process

Abstract

The present invention provides a process for producing a multi-layer coating system having at least two coating layers. The process includes: i) applying a first coating layer by spray coating to a wet film thickness of 50 to 300 μm; and ii) applying a second coating layer by spray coating to a wet film thickness of 50 to 300 μm. The second coating layer is applied directly onto the first coating layer 5 minutes to 6 hours after the first coating layer is applied. The first and second coating layers contain a polysiloxane-based coating composition including a) a polysiloxane-based binder system and b) a curing agent or crosslinker.

Description

[Technical Field]

[0001] The present invention relates to a process for producing a multi-layer coating system. In particular, the present invention provides a process for applying at least two coating layers containing a polysiloxane-based coating composition, where the second coating layer is applied at a specific time interval after the first coating layer. [Background technology]

[0002] Fouling release coatings are used on marine vessels to prevent fouling by marine organisms. These coatings work on the principle that the coefficient of friction of the fouling release surface is so low that marine organisms are less likely to adhere to the surface, especially while the vessel is underway, and the action of the sea can wash the marine organisms off the hull.

[0003] Thus, fouling release coatings are characterized by low surface tension and low modulus such that biofouling does not adhere to the surface or is easily washed away by friction of water against the surface.

[0004] Such coatings often contain polysiloxane binders with reactive (curable) groups such as hydroxyl and silyl units that can hydrolyze and condense in the presence of moisture and a catalyst.

[0005] Typically, fouling release coating systems are applied as a system consisting of two layers of primer, one layer of tie coat, and one layer of top coat. The coatings are spray applied with a small overlap width (usually 10-15 cm). U.S. Patent No. 6,048,580 describes applying a tie coat and a top coat to a substrate. European Patent No. 3,974,482 describes a fouling release coating based on a polysiloxane binder in combination with a biocide and a catalyst to accelerate curing. The coating is applied in one layer.

[0006] Recently, however, biocidal fouling release coatings have been applied with two top coats, as described, for example, in WO 2011 / 076856. The reason for applying two top coats is to provide better control over film thickness (i.e., to achieve a uniform film thickness) and to allow the top coat to be applied thicker so that it contains enough biocide to last for more than three years. An additional benefit is that the paint does not need to be as sag-resistant when two coats are applied, compared to the traditional application of a single thick coat of paint.

[0007] However, applying two top coats does have its risks and drawbacks. Polysiloxane-based fouling release coatings have a short recoatable window, and atmospheric conditions can interrupt the coating application, causing the second coat to be applied after the recoatable window has expired, resulting in poor adhesion or even making it impossible to apply the second coat. Additionally, applying two coats takes longer to apply and cure than applying one coat, even if the total film thickness is the same. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] U.S. Patent No. 6,048,580 [Patent Document 2] European Patent No. 3974482 [Patent Document 3] International Publication No. 2011 / 076856 Summary of the Invention [Problem to be solved by the invention]

[0009] Currently, suppliers of topcoats designed for two-coat applications specify an interval of at least eight hours between the application of the two coats. It is common practice to apply a multi-coat system by allowing one coat to dry / cure before applying the next. The challenge with polysiloxane-based coatings is that once the first coat has fully dried / cure, the next coat, even if it is also a polysiloxane-based coating, will not adhere well to the surface. This is, at least in part, a result of the fact that polysiloxane topcoats are designed to prevent the adhesion of objects (e.g., marine life) to the surface. Once cured, polysiloxane topcoats provide a surface that deters other substances from adhering to them. [Means for solving the problem]

[0010] In the present invention, the inventors have discovered that it is possible to apply a second coating layer immediately after applying the first. This method shortens work time at the dock and reduces the risk of adverse weather conditions and poor adhesion. The present invention applies two topcoats at once without waiting for the coating to cure before applying the second layer. Application of the second layer can begin five minutes after application of the first layer, allowing some of the solvent to evaporate and begin curing. Therefore, it will be appreciated that in the process of the present invention, the first coating layer is not fully cured before the second coating layer is applied. [Effects of the Invention]

[0011] This reduces the risk of rain interfering with the application of the two coats. Applying two coats at once also reduces the time required to apply the two layers of fouling release top coat, eliminating the need to wait for curing. This reduces the time needed at the dock.

[0012] The process of the present invention offers the potential additional benefits of more uniform film thickness and reduced risk of sagging in overlap areas where the film thickness is higher than specified. Furthermore, higher film thicknesses can be achieved with paints that are less sagging resistant. DETAILED DESCRIPTION OF THE INVENTION

[0013] [Summary of the Invention] In one aspect, the present invention provides a process for producing a multi-layer coating system comprising at least two coating layers, the process comprising: i) applying a first coating layer by spray coating so that the wet film thickness is 50 to 300 μm; ii) applying the second coating layer by spray coating to a wet film thickness of 50 to 300 μm; The second coating layer is applied directly onto the first coating layer 5 minutes to 6 hours after the first coating layer is applied; The first coating layer and the second coating layer each independently comprise: a) a polysiloxane-based binder system; b) a curing or crosslinking agent; and [Definition] As used herein, the term "fouling release composition" or "fouling release coating composition" refers to a composition that, when applied to a surface, forms a fouling release surface that is permanently resistant to the attachment of marine organisms. The term "fouling release coating system" will be understood to refer to a coating system having a similar definition.

[0014] As used herein, the term "topcoat" refers to a polysiloxane-based coating composition. Preferably, the polysiloxane-based coating composition is a fouling release coating composition.

[0015] As used herein, the term "binder system" refers to the film-forming component of the composition. The polysiloxane-based binder of the composition is the primary binder of the binder system, i.e., comprises at least 50% by weight, e.g., at least 75% by weight, of the binder system. As used herein, the term "binder system" does not include added oils. Added oils are not considered film-forming components herein.

[0016] In one embodiment, the binder system comprises a polysiloxane-based binder.

[0017] As used herein, the term "paint" refers to a composition that includes a coating composition described herein and, optionally, a solvent, and is ready to use (e.g., spray). Thus, the coating composition may be a paint itself or a concentrate to which a solvent is added to produce the paint.

[0018] As used herein, the term "polysiloxane" refers to a polymer containing siloxane, i.e., repeating --Si--O-- units.

[0019] The term "polysiloxane-based binder" as used herein refers to a binder containing at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, of repeating units comprising the motif -Si-O-, based on the total weight of the polymer. The polysiloxane-based binder may contain up to 99.99% by weight of repeating units comprising the motif -Si-O-, based on the total weight of the polymer. The repeating units -Si-O- may be linked in a single sequence or may be interrupted by non-siloxane moieties, e.g., organic moieties.

[0020] As used herein, the term "non-degradable polysiloxane-based binder" refers to a polysiloxane-based binder that does not hydrolyze or erode in seawater.

[0021] As used herein, the term "alkyl" refers to a saturated straight-chain group, a saturated branched-chain group, or a saturated cyclic group.

[0022] As used herein, the term "cycloalkyl" refers to a cyclic alkyl group.

[0023] As used herein, the term "alkylene" refers to a divalent alkyl group.

[0024] As used herein, the term "alkenyl" refers to an unsaturated straight chain group, an unsaturated branched chain group, or an unsaturated cyclic group.

[0025] As used herein, the term "aryl" refers to a group containing at least one aromatic ring. The term "aryl" encompasses fused ring systems in which one or more aromatic rings are fused to a cycloalkyl ring. Examples of aryl groups include phenyl, i.e., C6H5.

[0026] As used herein, the term "substituted" refers to a group in which one or more, for example up to six, more particularly one, two, three, four, five, or six, hydrogen atoms in the group are independently replaced with the corresponding number of described substituents.

[0027] As used herein, the term "arylalkyl" group refers to a group in which the bond to Si is through the alkyl portion.

[0028] As used herein, the term "polyether" refers to a compound containing two or more --O-- bonds interrupted by alkylene units.

[0029] As used herein, the terms "poly(alkylene oxide)," "poly(oxyalkylene)," and "poly(alkylene glycol)" refer to compounds containing repeating -alkylene-O- units. Typically, the alkylene is ethylene or propylene.

[0030] As used herein, the term "wt %" is based on the dry weight of the coating composition unless otherwise specified.

[0031] As used herein, the term "PDI" or polydispersity index refers to the Mw / Mn ratio, where Mw refers to the weight average molecular weight and Mn refers to the number average molecular weight. PDI is sometimes also referred to as D (dispersity).

[0032] As used herein, the term "volatile organic compounds (VOCs)" refers to compounds with a boiling point of 250°C or less.

[0033] As used herein, the term "antifouling agent" refers to a biologically active compound or mixture of biologically active compounds that prevents the attachment of marine organisms to a surface and / or prevents the growth of marine organisms on a surface and / or promotes the removal of marine organisms from a surface.

[0034] [Detailed Description of the Invention] The present invention provides a process for producing a coating system having at least two coating layers, comprising: The second coating layer is applied directly onto the first coating layer 5 minutes to 6 hours after the first coating layer is applied, and the first coating layer and the second coating layer are each independently: a) a polysiloxane-based binder system; b) a curing or crosslinking agent; and

[0035] [Polysiloxane binder system] The binder system in the coating composition contains at least one curable polysiloxane-based binder.

[0036] Any polysiloxane-based binder is preferably a non-decomposable curable polysiloxane-based binder.

[0037] Any polysiloxane binder present in the coating composition of the present invention contains at least 50 wt. % polysiloxane moieties, preferably greater than 60 wt. % polysiloxane moieties, more preferably greater than 70 wt. % polysiloxane moieties, e.g., 99.99 wt. % or greater polysiloxane moieties, based on the total weight of the binder. Typical ranges include 50-100 wt. %, 60-99.999 wt. %, or 70-99.99 wt. % polysiloxane moieties in the polysiloxane binder.

[0038] The polysiloxane moiety is defined as a repeating unit containing the motif -Si-O- based on the total weight of the polysiloxane binder. The weight percent of the polysiloxane moiety can be determined based on the stoichiometric weight ratio of the starting materials in the polysiloxane synthesis. Alternatively, the polysiloxane content can be determined using analytical techniques such as IR or NMR.

[0039] Typically, the weight percent of the polysiloxane moiety is calculated based on the molar ratio of the reactive starting materials in the polysiloxane synthesis. If a molar excess of monomer is present in the reaction mixture, such molar excess is not taken into account. Only the monomers that can react based on the stoichiometry of the reaction are taken into account.

