can enhance and / or prolong the antifouling properties of the coating. Unexpectedly, the inventors have discovered that poly(oxyalkylene) modified silicone oils (which are hydrophilic or amphiphilic) can be introduced into the antifouling coating by simply applying an emulsified composition to the surface of the (hydrophobic) antifouling coating.

[0021] In one respect, the present invention thus simply relates to a method of introducing one or more poly(oxyalkylene) modified silicone oils into a polysiloxane varnish coating.

[0022] In the context of this 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 this invention, the continuous phase comprises water, and the dispersed phase comprises one or more poly(oxyalkylene) modified silicone oils.

[0023] Therefore, the method includes the following steps:

[0024] a. Applying the emulsified composition to the surface of the antifouling paint coating; and

[0025] b. Keep the emulsified composition in contact with the surface of the antifouling coating for at least 2 hours;

[0026] The emulsified composition comprises a continuous liquid phase and a dispersed liquid phase, the continuous liquid phase comprising water, and the dispersed liquid phase comprising one or more poly(oxyalkylene) modified silicone oils.

[0027] In one embodiment, the total amount of water is 40-99 wt% of the emulsifying composition; and

[0028] The total amount of poly(oxyalkylene) modified silicone oil is 1-40 wt% of the emulsion composition.

[0029] In one embodiment, the total amount of water is 40-99 wt% or 40-95 wt%, 40-90 wt%, 40-85 wt%, or 40-80 wt%, or 40-75 wt%, or 40-70 wt% of the emulsifying composition, for example 45-99 wt% or 45-95 wt% or 45-90 wt% or 45-85 wt%, or 45-80 wt% or 45-75 wt%. -70wt%, for example 50-99wt%, or 50-95wt%, or 50-85wt%, or 50-80wt%, or 50-75wt%, or 50-70wt%, for example 55-99wt%, or 55-95wt%, or 55-90wt%, or 55-85wt%, or 55-80wt%, or 55-75wt%, or 55-70wt%, for example 60-99wt%. t% or 60-95wt% or 60-90wt% or 60-85wt%, or 60-80wt% or 60-75wt% or 60-70wt%, for example 63-99wt% or 63-95wt% or 63-92wt%, for example 65-99wt% or 65-95wt% or 65-90wt% or 65-85wt%, or 65-80wt% or 65-75wt% or 65- 70 wt%, for example 70-99 wt%, or 70-95 wt%, or 70-85 wt%, or 70-80 wt%, or 70-75 wt%, for example 75-99 wt%, or 70-95 wt%, or 70-85 wt%, or 70-80 wt%, for example 80-99 wt%, or 80-95 wt%, or 80-90 wt%, or 80-85 wt%. In a preferred embodiment, the total amount of water is 50-90 wt% of the emulsified composition, more preferably 50-80 wt%, for example 50-70 wt%.

[0030] In one embodiment, the total amount of poly(oxyalkylene) modified silicone oil is 1-40 wt%, 1-35 wt%, 1-30 wt%, or 1-25 wt% of the emulsion composition, for example, 2-40 wt%, 2-35 wt%, 2-30 wt%, or 2-25 wt%, for example, 5-40 wt%, 1-35 wt%, 5-30 wt%, or 5-25 wt%, for example, 10-40 wt%, 10-35 wt%, 10-30 wt%, or 10-25 wt%, for example, 15-40 wt%, 15-35 wt%, or 15-30 wt%, or 15-25 wt%. In a preferred embodiment, the total amount of poly(oxyalkylene) modified silicone oil is 5-30 wt% of the emulsion composition, more preferably 10-30 wt%, for example, 15-25 wt%.

[0031] Unexpectedly, the inventors have discovered that poly(oxyalkylene) modified silicone oil can be effectively introduced into the antifouling coating by applying the emulsion composition to the surface of the antifouling coating. The emulsion composition can be applied directly to the surface of the antifouling coating, for example, by brushing, spraying, or rolling. The composition can be applied to vertical surfaces, such as the sides of a hull. It is known from the method disclosed by Kolle et al. in Scientific Reports, Nature (2022) 12:11799 that hydrophobic silicone oil can be introduced into the antifouling coating by immersing the entire coated object (i.e., the hull) in hydrophobic silicone oil for a period of time. In contrast to the method of this invention, the method proposed by Kolle et al. is very cumbersome and requires a large amount of oil.

[0032] The post-curing treatment of the present invention can be used to extend the antifouling performance of aged antifouling coatings. This method implies many benefits. For example, replacing a coating or even simply covering a ship with a new antifouling coating often requires the ship to remain in dry dock for extended periods. Dry dock time can be advantageously reduced by simply replenishing the aged or worn antifouling coating with a poly(oxyalkylene) modified silicone oil using the method of the present invention. The terms "aged coating" and "worn coating" refer to a coating that has been applied and used for its purpose for at least a period of time (e.g., at least 6 months, at least one year, at least two years, etc.). For an aged antifouling coating, this means that the coating has been immersed in water for at least that period of time. In one embodiment, the aged coating is an antifouling paint coating originally prepared in a wet stage from an antifouling paint composition containing a hydrophilic modified oil. The post-curing treatment of the present invention is then performed after the hydrophilic modified oil has been partially or completely released from the coating. That is, the treatment serves to replenish the coating with the hydrophilic modified oil.

[0033] The method of the present invention can also be used to enhance the antifouling properties of newly applied coatings prepared from coating compositions that do not yet contain any poly(oxyalkylene) modified silicone oil. That is, the poly(oxyalkylene) modified silicone oil is simply introduced after curing rather than included in the coating composition. The term "newly 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 no later than 3 months after application, for example, no later than 2 months after application, for example, no later than 4 weeks, 3 weeks, 2 weeks, or only 1 week after application. In another embodiment, the newly applied coating has not been immersed in water. The newly applied coating is cured before the application of the emulsion composition. That is, the term "newly applied coating" refers to a coating that has been cured before the application of the emulsion composition. In one embodiment, the newly applied coating has been 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, 16, 20, or 24 hours before the application of the emulsion composition.

[0034] As another advantage, the emulsified compositions of the present invention can be prepared and transported at a concentration that allows for further dilution with water on-site prior to application, which reduces the amount of material to be transported. Furthermore, the emulsified compositions can be prepared in the absence of any volatile organic compounds (VOCs), providing a safe and environmentally friendly alternative for covering or replacing antifouling coatings.

[0035] The emulsified composition may optionally contain one or more light stabilizers and / or free radical scavengers, such as hindered amine light stabilizers (HALS), and / or one or more UV absorbers. Although not preferred, the emulsified composition may also contain one or more biocides.

[0036] The emulsified composition may also contain additives as further described below.

[0037] The emulsified composition is applied to the surface of an antifouling paint coating. The antifouling paint coating is preferably a corrosion-resistant coating, more preferably a polysiloxane paint coating prepared from a coating composition comprising a polysiloxane binder system. The polysiloxane binder system preferably comprises more than 50 wt% polysiloxane, for example, more than 55 wt%, more than 60 wt% or more than 65 wt%, preferably more than 70 wt%, for example, more than 75 wt%, or 80 wt%, or 85 wt%, or 90 wt%, or 95 wt% polysiloxane, based on the weight of the total binder system. Antifouling coatings comprising polysiloxane binder systems are well known to those skilled in the art and have been described, for example, in WO2011 / 079856, WO2013 / 000477 and WO2014 / 117786.

[0038] The emulsified composition is prepared from a main composition and an auxiliary composition. The main composition comprises a liquid carrier for the continuous phase, which includes water, and the auxiliary composition comprises one or more poly(oxyalkylene) modified silicone oils. In addition to water, the liquid carrier may optionally comprise one or more other liquids with suitable properties. The main composition and auxiliary composition may contain additional components, such as hindered amine light stabilizers, UV absorbers, and additives, as described below.

