Fouling release coating

Abstract

To provide a fouling release coating that prevents the settlement and growth of marine organisms.SOLUTION: A fouling release coating composition comprises: a) a curable polysiloxane based binder comprising at least 50 wt.% polysiloxane parts; b) an antifouling agent; and c) 10-30 wt.% (based on dry weight) of a non-ionic hydrophilic-modified polysiloxane having i) a hydrophilic-lipophilic balance (HLB) of 1-12, and ii) a Mn of 500-18,000 g / mol.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a fouling release coating composition, a method for preparing such a fouling release coating, and to marine structures coated with such a fouling release coating. [Background technology]

[0002] Submerged surfaces in seawater are prone to the fouling of marine organisms such as green and brown algae, slime molds, barnacles, mussels and tubeworms. In marine structures such as vessels (e.g. ships, tankers), oil platforms and buoys, such fouling is undesirable and has economic consequences. Fouling can lead to biological deterioration of the surface, increased loading and accelerated corrosion. In vessels, fouling increases frictional resistance, which causes a decrease in speed and / or an increase in fuel consumption. It can also reduce maneuverability.

[0003] Antifouling paints are used to prevent the settlement and growth of marine organisms. Traditionally, two types of antifouling paints have been used: self-polishing antifouling paints and fouling-releasing antifouling paints.

[0004] Self-polishing antifouling paints contain an antifouling agent and a binder that gradually dissolves and / or hydrolyzes in seawater, allowing the seawater to erode the coating surface, thereby exposing a new surface. The most successful self-polishing antifouling paints are based on hydrolyzable binders, such as (meth)acrylate binders with hydrolyzable silyl esters. The gradual hydrolysis in seawater results in the controlled release of the antifouling agent from the coating.

[0005] Fouling-releasing antifouling paints work by providing a coating with low surface tension and low modulus, providing a fouling-releasing surface to which marine organisms do not attach or which, if attached, are easily washed away by rubbing water against the surface or washing. Such coatings are often based on polysiloxane-based binders. The fouling-releasing surface created by polysiloxane binders is effective in preventing large foulants from permanently attaching to the surface. However, polysiloxane surfaces have not shown good resistance to soft foulants such as slime mold and algae over time.

[0006] Polysiloxane-based fouling release coatings (FRCs) are traditionally used without biocides. However, as mentioned above, the challenge of FRC is the adhesion of soft adherents such as slime molds and algae. The use of polyether modified silicone oil in FRC has been shown to reduce the adhesion of slime mold and algae. It is known that FRC reduces fouling. In addition, in recent years, biocides effective against slime molds and algae have been added to FRC to further improve fouling prevention. One type of biocide that has been shown to be effective is pyrithione salts, such as copper pyrithione. However, FRCs containing biocides have limitations, especially with regard to fouling prevention, long-term performance and adhesion. There is room for improvement.

[0007] The addition of biocides has been shown to provide many technical benefits, including fouling prevention, reduction of spray dust, and improved storage stability and enhanced fouling prevention coatings. Specifically, FRCs containing polyether modified polysiloxane oils have been shown to provide antifouling agents (e.g. Solid antifoulants (e.g., pyrithione salts such as zinc pyrithione (ZnPt) and copper pyrithione (CuPt)) are typically present at about 5-7% dry weight, and polyether modified silicone oils are typically present at about 1-5% dry weight. However, the addition of solid antifoulants adversely affects the viscosity of the paint (increases viscosity). The increase in viscosity can usually be compensated for by increasing the solvent concentration (thinning) to maintain good application properties, but this can lead to an increase in VOCs and the associated adverse health effects for the applicator and environmental impacts. This invention increases the solvent content (VOC) of the coating formulation. In some cases, the VOC of the original composition may be reduced without increasing the amount of VOC. A method for compensating for viscosity is disclosed.

[0008] The present inventors have surprisingly found that non-ionic surfactants having specific parameters (molecular weight and HLB) By incorporating a relatively large amount of hydrophilic modified silicone oil, low VOC, good adhesion, It has now been found that it is possible to obtain deposit release formulations containing antifouling agents that have improved application properties (viscosity), good film uniformity and improved antifouling properties.

[0009] It has been believed that polysiloxane-based fouling release coatings cannot have a large amount of polyether-modified silicone oil because it results in too much water uptake in the film, poor film uniformity, and high polarity resulting in poor adhesion. Patent Document 1 teaches a coating with an optimum concentration of 4-7 wt% polyether-modified silicone oil in combination with a copper pyrithione biocide. Patent Document 2 teaches a coating containing 0.13 wt% polyether-modified silicone oil in combination with a copper pyrithione biocide. Patent Document 2 also discusses that a large amount of polyether-modified silicone oil (more than 10 wt%) gives poor adhesion. Patent Document 3 discusses that 4 wt% polyether-modified silicone oil in combination with a copper pyrithione biocide gives poor adhesion. A coating composition containing a polyether modified silicone oil is disclosed.

[0010] Patent Document 4 discloses a higher amount of silicone oil, but relates to a different binder system based on a metal bridged organopolysiloxane-thioblock vinyl copolymer. Patent Document 5 discloses an antifouling composition, which has a polyether modified silicone oil, but with an HLB value of 0.1 to 0.2. The inventors have shown that such a high and high HLB value is present in the deposit release coating in the comparative examples, which are high (14.5) and in large amounts (greater than 30% by dry weight). These results indicate that the results are poor. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] International Publication No. 2011 / 076856 [Patent Document 2] International Publication No. 2014 / 077205 [Patent Document 3] International Publication No. 2017 / 009297 [Patent Document 4] European Patent No. 2514776 [Patent Document 5] European Patent No. 2103655 Summary of the Invention

[0012] In one aspect, the present invention comprises: a) a curable polysiloxane-based binder containing at least 50% by weight of polysiloxane moieties; And, b) an antifouling agent; c) 10 to 30% by dry weight, i) a hydrophilic-lipophilic balance (HLB) of 1 to 12, and ii) Mn between 500 and 18,000 g / mol A non-ionic hydrophilic modified polysiloxane having the formula: The present invention provides a release coating composition comprising:

[0013] Viewed from another aspect, the present invention comprises: a) a curable polysiloxane-based binder containing at least 50% by weight of polysiloxane moieties; And, b) an antifouling agent; c) 10 to 30% by dry weight, i) a hydrophilic-lipophilic balance (HLB) of 1 to 12, and ii) Mw of 1,000 to 50,000 g / mol and a non-ionic hydrophilically modified polysiloxane having the formula:

[0014] Viewed from another aspect, the present invention comprises: a) a curable polysiloxane-based binder containing at least 50% by weight of polysiloxane moieties; And, b) an antifouling agent; c) 10 to 30% by dry weight, i) a relative weight of the hydrophilic portion in the range of 5 to 60% by weight, and ii) Mn between 500 and 18,000 g / mol and a non-ionic hydrophilically modified polysiloxane having the formula:

[0015] Viewed from another aspect, the present invention comprises: a) a curable polysiloxane-based binder containing at least 50% by weight of polysiloxane moieties; And, b) an antifouling agent; c) 10 to 30% by dry weight, i) a relative weight of the hydrophilic portion in the range of 5 to 60% by weight, and ii) Mw of 1,000 to 50,000 g / mol and a non-ionic hydrophilic polysiloxane having the formula:

[0016] Viewed from another aspect, the present invention provides a marine structure comprising on at least a portion of its outer surface a fouling release coating as defined herein.

[0017] Viewed from another aspect, the present invention provides a method for preparing an adhesion release coating composition as defined herein, comprising the steps of: a) a curable polysiloxane-based binder containing at least 50% by weight of polysiloxane moieties; And, b) an antifouling agent; c) 10 to 30% by dry weight, i) HLB of 1 to 12, and ii) Mn of 500 to 18,000 g / mol and / or Mw of 1,000 to 50,000 g / mol and a non-ionic hydrophilic modified polysiloxane having the formula: Typically, a method is provided that includes the step of mixing in at least one solvent.

[0018] Viewed from another aspect, the present invention provides a method for preparing an adhesion release coating composition as defined herein, comprising the steps of: a) a curable polysiloxane-based binder containing at least 50% by weight of polysiloxane moieties; And, b) an antifouling agent; c) 10 to 30% by dry weight, i) the relative weight of the hydrophilic portion in the range of 5 to 60% by weight, and ii) Mn of 500 to 18,000 g / mol and / or Mw of 1,000 to 50,000 g / mol and a non-ionic hydrophilic modified polysiloxane having the formula: Typically, a method is provided that includes the step of mixing in at least one solvent.

[0019] Viewed from another aspect, the present invention provides a kit for preparing an adhesion release coating composition as defined herein, comprising: (i) A curable polysiloxane binder, a stain-resistant agent and / or a non-ionic hydrophilic modified polysiloxane a first container containing lysiloxane; (ii) a second container containing a crosslinker and / or curing agent, and optionally a catalyst; (iii) optionally, a third vessel containing a catalyst; (iv) Optionally, instructions for combining the contents of the containers described above.

[0020] definition 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.

[0021] 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., forms at least 50% by weight of the binder present. As used herein, the term "binder" does not include added oils. Added oils are not considered film-forming components herein.

[0022] As used herein, the term "paint" refers to a composition comprising a deposit release coating composition as described herein and, optionally, a ready-to-use solvent, such as a solvent for spraying. Thus, the deposit release coating composition may be a coating itself, or the deposit release coating composition may be a concentrate to which a solvent is added to produce a coating.

