Antifouling composition

Abstract

To provide an antifouling coating composition having a silyl ester copolymer which, by combining with medetomidine, can provide degradation control of the antifouling coating, resistance to cracking, and excellent antifouling properties, in particular excellent barnacle settlement prevention properties.SOLUTION: An antifouling coating composition comprises (i) a silyl ester copolymer, (ii) medetomidine, and (iii) rosin or a derivative thereof, wherein the silyl ester copolymer comprises as comonomers (a) triisopropylsilyl methacrylate; and (b) a compound represented by Formula (I), and wherein the content of volatile organic compounds (VOC) (ASTM D5201-01) is 400 g / L or less. In Formula (I), R1 is hydrogen or methyl, R2 is a cyclic ether, and X is C1-C4 alkylene.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a marine antifouling coating composition, particularly to a marine antifouling coating composition containing a silyl ester copolymer comprising triisopropylsilyl methacrylate and at least one hydrophilic (meth)acrylate as comonomers. Such marine antifouling coating compositions further contain medetomidine as a biocide. The present invention also relates to a method for antifouling an object, and to an object coated with the marine antifouling coating composition of the present invention. [Background technology]

[0002] The surface that is submerged in seawater is home to bacteria, diatoms, algae, tube worms, barnacles, They are subject to attachment by fouling organisms such as mussels. Of all marine organisms that grow on surfaces, the most tenaciously attached are barnacles. Given the right conditions, barnacles can grow very quickly. Barnacles are distributed worldwide and are the most frequently encountered fouling organisms in coastal waters.

[0003] The risk of barnacle fouling and attachment to ships is generally highest during the fitting-out period of newly constructed ships and during extended periods when ships are out of service at anchor or in trade. Fouling can significantly impair a ship's operational efficiency. It increases hydrodynamic drag, fuel consumption, speed, and range. A heavily fouled and uneven hull can increase fuel consumption by as much as 40%. It also incurs additional costs for drydocking. Attached barnacles and other calcareous organisms must be mechanically scraped away to remove them. Ship fouling can also encourage the proliferation of non-indigenous species. All of these are important economic factors that necessitate the prevention of biofouling, or biofouling.

[0004] Antifouling coatings are used to prevent the attachment and growth of marine organisms. These coatings typically contain a film-forming binder and a biologically active material along with various ingredients such as pigments, fillers, solvents, etc.

[0005] The most successful self-polishing antifouling systems on the market today are based on silyl ester copolymers. The binder matrix consists of a silyl ester copolymer, often containing other binders such as acrylates and rosin or rosin derivatives to adjust the self-polishing and mechanical properties of the antifouling coating film. These coating compositions are disclosed, for example, in U.S. Pat. Nos. 5,629,592, 5,629,597, 5,629,598, 5,629,59 ... [Prior art documents] [Patent documents]

[0006] [Patent Document 1] European Patent Application Publication No. 0646630 [Patent Document 2] European Patent Application Publication No. 0802243 [Patent Document 3] European Patent Application Publication No. 1342756 [Patent Document 4] European Patent Application Publication No. 1641862 [Patent Document 5] European Patent Application Publication No. 1695956 [Patent Document 6] European Patent Application Publication No. 2781567 [Patent Document 7] International Publication No. 00 / 77102 [Patent Document 8] International Publication No. 03 / 070832 [Patent Document 9] International Publication No. 2009 / 007276 [Patent Document 10] International Publication No. 2011 / 118526 [Patent Document 11] International Publication No. 2007 / 015676 [Patent Document 12] International Publication No. 2006 / 096129 [Patent Document 13] International Publication No. 00 / 42851 [Patent Document 14] International Publication No. 2010 / 071180 [Patent Document 15] Japanese Patent Application Laid-Open No. 2016-89167 [Patent Document 16] International Publication No. 2013 / 073580 [Patent Document 17] International Publication No. 2014 / 064048 [Patent Document 18] International Publication No. 03 / 080747 [Patent Document 19] U.S. Patent No. 4,593,055 [Patent Document 20] International Publication No. 97 / 044401 [Patent Document 21] European Patent Application Publication No. 2128208 [Patent Document 22] European Patent Application Publication No. 0204456 [Patent Document 23] European Patent Application Publication No. 0342276 [Patent Document 24] GB Patent Application Publication No. 2311070 [Patent Document 25] European Patent Application Publication No. 0982324 [Patent Document 26] European Patent Application Publication No. 0529693 [Patent Document 27] GB Patent Application Publication No. 2152947 [Patent Document 28] European Patent Application Publication No. 0526441 [Patent Document 29] European Patent Application Publication No. 1033392 [Patent Document 30] European Patent Application Publication No. 1072625 [Patent Document 31] International Publication No. 2009 / 100908 [Patent Document 32] International Publication No. 96 / 14362 [Patent Document 33] International Publication No. 2011 / 092143 [Patent Document 34] European Patent Application Publication No. 2725073 [Patent Document 35] European Patent Application Publication No. 2551309 Summary of the Invention [Problem to be solved by the invention]

[0007] Medetomidine is effective in preventing barnacle attachment to surfaces immersed in seawater. Medetomidine is a nitrogen heterocyclic compound. Such compounds are known to adversely affect the storage stability of antifouling coating compositions and the long-term mechanical properties of antifouling coating films containing hydrolyzable binders, particularly silyl ester copolymers.

[0008] Surprisingly, the inventors have found that a silyl ester copolymer, for example comprising triisopropylsilyl methacrylate and a hydrophilic (meth)acrylate comonomer, in combination with medetomidine provides a self-polishing antifouling system that exhibits improved antifouling performance, particularly in terms of preventing barnacle fouling on marine surfaces. Furthermore, the antifouling composition of the present invention has excellent cracking resistance and excellent self-polishing properties.

[0009] Antifouling coating compositions containing medetomidine have been disclosed. Patent Document 10 claims hydrolyzable copolymers such as silyl ester copolymers in antifouling coating formulations containing medetomidine. Only one example is given: a triisopropylsilyl acrylate copolymer that does not contain a hydrophilic comonomer.

