Contaminant-Release Coating Composition

Abstract

[Solution] The present invention provides an aqueous contaminant release coating composition comprising: (a) an aqueous polysiloxane-based binder emulsion, the emulsion comprising polysiloxane-based binder droplets having an average droplet size of 4 to 1000 nm; and (b) at least one pigment or filler; the coating composition comprising at least 10 wt. % water based on the total weight of the entire composition.

Description

[Technical field]

[0001] The present invention relates to fouling release coating compositions. In particular, the present invention provides an aqueous fouling release composition comprising an aqueous polysiloxane-based binder emulsion. The present invention further relates to a method of making the fouling release composition, a coating system comprising said composition, and a substrate coated with said coating composition. [Background technology]

[0002] background Fouling-releasing coatings are used on ships to prevent fouling by marine organisms. They work on the principle that the coefficient of friction of the fouling-releasing surface is so low that marine organisms have a hard time adhering to the surface, and that the action of the sea will wash the marine organisms off the hull, especially if the ship is underway.

[0003] Commercial ships (e.g., container ships, bulk carriers, tankers, passenger ships) often operate in different waters, on different trades and with different activities (including downtime). Fouling release coatings, with their very smooth surface and low surface energy, minimize the chance of fouling sticking to the surface, thereby providing excellent antifouling performance.

[0004] Thus, the contaminant-releasing coating is characterized by a low surface tension and a low modulus of elasticity so that biocontaminants do not adhere to the surface or are easily washed away by friction of water against the surface.

[0005] Such coatings often contain polysiloxane-based binders with reactive (curable) groups (e.g., hydroxyl or silyl units), such as those disclosed in WO2021 / 105429A1 and WO2018 / 134124, which can be hydrolyzed and condensed in the presence of moisture and catalysts.

[0006] The coatings industry is constantly facing increasing VOC regulations that limit the amount of organic solvents that can be used in antifouling paints. The most common methods of application of antifouling coatings are airless spray, brush, or roller. It is important that the paint can be applied by standard techniques, which requires coating compositions and paints to have a certain viscosity level while minimizing their VOC content and achieving satisfactory application properties. If solvent must be added to reduce viscosity during application, the VOC limit may be exceeded.

[0007] One solution to achieve VOC compliant and more sustainable antifouling paints is to use water-based technology. The water-based paint market is likely to expand to provide more sustainable coatings to meet VOC / HAP regulations. Water-based paints are gaining popularity in the interior market due to their low odor, ease of cleaning, quick drying, and being healthier for staff. With new technological advancements, the performance and durability of water-based coatings are approaching solvent-based coatings for most applications.

[0008] Water-based coatings are described, for example, in CN110358015, CN109575746, JP2006193731 and CN111393926. In addition, CN110643278 discloses a water-based low surface energy antifouling paint for ships. However, the binder is still dissolved in an organic solvent (xylene) and is not emulsified in water.

[0009] Commercial ships are usually protected by at least one layer of anti-corrosive paint, followed by a tie coat and an anti-fouling coating. The tie coat is therefore an additional layer that is mainly used to ensure good adhesion of the anti-fouling coating to the substrate. By developing an anti-fouling coating that shows direct and good adhesion to the anti-corrosive layer, a "less is more" system can be envisioned, saving time and resources and achieving a more sustainable coating system, since reducing the number of coating layers reduces VOCs. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] International Publication No. 2021 / 105429A1 Brochure [Patent Document 2] International Publication No. 2018 / 134124 Brochure [Patent Document 3] China Patent Publication No. 110358015 [Patent Document 4] China Patent Publication No. 109575746 [Patent Document 5] JP 2006-193731 A [Patent Document 6] China Patent Publication No. 111393926 [Patent Document 7] China Patent Publication No. 110643278 Summary of the Invention [Problem to be solved by the invention]

[0011] Therefore, the object of the present invention is to provide a new fouling release coating composition that addresses at least some of the problems mentioned above. In addition to the above-mentioned VOC requirements for the coating composition, the resulting antifouling coating should have good application properties, low surface energy, high contact angle, and good mechanical properties even at lower temperatures, and exhibit good fouling resistance. The challenge for water-based antifouling paints compared to solvent-based is to exhibit good film-forming behavior at lower temperatures. Ideally, the new coating will exhibit good film formation on several different substrates, including direct application on some anticorrosive primers. [Means for solving the problem]

[0012] The present inventors have unexpectedly found that the aqueous pollutant release coating composition of the present invention provides an attractive solution. In particular, the aqueous pollutant release coating composition of the present invention surprisingly has good adhesion to organic primers. As mentioned above, conventional polysiloxane-based pollutant release coatings have poor adhesion to organic primers, and therefore often require a tie coat that is a hybrid of a polysiloxane-based coating and an organic coating. By being able to apply the pollutant release coating directly to the organic primer, the entire coating system may provide lower VOCs because one less layer is used. Furthermore, reducing the number of coats may save both time and money, and simplify the paint application process, thereby improving work efficiency. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] [Summary of the invention] Viewed from a first aspect, the present invention provides a method for producing ... liquid crystal display comprising: (a) an aqueous polysiloxane-based binder emulsion, the emulsion comprising polysiloxane-based binder droplets having an average droplet size of 4 to 1000 nm; and (b) at least one pigment or filler; 1. An aqueous contamination release coating composition comprising: The coating composition provides an aqueous contaminant release coating composition that includes at least 10% by weight water based on the total weight of the entire composition.

[0014] Viewed from another aspect, the present invention provides a method for producing an aqueous contamination release coating composition as defined herein, said method comprising the steps of: (i) dispersing at least one pigment or filler in water to produce a dispersion; and, (ii) mixing the dispersion produced in step (i) with an aqueous polysiloxane-based binder emulsion to produce the coating composition. Includes.

[0015] Viewed from a further aspect, the present invention provides a coating system comprising at least two layers A and B, said layers A and B being adjacent, layer A being an organic primer layer and layer B comprising an aqueous contaminant release coating composition as defined herein.

[0016] Viewed from another aspect, the present invention provides a method of applying an aqueous pollutant release coating composition to a substrate, said method comprising applying, for example by spraying, an aqueous pollutant release coating composition as defined herein to a substrate and curing said coating composition.

[0017] Viewed from yet another aspect, the present invention provides a substrate coated with a cured aqueous contaminant release coating composition as defined herein, or a coating system as defined herein.

[0018] [Definition] The term "fouling releasing composition" or "fouling releasing coating composition" as used herein refers to a composition that, when applied to a surface, provides a fouling releasing surface that is permanently resistant to the attachment of marine organisms.

[0019] The term "aqueous composition" as used herein refers to a composition that contains water as a solvent. Typically, water forms at least 80% of the solvent used, and preferably 100% of said solvent is water.

[0020] The term "binder" or "binder system" as used herein refers to the film-forming component of the composition. The polysiloxane-based binder of the contamination-releasing composition is the main binder in the composition, i.e., forms at least 50 wt%, such as at least 70 wt%, at least 75 wt%, at least 80 wt%, or at least 90 wt% of the binder present. In a preferred embodiment, the polysiloxane-based binder forms 100 wt% of the binder present. The term "binder system" as used herein does not include added oils. Added oils are not considered to be film-forming components in the present specification.

[0021] The term "paint" as used herein refers to a composition comprising the pollutant releasing coating composition described herein and, optionally, a solvent, that is ready for use, e.g., spraying. Thus, the pollutant releasing coating composition may itself be a paint, or the pollutant releasing coating composition may be a concentrate to which a solvent is added to produce a paint.

[0022] The term "polysiloxane" as used herein refers to siloxane, i.e., a polymer containing --Si--O-- repeating units.

[0023] The term "polysiloxane-based binder" as used herein refers to a binder that contains at least 50 wt%, preferably at least 60 wt%, and more preferably at least 70 wt%, of repeating units containing the motif -Si-O-, based on the total weight of the polymer. The polysiloxane-based binder may contain up to 99.99 wt%, based on the total weight of the polymer, of repeating units containing the motif -Si-O-. The repeating units, -Si-O-, may be linked in series or may be interrupted by non-siloxane moieties, such as organic moieties.

[0024] The term emulsion as used herein refers to a fine dispersion of droplets of one liquid in another liquid in which they are not soluble or miscible. In the context of the present invention, The emulsion may be referred to as an "oil-in-water" emulsion, i.e., the dispersed phase is oil and the continuous phase is water. Thus, the emulsion used in the present invention may also be referred to as an "aqueous emulsion", meaning an emulsion in which the continuous phase (i.e., the solvent) is water. Ideally, the solvent consists of water.

[0025] The term "alkyl" as used herein refers to saturated, straight-chain, branched or cyclic groups.

[0026] As used herein, the term "cycloalkyl" refers to a cyclic alkyl group.

[0027] As used herein, the term "alkylene" refers to a divalent alkyl group.

[0028] The term "alkenyl" as used herein refers to unsaturated straight, branched or cyclic groups.

[0029] The term "aryl" as used herein refers to a group containing at least one aromatic ring. The term aryl includes fused ring systems in which one or more aromatic rings are fused to a cycloalkyl ring. An example of an aryl group is phenyl, i.e., C6H5.

[0030] The term "substituted" as used herein refers to a group in which one or more, for example up to six, more particularly 1, 2, 3, 4, 5 or 6 hydrogen atoms in said group are replaced, independently of one another, by the corresponding number of stated substituents.

[0031] The term "arylalkyl" group as used herein refers to a group in which the bond to Si is through an alkyl moiety.

[0032] The term "polyether" as used herein refers to a compound containing two or more -O- bonds interrupted by alkylene units.

[0033] As used herein, the terms "poly(alkylene oxide)", "poly(oxyalkylene)" and "poly(alkylene glycol)" refer to compounds that contain -alkylene-O- repeating units. Typically, the alkylene is ethylene or propylene.

