Soil release coating

Abstract

The invention provides a soil release coating. The present invention also provides a soil release coating composition comprising: a) a curable polysiloxane-based binder comprising at least 50 wt% of a polysiloxane moiety; b) a scale inhibitor; and c) from 10% to 30% by dry weight of a nonionic hydrophilically modified polysiloxane having i) a hydrophilic-lipophilic balance (HLB) of from 1 to 12, and ii) a Mn of from 500 to 18,000 g / mol.

Description

[0001] This application is a divisional application of the invention patent application with application date of November 27, 2020, application number 202080082611.9, and invention name “Dirt Release Coating”. Technical Field

[0002] The present invention relates to a fouling release coating composition, a method for preparing such a fouling release coating, and a marine structure coated with such a fouling release coating. Background Art

[0003] Surfaces submerged in seawater are subject to fouling by marine organisms such as green and brown algae, slime, barnacles, mussels and tube worms. On marine structures such as vessels (e.g., ships, tankers), oil platforms and buoys, this fouling is harmful and has economic consequences. Fouling can lead to surface biodegradation, increased loads and accelerated corrosion. On ships, fouling can increase frictional drag, which can lead to reduced speed and / or increased fuel consumption. It can also lead to reduced maneuverability.

[0004] In order to prevent the settlement and growth of marine organisms, antifouling paints are used. Traditionally, two types of antifouling paints are used, self-polishing antifouling paints and fouling release antifouling paints.

[0005] Self-polishing antifouling coatings contain an antifouling agent and a binder that gradually dissolves and / or hydrolyzes in seawater, which enables the seawater to erode the coating surface, exposing a new surface. The most successful self-polishing antifouling coatings are based on hydrolyzable binders, such as (meth)acrylate binders with hydrolyzable silyl esters. Gradual hydrolysis in seawater provides controlled release of the antifouling agent from the coating.

[0006] Foul-release antifouling coatings provide a coating with low surface tension and low elastic modulus and work by providing a foul-release surface to which marine organisms do not stick, or if they do stick, they are easily washed off by friction between water and the surface or by cleaning. Such coatings are usually based on polysiloxane-based binders. The foul-release surface created by polysiloxane binders is effective in preventing large foulants from permanently adhering to the surface. However, polysiloxane surfaces do not show good resistance to soft fouling (such as slime and algae) over time.

[0007] Traditionally, polysiloxane-based fouling release coatings (FRCs) have been used without the use of biocides. However, as mentioned above, a challenge faced by FRCs is the adhesion of soft foulants such as slime and algae. It is known that the use of polyether-modified silicone oils in FRCs can reduce the adhesion of slime and algae. In addition, in recent years, the addition of biocides that are effective against slime and algae to FRCs has further improved fouling protection. One biocide that has been found to work well is pyrithione salts such as copper pyrithione. However, FRCs with biocides still have room for improvement, especially in terms of fouling protection, long-term performance and adhesion.

[0008] It has been demonstrated that the addition of biocides provides a number of technical benefits, including antifouling, spray dust reduction, improved storage stability and enhanced antifouling coatings. Specifically, FRCs containing polyether-modified polysiloxane oils have been supplemented by the addition of antifouling agents (e.g., pyrithione salts, such as zinc pyrithione (ZnPt) and copper pyrithione (CuPt)). Antifouling agents (e.g., CuPt) are typically present in an amount of about 5 wt%-7 wt% dry weight while polyether-modified silicone oils are typically present in an amount of about 1 wt%-5 wt% dry weight. However, the addition of solid antifouling agents can have a negative impact on the viscosity of the coating (it increases it). Increased viscosity can typically be compensated by increasing the solvent level (dilution, thinning) to maintain good application performance, but this can result in increased VOCs and associated negative health effects on applicators and increased negative environmental effects. The present invention discloses a method for compensating for the increased viscosity without increasing the solvent content (VOC) of the coating formulation, and in some cases even reducing the VOC of the original composition.

[0009] The present inventors surprisingly found that by incorporating nonionic hydrophilic modified silicone oils having specific parameters (molecular weight and HLB) at relatively high amounts, it is possible to obtain anti-fouling agent-containing fouling release formulations having low VOC, good application properties (viscosity), good film uniformity and improved anti-fouling properties.

[0010] Traditionally, it is believed that polyether-modified silicone oil cannot be used in high amounts in polysiloxane-based fouling release coatings because it results in high polarity, resulting in excessive film water absorption, poor film uniformity and poor adhesion. WO2011 / 076856 teaches a coating with 4wt%-7wt% polyether-modified silicone oil as the optimal level in combination with a copper pyrithione biocide. WO2014 / 077205 teaches a coating comprising 0.13wt% of a polyether-modified silicone oil in combination with a copper pyrithione biocide. It is also argued in WO2014 / 077205 that large amounts of polyether-modified silicone oil (above 10wt%) result in poor adhesion. WO2017 / 009297 discloses a coating composition with 4wt% polyether-modified silicone oil.

[0011] EP2514776 discloses higher dosages of silicone oils but relates to a different binder system based on metal crosslinked organopolysiloxane-thioblock vinyl copolymers. EP2103655 discloses antifouling compositions and has comparative examples using polyether modified silicone oils but with high HLB values ​​(14.5) and in larger amounts (>30 wt% dry weight). We have demonstrated in our examples that such high dosages and high HLB values ​​lead to undesirable results for fouling release coatings. Summary of the invention

[0012] From one aspect, the present invention provides a fouling release coating composition comprising:

[0013] a) a curable silicone-based adhesive comprising at least 50 wt% silicone moieties; b) an antifouling agent; and

[0014] c) 10% to 30% by dry weight of a nonionic hydrophilic modified polysiloxane having

[0015] i) a hydrophile-lipophile balance (HLB) of 1-12, and

[0016] ii) 500-18,000 g / mol of Mn.

[0017] Viewed from another aspect, the present invention provides a fouling release coating composition comprising:

[0018] a) a curable silicone-based adhesive comprising at least 50 wt% silicone moieties; b) an antifouling agent; and

[0019] c) 10% to 30% by dry weight of a nonionic hydrophilic modified polysiloxane having

[0020] i) a hydrophile-lipophile balance (HLB) of 1-12, and

[0021] ii) Mw of 1,000-50,000 g / mol.

[0022] Viewed from another aspect, the present invention provides a fouling release coating composition comprising:

[0023] a) a curable silicone-based adhesive comprising at least 50 wt% silicone moieties; b) an antifouling agent; and

[0024] c) 10% to 30% by dry weight of a nonionic hydrophilic modified polysiloxane having

[0025] i) a relative weight of a hydrophilic portion in the range of 5 wt% to 60 wt%, and

[0026] ii) 500-18,000 g / mol of Mn.

[0027] Viewed from another aspect, the present invention provides a fouling release coating composition comprising:

[0028] a) a curable silicone-based adhesive comprising at least 50 wt% silicone moieties; b) an antifouling agent; and

[0029] c) 10% to 30% by dry weight of a nonionic hydrophilic modified polysiloxane having

[0030] i) a relative weight of a hydrophilic portion in the range of 5 wt% to 60 wt%, and

[0031] ii) Mw of 1,000-50,000 g / mol.

[0032] Viewed from another aspect the invention provides a marine structure comprising on at least a portion of its outer surface a fouling release coating as defined herein.

[0033] Viewed from another aspect, the present invention provides a process for preparing a fouling release coating composition as defined herein, comprising the steps of mixing the following components, usually in at least one solvent:

[0034] a) a curable silicone-based adhesive comprising at least 50 wt% silicone moieties;

[0035] b) antifouling agents; and

[0036] c) 10% to 30% by dry weight of nonionic hydrophilic modified polysiloxane having

[0037] i) HLB of 1-12, and

[0038] ii) Mn of 500-18,000 g / mol and / or Mw of 1,000-50,000 g / mol.

[0039] Viewed from another aspect, the present invention provides a method of preparing a fouling release coating composition as defined herein, comprising the steps of mixing the following components, usually in at least one solvent:

[0040] a) a curable silicone-based adhesive comprising at least 50 wt% silicone moieties;

[0041] b) antifouling agents; and

[0042] c) 10% to 30% by dry weight of nonionic hydrophilic modified polysiloxane having

[0043] i) a relative weight of a hydrophilic portion in the range of 5 wt% to 60 wt%, and

[0044] ii) Mn of 500-18,000 g / mol and / or Mw of 1,000-50,000 g / mol.

[0045] Viewed from another aspect, the present invention provides a kit for preparing a fouling release coating composition as defined herein, comprising:

[0046] (i) a first container containing a curable silicone-based adhesive, an antifouling agent and / or a nonionic hydrophilic modified silicone;

[0047] (ii) a second container containing a crosslinking agent and / or a curing agent and optionally a catalyst;

[0048] (iii) optionally a third container containing a catalyst; and

[0049] (iv) optionally instructions for mixing the contents of the container.

[0050] definition

[0051] As used herein, the term "fouling release composition" or "fouling release coating composition" refers to a composition that, when applied to a surface, provides a fouling release surface to which marine organisms have difficulty permanently attaching.

[0052] As used herein, the term "binder" refers to the film-forming component of the composition. The polysiloxane-based binder of the composition is the primary binder in the composition, i.e., it constitutes at least 50 wt % of the binder present. As used herein, the term "binder" does not include additive oils. Additive oils are not considered film-forming components herein.