[0010] The use of medetomidine (in combination with other biologically active compounds) to prevent barnacle attachment is disclosed in U.S. Patent Nos. 5,629,999, 5,729,965, 5,729,975, and 5,729,975, although these documents are not specific to binder technology.

[0011] Antifouling coating compositions containing triisopropylsilyl methacrylate and a hydrophilic comonomer are known. Patent Document 14 claims an antifouling coating composition containing a silyl copolymer containing triisopropylsilyl methacrylate and a methoxyalkyl methacrylate, and a copper salt of rosin or a copper salt of a rosin derivative. A preferred antifouling agent is cuprous oxide combined with an algaecide. This coating composition has insufficient performance in terms of barnacle adhesion inhibition.

[0012] Patent Document 15 claims a copper-free antifouling coating composition that contains a silyl copolymer containing triisopropylsilyl methacrylate and methoxyethyl (meth)acrylate, and tralopyril, which provides excellent storage stability, and that forms an antifouling coating film with excellent long-term water resistance (e.g., cracking resistance).

[0013] Patent Document 16 claims a silyl copolymer containing structural units from both triisopropylsilyl acrylate and triisopropylsilyl methacrylate in a specific ratio, which provides an antifouling coating composition with long-term storage stability and an antifouling coating film with long-term mechanical properties. Comparative Examples show the poor mechanical properties of triisopropylsilyl acrylate copolymer and triisopropylsilyl methacrylate copolymer. None of the exemplified silyl copolymers contain a hydrophilic comonomer.

[0014] Therefore, there is a need for silyl ester copolymers (and thus antifouling compositions) that can be combined with medetomidine to provide antifouling coating degradation control, cracking resistance, and excellent antifouling properties, especially excellent barnacle adhesion inhibition properties. There is also a need for long-term storage stability. [Means for solving the problem]

[0015] In one aspect, the present invention relates to an antifouling coating composition comprising: (i) a silyl ester copolymer; and (ii) medetomidine, wherein the silyl ester copolymer contains, as a comonomer: (a) triisopropylsilyl methacrylate; (b) A compound represented by the following formula (I):

[0016] [ka]

[0017] In formula (I), R 1 is hydrogen or methyl, and R 2 is a cyclic ether (for example, oxolane, oxane, dioxolane, or dioxane substituted or unsubstituted with an alkyl group), and X is a C1-C4 alkylene, and / or a compound represented by the following formula (II):

[0018] [ka]

[0019] In formula (II), R 3 is hydrogen or methyl, and R 4 is a C3-C18 substituent having at least one oxygen or nitrogen atom, preferably at least one oxygen atom, and optionally (c) one or more comonomers represented by formula (III):

[0020] [ka]

[0021] In formula (III), R 5 is hydrogen or methyl, and R 6 and one or more comonomers, wherein the comonomer is a C1 to C8 hydrocarbyl.

[0022] The silyl ester copolymer preferably has a glass transition temperature (Tg) of at least 20°C as measured by DSC according to the method described in the Examples herein.

[0023] The antifouling coating composition comprises medetomidine and, optionally, an additional antifouling agent. The additional antifouling agent may be cuprous oxide, copper pyrithione, tralopyril, or zinc pyrithione. In one embodiment, the antifouling coating composition comprises cuprous oxide and copper pyrithione in addition to medetomidine. In another embodiment, the antifouling coating composition comprises tralopyril and zinc pyrithione in addition to medetomidine. Thus, the antifouling coating composition may not comprise an inorganic copper-based antifouling agent.

[0024] In another aspect, the present invention provides a process for protecting an object from fouling (fouling, contamination), the process comprising coating at least a portion of the object to be fouled with the antifouling coating composition described herein.

[0025] The present invention further relates to objects coated with the antifouling coating compositions described herein.

[0026] According to another aspect, the present invention relates to the use of the silyl ester copolymers described herein in an antifouling coating composition comprising medetomidine, as the so-called binder of said composition.

[0027] definition The terms "marine antifouling coating composition," "antifouling coating composition," or simply "coating composition" refer to a composition suitable for use in a marine environment.

[0028] The term "hydrocarbyl group" refers to a group containing only carbon and hydrogen atoms, and includes alkyl, alkenyl, aryl, cycloalkyl, arylalkyl, and the like. It can be enjoyed.

[0029] The term "(meth)acrylate" means either methacrylate or acrylate.

[0030] The term "rosin" used in the following description includes "rosin or its derivatives."

[0031] The term "binder" refers to the portion of the composition that includes the silyl ester copolymer and other ingredients that form the matrix that provides the composition with rigidity and strength. Generally, as used herein, the term "binder" refers to the silyl ester copolymer and any rosin that may be used therewith. DETAILED DESCRIPTION OF THE INVENTION

[0032] In one embodiment, the antifouling coating composition of the present invention contains a silyl ester copolymer comprising at least triisopropylsilyl methacrylate and a hydrophilic (meth)acrylate as comonomers. As described herein, further silyl ester (meth)acrylate comonomers, hydrophilic (meth)acrylate comonomers, and / or non-hydrophilic (meth)acrylate comonomers may be added.

[0033] Silyl Ester Copolymer Comonomers In one embodiment, the silyl ester copolymer comprises as comonomers at least triisopropylsilyl methacrylate (a) and at least one hydrophilic monomer (b).

[0034] When the wt % of a comonomer in a silyl ester copolymer is listed, the wt % is based on the total (weight) of each comonomer contained in the silyl ester copolymer. Therefore, if triisopropylsilyl methacrylate (a) and hydrophilic (meth)acrylate monomer (b) are the only comonomers in a silyl ester copolymer, the wt% of triisopropylsilyl methacrylate can be calculated using the following formula: [triisopropylsilyl methacrylate (a) (wt) / (triisopropylsilyl methacrylate (wt) + hydrophilic (meth)acrylate monomer (b) (wt)] x 100%. If only triisopropylsilyl methacrylate (a), hydrophilic (meth)acrylate monomer (b), and methyl methacrylate are present, the wt% of triisopropylsilyl methacrylate can be calculated using the following formula: [triisopropylsilyl methacrylate (a) (wt) / (triisopropylsilyl methacrylate (wt) + hydrophilic (meth)acrylate monomer (b) (wt) + methyl methacrylate (wt)] x 100%.