[0039] In the context of this invention, when referring to an "emulsified composition," it means a mixed composition prepared for application to an antifouling coating.

[0040] Poly(oxyalkylene) modified silicone oil

[0041] According to the present invention, the emulsified composition comprises a dispersed phase comprising one or more poly(oxyalkylene) modified silicone oils.

[0042] Poly(oxyalkylene) modified silicone oils are widely used as surfactants and emulsifiers because they contain both hydrophilic and lipophilic groups in the same molecule. "Poly(oxyalkylene) modified silicone oil" generally refers to a silicone oil with hydrophobic properties that has been partially modified with poly(oxyalkylene) components (e.g., as inner chains and / or ends). Poly(oxyalkylene) refers to repeating units of oxygen and alkylene (usually ethylene and propylene).

[0043] Of particular interest are those poly(oxyalkylene) modified silicone oils having the following properties: wherein the relative weight of the poly(oxyalkylene) chains is 1% or more (e.g., 1-90%), such as 5% or more (e.g., 5-80%), particularly 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 the poly(oxyalkylene) chains is 25-60%, such as 30-50%, of the total weight of the poly(oxyalkylene) modified silicone oil. In another embodiment, the relative weight of the poly(oxyalkylene) chains is 15-50 wt%, such as 20-40 wt%.

[0044] When calculating the amount of the poly(oxoalkylene) moiety for a given poly(oxoalkylene) modified silicone oil, it is usually quite simply distinguished from the siloxane moiety. However, to dispel any doubt about any connection between the two, it should be understood that the poly(oxoalkylene) moiety includes, but does not include, all the silicon atoms adjacent to the poly(oxoalkylene) moiety. As an example, in a structure such as formula (I), the residues of formula (i) constitute the poly(oxoalkylene) moiety (hydrophilic moiety).

[0045] In a preferred embodiment, the number-average molecular weight (Mn) of the poly(oxyalkylene) modified silicone oil is... n The concentration is 100-100,000 g / mol, for example 250-75,000 g / mol, especially 500-50,000 g / mol or 500-30,000 g / mol.

[0046] In another preferred embodiment, the poly(oxyalkylene) modified silicone oil has a number average molecular weight (Mn) of 500-20,000 g / mol, for example 1,000-10,000 g / mol, or 1,000-7,500 g / mol, or even 1,500-5,000 g / mol.

[0047] In a preferred embodiment, the poly(oxyalkylene) modified silicone oil has the structure of formula (I):

[0048]

[0049] (I)

[0050] in:

[0051] Each R 1 The components are independently selected from C1-C5-alkyl groups (including straight-chain or branched hydrocarbon groups) and aryl groups (e.g., phenyl (-C6H5)), preferably methyl;

[0052] Each R 5 and R 6 Independently selected from R 1 and the residues of the following formula (i):

[0053]

[0054] (i)

[0055] Each R 2 Independently selected from –H, C1-C4-alkyl (e.g., -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2CH3), phenyl (-C6H5), and C1-C4-alkyl carbonyl (e.g., –C(=O)CH3, -C(=O)CH2CH3, and -C(=O)CH2CH2CH3), especially -H, methyl, and –C(=O)CH3;

[0056] Each R 3 Independently selected from C2-C5 alkylene groups (e.g., -CH2CH2-, -CH2CH(CH3), -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH(CH2CH3)-), aryl groups (e.g., 1,4-phenylene), and aryl-substituted C2-C5 alkylene groups (e.g., 1-phenylethylene), particularly selected from C2-C5 alkylene groups, such as -CH2CH2- and -CH2CH(CH3)-;

[0057] Each R 4 Selected from –(CH2) 2-6 -;

[0058] x is an integer from 0 to 2500 and y is an integer from 0 to 100, provided that x + y is 1 or greater;

[0059] n is 1-70;

[0060] The condition is that at least R 6 Or an R 5 It is a residue of formula (i).

[0061] Specifically, there are three variants within the structure of formula (I). These are polysiloxanes with poly(oxyalkylene) links branched thereto, polysiloxanes with poly(oxyalkylene) chains introduced into their main chain, and combinations of the two variants.

[0062] Graft chain

[0063] In one embodiment, the poly(oxyalkylene) modified silicone oil is a polysiloxane having poly(oxyalkylene) links branched thereto.

[0064] An illustrative example of the structure of such poly(oxyalkylene) modified silicone oil is the compound of formula (I), wherein:

[0065] Two Rs 5 Both are R1;

[0066] R 6 These are residues of formula (i);

[0067] x is an integer from 0 to 2500 and y is an integer from 1 to 100; and

[0068] R 1 R 2 R 3 R 4 And n as defined above.

[0069] Introducing the main chain

[0070] In one embodiment, the poly(oxyalkylene) modified silicone oil is a polysiloxane having poly(oxyalkylene) chains incorporated into its main chain.

[0071] An illustrative example of the structure of such poly(oxyalkylene) modified silicone oil is the compound of formula (I), wherein:

[0072] R 5 At least one of them is a residue of formula (i);

[0073] X is an integer from 1 to 2500 and y is 0; and

[0074] R 1 R 2 R 3 R 4 As defined above.

[0075] In one particular implementation scheme, two R 5 They are all residues of formula (i).

[0076] Introduction of combination and grafting chain

[0077] In one embodiment, the poly(oxyalkylene) modified silicone oil is a polysiloxane having poly(oxyalkylene) chains introduced into its main chain and simultaneously having poly(oxyalkylene) chains branched to the main chain.

[0078] An illustrative example of the structure of such poly(oxyalkylene) modified silicone oil is the compound of formula (I), wherein:

[0079] R 6 and at least one R 5 These are residues of formula (i);

[0080] X is an integer from 1 to 2500 and y is an integer from 1 to 100; and

[0081] R 1 R 2 R 3 R 4 And n as defined above.

[0082] In one particular implementation scheme, R 6 and two R 5 They are all residues of formula (i).

[0083] It should be understood that one or more non-reactive poly(oxyalkylene) modified silicone oils may be of different types, such as two or more of the types described above.

[0084] In formula (I), which includes the three variants described above, groups such as -CH2CH(CH3)- and -CH2CH(CH2CH3)- can be present in either of the two possible orientations. Similarly, it should be understood that segments appearing x and y times are typically randomly distributed or distributed as blocks within the polysiloxane structure.

[0085] In these embodiments and variations, the poly(oxyalkylene) is preferably selected from polyoxyethylene, polyoxypropylene, and poly(oxyethylene-co-oxypropylene), which are sometimes referred to as poly(ethylene glycol), poly(propylene glycol), and poly(ethylene glycol-co-propylene glycol). Therefore, in formula (I) above, each R connecting two oxygen atoms... 3 Preferably selected from -CH2CH2- and -CH2CH(CH3)-, however, each R connecting the silicon atom and the oxygen atom 4 Preferably selected from C2-C5-alkyl groups.

[0086] Preferably, the non-reactive poly(oxyalkylene) modified silicone oil does not contain aromatic substituents.

[0087] Therefore, the following implementation schemes involve the compound of formula (I) and the three variants described above.

[0088] In a preferred embodiment, n is 3-60, for example 3-50, 3-40, or 4-20. In another embodiment, n is 6-40, for example 6-30, 6-25, or 6-20.