[0053] As used herein, the term "paint" refers to a composition comprising a fouling release coating composition as described herein and optionally a solvent ready for use, such as for spraying. Thus, the fouling release coating composition itself can be a paint, or the fouling release coating composition can be a concentrate to which a solvent is added to produce a paint.

[0054] As used herein, the term "polysiloxane" refers to a polymer comprising siloxane, ie, -Si-O- repeating units.

[0055] As used herein, the term "polysiloxane-based adhesive" refers to an adhesive comprising at least 50 wt%, preferably at least 60 wt%, more preferably at least 70 wt% of repeating units comprising the motif -Si-O-, based on the total weight of the polymer. Polysiloxane-based adhesives may comprise up to 99.99 wt% of repeating units comprising the motif -Si-O-, based on the total weight of the polymer. The repeating units -Si-O- may be linked in a single sequence, or alternatively may be interrupted by non-siloxane moieties such as organic-based moieties.

[0056] As used herein, the term "non-degradable silicone-based adhesive" refers to a silicone-based adhesive that does not hydrolytically degrade or corrode in seawater.

[0057] As used herein, the term "alkyl" refers to a linear, branched or cyclic saturated group. The alkyl group may be substituted or unsubstituted.

[0058] As used herein, the term "cycloalkyl" refers to a cyclic alkyl group.

[0059] As used herein, the term "alkylene" refers to a divalent alkyl group.

[0060] As used herein, the term "alkenyl" refers to a linear, branched or cyclic unsaturated group. The alkenyl group may be substituted or unsubstituted.

[0061] As used herein, the term "aryl" refers to a group containing at least one aromatic ring. The term aryl includes heteroaryl groups as well as fused ring systems in which one or more aromatic rings are fused to a cycloalkyl ring. Aryl groups can be substituted or unsubstituted. An example of an aryl group is phenyl, i.e., C6H5. Phenyl groups can be substituted or unsubstituted.

[0062] As used herein, the term "substituted" refers to a group in which one or more, for example up to 6, more specifically 1, 2, 3, 4, 5 or 6 hydrogen atoms in the group are independently replaced by a corresponding number of said substituents. As used herein, the term "optionally substituted" refers to substituted or unsubstituted.

[0063] As used herein, the term "arylalkyl" refers to a group bonded to Si via an alkyl moiety.

[0064] As used herein, the term "polyether" refers to a compound containing two or more -O- bonds interrupted by alkylene units.

[0065] As used herein, the terms "poly(alkylene oxide)", "poly(oxyalkylene) and "poly(alkylene glycol)" all refer to compounds comprising repeating -alkylene-O- units. Typically the alkylene group is ethylene or propylene.

[0066] As used herein, the term "(meth)acrylate" includes methacrylate and acrylate.

[0067] As used herein, the term wt % is based on the dry weight of the coating composition unless otherwise indicated.

[0068] As used herein, the term "PDI" or polydispersity index refers to the ratio of Mw / Mn, where Mw refers to the weight average molecular weight and Mn refers to the number average molecular weight. PDI is sometimes also referred to as D (dispersity).

[0069] As used herein, the term "volatile organic compound (VOC)" refers to compounds having a boiling point of 250°C or less.

[0070] As used herein, "antifouling agent" refers to a biologically active compound or mixture of biologically active compounds that prevents the settlement of marine organisms on a surface and / or prevents the growth of marine organisms on a surface and / or promotes the migration of marine organisms away from a surface. DETAILED DESCRIPTION

[0071] The present invention relates to a fouling release coating composition comprising:

[0072] a) a curable silicone-based adhesive comprising at least 50 wt% silicone moieties;

[0073] b) antifouling agents; and

[0074] c) 10% to 30% by dry weight of nonionic hydrophilic modified polysiloxane having

[0075] i) a hydrophile-lipophile balance (HLB) of 1-12, and

[0076] ii) Mn of 500-18,000 g / mol and / or Mw of 1,000-50,000 g / mol.

[0077] Silicone-based adhesives

[0078] The binder in the fouling release coating composition comprises a curable silicone-based binder component (a). The silicone-based binder is preferably a non-degradable curable silicone-based binder. When the silicone is a non-degradable silicone-based binder, the fouling release coating composition of the present invention provides a pure fouling release coating.

[0079] The polysiloxane-based binder present in the coating composition of the present invention comprises at least 50 wt% polysiloxane moieties, preferably more than 60 wt% polysiloxane moieties, and more preferably more than 70 wt% polysiloxane moieties, such as 99.99 wt% polysiloxane moieties or more. Typical ranges in the polysiloxane-based binder include 50 wt%-100 wt% polysiloxane moieties, 60 wt%-99.999 wt% polysiloxane moieties, or 70 wt%-99.99 wt% polysiloxane moieties.

[0080] The polysiloxane portion is defined as comprising repeating units of the motif -Si-O- based on the total weight of the polysiloxane-based adhesive. The wt% of the polysiloxane portion 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.

[0081] Generally speaking, the wt% of the polysiloxane portion is calculated based on the molar ratio of the reactive starting materials in the polysiloxane synthesis. If there is a molar excess of monomer in the reaction mixture, this molar excess is not calculated. Only those monomers that are able to react based on the stoichiometry of the reaction are calculated.

[0082] Information on the wt% polysiloxane moiety in commercially available polysiloxane-based adhesives is readily available from the suppliers.

[0083] It will be appreciated that the polysiloxane based adhesive can consist of a single repeating sequence of siloxane units, or be interrupted by non-siloxane moieties, such as organic moieties. It is preferred that the polysiloxane based adhesive comprises only Si-O repeating units.

[0084] The organic moiety may include, for example, an alkylene, an arylene, a poly(alkylene oxide), an amide, a thioether, or a combination thereof, preferably the organic moiety may include, for example, an alkylene, an arylene, a poly(alkylene oxide), an amide, or a combination thereof. In a specific embodiment, the polysiloxane-based adhesive does not contain any thio groups.

[0085] The polysiloxane-based binder present in the fouling release coating composition of the present invention can in principle be any curable polysiloxane-based binder. Curable means that the polysiloxane-based binder contains functional groups that enable a crosslinking reaction to occur between the polysiloxane-based binder molecules or is capable of a crosslinking reaction via a crosslinking agent.

[0086] The adhesive based on polysiloxane is preferably an organopolysiloxane with terminal and / or pendant curing reactive functional groups. Each molecule preferably has a minimum of two curing reactive functional groups. Examples of curing reactive functional groups are silanols, alkoxy groups, acetoxy groups, alkenyloxy groups, ketoximes, alcohols, amines, epoxies and / or isocyanates. Preferred adhesives based on polysiloxanes include curing reactive functional groups selected from silanols, alkoxy groups or acetoxy groups. Curing reaction is typically a condensation curing reaction. The adhesive based on polysiloxanes may optionally include more than one type of curing reactive groups and may, for example, be cured by both condensation curing and amine / epoxy curing.

[0087] The silicone-based adhesive may consist of only one type of silicone or a mixture of different silicones.

[0088] The preferred silicone-based binder present in the fouling release coating composition of the present invention is represented by the following formula (D1):

[0089]

[0090] in

[0091] Each R 1 Independently selected from hydroxyl, C 1-6 -alkoxy, C 1-6 -Hydroxyl, C 1-6 -Epoxy groups, C 1-6 Amine or O-Si(R 5 ) 3-z (R 6 ) z

[0092] Each R 2 Independently selected from C 1-10 Alkyl, C 6-10 Aryl, C 7-10 Alkyl aryl or poly (alkylene oxide) and / or as for R 1 The group substituted C 1-6 alkyl;

[0093] R 3 and R 4 Each independently selected from C 1-10 Alkyl, C 6-10 Aryl, C 7-10 Alkyl aryl or poly (alkylene oxide) substituted C 1-6 alkyl;

[0094] Each R 5 is independently a hydrolyzable group such as C 1-6 Alkoxy, acetoxy, alkenyloxy or ketooxy;

[0095] Each R 6 are independently selected from unsubstituted or substituted C 1-6 alkyl;

[0096] z is 0 or an integer from 1 to 2;

[0097] x is an integer at least 2;

[0098] y is an integer of at least 2.

[0099] Preferred R 1 Selected from hydroxyl and O-Si(R 5 ) 3-z (R 6 ) z , where R 5 is a C1-C6 alkoxy group, R 6 It is C 1-6 alkyl, and z is 0 or an integer from 1 to 2. More preferably, R 1 Selected from hydroxyl and O-Si(R 5 ) 3-z (R 6 ) z , where R 5 is a C1-C3 alkoxy group, R 6 It is C 1-3 alkyl and z is 0 or an integer from 1 to 2. Still more preferably R 1 It's a hydroxyl group.

[0100] Preferred R 2 It is C 1-10 Alkyl. 2 More preferably C 1-4 Alkyl, more preferably C 1-2 Preferably each R 2 are the same.

[0101] Preferred R 3 It is C 1-10 Alkyl. 3 More preferably C 1-4 Alkyl, more preferably C 1-2 Preferably each R 3 are the same.

[0102] Preferred R 4 It is C 1-10 Alkyl. 4 More preferably C 1-4 Alkyl, more preferably C 1-2 Preferably each R 4 are the same.