[0034] As used herein, the term "volatile organic compounds (VOCs)" refers to compounds that have a boiling point at or below 250°C.

[0035] As used herein, "antifouling agent" or "biocide" refers to a biologically active compound or mixture of biologically active compounds that prevents the settlement of marine organisms on a surface and / or inhibits the growth of marine organisms on a surface and / or promotes the detachment of marine organisms from a surface. These terms are used interchangeably.

[0036] [Detailed Description of the Invention] The present invention relates to an aqueous contaminant release coating composition comprising an aqueous polysiloxane-based binder emulsion and at least one filler or pigment.

[0037] <Polysiloxane-based binder emulsion> The polysiloxane-based binder emulsion contains polysiloxane-based binder droplets having an average size of 4 to 1000 nm.

[0038] {Polysiloxane-based binder} The polysiloxane-based binder present in the coating composition of the present invention comprises at least 50 wt% polysiloxane moieties, preferably greater than 60 wt% polysiloxane moieties, more preferably greater than 70 wt% polysiloxane moieties, such as 99.99 wt% or more polysiloxane moieties. Typical ranges include 50-100 wt% polysiloxane moieties, 60-99.99 wt% polysiloxane moieties, or 70-99.99 wt% polysiloxane moieties in the polysiloxane-based binder.

[0039] The polysiloxane moieties are defined as repeating units containing the motif -Si-O-, based on the total weight of the polysiloxane binder. The wt% of the polysiloxane moieties can be determined based on the stoichiometric wt ratio of the starting materials in the polysiloxane synthesis. Alternatively, the polysiloxane content can be determined using analytical techniques such as IR or NMR.

[0040] Typically, the wt% of polysiloxane moieties is calculated based on the molar ratio of reactive starting materials in the polysiloxane synthesis. If molar excess of monomer is present in the reaction mixture, such excess moles are not counted. Only monomer that is reactive based on the stoichiometry of the reaction is counted.

[0041] Information regarding the wt. % polysiloxane moiety in commercially available polysiloxane-based binders is readily available from suppliers.

[0042] 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 contains only Si-O repeat units.

[0043] 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, the organic moiety may include, for example, an alkylene, an arylene, a poly(alkylene oxide), an amide, or a combination thereof.

[0044] By curable it is meant that the polysiloxane based binder contains functional groups capable of undergoing a crosslinking reaction between polysiloxane based binder molecules or via a crosslinking agent.

[0045] The polysiloxane-based binder is preferably an organopolysiloxane having terminal and / or pendant curing reactive functional groups. At least two curing reactive functional groups per molecule are preferred. Examples of curing reactive functional groups are silanol, alkoxy, acetoxy, enoxy, ketoxime alcohol, aminoxy, amine, epoxy, vinyl and / or isocyanate. The preferred polysiloxane-based binder comprises a curing reactive functional group selected from silanol, alkoxy or acetoxy groups. The curing reaction is typically a condensation curing reaction. The polysiloxane-based binder may optionally comprise two or more types of curing reactive groups, for example, curing via both condensation curing and amine / epoxy curing.

[0046] The polysiloxane-based binder may be a linear or branched polysiloxane-based binder. By branched, it is meant that the polysiloxane chain is branched. The branched polysiloxane-based binder may also include cage-like polysiloxane structures, also known as polysiloxane resins.

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

[0048] Said polysiloxane-based binder may be modified with hydrophilic groups to aid the process of emulsifying the binder in water.Examples of suitable hydrophilic groups may be 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 acids), amines and polyamines (e.g., polyvinylamine, (meth)acrylic polymers containing amine groups).

[0049] In one preferred embodiment, the polysiloxane-based binder is modified with amine, polyamine or polyether groups. Preferably, the polysiloxane-based binder is unmodified. The preferred polysiloxane binder present in the contamination release coating composition of the present invention is represented by the following formula (I):

[0050] [ka]

[0051] During the ceremony, Each R 1 is a hydroxyl group, C 1-6 -alkoxy group, 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, C 7-10 Alkaryl or O-Si(R 5 ) 3-z (R 6 ) z are independently selected from Each R 2 is C 1-10 Alkyl, C 6-10 Aryl, C 7-10 Alkylaryl or poly(alkylene oxide) substituted C 1-6 Alkyl and / or R 1 are independently selected from the groups described above; Each R 3 and R 4 is C 1-10 Alkyl, C 6-10 Aryl, C 7-10 Alkylaryl or poly(alkylene oxide) substituted C 1-6 independently selected from alkyl; Each R 5 are independently hydrolyzable groups, e.g., C 1-6 an alkoxy group, an acetoxy group, an enoxy group, or a ketoxy group; Each R 6 is C 1-6 independently selected from alkyl groups; z is 0 or an integer from 1 to 2; x is an integer of at least 2; y is an integer of at least 2.

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

[0053] Preferably, R 2 is C 1-10 Alkyl group, C 6-10 Aryl, C 7-10 Alkylaryl or O-Si(R 5 ) 3-z (R 6 ) z More preferably, R 2 is C 1-4 Alkyl groups, 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 groups, more preferably C 1-2 Preferably, each R 3are identical.

[0055] Preferably R 4 is C 1-10 More preferably, R 4 is C 1-4 Alkyl groups, 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 each a methyl group.

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

[0058] [ka]

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

[0060] Another preferred polysiloxane-based binder present in the contamination release coating composition of the present invention is represented by formula (III):

[0061] [ka]

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

[0063] Preferably, the polysiloxane-based binder of the present invention is represented by formula (I): Most preferably, the polysiloxane-based binder is polydimethylsiloxane.

[0064] Those skilled in the art will recognize that polysiloxane-based binders may contain small amounts of impurities, such as cyclic siloxanes, which are residues of polysiloxane synthesis. From health, safety, and environmental perspectives, it is preferable to limit the amount of cyclic polysiloxanes present in the coating. In one preferred embodiment, the polysiloxane-based binder contains less than 5% cyclic polysiloxanes, preferably less than 2%, more preferably less than 1%. In one particularly preferred embodiment, the polysiloxane-based binder does not contain cyclic polysiloxanes.

[0065] The weight average molecular weight of the polysiloxane binder is preferably 400 to 150,000, more preferably 1,000 to 140,000, still more preferably 5,000 to 130,000, and particularly preferably 10,000 to 120,000 g / mol.

[0066] The number average Mw of the polysiloxane binder is preferably 400 to 100,000 g / mol, more preferably 1,000 to 80,000 g / mol, still more preferably 2,000 to 70,000 g / mol, and particularly preferably 5,000 to 60,000 g / mol.

[0067] Alternatively, the viscosity of the polysiloxane-based binder is preferably 100 to 50,000 mPas, more preferably 200 to 40,000 mPas, and particularly preferably 400 to 30,000 mPas.

[0068] It will be appreciated that the polysiloxane binder droplets form the dispersed phase of the emulsion.

[0069] The polysiloxane binder is present in the emulsion in the form of droplets having an average size of 4-1000 nm, preferably 25-400 nm, more preferably 50-350 nm, for example 100-300 nm, as measured by dynamic light scattering at room temperature. The "average size" referred to in this context will be understood to be the Z-average size, the intensity weighted average size.

[0070] The amount of the polysiloxane binder in the coating composition is preferably 10 to 90 wt.%, more preferably 15 to 70 wt.%, and even more preferably 20 to 60 wt.%, of the total weight of the coating composition.

[0071] The amount of the polysiloxane binder in the coating composition is preferably 15 to 95 wt.%, more preferably 20 to 90 wt.%, and even more preferably 30 to 80 wt.%, of the total dry weight of the coating composition.

[0072] {Emulsion} In addition to the polysiloxane-based binder droplets, the emulsion comprises an aqueous medium (i.e., the continuous phase), which will be understood to comprise (and preferably consist of) water.

[0073] Thus, in a particularly preferred embodiment, the emulsion consists of the polysiloxane-based binder droplets and water.

[0074] The polysiloxane based binder droplets ideally form 30-90 wt% of the emulsion based on the total weight of the entire emulsion. A typical wt% range may be 35-80 wt%, for example 40-70 wt% based on the total weight of the entire emulsion.

[0075] The solvent, preferably water, forms 10-70 wt% of the emulsion based on the total weight of the entire emulsion, with typical wt% ranges being 20-65 wt%, for example 30-60 wt% based on the total weight of the entire emulsion.

[0076] The emulsion may be prepared by any suitable method known in the art.

[0077] The emulsion may contain an emulsifier, which may be nonionic, anionic, cationic or amphoteric.

[0078] Examples of non-ionic emulsifiers are alkylphenoxyethers, polyalkylene glycols, polyoxyalkylene sorbitan monooleates, polyvinyl alcohols, polyvinyl esters, polyether siloxanes and sorbitan stearates. Preferred non-ionic emulsifiers are polyalkylene glycols, such as polyoxyethylene-polyoxypropylene copolymers.

[0079] Examples of anionic emulsifiers are alkyl-, aryl-, alkaryl-sulfates, sulfonates, phosphates, sulfosuccinates, sulfosuccinamates, sulfoacetates and amino acid derivatives.

[0080] Particularly preferred anionic emulsifiers are alkylbenzenesulfonates, alkyl ether sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkyl naphthylsulfonates, unsaturated aliphatic sulfonates and hydroxylated aliphatic sulfonates.The alkyl groups mentioned here include medium and higher alkyl groups such as decyl, undecyl, dodecyl, tridecyl, tetradecyl, cetyl, and stearyl.The unsaturated aliphatic groups include oleyl, nonenyl, and octynyl.The counter ions include sodium ions, potassium ions, lithium ions, and ammonium ions, and the sodium ions are typically used among them.