[0089] In a preferred embodiment, x is 3-1000, for example 3-500, for example 3-200, for example 3-150, for example 3-100, for example 3-50, for example 3-30, for example 3-20, for example 3-15, or 4-12. In another embodiment, x is 6-200, for example 6-100, for example 6-50, for example 6-20. In yet another embodiment, x is 10-200, for example 10-100, for example 10-50, for example 10-20. In still another embodiment, x is 20-200, for example 20-100, for example 20-50.

[0090] In a preferred embodiment, n+x is 3-1000, for example 3-500, 3-200, 3-150, 3-100, or 3-50. In another embodiment, n+x is 6-100, for example 6-50, 6-40, or 6-30.

[0091] In a preferred embodiment, x+y is 3-1000, for example 3-500, for example 3-200, for example 3-150, for example 3-100, for example 3-50, for example 3-30, for example 8-30, or x+y is 3-15, for example 4-12, or x+y is 6-20, for example 8-15.

[0092] Commercially available non-reactive poly(oxyalkylene) modified silicone oils of interest include DOWSIL2-8692, OFX-5103, OFX-190, OFX 5211, OFX-5220, OFX-5247, OFX-5329, OFX-5330, OFX-3667 and OFX-193 (all from Xiameter) from DOW, BYK-331, BYK-378, BYK-Silclean 3701, BYK-Silclean 3710, BYK-3760, BYK-377 (all from BYK) from Gelest, DBE-621, CMS-222 from Gelest, and CoatOSil 3501, Silwet 7280, CoatOSil 7210, CoatOSil 7200 and CoatOSil 7280 from Gelest. 7602, CoatOSil 1220 (all from Momentive), TEGO Glide 410 and TEGO Glide 435 from Evonik Industries, Borchi GolLA200 (from Borchers), and KF352A, KF353, KF945, KF6012, KF-6015, KF6017, KF-6020, and KF-6701 from Shin-Etsu. In the context of this invention, poly(oxyalkylene) modified silicone oils preferably have an HLB (hydrophilic-lipophilic balance) of 1.5-14, for example 1.5-14, preferably 1.5-12, more preferably 1.5-10, for example 1.5-8, or 2-10. The HLB is typically determined in this paper using the equation “wt% hydrophilic groups” / 5 according to the Griffin model (Reference: Griffin, WC Calculation of HLB values ​​of non-ionic surfactants, J. Soc. Cosmet. Chem. 1954, 5, 249-256). The HLB parameter is a well-defined characterization method for nonionic surfactants.

[0093] Poly(oxyalkylene) modified silicone oils have been further described in, for example, WO2011 / 076856 and WO2014 / 117786.

[0094] Typically, the total amount of poly(oxyalkylene) modified silicone oil accounts for 1-40 wt%, 1-35 wt%, 1-30 wt%, or 1-25 wt% of the emulsion composition, for example, 2-40 wt%, 2-35 wt%, 2-30 wt%, or 2-25 wt%, for example, 5-40 wt%, 1-35 wt%, 5-30 wt%, or 5-25 wt%, for example, 10-40 wt%, 10-35 wt%, 10-30 wt%, or 10-25 wt%, for example, 15-40 wt%, 15-35 wt%, 15-30 wt%, or 15-25 wt%. Preferably, the total amount of poly(oxyalkylene) modified silicone oil accounts for 5-30 wt% of the emulsion composition, more preferably 10-30 wt%, for example, 15-25 wt%.

[0095] Other components

[0096] The emulsified composition may contain additional components, which, when present, will typically be included in the main composition or auxiliary composition prior to mixing.

[0097] The additional components may be selected from a non-limiting list of hindered amine light stabilizers, UV absorbers, and additives, as further described below.

[0098] Hindered amine light stabilizers (HALS)

[0099] In one embodiment, the emulsified composition further comprises one or more hindered amine light stabilizers (HALS) comprising a sterically hindered amine moiety, for example selected from 2,2,6,6-tetraalkylpiperidine derivatives. Such sterically hindered amine moietyes have been shown to improve the antifouling properties of polysiloxane antifouling coatings when used in combination with components comprising poly(oxyalkylene) chains (WO2019 / 233985).

[0100] The presence of a sterically hindered amine moiety (e.g., a 2,2,6,6-tetraalkylpiperidine moiety) appears to play a crucial role in the function of hindered amine light stabilizers. Furthermore, a wide range of derivatives are considered applicable, including derivatives existing as discrete molecules and derivatives that are part of oligomer or polymer structures.

[0101] In one embodiment, the hindered amine light stabilizer comprises the hindered amine moiety of general formula I:

[0102]

[0103] I

[0104] in:

[0105] Each R1 is independently selected from C1-C4 alkyl groups, preferably methyl;

[0106] R2 is selected from the substituted C1-C. 30 -alkyl, optionally substituted C2-C 30 -Alkenyl, optionally substituted aryl, optionally substituted C1-C 30 -alkoxy, optionally substituted C1-C 30 -Alkenyloxy, optionally substituted aryloxy, optionally substituted C1-C 30 -alkyl carbonyl, optionally substituted C1-C 30 -Alkenyl carbonyl and optionally substituted aryl carbonyl, -H and -OH (corresponding to NO) • );

[0107] R3 is an optionally substituted divalent group that, together with the intermediate –C(R1)2-N(R2)-C(R1)2- group, forms an N-heterocyclic 5-, 6-, or 7-membered ring; and

[0108] R2 and / or R3, having the above meaning, can be connected to 1-200, for example 1-150, for example 1-100, preferably 1-50, for example 1-40 or 1-30 or 1-20 or 1-10 hindered amine moieties, each independently having a general formula I.

[0109] In some implementations, R2 is selected from the optionally substituted C1-C 30 -alkyl, optionally substituted C1-C 30 -Alkenyl, optionally substituted aryl, optionally substituted C1-C8-alkoxy, optionally substituted C1-C8-alkenoxy, optionally substituted aryloxy, optionally substituted C1-C8-alkylcarbonyl, optionally substituted C1-C8-alkenylcarbonyl and optionally substituted arylcarbonyl.

[0110] In one embodiment, R2 is selected from C1-C4-alkyl, C1-C4-alkoxy, and C1-C4-alkylcarbonyl.

[0111] In some embodiments, R3 is selected from –CH2-C(~)-CH2- (corresponding to piperidine) and –CH2-N(~)-CH2- (corresponding to piperazine), especially –CH2-C(~)-CH2-, where “~” represents the attachment site of hydrogen atoms and / or substituents, linkers, backbones, dendritic macromolecules or polymers, etc.

[0112] In some embodiments, R3 is selected from –CH2-C(R4)-CH2- (corresponding to piperidine) and –CH2-N(R4)-CH2- (corresponding to piperazine), especially –CH2-C(R4)-CH2-, wherein R4 (generally and specifically) is as defined below with respect to general formula II.

[0113] In some embodiments, the hindered amine light stabilizer is a discrete molecule comprising only one hindered amine moiety (particularly the piperidine moiety of general formula II below).

[0114] In other embodiments, the hindered amine light stabilizer is an oligomer comprising, for example, 2-200 hindered amine moieties (particularly piperidine moieties of general formula II below). In the variants herein, the moieties are linked together.

[0115] In a preferred embodiment, the hindered amine light stabilizer is selected from 2,2,6,6-tetraalkylpiperidine derivatives, i.e., the hindered amine moiety is the 2,2,6,6-tetraalkylpiperidine moiety of general formula II:

[0116]

[0117] II

[0118] R1 and R2 are as defined above; and R4 represents the attachment point of hydrogen atoms and / or polymers.

[0119] In some implementations, R4 represents zero (where the 4th position of piperidine is unsubstituted).