[0035] Preferably, the silyl ester copolymer comprises >80 wt %, preferably >90 wt %, more preferably >95 wt %, especially >98 wt % of the sum of triisopropylsilyl methacrylate (a), hydrophilic (meth)acrylate comonomer (b) and non-hydrophilic (meth)acrylate comonomer (c).

[0036] Component (a) is triisopropylsilyl methacrylate and preferably forms 5 to 80 wt %, preferably 25 to 75 wt %, especially 30 to 70 wt % of the silyl ester copolymer.

[0037] Component (b) (total) preferably forms 2 to 50 wt % of the silyl ester copolymer, preferably 2 to 40 wt % of the silyl ester copolymer, especially 5 to 40 wt % and more especially 5 to 35 wt % of the silyl ester copolymer, these wt % values ​​referring to the sum of the comonomers of component (b) involved.

[0038] Preferably, the ratio (a):(b) (wt / wt) is in the range of 40:60 to 95:5, preferably in the range of 50:50 to 95:5, especially in the range of 50:50 to 90:10, most preferably in the range of 50:50 to 85:15. Preferably, the weight fraction of component (a) in the silyl ester copolymer is greater than the weight fraction of component (b).

[0039] The amount of (a)+(b) in the silyl ester copolymer is preferably at most 95 wt%, for example at most 90 wt%, in particular at most 85 wt%. The amount of (a)+(b) in the silyl ester copolymer may be in the range of 30 to 95 wt%, or in the range of 40 to 85 wt%.

[0040] Hydrophilic (meth)acrylate comonomer component (b) In some embodiments, the silyl ester copolymer comprises at least one comonomer according to formula (I).

[0041] [ka]

[0042] In formula (I), R 1 is hydrogen or methyl, and R 2 is a cyclic ether (for example, oxolane, oxane, dioxolane, or dioxane unsubstituted or substituted with an alkyl group), and X is C1 to C4 alkylene, preferably C1 to C2 alkylene.

[0043] The cyclic ether may contain a single oxygen atom in the ring, or may contain two or three oxygen atoms in the ring. The cyclic ether may also contain a ring having 2 to 8 carbon atoms, for example, 3 to 5 carbon atoms. The entire ring may contain 4 to 8 atoms, for example, 5 or 6 atoms.

[0044] The ring of the cyclic ether may be substituted, for example, with one or more, e.g., one, C1-C6 alkyl group. The substituents may be located at any position within the ring, including the position attached to the X group.

[0045] Suitable compounds of formula (I) include tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, isopropylidene glycerol methacrylate, glycerol formal methacrylate, and cyclic trimethylolpropane formal acrylate.

[0046] Most preferably, formula (I) is tetrahydrofurfuryl acrylate having the following structure:

[0047] [ka]

[0048] In a further embodiment, the silyl ester copolymer may comprise one or more comonomers represented by formula (II):

[0049] [ka]

[0050] In formula (II), R 3 is hydrogen or methyl, and R 4 is a C3 to C18 substituent containing at least one oxygen atom or nitrogen atom, preferably at least one oxygen atom.

[0051] As shown in formula (II) above, the term "hydrophilic (meth)acrylate" refers to an R group containing at least one oxygen or nitrogen atom, preferably at least one oxygen atom. 4 As will be explained in detail below, a group represented by formula (III) is required in formula (II), and R 6Further non-hydrophilic (meth)acrylate comonomers whose groups consist only of C and H atoms may be included.

[0052] In some embodiments, the silyl ester copolymer is represented by formula (II) above, and R 4 The group has the formula -(CH2CH2O) m -R 7 In this formula, R 7 is a C1-C10 hydrocarbyl substituent, preferably a C1-C10 alkyl or C6-C10 aryl group; m is an integer in the range of 1 to 6, preferably in the range of 1 to 3. Preferably, R 4 The chemical formula is (CH2CH2O) m -R 7 and R 7 is an alkyl substituent, preferably methyl or ethyl, and m is an integer ranging from 1 to 3, preferably 1 or 2.

[0053] In some embodiments, the silyl ester copolymer comprises one or more of 2-methoxyethyl methacrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, and 2-(2-ethoxyethoxy)ethyl acrylate.

[0054] Particularly preferred comonomers (b) include 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-(2-ethoxyethoxy)ethyl acrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, tetrahydrofurfuryl acrylate and tetrahydrofurfuryl methacrylate.

[0055] As used herein, Formula (I) and Formula (II) represent "polar" (meth)acrylate comonomers or "hydrophilic" (meth)acrylate comonomers. The use of these comonomers in conjunction with triisopropylsilyl methacrylate can ensure the formation of binders with reduced degradation.

[0056] Preferably, the silyl ester copolymer contains a comonomer of formula (I) or a comonomer of formula (II), although it is generally not preferred to contain monomers having both formulas.

[0057] Addition of a non-hydrophilic (meth)acrylate comonomer (c) The silyl ester copolymer may include one or more additional non-hydrophilic (meth)acrylate comonomers represented by formula (III).

[0058] [ka]

[0059] In formula (III), R 5 is hydrogen or methyl, and R 6 is a C1-C8 hydrocarbyl substituent, preferably a C1-C8 alkyl substituent, most preferably methyl, ethyl, n-butyl, or 2-ethylhexyl. Comonomers represented by formula (III) are referred to herein as "non-hydrophilic" comonomers.