[0103] Still more preferably R1 is a hydroxyl group and R 2 , R 3 and R 4 Each is a methyl group.

[0104] Another preferred silicone-based binder present in the fouling release coating composition of the present invention is represented by the following formula (D2):

[0105]

[0106] in

[0107] Each R 1 Independently selected from hydroxyl, C 1-6 -alkoxy, C 1-6 -Hydroxyl, C 1-6 -Epoxy groups, C 1-6 Amine or O-Si(R 5 ) 3-z (R 6 ) z

[0108] R 2 -R 4 Each is a methyl group;

[0109] Each R 5 are independently hydrolyzable groups, such as C 1-6 Alkoxy, acetoxy, alkenyloxy or ketooxy;

[0110] Each R 6 are independently selected from unsubstituted or substituted C 1-6 alkyl;

[0111] z is 0 or an integer from 1 to 2;

[0112] x is an integer at least 2;

[0113] y is an integer of at least 2.

[0114] Another preferred silicone-based binder present in the fouling release coating composition of the present invention is represented by the following formula (D3):

[0115]

[0116] Where R 1 , R 2 , R 3 , R 4 and x and y are as defined for (D1), R x It is C 2-3Alkyl, each L1 is 0-50, each L2 is 0-50, provided that L1+L2 equals 2-50, preferably 4-40, more preferably 4-20, most preferably 4-10, and L3 is 1-200, preferably 2-100, most preferably 5-50. The polysiloxane portion must account for a minimum of 50 wt% of the molecule.

[0117] It is preferred that the polysiloxane-based adhesive of the present invention is represented by Formula D1.

[0118] Those skilled in the art will appreciate that the polysiloxane-based adhesive may contain small amounts of impurities, such as cyclic siloxanes, such as D4, D5 and D6 cyclosiloxanes, which are residues of polysiloxane synthesis, wherein the name (D4, D5 or D6) refers to the number of repeating Si-O units in the cyclic polysiloxane (i.e., 4, 5 or 6 Si-O repeating units, respectively, in the cyclic polysiloxane). From a health, safety and environmental perspective, it is preferred to limit the amount of cyclic polysiloxane present in the coating. In a preferred embodiment, the polysiloxane-based adhesive contains less than 5%, preferably less than 2%, more preferably less than 1% cyclic polysiloxane. In a particularly preferred embodiment, the polysiloxane-based adhesive does not contain cyclic polysiloxane.

[0119] The weight average molecular weight of the polysiloxane-based binder present in the fouling release coating composition of the present invention is preferably 400-150,000 g / mol, more preferably 1000-120,000 g / mol, and still more preferably 5000-110,000 g / mol.

[0120] In one embodiment, the polysiloxane adhesive (a) does not meet the HLB parameters of the nonionic hydrophilic modified polysiloxane component (c). Specifically, the polysiloxane adhesive may have an HLB value of less than 0.5, such as less than 0.1.

[0121] Preferred coating compositions of the present invention comprise 30 wt% to 95 wt% of a polysiloxane-based binder, more preferably 40 wt% to 90 wt% of a polysiloxane-based binder, and still more preferably 50 wt% to 90 wt% of a polysiloxane-based binder, all based on the total dry weight of the composition.

[0122] Suitable silicone-based adhesives for use in the coating compositions of the present invention are commercially available. Representative commercially available non-degradable silicone-based adhesives include Dow Corning's OHX-0135, OHX-4000, OHX-4010, OHX-4040, OHX-4050, OHX-4060, Evonik's PolymerOH 0.08, PolymerOH 0.75, PolymerOH 1, PolymerOH 2, PolymerOH 3.5, PolymerOH 5, PolymerOH20, PolymerOH 80 and Gelest's DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S42, DMS-S51.

[0123] Antiscalant

[0124] The antifouling coating composition of the present invention comprises an antifouling agent (b).

[0125] The terms antifouling agent, biologically active compound, antiscalant, biocide, poison are used in the industry to describe known compounds used to prevent marine fouling on surfaces. The antifouling agent present in the composition of the present invention is preferably a marine antifouling agent. The antifouling agent may be inorganic, organometallic or organic. Preferably the antifouling agent is an organometallic antifouling agent. Suitable antifouling agents are commercially available.

[0126] Examples of the inorganic antiscalant include copper and copper compounds such as copper oxides, for example, cuprous oxide and cupric oxide; copper alloys, for example, copper-nickel alloys; and copper salts, for example, copper thiocyanate and copper sulfide.

[0127] Examples of organic metal antiscalants include zinc pyrithione; organic copper compounds such as copper pyrithione, copper acetate, copper naphthenate, oxine copper, copper nonylphenolsulfonate, copper bis(ethylenediamine)bis(dodecylbenzenesulfonate) and copper bis(pentachlorophenol); dithiocarbamate compounds such as zinc bis(dimethyldithiocarbamate) [ziram], zinc ethylenebis(dithiocarbamate) [zineb], manganese ethylenebis(dithiocarbamate) [maneb] and manganese ethylenebis(dithiocarbamate) [mancozeb] complexed with zinc salts.

[0128] Examples of organic antifouling agents include heterocyclic compounds such as 2-(tert-butylamino)-4-(cyclopropylamino)-6-(methylthio)-1,3,5-triazine [cybutryne], 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 [benthiazole] 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 acids, sulfonic acids and sulfinic acids, such as N-(dichlorofluoromethane)-1,1-dimethylurea [diuron]; sulfonyl)phthalimide, N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfonamide [dichlofluanid], N-dichlorofluoromethylthio-N',N'-dimethyl-N-toluenesulfonamide [tolylfluanid] and N-(2,4,6-trichlorophenyl)maleimide; other organic compounds such as pyridine triphenylborane [TPBP], amine triphenylborane, 3-iodo-2-propynyl N-butylcarbamate [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.

[0129] Other examples of antiscaling agents include tetraalkylphosphonium halides, halogenides, guanidine derivatives, imidazole-containing compounds such as 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole [metozolin] and its derivatives, macrolides (including avermectins and their derivatives, such as ivermectin, spinosyns and their derivatives such as spinosa, capsaicins and their derivatives such as phenyl capsaicin), and enzymes such as oxidases, enzymes with proteolytic activity, hemicellulolytic activity, cellulolytic activity, lipolytic activity and amylolytic activity.

[0130] Preferred anti-scaling 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 anti-scaling agents are zinc pyrithione and copper pyrithione, especially copper pyrithione.

[0131] In the present invention, FRCs containing nonionic hydrophilically modified polysiloxane oils are typically supplemented by the addition of pyrithione salt biocides (zinc pyrithione (ZnPt) and copper pyrithione (CuPt)). In the patent literature, CuPt is typically present at about 5wt%-7wt% dry weight, while the polyether modified oil is typically present at about 1wt%-5wt% dry weight. However, the addition of solid pyrithione salts with needle-like morphology has a negative impact on the viscosity of the coating (it increases it). The increased viscosity can usually be compensated by increasing the solvent level (thinning) to maintain good application performance, but with an increase in VOC and the associated negative health effects on the applicator and increased negative environmental impacts. The present invention discloses a method for compensating for the increased viscosity without increasing the solvent content (VOC) of the coating formulation, and in some cases even reducing the VOC of the original composition.

[0132] The biocide is typically present in an amount of 1% to 20% of the total coating composition dry weight, preferably 1% to 15%, 2% to 15% or 3% to 12% of the total coating composition dry weight. The use of these antiscalants is known in antiscaling coatings and their use is familiar to the skilled person. The antiscalants may be encapsulated or adsorbed on an inert carrier or combined with other materials to achieve controlled release. These percentages refer to the amount of active antiscalant present and therefore do not refer to any carrier used.

[0133] Nonionic hydrophilic modified polysiloxane

[0134] The coating composition of the present invention comprises a nonionic hydrophilic modified polysiloxane (c). It should be understood that this component is different from the polysiloxane binder component (a). Therefore, the coating composition must include two different components (a) and (c). In one embodiment, the polysiloxane binder (a) does not meet the HLB parameters of the nonionic hydrophilic modified polysiloxane component (c). Specifically, the polysiloxane binder can have an HLB value of less than 0.5, such as less than 0.1.

[0135] It should be understood that the nonionic hydrophilic modified polysiloxane does not contain reactive groups that react with the binder or crosslinker during the curing reaction at the relevant curing temperature (0-40° C.) Therefore, the nonionic hydrophilic modified polysiloxane is intended to be non-reactive in the curing reaction, especially with respect to the binder component.

[0136] It should be understood that the hydrophilic modified polysiloxane is selected so that it does not contain any groups that will react with the binder or the crosslinking agent (if present in the curing reaction) according to the curing reactive groups on the binder. Therefore, the non-ionic hydrophilic modified polysiloxane is a non-curable component in the coating composition. Non-curable herein means that the non-ionic hydrophilic modified polysiloxane does not react with the binder or the crosslinking agent during the curing reaction in the temperature range of 0-40°C.

[0137] In a preferred embodiment, the nonionic hydrophilic modified polysiloxane does not contain silicone reactive groups such as SiOH groups, Si-OR (alkoxy), alkenyloxy, ketoxime groups, etc. that are capable of reacting with the binder or crosslinker (if present) at the relevant curing temperature (0-40°C).