[0120] In some implementations, R4 represents one or two substituents selected from the following: C1-C 30 -alkyl, C1-C 30 -Alkenyl, aryl, hydroxyl, C1-C 30 -alkoxy group, C1-C 30 -Alkenyloxy, aryloxy, C1-C 30 -alkyl carbonyl, C1-C 30 -Alkenylcarbonyl, arylcarbonyl, C1-C 30 -alkylcarbonyloxy, C1-C 30 -Alkenyl carbonyloxy and aryl carbonyloxy; wherein the substituent R4 having the above meaning may be linked to 1-200 hindered amine moieties, each independently having general formula II.

[0121] In some embodiments, R4 represents one or two substituents selected from C1-C8-alkoxy, C1-C8-enoxy, aryloxy, C1-C8-alkylcarbonyloxy, C1-C8-enylcarbonyloxy and arylcarbonyloxy.

[0122] In other embodiments, R4 represents two substituents that form a spirostructure (e.g., a spirostructure of heterocyclic nature).

[0123] Variations of hindered amine light stabilizers (e.g., 2,2,6,6-tetraalkylpiperidine derivatives) are abundant in the literature and from commercial sources. Preferred types are those with the following characteristics: N-Cl-C 30 -alkylpiperidine derivatives, N-C1-C30 -Alkenylpiperidine derivatives, N-arylpiperidine derivatives, N-Cl-C 30 -Alkoxypiperidine derivatives, N-C1-C 30 -Alkenoxypiperidine derivatives, N-aryloxypiperidine derivatives, N-Cl-C 30 -alkylcarbonylpiperidine derivatives, N-C1-C 30 -Alkenylcarbonylpiperidine derivatives and N-arylcarbonylpiperidine derivatives.

[0124] In some implementations, the following type is preferred: N-C1-C 30 -alkylpiperidine derivatives, N-C1-C 30 -Alkenylpiperidine derivatives and N-arylpiperidine derivatives, especially N-Cl-C 30 -Alkylpiperidine derivatives.

[0125] In other embodiments, the following type is preferred: N-C1-C 30 -Alkoxypiperidine derivatives, N-C1-C 30 -Alkenyloxypiperidine derivatives and N-aryloxypiperidine derivatives, especially N-Cl-C 30 -Alkoxypiperidine derivatives.

[0126] In other embodiments, the following type is preferred: N-C1-C 30 -alkylcarbonylpiperidine derivatives, N-C1-C 30 -Alkenyl carbonyl piperidine derivatives and N-aryl carbonyl piperidine derivatives, especially N-C1-C 30 -Alkylcarbonylpiperidine derivatives.

[0127] Without being bound by any particular theory, it is generally accepted that the pKa value of 2,2,6,6-tetraalkylpiperidine derivatives should preferably be below 8.5. Therefore, it is preferred that N is substituted (i.e., not NH). More preferably, the pKa is below 8.0, for example below 7.0, for example below 6.0, or even below 5.0.

[0128] Furthermore, preferably, the 2,2,6,6-tetraalkylpiperidine derivatives (and generally sterically hindered amines) in the overall structure of Formula I or II do not include any primary or secondary amines. Additionally, the structure of Formula I or II should preferably not include any non-hindered tertiary amines.

[0129] In the context of this paper, any alkylene and alkenylene moiety includes both linear and branched moieties. For example, C1-C 30 -Alkyl groups include straight-chain and branched C1-C 30-alkyl. When any R group (specifically R1, R2, R3, and R4) is described as "optionally substituted," it means that it can be substituted at any suitable position with a halogen (-F, -Cl, -Br, or –I), -C1-C4 alkyl, or -OH. The term "spiro" has its conventional meaning in organic chemistry, referring to two or more rings sharing a common atom.

[0130] The hindered amine light stabilizer moiety (e.g., a derivative of formula I or II) may be present in the emulsion composition as a discrete molecule and / or as part of an oligomer or polymer structure. In one embodiment, the sterically hindered amine moiety (e.g., a derivative of formula I or II) is present in the emulsion composition as a discrete molecule. In another embodiment, the sterically hindered amine moiety is present in the emulsion composition as part of an oligomer or polymer structure.

[0131] Examples of hindered amine light stabilizers (e.g., particularly 2,2,6,6-tetraalkylpiperidine derivatives) are further described in WO2019 / 233985 and WO2016 / 105974, which are incorporated herein by reference.

[0132] Illustrative examples of commercial hindered amine light stabilizers of the 2,2,6,6-tetramethylpiperidine type are: Sabostab UV 65 (N-CH3), Sabostab UV 40 (NH), and Sabostab UV 79 (NH) from Sabostab S.pA; Hostavin 3058 (N-acyl), Hostavin 3070 (oligomer), and Hostavin 3050 from Clariant; and Tinuvin 622 (oligomer), Tinuvin 144 (N-CH3), Flamesterab NOR 116 (NOR), Chimassorb 944 (NH), Tinuvin 249 (NOR), Tinuvin 440 (N-acyl), Tinuvin 152 (NOR), Tinuvin 123 (NOR), Uvinul 4050 H (NH), Lignostab 1198 (NO•, monomer), and Uvinul from BASF. 5050 H (NH, polymer); ADK STAB LA-52 (N-CH3), ADKSTAB LA-68 (NH), ADK STAB LA-82 (N-CH3) from Adeka Palmarole; and UBS-0822 (NH, siloxane) and UBS-0541 (NH, siloxane) from Gelest. Tinuvin 123 (NOR), Hostavin 3050, and Tinuvin 292 are preferred.

[0133] If hindered amine light stabilizers are present in the emulsified composition, they will generally be present in an amount of up to 10 wt% of the emulsified composition, for example, in an amount of up to 5 wt%, 4 wt%, 3 wt%, or 2 wt%, or 1 wt%, preferably in an amount of 0.01-10 wt%, for example, in an amount of 0.1-5 wt%, such as 0.1-4 wt%, 0.1-3 wt%, 0.1-2 wt%, or 0.1-1 wt%, or in an amount of 0.01-4 wt%, such as 0.01-3 wt%, 0.01-2 wt%, or 0.01-1 wt%.

[0134] Any hindered amine light stabilizers included in the composition are typically included in the auxiliary composition before mixing the main composition and the auxiliary composition.

[0135] UV absorber

[0136] The emulsified composition may also contain one or more UV absorbers. UV absorbers function by absorbing destructive UV radiation, protecting the polymer from UV photodegradation, and acting as light stabilizers by dissipating the absorbed UV energy as heat without altering the polymer's properties due to their high UV absorption capacity. This mechanism complements the free radical scavenging mechanism of hindered amine light stabilizers, resulting in the ability to use UV absorbers alone or in combination with hindered amine light stabilizers to achieve higher performance.

[0137] However, in one embodiment, a UV absorber is present in the presence of a hindered amine light stabilizer at different times, as described above.

[0138] Examples of UV absorbers include benzotriazole, benzoates, benzophenone, cyanoacrylates, oxaloaniline, or triazine.

[0139] Preferred UV absorbers are benzotriazole or triazine.

[0140] Commercially available UV absorbers of interest include Tinuvin 99-2, Tinuvin 326, Tinuvin 900, Tinuvin 1130, ADK STAB LA-29, ADK STAB LA-46, and ADK STAB 1413.

[0141] If present, the total amount of UV absorber typically accounts for up to 10 wt% of the emulsion composition, for example, up to 5 wt%, 4 wt%, 3 wt%, or 2 wt% or 1 wt% of the emulsion composition, preferably 0.01-10 wt% of the emulsion composition, for example, 0.1-5 wt%, 0.1-4 wt%, 0.1-3 wt%, 0.1-2 wt%, or 0.1-1 wt% of the emulsion composition, or 0.01-4 wt%, for example, 0.01-3 wt%, 0.01-2 wt%, or 0.01-1 wt% of the emulsion composition.