[0060] In all embodiments of the present invention, the silyl ester copolymer preferably comprises at least one further non-hydrophilic methacrylate and / or non-hydrophilic acrylate comonomer. If one or more non-hydrophilic (meth)acrylate comonomers are present, the total amount of these non-hydrophilic (meth)acrylate comonomers in the silyl ester copolymer is preferably at most 60 wt%, preferably not more than 55 wt%, for example in the range of 10 to 55 wt%, especially in the range of 10 to 50 wt%.

[0061] In a preferred embodiment, the total comonomers combined, triisopropylsilyl methacrylate (a), component (b) and the non-hydrophilic (meth)acrylate comonomer represented by formula (III), form >80 wt %, preferably >90 wt %, especially >95 wt % of the total comonomers in the silyl ester copolymer.

[0062] In a preferred embodiment, the silyl ester copolymer includes one or more of the following non-hydrophilic comonomers: methyl methacrylate and / or n-butyl acrylate.

[0063] Methyl methacrylate is preferably included in all embodiments of the present invention. When methyl methacrylate is included, it is preferably included in an amount of 2 to 60 wt %, preferably 5 to 50 wt %, of the silyl ester copolymer. In a preferred embodiment, the sum of triisopropylsilyl methacrylate (a), component (b), and methyl methacrylate forms >50 wt %, preferably >55 wt %, especially >60 wt %, of the total comonomers in the silyl ester copolymer.

[0064] When n-butyl acrylate is contained, it is preferred that the n-butyl acrylate be contained in an amount of 1 to 30 wt %, and more preferably 2 to 25 wt %.

[0065] Addition of silyl (meth)acrylate comonomers The silyl ester copolymer may further comprise a silyl (meth)acrylate comonomer. When a silyl (meth)acrylate comonomer is included, it is preferred that the additional silyl (meth)acrylate comonomer other than triisopropylsilyl methacrylate form no more than 20 wt % of the silyl ester copolymer, preferably no more than 10 wt % of the silyl ester copolymer. When a silyl (meth)acrylate comonomer is included, a suitable silyl (meth)acrylate comonomer is preferably represented by the following formula (IV):

[0066] [ka]

[0067] In formula (IV), Each R 8 are independently selected from linear or non-linear C1-C4 alkyl groups; Each R 9 is a linear or non-linear C1-C20 alkyl group, a C3-C12 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, and -OSi(R 10 ) independently selected from the group consisting of: Each R 10 are independently a linear or non-linear C1-C4 alkyl group; n is an integer from 0 to 5; Y is an ethylenically unsaturated group such as acryloyloxy, methacryloyloxy, (methacryloyloxy)alkylenecarbonyloxy, and (acryloyloxy)alkylenecarbonyloxy. Needless to say, triisopropylsilyl methacrylate must be considered excluded from formula (IV) since it is always included in the silyl ester copolymers of the present invention.

[0068] The term "alkyl" is intended to include linear and non-linear alkyl groups such as methyl, ethyl, isopropyl, propyl, and butyl. Particularly preferred cycloalkyl groups include cyclohexyl and substituted cyclohexyl groups.

[0069] Examples of substituted aryl groups include aryl groups substituted with at least one substituent selected from halogen, alkyl groups having 1 to about 8 carbon atoms, acyl groups, and nitro groups. Particularly preferred aryl groups include substituted or unsubstituted phenyl groups, benzyl groups, phenakyl groups, and naphthyl groups.

[0070] Ideally, the preferred silyl ester monomers are compounds of formula (IV) where n is 0, i.e., compounds of formula Y-Si(R 9 )3 is based on it.

[0071] Examples of monomers having silyl ester functionality are well known. Monomers represented by general formula (IV) include: Silyl ester monomers of acrylic acid and methacrylic acid, such as triisopropyl Pyridylsilyl acrylate, triethylsilyl (meth)acrylate, tri-n-propylsilyl (meth)acrylate, tri-n-butylsilyl (meth)acrylate, triisobutylsilyl (meth)acrylate, tri-tert-butylsilyl (meth)acrylate, tri-sec-butylsilyl (meth)acrylate, tri-n-pentylsilyl (meth)acrylate, triisopentylsilyl (meth)acrylate, tri-n-hexylsilyl (meth)acrylate, tri-n-octylsilyl (meth)acrylate, tri-n-dodecylsilyl ( (meth)acrylate, triphenylsilyl (meth)acrylate, tri-(p-methylphenyl)silyl (meth)acrylate, tribenzylsilyl (meth)acrylate, ethyldimethylsilyl (meth)acrylate, n-propyldimethylsilyl (meth)acrylate, isopropyldimethylsilyl (meth)acrylate, n-butyldimethylsilyl (meth)acrylate, isobutyldimethylsilyl (meth)acrylate, tert-butyldimethylsilyl (meth)acrylate, n-pentyldimethylsilyl (meth)acrylate, n-hexyldimethylsilyl Methylsilyl (meth)acrylate, neohexyldimethylsilyl (meth)acrylate, thexyldimethylsilyl (meth)acrylate, n-octyldimethylsilyl (meth)acrylate, n-decyldimethylsilyl (meth)acrylate, dodecyldimethylsilyl (meth)acrylate, n-octadecyldimethylsilyl (meth)acrylate, cyclohexyldimethylsilyl (meth)acrylate, phenyldimethylsilyl (meth)acrylate, benzyldimethylsilyl (meth)acrylate, phenethyldimethylsilyl (meth)acrylate, (3-phenylpropyl)dimethylsilyl (meth)acrylate, p-tolyldimethylsilyl (meth)acrylate, isopropyldiethylsilyl (meth)acrylate, n-butyldiisopropylsilyl (meth)acrylate, n-octyldiisopropylsilyl (meth)acrylate, methyldi-n-butylsilyl (meth)acrylate, methyldicyclohexylsilyl (meth)acrylate, methyldiphenylsilyl (meth)acrylate, tert-butyldiphenylsilyl (meth)acrylate, nonamethyltetrasiloxy (meth)acrylate,Bis(trimethylsiloxy)methylsilyl(meth)acrylate, tris(trimethyl, These include (siloxy)silyl (meth)acrylates, etc. These are disclosed in Patent Documents 17 and 18.