[0138] In a specific embodiment, the nonionic hydrophilic modified polysiloxane does not contain any Si-OH groups or Si-OR (alkoxy, ie, R=alkyl) groups.

[0139] Due to the content of both hydrophilic group and lipophilic group in the same molecule, nonionic hydrophilic modified polysiloxane is widely used as surfactant and emulsifier.Nonionic hydrophilic modified polysiloxane according to the present invention is a polysiloxane that is modified with nonionic hydrophilic group and is more hydrophilic than the corresponding unsubstituted polysiloxane with the same number of polysiloxane units.This hydrophilicity can be obtained by modification with nonionic hydrophilic group such as ethers (for example, polyoxyalkylene groups such as polyethylene glycol and polypropylene glycol), alcohols (for example, poly(glycerol)), amides (for example, pyrrolidone, polyvinylpyrrolidone, (methyl) acrylamide), acids (for example, carboxylic acid, poly(methyl) acrylic acid), amines (for example, polyvinylamine, (methyl) acrylic acid polymers comprising amino groups).Generally speaking, this nonionic hydrophilic modified polysiloxane is oil.

[0140] "Nonionic" herein means that the hydrophilic modified polysiloxane does not contain any salt moieties; specifically, it generally does not contain any metal cations.

[0141] The hydrophilicity of the nonionic hydrophilic modified polysiloxane is determined according to the HLB (hydrophilic-lipophilic balance) parameter. The HLB (hydrophilic-lipophilic balance value) of the nonionic hydrophilic modified polysiloxane of the present invention is 1-12, preferably 1.0-10, more preferably 1.0-8.0, and most preferably 2.0-7.0. In a specific embodiment, the nonionic hydrophilic modified polysiloxane has an HLB in the range of 3.0-6.0.

[0142] The HLB is generally determined herein according to the Griffin model using the equation "hydrophilic group wt%" / 5 (reference: Griffin, WC Calculation of HLB values ​​of non-ionic surfactants, J.Soc.Cosmet.Chem.1954,5,249-256). Therefore, in a specific embodiment, the HLB is calculated according to the equation HLB='hydrophilic group wt%' / 5. The HLB parameter is a recognized parameter for non-ionic surfactants and can be easily obtained from suppliers of commercially available non-ionic hydrophilic modified polysiloxanes. The higher the HLB value of the surfactant, the stronger the hydrophilicity. The hydrophilic group wt% refers to the weight percentage of the hydrophilic group in the non-ionic hydrophilic modified polysiloxane. The hydrophilic group wt% can be converted into the HLB value, and vice versa. For example, an HLB value of 1-12 is equivalent to a hydrophilic group wt% of 5wt%-60wt%.

[0143] The role of the nonionic hydrophilic modified polysiloxane is to promote the dissolution and migration of the biocide to the coating surface. In addition, it is well known that the formation of a hydration layer at the coating-water interface is important for antifouling performance.

[0144] If the hydrophilicity of the nonionic hydrophilic modified polysiloxane is too high, for example, due to a large number of hydrophilic groups in the molecule, this may lead to premature depletion of the biocide and the nonionic hydrophilic modified polysiloxane due to a high leaching rate. High hydrophilicity can also lead to poor compatibility with the polysiloxane-based adhesive matrix, especially if high oil levels (over 10 wt%) are used, resulting in poor film uniformity and poor adhesion.

[0145] Methods for controlling the leaching rate of the biocide and the nonionic hydrophilic modified polysiloxane include the molecular weight, hydrophilicity and miscibility with the binder of the nonionic hydrophilic modified polysiloxane. Very low molecular weight nonionic hydrophilic modified polysiloxanes tend to allow high leaching rates, while too high molecular weights may not allow the leaching of the biocide and nonionic hydrophilic modified polysiloxane to reach the desired rate.

[0146] Therefore, in a preferred embodiment, the nonionic hydrophilic modified polysiloxane has a number average molecular weight (Mn) in the range of 500-18,000 g / mol, such as in the range of 1000-16,000 g / mol, in particular in the range of 2000-15,050 g / mol or 4000-15,050 g / mol. Further suitable Mn ranges for nonionic hydrophilic modified polysiloxanes include 500-15,000 g / mol, 1,000-13,000 g / mol or 3,000-10,000 g / mol. The number average molecular weight (Mn) values ​​referred to herein correspond to experimentally obtained values, for example, measured by GPC relative to polystyrene standards. The method is given in the experimental section below.

[0147] In a preferred embodiment, the nonionic hydrophilic modified polysiloxane has a weight average molecular weight (Mw) of 1,000-50,000 g / mol, preferably 2,000-45,000 g / mol, 3,000-42,000 g / mol, 4,000-40,000 g / mol, or 5,000-40,000 g / mol. Further suitable ranges include 5,000-30,000 g / mol, for example, 5,000-25,000 g / mol or 10,000-20,000 g / mol. The weight average molecular weight (Mw) values ​​referred to herein correspond to experimentally obtained values, for example, measured by GPC relative to polystyrene standards. The method is given in the experimental section below.

[0148] The specific range of Mn or Mw is important for the beneficial properties of the present invention. In fact, these molecular weights affect the viscosity, which in turn affects the ease of application and surface roughness. These molecular weights also affect the migration of biocides and nonionic hydrophilic modified polysiloxanes to the surface of the coating film, which in turn affects the antifouling properties.

[0149] It would also be preferred if the nonionic hydrophilic modified polysiloxane has a viscosity in the range of 20-4,000 mPa-s, such as in the range of 30-3,000 mPa-s, especially in the range of 50-2,500 mPa-s, when measured according to the method given in the experimental section.

[0150] The amount of nonionic hydrophilic modified polysiloxane included in the coating composition is also an important parameter. Too low an amount will produce a coating composition with high viscosity, which in turn may lead to poor application performance. Alternatively, more solvent needs to be added, thereby providing a coating composition with a higher VOC. Low amounts of nonionic hydrophilic modified polysiloxane may also result in poor long-term antifouling of the coating because the nonionic hydrophilic modified polysiloxane may be exhausted from the film prematurely. Too high an amount of nonionic hydrophilic modified polysiloxane results in poor film uniformity and poor antifouling performance.

[0151] The content of the nonionic hydrophilic modified polysiloxane in the coating composition is 10wt%-30wt% dry weight (e.g., 10wt%-25wt% dry weight), preferably 11wt%-29wt% dry weight, preferably 12wt%-28wt% dry weight, preferably 13wt%-27wt% dry weight, preferably 14wt%-26wt% dry weight, e.g., 15wt%-25wt% dry weight). When two or more different types of nonionic hydrophilic modified polysiloxanes are present, these amounts refer to the sum of the nonionic hydrophilic modified polysiloxane components.

[0152] Of particular interest are those nonionic hydrophilic modified polysiloxanes in which the relative weight of the hydrophilic portion (e.g., polyether group) is 5% or more (e.g., 5%-60%) of the total weight, for example, 6% or more (e.g., 6%-50%), and particularly 10% or more (e.g., 10%-40%) of the total weight of the nonionic hydrophilic modified polysiloxane. Other suitable ranges of the relative weight of the hydrophilic portion in the nonionic hydrophilic modified polysiloxane include 5 wt%-60 wt%, preferably 5 wt%-50 wt%, more preferably 5 wt%-40 wt%, most preferably 10 wt%-35 wt%, and particularly 15 wt%-30 wt%.

[0153] The wt% of the hydrophilic portion can be calculated based on the stoichiometric ratios of the starting materials in the synthesis of the nonionic hydrophilically modified polysiloxane, or can be determined using analytical techniques such as IR or NMR.

[0154] If there is a molar excess of reactants, this molar excess is not calculated in determining the wt% of the hydrophilic portion. Only those monomers that can react according to the stoichiometry of the reaction are calculated.

[0155] If the HLB is known, the wt% of the hydrophilic portion can also be calculated according to the Griffin model using the formula HLB = "hydrophilic group wt%" / 5.

[0156] The nonionic hydrophilic modified polysiloxane may contain small amounts of impurities, such as cyclic siloxanes, such as D4, D5 and D6 cyclosiloxanes, which are residues of polysiloxane synthesis, wherein the names (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 polysiloxane present in the coating composition. In a preferred embodiment, the nonionic hydrophilic modified polysiloxane contains less than 5% of cyclic polysiloxane, preferably less than 2%, more preferably less than 1%. In a particularly preferred embodiment, the nonionic hydrophilic modified polysiloxane does not contain cyclic polysiloxane.

[0157] In a preferred embodiment, the nonionic hydrophilic modified polysiloxane is a polyether modified polysiloxane, that is, the hydrophilic part is a polyether group.

[0158] Preferably the polyether group comprises at least 3 repeating units, such as at least 5 repeating units. In many interesting embodiments, the oligomer or polymer comprises 5-100 repeating units, such as 5-50, or 8-50, or 8-20 repeating units.

[0159] In some preferred embodiments, the polyether group (ie, oligomeric or polymeric group) has a number average molecular weight (n) in the range of 100-2500 g / mol, such as in the range of 200-2000 g / mol, particularly in the range of 300-2000 g / mol, or in the range of 400-1000 g / mol.

[0160] Of particular interest are those polyether-modified polysiloxanes in which the relative weight of the polyether portion is 5% or more (e.g., 5%-60%) of the total weight, for example, 6% or more (e.g., 6%-50%), and particularly 10% or more (e.g., 10%-40%) of the total weight of the polyether-modified polysiloxane.