[0040] Information regarding the weight percent polysiloxane moiety in commercially available polysiloxane-based binders is readily available from suppliers.

[0041] It is understood that the polysiloxane-based binder may consist of a single repeating sequence of siloxane units or may be interrupted by non-siloxane moieties, e.g., organic moieties. It is preferred that the polysiloxane-based binder contain only Si-O repeating units.

[0042] The organic moiety may include, for example, an alkylene, an arylene, a poly(alkylene oxide), an amide, a thioether, or a combination thereof, and preferably, for example, an alkylene, an arylene, a poly(alkylene oxide), an amide, or a combination thereof.

[0043] By curable, it is meant that the polysiloxane binder contains functional groups that allow crosslinking reactions to occur between the polysiloxane binder molecules or via a crosslinking agent.

[0044] Any polysiloxane-based binder is preferably an organopolysiloxane having terminal and / or pendant curing reactive functional groups. Preferably, there are at least two curing reactive functional groups per molecule. Examples of curing reactive functional groups include silanol, alkoxy, acetoxy, enoxy, ketoxime, aminoxy, amine, epoxy, vinyl, and / or isocyanate. Preferred polysiloxane-based binders contain curing reactive functional groups selected from silanol, alkoxy, or acetoxy groups. The curing reaction is typically a condensation curing reaction. The polysiloxane-based binder may optionally contain two or more types of curing reactive groups, allowing it to be cured, for example, via both condensation curing and amine / epoxy curing.

[0045] The polysiloxane binder may consist of only one type of polysiloxane or may be a mixture of different polysiloxanes, as long as it satisfies the requirements of the present invention.

[0046] The polysiloxane binder may be a linear or branched polysiloxane binder. Branched means that the polysiloxane chain is branched. The branched polysiloxane binder may also contain cage-like polysiloxane structures, also known as polysiloxane resins.

[0047] In one preferred embodiment, the polysiloxane binder is linear.

[0048] A preferred polysiloxane binder present in the fouling release coating composition of the present invention is represented by the following formula (D1):

[0049] [ka]

[0050] During the ceremony, Each R 1 are independently a hydroxyl group, C 1-6 -alkoxy group, O-Si(R 5 ) 3-z (R 6 ) z , C 1-6 -hydroxyl group, C 1-6 -epoxy-containing group, C 1-6 Amine group, C 1-10 Alkyl group, C 6-10 Aryl, or C 7-10 Preferably, each R is selected from alkaryl. 1 are independently a hydroxyl group, C 1-6 -alkoxy group, or O-Si(R 5 ) 3-z (R 6 ) z is selected from.

[0051] Each R 2 independently, C 1-10 Alkyl, C 6-10 Aryl, C 7-10 alkylaryl, or poly(alkylene oxide) and / or R 1C substituted with groups described for 1-6 alkyl, Each R 3 and R 4 independently, C 1-10 Alkyl, C 6-10 Aryl, C 7-10 Alkylaryl or poly(alkylene oxide) substituted C 1-6 alkyl, Each R 5 independently, C 1-6 a hydrolyzable group such as an alkoxy group, an acetoxy group, an enoxy group, or a ketoxy group; Each R 6 independently, C 1-6 alkyl groups, z is 0 or an integer of 1 to 2, x is an integer equal to or greater than 2, y is an integer of 2 or greater.

[0052] Preferably, R 1 is a hydroxyl group and O-Si(R 5 ) 3-z (R 6 ) z Selected from R 5 is a C1-C6 alkoxy group, and R 6 is C 1-6 alkyl, and z is 0 or an integer of 1 to 2. More preferably, R 1 is a hydroxyl group and O-Si(R 5 ) 3-z (R 6 ) z Selected from R 5 is a C1-C3 alkoxy group, and R 6 is C 1-3 alkyl, and z is 0 or an integer of 1 to 2. More preferably, R 1 is a hydroxyl group.

[0053] Preferably, R 2 is C 1-10 More preferably, R 2 is C1-4 alkyl group, more preferably C 1-2 Preferably, each R 2 are identical.

[0054] Preferably, R 3 is C 1-10 More preferably, R 3 is C 1-4 alkyl group, more preferably C 1-2 Preferably, each R 3 are identical.

[0055] Preferably, R 4 is C 1-10 More preferably, R 4 is C 1-4 alkyl group, more preferably C 1-2 Preferably, each R 4 are identical.

[0056] More preferably, R 1 is a hydroxyl group, and R 2 , R 3 , and R 4 are methyl groups.

[0057] Another preferred polysiloxane binder present in the fouling release coating composition of the present invention is represented by the following formula (D2):

[0058] [ka]

[0059] During the ceremony, Each R 1 are independently a hydroxyl group, C 1-6 -alkoxy group or O-Si(R 5 ) 3-z (R 6 ) z is selected from Each R 2 ~R 4 is methyl, Each R 5 independently, C 1-6 a hydrolyzable group such as an alkoxy group, an acetoxy group, an enoxy group, or a ketoxy group; Each R 6 independently, C 1-6 alkyl groups, z is 0 or an integer of 1 to 2, x is an integer equal to or greater than 2, y is an integer of 2 or greater.

[0060] Another preferred polysiloxane binder present in the fouling release coating composition of the present invention is represented by formula (D3):

[0061] [ka]

[0062] During the ceremony, R 1 , R 2 , R 3 , R 4 , x, and y are as defined for (D1), and R x is C 2-3 Each L1 is 0 to 50, each L2 is 0 to 50, and L3 is 1 to 200, preferably 2 to 100, most preferably 5 to 50, provided that L1+L2 is alkyl and L1 is 2 to 50, preferably 4 to 40, more preferably 4 to 20, and most preferably 4 to 10. The polysiloxane moiety must constitute at least 50% by weight of the molecule.

[0063] Preferably, the polysiloxane binder of the present invention is represented by formula (D1).

[0064] Any polysiloxane binder of the present invention is preferably polydimethylsiloxane.

[0065] Those skilled in the art will recognize that polysiloxane-based binders may contain small amounts of impurities, such as cyclic siloxanes, such as D4, D5, and D6 cyclosiloxanes, which are residues from polysiloxane synthesis. Here, the designation (D4, D5, or D6) refers to the number of Si-O repeating units in the cyclic polysiloxane (i.e., there are four, five, or six Si-O repeating units in the cyclic polysiloxane, respectively). From health, safety, and environmental perspectives, it is preferable to limit the amount of cyclic polysiloxanes present in the coating. In a preferred embodiment, the polysiloxane-based binder contains less than 5%, preferably less than 2%, and more preferably less than 1% cyclic polysiloxanes. In a particularly preferred embodiment, the polysiloxane-based binder does not contain cyclic polysiloxanes.

[0066] The weight average molecular weight of the polysiloxane binder or any combination of polysiloxane binders present in the fouling release coating composition of the present invention is preferably 400 to 150,000 g / mol, more preferably 1000 to 120,000 g / mol, and even more preferably 5000 to 110,000 g / mol.

[0067] The polysiloxane binder or combination of polysiloxane binders typically constitutes at least 35 wt. % of the polysiloxane coating composition (dry weight), such as at least 40 wt. % of the fouling release coating composition (dry weight), in particular at least 45 wt. %, for example 35 to 75 wt. %.

[0068] In one embodiment, the required polysiloxane-based binder system contains two separate polysiloxane polymers A and B that differ in molecular weight or viscosity, where each of polysiloxane polymers A and B may be as defined herein and as described in WO2022069482A1 and WO2022069487A1. In one embodiment, the required polysiloxane-based binder system contains three separate polysiloxane polymers A, B, and C, as described in WO2022069487A1.

[0069] When a combination of polysiloxane-based binder A and polysiloxane-based binder B is present, the preferred molecular weights and viscosities are as outlined below.

[0070] The weight average molecular weight (Mw) of the polysiloxane binder A is preferably 50,000 g / mol or less, for example, 3,500 to 50,000, preferably 8,000 to 50,000 g / mol. In a more preferred embodiment, the weight average molecular weight of the polysiloxane binder A is 10,000 to 48,000, more preferably 15,000 to 45,000, and particularly 20,000 to 40,000 g / mol.

[0071] In one embodiment, the number average molecular weight (Mn) of the polysiloxane binder A is less than 25,000 g / mol, e.g., 1,000 to 24,000 g / mol, preferably 2,000 to 24,000 g / mol. In a more preferred embodiment, the number average molecular weight of the polysiloxane binder A is 3,000 to 19,500 g / mol, more preferably 4,000 to 19,500 g / mol, and especially 5,000 to 19,500 g / mol. The molecular weight (Mn and Mw) values ​​referred to herein correspond to values ​​obtained experimentally, e.g., by GPC measurement against polystyrene standards. The method is described in the experimental section below.

[0072] In one embodiment, the weight average Mw of the polysiloxane binder B is preferably 55,000 or more, for example, 60,000 to 120,000 g / mol, and more preferably 65,000 to 110,000 g / mol.

[0073] The viscosity of the polysiloxane binder A is preferably 2,800 mPas or less, for example, 400 to 2,800, more preferably 400 to 2,000, and particularly preferably 500 to 1,500 mPas.

[0074] The viscosity of the polysiloxane binder B is preferably 3,500 mPas or more, for example, 4,000 to 30,000 mPas, and more preferably 5,000 to 25,000 mPas.

[0075] When two binders are included, each binder preferably constitutes at least 27% by weight, more preferably at least 40% by weight, of the binder system. The ratio of binder A to binder B is preferably in the range of 30:70 to 70:30, more preferably 40:60 to 60:40, and even more preferably 45:55 to 55:45.

[0076] Viewed another way, each binder comprises at least 20% by weight of the coating composition.

[0077] When a mixture of binder A and binder B is used, the PDI of the binder mixture is preferably at least 2.5, for example, from 2.5 to 10, particularly from 3.0 to 8.0.

[0078] When a mixture of binder A and binder B is used in the binder system, the viscosity of the binder system is preferably 400 to 30,000 mPas, more preferably 1000 to 25,000 mPas, and even more preferably 2000 to 15,000 mPas, for example, 2500 to 11,000 mPas.

[0079] When a mixture of binder A and binder B is used in the binder system, the weight average molecular weight of the binder system is preferably 25,000 to 100,000 g / mol, more preferably 30,000 to 80,000 g / mol, and even more preferably 40,000 to 80,000 g / mol. When a mixture of binder A and binder B is used in the binder system and the weight average molecular weight of the binder system exceeds 50,000, it is also preferred that the PDI of the binder system be at least 2.5.