[0072] The silyl ester copolymer may include both triisopropylsilyl acrylate and triisopropylsilyl methacrylate.

[0073] Physical properties of silyl ester copolymers The polymer containing an organic silyl ester group can be obtained by polymerizing a monomer mixture in the presence of a polymerization initiator using a conventional method such as solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization, or by using a controlled polymerization technique.When preparing a coating composition using the polymer containing an organic silyl ester group, it is preferable to dilute the polymer with an organic solvent to produce a polymer solution with an appropriate viscosity.In this regard, it is preferable to use solution polymerization.

[0074] Examples of the polymerization initiator include azo compounds such as dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(isobutyronitrile), and 1,1'-azobis(cyanocyclohexane), and peroxides such as tert-amyl peroxypivalate, tert-butyl peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, tert-butyl peroxydiethyl acetate, tert-butyl peroxyisobutyrate, tert-butyl peroxybenzoate, 1,1-di(tert-amylperoxy)cyclohexane, tert-amyl peroxy-2-ethylhexyl carbonate, tert-butyl peroxy Examples of suitable peroxides include diisopropyl carbonate, tert-butylperoxy-2-ethylhexyl carbonate, polyether poly-tert-butyl peroxycarbonate, di-tert-butyl peroxide, and dibenzoyl peroxide. These compounds may be used alone or in combination.

[0075] Examples of organic solvents include aromatic hydrocarbons such as xylene, toluene, and mesitylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, cyclopentanone, and cyclohexanone; esters such as butyl acetate, tert-butyl acetate, amyl acetate, and ethylene glycol methyl ether acetate; ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, dioxane, and tetrahydrofuran; alcohols such as n-butanol, isobutanol, and benzyl alcohol; ether alcohols such as butoxyethanol and 1-methoxy-2-propanol; aliphatic hydrocarbons such as white spirit; and, in some cases, mixtures of two or more solvents. These compounds can be used alone or in combination. Preferably, the silyl ester copolymer is a random copolymer.

[0076] Preferably, the polymer containing an organic silyl ester group thus obtained has a weight average molecular weight of 5,000 to 100,000, preferably 10,000 to 80,000, and more preferably 20,000 to 60,000. Mw is measured by the method described in the Examples.

[0077] Preferably, the silyl ester copolymer has a glass transition temperature (Tg) of at least 15° C., preferably at least 20° C., such as at least 22° C. These values ​​are measured according to the Tg test method described in the Examples. Values ​​of less than 80° C., such as less than 75° C., such as less than 60° C., are preferred.

[0078] The silyl ester copolymer may be provided as a polymer solution, which is desirably adjusted to have a solids content of 30 to 90 wt %, preferably 40 to 85 wt %, and more preferably 40 to 75 wt %.

[0079] Preferably, the final antifouling coating composition according to the invention contains 0.5 to 45 wt%, for example 1 to 30 wt%, especially 5 to 25 wt%, of the silyl ester copolymer based on the total coating composition.

[0080] In some cases, the antifouling coating composition of the present invention may contain a mixture of the silyl ester copolymer of the present invention with other silyl ester copolymers, for example, as described in U.S. Patent No. 5,629,299; ... and U.S. Patent No. 5,629,299.

[0081] Rosin ingredients Rosin can be used to adjust the self-polishing and mechanical properties of the antifouling coating film. Preferably, the antifouling coating composition of the present invention contains at least 0.5 wt% rosin, for example at least 1 wt% rosin. The upper limit of the rosin content may be 25 wt%, for example 15 wt%.

[0082] The rosin used in the present invention may be any of the rosins described below or derivatives thereof, such as rosin salts. Examples of rosin materials include wood rosin, tall oil rosin, gum rosin, and rosin derivatives, such as hydrogenated rosin, partially hydrogenated rosin, disproportionated rosin, dimerized rosin, polymerized rosin, and maleic esters of rosin. rosin, fumaric acid esters of rosin, glycerol esters of rosin, methyl esters of rosin, pentaerythritol esters of rosin, other rosin esters, other hydrogenated rosins, copper resinates of rosin and polymerized rosin, zinc resinates of rosin and polymerized rosin, calcium resinates of rosin and polymerized rosin, magnesium resinates of rosin and polymerized rosin, other metal resinates of rosin and polymerized rosin, etc. These are disclosed in Patent Document 20. Gum rosin and derivatives of gum rosin are preferred.

[0083] In the present invention, the antifouling coating composition preferably contains 0.5 to 25 wt %, preferably 1 to 20 wt %, and preferably 2 to 15 wt % of a rosin material.

[0084] The physical properties of the antifouling coating composition can be adjusted by varying the relative amounts of the silyl ester copolymer component and the rosin component.

[0085] Other binder ingredients In addition to the silyl ester copolymer and optional rosin, additional binders may be used to adjust the properties of the antifouling coating film. Examples of binders that can be used in addition to the silyl ester copolymer and rosin of the present invention include: (Meth)acrylic polymers and (meth)acrylic copolymers, in particular acrylate binders, such as poly(n-butyl acrylate), poly(n-butyl acrylate-co-isobutyl vinyl ether), as described in Patent Documents 8 and 21; vinyl ether polymers and vinyl ether copolymers, such as poly(methyl vinyl ether), poly(ethyl vinyl ether), poly(isobutyl vinyl ether), poly(vinyl chloride-co-isobutyl vinyl ether); Acid functional polymers in which the acid groups are blocked with divalent metals bound to monovalent organic residues, as described, for example, in U.S. Patent Nos. 5,629,992 and 5,629,993, or in which the acid groups are blocked with divalent metals bound to hydroxyl residues, as described, for example, in U.S. Patent Nos. 5,629,992 and 5,629,993, or in which the acid groups are blocked with amines, as described, for example, in U.S. Patent Nos. 5,629,992 and 5,629,993; Hydrophilic copolymers, such as the (meth)acrylate copolymers described in US Pat. No. 5,629,499 and the poly(N-vinylpyrrolidone) copolymers or other copolymers described in US Pat. No. 5,629,499; Aliphatic polyesters, such as poly(lactic acid), poly(glycolic acid), poly(2-hydroxybenzoates) poly(3-hydroxybutyric acid), poly(4-hydroxyvaleric acid), polycaprolactone, and aliphatic polyester copolymers containing two or more units selected from the above-mentioned units; Metal-containing polyesters, such as those described in U.S. Pat. No. 5,629,491 and U.S. Pat. No. 5,629,491; Polyoxalates as described in US Pat. No. 5,699,499 and other condensation polymers as described in US Pat. No. 5,699,499; Alkyd resins and modified alkyd resins; and For example, the hydrocarbon resins described in Patent Document 33 include hydrocarbon resins formed solely from the polymerization of at least one monomer selected from C5 aliphatic monomers, C9 aromatic monomers, indene coumarone monomers, or terpenes, or mixtures thereof.