[0023] As used herein, the term "polysiloxane" refers to siloxane, i.e., a polymer containing --Si--O-- repeating units.

[0024] As used herein, the term "polysiloxane-based binder" refers to a binder that contains repeat units containing the motif -Si-O- in an amount of at least 50% by weight, based on the total weight of the polymer. Preferably, the polysiloxane-based binder comprises at least 60% by weight, more preferably at least 70% by weight, of the motif -Si-O-, based on the total weight of the polymer. The repeating units -Si-O- may be linked in a single sequence or may be interrupted by non-siloxane moieties, such as organic moieties.

[0025] As used herein, the term "non-degradable polysiloxane-based binder" refers to a polysiloxane-based binder that does not undergo hydrolysis or erosion in seawater.

[0026] As used herein, the term "alkyl" refers to a saturated, straight-chain, branched or cyclic group. Alkyl groups can be substituted or unsubstituted.

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

[0028] As used herein, the term "alkylene" refers to a divalent alkyl group.

[0029] As used herein, the term "alkenyl" refers to an unsaturated, linear, branched or cyclic group. Alkenyl groups can be substituted or unsubstituted.

[0030] As used herein, the term "aryl" refers to a group containing at least one aromatic ring. The term aryl refers to groups containing heteroaryl as well as cycloaryl in which one or more aromatic rings are cycloaryl. The aryl group may be substituted or unsubstituted. An example of an aryl group is phenyl, i.e., C 6 H 5 The phenyl group can be substituted or unsubstituted.

[0031] As used herein, the term "substituted" refers to the replacement of one or more hydrogen atoms in a group, e.g. For example, up to six, more specifically one, two, three, four, five or six, may be present in the corresponding number of listed substituents. Thus, they refer to groups that are substituted independently of each other. As used herein, the term "optionally substituted" means substituted or unsubstituted.

[0032] As used herein, the term "arylalkyl" group refers to a group in which the bond to Si is through an alkyl moiety.

[0033] As used herein, the term "polyether" refers to a compound containing two or more --O-- bonds interrupted by alkylene units.

[0034] As used herein, the terms "poly(alkylene oxide)", "poly(oxyalkylene)" and "poly(alkylene glycol)" refer to repeating -alkylene-O- units. It refers to compounds containing repeating units. Typically, the alkylene is ethylene or propylene.

[0035] As used herein, the term "(meth)acrylate" encompasses both methacrylates and acrylates.

[0036] As used herein, the term weight percent is based on the dry weight of the coating composition, unless otherwise specified.

[0037] 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 called D (dispersity).

[0038] As used herein, the term "volatile organic compounds (VOCs)" refers to compounds that have a boiling point below 250°C.

[0039] 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 detachment of marine organisms from a surface. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0040] The present invention relates to a) a curable polysiloxane-based binder containing at least 50% by weight of polysiloxane moieties; And, b) an antifouling agent; c) 10 to 30% by dry weight, i) a hydrophilic-lipophilic balance (HLB) of 1 to 12, and ii) Mn of 500 to 18,000 g / mol and / or Mw of 1,000 to 50,000 g / mol A non-ionic hydrophilic modified polysiloxane having the formula: The present invention relates to a release coating composition comprising:

[0041] Polysiloxane binder The binder in the adhesion release coating composition comprises a curable polysiloxane-based binder component (a). The polysiloxane-based binder is preferably a non-degradable curable polysiloxane. When the polysiloxane is a non-degradable polysiloxane-based binder, the adhesion release coating composition of the present invention provides a pure adhesion release coating.

[0042] The polysiloxane binder present in the coating composition of the present invention comprises at least 50% by weight of polysiloxane moieties, preferably greater than 60% by weight of polysiloxane moieties, even more preferably greater than 70% by weight of polysiloxane moieties, such as 99.99% by weight or more of polysiloxane moieties. Typical ranges include 50-100% by weight of polysiloxane moieties, 60-99.999% by weight of polysiloxane moieties, or 70-99.99% by weight of polysiloxane moieties in the polysiloxane binder.

[0043] The polysiloxane moiety is defined as a repeating unit containing the motif -Si-O-, based on the total weight of the polysiloxane binder. The polysiloxane content can be determined based on the stoichiometric weight ratio of the starting materials in the polysiloxane synthesis. Alternatively, the polysiloxane content can be determined using analytical techniques such as IR or NMR. can.

[0044] Typically, the weight percent of the polysiloxane portion is calculated based on the molar ratio of the reactive starting materials in the polysiloxane synthesis. If a molar excess of monomer is present in the reaction mixture, such molar excess is not counted. Only monomer that can react based on the stoichiometry of the reaction is taken into account.

[0045] Information regarding the weight percent polysiloxane moiety in commercially available polysiloxane-based binders is readily available from suppliers.

[0046] It is to be understood that the polysiloxane-based binder can consist of a single repeating sequence of siloxane units or can be interrupted by non-siloxane moieties, e.g., organic moieties. Preferably, the polysiloxane-based binder contains only Si-O repeat units.

[0047] The organic moieties may include, for example, alkylene, arylene, poly(alkylene oxide), amide, thioether, or combinations thereof, and preferably, the organic moieties may include, for example, alkylene, arylene, poly(alkylene oxide), amide, or combinations thereof. In certain embodiments, the polysiloxane-based binder does not include a thio group.

[0048] The polysiloxane-based binder present in the inventive release coating composition can in principle be any curable polysiloxane-based binder, where curable means that the polysiloxane-based binder contains functional groups that allow crosslinking reactions to occur between the polysiloxane-based binder molecules or via a crosslinking agent.

[0049] The polysiloxane-based binder is preferably an organopolysiloxane having terminal and / or pendant curing reactive functional groups. A minimum of two curing reactive functional groups per molecule is preferred. Examples of curing reactive functional groups are silanol, alkoxy, acetoxy, enoxy, ketoxime, alcohol, amine, epoxy and / or isocyanate. Preferred polysiloxane-based binders contain curing reactive functional groups selected from silanol, alkoxy or acetoxy groups. The curing reaction is typically a condensation curing reaction. Polysiloxane The olefin-based binder optionally contains two or more types of cure reactive groups, e.g., condensation cure and May be cured by both amine / epoxy cure.

[0050] The polysiloxane binder may consist of only one type of polysiloxane. , it may also be a mixture of different polysiloxanes.

[0051] The preferred polysiloxane binder present in the adhesion release coating composition of the present invention is represented by the following formula (D1):

[0052] [ka]

[0053] During the ceremony, Each R 1 are independently a hydroxyl group, C 1~6 -alkoxy group, C 1~6 -hydroxyl group, C 1~6 -epoxy-containing group, C 1~6Amine group, or O-Si(R 5 ) 3-z (R 6 ) z is selected from Each R 2 is independently 1~10 Alkyl, C 6~10 Aryl, C 7-10 alkylaryl, or poly(alkylene oxide) and / or R 1 C substituted with a group described as 1~6 Alki are selected from Each R 3 and R 4 is independently 1~10 Alkyl, C 6~10 Aryl, C 7~10 Alkylaryl or poly(alkylene oxide) substituted C 1~6 alkyl, Each R 5 is independently 1~6 Alkoxy groups, acetoxy groups, enoxy groups, or ketoxy groups Which hydrolyzable group is Each R 6 are independently unsubstituted C 1~6 Alkyl or substituted C 1~6 alkyl groups, z is 0 or an integer of 1 to 2, x is an integer equal to or greater than 2; y is an integer of 2 or greater.

[0054] Preferably, R 1 is a hydroxyl group and O-Si(R 5 ) 3-z (R 6 ) z wherein R 5 is C 1 ~C 6 is an alkoxy group, R 6 is C 1~6 alkyl, and z is an integer of 0 or 1-2. More preferably, R 1 is a hydroxyl group and O-Si(R 5 )3-z (R 6 ) z wherein R 5 is C 1 ~C 3 is an alkoxy group, R 6 is C 1~3 alkyl, and z is an integer of 0 or 1 to 2. More preferably, R 1 is a hydroxyl group.

[0055] Preferably, R 2 is C 1~10 More preferably, R 2 is C 1~4 Alkyl group , more preferably C 1~2 An alkyl group is more preferred, and a methyl group is even more preferred. is each R 2 is the same.

[0056] Preferably, R 3 is C 1~10 More preferably, R 3 is C 1~4 Alkyl group , more preferably C 1~2 An alkyl group is more preferred, and a methyl group is even more preferred. is each R 3 is the same.

[0057] Preferably, R 4 is C 1~10 More preferably, R 4 is C 1~4 Alkyl group , more preferably C 1~2 An alkyl group is more preferred, and a methyl group is even more preferred. is each R 4 is the same.

[0058] More preferably, R 1 is a hydroxyl group, and R 2 , R 3 and R 4are methyl groups. The preferred polysiloxane binder present in the adhesion release coating composition of the present invention is represented by the formula (D2):

[0059] [ka]

[0060] During the ceremony, Each R 1 are independently a hydroxyl group, C 1~6 -alkoxy group, C 1~6 -hydroxyl group, C 1~6 -epoxy-containing group, C 1~6 Amine group, or O-Si(R 5 ) 3-z (R 6 ) z is selected from Each R 2 From R 4 is methyl, Each R 5 is independently 1~6 Alkoxy groups, acetoxy groups, enoxy groups, or ketoxy groups Which hydrolyzable group is Each R 6 are independently unsubstituted C 1~6 Alkyl or substituted C 1~6 alkyl groups, z is 0 or an integer of 1 to 2, x is an integer equal to or greater than 2; y is an integer of 2 or greater.