[0080] [Added oil] The coating composition of the present invention may contain additive oils. These additive oils do not contain any curing reactive groups, and therefore, the additive oils are intended to be non-reactive in the curing reaction. Depending on the curing mechanism of the binder system, the functional groups on the additive oil should be selected so as not to react in the curing reaction of the polysiloxane binder. The additive oils are intended to be free in the coating film so that they can migrate to the surface of the coating film and improve the antifouling properties of the coating film.

[0081] Examples of suitable additive oils include hydrophilically modified polysiloxane oils and hydrophobically modified polysiloxane oils.Other additive oils that can be used include petroleum oils, polyolefin oils, polyaromatic oils, fluororesins such as polytetrafluoroethylene or fluorinated alkyl- or alkoxy-containing fluid polymers, lanolin and lanolin derivatives, other sterols and / or sterol derivatives (disclosed in WO2013024106A1), poly(oxyalkylene)-modified alcohols such as poly(oxyalkylene)-modified sterols (disclosed in WO2016004961A1), or combinations thereof.

[0082] Other additive oils that are optionally present in the coating compositions of the present invention include fluorinated amphiphilic polymers / oligomers such as those described in WO2014131695.

[0083] Suitable additive oils may be based on (meth)acrylate copolymers with polysiloxane side chains and polyether or nitrogen-containing hydrophilic groups, as described in WO2019101912 A1 and WO2019101920 A1.

[0084] Preferably, the additive oil is a hydrophilically modified polysiloxane oil and / or a hydrophobically modified polysiloxane oil. Hydrophilically modified polysiloxane oils and hydrophobically modified polysiloxane oils may be used in combination. Suitable hydrophilically modified polysiloxane oils and hydrophobically modified polysiloxane oils are described in more detail below.

[0085] [Hydrophilic modified polysiloxane] The coating compositions of the present invention may further contain a hydrophilically modified polysiloxane, it being understood that this component is distinct from the polysiloxane-based binders described above.

[0086] It will be understood that the hydrophilically modified polysiloxane is intended to be non-reactive in the curing reaction, particularly with respect to the binder component, since the hydrophilically modified polysiloxane does not contain silicone reactive groups, such as Si-OH groups or Si-OR (alkoxy) groups, that can react with the binder or crosslinker (if present) at the corresponding curing temperatures (0-40°C). This component is not considered part of the binder system.

[0087] Depending on the cure mechanism, the functional groups on the hydrophilically modified polysiloxane should be selected so that they do not react in the cure reaction.

[0088] Hydrophilically modified polysiloxanes are widely used as surfactants and emulsifiers because they contain both hydrophilic and lipophilic groups within the same molecule. The hydrophilically modified polysiloxane of the present invention is a polysiloxane modified with hydrophilic groups to make it more hydrophilic than a corresponding unsubstituted polysiloxane having the same number of polysiloxane units. Hydrophilicity can be achieved by modification with hydrophilic groups such as ethers (e.g., polyoxyalkylene groups such as polyethylene glycol and polypropylene glycol), alcohols (e.g., poly(glycerol)), amides (e.g., pyrrolidone, polyvinylpyrrolidone, (meth)acrylamide), acids (e.g., carboxylic acids, poly(meth)acrylic acid), and amines (e.g., polyvinylamine, amine-group-containing (meth)acrylic polymers). Typically, the hydrophilically modified polysiloxane is an oil.

[0089] In a preferred embodiment, the hydrophilic groups are non-ionic.

[0090] By "nonionic" herein is meant that the hydrophilically modified polysiloxane does not contain any salt moieties, and in particular, typically does not contain any metal cations.

[0091] The hydrophilicity of the nonionic hydrophilic modified polysiloxane can be determined according to the HLB (hydrophilic-lipophilic balance) parameter. When the hydrophilic modified polysiloxane of the present invention is nonionic, the HLB (hydrophilic-lipophilic balance) is in the range of 0.5 to 12, preferably 0.5 to 10, more preferably 0.5 to 8.0, and most preferably 0.5 to 7.0. In a specific embodiment, the nonionic hydrophilic modified polysiloxane has an HLB in the range of 3.0 to 6.0.

[0092] As used herein, HLB is typically determined according to Griffin's model using the formula "wt% hydrophilic groups" / 5 (Reference: Griffin, W.C. Calculation of HLB values ​​of non-ionic surfactants, J. Soc. Cosmet. Chem. 1954, 5, 249-256). HLB parameters are established parameters for non-ionic surfactants and are readily available from suppliers of commercially available hydrophilically modified polysiloxanes. The higher the HLB value of a surfactant, the more hydrophilic it is. Wt% hydrophilic groups refers to the weight percent of hydrophilic groups in the hydrophilically modified polysiloxane.

[0093] One of the functions of hydrophilically modified polysiloxanes is to facilitate the dissolution and transport of any biocide to the coating surface. Furthermore, it is well known that the formation of a hydration layer at the coating-water interface is important for antifouling performance.

[0094] If the hydrophilicity of the hydrophilic modified polysiloxane is too high, for example, due to the large number of hydrophilic groups in the molecule, the dissolution rate may be too high, leading to early depletion of the biocide and the hydrophilic modified polysiloxane. Also, if the hydrophilicity is too high, the compatibility with the polysiloxane-based binder matrix may be poor, and the coating film may become less uniform and have poor adhesion, especially when the oil content is high (more than 10 wt%).

[0095] Methods for controlling the dissolution rate of the biocide and hydrophilically modified polysiloxane include the molecular weight, hydrophilicity, and miscibility with the binder of the hydrophilically modified polysiloxane. If the molecular weight of the hydrophilically modified polysiloxane is very low, the dissolution rate tends to be high, but if the molecular weight is too high, the dissolution rate of the biocide and hydrophilically modified polysiloxane may not be as fast as desired.

[0096] Thus, in a preferred embodiment, the hydrophilically modified polysiloxane has a number average molecular weight (Mn) in the range of 500 to 18,000 g / mol, for example, 1,000 to 16,000 g / mol, particularly 2,000 to 15,050 g / mol or 4,000 to 15,050 g / mol. More preferred Mn ranges for the hydrophilically modified polysiloxane include 500 to 15,000 g / mol, 1,000 to 13,000 g / mol, or 3,000 to 10,000 g / mol. The number average molecular weight (Mn) values ​​referred to herein correspond to values ​​obtained experimentally, for example, by GPC measurement against polystyrene standards. The method is described in the experimental section below.

[0097] In a preferred embodiment, the hydrophilically modified polysiloxane has a weight-average molecular weight (Mw) in the range of 1,000 to 50,000 g / mol, preferably 2,000 to 45,000 g / mol, 3,000 to 42,000 g / mol, 4,000 to 40,000 g / mol, or 5,000 to 40,000 g / mol. More preferred ranges include 5,000 to 30,000 g / mol, e.g., 5,000 to 25,000 g / mol, or 10,000 to 20,000 g / mol. The weight-average molecular weight (Mw) values ​​referred to herein correspond to experimentally determined values, e.g., by GPC measurement against polystyrene standards. The method is described in the experimental section below.

[0098] The viscosity of the hydrophilically modified polysiloxane is preferably in the range of 20 to 4,000 mPa·s, for example, in the range of 30 to 3,000 mPa·s, and particularly preferably in the range of 50 to 2,500 mPa·s.

[0099] The hydrophilically modified polysiloxane may be contained in the coating composition in an amount of 1.0 to 30% by dry weight, preferably 2.0 to 20% by dry weight, and more preferably 4 to 15% by dry weight. When two or more different types of hydrophilically modified polysiloxanes are present, these amounts refer to the sum of the hydrophilically modified polysiloxane components.

[0100] Of particular interest are hydrophilically modified polysiloxanes in which the relative weight of the hydrophilic moieties is 5% or more (e.g. 5-60%), for example 6% or more (e.g. 6-50%), in particular 10% or more (e.g. 10-40%) of the total weight of the hydrophilically modified polysiloxane.

[0101] The weight percent of the hydrophilic moieties can be calculated based on the stoichiometric ratio of the starting materials in the synthesis of the hydrophilically modified polysiloxane, or can be determined using analytical techniques such as IR or NMR.

[0102] If there is a molar excess of reactants, such molar excess is not taken into account when determining the weight percent of hydrophilic moieties. Only monomers that can react based on the stoichiometry of the reaction are considered.

[0103] The hydrophilically modified polysiloxane may contain small amounts of impurities, such as cyclic siloxanes, such as D4, D5, and D6 cyclosiloxanes, which are residues from polysiloxane synthesis. Here, the designations (D4, D5, and D6) refer to the number of Si-O repeating units in the cyclic polysiloxane (i.e., there are four, five, or six Si-O repeating units in the cyclic polysiloxane, respectively). From the perspectives of health, safety, and the environment, it is preferable to limit the amount of cyclic polysiloxanes present in the coating composition. In a preferred embodiment, the hydrophilically modified polysiloxane contains less than 5%, preferably less than 2%, and more preferably less than 1% of cyclic polysiloxanes. In a particularly preferred embodiment, the hydrophilically modified polysiloxane does not contain cyclic polysiloxanes.

[0104] In one preferred embodiment, the hydrophilically modified polysiloxane is a polyether modified polysiloxane.

[0105] Preferably, the polyether group comprises at least 3 repeat units, for example at least 5 repeat units. In many interesting embodiments, the oligomer or polymer comprises 5 to 100 repeat units, for example 5 to 50, or 8 to 50, or 8 to 20 repeat units.

[0106] In some preferred embodiments, the polyether group (i.e., the oligomeric or polymeric group) has a number average molecular weight (n) in the range of 100 to 2500 g / mol, for example in the range of 200 to 2000 g / mol, particularly in the range of 300 to 2000 g / mol, or in the range of 400 to 1000 g / mol.

[0107] Of particular interest are polyether-modified polysiloxanes in which the relative weight of the polyether moiety is 5% or more (e.g., 5 to 60%), for example 6% or more (e.g., 6 to 50%), in particular 10% or more (e.g., 10 to 40%) of the total weight of the polyether-modified polysiloxane.

[0108] In one variation, the polyether-modified polysiloxane is a polysiloxane to which poly(oxyalkylene) chains are grafted. The structure of such a polyether-modified polysiloxane is represented by formula (A):

[0109] [ka]

[0110] An example is shown below.