[0081] Examples of the cationic emulsifier include quaternary ammonium salt surfactants, such as alkyltrimethylammonium salts, for example, octadecyltrimethylammonium chloride and hexadecyltrimethylammonium chloride, and dialkyldimethylammonium salts, for example, dioctadecyldimethylammonium chloride, dihexadecyldimethylammonium chloride and didecyldimethylammonium chloride.

[0082] Examples of the amphoteric surfactant include alkyl betaines and alkyl imidazolines.

[0083] The emulsion may also contain crosslinkers, curing catalysts, antifoam agents, preservatives, pH adjusters and buffers.

[0084] Examples of suitable commercially available emulsions include Coatosil DRI from Momentive, Dowsil 8005 and Dowsil 8016 from Dow, and Powersil 577 Plus from Wacker.

[0085] The emulsion preferably forms 50-90 wt% of the contamination release coating composition, based on the total weight of the entire composition. Typical wt% ranges may be 55-85 wt%, for example 60-80 wt%, based on the total weight of the entire composition.

[0086] <Crosslinking and / or curing agent> The polysiloxane-based binders of the present invention are curable and contain curing reactive functional groups such as silanol, alkoxysilane, ketoxime, carbinol, amine, epoxy and / or alkoxy groups.

[0087] Preferably, the polysiloxane-based binder comprises at least two curing reactive functional groups. Optionally, the polysiloxane-based binder comprises two or more types of curing reactive functional groups. Preferably, the polysiloxane-based binder comprises a single type of curing reactive functional group. The appropriate crosslinker and / or curing agent is selected according to the curing reactive functional groups present in the polysiloxane-based binder.

[0088] In a preferred polysiloxane-based binder, the curing reactive functional group is a silanol or an alkoxysilane. In a more preferred polysiloxane-based binder, the curing reactive functional group is a silanol.

[0089] To obtain the desired crosslink density, it may be necessary to add a crosslinker. The crosslinker may be added separately to the coating composition or the crosslinker may be part of the polysiloxane-based binder emulsion. Preferably, the crosslinker is part of the polysiloxane-based binder emulsion.

[0090] When the curing reactive functional group is a silanol, the preferred crosslinking agent is an organosilicon compound represented by the general formula shown below, a partial hydrolysis condensate thereof, or a mixture of the two.

[0091] R d -Si-K 4-d

[0092] During the ceremony, Each R is a monovalent hydrocarbon group of 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 wherein r', r1', s' and s1' are integers from 0 to 10, and each R D is H or C 1-4 alkyl, each R PP is 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 a hydrolyzable group, e.g., an alkoxy group; d is 0, 1 or 2, more preferably 0 or 1.

[0093] Preferred crosslinkers of this type include tetraethoxysilane, vinyltris(methylethyloximo)silane, methyltris(methylethyloximo)silane, vinyltrimethoxysilane, methyltrimethoxysilane and vinyltriisopropenoxysilane and their hydrolytic condensates.

[0094] When the curable reactive functional groups are di- or tri-alkoxy, a separate crosslinker is generally not required.

[0095] The crosslinker is preferably present in an amount of 0-10 wt%, preferably 2.0-8.0 wt%, based on the total dry weight of the coating composition. Suitable crosslinkers are commercially available, such as Silicate TES-40 WN from Wacker and Dynasylan A from Evonik.

[0096] When the curing reactive functional group is a carbinol, preferred curing agents are monomeric isocyanates, polymeric isocyanates and isocyanate prepolymers. Polyisocyanates are preferred over monomeric isocyanates due to their lower toxicity. Polyisocyanates can be based on, for example, diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) chemistry. These are supplied, for example, under the trade names Desmodur by Covestro and Tolonate by Vencorex. Examples of polyisocyanates offered by Covestro include Desmodur N3300, Desmodur 3390 BA / SN, Desmodur N3400, Desmodur N3600, Desmodur N75, Desmodur XP2580, Desmodur Z4470, Desmodur XP2565 and Desmodur VL.

[0097] Polyisocyanates can be produced with different NCO-functionalities, the NCO-functionality being the amount of NCO-groups per polyisocyanate molecule or per isocyanate prepolymer molecule. Polyisocyanate curing agents with different NCO-functionalities can be used.

[0098] The curing 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, preferably 0.9 to 2.0 equiv, more preferably 0.95 to 1.7 equiv, even more preferably 1 to 1.5 equiv.

[0099] When the curing reactive functional group is amine, epoxy or isocyanate, the curing agent is preferably amine, sulfur or epoxy functional. The curing agent may be, for example, a dual curing agent that includes both an amine / sulfur / epoxy / isocyanate and an alkoxysilane. A preferred dual curing agent is represented by the general formula:

[0100] [ka]

[0101] During the ceremony, LL is independently selected from unsubstituted or substituted monovalent hydrocarbon groups of 1 to 6 carbon atoms; Each M is independently selected from a hydrolyzable group, e.g., an alkoxy group; a is 0, 1 or 2, preferably 0 or 1; b is an integer from 1 to 6; Fn is an amine, epoxy, glycidyl ether, isocyanate or sulfur group.

[0102] Preferred examples of such dual curing agents include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, (3-glycidoxypropyl)trimethoxysilane, 3-mercaptopropyltrimethoxysilane. One particularly preferred curing agent is 3-aminopropyltriethoxysilane, such as Dynasylan AMEO from Evonik.

[0103] This type of dual curative can be used as a separate curing agent or can be used to end-capping the polysiloxane binder such that the end groups of the polysiloxane binder are modified prior to the curing reaction.

[0104] <Catalyst components> To aid in the curing process, the coating composition of the present invention may include a catalyst component. The catalyst may be an organic catalyst or an inorganic catalyst or an organometallic catalyst. The catalyst component may be part of the polysiloxane-based binder emulsion or may be added separately to the coating composition. Preferably, when present, the curing catalyst is part of the polysiloxane-based binder emulsion.

[0105] {Metal catalyst} In one embodiment, the coating composition of the present invention includes a metal catalyst. Representative examples of catalysts that can be used include catalysts containing Sn, Zn, Li, K, Bi, Fe, Ce or Zr, such as their salts and organometallic complexes. The salts are preferably salts of long-chain carboxylic acids and / or chelates or organometallic salts.

[0106] 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 lithium being particularly preferred.

[0107] Examples of anionic organic radicals include methoxide, ethoxide, n-propoxide, isopropoxide, n-butoxide, isobutoxide, sec-butoxide, tert-butoxide, triethanolamine, and 2-ethylhexyloxide radicals; Carboxylic acid ester radicals such as acetate, formate, n-octoate, 2-ethylhexanoate, 2,4,4-trimethylpentanoate, 2,2,4-trimethylpentanoate, 6-methylheptanoate, oleate, ricinoleate, palmitate, hexoate, hexadecanoate, 2-ethylhexanoate, benzoate, 1,4-dibenzoate, stearate, acrylate, laurate, methacrylate, 2-carboxyethylacrylate, oxalate, 10-undecylenate, dodecanoate, citrate, 3-oxopentanoate, 3-oxobutanoate, neodecanoate radicals; Amido radicals such as dimethylamido, diethylamido, ethylmethylamido and dipropylamido radicals; Lactic acid radical; Included are trialkylsiloxy radicals, more particularly trimethylsiloxy and triethylsiloxy radicals, as well as carbonate radicals (O-CO-OR') and carbamate radicals (O-CO-NR'2), where R' may be the same or different, is monovalent or divalent, is an optionally substituted hydrocarbon radical, and may further be hydrogen, trimethoxysilylpropyl, triethoxysilylpropyl, dimethoxymethylsilylpropyl, diethoxymethylsilylpropyl, N-[3-(trimethoxysilyl)propyl]-2-aminoethyl, N-[3-(triethoxysilyl)propyl]-2-aminoethyl, N-[3-(dimethoxymethylsilyl)propyl]-2-aminoethyl or N-[3-(diethoxymethylsilyl)propyl]-2-aminoethyl radicals.

[0108] Examples of metal salt compounds are 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, zinc(II) acetate, zinc(II) formate, zinc(II) benzoate, zinc(II) 2-ethylhexanoate, cerium(III) neodecanoate, zinc(II) n-octanoate, zinc(II) stearate, zinc(II) ethoxide, zinc(II) acetylacetone ... acrylate, zinc(II) methacrylate, 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, zirconium(IV) 2-carboxyethylacrylate, zirconium(IV) tetrakis(diethylamide), zirconium(IV) tetrakis(ethylmethylamide), zirconium(IV) bis(diethylcitrate)-di-n-propoxide.

[0109] 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, zinc(II) 2-acetyl ... cyclohexanoate, 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, as well as 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.

[0110] Examples of suitable tin catalysts are dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin diacetate, dioctyltin dilaurate. Examples of commercially available tin catalysts include BNT-CAT 400 and BNT-CAT 500 from BNT Chemicals, FASCAT 4202 from PMC Organometallix, and Metatin Katalysator 702 from DOW.

[0111] Examples of suitable lithium catalysts are lithium 2-ethylhexanoate and lithium neodecanoate. Examples of commercially available lithium catalysts include Borchers Deca Lithium 2 manufactured by Borchers.

[0112] Examples of suitable potassium catalysts are potassium 2-ethylhexanoate and potassium neodecanoate. Commercially available examples of potassium catalysts include 15% potassium Hex-Cem® EU from Borchers and TIB KAT K30 from TIB Chemicals.

[0113] Examples of suitable zinc catalysts are zinc 2-ethylhexanoate, zinc naphthenate and zinc stearate. Commercially available examples of zinc catalysts include K-KAT XK-672 and K-KAT670 from King Industries, and Borchi Kat 22 from Borchers.