[0061] Another preferred polysiloxane-based binder present in the deposit release coating composition of the present invention is represented by formula (D3):

[0062] [ka]

[0063] In the formula, R 1 , R2 , R 3 , R 4 and x and y are as defined for (D1), R x is C 2~3 each L1 is 0 to 50 and each L2 is 0 to 50, provided that L1+L2 is 2 to 50; , preferably 4 to 40, more preferably 4 to 20, and most preferably 4 to 10; L3 is 1 to 200 , preferably 2 to 100, most preferably 5 to 50. The polysiloxane moiety must form a minimum of 50% by weight of the molecule.

[0064] The polysiloxane binder of the present invention is preferably represented by formula D1.

[0065] Those skilled in the art will recognize that polysiloxane-based binders may contain small amounts of impurities, such as cyclic siloxanes, such as D4, D5 and D6 cyclic siloxanes, which are residues from polysiloxane synthesis, where the (D4, D5, or D6) designation refers 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). From health, safety, and environmental perspectives, the presence of cyclic siloxanes in the coating may be important. It is preferred to limit the amount of cyclic polysiloxanes. In one preferred embodiment, the polysiloxane binder contains less than 5%, preferably less than 2%, more preferably less than 1% cyclic polysiloxanes. In one particularly preferred embodiment, the polysiloxane-based binder is free of cyclic polysiloxanes.

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

[0067] In one embodiment, the polysiloxane binder (a) is a non-ionic hydrophilically modified polysiloxane. In particular, the polysiloxane binder may have an HLB value of less than 0.5, for example less than 0.1, so as to satisfy the HLB parameters of the polysiloxane component (c).

[0068] Preferred coating compositions of the present invention contain from 30 to 95 weight percent polysiloxane-based binder, more preferably from 40 to 90 weight percent polysiloxane-based binder, and even more preferably from 50 to 90 weight percent polysiloxane-based binder, based on the total dry weight of the composition.

[0069] Polysiloxane-based binders suitable for use in the coating compositions of the present invention are commercially available. Representative commercially available non-degradable polysiloxane-based binders include Xiameter® OHX-0135, Xiameter® OHX-4000, and Xiameter® OHX-4000 manufactured by Dow Corning. Xiameter® OHX-4010, Xiameter® OHX-4040, Xiameter® OHX-4050 , Xiameter® OHX-4060, PolymerOH 0.08, PolymerOH 0.75, PolymerOH 1, PolymerOH 2, PolymerOH 3.5, PolymerOH 5, PolymerOH 20, PolymerOH 80 from Evonik, and DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S42, DMS-S51 from Gelest.

[0070] Antifouling agent The antifouling coating composition of the present invention comprises an antifouling agent (b).

[0071] The terms antifouling agent, biologically active compound, antifouling agent, biocide, toxicant are used in the industry to describe known compounds that act 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.

[0072] 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.

[0073] Examples of organometallic antifoulants include zinc pyrithione; organocopper compounds such as copper pyrithione, copper acetate, copper naphthenate, copper oxine, 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].

[0074] 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], and encapsulated 4 ,5-Dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], 1,2-Benzisothiazolin-3-one, 2-(thiocyanatomethylthio)-1,3-benzothiazole [benzthiazole], and 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine. Urea derivatives, for example, 3-(3,4-dichlorophenyl)-1,1-dimethylurea [diuro amides and imides of carboxylic, sulfonic and sulfenic acids, such as N-(diamines); Chlorofluoromethylthio)phthalimide, N-dichlorofluoromethylthio-N',N' -Dimethyl-N-phenylsulfamide [dichlohlanid], N-dichlorofluoromethylthio-N',N'-dimethyl-Np-tolylsulfamide [tolylfluanid], and N -(2,4,6 trichlorophenyl)maleimide; other organic compounds, e.g., pyridine trichloride Phenylborane [TPBP], Aminetriphenylborane, 3-iodo-2-propynyl N-borane Tylcarbamate [iodocarb], 2,4,5,6-tetrachloroisophthalonitrile, p -((diiodomethyl)sulfonyl)toluene, and 4-bromo-2-(4-chlorophenyl and quaternary ammonium salts.

[0075] 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 its derivatives such as ivermectin, spinosyns and its derivatives such as spinosad, capsaicin and its derivatives such as phenylcapsaicin, and macrocyclic lactones including enzymes such as oxidases, proteolytically, hemicellulolytically, cellulolytically, lipolytically and aminolytically active enzymes.

[0076] 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. Particularly preferred antifouling agents are zinc pyrithione and copper pyrithione, especially copper pyrithione. It is lithium.

[0077] In the present invention, the FRC containing the nonionic hydrophilically modified polysiloxane oil is typically This has been complemented by the addition of pyrithione salt biocides (zinc pyrithione (ZnPt) and copper pyrithione (CuPt)). In the patent literature, CuPt is typically present at about 5-7% dry weight, and polyether modified oils are typically present at about 1-5% dry weight. However, the addition of solid pyrithione salts with acicular morphology adversely affects the viscosity of the paint (increases viscosity). The increase in viscosity can usually be compensated for by increasing the concentration of the solvent (thinning) to maintain good application properties, but this can be countered by the increase in VOCs and the associated adverse health effects for the applicator and environmental impacts. This invention increases the solvent content (VOC) of the coating formulation. Without, in some cases, reducing the VOC of the original composition, the increased viscosity mentioned above A method for compensating for the above is disclosed.

[0078] The biocide typically comprises 1-20% by dry weight of the total coating composition, preferably 10% by dry weight of the total coating composition. These protective agents are present in amounts of 1-15%, 2-15%, or 3-12% by dry weight of the coating composition. The use of antifouling agents is known in antifouling coatings and their use is well known to those skilled in the art. The antifouling agents may be encapsulated or adsorbed onto an inert carrier or bound to other materials for controlled release. These percentages refer to the amount of active antifouling agent present and therefore not the amount of carrier used.

[0079] Non-ionic hydrophilic modified polysiloxane The coating composition of the present invention comprises a non-ionic hydrophilically modified polysiloxane (c). It will be understood that this component is different from the polysiloxane binder component (a). That is, the coating composition must contain two distinct components (a) and (c). In one embodiment, the polysiloxane binder (a) is a non-ionic hydrophilically modified polysiloxane. In particular, the polysiloxane binder may have an HLB value of less than 0.5, for example less than 0.1, so as to satisfy the HLB parameters of the polysiloxane component (c).

[0080] Non-ionic hydrophilic modified polysiloxanes undergo a curing reaction at an appropriate curing temperature (0 to 40°C). It should be understood that the nonionic hydrophilically modified polysiloxane does not contain reactive groups that react with the binder or crosslinker. Thus, the nonionic hydrophilically modified polysiloxane is intended to be non-reactive in the curing reaction, particularly with respect to the binder component.

[0081] It should be understood that depending on the curing reactive groups on the binder, the hydrophilically modified polysiloxane is selected so that it does not contain groups that, when present during the curing reaction, will react with the binder or the crosslinker. Thus, the non-ionic hydrophilically modified polysiloxane is a non-curable component in the coating composition. In this specification, non-curable means that the non-ionic hydrophilically modified polysiloxane will not react with the binder or the crosslinker during the curing reaction in the temperature range of 0 to 40°C. This means that they do not.

[0082] In a preferred embodiment, the non-ionic hydrophilically modified polysiloxane has Si-OH groups, Si-OR groups, which can react with the binder or crosslinker (if present) at a suitable curing temperature (0-40° C.). It does not contain silicone reactive groups such as alkoxy, enoxy, or ketoximul-up.

[0083] In certain embodiments, the non-ionic hydrophilically modified polysiloxane does not contain any Si-OH or Si-OR (alkoxy, ie, R=alkyl) groups.

[0084] Nonionic hydrophilically modified polysiloxanes are widely used as surfactants and emulsifiers because they contain both hydrophilic and lipophilic groups in the same molecule. The nonionic hydrophilically modified polysiloxane according to the present invention is a polysiloxane modified with a nonionic hydrophilic group, which makes it more hydrophilic than the corresponding unsubstituted polysiloxane having the same number of polysiloxane units. Hydrophilicity can be obtained by modification with nonionic 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 nonionic hydrophilically modified polysiloxane is an oil.

[0085] "Nonionic" in this specification means that the hydrophilically modified polysiloxane does not contain salt moieties, and in particular, typically does not contain metal cations.

[0086] The hydrophilicity of non-ionic hydrophilic modified polysiloxane is determined by the HLB (hydrophilic-lipophilic balance) parameter. The nonionic hydrophilic modified polysiloxane of the present invention is determined according to the following parameters: Preferably, the nonionic hydrophilic modified polysiloxane has an HLB (hydrophilic-lipophilic balance) in the range of 1.0 to 10, more preferably 1.0 to 8.0, and most preferably 2.0 to 7.0. In a particular embodiment, the nonionic hydrophilic modified polysiloxane has an HLB in the range of 3.0 to 6.0.