[0086] When an additional binder is included in addition to the rosin and silyl ester copolymer, the weight ratio of silyl copolymer to binder may range from 30:70 to 95:5, preferably from 35:65 to 90:10, and especially 40:60 or 80:20. These preferred ratios relate to the amounts of silyl copolymer and additional binder only, i.e., rosin is not included.

[0087] Particularly suitable further binders are (meth)acrylic polymers and (meth)acrylic copolymers.

[0088] biocides The antifouling coating composition further contains a compound capable of preventing adhesion (fouling, fouling) of marine organisms to a surface or removing attached marine organisms from a surface, which requires the presence of 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole [medetomidine].

[0089] In addition to the biocide, other antifouling compounds may be present. The terms antifouling agent, antifouling material, biocide, and toxic material are used in the industry to describe known compounds that act to prevent the attachment of marine organisms to surfaces. The antifouling material of the present invention is a marine antifouling material.

[0090] The antifouling coating composition may contain a copper-based biocide, preferably cuprous oxide (CuO) and / or copper pyrithione. Cuprous oxide has a typical particle diameter distribution of 0.1-70 μm, with an average particle size (d50) of 1-25 μm. Cuprous oxide is satisfactory as a stabilizer to prevent surface oxidation and surface agglomeration. Commercially available examples of cuprous oxide include Nordox Cuprous Oxide Red Paint Grade and Nordox XLT from Nordox AS; Cuprous oxide from Furukawa Chemicals Co., Ltd.; and American Red Copp 97N, Purple Copp, Lolo Tint 97N, Chemet CDC from Chemet Corporation; Cuprous Oxide Red from Spiess-Urania; and Cuprous oxide Roast, Cuprous oxide Electrolytic from Taixing Smelting Plant Co., Ltd.

[0091] The antifouling coating composition of the present invention may also contain other biocides, such as those described in US Pat. No. 5,699,999. Preferred additional biologically active agents include cuprous oxide, copper thiocyanate, zinc pyrithione, copper pyrithione, zinc ethylenebis(dithiocarbamate) [zineb], 2-(tertbutylamino)-4-(cyclopropylamino)-6-(methylthio)-1,3,5-triazine [sibutrin], 4,5-dichloro-2-n-octyl-4-isothiazolon-3-one [DCOIT], N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfamide [dichlorofluanid], N-dichlorofluoromethylthio-N',N'-dimethyl-Np-tolylsulfamide [tolylfluanid], triphenylborane pyridine [TPBP], and 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile [tralopyril].

[0092] As is known in the art, mixtures of biocides may be used as different biocides act against different marine organisms.

[0093] More preferably, a mixture of a biocide effective against marine invertebrates such as barnacles, tube worms, bryozoans and hydrops, a biocide effective against plants such as seaweed, algae and diatoms, and a biocide effective against bacteria is used.

[0094] In one embodiment, the antifouling coating composition is free of inorganic copper-based biocides. For this reason, the most preferred options are medetomidine and tralopyril. and one or more selected from zinc pyrithione, zineb, and 4,5-dichloro-2-octyl-4-isothiazolon-3-one.

[0095] In other embodiments, the antifouling coating composition contains, in addition to medetomidine, cuprous oxide and / or copper thiocyanate and one or more biocides selected from copper pyrithione, zineb, and 4,5-dichloro-2-octyl-4-isothiazolon-3-one.

[0096] In other embodiments, the antifouling coating composition is adapted to contain copper.

[0097] The total amount of biocides may form up to 70 wt% of the antifouling coating composition, for example, 0.1-60 wt%, for example, 0.2-60 wt%. When inorganic copper compounds are present, a suitable amount of biocide may be 20-60 wt% of the antifouling coating composition. When inorganic copper compounds are avoided, the amount used may be less, for example, 0.1-20 wt%, for example, 0.2-15 wt%. Of course, the amount of biocide will vary depending on the end use and on the biocide used.

[0098] Medetomidine is used in small amounts, typically in antifouling coating compositions in the range of 0.02 to 1.0 wt %, for example 0.05 to 0.5 wt %, especially 0.1 to 0.4 wt %.

[0099] Some biocides may be encapsulated or adsorbed by inert carriers or bound to other materials to control their release. The percentages given above refer to the amount of active biocide present, not the carrier used.

[0100] Other ingredients The antifouling coating composition of the present invention contains a silyl ester copolymer and any of the optional components described above, and optionally one or more components selected from other binders, inorganic or organic pigments, extenders, fillers, additives, solvents, and thinners.

[0101] Examples of pigments include inorganic pigments such as titanium dioxide, iron oxide, zinc oxide, zinc phosphate and graphite, organic pigments such as phthalocyanine compounds, azo pigments and carbon black. Bonblack is one example.