[0114] Examples of suitable bismuth catalysts are organobismuth compounds such as bismuth 2-ethylhexanoate, bismuth octanoate and bismuth neodecanoate. Commercially available organobismuth catalysts are Borchi Kat 24 and Borchi Kat 315 from Borchers, K-KAT XK-651 from King Industries, Reaxis C739E50 from Reaxis, and TIB KAT 716 from TIB Chemicals.

[0115] An example of a suitable cerium catalyst is cerium(III) neodecanoate.

[0116] Other suitable catalysts are iron catalysts (e.g., iron stearate and iron 2-ethylhexanoate) and zirconium catalysts (e.g., zirconium naphthenate, tetrabutyl zirconate, tetrakis(2-ethylhexyl)zirconate, triethanolamine zirconate, tetra(isopropenyloxy)-zirconate, zirconium tetrabutanolate, zirconium tetrapropanolate and zirconium tetraisopropanoate). Further suitable catalysts are zirconate esters.

[0117] In one preferred embodiment, the metal catalyst is a tin, zinc and / or cerium catalyst.

[0118] In one preferred embodiment, the catalyst is tin-free.

[0119] Preferably, the metal catalyst is 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.

[0120] {Organic catalyst} The catalyst may also be organic, such as a low molecular weight amidine or low molecular weight amine compound (e.g. aminosilane). The term low molecular weight means that the molecular weight is less than 1000 g / mol, for example 50-500 g / mol, preferably 100-400 g / mol.

[0121] Suitable amidines have the motif:

[0122] [ka]

[0123] It is a compound comprising: Preferably the amidine has the general formula:

[0124] [ka]

[0125] 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, and combinations thereof; and / or Any two or more of R1, R2, R3, and R4 may be bonded together to form a ring structure.

[0126] R1, R2 and R4 are preferably hydrogen or C1-6 alkyl or phenyl groups.

[0127] R3 is C 1-6 It is an alkyl or phenyl group.

[0128] More preferably, R2+R4 together form a ring and / or R1+R3 together form a ring, which is preferably an aliphatic 5- to 7-membered ring.

[0129] Preferred choices include cyclic amidines, preferably bicyclic amidines, such as 1,8-diazabicyclo-5.4.0-7-undecene (DBU), the chemical structure of which is shown below:

[0130] [ka]

[0131] The catalyst may be a low molecular weight organic amine compound such as triethylamine, cyclic amines, tetramethylethylenediamine, 1,4-ethylenepiperazine, and pentamethyldiethylenetriamine.

[0132] However, preferred amines are aminosilanes, such as aminoalkyltrialkoxysilanes (e.g., 3-aminopropyltriethoxysilane or 3-aminopropyltrimethoxysilane) or bis(alkyltrialkoxysilyl)amines, preferably including bis(3-propyltrimethoxysilyl)amine or bis(3-propyltriethoxysilyl)amine. Another option is N,N-dibutylaminomethyl-triethoxysilane.

[0133] Suitable aminosilanes are represented by the general formula (IV) or (V):

[0134] (IV) YR (4-z) Six z

[0135] During the ceremony, and z is an integer from 1 to 3.

[0136] (V) YR (3-y) R 1 Six y

[0137] In the formula, y is an integer of 1 to 2, Each R is a hydrocarbyl group having 1 to 12 C atoms, optionally containing an ether or amino linker; R 1 is a hydrocarbyl group having 1 to 12 C atoms; Each X independently represents an alkoxy group. Y is an amino bonded to R. The Y group may be attached to any part of the R chain.

[0138] The amino group is preferably N-di-C1-6-alkyl or NH2.

[0139] It is particularly preferred when X is a C1-6 alkoxy group, especially a methoxy or ethoxy group. It is also particularly preferred when 2 or 3 alkoxy groups are present. Thus z is ideally 2 or 3, especially 3.

[0140] The subscript y is preferably 2.

[0141] R 1 is preferably C 1-4 Alkyl, for example methyl. R is a hydrocarbyl group having up to 12 carbon atoms. By hydrocarbyl is meant a group containing only C and H atoms. It may contain 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 is interrupted in the chain by an -O- or -NH- group.

[0142] R is preferably an unsubstituted (obviously with the exception of Y), unbranched alkyl chain having 2 to 8 C atoms.

[0143] Thus, the preferred silane general formula is structure (VI):

[0144] (VI) Y'-R' (4-z') Six' z

[0145] During the ceremony, z' is an integer from 2 to 3; R' is an unsubstituted unbranched alkyl chain having 2 to 8 C atoms, optionally containing an ether or amino linker, Y' is an amino functional group attached to the R' group; X' represents an alkoxy group.

[0146] Examples of such silanes are the numerous representative products manufactured by Degussa of Leinfelden and sold under the trade name Dynasylan® D, Silquest® silane manufactured by Momentive, and GENOSIL® silane manufactured by Wacker.

[0147] Preferred aminosilanes include aminopropyltrimethoxysilane (Dynasylan AMMO; Silquest Al 110), aminopropyltriethoxysilane (Dynasylan AMEO) or N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (Dynasylan DAMO, Silquest Al 120), N-(2-aminoethyl)-3-aminopropyltriethoxysilane, triamino-functional trimethoxysilane (Silquest A-1130), bis(gamma-trimethoxysilylpropyl)amine (Silquest Al 170), N-ethyl-gamma-aminoisobytyltrimethoxysilane (Silquest A-Link 15), N-phenyl-gamma-aminopropyltrimethoxysilane (Silquest Y-9669), 4-amino-3,3-dimethylbutyltrimethoxysilane (Silquest Y ... Y-1130), bis(gamma-trimethoxysilylpropyl)amine (Silquest Y-1130), bis(gamma-trimethoxysilylpropyl)amine (Silquest Y-1130), bis(gamma-trimethoxysilylpropyl)amine (Silquest Y-1130), bis(gamma-trimethoxysilylpropyl)amine (Silquest Y-1130), bis(gamma-trimethoxysilylpropyl)amine (Silquest Y-1130), bis(gamma-trimethoxysilylpropyl)amine (Silquest Y-113 1637), (N-cyclohexylaminomethyl)triethoxysilane (Genosil XL 926), (N-phenylaminomethyl)trimethoxysilane (Genosil XL 973), and mixtures thereof.

[0148] Other specific silanes of interest include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(aminoethyl)-aminopropyltrimethoxysilane H2NCH2CH2NHCH2CH2CH2Si(OCH3)3, 3-aminopropylmethyldiethoxysilane, 3-(2-aminoethylamino)propylmethyldimethoxysilane (H2NCH2CH2NHCH2CH2CH2SiCH3(OCH3)2).

[0149] It should be understood that if the binder contains silicone reactive groups, such as Si-OH groups, Si-OR (alkoxy) groups, etc., the aminosilane can act as both a catalyst and a crosslinker, since the silane groups can react with the polysiloxane binder.

[0150] The amount of organic catalyst present in the coating composition may be 0.05-5.0 wt.%, preferably 0.1-4.0 wt.%, for example 0.1-2.0 wt.%, more preferably 0.1-1.0 wt.% of the coating composition (dry weight).

[0151] <Added oil> The coating composition of the present invention may include additive oils. These additive oils do not include 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 oils should be selected. As a result, they do not react in the curing reaction of the polysiloxane-based binder. The additive oils are intended to be free in the coating film. As a result, they can migrate to the surface of the coating film and improve the antifouling properties of the coating film.

[0152] Examples of suitable additive oils include hydrophilic modified polysiloxane oils and hydrophobic modified polysiloxane oils.Other additive oils can also be used, such as petroleum oils, polyolefin oils, polyaromatic oils, fluororesins such as polytetrafluoroethylene or liquid fluorinated alkyl- or alkoxy-containing polymers, or lanolin and lanolin derivatives and other sterols and / or sterol derivatives disclosed in WO2013024106A1, or poly(oxyalkylene) modified alcohols (e.g., poly(oxyalkylene) modified sterols) disclosed in WO2016004961A1, or combinations thereof.

[0153] Further additive oils optionally present in the coating composition of the present invention are fluorinated amphiphilic polymers / oligomers, as described in WO2014131695.

[0154] Suitable additive oils may be based on methacrylate copolymers with polysiloxane side chains and polyether or nitrogen-containing hydrophilic groups, as described in WO2019101912A1 and WO2019101920A1.

[0155] Preferably, the additive oil is a hydrophilically modified polysiloxane oil and / or a hydrophobically modified polysiloxane oil. The hydrophilically modified polysiloxane oil and the hydrophobically modified polysiloxane oil can be used in combination. Suitable hydrophilically modified polysiloxane oils and the hydrophobically modified polysiloxane oils are described in more detail below.

[0156] <Hydrophilic modified polysiloxane oil> The coating composition of the present invention may further comprise a hydrophilically modified polysiloxane, it being understood that this component is distinct from the polysiloxane-based binder described above.

[0157] It should be understood that the hydrophilically modified polysiloxane does not contain curing reactive groups, such as Si-OH groups, Si-OR (alkoxy) groups, etc., that can react with the binder at the appropriate curing temperature (0-40°C), and thus the hydrophilically modified polysiloxane is intended to be non-reactive in the curing reaction, particularly with the binder component. Generally, this component is not considered to be part of the binder system. The functional groups on the hydrophilically modified polysiloxane should be selected according to the curing mechanism so that they do not react in the curing reaction.

[0158] Preferably, the hydrophilically modified polysiloxane does not contain silicone reactive groups, such as Si-OH groups, Si-OR (alkoxy) groups, etc., that can react with the binder at an appropriate curing temperature (0 to 40° C.).

[0159] Hydrophilically modified polysiloxanes are widely used as surfactants and emulsifiers because they contain both hydrophilic and lipophilic groups in the same molecule. The hydrophilically modified polysiloxane according to the present invention is a polysiloxane modified with hydrophilic groups that makes it more hydrophilic compared to the corresponding unsubstituted polysiloxane with the same number of polysiloxane units. Those skilled in the art will understand that by "hydrophilic", we mean a substance or group that has an affinity for water. Hydrophilicity can be obtained 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), amines (e.g., polyvinylamine, (meth)acrylic polymers containing amine groups). Typically, the hydrophilically modified polysiloxane is an oil.