[0161] In one variation thereof, the polyether-modified polysiloxane is a polysiloxane having poly(oxyalkylene) chains grafted thereto. An illustrative example of the structure of such a polyether-modified polysiloxane is formula (A):

[0162]

[0163] Each R 7 Independently selected from C 1-5 - alkyl (including straight-chain or branched hydrocarbon groups) and aryl (e.g., phenyl (-C6H5)), especially methyl;

[0164] Each R 8 Independently selected from -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 -H, methyl and -C(=O)CH3;

[0165] Each R 9 Independently selected from C 2-5-alkylene (e.g., -CH2CH2-, -CH2CH(CH3), -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH(CH2CH3)-), arylene (e.g., 1,4-phenylene), and C substituted with aryl 2-5 -alkylene (e.g., 1-phenylethylene), specifically selected from C 2-5 -alkylene, such as -CH2CH2- and -CH2CH(CH3)-);

[0166] k is 0-240, l is 1-60, k+l is 1-240; and

[0167] n is 0-50, m is 0-50, and m+n is 1-50.

[0168] Especially R. 7 It is methyl;

[0169] Each R 8 Independently selected from -H or C 1-4 -alkyl or -C(=O)CH3;

[0170] Each R 9 is -CH2CH2-, or -CH2CH2CH2-, or -CH2CH(CH3)-);

[0171] k is 0-240, l is 1-60, k+l is 1-240; and

[0172] n is 0-50, m is 0-50, and m+n is 1-50.

[0173] Prefer all R 7 The groups are the same.

[0174] Examples of commercially available polyether-modified polysiloxanes of this type are KF352A, KF353, KF945, KF6012, KF6017 from ShinEtsu, XIAMETER OFX-5220, DOWSIL OFX-5247, XIAMETER OFX-5329, XIAMETER OFX-5330 from Dow.

[0175] In another variation of the present invention, the polyether-modified polysiloxane is a polysiloxane having a poly(oxyalkylene) chain incorporated into its main chain. An illustrative example of such a hydrophilic modified polysiloxane structure is formula (B):

[0176]

[0177] Each R 7 Independently selected from C 1-5- alkyl (including straight-chain or branched hydrocarbon groups) and aryl (e.g., phenyl (-C6H5)), especially methyl;

[0178] Each R 8 Independently selected from -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 -H, methyl and -C(=O)CH3;

[0179] Each R 9 Independently selected from C 2-5 -alkylene (e.g., -CH2CH2-, -CH2CH(CH3)-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH(CH2CH3)-), arylene (e.g., 1,4-phenylene), and C substituted with aryl 2-5 -alkylene (e.g., 1-phenylethylene), specifically selected from C 2-5 -alkylene, for example, -CH2CH2- and -CH2CH(CH3)-);

[0180] k is 0-240;

[0181] n is 0-50, m is 0-50, and m+n is 1-50.

[0182] Specifically, R 7 It is methyl;

[0183] Each R 8 Independently selected from -H or C 1-4 -alkyl or -C(=O)CH3;

[0184] Each R 9 is -CH2CH2-, -CH2CH(CH3)- or -CH2CH2CH2-;

[0185] k is 0-240;

[0186] And n is 0-50, m is 0-50, and m+n is 1-50.

[0187] Prefer all R 7 The groups are the same.

[0188] Commercially available hydrophilic modified polysiloxanes of this type include DOWSIL 2-8692 and XIAMETER OFX-3667 from DOW.

[0189] In yet another variation, the polyether-modified polysiloxane is a polysiloxane having polyoxyalkylene chains incorporated into its main chain and having polyoxyalkylene chains grafted thereon. An illustrative example of such a hydrophilic modified polysiloxane structure is formula (C):

[0190]

[0191] Each R 7 Independently selected from C 1-5 - alkyl (including straight-chain or branched hydrocarbon groups) and aryl (e.g., phenyl (-C6H5)), especially methyl;

[0192] Each R 8 Independently selected from -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 -H, methyl and -C(=O)CH3;

[0193] Each R 9 Independently selected from C 2-5 -alkylene (e.g., -CH2CH2-, -CH2CH(CH3)-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH(CH2CH3)-), arylene (e.g., 1,4-phenylene), and C substituted with aryl 2-5 -alkylene (e.g., 1-phenylethylene), specifically selected from C 2-5 -alkylene, such as -CH2CH2- and -CH2CH(CH3)-);

[0194] k is 0-240, l is 1-60, and k+l is 1-240;

[0195] n is 0-50, m is 0-50, and m+n is 1-50.

[0196] Specifically, R 7 It is methyl;

[0197] Each R 8 Yes -H, or C 1-4 -alkyl or -C(=O)CH3;

[0198] Each R 9 is -CH2CH2-, -CH2CH2CH2- or -CH2CH(CH3)-;

[0199] k is 0-240, y is 1-60, and x+y is 1-240;

[0200] n is 0-50, m is 0-50, and m+n is 1-50.

[0201] In the above structures (A), (B) and (C), the groups -CH2CH(CH3)-, -CH2CH(CH2CH3)-, etc. can exist in either of two possible orientations. Similarly, it should be understood that the k and l-th occurrences of the segments are generally randomly distributed in the polysiloxane structure.

[0202] In these embodiments and variations, the polyether or poly(oxyalkylene) is preferably selected from polyethylene oxide, polypropylene oxide and poly(oxyethylene-co-oxypropylene), which are sometimes referred to as polyethylene glycol, polypropylene glycol and poly(ethylene glycol-co-propylene glycol). Thus, in the above structures (A), (B) and (C), each R connecting two oxygen atoms is 9 Preferably, it is selected from -CH2CH2- and -CH2CH(CH3)-, and each R connecting the silicon atom and the oxygen atom is 9 Preferably selected from C 2-5 -alkyl.

[0203] In some embodiments of the above structures (A), (B) and (C), R 8 Preferably it is not hydrogen.

[0204] It should be understood that the one or more polyether-modified polysiloxanes may be of different types, for example, two or more of the types described above.

[0205] In another preferred embodiment, the nonionic hydrophilic modified polysiloxane comprises a polyglycerol group or a pyrrolidone group.

[0206] Crosslinking agent and / or curing agent

[0207] As mentioned above, the adhesive based on polysiloxane of the present invention is curable and contains curing reactive functional groups, such as silanol, carbinol, carboxyl, ester, hydride, alkenyl, vinyl ether, allyl ether, alkoxysilane, ketoxime, amine, epoxy resin, isocyanate and / or alkoxy. Preferably, the adhesive based on polysiloxane comprises at least two curing reactive functional groups. Alternatively, the adhesive based on polysiloxane comprises more than one type of curing reactive functional groups. Preferably, the adhesive based on polysiloxane comprises a single type of curing reactive functional groups. Suitable crosslinking agents and / or curing agents are selected according to the curing reactive functional groups present in the adhesive based on polysiloxane.

[0208] In preferred polysiloxane-based adhesives, the curing reactive functional groups are silanols, carbinols, alkoxysilanes, isocyanates, amines and / or epoxies. In still further preferred polysiloxane-based adhesives, the curing reactive functional groups are silanols, carbinols and / or alkoxysilanes.

[0209] It may be necessary to add a crosslinking agent to obtain the desired crosslinking density. If 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 condensation product thereof, or a mixture of the two:

[0210] R d -Si-K 4-d

[0211] in,

[0212] Each R is independently selected from unsubstituted or substituted monovalent hydrocarbon groups of 1 to 6 carbon atoms, C substituted by poly(alkylene oxide) 1-6 Alkyl or (O-(CR D 2) r' ) r1' -(O-(CR D 2) s' ) s1' -(Si(R PP )2-O) t' -Si(R PP )3 polysiloxane; wherein r', r1', s' and s1' are integers of 0-10, each R D Independently selected from H or C 1-4 Alkyl, each R PP Independently selected from C 1-10 Alkyl, C 6-10 Aryl, C 7-10 Alkyl aryl, and t' is an integer from 1 to 50;

[0213] Each K is independently selected from a hydrolyzable group, such as an alkoxy group; and d is 0, 1 or 2, more preferably 0 or 1.

[0214] Preferred crosslinking agents of this type include tetraethoxysilane, vinyltri(methylethyloxime)silane, methyltri(methylethyloxime)silane, vinyltrimethoxysilane, methyltrimethoxysilane and vinyltriisopropenoxysilane and hydrolysis-condensation products thereof.

[0215] If the cure-reactive functional groups are di- or trialkoxy groups, a separate crosslinking agent is generally not required.

[0216] The crosslinking agent is preferably present in an amount of 0-10 wt% based on the total dry weight of the coating composition. Suitable crosslinking agents are commercially available, such as Silcate TES-40WN from Wacker and Dynasylan A from Evonik.

[0217] If the curing reactive functional group is a methylol (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, for example, be based on diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) chemistry. For example, these are provided by Covestro under the trade name Desmodur and by Vencorex under Tolonate. Examples of polyisocyanates include Desmodur N3300, Desmodur 3390BA / SN, Desmodur N3400, Desmodur N3600, Desmodur N75, DesmodurXP2580, Desmodur Z4470, Desmodur XP2565 and Desmodur VL provided by Covestro.