[0087] HLB is typically determined herein according to Griffin's model using the formula "wt% of hydrophilic groups" / 5 (reference: Griffin, W Calculation of HLB values of non-ionic surfactants, J. Soc. Cosmet. Chem. 1954, 5, 249-256). In certain embodiments, the HLB is calculated according to the formula HLB="weight percent of hydrophilic groups" / 5. The HLB parameter is a well-established parameter for nonionic surfactants and is used for commercially available nonionic surfactants. These are readily available from suppliers of ionic hydrophilically modified polysiloxanes. The higher the HLB value of the surfactant, the more hydrophilic it is. The weight percent of hydrophilic groups is calculated based on the weight percent of non-ionic hydrophilically modified polysiloxanes. This means the weight percent of hydrophilic groups in the polysiloxane. Convert the weight percent of hydrophilic groups to the HLB value. An HLB value of 1 to 12 can be, for example, 5 to 60% by weight of hydrophilic groups, and vice versa. Equivalent to weight percent.

[0088] The function of the non-ionic hydrophilically modified polysiloxane is to facilitate the dissolution and migration of the biocide to the surface of the coating film. It is also well known that the formation of a hydration layer at the coating-water interface is important for antifouling performance.

[0089] For example, if the hydrophilicity of the nonionic hydrophilic modified polysiloxane is too high due to the amount of hydrophilic groups in the molecule, this may lead to early depletion of the biocide and the nonionic hydrophilic modified polysiloxane due to too high leaching rate.High hydrophilicity also leads to poor compatibility with the polysiloxane-based binder matrix, resulting in poor film uniformity and poor adhesion, especially when high oil amounts (more than 10 wt%) are used.

[0090] The method of controlling the leaching rate of the biocide and the non-ionic hydrophilic modified polysiloxane includes the molecular weight of the non-ionic hydrophilic modified polysiloxane, hydrophilicity and miscibility with the binder.Very low molecular weight non-ionic hydrophilic modified polysiloxanes tend to allow high leaching rates, but if the molecular weight is too high, the leaching rate of the biocide and the non-ionic hydrophilic modified polysiloxane may not be able to be as high as desired.

[0091] Thus, in a preferred embodiment, the nonionic hydrophilically modified polysiloxane has a number average molecular weight (Mn) 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. More suitable Mn ranges for the xanthane include 500 to 15,000 g / mol, 1,000 to 13,000 g / mol, or 3,000 to 10,000 g / mol. For example, experimentally obtained values ​​obtained by GPC measured against polystyrene standards This method is described in the experimental section below.

[0092] In a preferred embodiment, the nonionic hydrophilic modified polysiloxane has a weight average molecular weight (Mw) in the range of 1,000 to 50,000 g / mol, preferably 2,000 to 45,000 g / mol, 3,000 to 42,000 g / mol, 4,000 to 40,000 g / mol, or 5,000 to 40,000 g / mol. The weight average molecular weight (Mw) value referred to in this specification corresponds to the value experimentally obtained by, for example, GPC measured against polystyrene standards. This method is as follows: As described in the Experimental Section.

[0093] 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 affects the ease of application and the surface roughness. These molecular weights also affect the migration of the biocide and non-ionic hydrophilic modified polysiloxane to the surface of the coating film, which affects the anti-fouling performance. The nonionic hydrophilically modified polysiloxane also preferably has a viscosity, measured according to the method set forth in the experimental section, 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.

[0094] The amount of non-ionic hydrophilically modified polysiloxane contained in the coating composition is also an important parameter. If the amount is too low, a high viscosity coating composition is obtained, which may result in poor application properties. Alternatively, more solvent needs to be added, which may result in poor application properties. The resulting coating composition has a lower VOC than the non-ionic hydrophilic modified polysiloxane. Too little polysiloxane may cause the coating to have poor long-term fouling protection because the non-ionic hydrophilically modified polysiloxane may be depleted from the membrane too quickly, whereas too much non-ionic hydrophilically modified polysiloxane may cause the membrane to have poor uniformity and poor fouling protection.

[0095] The nonionic hydrophilically modified polysiloxane is contained in the coating composition in an amount of 10 to 30% by dry weight (for example, 10 to 25% by dry weight), preferably 11 to 29% by dry weight, preferably 12 to 28% by dry weight, preferably 13 to 27% by dry weight, preferably 14 to 26% by dry weight, for example, 15 to 25% by dry weight. When additional non-ionic hydrophilically modified polysiloxanes are present, these amounts refer to the total of the non-ionic hydrophilically modified polysiloxane components.

[0096] Of particular interest are those in which the relative weight of the hydrophilic moieties (e.g. polyether groups) is less than 5% of the total weight. (e.g., 5 to 60%), for example, 6% or more (e.g., 6 to 50%), particularly 10% or more (e.g., 10 to 40%) of the total weight of the nonionic hydrophilic modified polysiloxane. Other suitable ranges for the relative weight of the hydrophilic moiety in the nonionic hydrophilically modified polysiloxane include 5 to 60% by weight, preferably 5 to 50% by weight, more preferably 5 to 40% by weight, most preferably 10 to 35% by weight, and especially 15 to 30% by weight.

[0097] The weight percent of hydrophilic moieties can be calculated based on the stoichiometric ratios of starting materials in the synthesis of the non-ionic hydrophilically modified polysiloxane, or can be determined using analytical techniques such as IR or NMR. It can be determined.

[0098] If there is a molar excess of reactants, such molar excess is not taken into account when determining the weight percent of hydrophilic moieties. Only monomers that are able to react based on the stoichiometry of the reaction are taken into account.

[0099] If the HLB is known, the weight percent of hydrophilic moieties is calculated using the formula HLB = "weight percent of hydrophilic groups" / 5. It can also be calculated according to the Griffin model using

[0100] The non-ionic hydrophilically modified polysiloxanes may contain small amounts of impurities, e.g., cyclic siloxanes, such as D4, D5 and D6 cyclic siloxanes, which are residues of the polysiloxane synthesis, where the (D4, D5 and D6) designations refer to the number (number) of repeating Si-O units in the cyclic polysiloxane. (i.e., 4, 5 or 6 repeating Si-O units in the cyclic polysiloxane). For health, safety and environmental reasons, it is preferable to limit the amount of cyclic polysiloxane present in the coating composition. In one preferred embodiment, the non-ionic hydrophilically modified polysiloxane contains less than 5%, preferably less than 2%, more preferably less than 1% of cyclic polysiloxane. In one particularly preferred embodiment, the non-ionic hydrophilically modified polysiloxane does not include a cyclic polysiloxane.

[0101] In one preferred embodiment, the non-ionic hydrophilically modified polysiloxane is a polyether modified polysiloxane, in other words the hydrophilic moieties are polyether groups.

[0102] 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 5 to 100 repeat units, such as 5 to 50, or 8 to 50, or 8 to 20 repeat units. .

[0103] In some preferred embodiments, the polyether group (i.e., the oligomeric group or poly The number average molecular weight (n) of the aryl group (mer group) is in the range of 100 to 2500 g / mol, for example 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.

[0104] Of particular interest are polyether modified polysiloxanes in which the relative weight of the polyether moiety is 5% or more (e.g. 5-60%) of the total weight, 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.

[0105] In one variant of the invention, the polyether-modified polysiloxane is a polysiloxane to which poly(oxyalkylene) chains have been grafted. An illustrative example of the structure of such a polyether-modified polysiloxane is formula (A):

[0106] [ka]

[0107] In the formula, each R 7 is independently 1~5 -Alkyl (including linear or branched hydrocarbon groups) and aryl (e.g., phenyl (-C 6 H 5)), in particular methyl, Each R 8 are independently -H, C 1~4 -Alkyl (e.g., -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH(CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 ), phenyl(-C 6 H 5 ), and C 1~4 -Alkyl carbonyl (e.g., -C(=O)CH 3 , -C(=O)CH 2 CH 3 and -C(=O)CH 2 CH 2 CH 3 ), especially -H, Methyl, and -C(=O)CH 3 is selected from Each R 9 is independently 2~5 -Alkylene (e.g., -CH 2 CH 2 -, -CH 2 CH(CH 3 ), -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -, -CH 2 CH(CH 2 CH 3 )-), arylene (e.g., 1,4- phenylene) and aryl substituted C 2~5 -Alkylene (e.g. 1-phenylethylene), especially -CH 2 CH 2 - and -CH 2 CH(CH 3 )- and other C 2~5 -alkylene, 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.

[0108] For more details, see R 7 is methyl, Each R 8 are independently -H or C 1~4 -Alkyl or -C(=O)CH 3 is selected from Each R 9 -CH 2 CH 2 - or -CH 2 CH 2 CH 2 - or -CH 2 CH(CH 3 )-and 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.

[0109] All R 7 It is preferred that the groups are the same.

[0110] Examples of commercially available polyether modified polysiloxanes of this type are KF352A, KF353, KF945, KF6012, KF6017 manufactured by ShinEtsu, and XIAMETER OFX-5220, DOWSIL OFX-5247, XIAMETER OFX-5329, XIAMETER OFX-5330 manufactured by DOW.