[0160] In one preferred embodiment, the hydrophilic groups are non-ionic. By "non-ionic" herein is meant that the hydrophilically modified polysiloxane does not contain salt moieties; in particular, it typically does not contain metal cations.

[0161] 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 1 to 12, preferably 1.0 to 10, more preferably 1.0 to 8.0, and most preferably 2.0 to 7.0. In a specific embodiment, the HLB of the nonionic hydrophilic modified polysiloxane is in the range of 3.0 to 6.0.

[0162] HLB as used herein is typically determined according to Griffin's model using the formula "wt% hydrophilic groups" / 5 (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-established parameter for non-ionic surfactants and is 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 wt% of hydrophilic groups in the hydrophilically modified polysiloxane.

[0163] One function of the hydrophilically modified polysiloxane is to facilitate the dissolution and transport of biocides to the surface of the coating film. In addition, it is well known that the formation of a hydration layer at the coating-water phase interface is important for fouling protection performance.

[0164] If the hydrophilic modified polysiloxane is too hydrophilic, for example due to a high amount of hydrophilic groups in the molecule, this may cause the biocide(s) and the hydrophilic modified polysiloxane to be depleted early due to too fast leaching rate. High hydrophilicity also leads to poor compatibility with the polysiloxane-based binder matrix. Film uniformity is reduced and adhesion is reduced, especially when high oil amounts (more than 10 wt.%) are used.

[0165] Methods for controlling the leaching rate of the biocide and the hydrophilically modified polysiloxane include the molecular weight, hydrophilicity, and miscibility with the binder of the hydrophilically modified polysiloxane. A very low molecular weight hydrophilically modified polysiloxane tends to leach faster, while a molecular weight that is too high may not leach the biocide and the hydrophilically modified polysiloxane at the desired rate.

[0166] Thus, in a preferred embodiment, the number average molecular weight (Mn) of the hydrophilically modified polysiloxane is in the range of 500 to 18,000 g / mol, for example in the range of 1000 to 16,000 g / mol, in particular in the range of 2000 to 15,050 g / mol or 4000 to 15,050 g / mol. Further suitable Mn ranges of 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 experimentally obtained values, for example by GPC measured against polystyrene standards. The method is described in the experimental section below.

[0167] In a preferred embodiment, the weight average molecular weight (Mw) of the hydrophilically modified polysiloxane is 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 suitable ranges include 5,000 to 30,000 g / mol, such as 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 obtained values, for example by GPC measured against polystyrene standards.

[0168] It is also preferable that the viscosity of the hydrophilic modified polysiloxane is in the range of 20 to 4,000 mPa·s, for example, in the range of 30 to 3,000 mPa·s, and particularly in the range of 50 to 2,500 mPa·s.

[0169] Of particular interest are hydrophilically modified polysiloxanes in which the relative weight of the hydrophilic moieties is 5% or more (e.g. 5-60%), such as 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.

[0170] The wt.% 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.

[0171] If a molar excess of reactant is present, such molar excess is not counted in determining the wt.% of hydrophilic moieties. Only monomers that are capable of reacting based on the stoichiometry of the reaction are counted.

[0172] The hydrophilically modified polysiloxane may contain low amounts of impurities, such as cyclic siloxanes, such as D4, D5 and D6 cyclosiloxanes, which are residues from polysiloxane synthesis, where the designations (D4, D5 and D6) refer to the number of repeating Si-O units in the cyclic polysiloxane (i.e., 4, 5 or 6 repeating Si-O units in the cyclic polysiloxane, respectively). From health, safety and environmental aspects, it is preferred to limit the amount of cyclic polysiloxanes present in the coating composition. In a preferred embodiment, the hydrophilically modified polysiloxane contains less than 5% cyclic polysiloxanes, preferably less than 2%, more preferably less than 1%. In a particularly preferred embodiment, the hydrophilically modified polysiloxane does not contain cyclic polysiloxanes.

[0173] In one preferred embodiment, the hydrophilically modified polysiloxane is a polyether modified polysiloxane.

[0174] Preferably, the polyether group comprises at least 3 repeat units, such as at least 5 repeat units. In many interesting embodiments, the oligomer or polymer comprises from 5 to 100 repeat units, such as from 5 to 50, or from 8 to 50, or from 8 to 20 repeat units.

[0175] In some preferred embodiments, the number average molecular weight (n) of the polyether group (i.e., oligomeric or polymeric group) is in the range of 100 to 2500 g / mol, such as in the range of 200 to 2000 g / mol, in particular in the range of 300 to 2000 g / mol or in the range of 400 to 1000 g / mol.

[0176] Of particular interest are polyether-modified polysiloxanes in which the relative weight of the polyether 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 polyether-modified polysiloxane.

[0177] In one variation, the polyether-modified polysiloxane is a polysiloxane having poly(oxyalkylene) chains grafted thereto. An exemplary structure of such a polyether-modified polysiloxane is formula (VII).

[0178] [ka]

[0179] During the ceremony, Each R 7 is C 1-5 - independently selected from alkyl (including linear or branched hydrocarbon groups) and aryl (e.g., phenyl (-C6H5)), in particular methyl; Each R 8 -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 independently selected from -H, methyl and -C(=O)CH3; Each R 9 is 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 2-5 - alkylene, e.g., -CHCH- and -CHCH(CH)-; k is 0 to 240, l is 1 to 60, and k+l is 1 to 240; and n is an integer from 0 to 50, m is an integer from 0 to 50, and m+n is an integer from 1 to 50.

[0180] Especially R 7 is methyl; Each R 8 is -H or C 1-4 -alkyl or -C(=O)CH3; Each R 9 is -CH2CH2- or -CH2CH2CH2- or -CH2CH(CH3)-); k is 0 to 240, l is 1 to 60, and k+l is 1 to 240; and n is a number from 0 to 50, m is a number from 0 to 50, and m+n is a number from 1 to 50.

[0181] All R 7 It is preferred that the groups are identical.

[0182] Commercially available examples of this type of polyether-modified polysiloxane are KF352A, KF353, KF945, KF6012, KF6017 from Shin-Etsu Chemical Co., Ltd., XIAMETER OFX-5220, DOWSIL OFX-5247, XIAMETER OFX-5329, XIAMETER OFX-5330 from DOW.

[0183] In another embodiment, the polyether-modified polysiloxane is a polysiloxane having poly(oxyalkylene) chains incorporated into its backbone.

[0184] An example of such a hydrophilically modified polysiloxane structure is formula (VIII).

[0185] [ka]

[0186] During the ceremony, Each R 7 is C 1-5 - independently selected from alkyl (including linear or branched hydrocarbon groups) and aryl (e.g., phenyl (-C6H5)), in particular methyl; Each R 8 -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 independently selected from -H, methyl and -C(=O)CH3; Each R 9 is 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 2-5 - alkylene, e.g., -CHCH- and -CHCH(CH)-; k is 0 to 240; and n is a number from 0 to 50, m is a number from 0 to 50, and m+n is a number from 1 to 50.

[0187] 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-, -CH2CH(CH3)- or -CH2CH2CH2-; k is 0 to 240; and n is a number from 0 to 50, m is a number from 0 to 50, and m+n is a number from 1 to 50.

[0188] All R 7 It is preferred that the groups are identical. Commercially available examples of this type of hydrophilically modified polysiloxane are DOW's DOWSIL 2-8692 and XIAMETER OFX-3667.

[0189] In yet another embodiment, the polyether-modified polysiloxane is a polysiloxane having polyoxyalkylene incorporated into its backbone and having polyoxyalkylene chains grafted thereto. An exemplary structure of such a hydrophilically modified polysiloxane is shown by formula (IX):

[0190] [ka]

[0191] During the ceremony, Each R 7 is C 1-5 - independently selected from alkyl (including linear or branched hydrocarbon groups) and aryl (e.g., phenyl (-C6H5)), in particular methyl; Each R 8 -H, C 1-4 -Alkyl (e.g., -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2CH3), phenyl (-C6H5), and C 1-4 - independently selected from alkylcarbonyl (e.g., -C(=O)CH3, -C(=O)CH2CH3 and -C(=O)CH2CH2CH3), in particular independently selected from -H, methyl and -C(=O)CH3; Each R 9 is C2-5 -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 2-5 - alkylene, e.g., -CHCH- and -CHCH(CH)-; k is 0 to 240, l is 1 to 60, and k+l is 1 to 240; n is a number from 0 to 50, m is a number from 0 to 50, and m+n is a number from 1 to 50.

[0192] 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 a number from 0 to 50, m is a number from 0 to 50, and m+n is a number from 1 to 50.

[0193] In the above structures (VII), (VIII) and (IX), the groups -CH2CH(CH3)-, -CH2CH(CH2CH3)-, etc. may be present in either of two possible orientations. Similarly, it should be understood that the segments present k and l times are typically randomly distributed in the polysiloxane structure.

[0194] In these embodiments and aspects, the polyether or poly(oxyalkylene) is preferably selected from polyoxyethylene, polyoxypropylene, and poly(oxyethylene-co-oxypropylene), which may also be referred to as polyethylene glycol, polypropylene glycol, and poly(ethylene glycol-co-propylene glycol). Thus, in the above structures (VII), (VIII), and (IX), each R bonded to two oxygen atoms is 9 is preferably selected from -CH2CH2- and -CH2CH(CH3)-, while each R bonded to a silicon atom and an oxygen atom 9 is preferably C 2-5 -alkyl.

[0195] In some embodiments of structures (VII), (VIII) and (IX) above, R 8 is preferably not hydrogen.