[0111] During the ceremony, Each R 7 independently, C 1-5 - selected from alkyl (including straight or branched chain hydrocarbon groups) and aryl (e.g., phenyl (-C6H5)), in particular methyl; Each R 8 are independently -H, C 1-4-Alkyl (e.g., -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2CH3), phenyl (-C6H5), and C 1-4 - alkylcarbonyl (e.g., -C(=O)CH3, -C(=O)CH2CH3, and -C(=O)CH2CH2CH3), in particular selected from -H, methyl, and -C(=O)CH3; Each R 9 independently, C 2-5 -Alkylene (e.g., -CH2CH2-, -CH2CH(CH3), -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH(CH2CH3)-), arylene (e.g., 1,4-phenylene), and aryl-substituted C 2-5 -C alkylene (e.g., 1-phenylethylene), especially -CH2CH2- and -CH2CH(CH3)- 2-5 - alkylene, k is 0 to 240, l is 1 to 60, and k+l is 1 to 240; n is an integer of 0 to 50, m is an integer of 0 to 50, and m+n is an integer of 1 to 50.

[0112] In particular, R 7 is methyl, Each R 8 are independently -H or C 1-4 -alkyl or -C(=O)CH3; Each R 9 is -CH2CH2-, -CH2CH2CH2-, or -CH2CH(CH3)-), k is 0 to 240, l is 1 to 60, and k+l is 1 to 240; n is an integer of 0 to 50, m is an integer of 0 to 50, and m+n is an integer of 1 to 50.

[0113] All R 7 It is preferred that the groups are identical.

[0114] Commercially available examples of this type of polyether-modified polysiloxane include KF352A, KF353, KF945, KF6012, and KF6017 (manufactured by Shin-Etsu Chemical Co., Ltd.), as well as XIAMETER OFX-5220, DOWSIL OFX-5247, XIAMETER OFX-5329, and XIAMETER OFX-5330 (manufactured by DOW).

[0115] In another variation, the polyether-modified polysiloxane is a polysiloxane having a poly(oxyalkylene) chain incorporated into its backbone. The structure of such a hydrophilically modified polysiloxane can be represented by formula (B):

[0116] [ka]

[0117] An example is shown below.

[0118] During the ceremony, Each R 7 independently, C 1-5 - selected from alkyl (including straight or branched chain hydrocarbon groups) and aryl (e.g., phenyl (-C6H5)), in particular methyl; Each R 8 are independently -H, C 1-4 -Alkyl (e.g., -CH3, -CH2CH3, -CH2CH2CH -CH(CH3)2, -CH2CH2CH2CH3), phenyl (-C6H5), and C 1-4 - alkylcarbonyl (e.g., -C(=O)CH3, C(=O)CH2CH3, and -C(=O)CH2CH2CH3), in particular selected from -H, methyl, and -C(=O)CH3; Each R 9 independently, C 2-5 -Alkylene (e.g., -CH2CH2-, -CH2CH(CH3)-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH(CH2CH3)-), arylene (e.g., 1,4-phenylene), and aryl-substituted C 2-5-Alkylene (e.g., 1-phenylethylene), in particular C such as -CHCH- and -CHCH(CH)- 2-5 - alkylene, k is 0 to 240; n is an integer of 0 to 50, m is an integer of 0 to 50, and m+n is an integer of 1 to 50.

[0119] In particular, R 7 is methyl, Each R 8 are independently -H or C 1-4 -alkyl or -C(=O)CH3; Each R 9 is -CH2CH2-, -CH2CH(CH3)-, or -CH2CH2CH2-, k is 0 to 240; n is an integer of 0 to 50, m is an integer of 0 to 50, and m+n is an integer of 1 to 50.

[0120] All R 7 It is preferred that the groups are identical.

[0121] Commercially available hydrophilically modified polysiloxanes of this type include DOWSIL 2-8692 and XIAMETER OFX-3667 (manufactured by DOW Corporation).

[0122] In yet another variation, the polyether-modified polysiloxane is a polysiloxane having a polyoxyalkylene chain incorporated into its backbone and grafted thereto. The structure of such a hydrophilically modified polysiloxane can be represented by formula (C):

[0123] [ka]

[0124] An example is shown below.

[0125] During the ceremony, Each R 7 independently, C1-5 - selected from alkyl (including straight or branched chain hydrocarbon groups) and aryl (e.g., phenyl (-C6H5)), in particular methyl; Each R 8 are independently -H, C 1-4 - alkyl (e.g., -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2CH3), phenyl (-C6H5), and C 1-4 - alkylcarbonyl (e.g., -C(=O)CH3, -C(=O)CH2CH3, and -C(=O)CH2CH2CH3), in particular selected from -H, methyl, and -C(=O)CH3; Each R 9 independently, C 2-5 -Alkylene (e.g., -CH2CH2-, -CH2CH(CH3)-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH(CH2CH3)-), arylene (e.g., 1,4-phenylene), and aryl-substituted C 2-5 -C alkylene (e.g., 1-phenylethylene), especially -CH2CH2- and -CH2CH(CH3)- 2-5 - alkylene, k is 0 to 240, l is 1 to 60, and k+l is 1 to 240; n is an integer of 0 to 50, m is an integer of 0 to 50, and m+n is an integer of 1 to 50.

[0126] In particular, R 7 is methyl, Each R 8 is -H or C 1-4 -alkyl or -C(=O)CH3, Each R 9 is -CH2CH2-, -CH2CH2CH2-, - or -CH2CH(CH3)-, k is 0 to 240, y is 1 to 60, and x+y is 1 to 240; n is an integer of 0 to 50, m is an integer of 0 to 50, and m+n is an integer of 1 to 50.

[0127] In the above structures (A), (B), and (C), the groups -CHCH(CH)-, -CHCH(CHCH)-, etc., may be present in either of two possible orientations. Similarly, it will be understood that the segments present k and l times are typically randomly distributed in the polysiloxane structure.

[0128] In these embodiments and variations, the polyether or poly(oxyalkylene) is preferably selected from polyoxyethylene, polyoxypropylene, and poly(oxyethylene-co-oxypropylene), which are sometimes referred to as polyethylene glycol, polypropylene glycol, and poly(ethylene glycol-co-propylene glycol). Thus, in structures (A), (B), and (C) above, each R linking two oxygen atoms 9 is preferably selected from —CH2CH2— and —CH2CH(CH3)—, and each R linking a silicon atom and an oxygen atom 9 is preferably C 2-5 -alkyl.

[0129] In some embodiments of structures (A), (B), and (C) above, R 8 is preferably not hydrogen.

[0130] It will be appreciated that the one or more polyether-modified polysiloxanes may be of different types, for example, two or more of the types described above.

[0131] In another preferred embodiment, the hydrophilically modified polysiloxane contains polyglycerol or pyrrolidone groups.

[0132] [Hydrophobic modified polysiloxane] The coating composition of the present invention optionally further contains a hydrophobically modified polysiloxane oil. It is understood that the hydrophobically modified polysiloxane is intended to be non-reactive in the curing reaction, particularly with respect to the binder component, because the hydrophobically modified polysiloxane does not contain curing-reactive groups, such as Si-OH groups or Si-OR (alkoxy) groups, that can react with the binder at the corresponding curing temperature (0-40°C). Generally, this component is not considered part of the binder system. Depending on the curing mechanism, the functional groups on the hydrophobically modified polysiloxane should be selected so that they do not react in the curing reaction.

[0133] The hydrophobically modified polysiloxane of the present invention is a polysiloxane modified with a hydrophobic group to be more hydrophobic than the corresponding unsubstituted polysiloxane having the same number of polysiloxane units. The hydrophobicity can be achieved by modification with a hydrophobic group such as an alkyl group, a cycloalkyl group, or an aryl group. Typically, the hydrophobically modified polysiloxane is an oil.

[0134] Preferred hydrophobically modified polysiloxanes are methylphenyl-functional polysiloxanes and methylaryl-functional polysiloxanes.

[0135] When present, the hydrophobically modified polysiloxane is preferably present in an amount of from 2.5 to 30% by weight, more preferably from 5 to 25% by weight, based on the total dry weight of the composition.

[0136] When present, the hydrophobically modified polysiloxane is preferably present in an amount of from 1.0 to 30% by weight, more preferably from 4 to 20% by weight, based on the total weight of the entire composition.

[0137] While it is within the scope of the present invention for a mixture of two or more hydrophobically modified polysiloxanes to be present, it is preferred that only a single hydrophobically modified polysiloxane be present. When two or more different types of hydrophobically modified polysiloxanes are present, the weight percent ranges cited above refer to the sum of the hydrophobically modified polysiloxane components. In one embodiment, the coating composition contains a mixture of a hydrophilically modified polysiloxane and a hydrophobically modified polysiloxane. In this embodiment, each of the hydrophilically modified polysiloxane and the hydrophobically modified polysiloxane may be present individually in an amount of 2.5 to 20 weight percent, for example, 5 to 15 weight percent, based on the total dry weight of the composition.

[0138] [Crosslinking agent and / or curing agent] The polysiloxane-based binders of the present invention are curable and contain curing reactive functional groups such as silanol groups, alkoxysilane groups, ketoxime groups, carbinol groups, amine groups, epoxy groups, and / or alkoxy groups.

[0139] Preferably, the polysiloxane binder contains at least two curing reactive functional groups. The polysiloxane binder optionally contains two or more types of curing reactive functional groups. Preferably, the polysiloxane binder contains a single type of curing reactive functional group.

[0140] In preferred polysiloxane binders, the curing reactive functional groups are silanol and / or alkoxysilane, and in more preferred polysiloxane binders, the curing reactive functional groups are silanol.

[0141] To obtain the desired crosslink density, it is necessary to add a crosslinking agent or curing agent. The appropriate crosslinking agent and / or curing agent is selected depending on the curing reactive functional groups present in the polysiloxane binder. The terms "crosslinking agent," "crosslinker," and "curing agent" are used interchangeably herein.

[0142] When the curing reactive functional group is a silanol, the preferred crosslinker / curing agent is of the general formula (I) shown below:

[0143] [ka]

[0144] an organosilicon compound represented by the formula (I), a partial hydrolysis condensate thereof, or a mixture of these two, During the ceremony, Each R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, a C substituted with poly(alkylene oxide), 1-6 Alkyl, or the structure (O-(CR D 2) r' ) r1' -(O-(CR D 2) s' ) s1' -(Si(R PP )2-O) t' -Si(R PP ) 3 polysiloxanes, where r', r1', s', and s1' are integers from 0 to 10, and each R D are independently H or C 1-4 alkyl, and each R PP independently, C 1-10 Alkyl, C 6-10 Aryl, C 7-10 alkylaryl, and t' is an integer from 1 to 50; Each K is independently selected from hydrolyzable groups such as alkoxy groups, and d is 0, 1, or 2, more preferably 0 or 1.