[0111] In another variation of the present invention, the polyether-modified polysiloxane is a polysiloxane having poly(oxyalkylene) chains incorporated into its backbone. An illustrative example of the structure of such a hydrophilically modified polysiloxane is formula (B):

[0112] [ka]

[0113] In the formula, each R 7 is independently 1~5 -Alkyl (including linear or branched hydrocarbon groups) and aryl (e.g., phenyl (-C 6 H 5 )), in particular methyl, Each R 8 are independently -H, C 1~4 -Alkyl (e.g., -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH-CH(CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 ), phenyl(-C 6 H 5 ), and C 1~4 -Alkylcarbonyl (e.g., -C(=O)CH 3 , C(=O)CH 2 CH 3 and -C(=O)CH 2 CH 2 CH 3 ), especially -H, methyl , and -C(=O)CH 3 is selected from Each R 9 is independently 2~5 -Alkylene (e.g., -CH 2 CH 2 -, -CH 2 CH(CH 3 ), -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -, -CH 2 CH(CH 2 CH 3 )-), arylene (e.g., 1,4- phenylene) and aryl substituted C 2~5-Alkylene (e.g. 1-phenylethylene), especially -CH 2 CH 2 - and -CH 2 CH(CH 3 )- and other C 2~5 -alkylene, k is 0 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.

[0114] In particular, in the formula R 7 is methyl, Each R 8 are independently -H or C 1~4 -Alkyl or -C(=O)CH 3 is selected from Each R 9 -CH 2 CH 2 -, -CH 2 CH(CH 3 )- or -CH 2 CH 2 CH 2 - and k is 0 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. All R 7 It is preferred that the groups are the same.

[0115] Commercially available hydrophilically modified polysiloxanes of this type are DOWSIL 2-8692 and XIAMETER OFX-3667 manufactured by DOW.

[0116] In yet another variation, the polyether-modified polysiloxane is a polysiloxane having polyoxyalkylene chains incorporated into its backbone and grafted thereto. An illustrative example of the structure of such a hydrophilically modified polysiloxane is formula (C):

[0117] [ka]

[0118] In the formula, each R 7 is independently 1~5 -Alkyl (including linear or branched hydrocarbon groups) and aryl (e.g., phenyl (-C 6 H 5 )), in particular methyl, Each R 8 are independently -H, C 1~4 -Alkyl (e.g., -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH(CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 ), phenyl(-C 6 H 5 ), and C 1~4 -Alkyl carbonyl (e.g., -C(=O)CH 3 , -C(=O)CH 2 CH 3 and -C(=O)CH 2 CH 2 CH 3 ), especially -H, Methyl, and -C(=O)CH 3 is selected from Each R 9 is independently 2~5 -Alkylene (e.g., -CH 2 CH 2 -, -CH 2 CH(CH 3 )-, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -, -CH 2 CH(CH 2 CH 3 )-), arylene (e.g., 1,4- Phenylene) and aryl-substituted C 2~5-Alkylene (e.g. 1-phenylethylene), especially -CH 2 CH 2 - and -CH 2 CH(CH 3 )- and other C 2~5 -alkylene, 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.

[0119] In particular, in the formula R 7 is methyl,

[0120] Each R 8 is -H or C 1~4 -Alkyl or -C(=O)CH 3 and Each R 9 -CH 2 CH 2 -, -CH 2 CH 2 CH 2 - or -CH 2 CH(CH 3 )-and 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.

[0121] In the above structures (A), (B) and (C), the group -CH 2 CH(CH 3 )-, -CH 2 CH(CH 2 CH 3 )-, etc. can exist in either of two possible orientations. Similarly, k-fold and l-fold It should be understood that the present segments are typically randomly distributed within the polysiloxane structure.

[0122] In these embodiments and variations, 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 (A), (B), and (C), each R linking two oxygen atoms is 9 is preferably -CH 2 CH 2 - and -CH 2 CH(CH 3 )-, while each R linking a silicon atom and an oxygen atom is selected from 9 is preferably C 2~5 -alkyl.

[0123] In some embodiments of the above structures (A), (B) and (C), R 8 is preferably hydrogen do not have.

[0124] The one or more polyether-modified polysiloxanes may be of different types, such as those of the types described above. It should be understood that there may be more than one of them.

[0125] In another preferred embodiment, the non-ionic hydrophilically modified polysiloxane comprises polyglycerol or pyrrolidone groups.

[0126] Crosslinking and / or curing agents As previously explained, the polysiloxane-based binders of the present invention are curable and contain curing reactive functional groups such as silanol groups, carbinol groups, carboxyl groups, ester groups, hydride groups, alkenyl groups, vinyl ether groups, allyl ether groups, alkoxysilane groups, ketoxime groups, amine groups, epoxy groups, isocyanate groups and / or alkoxy groups. Preferably, the polysiloxane-based binders contain at least two curing reactive functional groups. Optionally, the polysiloxane-based binder contains two or more types of curing reactive functional groups. Preferably, the polysiloxane-based binder contains a single type of curing reactive functional group. Suitable crosslinkers and / or curing agents are selected depending on the curing reactive functional groups present in the polysiloxane-based binder.

[0127] In preferred polysiloxane-based binders, the curing reactive functional groups are silanols, carbinols, alkoxysilanes, isocyanates, amines and / or epoxies. In more preferred polysiloxane-based binders, the curing reactive functional groups are silanols, carbinols and / or alkoxysilanes.

[0128] In order to obtain the desired crosslink density, it may be necessary to add a crosslinking agent. 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.

[0129] R d -Si-K 4-d During the ceremony, Each R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms, poly (alkylene oxide) substituted C 1~6 Alkyl, or the structure (O-(CR D 2 ) r’ ) r1’ -(O-(CR D 2 ) s’ ) s1’ -(Si(R PP ) 2 -O) t’ -Si(R PP ) 3 wherein r', r1', s' and s1' are integers from 0 to 10, and each R D is H or C 1~4 Alki Each R PP is C 1~10 Alkyl, C 6~10 Aryl, C7~10 Alkylia aryl, t' is an integer from 1 to 50, and each K is an alkoxy group, is independently selected from hydrolyzable groups; d is 0, 1 or 2, more preferably 0 or 1.

[0130] Preferred crosslinkers of this type include tetraethoxysilane, vinyltris(methylethyloximo)silane, methyltris(methylethyloximo)silane, vinyltrimethoxysilane, methyltrimethoxysilane and vinyltriisopropenoxysilane and their hydrolytic condensation products.

[0131] When the cure reactive functional groups are di- or trialkoxy, a separate crosslinker is generally not required.

[0132] The crosslinking agent is preferably present in an amount of 0 to 10% by weight of the total dry weight of the coating composition. Suitable crosslinkers include, for example, Silcate TES-40 WN from Wacker and Dynasylan A from Evonik. is commercially available.

[0133] When the curing reactive functional group is a carbinol, the preferred curing agent is a monomeric isocyanate. Polyisocyanates are preferred over monomeric isocyanates due to their lower toxicity. Polyisocyanates include, for example, diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI). ) chemistry. These are, for example, supplied by Covestro under the trade name Desmodur and by Vencorex under the trade name Tolonate. Examples of polyisocyanates are Desmodur N3300, Desmodur 3390 BA / SN, Desmodur N3400, Desmodur N3600, Desmodur N75, Desmodur XP2580, Desmodur Z4470, Desmodur XP2565 and Desmodur VL, supplied by Covestro.

[0134] Polyisocyanates can be made with different NCO functionalities, which is the amount of NCO groups per molecule of polyisocyanate or per molecule of isocyanate prepolymer. Polyisocyanate curing agents with different NCO functionalities can be used.

[0135] The curing agent is preferably present in an amount of 0.8 to 2.5 equivalents of NCO groups relative to the amount of hydroxyl groups. Preferably, it is present in an amount of 0.9 to 2.0 equivalents, more preferably 0.95 to 1.7 equivalents, and even more preferably 1 to 1.5 equivalents.

[0136] When the curing reactive functional group is amine, epoxy or isocyanate, the curing agent is preferably amine, sulfur or epoxy functional.

[0137] The curing agent may be, for example, a dual curing agent containing both an amine / sulfur / epoxy / isocyanate and an alkoxysilane. A preferred dual curing agent is represented by the general formula:

[0138] [ka]

[0139] During the ceremony, LL is independently selected from unsubstituted or substituted monovalent hydrocarbon groups having 1 to 6 carbon atoms; Each M is independently selected from hydrolyzable groups, such as alkoxy groups; a is 0, 1 or 2, preferably 0 or 1; b is an integer from 1 to 6; Fn is an amine group, an epoxy group, a glycidyl ether group, an isocyanate group or a sulfur group.

[0140] A preferred example of such a dual curing agent is 3-isocyanatopropyltrimethoxysilane. Silanes include 3-isocyanatopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, (3-glycidoxypropyl)trimethoxysilane, and 3-mercaptopropyltrimethoxysilane. One particularly preferred curing agent is 3-aminopropyltriethoxysilane, such as Dynasylan AMEO manufactured by Evonik. be.

[0141] This type of dual curing agent can be used as a separate curing agent or can be combined with the polysiloxane binder so that the end groups of the polysiloxane binder are modified prior to the curing reaction. For example, the polysiloxane binder can be mixed with the curing agent just prior to applying the coating to the article, for example, one hour or less prior to coating, or the polysiloxane binder can be mixed with the curing agent to form a curable coating. It can be provided in a curing agent / endcapping form, but can be left dry to prevent premature curing. In some compositions, the curing agent / endcapping agent is preferably provided separately to the remainder of the coating composition to prevent the coating from curing before it is applied to an object. Thus, the coating composition of the present invention can be provided as a multi-part (preferably three-part) formulation, which is discussed in more detail below.