[0196] It should be understood that the one or more polyether-modified polysiloxanes may be of different types, for example, two or more of the above types.

[0197] In another preferred embodiment, the hydrophilically modified polysiloxane comprises polyglycerol groups or pyrrolidone groups.

[0198] When present, the hydrophilically modified polysiloxane is preferably present in an amount of from 1.0 to 30 wt %, more preferably from 2.0 to 20 wt %, and most preferably from 4 to 15 wt %, based on the total dry weight of the composition.

[0199] When present, the hydrophilically modified polysiloxane is preferably present in an amount of from 0.5 to 25 wt.%, more preferably from 1.0 to 20 wt.%, and most preferably from 3 to 15 wt.%, based on the total weight of the coating composition.

[0200] It is within the scope of the present invention for a mixture of more than one hydrophilically modified polysiloxane to be present, however, it is preferred that only a single hydrophilically modified polysiloxane is present. When two or more different types of hydrophilically modified polysiloxanes are present, these wt% ranges cited above refer to the sum of the hydrophilically modified polysiloxane components.

[0201] <Hydrophobic modified polysiloxane oil> The coating composition of the present invention optionally further comprises a hydrophobically modified polysiloxane oil. The hydrophobically modified polysiloxane does not contain curing reactive groups, such as Si-OH groups, Si-OR (alkoxy) groups, etc., that can react with the binder at the appropriate curing temperature (0-40°C), and therefore it should be understood that the hydrophobically modified polysiloxane is intended to be non-reactive in the curing reaction, particularly with respect to the binder component. In general, this component is not considered part of the binder system. The functional groups on the hydrophobically modified polysiloxane should be selected so that they do not react in the curing reaction depending on the curing mechanism.

[0202] Preferably, the hydrophobically modified polysiloxane does not contain silicone reactive groups, such as Si-OH groups, Si-OR (alkoxy) groups, etc., that can react with the binder at an appropriate curing temperature (0 to 40° C.).

[0203] The hydrophobically modified polysiloxane according to the present invention is a polysiloxane modified with hydrophobic groups to increase its hydrophobicity compared to the corresponding unsubstituted polysiloxane having the same number of polysiloxane units. Those skilled in the art will understand that by "hydrophobic" we mean a substance or group that repels water, i.e. has no affinity for water. Hydrophobicity can be obtained by modifying with hydrophobic groups such as alkyl groups, cycloalkyl groups, aryl groups, etc. Typically, the hydrophobically modified polysiloxane is an oil.

[0204] Preferred hydrophobically modified polysiloxanes are methylphenyl-functional polysiloxanes and methylaryl-functional polysiloxanes.

[0205] When present, the hydrophobically modified polysiloxane is preferably present in an amount of from 2.5 to 30 wt %, more preferably from 5 to 25 wt %, based on the total dry weight of the composition.

[0206] When present, the hydrophobically modified polysiloxane is preferably present in an amount of from 1.0 to 30 wt.%, more preferably from 4 to 20 wt.%, based on the total weight of the entire composition.

[0207] While it is within the scope of the present invention for a mixture of more than one hydrophobically modified polysiloxane to be present, it is preferred that only a single hydrophobically modified polysiloxane is present. When two or more different types of hydrophobically modified polysiloxanes are present, the wt% ranges cited above refer to the sum of the hydrophobically modified polysiloxane components.

[0208] In one embodiment, the contamination release coating composition comprises a mixture of a hydrophilically modified polysiloxane and a hydrophobically modified polysiloxane, in which each of the hydrophilically modified polysiloxane and the hydrophobically modified polysiloxane may be present in an amount of from 2.5 to 20 wt%, such as from 5 to 15 wt%, based on the total dry weight of the composition.

[0209] <Antifouling agents / biocides> The fouling release coating composition of the present invention may also include an antifouling agent / biocide.

[0210] The terms antifouling agent, biologically active compound, antifouling agent, biocide, toxic agent are used in the art to describe known compounds that act to prevent marine fouling on surfaces. Thus, these terms can be 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.

[0211] 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.

[0212] Examples of organometallic antifoulants include zinc pyrithione; organocopper compounds such as copper pyrithione, copper acetate, copper di(ethyl 4,4,4-trifluoroacetoacetate), copper naphthenate, oxine copper, copper nonylphenolsulfonate, copper bis(ethylenediamine)bis(dodecylbenzenesulfonate), and copper bis(pentachlorophenolate); dithiocarbamate compounds such as zinc bis(dimethyldithiocarbamate) [ziram], zinc ethylenebis(dithiocarbamate) [zineb], manganese ethylenebis(dithiocarbamate) [maneb], and manganese ethylenebis(dithiocarbamate) complexed with a zinc salt [mancozeb].

[0213] 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]; amides and imides of carboxylic, sulfonic and sulfenic acids, such as N-(dichlorofluoromethylthio)phthalimide, N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfamide [dichlohlanide], N-dichlorofluoromethylthio-N',N'-dimethyl-Np-tolylsulfamide [tolylfluanid] and N-(2,4,6-trichlorophenyl)maleimide; other organic compounds, such as pyridinetriphenylborane [TPBP], aminetriphenylborane, 3-iodo-2-propynyl Includes N-butyl carbamate [iodocarb], 2,4,5,6-tetrachloroisophthalonitrile, p-((diiodomethyl)sulfonyl)toluene and 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile [tralopyril] and quaternary ammonium salts.

[0214] Other examples of antifouling agents include tetraalkylphosphonium halides, guanidine derivatives, imidazole-containing compounds such as 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole [medetomidine] and its derivatives, avermectins and their derivatives, such as ivermectin, macrocyclic lactones including spinosyns and their derivatives, such as spinosad, capsaicins and their derivatives, such as phenylcapsaicin, and enzymes, such as oxidases, proteolytic enzymes, hemicellulolytic enzymes, cellulolytic enzymes, lipolytic enzymes, amylolytic enzymes.

[0215] Preferred antifouling agents are 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 are zinc pyrithione and copper pyrithione, especially copper pyrithione.

[0216] When present, the biocide may form 0.5 to 20% by weight, preferably 0.75 to 10%, for example 1 to 5% by weight relative to the total weight of the coating composition.

[0217] When present, the biocide may form 0.5 to 20% by weight, preferably 1.0 to 15% by weight, more preferably 2.0 to 12% by weight, based on the total dry weight of the coating composition.

[0218] <Pigments and fillers> The coating composition of the present invention comprises at least one filler or pigment. The pigment(s) may be inorganic, organic or a mixture thereof. Inorganic pigments are preferred. The pigment may be surface treated.

[0219] 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, carbazodioxazine, isoindoline orange, bis-acetoaceto-tridiol, benzimidazolone, quinaphthalone yellow, isoindoline yellow, tetrachloroisoindolinone, and quinophthalone yellow, metal flake materials (e.g., aluminum flakes). Preferred pigments are black iron oxide, red iron oxide, yellow iron oxide, phthalocyanine blue, and titanium dioxide. In one preferred embodiment, the titanium dioxide is surface-treaded with a silicone compound, a zirconium compound, or a zinc compound.

[0220] Examples of fillers that can be used in the coating composition of the present invention are zinc oxide, barium sulfate, calcium sulfate, calcium carbonate, dolomite (Microdol), mica, fumed silica, silica or silicate, including bentonite and other clays (e.g., talc, feldspar, china clay and nepheline cynite), and solid silicone resins, which are generally condensed branched polysiloxanes.Fillers such as fumed silica may have a thickening effect on the coating composition.

[0221] An example of a preferred filler is a fumed silica filler. The fumed silica filler may have an untreated surface or a hydrophobically modified surface. Preferably, the fumed silica filler has a hydrophobically modified surface. Examples of commercially available fumed silica fillers are TS-610, TS-530, EH-5, H-5 and M-5 from Cabot 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, Aerosil® R711 from Evonik.

[0222] The amount of the at least one filler or pigment is preferably in the range of 0.05 to 25 wt %, more preferably 0.1 to 15 wt %, and even more preferably 0.5 to 10 wt %, based on the total weight of the coating composition.

[0223] The amount of at least one filler or pigment is preferably in the range of 0.1 to 30 wt.%, more preferably 0.5 to 20 wt.%, and even more preferably 1.0 to 15 wt.%, based on the total dry weight of the coating composition.

[0224] <Additives> The coating composition of the present invention optionally includes one or more additives. Examples of additives that may be present in the coating composition of the present invention include reinforcing agents, rheology modifiers (e.g., thixotropic agents, thickeners, and anti-settling agents), dispersants, wetting agents, coalescing agents, extenders, surfactants, binders, plasticizers, and dyes.

[0225] As rheology modifiers, thixotropic agents suitable for water-based formulations, such as cellulose-based thickeners, xanthan gum, guar gum, organically modified clays (e.g., bentonite, hectorite, and attapulgite clays), organic wax thixotropic agents based on castor oil and castor oil derivatives, polyamide waxes, urethane-based rheology modifiers, and fumed silica can be used.

[0226] Preferably, the thixotropic agent, thickener and anti-settling agent are each present in the composition of the present invention in an amount of 0-10 wt%, more preferably 0.1-6 wt%, and even more preferably 0.1-2.0 wt%, based on the total dry weight of the composition.

[0227] A flocculant may also be included optionally. In water-based coating compositions, the applied wet product is non-uniform, whereas solvent-based compositions are uniform when applied. To form a film, the droplets of the polysiloxane-based binder emulsion must coalesce. Flocculants aid this process in the water phase. Examples of suitable flocculants are ester alcohols, benzyl alcohol, propylene glycol monomethyl ether (PM), propylene glycol propyl ether (PnP), dipropylene glycol n-butyl ether (DPnB), propylene glycol phenyl ether (PPh), tripropylene glycol n-butyl ether (TPnB), ethylene glycol propyl ether (EP), ethylene glycol butyl ether (EB), diacetone alcohol (DAA) and dipropylene glycol methyl ether (DPM).