[0145] Preferred crosslinking agents of this type include tetraethoxysilane, vinyltris(methylethyloxime)silane, methyltris(methylethyloxime)silane, vinyltrimethoxysilane, methyltrimethoxysilane, and vinyltriisopropenoxysilane, as well as hydrolysis condensates thereof.

[0146] When the cure reactive functional groups are dialkoxy or trialkoxy, a separate crosslinker is generally not required.

[0147] In any embodiment of the present invention, the crosslinker is preferably present in an amount of up to 10 wt.%, more preferably 2.0-8.0 wt.%, based on the total dry weight of the coating composition. Suitable crosslinkers are commercially available, for example, Silicate TES-40 WN (Wacker) and Dynasylan (Evonik).

[0148] When the curing reactive functional group is a carbinol, preferred crosslinkers include monomeric isocyanates, polyisocyanates, and isocyanate prepolymers. Polyisocyanates are preferred over monomeric isocyanates due to their lower toxicity. Polyisocyanates can be based on the chemical structures of, for example, diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI). These are available, for example, under the trade names Desmodur (manufactured by Covestro) and Tolonate (manufactured by Vencorex). Examples of polyisocyanates include Desmodur N3300, Desmodur 3390 BA / SN, Desmodur N3400, Desmodur N3600, Desmodur N75, Desmodur XP2580, Desmodur Z4470, Desmodur XP2565, and Desmodur VL (supplied by Covestro).

[0149] Polyisocyanates can have different NCO functionalities, which is the amount of NCO groups per polyisocyanate molecule or per isocyanate prepolymer molecule. Polyisocyanate curing agents with different NCO functionalities can be used.

[0150] The crosslinking agent is preferably present in an amount of 0.8 to 2.5 equivalents (equiv) of NCO groups relative to the amount of hydroxyl groups, more preferably 0.9 to 2.0 equiv, more preferably 0.95 to 1.7 equiv, and even more preferably 1 to 1.5 equiv.

[0151] When the cure reactive functionality is amine, epoxy, or isocyanate, the crosslinker is preferably amine, sulfur, or epoxy functional.

[0152] The crosslinker / curing agent can also be a dual crosslinker / curing agent, for example, comprising both an amine / sulfur / epoxy / isocyanate and an alkoxysilane. A preferred dual curing agent is represented by the following general formula (II):

[0153] [ka]

[0154] During the ceremony, LL is independently selected from unsubstituted or substituted monovalent hydrocarbon groups having 1 to 6 carbon atoms; each M is independently selected from hydrolyzable groups such as alkoxy groups; a is 0, 1, or 2, preferably 0 or 1; b is an integer from 1 to 6; Fn is an amine group, an epoxy group, a glycidyl ether group, an isocyanate group, or a sulfur group.

[0155] Preferred examples of such dual curing agents include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, (3-glycidoxypropyl)trimethoxysilane, and 3-mercaptopropyltrimethoxysilane. One particularly preferred curing agent is 3-aminopropyltriethoxysilane, such as Dynasylan AMEO (Evonik).

[0156] This type of dual curative can be used as a separate curing agent or can be used to end-capping the polysiloxane binder so that the end groups of the polysiloxane binder are modified prior to the curing reaction.

[0157] Preferably, the composition contains a crosslinker of formula I or a dual crosslinker of formula II, or a mixture thereof.

[0158] It is preferred that the binder is not a one-part room temperature vulcanizing (RTV-1) or self-curing binder.

[0159] In a particularly preferred embodiment, the crosslinker / curing agent of the present invention is not water.

[0160] [Catalyst component] To aid in the curing process, the coating compositions of the present invention may contain a catalyst component. The catalyst may be an organic catalyst, an inorganic catalyst, or an organometallic catalyst.

[0161] [Metal catalyst] In one embodiment, the coating composition of the present invention contains a metal catalyst. Representative examples of catalysts that can be used include Sn-containing catalysts, Zn-containing catalysts, Li-containing catalysts, K-containing catalysts, Bi-containing catalysts, Fe-containing catalysts, Ce-containing catalysts, or Zr-containing catalysts, such as their salts and organometallic complexes. The salts are preferably salts and / or chelates of long-chain carboxylic acids or organometallic salts.

[0162] The metal catalyst is preferably a tin(IV), bismuth(III), iron(II), iron(III), zinc(II), zirconium(IV), cerium(III), potassium, or lithium compound, with tin(IV), bismuth(III), zinc(II), and cerium(III) being particularly preferred.

[0163] Examples of anionic organic radicals include methoxide radical, ethoxide radical, n-propoxide radical, isopropoxide radical, n-butoxide radical, isobutoxide radical, sec-butoxide radical, tert-butoxide radical, triethanolamine radical, and 2-ethylhexyloxide radical; acetate radical, formate radical, n-octoate radical, 2-ethylhexanoate radical, 2,4,4-trimethylpentanoate radical, 2,2,4-trimethylpentanoate radical, 6-Methylheptanoic acid radical, oleic acid radical, ricinoleic acid radical, palmitic acid radical, hexoate radical, hexadecanoic acid radical, 2-ethylhexanoic acid radical, benzoic acid radical, 1,4-dibenzoic acid radical, stearic acid radical, acrylic acid radical, lauric acid radical, methacrylic acid radical, 2-carboxyethylacrylic acid radical, oxalic acid radical, 10-undecylenic acid radical, dodecanoic acid radical, citric acid radical, 3-oxopentanoic acid radical, 3-oxobutanoic acid radical carboxylic acid radicals such as methyl amide, methyl methyl amide, and neodecanoic acid radicals; amide radicals such as dimethylamide, diethylamide, ethylmethylamide, and dipropylamide radicals; lactic acid radicals; trialkylsiloxy radicals, more particularly trimethylsiloxy and triethylsiloxy radicals, and carbonate radicals (O—CO—OR′) and carbamate radicals (O—CO—NR′2), where R′ may be the same or different, monovalent or divalent, and optionally substituted hydrocarbon radicals. radical, and may further be a hydrogen radical, a trimethoxysilylpropyl radical, a triethoxysilylpropyl radical, a dimethoxymethylsilylpropyl radical, a diethoxymethylsilylpropyl radical, an N-[3-(trimethoxysilyl)propyl]-2-aminoethyl radical, an N-[3-(triethoxysilyl)propyl]-2-aminoethyl radical, an N-[3-(dimethoxymethylsilyl)propyl]-2-aminoethyl radical, or an N-[3-(diethoxymethylsilyl)propyl]-2-aminoethyl radical.

[0164] Examples of metal salt compounds include dibutyltin diacetate, dioctyltin dilaurate, dibutyltin dilaurate, dibutyltin oxide, bismuth(III) 2-ethylhexanoate, bismuth(III) neodecanoate, bismuth(III) acetate, bismuth(III) octanoate, iron(II) acetate, iron(III) tert-butoxide, iron(III) citrate, iron(II) lactate, iron(II) oxalate, iron(III) oxalate, iron(III) 2-ethylhexanoate, cerium(III) neodecanoate, zinc(II) acetate, zinc(II) formate, zinc(II) benzoate, zinc(II) 2-ethylhexanoate, zinc(II) n-octoate, zinc(II) stearate, zinc(II) ethoxide, zinc(II) acrylate, methacrylate, Examples of suitable cation exchangers include zinc(II) phosphate, zinc(II) naphthenate, zinc(II) oxalate, zinc(II) 10-undecylenate, zinc(II) 3-oxopentanoate, zinc(II) 3-oxobutanoate, zirconium(IV) acetate, zirconium(IV) 2-ethylhexanoate, zirconium(IV) lactate, zirconium(IV) n-butoxide, zirconium(IV) tert-butoxide, zirconium(IV) isopropoxide, zirconium(IV) n-propoxide, 2-carboxyethyl zirconium(IV) acrylate, zirconium(IV) tetrakis(diethylamide), zirconium(IV) tetrakis(ethylmethylamide), and zirconium(IV) bis(diethylcitrate)-di-n-propoxide.

[0165] Examples of metal chelate compounds include bismuth(III) 2,2,6,6-tetramethyl-3,5-heptanedionate, bismuth(III) acetylacetonate, iron(II) acetylacetonate, iron(III) acetylacetonate, iron(III) 2,2,6,6-tetramethyl-3,5-heptanedionate, iron(II) 2,2,6,6-tetramethyl-3,5-heptanedionate, zinc(II) hexafluoroacetylacetonate, zinc(II) 1,3-diphenyl-1,3-propanedionate, zinc(II) 1-phenyl-5-methyl-1,3-hexanedionate, zinc(II) 1,3-cyclohexanedionate, and zinc(II) 2-acetylcyclohexanedionate. hexanoate, zinc(II) 2-acetyl-1,3-cyclohexanedionate, zinc(II) ethyl salicylate, zinc(II) diethyl malonate, zinc(II) ethyl acetoacetate, zinc(II) benzyl salicylate, zinc(II) acetylacetonate, and zinc(II) 2,2,6,6-tetramethyl-3,5-heptanedionate, tin(II) acetylacetonate, zirconium(IV) acetylacetonate, zirconium(IV) 2,2,6,6-tetramethyl-3,5-heptanedionate, zirconium(IV) trifluoroacetylacetonate, and zirconium(IV) hexafluoroacetylacetonate.

[0166] Examples of suitable tin catalysts include dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin diacetate, and dioctyltin dilaurate. Examples of commercially available tin catalysts include BNT-CAT 400 and BNT-CAT 500 (BNT Chemicals), FASCAT 4202 (PMC Organometallix), and Metatin Katalysator 702 (DOW).

[0167] Examples of suitable lithium catalysts include lithium 2-ethylhexanoate and lithium neodecanoate. An example of a commercially available lithium catalyst is Borchers Deca Lithium 2 (manufactured by Borchers).

[0168] Examples of suitable potassium catalysts include potassium 2-ethylhexanoate and potassium neodecanoate. Examples of commercially available potassium catalysts include 15% Potassium Hex-Cem® EU (Borchers) and TIB KAT K30 (TIB Chemicals).

[0169] Examples of suitable zinc catalysts include zinc 2-ethylhexanoate, zinc naphthenate, and zinc stearate. Commercially available zinc catalysts include K-KAT XK-672 and K-KAT670 (King Industries) and Borchi Kat 22 (Borchers).