[0102] Examples of extender pigments and fillers include minerals such as dolomite, plastrite, calcite, quartz, barite, magnesite, aragonite, silica, wollastonite, talc, chlorite, mica, kaolin, and feldspar; synthetic inorganic compounds such as calcium carbonate, magnesium carbonate, barium sulfate, calcium silicate, and silica; polymeric and inorganic microspheres such as coated or uncoated hollow and solid glass beads, coated or uncoated hollow and solid ceramic beads, and porous and compact beads made of polymeric materials such as poly(methyl methacrylate), poly(methyl methacrylate-co-ethylene glycol dimethacrylate), poly(styrene-co-ethylene glycol dimethacrylate), poly(styrene-co-divinylbenzene), polystyrene, and poly(vinyl chloride).

[0103] Examples of additives that can be added to the antifouling coating composition include reinforcing agents, thixotropic agents, thickeners, anti-settling agents, wetting agents, dispersants, plasticizers, and solvents.

[0104] Examples of reinforcing agents include flakes and fibers. Fibers include natural and synthetic inorganic fibers, such as silicon-containing fibers, carbon fibers, oxide fibers, carbide fibers, nitride fibers, sulfide fibers, phosphate fibers, and mineral fibers; metal fibers; and natural and synthetic inorganic fibers, such as cellulose fibers, rubber fibers, acrylic fibers, polyamide fibers, polyimides, polyester fibers, polyhydrazide fibers, polyvinyl chloride fibers, and polyethylene fibers. These are described in Patent Document 7. Preferably, the fibers have an average length of 25 to 2,000 μm, an average thickness of 1 to 50 μm, and a ratio between the average length and the average thickness of at least 5.

[0105] Examples of thixotropic agents, thickeners and anti-settling agents include silica such as fumed silica, organically modified clays, amide waxes, polyamide waxes, amide derivatives, polyethylene waxes, oxidized polyethylene waxes, hydrogenated castor wax, ethyl cellulose, Examples of suitable surfactants include aluminum stearate, aluminum stearate, and mixtures thereof.

[0106] Examples of plasticizers include polymeric plasticizers, chlorinated paraffins, phthalates, phosphates, sulfonamides, adipates, epoxidized vegetable oils, and sucrose isobutyl acetate.

[0107] Examples of dehydrating and drying agents include anhydrous calcium sulfate, calcium sulfate hemihydrate, anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous zinc sulfate, molecular sieves, zeolites, as well as orthoesters such as trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, triisopropyl orthoformate, tributyl orthoformate, trimethyl orthoacetate, and triethyl orthoacetate; ketals; acetals; enol ethers; orthoborate esters such as trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate, and tri-tert-butyl borate; silanes such as tetraethoxysilane, trimethoxymethylsilane, triethoxymethylsilane, phenyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and ethylpolysilicate; and isocyanate esters such as p-toluenesulfonyl isocyanate.

[0108] Preferred dehydrating and drying agents are silanes such as tetraethoxysilane and inorganic compounds. It is particularly preferred to use silanes and rosin or derivatives thereof.

[0109] Examples of stabilizers that contribute to the storage stability of antifouling coating compositions include carbodiimide compounds such as bis(2,6-diisopropylphenyl)carbodiimide and 1,3-di-p-tolylcarbodiimide described in Patent Document 34. Generally, any of these optional ingredients can be present in an amount of 0.1 to 20 wt %, typically 0.5 to 20 wt %, and preferably 0.75 to 15 wt % of the antifouling coating composition. Of course, the amounts of these optional ingredients will vary depending on the end use application.

[0110] It is highly preferred that the antifouling coating composition contains a solvent. This solvent is preferably volatile and is preferably an organic solvent. Examples of organic solvents and thinners include aromatic hydrocarbons such as xylene, toluene, and mesitylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, methyl amyl ketone, diisobutyl ketone, methyl propyl ketone, cyclopentanone, and cyclohexanone; and esters such as butyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, and ethylene 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.

[0111] Preferred solvents are aromatic solvents, especially mixtures of xylene and aromatic hydrocarbons.

[0112] Preferably, the amount of solvent is as low as possible. The solvent content may be up to 50 wt % of the antifouling coating composition, preferably up to 45 wt %, such as up to 40 wt %, but may be 15 wt % or less, such as 10 wt % or less, by weight of the antifouling coating composition. Again, the solvent content will of course vary depending on the other components present and on the end use of the coating composition.

[0113] Alternatively, the coating may be dispersed in an organic non-solvent for the film-forming components of the antifouling coating composition or may be dispersed in an aqueous dispersion.

[0114] Preferably, the antifouling coating composition according to the present invention should have a solids content of more than 40 vol%, such as more than 45 vol%, for example more than 50 vol%, preferably more than 55 vol%.

[0115] More preferably, the antifouling coating composition should have a volatile organic compound (VOC) content of less than 500 g / L, preferably less than 400 g / L, for example less than 390 g / L. The VOC content may be determined by calculation (ASTM D5201-01) or by measurement, preferably by measurement.

[0116] The antifouling coating composition of the present invention may be applied to the entire or partial surface of the object to be coated. The surface of the object to be coated may be permanently or intermittently submerged (e.g., due to the tides, different cargo loads, or wave swells). The surface of the object to be coated is typically the hull of a ship or the surface of a marine fixture such as an oil platform or buoy. Coating of the antifouling coating composition may be achieved by any convenient means, for example, by painting (using a brush or roller) or by spraying the coating onto the marine fixture. Typically, the surface to be coated must be isolated from seawater to allow coating. Coating of the antifouling coating composition can be achieved using techniques conventionally known in the art.

[0117] When applying an antifouling coating composition to an object (e.g., the hull of a ship), the surface of the object is not protected by just a single coat of the antifouling coating composition. Depending on the surface type of the object, the antifouling coating composition may be applied directly to an existing coating system consisting of several different paint layers (e.g., epoxy, polyester, vinyl, acrylic, or a mixture thereof). When starting with an unpainted surface (e.g., steel, aluminum, plastic, composite, fiberglass, or carbon fiber), the entire coating system usually consists of one or two layers of an anticorrosion coating, one layer of a tie coat, and one or two layers of an antifouling paint. In exceptional cases, several additional layers of antifouling paint may be applied. If the surface has a clean and undamaged antifouling coating from a previous application, the new antifouling paint is usually applied directly in one or two layers, and in exceptional cases, three or more layers may be applied directly.