[0228] To improve or facilitate the dispersion of pigments, fillers and biocides, it may be desirable to incorporate wetting / dispersing additives that are compatible with the aqueous coating composition.

[0229] Examples of suitable dispersants are polyalkylene glycols, polyacrylamides, polyether carboxylates and polycarboxylates.

[0230] <Solvent> The contamination release coating composition of the present invention is an aqueous composition, ie, contains water as a solvent.

[0231] The contamination-releasing coating composition of the present invention preferably comprises water as the only solvent, i.e. the solvent consists of water. The coating composition is therefore preferably free of organic solvents and / or thinners.

[0232] Small amounts of organic co-solvents such as ketones, alcohols, glycol ethers or other oxygen-containing solvents that are soluble or miscible with water may also be present.

[0233] The coating composition comprises at least 10 wt% water based on the total weight of the entire composition. Preferably, the composition comprises 10-60 wt%, more preferably 20-50 wt%, for example 30-45 wt% water based on the total weight of the entire composition.

[0234] <Composition and coating material> The present invention also relates to a method for producing a contamination release coating composition as described herein, said method comprising the steps of: (i) dispersing at least one pigment or filler in water to produce a dispersion; and, (ii) mixing the dispersion produced in step (i) with an aqueous polysiloxane-based binder emulsion to produce the coating composition.

[0235] The compositions described herein can be prepared in a concentration suitable for use in, for example, spray painting. In this case, the composition is itself a paint. Alternatively, the composition can be a concentrate for preparing a paint. In this case, further solvents and optionally other ingredients are added to the compositions described herein to form a paint. Preferred solvents are as previously described herein for the compositions.

[0236] After mixing, and optionally adding a solvent, the pollutant release coating composition or paint is preferably filled into containers. Suitable containers include cans, drums, tanks, and the like.

[0237] The contamination release coating composition may be supplied as a one-pack, two-pack, or three-pack. Preferably, the composition is supplied as a one-pack.

[0238] The pollution release coating compositions and paints of the present invention preferably have a solids content of 40-90 wt%, more preferably 50-80 wt% and even more preferably 55-70 wt%.

[0239] Preferably, the pollution-releasing coating compositions and paints of the present invention have a volatile organic compound (VOC) content of less than 80 g / L, more preferably less than 50 g / L, such as less than 25 g / L, such as 0 g / L. The VOC content can be calculated (ASTM D5201-05A) or measured (US EPA Method 24 or ISO 11890-1).

[0240] The coating composition of the present invention can be applied to any pre-treated coating layer designed for polysiloxane-based pollutant release coatings. Preferably, however, the coating composition is applied directly on top of an anticorrosive organic primer layer. The organic primer layer can be based on epoxy, modified epoxy (e.g., modified with polyvinyl butyral), polyurethane, acrylic, vinyl, polysiloxane, silicate, chlorinated rubber. Preferably, the primer layer is an epoxy-based primer or a vinyl-based primer or a combination thereof.

[0241] The coating composition according to the invention can be applied in one or two or more layers. Preferably, the coating composition according to the invention is applied in one layer.

[0242] Thus, in a further embodiment, the present invention relates to a coating system comprising at least two layers A and B, said layers A and B being adjacent, layer A being an organic primer layer and layer B comprising said aqueous contaminant release coating composition of the present invention.

[0243] The organic primer layer is preferably an epoxy primer layer. Such epoxy primers are well known in the art and can be purchased commercially.

[0244] The pollution release composition of the present invention has good adhesion to organic primers. Therefore, it is usually not necessary to use silicone-organic hybrid tie coat. This means that the entire coating system has one less coating layer and lower VOC. Therefore, in a preferred embodiment, the coating system of the present invention does not include a tie coat layer.

[0245] In one embodiment, the coating system defined above comprises layers A and B, wherein layer A and / or layer B are cured.

[0246] The dry film thickness of each of said coating layers of the coating composition of the present invention is preferably from 50 to 500 μm, more preferably from 100 to 400 μm, and most preferably from 150 to 300 μm.

[0247] The contamination release coating compositions of the present invention are typically cured at a humidity of 20-90%, preferably 30-85%, more preferably 40-80%.

[0248] The present invention also relates to substrates coated with a cured aqueous pollutant release coating as defined herein, as well as to a method of applying an aqueous pollutant release coating composition to a substrate, the method comprising, for example, applying, for example by spraying, an aqueous pollutant release coating composition as defined herein to a substrate and curing the coating composition.

[0249] The substrate is typically a marine structure, preferably a surface of a marine structure that is submerged in use. Such a surface may optionally be coated with an organic primer layer.

[0250] The fouling release coating compositions and paints of the present invention can be applied to the whole or part of any article surface that is subject to marine fouling. The surface is permanently or intermittently submerged (e.g., due to tidal movements, loading of different cargoes or swells). The article surface is typically the hull of a ship or the surface of a fixed marine object such as an oil platform or a buoy. Application of the coating compositions and paints can be achieved by any convenient means, such as painting (e.g., with a brush or roller) or, more preferably, spraying the coating onto the article. Usually, the surface needs to be separated from the seawater to allow coating. Application of the coating can be carried out as conventionally known in the art. After the coating is applied, it is preferably dried and / or cured.

[0251] <Applicable> Said fouling release coating of the present invention is usually applied to the surface of marine structures, preferably the part of the marine structure that is submerged in use.Typical marine structures include ships (including but not limited to boats, yachts, motorboats, motor launches, ocean liners, tugboats, tankers, container ships, other cargo ships, submarines, and all types of naval vessels), pipes, onshore and offshore machinery, all types of structures and objects, such as piers, pilings, bridge substructures, hydraulic equipment and structures, underwater oil well structures, nets and other aquaculture equipment, buoys, etc.The surface of the substrate may be a "natural" surface (e.g., a steel surface) or a surface that has already been coated with an organic primer layer.

[0252] [Example] <Material>

[0253] [Table 1]

[0254] [Table 2]

[0255] [Table 3]

[0256] [Table 4]

[0257] <Decision method> {Particle size measurement} The particle size of the emulsions was determined using a Malvern Zetasizer Nano S ZEN 1600 (Malvern Panalytical Ltd, UK) at a wavelength of 633 nm and a constant angle of 173° at room temperature.

[0258] {Measurement of polymer average molecular weight distribution} The hydrophilic and hydrophobic modified polysiloxane oils were characterized by gel permeation chromatography (GPC) measurements. Molecular weight distributions (MWDs) were measured using a Malvern Omnisec Resolve and Reveal system with two Agilent PLgel 5 μm mixed-D columns connected in series. The columns were calibrated with narrow polystyrene standards by routine calibration. The analytical conditions were set as shown in Table 4 below.

[0259] [Table 5]

[0260] Samples were prepared by dissolving an amount of hydrophobic or hydrophilic modified polysiloxane 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. Weight average molecular weight (Mw) and number average molecular weight (Mn) are reported.

[0261] {Contact angle and surface free energy measurements} The pure binder was applied directly to a PVC panel using a film applicator with a clearance of 300 μm. The panels were used to measure static contact angles and surface free energy using a drop shape analyzer. Five different points were measured for each coating, and the average values ​​were recorded.

[0262] {VOC} VOC content can be calculated (ASTM D5201-05A) or measured (US EPA Method 24 or ISO 11890-1). All coating compositions of the present invention have 0 g / L VOC calculated by ASTM D5201-05A.

[0263] {Anti-stain performance test} PVC panels were painted under the specified conditions using an airless spray with a first coat of Jotacote Universal N10 primer (a two-part polyamine cured epoxy primer) and a second coat of Safeguard Plus (a two-part polyamide cured vinyl epoxy primer) from Jotun A / S. The coating compositions of the invention and comparative examples were applied to PVC panels precoated with an organic primer using a film applicator with a clearance of 300 μm.

[0264] The panels were used in static antifouling performance tests on a raft in Singapore, where the panels were submerged 0.3 to 1.3 m below sea level. The panels were evaluated by visual inspection using the scale shown below.

[0265] [Table 6]

[0266] {Adhesion test} {Adhesion Tests of Examples 1 to 72} A coat of Jotacote Universal N10 primer (a two-part polyamine cured epoxy primer) from Jotun A / S or a coat of Safeguard Plus primer (a two-part polyamide cured vinyl epoxy primer) from Jotun A / S was applied to the PVC panels using an airless sprayer under the specified conditions. The coating compositions of the inventive and comparative examples were applied to the precoated panels using a film applicator with a clearance of 300 μm. The panels were left at room temperature for 48 hours. The panels were then exposed to seawater at 25° C. before evaluation, and the panels were removed from the seawater and left at room temperature for 24 hours. The cross-hatch method based on the non-approved abstract of ISO 2409 was used to evaluate the adhesion. Six parallel cutting lines were made vertically and horizontally using a cutting tool. The surface was then gently cleaned using a soft brush. The adhesion was then evaluated according to the following table:

[0267] [Table 7]

[0268] {Adhesion Tests of Examples 73 to 79} The PVC panels were coated with a coat of Safeguard Plus (a two-part polyamide curing vinyl epoxy based primer) primer from Jotun A / S using an airless spray under the specified conditions.

[0269] A first layer of the coating composition of the present invention was applied to the precoated panels using a film applicator with a clearance of 300 μm. After application of the first layer, the panels were kept at room temperature for 4 days, after which a second coating was applied using a film applicator with a clearance of 300 μm. After 3 days, the panels were exposed to seawater at 20° C. The panels were removed from the water and kept at room temperature for 24 hours before evaluation. Adhesion was evaluated according to the method described above for Examples 1-72.