[0142] catalyst To aid in the curing process, the coating composition of the present invention preferably includes a catalyst.Representative examples of catalysts that can be used include transition metal compounds, metal salts and organometallic complexes of various metals, such as tin, iron, lead, barium, cobalt, zinc, antimony, cadmium, manganese, chromium, nickel, aluminum, gallium, germanium, titanium, boron, lithium, potassium, bismuth and zirconium.The salts are preferably salts and / or chelates of long-chain carboxylic acids or organometallic salts.

[0143] Examples of suitable tin-based catalysts include, for example, dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin diacetate, dibutyltin 2-ethylhexano ... Butyltin dineodecanoate, dibutyltin dimethoxide, dibutyltin dibenzoate, dibutyltin acetoacetonate, dibutyltin acetylacetonate, dibutyltin alkylacetoacetonate, dioctyltin dilaurate, dioctyltin dioctoate, dioctyltin diacetate, dioctyltin 2-ethylhexanoate, dioctyltin dilaurate, dioctyltin dioctoate, dioctyltin diacetate, dioctyltin 2-ethylhexanoate, dioctyltin dilaurate, dioctyltin dimethoxide, dioctyltin dibenzo ... Examples of commercially available tin catalysts include tin tin dimethyl tin dimethoxide, tin dibenzoate, tin tin acetoacetonate, tin tin acetylacetonate, tin tin alkylacetoacetonate, tin dibutyrate, tin bisneodecanoate, tin dineodecanoate, tin naphthenate, tin butyrate, tin oleate, tin caprylate, tin octanoate, tin stearate, tin triethyl tartrate, isobutyltin trichlorate and tin octanoate. 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.

[0144] Examples of suitable zinc catalysts are zinc 2-ethylhexanoate, zinc naphthenate and zinc stearic acid. Zinc. Examples of commercially available zinc catalysts include K-KAT XK-672 and K-KAT670 from King Industries, and Borchi Kat22 from Borchers.

[0145] Examples of suitable bismuth catalysts are bismuth 2-ethylhexanoate, bismuth octoate and Organobismuth compounds such as bismuth neodecanoate. Examples of 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 KAT716 from TIB Chemicals.

[0146] Examples of suitable titanium catalysts are organotitanium catalysts such as titanium naphthenate, tetrabutyl titanate, tetrakis(2-ethylhexyl) titanate, triethanolamine titanate, Titanate, tetra(isopropenyloxy)titanate, titanium tetrabutanolate, titanium tetrapropanolate, titanium tetraisopropanolate and chelated titanates such as diisopropyl bis(acetylacetonyl)titanate, diisopropyl bis(ethylacetoacetonyl)titanate and diisopropoxytitanium bis(ethylacetoacetate). Examples of suitable commercially available titanium catalysts are Tyzor IBAY and TIB Ch manufactured by Dorf Ketal. It is the TIB KAT 517 made by emicals.

[0147] Other suitable catalysts include iron catalysts such as iron stearate and iron 2-ethylhexanoate; lead catalysts such as lead phosphate and lead 2-ethyloctanoate; cobalt catalysts such as cobalt-2-ethylhexanoate and cobalt naphthenate; manganese catalysts such as manganese 2-ethylhexanoate. catalyst, zirconium naphthenate, tetrabutyl zirconate, tetrakis(2-ethyl and zirconium catalysts such as tetra(hexyl)zirconate, triethanolamine zirconate, tetra(isopropenyloxy)-zirconate, zirconium tetrabutanolate, zirconium tetrapropanolate and zirconium tetraisopropanolate.

[0148] More preferred catalysts are zirconate esters.

[0149] The catalyst may also be an organic compound such as triethylamine, guanidine, amidine, cyclic amines, tetramethylethylenediamine, 1,4-ethylenepiperazine, and pentamethyldiethylenetriamine. Further examples include aminosilanes, e.g., 3-aminosilanes, e.g., propyltriethoxysilane and N,N-dibutylaminomethyl-triethoxysilane.

[0150] In a preferred embodiment, the catalyst is a tin, bismuth and / or zinc catalyst, more preferably a tin and / or bismuth catalyst.

[0151] Preferably, the catalyst is present in an amount of from 0.01 to 5 wt. %, based on the total dry weight of the coating composition; More preferably, it is present in the coating compositions of the present invention in an amount of from 0.05 to 4 weight percent.

[0152] added oil The coating composition of the present invention optionally contains an additive oil. Preferably, the coating composition of the present invention contains 0 to 30% by weight of additive oil, more preferably 0 to 30% by weight of additive oil, based on the solids content of the coating composition. The non-ionic hydrophilic modified polysiloxane described herein contains 0.1 to 15% by weight of added oil. The polysiloxanes are not considered "additive oils." Thus, the additive oils are different oils than the nonionic hydrophilically modified polysiloxanes described herein.

[0153] Suitable non-reactive additive oils are silicone oils such as methylphenyl silicone oils, petroleum oils, polyolefin oils, polyaromatic oils, fluororesins such as polytetrafluoroethylene or fluid fluorinated alkyl or alkoxy-containing polymers, or lanolin and lanolin derivatives, and other sterols and / or sterol derivatives as disclosed in WO2013024106, or combinations thereof. A preferred non-reactive additive oil is methylphenyl silicone oil.

[0154] Further additive oils optionally present in the coating composition of the present invention are fluorinated amphiphilic polymers / oligomers as described in WO2014131695.

[0155] The coating composition of the present invention optionally comprises 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.

[0156] Non-reactive hydrophilic modified additive oils are typically modified by the addition of non-ionic monomeric, oligomeric or polymeric groups that may be polar and / or capable of hydrogen bonding to enhance interactions with polar solvents, especially 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-dimethacrylamide), acids (e.g., poly(acrylic acid)), alcohols (e.g., poly(glycerol), polyHEMA, polysaccharides, poly(vinyl alcohol)), ketones (polyketones), aldehydes (e.g., poly(aldehyde guluronate), amines (e.g., polyvinylamine), esters (e.g., polycaprolactone, poly(vinyl acetate)), imides (e.g., poly(2-methyl-2-oxazoline)), and copolymers of the foregoing.

[0157] Cobinder Optionally, in addition to the polysiloxane-based binder, a co-binder may be present in the coating composition of the present invention.Preferably, the co-binder comprises a curing reactive group that can react with the polysiloxane-based binder in a curing reaction.Representative examples of such co-binder include silicone resin, silicone-epoxy resin, silicone-polyester resin, polyurethane-based binder, polyol-based binder such as acrylic-polyol binder, polyester-based binder and acrylic-based binder.

[0158] Pigments 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.

[0159] Representative examples of pigments include black iron oxide, red iron oxide, yellow iron oxide, titanium dioxide, zinc oxide, carbon black, graphite, red molybdate, yellow molybdate, zinc sulfide, antimony oxide, sodium aluminum sulfosilicate, quinacridone, phthalocyanine blue, phthalocyanine green, indanthrone blue, aluminum cobalt oxide, carbazole dioxazine, isoindoline orange, bis-acetoacetoacetotridiol, benzimidazolone, quinaphthrone yellow, isoindoline yellow, tetrachloroisoindolinone, and quinophthalone yellow, metal flake material (e.g., aluminum flake).Preferred pigments are black iron oxide, red iron oxide, yellow iron oxide, phthalocyanine blue, and titanium dioxide.In a preferred embodiment, titanium dioxide is surface-treated with a silicone compound, a zirconium compound, or a zinc compound.

[0160] The amount of pigment present in the coating composition of the present invention is preferably from 0 to 25% by weight, more preferably from 0.5 to 15% by weight, based on the total dry weight of the coating composition.

[0161] solvent The release coating composition of the present invention preferably includes a solvent. Solvents suitable for use in the compositions of the present invention are commercially available.

[0162] Examples of suitable organic solvents and diluents are aromatic hydrocarbons such as xylene, toluene, mesitylene, etc.; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, cyclopentanone, cyclohexanone, etc.; esters such as butyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, ethylene glycol methyl ether acetate, propylene glycol methyl ether acetate, etc.; ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, dioxane, tetrahydrofuran, etc.; n-butanol, isobutanol, alcohols such as 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 diluents.

[0163] The amount of solvent present in the release coating composition of the present invention minimizes the VOC content. Preferably, the solvent is present in the composition of the present invention in an amount of 0-35% by weight, more preferably 1-30% by weight, based on the total weight of the composition. Those skilled in the art will appreciate that the content of the solvent will vary depending on the other ingredients present.

[0164] Filler The coating compositions of the present invention optionally include a filler.

[0165] Examples of fillers that can be used in the coating composition according to the present invention are zinc oxide, barium sulfate, calcium sulfate, calcium carbonate, fumed silica, silica or silicate, including bentonite and other clays (such as talc, feldspar, kaolin, and nepheline syaenite), and solid silicone resins, which are generally condensed branched polysiloxanes.Some fillers, such as fumed silica, can have a thickening effect on the coating composition.

[0166] 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. An example of a commercially available fumed silica filler is Cabot's TS-610, TS-530, EH-5, H-5, and M-5 from Aerosil, and Aerosil® R972, Aerosil® R974, Aerosil® R976, Aerosil® R104, Aerosil® R202, Aerosil® R208, Aerosil® R805, Aerosil® R106, Aerosil® R108, Aerosil® R109, Aerosil® R210, Aerosil® R212, Aerosil® R214, Aerosil® R216, Aerosil® R218, Aerosil® R220, Aerosil® R222, Aerosil® R224, Aerosil® R226, Aerosil® R228, Aerosil® R228, Aerosil® R229, Aerosil® R230, Aerosil® R232, Aerosil® R2 (registered trademark) R812, Aerosil (registered trademark) 816, Aerosil (registered trademark) R7200, Aerosil (registered trademark) Aerosil® R8200, Aerosil® R9200, and Aerosil® R711.