[0142] Any UV absorbers included in the composition are typically included in the auxiliary composition before the main composition and auxiliary composition are mixed.

[0143] biocides

[0144] The claimed post-curing treatment provides effective antifouling without including biocides in the emulsion composition. Therefore, in a preferred embodiment, the emulsion composition does not contain any biocides intended to provide antifouling effects. While including biocides is not preferred, the emulsion composition may contain biocides. Biocides associated with antifouling systems are well known to those skilled in the art and may be selected, for example, from the biocides listed in WO2023 / 036923.

[0145] additive

[0146] The emulsified composition and / or main composition may contain additives such as rheology modifiers (including thixotropic agents, thickeners, and antisettling agents), dispersants, wetting agents, surfactants, binders, plasticizers, and dyes. Examples of rheology modifiers are colloidal silica, hydrated aluminum silicate (bentonite), aluminum tristearate, aluminum monostearate, xanthan gum, chrysotile asbestos, pyrolytic silica, hydrogenated castor oil, hydroxyethyl cellulose, organically modified clay, polyamide wax, and polyethylene wax. Additives are typically included in the main composition before mixing the main composition and auxiliary compositions. Rheology modifiers are typically present in the emulsified composition in an amount of 0-10 wt%, more preferably 0.1-5.0 wt%, and even more preferably 0.1-2.0 wt%.

[0147] Because the claimed composition is water-based, it may include antifungal components known to those skilled in the art as additional additives to improve shelf life.

[0148] Preparation of emulsified compositions

[0149] The emulsified composition is prepared from a primary composition and an auxiliary composition. The primary composition comprises a liquid carrier (typically water) for the continuous phase, and the auxiliary composition comprises one or more poly(oxyalkylene) modified silicone oils. The primary and auxiliary compositions may contain additional components, such as hindered amine light stabilizers, UV absorbers, and additives, as described below.

[0150] The emulsified composition can be prepared by first preparing a main composition as described above, comprising water and optional additives; separately preparing an auxiliary composition as described above, comprising a poly(oxyalkylene) modified silicone oil and optional hindered amine light stabilizer and UV absorber; and subsequently mixing the main composition and the auxiliary composition. A specific method for preparing the emulsified composition is described below.

[0151] All components of the main composition can be mixed at 3500 rpm for at least 15 min in a high-speed dissolver equipped with an impeller disk. The components of the auxiliary composition can be mixed manually for at least 2 min. Then, shortly before application, the main composition and auxiliary composition can be mixed together at 3500 rpm for at least 15 min in a high-speed dissolver equipped with an impeller disk. Similar methods and variations of the methods described herein can be used by those skilled in the art.

[0152] It should be understood that when referring to "emulsified composition", it means a mixed composition prepared to be applied to an antifouling coating, which contains the desired amounts of each component contained in the continuous phase and the dispersed phase.

[0153] Application of emulsifying composition

[0154] The emulsified composition of the present invention is applied on top of an antifouling coating (preferably a polysiloxane coating).

[0155] The term "apply" is used in the coatings industry in its normal sense. Therefore, it is "applied" by any conventional means, such as by brush, by roller, by spray, etc. The most commercially interesting way to "apply" an emulsion composition is by roller or by spray. Therefore, the emulsion composition is preferably sprayable. Spraying is performed using conventional spraying equipment known to those skilled in the art. The emulsion composition is typically applied with a wet film thickness of 30-400 μm, for example 50-400 μm, for example 75-300 μm, or 75-200 μm, for example about 100 μm.

[0156] Typically at 0.03-0.4 L / m 2 For example, 0.05-0.4 L / m 2 For example, 0.075-0.3 L / m 2 The amount of the emulsified composition applied is [amount].

[0157] After contact with the surface for at least 2 hours, any remaining emulsified composition left on the surface can be removed by direct removal or by dissolving during navigation. The composition is typically removed using water, for example by rinsing the surface with water, or by scrubbing with a brush or sponge, or by aeration. The water may optionally contain soap, and the soap may optionally be removed subsequently by rinsing with water. Another way to remove excess composition is by polishing, for example by wiping with a cloth. In one embodiment, excess composition is left on the surface without removal.

[0158] The term "at least a portion of the substrate surface" refers to the fact that the emulsified composition can be applied to any portion of the surface. This means applying the emulsified composition to at least a portion of a substrate (e.g., an antifouling coating) whose surface can come into contact with water (e.g., seawater).

[0159] In this context, the term "substrate" refers to the topcoat of the antifouling coating. Substrate typically comprises a polysiloxane coating. Alternative substrates, such as other corrosion-resistant coatings, may also be relevant, for example, acrylic coatings.

[0160] The term "surface" is used in its normal sense, referring to the outer boundary of an object. In the context of this invention, the emulsion composition is applied to the surface of the antifouling paint coating. Antifouling paint coatings (to which the emulsion composition is applied) are typically present on the surfaces of marine structures, such as ships, including but not limited to boats, yachts, motorboats, motorboats, ocean liners, tugboats, tankers, container ships and other cargo vessels, submarines, and all types of naval vessels. In one embodiment, the antifouling paint coating is present on pipes, coastal and offshore machinery, and structures, such as breakwaters, piles, bridge understructures, hydroelectric installations and structures, subsea oil well structures, etc.

[0161] In one embodiment, the emulsified composition is applied to a newly applied antifouling paint coating as previously described. In another embodiment, the emulsified composition is applied to an aged coating (e.g., a worn antifouling paint coating).

[0162] Numbering Implementation Plan

[0163] Embodiments of the present invention are disclosed below. It should be understood that various aspects, embodiments, implementations, and features of the invention mentioned herein may be claimed individually or in any combination.

[0164] E1. A method for post-curing treatment of an antifouling paint coating, comprising the following steps:

[0165] a. Apply the emulsified composition to the surface of the antifouling paint coating;

[0166] b. Keep the emulsified composition in contact with the surface of the antifouling coating for at least 2 hours;

[0167] The emulsified composition comprises a continuous liquid phase and a dispersed liquid phase, the continuous liquid phase comprising water, and the dispersed liquid phase comprising one or more poly(oxyalkylene) modified silicone oils.

[0168] E2. The method according to embodiment E1, wherein the total amount of water accounts for 40-99 wt% or 40-95 wt%, 40-90 wt%, 40-85 wt%, or 40-80 wt%, or 40-75 wt%, or 40-70 wt% of the emulsified composition, for example 45-99 wt% or 45-95 wt% or 45-90 wt% or 45-85 wt%, or 45-80 wt% or 45-75 wt%, or 45-70 wt%, for example 50-99 wt% or 50-95 wt% or 50-90 wt% or 50-85 wt%, or 50-80 wt% or 50-75 wt%, or 55-70 wt%, for example 60 wt% or 55-95 wt% or 55-90 wt% or 55-85 wt%, or 55-80 wt% or 55-75 wt%, or 55-70 wt%, for example 60 wt%. -99wt% or 60-95wt% or 60-90wt% or 60-85wt%, or 60-80wt% or 60-75wt% or 60-70wt%, for example 63-99wt% or 63-95wt% or 63-92wt%, for example 65-99wt% or 65-95wt% or 65-90wt% or 65-85wt%, or 65-80wt% or 65-75wt% or 6 5-70 wt%, for example 70-99 wt%, or 70-95 wt%, or 70-90 wt%, or 70-85 wt%, or 70-80 wt%, or 70-75 wt%, for example 75-99 wt%, or 70-95 wt%, or 70-90 wt%, or 70-85 wt%, or 70-80 wt%, for example 80-99 wt%, or 80-95 wt%, or 80-90 wt%, or 80-85 wt%.