[0170] Examples of suitable bismuth catalysts include organobismuth compounds such as bismuth 2-ethylhexanoate, bismuth octoate, and bismuth neodecanoate. Commercially available organobismuth catalysts include Borchi Kat 24 and Borchi Kat 315 (Borchers), K-KAT XK-651 (King Industries), Reaxis C739E50 (Reaxis), and TIB KAT 716 (TIB Chemicals).

[0171] An example of a suitable cerium catalyst is cerium(III) neodecanoate.

[0172] Other suitable catalysts include iron catalysts such as iron stearate and iron 2-ethylhexanoate, and zirconium catalysts such as zirconium naphthenate, tetrabutyl zirconate, tetrakis(2-ethylhexyl) zirconate, triethanolamine zirconate, tetra(isopropenyloxy) zirconate, zirconium tetrabutanolate, zirconium tetrapropanolate, and zirconium tetraisopropanolate. Further suitable catalysts include zirconate esters.

[0173] In one preferred embodiment, the added metal is a tin, zinc, and / or cerium catalyst.

[0174] In one preferred embodiment, the catalyst is tin-free.

[0175] The metal catalyst is preferably present in the coating composition of the present invention in an amount of 0.05 to 5.0 wt %, more preferably 0.1 to 2.0 wt %, based on the total dry weight of the coating composition.

[0176] This component is not considered part of the binder system.

[0177] [Organic catalyst] The catalyst may be an organic catalyst, such as a low-molecular-weight amidine or a low-molecular-weight amine compound, such as an aminosilane. The term "low molecular weight" means that the molecular weight is less than 1000 g / mol, for example, 50 to 500 g / mol, preferably 100 to 400 g / mol. In a preferred embodiment, the low-molecular-weight amidine or low-molecular-weight amine compound is not guanidine or a guanidine derivative. In a more preferred embodiment, the coating composition disclosed herein does not contain any guanidine-based catalyst.

[0178] Guanadine derivatives are compounds containing the following motifs:

[0179] [ka]

[0180] Suitable amidines are compounds containing the following motif:

[0181] [ka]

[0182] Preferably, the amidine is represented by the general formula:

[0183] [ka]

[0184] During the ceremony, R1, R2, and R4 are each independently selected from hydrogen, a monovalent organic group, a monovalent heteroorganic group, and combinations thereof; R3 is a monovalent organic group, a monovalent heteroorganic group, or a combination thereof; and / or any two or more of R1, R2, R3, and R4 can optionally be joined to form a ring structure.

[0185] R1, R2, and R4 are preferably hydrogen, a C1-6 alkyl group, or a phenyl group.

[0186] R3 is C 1-6 It is an alkyl group or a phenyl group.

[0187] More preferably, R2 and R4 together form a ring, and / or R1 and R3 together form a ring, which is preferably an aliphatic 5- to 7-membered ring.

[0188] Preferred choices include cyclic amidines, preferably bicyclic amidines such as 1,8-diazabicyclo-5.4.0-7-undecene (DBU). The chemical structure of DBU is shown below:

[0189] [ka]

[0190] The catalyst may be a low molecular weight organic amine compound such as triethylamine, cyclic amines, tetramethylethylenediamine, 1,4-ethylenepiperazine, pentamethyldiethylenetriamine, and the like.

[0191] However, preferred amines are aminosilanes, for example, aminoalkyltrialkoxysilanes such as 3-aminopropyltriethoxysilane or 3-aminopropyltrimethoxysilane. Alternatively, the bis(alkyltrialkoxysilyl)amine preferably comprises bis(3-propyltrimethoxysilyl)amine or bis(3-propyltriethoxysilyl)amine. Another option is N,N-dibutylaminomethyl-triethoxysilane.

[0192] Suitable aminosilanes are represented by general formula (I) or (II):

[0193] [ka]

[0194] In the formula, z is an integer of 1 to 3.

[0195] [ka]

[0196] In the formula, y is an integer of 1 to 2.

[0197] Further, each R is a hydrocarbyl group having 1 to 12 carbon atoms, optionally containing an ether or amino linker; R 1 is a hydrocarbyl group having 1 to 12 carbon atoms, Each X independently represents an alkoxy group.

[0198] Y is an amino bonded to R.

[0199] The Y group can be attached to any part of the R chain.

[0200] The amino group is preferably N-di-C1-6-alkyl or NH2.

[0201] It is particularly preferred that X is a C1-6 alkoxy group, especially a methoxy or ethoxy group. It is also particularly preferred that there are two or three alkoxy groups. Thus, z is ideally 2 or 3, especially 3.

[0202] The subscript y is preferably 2.

[0203] R 1 is preferably C1-4 alkyl such as methyl.

[0204] R is a hydrocarbyl group containing up to 12 carbon atoms. Hydrocarbyl refers to a group consisting only of C and H atoms. It can include an alkylene chain or a combination of an alkylene chain and a ring such as a phenyl or cyclohexyl ring. The term "optionally containing an ether or amino linker" means that the carbon chain can be interrupted by an -O- or -NH- group within the chain.

[0205] R is preferably an unsubstituted (excluding, of course, Y) and unbranched alkyl chain having 2 to 8 carbon atoms.

[0206] Thus, the preferred silane general formula is that of structure (III).

[0207] [ka]

[0208] In the formula, z' is an integer of 2 to 3, R' is an unsubstituted and unbranched alkyl chain of 2 to 8 carbon atoms, optionally containing an ether or amino linker; Y' is an amino functional group attached to the R' group; X' represents an alkoxy group.

[0209] Examples of such silanes include many representative products sold under the trade name Dynasylan® D (Degussa, Rheinfelden), Silquest® silane (Momentive), and GENOSIL® silane (Wacker).

[0210] Preferred aminosilanes include aminopropyltrimethoxysilane (Dynasylan AMMO; Silquest Al 110), aminopropyltriethoxysilane (Dynasylan AMEO), N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (Dynasylan DAMO; Silquest Al 120), N-(2-aminoethyl)-3-aminopropyltriethoxysilane, triaminofunctional trimethoxysilane (Silquest A-1130), bis(γ-trimethoxysilylpropyl)amine (Silquest Al 170), N-ethyl-γ-aminoisobutyltrimethoxysilane (Silquest A-Link 15), N-phenyl-γ-aminopropyltrimethoxysilane (Silquest Y-9669), 4-amino-3,3-dimethylbutyl ... 1637), (N-cyclohexylaminomethyl)triethoxysilane (Genosil XL 926), (N-phenylaminomethyl)trimethoxysilane (Genosil XL 973), and mixtures thereof.

[0211] Other particular silanes of interest include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(aminoethyl)-aminopropyltrimethoxysilane HNCHCHNHCHCHCHSi(OCH), 3-aminopropylmethyldiethoxysilane, 3-(2-aminoethylamino)propylmethyldimethoxysilane (HNCHCHNHCHCHCHSiCH(OCH)).

[0212] It will be appreciated that the aminosilane can act as both a catalyst and a crosslinker due to the presence of the alkoxysilane group.

[0213] The amount of organic catalyst present in the coating composition may be 0.05 to 5.0 wt. %, preferably 0.1 to 4.0 wt. %, for example 0.25 to 4.0 wt. %, more preferably 0.5 to 3.0 wt. %, based on the coating composition (dry weight).

[0214] [Antifouling Agent / Biocide] The fouling release coating composition of the present invention may contain an antifouling agent / biocide.

[0215] The terms "antifouling agent," "biologically active compound," "antifoulant," "biocide," and "toxin" are used in the industry to refer to known compounds that act to prevent marine fouling of surfaces. These terms are used interchangeably herein. When present, the antifouling agent may be inorganic, organometallic, or organic. Preferably, when present, the antifouling agent is an organometallic antifouling agent. Suitable antifouling agents are commercially available.

[0216] Examples of inorganic antifouling agents include copper and copper compounds such as copper oxides, for example, cuprous oxide and cupric oxide; copper alloys, for example, copper-nickel alloys; copper salts, for example, copper thiocyanate and copper sulfide.

[0217] Examples of organometallic antifouling agents include zinc pyrithione; organocopper compounds such as copper pyrithione, copper acetate, copper di(ethyl 4,4,4-trifluoroacetoacetate), copper naphthenate, copper oxine, copper nonylphenolsulfonate, copper bis(ethylenediamine)bis(dodecylbenzenesulfonate), and copper bis(pentachlorophenolate); and dithiocarbamate compounds such as zinc bis(dimethyldithiocarbamate) [ziram], zinc ethylenebis(dithiocarbamate) [zineb], manganese ethylenebis(dithiocarbamate) [maneb], and manganese ethylenebis(dithiocarbamate) [mancozeb] complexed with a zinc salt.

[0218] Examples of organic antifouling agents include heterocyclic compounds such as 2-(tert-butylamino)-4-(cyclopropylamino)-6-(methylthio)-1,3,5-triazine [sibutrin], 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], encapsulated 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], 1,2-benzisothiazolin-3-one, 2-(thiocyanatomethylthio)-1,3-benzothiazole [benzazole], and 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine; urea derivatives such as 3-(3,4-dichlorophenyl)-1,1-dimethylurea [diuron]; N-(dichlorofluoromethylthio)phthalimide, N-dichlorofluoromethylthio-N',N'- Amides and imides of carboxylic acids, sulfonic acids, and sulfenic acids, such as dimethyl-N-phenylsulfamide [dichlfluanid], N-dichlorofluoromethylthio-N',N'-dimethyl-Np-tolylsulfamide [tolylfluanid], and N-(2,4,6-trichlorophenyl)maleimide; and other organic compounds, such as pyridinetriphenylborane [TPBP], aminetriphenylborane, 3-iodo-2-propynyl N-butylcarbamate [iodocarb], 2,4,5,6-tetrachloroisophthalonitrile, p-((diiodomethyl)sulfonyl)toluene, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile [tralopyril], and quaternary ammonium salts.

[0219] Other examples of antifouling agents include tetraalkylphosphonium halides, guanidine derivatives, imidazole-containing compounds and derivatives thereof such as 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole [medetomidine], macrocyclic lactones including avermectins and derivatives thereof such as ivermectin, spinosyns and derivatives thereof such as spinosad, capsaicins and derivatives thereof such as phenylcapsaicin, and enzymes such as oxidases, proteolytic enzymes, hemicellulolytic enzymes, cellulolytic enzymes, lipolytic enzymes, and amylolytic enzymes.