[0167] The amount of filler present in the coating composition of the present invention is preferably from 0 to 25 wt.%, more preferably from 0.1 to 10 wt.%, and even more preferably from 0.15 to 5 wt.%, based on the total dry weight of the coating composition.

[0168] 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 include reinforcing agents, thixotropic agents, thickening agents, anti-settling agents, dehydrating agents, dispersing agents, wetting agents, surfactants, binders, plasticizers, and dyes. Examples of thixotropic agents, thickeners and anti-settling agents are silicas such as fumed silica, organomodified clays, amide waxes, polyamide waxes, amide derivatives, polyethylene waxes, oxidized polyethylene waxes, hydrogenated castor oil waxes and mixtures thereof. Preferably, the thixotropic agents, thickeners and anti-settling agents are each present in the composition of the present invention in an amount of 0 to 10% by weight, more preferably 0.1 to 6% by weight, even more preferably 0.2 to 10% by weight, based on the total dry weight of the composition. More preferably, it is present in an amount of 0.1 to 2.0% by weight.

[0169] Dehydrating agents and drying agents that can be used in the deposit release coating composition include organic and inorganic compounds. Dehydrating agents can be hygroscopic materials that absorb water or bind water as water of crystallization, often referred to as desiccants. Examples of drying agents 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. 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; and the like. 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 ethyl polysilicate.

[0170] Preferably, the dehydrating agent is present in the composition of the invention in an amount of 0 to 5 wt.%, more preferably 0.5 to 2.5 wt.%, even more preferably 1.0 to 2.0 wt.%, based on the total dry weight of the composition.

[0171] Compositions and coatings The present invention also relates to a process for preparing the composition as described hereinbefore, by mixing the ingredients present in the composition. Any conventional manufacturing process can be used.

[0172] 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, additional solvent and optionally other ingredients are added to the compositions described herein to form a paint. Preferred solvents are as described above for the compositions.

[0173] After mixing, and optionally after addition of a solvent, the deposit release coating composition or paint is preferably filled into containers. Suitable containers include cans, drums and tanks.

[0174] The release coating composition may be supplied as a one-part, two-part or three-part composition. Preferably, the composition is provided as a two-part or three-part composition, even more preferably as a three-part composition. will be provided.

[0175] When supplied as a one-part formulation, the composition is preferably in a ready-to-mix or ready-to-use form. Supplied in ready-to-use form. Optionally, one-component products can be thinned with a solvent prior to application. This can be done.

[0176] When supplied as a two-part formulation, the first container preferably contains the polysiloxane-based binder, the non-ionic hydrophilically modified polysiloxane, and the stain repellent, and the second container preferably contains , a crosslinker / curing agent and / or a catalyst. Optionally, instructions for mixing the contents of the container may be provided.

[0177] When supplied as a three-part system, the first container preferably contains the polysiloxane binder, the soil repellent and the non-ionic hydrophilically modified polysiloxane, and the second container preferably contains the crosslinking agent. The first container preferably contains a crosslinker / curing agent, and the third container preferably contains a catalyst. Optionally, the contents of the containers Instructions for mixing the components may be provided.

[0178] In certain embodiments, the present invention provides a kit for preparing the deposit stripping composition defined herein.

[0179] The adhesion release coating composition and paint of the present invention preferably have a solids content of 50 to 99% by weight, more preferably 60 to 99% by weight, and even more preferably 65 to 99% by weight. Preferably, the release coating compositions and paints of the present invention have a concentration of 50 to 400 g / L, preferably Preferably, the volatile organic compounds (VOC) content is between 50 and 350 g / L, e.g., between 50 and 300 g / L. The VOC content can be calculated (ASTM D5201-05A) or measured (US EPA Method 24 or ISO 11890-1).

[0180] Preferably, the release coating compositions and paints of the present invention have a viscosity of 700 to 1100 mPa under a shear rate of 100 / s.

[0181] The coating composition of the present invention can be applied to any pre-treated coating layer designed for polysiloxane-based fouling release coating. Examples of such coating layers are epoxy 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.

[0182] The coating composition of the present invention may also be applied to a substrate containing an old antifouling coating layer or a fouling release layer, which is cleaned with a high pressure water wash to remove the fouling prior to application of the coating composition of the present invention to the old layer.

[0183] 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.

[0184] The dry thickness of each coating layer of the coating composition of the present invention is preferably 50 to 500 μm, more preferably 100 to 400 μm, and most preferably 150 to 300 μm.

[0185] The fouling release coating compositions and paints of the present invention can be applied to the whole or part of the surface of any article exposed to marine fouling. The surface may be permanently submerged or may be intermittently submerged (e.g., due to tidal movements, different cargo weights or wave swells). The surface of the article is typically the surface of a ship's hull or a fixed marine object such as an oil platform or buoy. Application of the coating compositions and paints 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 needs to be isolated from seawater to allow coating. Application of the coating can be accomplished as conventionally known in the art. After application of the coating, the coating is preferably dried and / or cured.

[0186] Coating The fouling release coating of the present invention is typically 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 boats, marine liners, tugboats, tankers, container ships and other cargo ships, submarines, and all types of naval vessels), pipes, onshore and offshore machinery, structures, and all types of objects, such as piers, pilings, bridge substructures, hydraulic equipment and structures, underwater oil well structures, nets and other aquaculture equipment, and buoys.The surface of the substrate may be a "natural" surface (e.g., a steel surface).

[0187] [Example] Quantitative method Determination of polymer average molecular weight distribution The polymers were characterized by gel permeation chromatography (GPC) measurements. Molecular weight distributions (MWD) were determined using a Malvern Omnisec Resolve and Reveal system equipped with two PLgel 5 μm Mixed-D columns in series from Agilent. The columns were fitted with narrow polystyrene. The analytical conditions were as shown in Table 1 below. I did.

[0188] [Table 1]

[0189] Samples were prepared by dissolving an amount of non-ionic hydrophilically modified polysiloxane equivalent to 25 mg of dry polymer in 5 ml of THF. The samples were kept at room temperature for a minimum of 3 hours and then sampled for GPC measurement. Before analysis, the samples were filtered through a 0.45 μm nylon filter. Weight average Record the molecular weight (Mw) and number average molecular weight (Mn).

[0190] Measurement of the viscosity of non-ionic hydrophilically modified polysiloxanes. The viscosity of the non-ionic hydrophilically modified polysiloxane was measured using a Brookfield viscometer and spindle. The viscosity was measured at 25° C. using a Brookfield LVT viscometer and corresponding LV spindle. The spindle was measured according to the BROOKFIELD DIAL VISCOMETER Operating Instructions. , in accordance with Manual No. M / 85-150-P700, Brookfield Engineering Laboratories, Inc. The nonionic hydrophilically modified polysiloxane was appropriately selected for its specification range.

[0191] Measuring the viscosity of paint formulations The viscosity of the paint formulations (inventive examples and comparative examples) was measured at 23°C using a cone plate. The cone diameter was 40 mm, the cone angle was 4°, and the shear rate was increased from 0.01 / s to 100 / s. The shear rate dependent viscosity was obtained.

[0192] Preparation of the Coating Composition First, using a high-speed dissolver equipped with an impeller disk, the (A) part shown in Tables 5 and 6 below was dissolved. The coating composition was prepared by mixing the components of part (B) with the components of part (A) immediately prior to applying the coating. The non-ionic hydrophilically modified polysiloxane was added to the coating composition after the milling step. The components of part (B) were mixed with the components of part (A).

[0193] Antifouling performance testing in Singapore The PVC panels were primed with a first coat of Jotun Jotacote Universal N10 primer and then Jotun SeaQ Coat using airless spray under specified conditions with a second coat of uest Tiecoat. The inventive and comparative coating compositions were applied to PVC panels that had been precoated with primer and tie coat using a film applicator with a clearance of 300 μm.

[0194] The panels were used in static testing on a floating platform in Singapore, where the panels were submerged 0.3-1.3m below sea level. The panels were visually rated using the scale shown in Table 2 below.

[0195] [Table 2]

[0196] Determining the adhesion of coatings The adhesion of the coating was judged according to ASTM D6677:18. A rating of 5 or above was considered a pass. ("OK" in Tables 5 and 6).

[0197] Determining Coating Uniformity The coating uniformity was judged by visual observation according to Table 3.

[0198] [Table 3]

[0199] [Table 4]

[0200] Non-ionic hydrophilically modified polysiloxanes having the properties listed in Table 4 are commercially available. , and are readily available from commercial suppliers.

[0201] The coating compositions and antifouling performance of the inventive and comparative examples are shown in the table below.

[0202] [Table 5]

[0203] [Table 6A]

[0204] [Table 6B]

[0205] With respect to the above example, the following observations can be made. In Comparative Example 2, copper pyrithione was added to a coating containing polyether-modified polysiloxane. The addition of this shows an increase in the viscosity of the coating compared to Comparative Example 1. Viscosity The increase in oil content can adversely affect application properties and surface roughness. Furthermore, 5% by weight of oil reduces the copper pin content. It is not enough to reduce the viscosity increase caused by the addition of lithion.