[0218] Polyisocyanates can be prepared with different NCO functionalities. The NCO functionality is the amount of NCO groups per polyisocyanate molecule or isocyanate prepolymer molecule. Polyisocyanate curing agents with different NCO functionalities can be used.

[0219] The curing agent is preferably present in an amount of 0.8-2.5 equiv. NCO groups relative to the amount of hydroxyl groups, preferably 0.9-2.0 equiv., more preferably 0.95-1.7 equiv., and even more preferably 1-1.5 equiv.

[0220] If the curing reactive functional group is an amine, epoxy or isocyanate, then the curing agent is preferably amine, sulfur or epoxy functional.

[0221] The curing agent can also be, for example, a dual curing agent comprising both amine / sulfur / epoxy / isocyanate and alkoxysilane. A preferred dual curing agent is represented by the following general formula:

[0222]

[0223] in

[0224] LL is independently selected from unsubstituted or substituted monovalent hydrocarbon groups of 1 to 6 carbon atoms;

[0225] Each M is independently selected from a hydrolyzable group such as an alkoxy group;

[0226] a is 0, 1 or 2, preferably 0 or 1;

[0227] b is an integer from 1 to 6; and

[0228] Fn is an amine, epoxy, glycidyl ether, isocyanate or thiol group.

[0229] Preferred examples of such dual curing agents include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, (3-glycidoxypropyl)trimethoxysilane, 3-mercaptopropyltrimethoxysilane. A particularly preferred curing agent is 3-aminopropyltriethoxysilane, such as Dynasylan AMEO from Evonik.

[0230] This type of dual curing agent can be used as a separate curing agent or for end-capping the polysiloxane-based adhesive, so that the end groups of the polysiloxane-based adhesive are modified before the curing reaction. For example, the mixing of the polysiloxane-based adhesive and the curing agent can be carried out shortly before the coating is applied to the article, for example, 1 hour or less before the coating or the polysiloxane-based adhesive can be provided in a curable form but kept dry to prevent premature curing. In some compositions, it is preferred that the curing agent / end-capping agent is provided in the remainder of the coating composition respectively to prevent curing before the coating is applied to the object. Therefore, the coating composition of the present invention can be provided as a multi-pack (preferably three-pack) preparation to be discussed in more detail below.

[0231] catalyst

[0232] In order to assist the curing process, the coating composition of the present invention preferably comprises a catalyst. Representative examples of catalysts that can be used include transition metal compounds, metal salts and various metals such as organometallic complexes of tin, iron, lead, barium, cobalt, zinc, antimony, cadmium, manganese, chromium, nickel, aluminum, gallium, germanium, titanium, boron, lithium, potassium, bismuth and zirconium. The salt is preferably a long-chain carboxylate and / or a chelate or an organometallic salt.

[0233] Examples of suitable tin-based catalysts include, for example, dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin diacetate, dibutyltin 2-ethylhexanoate, dibutyltin dineodecanoate, dibutyltin dimethoxy, dibutyltin dibenzoate, dibutyltin acetylacetonate, dibutyltin acetylacetonate, dibutyltin alkyl acetylacetonates, dioctyltin dilaurate, dioctyltin dioctoate, dioctyltin diacetate, dioctyltin 2-ethylhexanoate, dioctyltin dineodecanoate, dioctyltin dimethoxy, dioctyltin dibenzoate, dioctyltin acetylacetonate, dioctyltin acetylacetonate, dioctyltin alkyl acetylacetonates, dimethyltin dibutyrate, dimethyltin dineodecanoate, dimethyltin dineodecanoate, tin naphthenate, tin butyrate, tin oleate, tin caprylate ... Tin octanoate, tin stearate, triethyltin tartrate, isobutyltin triceroate and tin octoate. 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. Preferred tin catalysts are dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin diacetate, dioctyltin dilaurate and dibutyltin dioctanoate.

[0234] Examples of suitable zinc catalysts are zinc 2-ethylhexanoate, zinc naphthenate and zinc stearate. Examples of commercially available zinc catalysts include K-KAT XK-672 and K-KAT670 from King Industries and BorchiKat 22 from Borchers.

[0235] Examples of suitable bismuth catalysts include organic bismuth compounds such as bismuth 2-ethylhexanoate, bismuth octanoate and bismuth neodecanoate. Examples of commercially available organic bismuth catalysts include Borchi Kat 24 and Borchi Kat 315 from Borchers, K-KAT XK-651 from King Industries, Reaxis C739E50 from Reaxis and TIB KAT716 from TIB Chemicals.

[0236] Examples of suitable titanium catalysts include organic titanium catalysts such as titanium naphthenate, tetrabutyl titanate, tetra(2-ethylhexyl) titanate, triethanolamine titanate, tetra(isopropyleneoxy)-titanate, titanium tetrabutyrate, titanium tetrapropionate, titanium tetraisopropionate and chelated titanates such as diisopropyl bis(acetylacetonato) titanate, diisopropyl bis(ethylacetylacetonato) titanate and diisopropoxy titanium bis(ethylacetoacetate). Examples of suitable commercially available titanium catalysts include TyzorIBAY from Dorf Ketal and TIB KAT 517 from TIB Chemicals.

[0237] Other suitable catalysts are iron catalysts such as iron stearate and iron 2-ethylhexanoate, lead catalysts such as lead octoate and lead 2-ethyloctoate, cobalt catalysts such as cobalt 2-ethylhexanoate and cobalt naphthenate, manganese catalysts such as manganese 2-ethylhexanoate and zirconium catalysts such as zirconium naphthenate, tetrabutyl zirconate, tetra(2-ethylhexyl) zirconate, triethanolamine zirconate, tetra(isopropyleneoxy)zirconate, zirconium tetrabutanoate, zirconium tetrapropanoate and zirconium tetraisopropanoate.

[0238] Other suitable catalysts are zirconates.

[0239] The catalyst may also be an organic compound such as triethylamine, guanidine, amidine, cyclic amine, tetramethylethylenediamine, 1,4-ethylenepiperazine and pentamethyldiethylenetriamine. Other examples include aminosilanes such as 3-aminopropyltriethoxysilane and N,N-dibutylaminomethyl-triethoxysilane.

[0240] In a preferred embodiment, the catalyst is a tin, bismuth and / or zinc catalyst, more preferably a tin and / or bismuth catalyst.

[0241] Preferably the catalyst is present in the coating composition of the present invention in an amount of 0.01 wt% to 5 wt%, more preferably 0.05 wt% to 4 wt%, based on the total dry weight of the coating composition.

[0242] Additive oil

[0243] The coating composition of the present invention optionally comprises an additive oil. Preferably, the coating composition of the present invention comprises 0-30 wt%, more preferably 0.1 wt%-15 wt% of an additive oil based on the solid content of the coating composition. The nonionic hydrophilic modified polysiloxane described herein is not considered an "additive oil". Therefore, an additive oil is an oil different from the nonionic hydrophilic modified polysiloxane described herein.

[0244] Suitable non-reactive additive oils are silicone oils such as methylphenyl silicone oil, petroleum, polyolefin oils, polyaromatic compound oils, fluororesins such as polytetrafluoroethylene or fluid fluorinated alkyl or alkoxy polymers, or lanolin and lanolin derivatives disclosed in WO2013024106A1 and other sterols and / or sterol derivatives or combinations thereof. Preferred non-reactive additive oils are methylphenyl silicone oils.

[0245] Another additive oil that may be optionally present in the coating composition of the present invention is a fluorinated amphiphilic polymer / oligomer as described in WO2014131695.

[0246] The coating composition of the present invention may optionally contain a hydrophilically modified additive oil. The hydrophilically modified additive oil may be a hydrophilically modified sterol and / or sterol derivative as described in WO2016004961 or a hydrophilically modified acrylic polymer as described in WO2019101920 and WO2019101912.

[0247] The non-reactive hydrophilic modified additive oil is usually modified by adding nonionic monomeric, oligomeric or polymeric groups that are polar and / or capable of hydrogen bonding, enhancing their interaction with polar solvents, particularly water, or with other polar oligomeric or polymeric groups. Examples of these groups include: amides (e.g., pyrrolidone, poly(vinylpyrrolidone), poly[N-(2-hydroxypropyl)methacrylamide]), poly(N,N-dimethylacrylamide), acids (e.g., poly(acrylic acid)), alcohols (e.g., poly(glycerol), polyHEMA, polysaccharides, poly(vinyl alcohol)), ketones (polyketones), aldehydes (e.g., poly(aldehyde-guluronic acid), amines (e.g., polyvinylamine), esters (e.g., polycaprolactone, poly(vinyl acetate)), imides (e.g., poly(2-methyl-2-oxazoline)), etc., including copolymers of the above.

[0248] Adhesion promoter

[0249] Optionally, in addition to the polysiloxane-based adhesive, a co-binder may also be present in the coating composition of the present invention. Preferably, the co-binder contains a curing reactive group that can react with the polysiloxane-based adhesive in the curing reaction. Representative examples of such co-binders include silicone resins, silicone-epoxy resins, silicone-polyester resins, polyurethane-based adhesives, polyol-based adhesives such as acrylic acid-polyol adhesives, polyester-based adhesives, and acrylic acid-based adhesives.

[0250] pigment

[0251] The coating composition of the present invention preferably comprises one or more pigments. The pigment may be an inorganic pigment, an organic pigment or a mixture thereof. Inorganic pigments are preferred. The pigment may be surface treated.