[0220] Preferred antifouling agents include zinc pyrithione, copper pyrithione, zinc ethylenebis(dithiocarbamate) [Zineb], 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], and encapsulated 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT]. Particularly preferred antifouling agents include zinc pyrithione and copper pyrithione, especially copper pyrithione.

[0221] When present, the biocide may comprise 1-20% by dry weight of the total coating composition, preferably 1-15%, 2-15%, or 3-12% by dry weight of the total coating composition.

[0222] This component is not considered part of the binder system.

[0223] [Pigment] The coating composition of the present invention preferably contains one or more pigments. The pigments may be inorganic pigments, organic pigments, or mixtures thereof. Inorganic pigments are preferred. The pigments may be surface-treated.

[0224] Representative examples of pigments include black iron oxide, red iron oxide, yellow iron oxide, titanium dioxide, zinc oxide, carbon black, graphite, red molybdate, yellow molybdate, zinc sulfide, antimony oxide, sodium aluminum sulfosilicate, quinacridone, phthalocyanine blue, phthalocyanine green, indanthrone blue, aluminum cobalt oxide, carbazole dioxazine, isoindoline orange, bis-acetoacetotridiol, benzimidazolone, quinaphthalone yellow, isoindoline yellow, tetrachloroisoindolinone, quinophthalone yellow, and metal flake materials (e.g., aluminum flakes). Preferred pigments include black iron oxide, red iron oxide, yellow iron oxide, phthalocyanine blue, and titanium dioxide. In a preferred embodiment, the titanium dioxide is surface-treated with a silicone compound, a zirconium compound, an aluminum compound, and / or a zinc compound.

[0225] The amount of pigment present in the coating composition of the present invention is preferably 0 to 25 wt %, more preferably 0.5 to 15 wt %, based on the total dry weight of the coating composition.

[0226] This component is not considered part of the binder system.

[0227] [solvent] The coating composition of the present invention preferably contains a solvent. Suitable solvents that can be used in the composition of the present invention are commercially available.

[0228] Examples of suitable organic solvents and thinners include aromatic hydrocarbons such as xylene, toluene, and mesitylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, cyclopentanone, and cyclohexanone; esters such as butyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, ethylene glycol methyl ether acetate, and propylene glycol methyl ether acetate; ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, dioxane, and tetrahydrofuran; alcohols such as n-butanol, isobutanol, and benzyl alcohol; ether alcohols such as butoxyethanol and 1-methoxy-2-propanol; aliphatic hydrocarbons such as white spirit; and, optionally, mixtures of two or more of these solvents and thinners.

[0229] It is preferred that the amount of solvent present in the fouling release coating composition of the present invention be as low as possible, as this minimizes the VOC content. The solvent is preferably present in the composition of the present invention in an amount of 0 to 35 wt. %, more preferably 1 to 30 wt. %, based on the total weight of the composition. Those skilled in the art will recognize that the solvent content will vary depending on the other components present.

[0230] This component is not considered part of the binder system.

[0231] [Filler] The coating composition of the present invention optionally contains filler.Examples of fillers that can be used in the coating composition of the present invention include zinc oxide, barium sulfate, calcium sulfate, calcium carbonate, fumed silica, silica or silicate, including bentonite and other clays (for example, talc, feldspar, china clay, and nepheline syenite), and solid silicone resin, which is generally condensed branched polysiloxane.Some fillers, such as fumed silica, may have a thickening effect on the coating composition.

[0232] Preferred fillers include fumed silica fillers. The fumed silica fillers may have an untreated surface or a hydrophobically modified surface. Preferably, the fumed silica fillers have a hydrophobically modified surface. Examples of commercially available fumed silica fillers include TS-610, TS-530, EH-5, H-5, and M-5 (manufactured by Cabot Corporation), and Aerosil® R972, Aerosil® R974, Aerosil® R976, Aerosil® R104, Aerosil® R202, Aerosil® R208, Aerosil® R805, Aerosil® R812, Aerosil® 816, Aerosil® R7200, Aerosil® R8200, Aerosil® R9200, and Aerosil® R711 (manufactured by Evonik).

[0233] The amount of filler present in the coating composition of the present invention is preferably 0 to 25 wt %, more preferably 0.1 to 10 wt %, and even more preferably 0.15 to 5.0 wt %, based on the total dry weight of the coating composition.

[0234] This component is not considered part of the binder system.

[0235] [Additives] The coating composition of the present invention optionally contains one or more additives. Examples of additives that may be present in the coating composition of the present invention include reinforcing agents, thixotropic agents, thickeners, anti-settling agents, dehydrating agents, dispersants, wetting agents, surfactants, binders, plasticizers, and pigments.

[0236] Examples of thixotropic agents, thickeners, and anti-settling agents include silica such as fumed silica, organically modified clays, amide waxes, polyamide waxes, amide derivatives, polyethylene waxes, oxidized polyethylene waxes, hydrogenated castor oil waxes, and mixtures thereof. The thixotropic agents, thickeners, and anti-settling agents are each preferably present in the compositions of the present invention in an amount of 0 to 10 wt %, more preferably 0.1 to 6 wt %, and even more preferably 0.1 to 2.0 wt %, based on the total dry weight of the composition.

[0237] Dehydrating agents and drying agents that can be used in the coating composition can include organic and inorganic compounds. Dehydrating agents can be hygroscopic materials that absorb water or bind water as crystal water. These are often called desiccants. Examples of desiccants include calcium sulfate hemihydrate, anhydrous calcium sulfate, anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous zinc sulfate, molecular sieves, and zeolites. Dehydrating agents can also be compounds that chemically react with water. Examples of dehydrating agents that react with water include orthoesters such as trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, triisopropyl orthoformate, tributyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, tributyl orthoacetate, and triethyl orthopropionate; ketals; acetals; enol ethers; orthoborates such as trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate, and tri-tert-butyl borate; and organosilanes such as trimethoxymethylsilane, vinyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, and ethyl polysilicate.

[0238] The dehydrating agent is preferably present in the composition of the present invention in an amount of 0 to 5 wt. %, more preferably 0.5 to 2.5 wt. %, and even more preferably 1.0 to 2.0 wt. %, based on the total dry weight of the composition.

[0239] [Compositions and coatings] The coating compositions described herein may be prepared in a concentration suitable for use (e.g., spray coating). In this case, the composition is a paint itself. Alternatively, the composition may be a concentrate for preparing a paint. In this case, additional solvents and optionally other ingredients are added to the compositions described herein to form a paint. Preferred solvents are as described above for the compositions.

[0240] After mixing (and optionally adding a solvent), the fouling release coating composition or paint is preferably placed in a container. Suitable containers include cans, drums, and tanks.

[0241] The coating composition may be supplied as a one-part, two-part, or three-part composition. Preferably, the composition is supplied as a two-part or three-part composition.

[0242] When supplied as a two-part product, one container preferably contains a polysiloxane binder, and the other container preferably contains any type of curing agent and catalyst. Instructions for mixing the contents of these containers may optionally be provided. Any type of hydrophilically modified polysiloxane is preferably contained in part in one container. Any type of catalyst is preferably contained in part in the other container.

[0243] The coating composition and paint of the present invention preferably have a solid content of 50 to 99% by weight, more preferably 60 to 99% by weight, and even more preferably 65 to 99% by weight.

[0244] Preferably, the coating compositions and paints of the present invention have a volatile organic compound (VOC) content of 0 to 400 g / L, preferably 0 to 350 g / L, for example 0 to 300 g / L. The VOC content can be calculated (ASTM D5201-05A) or measured (US EPA Method 24 or ISO 11890-1).

[0245] The coating composition of the present invention can be applied to any pre-treated coating layer designed for use with polysiloxane-based fouling release coatings. Examples of such coating layers include epoxy anticorrosion primer layers and silicone-containing tie layers designed to ensure adhesion between the substrate and the final polysiloxane-based coating composition layer. Examples of such tie layers include those described in WO 2013 / 107827. The tie layer may optionally contain an antifouling agent. Such epoxy primers and tie coats are well known in the art and are commercially available.

[0246] [process] The process of the present invention comprises applying at least two coating layers of a polysiloxane-based coating composition as defined above. Specifically, the process comprises: i) applying a first coating layer by spray coating so that the wet film thickness is 50 to 300 μm; ii) applying the second coating layer by spray coating to a wet film thickness of 50 to 300 μm; The second coating layer is characterized by being applied directly onto the first coating layer 5 minutes to 6 hours after the first coating layer is applied.

[0247] The polysiloxane-based coating composition of the first coating layer can be the same or different from the polysiloxane-based coating composition of the second coating layer. In certain embodiments, the first and second coating layers can be identical. If the first and second coating layers are not identical, they are preferably substantially identical. As used herein, the term "substantially identical" refers to coating layers that differ only in the type and amount of pigments and / or additives that may be present. When coating layers are substantially identical, the type and amount of crosslinker, binder, additive oil, and biocide will be the same. However, the pigments may be different.

[0248] The first and second coating compositions preferably have the same crosslinker, binder, additive oil, and biocide (if any) which may be present in different amounts in the first and second coating compositions or may be present in the same amounts in the first and second coating compositions.

[0249] It is preferable to apply two thin topcoat layers (i.e., wet film thickness of 50 to 300 μm, preferably 100 to 2750 μm, e.g., 125 to 275 μm) instead of one thick topcoat layer (i.e., wet film thickness of more than 250 μm, especially more than 300 μm, e.g., 300 to 600 μm). It is more preferable that the wet film thicknesses of both coating layers are equal or the difference between them is within 50 μm.

[0250] In one embodiment, the first and second coating layers are topcoat layers and are present in addition to any tie layers and / or primer layers that may be present.

[0251] It will be appreciated that once applied, the coating composition begins to cure.

[0252] The coating composition of the present invention will typically be applied (and cured) at a temperature of 5 to 50°C, preferably 10 to 40°C, and more preferably 10 to 30°C.

[0253] The coating compositions of the present invention will typically be applied (and cured) at a humidity of 20 to 90%, preferably 30 to 85%, more preferably 40 to 85%.

[0254] The coating composition and paint of the present invention can be applied to the whole or part of any surface of an article that is susceptible to marine fouling.The surface can be permanently submerged or intermittently submerged (for example, due to tidal movements, loading of different cargoes, or swells).The surface of the article is typically the hull of a ship or the surface of a fixed marine object, such as an oil platform or buoy.