[0206] Example 1 and Example 2 of the present invention illustrate coating compositions containing copper pyrithione, and 15-25% by weight of oil-based polyether-modified polysiloxane is effective in reducing the amount of VOC while maintaining low levels. Therefore, it has good film uniformity and good adhesion. Furthermore, the increase in viscosity observed in Comparative Example 2 is This is offset by a higher oil content. The antifouling performance is also improved compared to Comparative Example 2.

[0207] Comparative Example 2 shows that 5 wt. % oil is insufficient to achieve satisfactory antifouling performance.

[0208] Comparative Examples 3 and 4 show that dilution with a solvent can reduce the viscosity of a copper pyrithione-containing coating to its original level, but at the expense of increased VOCs, which have adverse effects in terms of health and environmental concerns.

[0209] Comparative Example 5 shows that further increasing the oil to 35 wt% (dry weight basis) further reduces the VOC and viscosity, but at the expense of coating uniformity and antifouling performance.

[0210] Examples 3-6 of the present invention show that there are several possible polyether modified polysiloxane oils that exhibit good antifouling performance while maintaining good film uniformity and adhesion at oil amounts as high as 16 wt% (dry weight basis). Lower viscosity oils reduce the final viscosity of the coating to a greater extent.

[0211] Comparative Examples 6 and 7 show that the oil having an HLB level of more than 12 is present at 16% and 25% by weight, respectively. (on a dry weight basis) has been shown to adversely affect coating uniformity and adhesion.

[0212] Comparative Examples 8-10 show that oils with number average molecular weights above 18,000 give good film uniformity and good adhesion at oil concentrations up to 34 wt.% (dry weight basis), but poor antifouling performance. This is probably because too high a molecular weight limits the movement of the oil through the film. If the viscosity of the oil is too high, more oil is also needed to reduce the viscosity of the paint formulation.

[0213] In summary, the present invention uses non-ionic surfactants having specific parameters (amount, molecular weight and HLB). By selecting a hydrophilic modified polysiloxane, low VOC, good application properties, and good film formation are achieved. It has now been found possible to obtain a deposit release formulation having uniformity and adhesion as well as improved antifouling properties and containing a biocide such as copper pyrithione.

Claims

1. a) a curable polysiloxane-based binder containing at least 50% by weight of polysiloxane moieties; And, b) a stain repellent; c) 10 to 30% by dry weight, i) a hydrophilic-lipophilic balance (HLB) of 1 to 12, and ii) Mn between 500 and 18,000 g / mol A non-ionic hydrophilic modified polysiloxane having the formula:

1. A release coating composition comprising:

2. a) a curable polysiloxane-based binder containing at least 50% by weight of polysiloxane moieties; And, b) a stain repellent; c) 10 to 30% by dry weight, i) a hydrophilic-lipophilic balance (HLB) of 1 to 12, and ii) Mw between 1,000 and 50,000 g / mol A non-ionic hydrophilic modified polysiloxane having the formula:

1. A release coating composition comprising:

3. 3. The release coating composition of claim 1, comprising 30-95% by weight of polysiloxane-based binder, more preferably 40-90% by weight of polysiloxane-based binder, and even more preferably 50-90% by weight of polysiloxane-based binder, based on the total dry weight of the composition.

4. the soil release agent is present in an amount of from 1 to 15 wt. % on a dry weight basis, based on the total dry weight of the composition; The release coating composition according to any one of claims 1 to 3, preferably present in an amount of 2 to 15 wt.%, more preferably 3 to 12 wt.%.

5. 5. A deposit release coating composition according to any one of claims 1 to 4, wherein the non-ionic hydrophilically modified polysiloxane is present in an amount of 11 to 29 wt.-% (dry weight basis), preferably 12 to 28 dry wt.-%, preferably 13 to 27 dry wt.-%, preferably 14 to 26 dry wt.-%, for example 15 to 25 dry wt.-%, based on the total dry weight of the composition.

6. A deposit release coating composition according to any one of claims 1 to 5, wherein the antifouling agent is zinc pyrithione or copper pyrithione, preferably copper pyrithione.

7. The nonionic hydrophilically modified polysiloxane has a molecular weight in the range of 500 to 18,000 g / mol, for example 1000 7. The release coating composition according to claim 1, having a number average molecular weight (Mn) in the range of from 2000 to 15,050 g / mol, in particular from 4000 to 15,050 g / mol.

8. The nonionic hydrophilic modified polysiloxane has a viscosity in the range of 20 to 4,000 mPa-s, preferably 30 8. The release coating composition according to claim 1, having a viscosity in the range of 1 to 3,000 mPa-s, in particular in the range of 50 to 2,500 mPa-s.

9. 9. The release coating composition according to claim 1, wherein the non-ionic hydrophilically modified polysiloxane has a weight average molecular weight (Mw) of 2,000 to 45,000 g / mol, preferably 3,000 to 42,000 g / mol, 4,000 to 40,000 g / mol or 5,000 to 40,000 g / mol.

10. 10. The method according to claim 1, wherein the non-ionic hydrophilically modified polysiloxane has an HLB (hydrophilic-lipophilic balance) in the range of 1.0 to 10, more preferably 1.0 to 8.0, and most preferably 2.0 to 7.

0.

2. The release coating composition according to claim 1 .

11. The polysiloxane binder is represented by the following formula (D1): 【Chemistry 1】 [In the formula, Each R 1 are independently a hydroxyl group, C 1～6 -alkoxy group, C 1～6 - Hydroxyl group, C 1～6 -epoxy-containing group, C 1～6 Amine group, or O-Si(R 5 ) 3－z (R 6 ) z is selected from Each R 2 is independently 1～10 Alkyl, C 6～10 Aryl, C 7－10 alkylaryl, or poly(alkylene oxide) and / or R 1 C substituted with a group described as 1～6 Alki are selected from Each R 3 and R 4 is independently 1～10 Alkyl, C 6～10 Aryl, C 7～10 Alkylaryl or poly(alkylene oxide) substituted C 1～6 alkyl, Each R 5 is independently 1～6 Alkoxy groups, acetoxy groups, enoxy groups, or ketoxy groups Which hydrolyzable group is Each R 6 are independently unsubstituted C 1～6 Alkyl or substituted C 1～6 alkyl groups, z is 0 or an integer from 1 to 2; x is an integer equal to or greater than 2, y is an integer equal to or greater than 2. The release coating composition according to any one of claims 1 to 10.

12. At least one of a filler, a pigment, a solvent, an additive, a curing agent, and a catalyst; or The adhesion release coating composition according to claims 1 to 12, and a filler, a pigment, a solvent, an additive, The release coating composition of any one of claims 1 to 11, further comprising a coating comprising at least one of an additive, a curing agent, and a catalyst.

13. 13. The release coating composition according to claim 1, wherein the non-ionic hydrophilically modified polysiloxane is a polyether modified polysiloxane.

14. The nonionic hydrophilic modified polysiloxane is a binder curing agent having a hardening property at 0 to 40° C. The release coating according to any one of claims 1 to 13, which is non-curable in the reaction. Composition.

15. a) a curable polysiloxane-based binder containing at least 50% by weight of polysiloxane moieties; And, b) a stain repellent; c) 10 to 30% by dry weight, i) a relative weight of the hydrophilic portion in the range of 5 to 60% by weight, and ii) Mn between 500 and 18,000 g / mol and a non-ionic hydrophilically modified polysiloxane having the formula:

16. a) a curable polysiloxane-based binder containing at least 50% by weight of polysiloxane moieties; And, b) a stain repellent; c) 10 to 30% by dry weight, i) a relative weight of the hydrophilic portion in the range of 5 to 60% by weight, and ii) Mw between 1,000 and 50,000 g / mol and a non-ionic hydrophilically modified polysiloxane having the formula:

17. The deposit removing composition is as defined in any one of claims 1 to 14.

17. The adhesion removing composition according to claim 15 or 16.

18. The adhesion release coating composition according to any one of claims 1 to 17 is applied to a part of the outer surface of the At least a part of the marine structure.

19. A method for preparing a release coating composition according to any one of claims 1 to 14. And, a) a curable polysiloxane-based binder containing at least 50% by weight of polysiloxane moieties; And, b) a stain repellent; c) 10 to 30% by dry weight, i) HLB from 1 to 12, and ii) Mn of 500 to 18,000 g / mol and / or Mw of 1,000 to 50,000 g / mol and a non-ionic hydrophilic modified polysiloxane having the formula: The method typically includes the step of mixing in at least one solvent.

20. A method for preparing an adhesion release coating composition according to any one of claims 15 to 17, comprising the steps of: a) a curable polysiloxane-based binder containing at least 50% by weight of polysiloxane moieties; And, b) a stain repellent; c) 10 to 30% by dry weight, i) the relative weight of the hydrophilic portion in the range of 5 to 60% by weight, and ii) Mn of 500 to 18,000 g / mol and / or Mw of 1,000 to 50,000 g / mol and a non-ionic hydrophilic modified polysiloxane having the formula: The method typically includes the step of mixing in at least one solvent.

21. For preparing the adhesion release coating composition according to any one of claims 1 to 17 A kit comprising: (i) A curable polysiloxane binder, a stain-resistant agent and / or a non-ionic hydrophilic modified polysiloxane a first container containing lysiloxane; (ii) a second container containing a crosslinker and / or curing agent, and optionally a catalyst; (iii) optionally, a third vessel containing a catalyst; (iv) optionally, instructions for combining the contents of said containers.

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