[0252] Representative examples of pigments include black iron oxide, red iron oxide, yellow iron oxide, titanium dioxide, zinc oxide, carbon black, graphite, molybdate red, molybdate yellow, zinc sulfide, antimony oxide, sodium aluminum sulfosilicate, quinacridone, phthalocyanine blue, phthalocyanine green, indanthrone blue, cobalt aluminum oxide, carbazole dioxazine, isoindoline orange, bis-acetoaceto-tolidiole, benzimidazolone, quinophthalone 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 a preferred embodiment, the titanium dioxide surface is treated with a silicone compound, a zirconium compound or a zinc compound.

[0253] The amount of pigment present in the coating composition of the present invention is preferably 0-25 wt%, more preferably 0.5 wt%-15 wt%, based on the total dry weight of the coating composition.

[0254] Solvents

[0255] The fouling release coating composition of the present invention preferably comprises a solvent. Suitable solvents for use in the composition of the present invention are commercially available.

[0256] Examples of suitable organic solvents and thinners are aromatic hydrocarbons, such as xylene, toluene, mesitylene; ketones, such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, cyclopentanone, cyclohexanone; esters, such as butyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, ethylene glycol methyl ether acetate, propylene glycol methyl ether acetate; ethers, such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, dioxane, tetrahydrofuran; alcohols, such as n-butanol, isobutanol, benzyl alcohol; ether alcohols, such as butoxyethanol, 1-methoxy-2-propanol; aliphatic hydrocarbons, such as white spirit; and optionally mixtures of two or more solvents and thinners.

[0257] The amount of solvent present in the fouling release coating composition of the present invention is preferably as low as possible, as this will minimize the VOC content. Preferably, the solvent is present in the composition of the present invention in an amount of 0-35 wt%, more preferably 1 wt%-30 wt%, based on the total weight of the composition. The skilled person will understand that the solvent content will vary depending on the other components present.

[0258] filler

[0259] The coating composition of the present invention may optionally contain a filler.

[0260] Examples of suitable fillers for use in the coating compositions according to the invention are zinc oxide, barium sulfate, calcium sulfate, calcium carbonate, silicon oxide or silicates (e.g., talc, feldspar, china clay and nepheline syenite), including fumed silica, bentonite and other clays, and solid silicone resins, which are generally condensed branched polysiloxanes. Some fillers such as fumed silica may have a thickening effect on the coating composition.

[0261] The 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 include Cabot's TS-610, TS-530, EH-5, H-5 and M-5 and Evonik's R972, R974, R976, R104, R202, R208, R805, R812, 816, R7200, R8200, R9200, R711.

[0262] The amount of filler present in the coating composition of the present invention is preferably 0-25 wt%, more preferably 0.1 wt%-10 wt%, and even more preferably 0.15 wt%-5 wt%, based on the total dry weight of the coating composition.

[0263] additive

[0264] The coating composition of the present invention may optionally contain one or more additives. Examples of additives that can be present in the coating composition of the present invention include reinforcing agents, thixotropic agents, thickeners, anti-settling agents, dehydrating agents, dispersants, wetting agents, surfactants, binders, plasticizers and dyes.

[0265] Examples of thixotropic agents, thickeners and anti-settling agents are silicon oxides, such as fumed silica, organic modified clays, amide waxes, polyamide waxes, amide derivatives, polyethylene waxes, oxidized polyethylene waxes, hydrogenated castor oil waxes and mixtures thereof. Based on the total dry weight of the composition, 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 wt %-6 wt %, and even more preferably 0.1 wt %-2.0 wt %.

[0266] Dehydrating agents and desiccants that can be used in the fouling release coating composition include organic and inorganic compounds. Dehydrating agents can be hygroscopic materials that absorb water or combine water to form water of crystallization, commonly known as desiccants. Examples of desiccants include calcium sulfate hemihydrate, anhydrous calcium sulfate, anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous zinc sulfate, molecular sieves and zeolites. Dehydrating agents can be compounds that react chemically with water. Examples of dehydrating agents that react with water include orthoesters such as trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, triisopropyl orthoformate, tributyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, tributyl orthoacetate, and triethyl orthopropionate; ketals; acetals; enol ethers; orthoborates such as trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate, and tri-tert-butyl borate; organosilanes such as trimethoxymethylsilane, vinyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, and polyethyl silicate.

[0267] Preferably, the dehydrating agent is present in the composition of the present invention in an amount of 0-5 wt%, more preferably 0.5 wt%-2.5 wt%, still more preferably 1.0 wt%-2.0 wt%, based on the total dry weight of the composition.

[0268] Composition and coating

[0269] The invention also relates to a process for the preparation of the above-mentioned composition, wherein the components present in the composition are mixed. Any conventional production process can be used.

[0270] Compositions as described herein can be prepared in, for example, suitable concentrations for spraying. In this case, the composition itself is a kind of coating (paint). Alternatively, the composition can be a concentrate for preparing a coating. In this case, additional solvents and optional other components are added to the composition as described herein to form a coating. Preferred solvents are as described above for the composition.

[0271] After mixing, and optionally after adding a solvent, the fouling release coating composition or coating is preferably filled into a container. Suitable containers include cans, drums and tanks.

[0272] The descaling coating composition can be provided in the form of a single pack, a double pack or a triple pack. Preferably, the composition is provided in the form of a two pack or a three pack, more preferably in the form of a three pack.

[0273] When provided in a single-pack form, the composition is preferably provided in an easily pre-mixed or ready-to-use form. Optionally, the single-pack product may be thinned with a solvent prior to application.

[0274] When provided as a two-pack, the first container preferably contains the polysiloxane-based adhesive, nonionic hydrophilic modified polysiloxane and anti-fouling agent; the second container preferably contains the crosslinking agent / curing agent and / or catalyst. Instructions for mixing the container contents may optionally be provided.

[0275] When provided as a three-pack, the first container preferably contains the silicone-based adhesive, anti-fouling agent, and nonionic hydrophilic modified silicone; the second container preferably contains the crosslinker / curing agent; and the third container preferably contains the catalyst. Instructions for mixing the container contents may optionally be provided.

[0276] In one embodiment, the present invention provides a kit for preparing a soil release composition as defined herein.

[0277] The fouling release coating compositions and coatings of the present invention preferably have a solids content of 50 wt% to 99 wt%, more preferably 60 wt% to 99 wt%, and even more preferably 65 wt% to 99 wt%.

[0278] Preferably, the fouling release coating composition and coating of the present invention have a volatile organic compound (VOC) content of 50-400 g / L, preferably 50-350 g / L, for example, 50-350 g / L. The VOC content can be calculated (ASTM D5201-05A) or measured (US EPA method 24 or ISO 11890-1).

[0279] Preferably, the fouling release coating compositions and coatings of the present invention have a viscosity of 700-1100 mPa at a shear rate of 100 / s.

[0280] The coating composition of the present invention can be applied to any pretreatment coating designed for a polysiloxane-based fouling release coating. Examples of such coatings are epoxy resin anticorrosive layers and silicone-containing tie-layers designed to ensure adhesion between the substrate and the final polysiloxane-based fouling release layer. An example of such a tie-layer is described in WO2013 / 107827. Optionally, the tie-layer may contain an antifouling agent.

[0281] It is also possible to apply the coating composition according to the invention to substrates containing aged antifouling coatings or fouling release layers. Before applying the coating composition according to the invention to such aged layers, the old layer is cleaned by high pressure water washing to remove any scale.

[0282] The coating composition according to the invention can be applied in one layer or in two or more layers. Preferably, the coating composition according to the invention is applied in one layer.

[0283] The dry film thickness of each coating layer of the coating composition of the present invention is preferably 50-500 μm, more preferably 100-400 μm, most preferably 150-300 μm.

[0284] The fouling release coating compositions and coatings of the present invention can be applied to all or part of the surface of any article subject to marine fouling. The surface may be permanently or intermittently underwater (e.g., by tidal motion, different cargo loadings, or swelling). The article surface will typically be the hull of a ship or the surface of a fixed marine object such as an oil platform or buoy. The application of the coating composition and coating can be accomplished by any convenient means, for example, by painting (e.g., with a brush or roller) or more preferably by spraying the coating onto the article. Typically the surface will need to be separated from the seawater for coating. The application of the coating can be accomplished as is conventionally known in the art. After application of the coating, it is preferably dried and / or cured.

[0285] Application

[0286] The fouling release coating of the present invention is typically applied to the surface of a marine structure, preferably a portion of a marine structure that is submerged when in use. Typical marine structures include vessels (including, but not limited to, ships, yachts, motorboats, motorboats, ocean liners, tugboats, tankers, container ships and other cargo ships, submarines and all types of naval vessels), pipelines, onshore and offshore machinery, all types of buildings and objects (such as piers, piles, bridge underwater structures, hydraulic facilities and structures, underwater oil well structures, nets and other aquaculture facilities and buoys, etc.). The surface of the substrate can be a "native" surface (e.g., a steel surface).

[0287] Example

[0288] Determination method

[0289] Determination of average molecular weight distribution of polymers

[0290] The polymers were characterized by gel permeation chromatography (GPC) measurements. Molecular weight distribution (MwD) was determined using a Malvern Omnisec Resolve and Reveal system using two Agilent PLgel 5μmMixed-D columns in series. The columns were calibrated by conventional calibration using narrow polystyrene standards. The analytical conditions are shown in Table 1 below.