[0255] The application of the coating composition and paint can be carried out by any convenient spray application means. For example, the first and second coating layers can be applied by two separate cherry pickers that move in sequence along the ship. Application can also be carried out by an automated process or a paint application robot. Typically, the surface must be isolated from seawater to allow coating. Application of the coating can be carried out as conventionally known in the art. After application, the coating is preferably dried and / or cured.

[0256] [Coating systems and applications] The coating system of the present invention is ideally a fouling release coating system. As described above, the coating system of the present invention comprises at least a first coating layer and a second coating layer. It will be understood that the coating system may include additional layers, such as at least one tie coat layer and / or at least one epoxy primer layer. As described above, such layers are known in the art. In such embodiments, the tie coat layer and the epoxy primer layer are typically allowed to cure for at least 24 hours before applying the subsequent layer.

[0257] Typically, the first and second coating layers constitute the outermost layers of the coating system, and preferably the second coating layer is the outermost layer of the coating system.

[0258] The coating system of the present invention is typically applied to marine substrates, preferably to the surface of a portion of a marine structure that will be submerged in seawater during use. Typical marine substrates include all types of structures and objects, such as ships (including, but not limited to, boats, ships, yachts, motorboats, motor launches, ocean liners, tugboats, tankers, container ships and other cargo ships, submarines, and all types of naval vessels), pipes, land and sea machinery, piers, pilings, bridge substructures, hydraulic equipment and structures, underwater oil well structures, nets and other aquaculture equipment, and buoys. The surface of the substrate may be an "untreated" surface (e.g., a steel surface).

[0259] [Example] <Measurement of binder viscosity> Binder viscosity was measured using a Brookfield DV-I Prime digital viscometer with an LV-2 or LV-4 spindle at 12 rpm according to ASTM D2196 Test Method A. The binder was conditioned to 23.0°C ± 0.5°C before measurements.

[0260] <Measurement of polymer average molecular weight distribution> The polymer was characterized by gel permeation chromatography (GPC). Molecular weight distribution (MWD) was measured using an Omnisec Resolve and Reveal system (Malvern) with two PLgel 5 μm Mixed-D columns (Agilent) connected in series. Column calibration was performed by conventional calibration using narrow polystyrene standards. The analytical conditions were as follows:

[0261] [Table 1]

[0262] Samples were prepared by dissolving an amount of polymer solution equivalent to 25 mg of dry polymer in 5 mL of THF. Samples were kept at room temperature for a minimum of 3 hours before sampling for GPC measurements. Samples were filtered through a 0.45 μm nylon filter before analysis. The number average molecular weight (Mn), weight average molecular weight (Mw), and polydispersity index are reported.

[0263] <Preparation of Fouling Release Coating Composition> The coating compositions were prepared by first mixing the ingredients in Part (A) shown in Table 1 below using a high-speed dissolver equipped with an impeller disc. First, the polysiloxane binder, copper pyrithione, hydrophobic silica, and red iron oxide were stirred at high speed until a grinding level of less than 20 μm was reached. The remaining ingredients were then added while stirring at low speed. The ingredients in Part (B) were mixed with the ingredients in Part (A) immediately prior to coating application.

[0264] <Preparation of coating system> A fouling release topcoat (composition shown in Table 1) was applied by airless spray onto upright PVC panels coated with a commercial system consisting of 1 x 200 μm epoxy primer (Jotacoat Universal N10, manufactured by Jotun) and 1 x 160 μm fouling release tie coat (Safeguard FRC PE, manufactured by Jotun) according to the corresponding product technical data sheets. Both the epoxy primer and tie coat were allowed to cure for 24 hours before applying the next layer. The topcoat was cured under various conditions using a climate chamber with controlled temperature and relative humidity. The two topcoats were applied at set time intervals ranging from 5 to 120 minutes. Sagging resistance and adhesion were measured for 23 examples and two comparative examples. The results are reported in Table 2.

[0265] <Evaluation of sagging> The topcoat was applied using an airless spray pump with a pressure of 4.5 bar and a nozzle size of 627 μm. The application was performed on the upright panel with a 50% overlap to achieve a uniform film thickness. The film thickness was measured immediately after application with a wet film thickness (WFT) meter. Sagging was controlled by scoring a horizontal line in the paint with a spatula on the bottom of the panel.

[0266] The resulting lines were observed for sagging, which was assessed and reported for each WFT applied once the coating was fully cured, typically the day after application.

[0267] <Evaluation of Adhesion> The adhesion between the two topcoats was evaluated both on panels that were immersed in seawater 24 hours after the last coat was applied (wet adhesion) and on panels that were not immersed in seawater after application (dry adhesion).

[0268] Panels of the coating system were prepared by airless spraying according to the coating intervals and selected intervals between topcoats as specified on the product's technical data sheet. Panels were cured for 24 hours at the selected cure conditions.

[0269] To evaluate wet adhesion, the panels were immersed in seawater for 48 hours.

[0270] To assess dry adhesion, the panels were kept at RT / 50°C for at least 48 hours.

[0271] Both wet and dry adhesion was evaluated by the cross-cut method and visual evaluation of interlayer adhesion or delamination between the topcoats.

[0272] [Table 2]

[0273] [Table 3]

Claims

1. 1. A process for producing a multi-layer coating system comprising at least two coating layers, comprising: i) applying a first coating layer by spray coating to a wet film thickness of 50 to 300 μm; ii) applying the second coating layer by spray coating to a wet film thickness of 50 to 300 μm; the second coating layer is applied directly onto the first coating layer 5 minutes to 6 hours after the first coating layer is applied; The first coating layer and the second coating layer each independently comprise: a) a polysiloxane-based binder system; b) a curing or crosslinking agent; and a polysiloxane-based coating composition comprising:

2. 2. The process of claim 1, wherein the second coating layer is applied 5 minutes to 4 hours after the first coating layer is applied, preferably 5 minutes to 2 hours after the first coating layer is applied.

3. 3. The process of claim 1 or claim 2, wherein the coating system is a fouling release coating system.

4. The process of any of claims 1 to 3, wherein the first coating layer and the second coating layer comprise the same or different polysiloxane-based coating compositions, preferably the same polysiloxane-based coating composition.

5. The process of any one of claims 1 to 4, wherein the first coating layer and the second coating layer are outermost layers of the coating system.

6. The process of any one of claims 1 to 5, wherein the second coating layer is the outermost layer of the coating system.

7. The process of any one of claims 1 to 6, wherein the first coating layer and / or the second coating layer comprises one or more additive oils.

8. The process according to any one of claims 1 to 7, wherein the first coating layer and / or the second coating layer comprises a hydrophilically modified polysiloxane and / or a hydrophobically modified polysiloxane.

9. The process according to any one of claims 1 to 8, wherein the first coating layer and / or the second coating layer contains a biocide.

10. The polysiloxane-based binder system has the formula (D1): 【Chemistry 16】 [In the formula, Each R 1 are independently a hydroxyl group, C 1-6 -alkoxy group, O—Si(R 5 ) 3-z (R 6 ) z , C 1-6 -hydroxyl group, C 1-6 -epoxy-containing group, C 1-6 Amine group, C 1-10 Alkyl group, C 6-10 aryl, or C 7-10 selected from alkaryl, Each R 2 are independently 1-10 Alkyl, C 6-10 Aryl, C 7-10 alkylaryl, or poly(alkylene oxide) and / or R 1 C substituted with groups described for 1-6 alkyl, Each R 3 and R 4 are independently 1-10 Alkyl, C 6-10 Aryl, C 7-10 C substituted with alkylaryl or poly(alkylene oxide) 1-6 alkyl, Each R 5 are independently 1-6 a hydrolyzable group such as an alkoxy group, an acetoxy group, an enoxy group, or a ketoxy group; Each R 6 are independently 1-6 alkyl groups, z is 0 or an integer from 1 to 2; x is an integer of 2 or greater; and y is an integer of 2 or greater. The process of any one of claims 1 to 9, comprising a polysiloxane of formula:

11. The process of any of claims 1 to 10, wherein the polysiloxane-based binder comprises at least 50 wt% of the polysiloxane-based coating composition, based on the total weight of the polysiloxane-based coating composition.

12. The process of any preceding claim, wherein the coating system is applied to a substrate, such as a marine substrate.

13. The process of any of claims 1 to 12, wherein the coating system further comprises at least one tie coat layer and / or at least one epoxy primer layer.

14. The crosslinking agent is represented by the following general formula (I): 【Chemistry 17】 [In the formula, Each R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, a C substituted with poly(alkylene oxide), 1-6 alkyl, or the structure (O—(CR D 2 ) r' ) r1' -(O-(CR D 2 ) s' ) s1' -(Si(R PP ) 2 -O) t' -Si(R PP ) 3 wherein: r', r1', s', and s1' are integers from 0 to 10; Each R D are independently H or C 1-4 alkyl, Each R PP are independently 1-10 Alkyl, C 6-10 Aryl, C 7-10 alkylaryl; t' is an integer from 1 to 50, each K is independently selected from hydrolyzable groups such as alkoxy groups; d is 0, 1, or 2, more preferably 0 or 1. or a partial hydrolysis condensate thereof, or a mixture of these two, or The crosslinking agent has the formula (II) [Chemistry 18] [In the formula, LL is independently selected from unsubstituted or substituted monovalent hydrocarbon groups having 1 to 6 carbon atoms; each M is independently selected from hydrolyzable groups such as alkoxy groups; a is 0, 1, or 2, preferably 0 or 1; b is an integer from 1 to 6, Fn is an amine group, an epoxy group, a glycidyl ether group, an isocyanate group, or a sulfur group. The process according to any one of claims 1 to 13, wherein the double crosslinking agent is

15. The process of any of claims 1 to 14, wherein the crosslinker comprises 2.0 to 8.0 wt% of the polysiloxane-based coating composition.

16. 16. The process of any of claims 1 to 15, wherein the polysiloxane-based coating composition of the first coating layer contains the same crosslinker, binder, additive oil, and biocide as the polysiloxane-based coating composition of the second layer.

17. 16. The process of any of claims 1 to 15, wherein the polysiloxane-based coating composition of the first coating layer contains the same crosslinker, binder, additive oil, and biocide as the polysiloxane-based coating composition of the second layer and in the same amounts of crosslinker, binder, additive oil, and biocide as the polysiloxane-based coating composition of the second layer.

18. The process of any of claims 1 to 15, wherein the polysiloxane-based coating composition of the first coating layer is the same as the polysiloxane-based coating composition of the second layer.

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