[0169] E3. The method according to any one of embodiments E1-E2, wherein the total amount of poly(oxyalkylene) modified silicone oil accounts for 1-40 wt%, 1-35 wt%, 1-30 wt%, or 1-25 wt% of the emulsified composition, for example 2-40 wt%, or 2-35 wt%, or 2-30 wt%, or 2-25 wt%, for example 5-40 wt%, or 1-35 wt%, or 5-30 wt%, or 5-25 wt%, for example 10-40 wt%, or 10-35 wt%, or 10-30 wt%, or 10-25 wt%, for example 15-40 wt%, or 15-35 wt%, or 15-30 wt%, or 15-25 wt%.

[0170] E4. The method according to any one of embodiments E1-E3, wherein the total amount of water accounts for 40-99 wt% or 40-95 wt%, 40-90 wt%, 40-85 wt%, or 40-80 wt%, or 40-75 wt%, or 40-70 wt% of the emulsified composition, for example 45-99 wt% or 45-95 wt% or 45-90 wt% or 45-85 wt%, or 45-80 wt% or 45-75wt% or 45-70wt%, for example 50-99wt% or 50-95wt% or 50-90wt% or 50-85wt%, or 50-80wt% or 50-75wt% or 50-70wt%, for example 55-99wt% or 55-95wt% or 55-90wt% or 55-85wt%, or 55-80wt% or 55-75wt% or 55-70wt%, for example For example, 60-99wt%, or 60-95wt%, or 60-90wt%, or 60-85wt%, or 60-80wt%, or 60-75wt%, or 60-70wt%, for example, 63-99wt%, or 63-95wt%, or 63-92wt%, for example, 65-99wt%, or 65-95wt%, or 65-90wt%, or 65-85wt%, or 65-80wt%, or 65-75wt%, or 65-70 wt%, for example 70-99 wt%, or 70-95 wt%, or 70-90 wt%, or 70-85 wt%, or 70-80 wt%, or 70-75 wt%, for example 75-99 wt%, or 70-95 wt%, or 70-90 wt%, or 70-85 wt%, or 70-80 wt%, for example 80-99 wt%, or 80-95 wt%, or 80-90 wt%, or 80-85 wt%; and

[0171] The total amount of poly(oxyalkylene) modified silicone oil is 1-40 wt%, 1-35 wt%, 1-30 wt%, or 1-25 wt% of the emulsion composition, for example, 2-40 wt%, 2-35 wt%, 2-30 wt%, or 2-25 wt%, for example, 5-40 wt%, 1-35 wt%, 5-30 wt%, or 5-25 wt%, for example, 10-40 wt%, 10-35 wt%, 10-30 wt%, or 10-25 wt%, for example, 15-40 wt%, 15-35 wt%, 15-30 wt%, or 15-25 wt%.

[0172] E5. The method according to any one of embodiments E1-E4, wherein the emulsified composition is contacted with the surface of the antifouling 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.

[0173] E6. The method according to any one of embodiments E1-E5, wherein the emulsified composition is contacted with the surface of the antifouling coating for 4-48 hours, such as 4-40 hours, 4-36 hours, 4-32 hours, 4-28 hours or 4-24 hours, or 6-48 hours, such as 6-40 hours, 6-36 hours, 6-32 hours, 6-28 hours or 6-24 hours.

[0174] E7. The method according to any one of embodiments E1-E6, wherein the emulsifying composition is prepared from a main composition comprising water and an auxiliary composition comprising poly(oxyalkylene) modified silicone oil.

[0175] E8. The method according to embodiment E7, wherein the main composition contains at least 70 wt%, for example at least 80 wt%, for example at least 90 wt%, preferably at least 95 wt%, for example at least 99 wt% water; and the auxiliary composition contains at least 1 wt%, for example at least 5 wt%, for example at least 10 wt%, for example at least 15 wt%, for example at least 20 wt% poly(oxyalkylene) modified silicone oil.

[0176] E9. The method according to any one of embodiments E1-E8, wherein the method further comprises the step of: c. removing excess emulsified composition from the surface of the antifouling coating after step b, wherein the removal is performed by rinsing the surface with water or by cleaning with a brush or sponge;

[0177] E10. The method according to embodiment E9, wherein the removal is further performed by washing the surface with soap and then rinsing with water.

[0178] E11. The method according to any one of embodiments E1-E10, wherein the poly(oxyalkylene) modified silicone oil is characterized by having an HLB value of 1.5-14, for example 1.5-14, preferably 1.5-12, more preferably 1.5-10, for example 1.5-8 or 2-10.

[0179] E12. The method according to any one of embodiments E1-E11, wherein the poly(oxyalkylene) modified silicone oil has a poly(oxyalkylene) portion selected from polyoxyethylene, polyoxypropylene and / or poly(oxyethylene-co-oxypropylene), preferably polyoxyethylene.

[0180] E13. The method according to any one of embodiments E1-E12, wherein the emulsified composition is applied with a wet film thickness of 30-400 μm, for example 50-400 μm, for example 75-300 μm, or 75-200 μm, for example about 100 μm.

[0181] E14. The method according to any one of embodiments E1-E13, wherein the emulsifying composition and / or the auxiliary composition further comprises:

[0182] i) one or more hindered amine light stabilizers, and / or

[0183] ii) One or more UV absorbers.

[0184] E15. The method according to embodiment E14, wherein the one or more hindered amine light stabilizers are selected from 2,2,6,6-tetraalkylpiperidine derivatives.

[0185] E16. The method according to any one of embodiments E14-E15, wherein the one or more hindered amine light stabilizers are present in an amount of up to 10 wt%, for example up to 5 wt%, 4 wt%, 3 wt%, or 2 wt% or 1 wt% of the emulsified composition.

[0186] E17. The method according to any one of embodiments E14-E16, wherein the one or more hindered amine light stabilizers are present in an amount of 0.01-10 wt%, for example 0.1-5 wt%, for example 0.1-4 wt%, or 0.1-3 wt%, or 0.1-2 wt%, or 0.1-1 wt% of the emulsified composition, or in an amount of 0.01-4 wt%, for example 0.01-3 wt%, or 0.01-2 wt%, or 0.01-1 wt% of the emulsified composition.

[0187] E18. The method according to any one of embodiments E14-E17, wherein the one or more UV absorbers are selected from benzotriazole, benzoate, benzophenone and triazine.

[0188] E19. The method according to any one of embodiments E14-E18, wherein the one or more UV absorbers are present in an amount of up to 10 wt%, such as up to 5 wt%, up to 4 wt%, up to 3 wt%, up to 2 wt%, or up to 1 wt%, of the emulsified composition.

[0189] E20. The method according to any one of embodiments E14-E19, wherein the one or more UV absorbers are present in an amount of 0.01-5 wt%, for example 0.1-5 wt%, for example 0.1-4 wt%, or 0.1-3 wt%, or 0.1-2 wt%, or 0.1-1 wt%, of the emulsified composition, or in an amount of 0.01-4 wt%, for example 0.01-3 wt%, or 0.01-2 wt%, or 0.01-1 wt%, of the emulsified composition.

[0190] E21. The method according to any one of embodiments E1-E21, wherein the emulsifying composition and / or the main composition further comprises one or more additives, such as one or more rheology modifiers, such as thixotropic agents, thickeners and / or antisettling agents.

[0191] E22. The method according to embodiment E21, wherein the rheology modifier is selected from colloidal silica, hydrated aluminum silicate (bentonite), aluminum tristearate, aluminum monostearate, xanthan gum, chrysotile asbestos, pyrolytic silica, hydrogenated castor oil, hydroxyethyl cellulose, organic modified clay, polyamide wax, and polyethylene wax.