[0270] {Adhesion Test of Examples 80 and 81} PVC panels were coated with a coat of a two-part amine-cured water-based epoxy primer to a wet film thickness of 300 μm by airless spray. The panels were allowed to dry at room temperature for 48 hours. An example coating composition was applied to the precoated panels using a film applicator with a clearance of 300 μm. The panels were allowed to stand at room temperature for 48 hours. The panels were then exposed to seawater at 20° C. before evaluation, and the panels were removed from the seawater and allowed to stand at room temperature for 24 hours. Adhesion was evaluated according to the method described above for Examples 1-72.

[0271] {Testing coating film properties upon exposure} Degradation of the coating film was evaluated by applying ISO 4628-1 and ISO 4628-2 and assessing the degree of cracking and blistering (Table 7). The coating compositions were applied at 300 μm WFT to PVC panels precoated with Safeguard Plus primer. The panels were left at room temperature for 48 hours and then at 52°C for 24 hours. The panels were then exposed to seawater at 40°C. Before each evaluation, the panels were removed from the seawater and left at room temperature for 24 hours and then at 52°C for 24 hours.

[0272] [Table 8]

[0273] [Paint preparation] For the preparation of component B, copper pyrithione (if present), water, dispersant, and solubilizer were added and mixed gradually for 15 minutes. Then Microdol, surfactant, and more water were added and mixed for 15 minutes. Then iron oxide red and water were added and mixed for 60-90 minutes. All raw materials were well ground and the fineness of grinding was checked with a grindmeter. The target grinding degree was less than 40 μm.

[0274] Component A (polysiloxane-binder emulsion) was then added to component B and mixed for 2-3 minutes, and in a final step component C (additive oil) was added and mixed for a further 2-3 minutes.

[0275] In all formulations, component C (additive oil) is not considered in the calculation of the PVC. All examples had a homogenous, solid film formation.

[0276] [Table 9]

[0277] [Table 10]

[0278] [Table 11]

[0279] [Table 12]

[0280] [Table 13]

[0281] [Table 14] TIFF2024546975000025.tif255164

[0282] [Table 15]

[0283] [Table 16]

[0284] [Table 17]

[0285] Regarding the above examples, the following observations are made.

[0286] *Inventive Examples 1-10 (Table 8) show that biocidal stain release formulations based on the polysiloxane binder emulsion Coatosil DRI have antifouling effects compared to unpainted PVC panels (Comparative Example 1). Examples 1-9 show that antifouling performance is improved by the addition of hydrophobically and hydrophilically modified polysiloxane oils.

[0287] *Inventive Examples 11-19 (Table 9) show that non-biocidal formulations based on the polysiloxane binder emulsion Coatosil DRI improve the fouling release properties compared to unpainted PVC panels (Comparative Example 2). The addition of hydrophobically and hydrophilically modified polysiloxane oils improved the fouling resistance performance.

[0288] *Inventive Examples 20-23 (Table 10) show that biocidal and non-biocidal formulations based on the polysiloxane binder emulsions Dowsil 8005 and Dowsil 8016 improve the fouling release properties compared to unpainted PVC panels (Comparative Example 3). The addition of hydrophilic and hydrophobically modified polysiloxane oils improved the antifouling performance.

[0289] *Inventive Examples 24-35 (Table 11) show that different PVC levels do not affect the pollution release properties. Using only hydrophilic oils, excellent pollution release properties are obtained without the use of hydrophobically modified polysiloxane oils. Different hydrophilically modified polysiloxane oils can be used.

[0290] *Inventive Examples 36-47 (Table 12) show that different PVC levels do not affect the pollution release properties. Using only hydrophobic oils, excellent pollution release properties are obtained without the use of hydrophilically modified polysiloxane oils. Different hydrophobically modified polysiloxane oils can be used.

[0291] *Inventive Examples 48-59 (Table 13) show that aqueous coating compositions containing different polysiloxane-based binder emulsions (Coatosil DRI and Dowsil 8005) and different PVCs have surprisingly good adhesion to organic primers, indicating that a polysiloxane-organic hybrid tie coat is not necessary when using the aqueous coating compositions of the present invention.

[0292] *Comparative examples 6 and 7 show that conventional solvent-based contamination release formulations, in which the polysiloxane binder is dissolved in an organic solvent, provide very poor adhesion to organic primers. Without being bound by any theory, it is believed that the reason for the difference in adhesion is related to film formation. There is a significant difference in the film formation mechanism of solvent-based and water-based coating formulations. In solvent-based formulations, the polymer chains are dissolved in the solvent, whereas in water-based formulations, the polymer binder exists as droplet emulsions in water. The film formation of solvent-based coatings is based on the evaporation of the solvent and cross-linking of the polymer chains. In water-based technology, the water evaporates, the polymer droplets coalesce, and the polymer chains cross-link to form the coating film. It is believed that this difference in the mechanism of film formation is the reason why the water-based contamination release coating of the present invention has good adhesion to organic primers, while conventional solvent-based contamination release coatings have very poor adhesion to such primers.

[0293] * Inventive Examples 60-65 (Table 14) show that different polysiloxane binders with different PVCs and with or without added oil can withstand prolonged exposure to hot seawater without mechanical damage, cracking or blistering of the coating film.

[0294] *Inventive Examples 66-72 (Table 15) show that combinations of different biocides can be used in the aqueous pollutant release formulations of the present invention. All of the coating compositions have good adhesion to the primer.

[0295] *Examples 73-79 show that the aqueous formulation can be applied in several layers while still obtaining good adhesion.

[0296] *Examples 73 and 76 demonstrate that two identical layers can be applied while maintaining good adhesion to the undercoat and between the pollution release coatings of the present invention.

[0297] *Examples 74 and 77 demonstrate that one pollution release layer may contain a biocide and the other may not contain a biocide and still maintain desirable adhesion.

[0298] *Examples 75 and 79 show that desirable adhesion between layers can be maintained even when one layer has a higher biocide content (eg, adding an organic biocide to one layer).

[0299] * Example 78 shows that two coats of slightly different colors can be applied on top of each other while maintaining good adhesion. This may be appropriate, for example, on a dog, to visualize where to apply the next coat.

[0300] *Examples 80 and 81 show that the water-based pollutant release coatings of the present invention also have good adhesion to water-based primers.

Claims

1. (a) an aqueous polysiloxane-based binder emulsion, the emulsion comprising polysiloxane-based binder droplets having an average droplet size of 4 to 1000 nm; and (b) at least one pigment or filler; 1. An aqueous contamination release coating composition comprising: The coating composition comprises at least 10% by weight of water based on the total weight of the entire composition. Aqueous contamination-releasing coating compositions.

2. the composition has a volatile organic compound (VOC) content of less than 80 g / L, preferably less than 50 g / L, more preferably less than 25 g / L, and even more preferably less than 0 g / L; The aqueous contaminant release coating composition of claim 1.

3. the polysiloxane binder droplets have an average size of 50 to 350 nm, preferably 100 to 300 nm; The aqueous contaminant release coating composition of claim 1.

4. 10. The aqueous contaminant release coating composition of claim 1, wherein the polysiloxane binder is a linear or branched polysiloxane binder.

5. The polysiloxane binder has the general formula (I): The aqueous contaminant release coating composition of claim 1. 【Chemistry 11】 [In the formula, Each R 1 is a hydroxyl group, C 1-6 -alkoxy group, 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, C 7-10 Alkaryl or O—Si(R 5 ) 3-z (R 6 ) z are independently selected from Each R 2 is C 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 independently selected from alkyl; Each R 3 and R 4 is C 1-10 Alkyl, C 6-10 Aryl, C 7-10 C substituted with alkylaryl or poly(alkylene oxide) 1-6 independently selected from alkyl; Each R 5 is a hydrolyzable group, e.g., C 1-6 independently selected from an alkoxy group, an acetoxy group, an enoxy group, or a ketoxy group; Each R 6 is C 1-6 independently selected from alkyl groups; z is 0 or an integer from 1 to 2; x is an integer of at least 2; y is an integer of at least 2.

6. The weight average molecular weight of the polysiloxane binder is 400 to 150,000, preferably 1,000 to 140,000, more preferably 5,000 to 130,000, and even more preferably 10,000 to 120,000 g / mol. The aqueous contaminant release coating composition of claim 1.

7. The composition further comprises an additive oil, preferably a hydrophilically modified polysiloxane oil and / or a hydrophobically modified polysiloxane oil; The aqueous contaminant release coating composition of claim 1.

8. the composition further comprises a biocide; The aqueous contaminant release coating composition of claim 1.

9. The composition comprises 50 to 90 wt. % of an aqueous polysiloxane binder emulsion, based on the total weight of the entire composition; The aqueous contaminant release coating composition of claim 1.

10. A method for producing the aqueous contaminant-releasing coating composition of claim 1, comprising: The method comprises the following steps: (i) dispersing at least one pigment or filler in water to produce a dispersion; and subsequently (ii) mixing the dispersion prepared in step (i) with an aqueous polysiloxane binder emulsion to prepare the coating composition. A method comprising:

11. A coating system comprising at least two layers A and B, said layers A and B being adjacent; Layer A is an organic primer layer, Layer B comprises the aqueous contaminant release coating composition of claim 1. Coating system.

12. Layer A is an epoxy primer layer; The coating system of claim 11.

13. Layer A and / or Layer B are cured; 13. The coating system according to claim 11 or 12.

14. 1. A method of applying an aqueous contaminant release coating composition to a substrate, comprising: The method comprises applying, e.g., by spraying, the aqueous contaminant-releasing coating composition of claim 1 to a substrate; curing said coating composition.

15. 12. A substrate coated with the cured aqueous contaminant-release coating composition of claim 1 or the coating system of claim 11.

16. The substrate is a surface of a marine structure, preferably a marine structure that is submerged in use. The substrate of claim 15.

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