[0291] Table 1

[0292]

[0293] The samples were prepared by dissolving an amount of nonionic hydrophilic modified polysiloxane corresponding to 25 mg of dry polymer in 5 mL of THF. The samples were kept at room temperature for a minimum of 3 hours before sampling for GPC measurements. Before analysis, the samples were filtered through a 0.45 μm nylon filter. The weight average molecular weight (Mw) and number average molecular weight (Mn) are reported.

[0294] Determination of Viscosity of Nonionic Hydrophilic Modified Polysiloxane

[0295] The viscosity of the nonionic hydrophilic modified polysiloxane is measured by using a Brookfield viscometer and a spindle. The viscosity is measured at 25°C on a Brookfield LVT viscometer and a corresponding LV spindle. According to the Brookfield DIAL VISCOMETER Operating Instructions of Brookfield Engineering Laboratories, Inc., Manual No. M / 85-150-P700, a spindle suitable for the specification range of the nonionic hydrophilic modified polysiloxane is selected.

[0296] Viscosity determination of coating formulations

[0297] The viscosity of the coating formulations (inventive and comparative examples) was measured by the cone and plate method at 23°C. The cone diameter was 40 mm and the cone angle was 4°. The shear rate was increased from 0.01 / s to 100 / s to obtain the shear rate dependent viscosity of the samples.

[0298] Preparation of coating composition

[0299] The coating composition was prepared by first mixing the components in part (A) shown in Tables 5 and 6 below using a high speed dissolver equipped with an impeller disc. The nonionic hydrophilic modified polysiloxane was added to the coating composition after the grinding stage. The components in part (B) were mixed with the components in part (A) shortly before applying the coating.

[0300] Anti-fouling performance test in Singapore

[0301] Under specified conditions, the PVC panels were coated with a first coat of Jotun Jotacote Universal N10 primer and a second coat of Jotun SeaQuest Tiecoat using an airless spray method. The coating compositions of the present invention and comparative examples were applied to the PVC panels pre-coated with primer and tiecoat using a film applicator with a clearance of 300 μm.

[0302] The panels were used in static testing on a raft in Singapore where the panels were submerged 0.3-1.3 m below the sea surface. The panels were evaluated by visual inspection using the ratings shown in Table 2 below.

[0303] Table 2: Rating of area covered by fouling

[0304] Rating Area covered by scaling Excellent 0-10％ good 11％-20％ generally 21％-30％ Difference 31％-50％ Very bad More than 50%

[0305] Determination of coating adhesion

[0306] Coating adhesion was determined according to ASTM D6677: 18. A rating of 5 or higher was considered acceptable ("OK" in Tables 5 and 6).

[0307] Determination of coating uniformity

[0308] According to Table 3, coating uniformity was determined by visual inspection.

[0309] Table 3: Visual Rating

[0310] Rating Visual inspection Excellent The surface is uniform and smooth without defects good Uniform, with traces of unevenness (color difference, small flaws) generally Fair uniformity, small scale roughness, signs of phase separation Difference Poor homogeneity, rough surface, obvious phase separation Very bad Very inhomogeneous, very rough, large-scale phase separation

[0311] Table 4: Nonionic hydrophilic modified polysiloxane

[0312]

[0313]

[0314] 1 HLB values ​​were obtained from commercial suppliers. 2 Theoretical calculated value. 3 Calculated based on HLB value.

[0315] Nonionic hydrophilic modified polysiloxanes having the properties given in Table 4 are commercially available and can be readily obtained from commercial suppliers.

[0316] The coating compositions and antifouling performance of the present invention and comparative examples are provided in the table below.

[0317] Table 5: Preparation

[0318]

[0319]

[0320] Table 6: Formulation

[0321]

[0322]

[0323] With respect to the above-described embodiments, the following observations can be made.

[0324] Comparative Example 2 shows that the addition of copper pyrithione to a coating containing a polyether-modified polysiloxane increases the viscosity of the coating compared to Comparative Example 1. The increased viscosity negatively affects the application properties and surface roughness. In addition, 5 wt% of oil is not sufficient to reduce the viscosity increase caused by the addition of copper pyrithione.

[0325] Inventive Examples 1 and 2 show that coating compositions containing copper pyrithione and polyether modified polysiloxane at oil levels of 15 wt% to 25 wt% have good film uniformity and good adhesion while maintaining low VOC. In addition, the viscosity increase seen in Comparative Example 2 is offset by the higher oil level. Antifouling performance is also improved compared to Comparative Example 2 containing 5 wt% polyether modified polysiloxane.

[0326] Comparative Example 2 shows that 5 wt% of oil is not sufficient to achieve satisfactory antifouling performance.

[0327] Comparison of Examples 3 and 4 shows that thinning with solvents can reduce the viscosity of copper pyrithione-containing coatings to the original level, but at the expense of increased VOCs, which has negative consequences in terms of health and environmental issues

[0328] Comparative Example 5 shows that further increasing the oil to 35 wt% (on a dry basis) further reduces VOC and viscosity, but at the expense of coating uniformity and antifouling performance.

[0329] Inventive Examples 3-6 show that several possible polyether-modified polysiloxane oils exhibit good antifouling properties while maintaining good film uniformity and adhesion at high oil levels of 16 wt% (on a dry basis). Oils with lower viscosities reduce the final viscosity of the coating to a higher degree.

[0330] Comparison of Examples 6 and 7 shows that oils with HLB levels above 12 can have a negative impact on coating uniformity and adhesion at oil levels of 16 wt% and 25 wt% (by dry weight).

[0331] Comparison of Examples 8-10 shows that oils with a number average molecular weight above 18,000 have good film uniformity and good adhesion, but poor antifouling performance at oil levels up to 34 wt% (on a dry basis). This is probably because if the molecular weight is too high, the migration of the oil through the film is limited. If the viscosity of the oil is too high, more oil is required to reduce the viscosity of the coating formulation.

[0332] In summary, it has been discovered in the present invention that by selecting a nonionic hydrophilic modified polysiloxane with specific parameters (dosage, molecular weight and HLB), it is possible to obtain a biocide (e.g., copper pyrithione) containing scale release formulation with low VOC, good application properties, good film uniformity and adhesion, and improved antifouling properties.

Claims

1. A fouling release coating composition comprising: a) a curable silicone-based adhesive comprising at least 50 wt% of silicone moieties; b) antifouling agents; and c) 10% to 30% by dry weight of nonionic hydrophilic modified polysiloxane having i) a hydrophile-lipophile balance (HLB) of 1-12, and ii) 500-18,000 g / mol of Mn.

2. A fouling release coating composition comprising: a) a curable silicone-based adhesive comprising at least 50 wt% of silicone moieties; b) antifouling agents; and c) 10% to 30% by dry weight of nonionic hydrophilic modified polysiloxane having i) a hydrophile-lipophile balance (HLB) of 1-12, and ii) Mw of 1,000-50,000 g / mol.

3. A fouling release coating composition according to any one of the preceding claims, wherein the composition comprises 30 wt% to 95 wt% of a polysiloxane-based binder, more preferably 40 wt% to 90 wt% of a polysiloxane-based binder, and still more preferably 50 wt% to 90 wt% of a polysiloxane-based binder, based on the total dry weight of the composition.

4. A fouling release coating composition according to any one of the preceding claims, wherein the antifouling agent is present in an amount of 1 wt% to 15 wt%, preferably 2 wt% to 15 wt%, more preferably 3 wt% to 12 wt% on a dry weight basis based on the total dry weight of the composition.

5. A fouling release coating composition according to any one of the preceding claims, wherein the nonionic hydrophilic modified polysiloxane is present in an amount of 11 wt% to 29 wt% dry weight, preferably 12 wt% to 28 wt% dry weight, preferably 13 wt% to 27 wt% dry weight, preferably 14 wt% to 26 wt% dry weight, for example, 15 wt% to 25 wt% dry weight, based on the total dry weight of the composition.

6. A fouling release coating composition according to any one of the preceding claims, wherein the antifouling agent is zinc pyrithione or copper pyrithione, preferably copper pyrithione.

7. A fouling release coating composition according to any one of the preceding claims, wherein the nonionic hydrophilic modified polysiloxane has a number average molecular weight (Mn) in the range of 500-18,000 g / mol, such as in the range of 1000-16,000 g / mol, in particular in the range of 2000-15,050 g / mol or 4000-15,050 g / mol.

8. A fouling release coating composition according to any one of the preceding claims, wherein the nonionic hydrophilic modified polysiloxane has a viscosity in the range of 20-4,000 mPa-s, preferably in the range of 30-3,000 mPa-s, especially in the range of 50-2,500 mPa-s.

9. A fouling release coating composition according to any one of the preceding claims, wherein the nonionic hydrophilic modified polysiloxane has a weight average molecular weight (Mw) of 2,000-45,000 g / mol, preferably 3,000-42,000 g / mol, 4,000-40,000 g / mol, or 5,000-40,000 g / mol.

10. A fouling release coating composition according to any one of the preceding claims, wherein the nonionic hydrophilic modified polysiloxane has an HLB (hydrophile-lipophile balance) in the range of 1.0-10, more preferably 1.0-8.0, most preferably 2.0-7.0.

Images