[0192] E23. The method according to any one of embodiments E21-E22, wherein the rheology modifier is present in an amount of 0-10 wt%, more preferably 0.1-5.0 wt%, or even more preferably 0.1-2.0 wt%.

[0193] E24. The method according to any one of embodiments E1-E23, wherein the emulsified composition is applied by brush or roller or by spraying, preferably by spraying.

[0194] E25. The method according to any one of embodiments E1-E24, wherein the antifouling coating has been applied to the outer surface of a substrate, wherein the substrate is a substrate intended for immersion in water, such as a local vessel.

[0195] E26. A method according to any one of embodiments E1-E25, comprising an initial step of identifying a substrate on an outer surface containing the antifouling paint coating.

[0196] E27. The method according to any one of embodiments E1-E26, wherein the antifouling paint coating is a paint coating that is not easily corroded, preferably a polysiloxane paint coating.

[0197] E28. The method according to any one of embodiments E1-E27, wherein the antifouling paint coating is a newly applied coating.

[0198] E29. The method according to any one of embodiments E1-E28, wherein the antifouling coating is an aged coating, such as an abraded coating.

[0199] E30. The method according to any one of embodiments E1-E29, wherein the antifouling paint coating constitutes the outermost layer of an antifouling system that further comprises a primer and / or a connecting coating.

[0200] E31. The method according to any one of embodiments E1-E30, wherein the emulsifying composition comprises or is substantially comprised of the following:

[0201] A continuous liquid phase containing water.

[0202] A liquid dispersion containing one or more poly(oxyalkylene) modified silicone oils,

[0203] Optionally, one or more hindered amine light stabilizers, preferably 2,2,6,6-tetraalkylpiperidine derivatives,

[0204] Optionally, one or more UV absorbers, and

[0205] One or more, preferably two or more, rheology modifiers.

[0206] E32. The method according to any one of embodiments E1-E31, wherein the emulsifying composition comprises or is composed of the following:

[0207] The emulsified composition comprises at least 60 wt% of a water-containing continuous liquid phase.

[0208] The emulsion composition comprises 1-25 wt% of one or more poly(oxyalkylene) modified silicone oils.

[0209] One or more hindered amine light stabilizers, preferably 2,2,6,6-tetraalkylpiperidine derivatives, constitute 1-10 wt% of the emulsified composition.

[0210] Two or more rheology modifiers comprising 0.1-10 wt% of the emulsified composition.

[0211] E33. The method of any one of the implementation schemes E1-E32 is used to improve the antifouling performance of an antifouling coating.

[0212] E34. An antifouling paint coating, preferably a paint coating that is not easily corroded, such as a polysiloxane paint coating, which has been treated by the method of any one of embodiments E1-E32.

[0213] E35. The antifouling paint coating according to embodiment E32, having on at least a portion of its outer surface a multilayer system comprising:

[0214] i) One or more cured primer layers;

[0215] ii) One or more cured bonding coatings, and

[0216] iii) One or more additional cured antifouling paint coatings;

[0217] The antifouling coating has been treated by any one of the methods in embodiments E1-E32.

[0218] All references cited in this document (including publications, patent applications and patents) are incorporated herein by reference in their entirety, to the extent that each reference is independently and explicitly stated to be incorporated by reference and is listed herein in its entirety (to the maximum extent permitted by law), regardless of whether the specific reference is provided separately elsewhere in this document.

[0219] Unless otherwise stated herein or clearly contradicted by the context, the terms “a”, “an”, “the”, and similar designations used in the context of describing the invention shall be interpreted to cover both the singular and plural. For example, the phrase “the composition” shall be understood to refer to various “compositions” of the invention or a particular aspect of the description, unless otherwise indicated.

[0220] The use of terms such as “comprising,” “having,” “including,” or “containing” to describe any aspect or aspect of the invention is intended to support similar aspects or aspects of the invention that support the description of “consisting of,” “consisting substantially of,” or “substantially containing” the particular one or more elements, unless otherwise indicated or clearly contradicted by the context (e.g., a description herein of a composition comprising a particular element should be understood to also describe a composition consisting of that element, unless otherwise indicated or clearly contradicted by the context).

[0221] The use of any and all instances or exemplary language (including “for instance”, “for example”, “eg”, and “such as”) in this specification is intended only to better illustrate the invention and not to limit the scope of the invention, unless otherwise indicated.

[0222] The titles and subtitles herein are for convenience only and should not be construed as limiting the invention in any way. The use of any and all instances or exemplary language (including “for instance,” “for example,” “eg,” and “such as”) in this specification is intended only to better illustrate the invention and not to limit its scope, unless otherwise indicated. References to and incorporation of patent documents herein are for convenience only and do not reflect any opinion on the validity, patentability, and / or enforceability of such patent documents.

[0223] It should be understood that each aspect, embodiment, implementation and feature of the invention mentioned herein may be claimed individually or in any combination. Example

[0224] The invention will be illustrated by the following non-limiting embodiments.

[0225] experiment

[0226] Testing of antifouling performance

[0227] A 150mm x 200mm acrylic panel was used for a static immersion test. The emulsion composition was applied to the top of the polysiloxane coating using an airless sprayer, doctor blade applicator, brush, or roller. After the specified time, the emulsion was removed using tap water and a sponge for approximately 1 minute. Any residue of the emulsion composition was removed using soap. Further rinsing with water was used to remove any soap residue.

[0228] In the case of a newly applied polysiloxane coating, the coating is applied over a suitable bonding coating according to the specifications of the polysiloxane coating, and then allowed to cure for at least 6 hours to ensure that the coating is dry to the touch before the application of the emulsion composition. The polysiloxane coating is applied with a dry film thickness of approximately 66-200 µm. In most embodiments, the dft is 200 µm.

[0229] The antifouling performance was tested on the panels at Vilanova i la Geltrú, located in northeastern Spain. At this test location, the panels were immersed in seawater with a salinity of 37-38 PPT (parts per thousand) at an average temperature of 17-18°C.

[0230] Check the panel every 4-12 weeks and evaluate it according to the following levels:

[0231] GPC was used to extract and quantify poly(oxyalkylene) modified silicone oil.

[0232] The siloxane-coated sample was cut with a scalpel and added to 0.5–1 ml of tetrahydrofuran (THF) containing polystyrene internal standard (C = 0.554 µmol / L and Mw = 130 kg / mol). The sample was extracted on a shaker for 2 hours and then decanted into 1 ml vials.

[0233] The amount of poly(oxyalkylene) modified silicone oil absorbed by the poly(siloxane)-based coating was quantified using gel permeation chromatography (GPC). The GPC system consisted of three columns: a 2×PLgel 5µm mixed D (300×7.5mm) and a PLgel 5µm mixed Cº (300×7.5mm). GPC curves were recorded using an ELS detector and an eluent mixture 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 prepared when the poly(oxyalkylene) modified silicone oil was added to the liquid poly(siloxane)-based coating mixture prior to application. (BYK-3764 was used as the poly(oxyalkylene) modified silicone oil.) A calibration curve was prepared and used to calibrate all poly(oxyalkylene) modified silicone oil.

[0234] Material

[0235] Table 1: List of materials used in polysiloxane coating compositions and emulsion compositions.

[0236] Table 2: Polysiloxane Alkyl Coating Compositions (abbreviated SC).

[0237] Polysiloxane coatings (SC) were prepared by mixing all components of Part I in a bead mill at 75°C for 30 minutes and then filtering through a filter. The components of Part II were then mixed manually for 2 minutes.

[0238] antifouling performance

[0239] The composition presented below was prepared according to the specifications provided in this document. The emulsified composition was then applied to the newly applied coating using a doctor blade applicator with a 300µm gap size. After 96 hours, the emulsified composition was removed from the substrate by gently washing with a sponge containing hot water and detergent for approximately 1 minute. Residual soap was removed with hot water. The substrate was then dried vertically at room temperature. The stain resistance of the treated panel was tested according to the specifications provided above.

[0240] Table 3A: Various concentrations of poly(oxyalkylene) modified silicone oils. The amounts are based on wt% of the total weight of the emulsion composition.

[0241] N / A means that the amount extracted is lower than the detection level.

[0242] Table 3A shows that post-treatment of the siloxane coating with an emulsion composition containing various concentrations of hydrophilic modified oil significantly improved its antifouling properties compared to the untreated counterpart. Furthermore, it can be seen that the amount of poly(oxyalkylene) modified silicone oil extractable after treatment with the emulsion composition is comparable to up to 2 wt% of poly(oxyalkylene) modified silicone oil added to the liquid poly(siloxane)-based mixture before coating application. Example 3A.4 is below the detection limit of the extraction and quantification methods.

[0243] Table 3B: Various concentrations of poly(oxyalkylene) modified silicone oils. The amounts are based on wt% of the total weight of the emulsion composition.

[0244] Table 3B shows that post-treatment of the siloxane coating with an emulsion containing various concentrations of hydrophilic modified oil significantly improved antifouling performance compared to both the emulsion composition without hydrophilic modified oil and the untreated counterpart.

[0245] Table 4: Time before removal of the emulsion composition. Amounts are based on wt% of the total weight of the emulsion composition.

[0246] Table 4 shows that the absorption of poly(oxyalkylene) modified silicone oil increased with increasing exposure time, and the antifouling performance increased with further increases in exposure time. Untreated comparative example 4.9 showed poor performance after 4 weeks.

[0247] Table 5: Variations in poly(oxyalkylene) modified silicone oils. Amounts are based on wt% of the total weight of the emulsion composition.

[0248] Table 5 shows that for all types of poly(oxyalkylene) modified silicone oils tested, Raft performance was “good” or “excellent” after 20 weeks in seawater in Spain. Comparative Example 5.6 showed poor performance after 20 and 36 weeks.

[0249] Table 6: HLB variation of poly(oxyalkylene) modified silicone oils. The amounts are based on wt% of the total weight of the emulsion composition.

[0250] Table 6 shows that Raft performance was “good” in seawater in Spain after 29 weeks when HLB=10, but performance declined when HLB increased to 14.

[0251] Table 7: Various concentrations of poly(oxyalkylene) modified silicone oils and HALS. The amounts are based on wt% of the total weight of the emulsion composition.

[0252] Table 7 shows the methods for using compositions of poly(oxyalkylene) modified silicone oil and HALS at different concentrations. The treated panels exhibited high performance for different concentrations.

[0253] The antifouling performance of the embodiments from Tables 3A and 7 was tested in the same test series. That is, the blank coatings (reference) in Tables 3A and 7 are the same.

[0254] Table 8: Various dry film thicknesses (DFT). The amounts are based on the total weight (wt%) of the emulsion composition.

[0255] Table 8 demonstrates the superior performance of substrates with different thicknesses. It is also noted that increasing the film thickness resulted in the absorption of a higher amount of oil.

[0256] The antifouling performance of the embodiments from Tables 3A, 7, and 8 was tested in the same test series. That is, the blank coatings (reference) in Tables 3A, 7, and 8 are the same.

[0257] Table 9: Concentrations of HALS and UV absorbers in the formulation. The amounts are based on wt% of the total weight of the emulsion composition.

[0258] Table 9 shows the methods for using compositions of hindered amine light stabilizers and UV absorbers at different concentrations. The treated panels exhibited high performance for each concentration.

Claims

1. A method for post-curing treatment of an antifouling paint coating, comprising the following steps: a. Apply the emulsified composition to the surface of the antifouling paint coating; b. Keep the emulsified composition in contact with the surface of the antifouling coating for at least 2 hours; The emulsified composition comprises a continuous liquid phase and a dispersed liquid phase, the continuous liquid phase comprising water, and the dispersed liquid phase comprising one or more poly(oxyalkylene) modified silicone oils.

2. The method according to claim 1, wherein the total amount of water accounts for 40-99 wt% of the emulsified composition, and the total amount of poly(oxyalkylene) modified silicone oil accounts for 1-40 wt% of the emulsified composition.

3. The method according to claim 1 or 2, wherein the emulsified composition is in contact with the surface of the antifouling 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.

4. The method according to any one of claims 1-3, wherein the method further comprises the following step: c. After step b, remove excess emulsified composition from the surface of the antifouling coating, wherein the removal is performed by rinsing the surface with water or by cleaning with a brush or sponge.

5. The method according to any one of claims 1-4, wherein the poly(oxyalkylene) modified silicone oil is characterized by having an HLB value of 1.5-14, for example 1.5-14, preferably 1.5-12, more preferably 1.5-10, for example 1.5-8 or 2-10.

6. The method according to any one of claims 1-5, wherein the antifouling paint coating is a paint coating that is not easily corroded, preferably a polysiloxane paint coating.

7. The method according to any one of claims 1-6, wherein the emulsified composition is applied with a wet film thickness of 30-400 μm, for example 50-400 μm, for example 75-300 μm, or 75-200 μm, for example about 100 μm.

8. The method according to any one of claims 1-7, wherein the emulsifying composition is prepared from a main composition comprising water and an auxiliary composition comprising poly(oxyalkylene) modified silicone oil.

9. The method according to any one of claims 1-8, wherein the emulsifying composition and / or the auxiliary composition further comprises: i) one or more hindered amine light stabilizers, and / or ii) One or more UV absorbers.

10. The method of claim 9, wherein the one or more hindered amine light stabilizers are present in an amount of 0.01-10 wt%, for example 0.1-5 wt%, for example 0.1-4 wt%, or 0.1-3 wt%, or 0.1-2 wt%, or 0.1-1 wt%, or 0.01-4 wt%, for example 0.01-3 wt%, or 0.01-2 wt%, or 0.01-1 wt% of the emulsified composition.

11. The method according to any one of claims 1-10, 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.

12. The method according to any one of claims 1-11, wherein the antifouling paint coating is a newly applied coating.

13. The method according to any one of claims 1-11, wherein the antifouling coating is an aged coating, such as an abraded coating.

14. The method according to any one of claims 1-13, wherein the emulsifying composition and / or the main composition comprises one or more additives, such as one or more, preferably two or more, rheology modifiers, such as thixotropic agents, thickeners and / or antisettling agents.

15. The method according to any one of the preceding claims, wherein the emulsifying composition comprises or substantially comprises the following: A continuous liquid phase containing water; A liquid dispersion 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, rheology modifiers.

16. The method according to any one of the preceding claims, wherein the emulsifying composition comprises or is composed of the following: The emulsified composition comprises at least 60 wt% of a water-containing continuous liquid phase; The emulsion composition comprises 1-25 wt% of one or more poly(oxyalkylene) modified silicone oils; One or more hindered amine light stabilizers, preferably 2,2,6,6-tetraalkylpiperidine derivatives, are 1-10 wt% of the emulsified composition; Two or more rheology modifiers comprising 0.1-10 wt% of the emulsified composition.

17. Use of the method of any one of claims 1-16 for improving the antifouling properties of an antifouling paint coating.

18. An antifouling paint coating, preferably a corrosion-resistant antifouling paint coating, such as a polysiloxane paint coating, which has been treated by the method described in any one of claims 1-16.

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