[0118] The invention will now be described with reference to illustrative examples.

[0119] Example material and method test Viscosity measurement of polymer solutions The viscosity of the polymer is determined according to ASTM D2196 using a Brookfield DV-I viscometer equipped with an LV-2 or LV-4 spindle at 12 rpm. Prior to measurement, the polymer is tempered at 23.0°C ± 0.5°C.

[0120] Determination of the solids content of polymer solutions The solids content in polymer solutions is determined according to ISO 3251. A test sample of 0.5 g ± 0.1 g is removed and dried in a ventilated oven at 150 °C for 30 minutes. The weight of the residue is considered to be the non-volatile matter (NVM). The non-volatile content is expressed as a percentage by weight. The value given is the average of three parallel tests.

[0121] Measurement of average molecular weight distribution of polymers Polymers were characterized by gel permeation chromatography (GPC). Molecular weight distributions (MWDs) were determined using a Polymer Laboratories PL-GPC 50 instrument with two PLgel 5 μm Mixed D columns (Polymer Laboratories) connected in series, using tetrahydrofuran (THF) as the eluent and a refractive index (RI) detector, at a constant flow rate of 1 mL / min at ambient temperature. The two columns were calibrated using Easivials PS-H polystyrene standards (Polymer Laboratories). Data were processed using Cirrus software (Polymer Laboratories). Samples were prepared by dissolving a volume of polymer solution corresponding to 25 mg of dry polymer in 5 mL of THF. These samples were kept at room temperature for a minimum of 3 hours before sampling for GPC. The weight-average molecular weight (Mw), number-average molecular weight (Mn), and polydispersity index (PDI), expressed as Mw / Mn, are reported in the table.

[0122] Glass transition temperature measurement Glass transition temperatures (Tg) were determined by differential scanning calorimetry (DSC) measurements. DSC measurements were performed using a TA Instruments DSC Q200. Samples were prepared by transferring a small amount of polymer solution into an aluminum pan and drying the sample at 50°C for a minimum of 10 h, followed by drying at 150°C for 3 h. Approximately 10 mg of dried polymer material was measured in an open aluminum pan, and scan data were recorded relative to an empty pan at a heating rate of 10°C / min and a cooling rate of 10°C / min over the temperature range of -50°C to 150°C. Data were processed using Universal Analysis software from TA Instruments. The inflection point of the glass transition range on the second heat, as specified in ASTM E1356-08, is reported as the polymer's Tg.

[0123] General Procedure for Preparation of Antifouling Coating Composition The components were mixed in the proportions listed in Table 2. The mixture was dispersed in a 250 ml paint can using a shaker for 15 minutes in the presence of glass beads (approximately 2 mm in diameter). The glass beads were removed with a filter before testing.

[0124] Measurement of paint viscosity using a cone-and-plate viscometer In accordance with ISO2884-1:1999, the viscosity of the antifouling coating composition was measured at 10,000 s using a digital cone-and-plate viscometer set at a temperature of 23°C. -1 The viscosity was measured at a shear rate of 0 to 10 P. The results are reported as the average of three measurements.

[0125] Calculating the Volatile Organic Compound (VOC) Content of Antifouling Coating Compositions The volatile organic compound (VOC) content of the antifouling coating composition is calculated according to ASTM D5201.

[0126] Accelerated crack testing of coating films The PVC panels are coated with a suitable anti-corrosion primer. The antifouling coating was applied to PVC panels using a pressease film applicator. The PVC panels were dried at 52°C for 72 hours and then immersed in seawater at 40°C. The PVC panels were removed and evaluated at regular intervals. The PVC panels were dried at room temperature for 24 hours and then again at 52°C for 24 hours and visually evaluated for the presence of cracks under 10x magnification. The PVC panels were then immersed again. The evaluation results after drying at 52°C are reported in Table 3.

[0127] The PVC panels were rated as follows: 0 - no cracks 1 - A few cracks 2 - Moderate number of cracks 3 - Numerous cracks 4 - Very many cracks

[0128] Measurement of the removal rate of antifouling coating films on rotating disks in seawater The polishing rate is determined by measuring the decrease in film thickness of the coating film over time. A PVC disk is used for this test. The antifouling coating composition is applied as radial stripes onto the PVC disk using a film applicator with a 300 μm gap size. The thickness of the dried coating film is measured using a surface profilometer / roughness tester. Typical initial dry films vary depending on the solids content of the antifouling coating composition applied and the application speed. Typical initial film thicknesses for the test coatings in the examples are 100 ± 10 μm. The PVC disk is mounted on a shaft and rotates in a container of flowing seawater. The shaft rotation speed produces an average simulated speed of 16 knots on the PVC disk. Filtered, natural seawater temperature-controlled at 25°C ± 2°C is used. The PVC disk is removed at regular intervals for film thickness measurement. The PVC disk is rinsed, dried overnight at room temperature, and the film thickness is measured. The film thickness measurement is recorded as the film thickness loss, i.e., the difference between the initial film thickness and the film thickness measured at a given time. The coating film is considered to be polished through when a thin non-polished leached layer, typically 10-20 μm thick, remains on the surface, i.e., when the coating film is completely removed from the surface. This polishing time is designated as PT in the measurement table.

[0129] Measuring barnacle resistance by static immersion tests in seawater The PVC panels were prepared by applying one coat of vinyl epoxy tie coat (Safeguar Plus manufactured by Jotun) and one coat of antifouling coating (SeaQuantum Ultra S manufactured by Jotun). 2 The antifouling coating composition of the present invention was applied using a film applicator with a gap size of 400 μm to form a total test area of ​​100 μm. The device was immersed in subtropical waters outside the state of Florida and tested at regular intervals.

[0130] Barnacle resistance was assessed as follows: 0: Not detected, 1: <5% barnacle coverage 2: 5-10% barnacle coverage 3: 10-15% barnacle coverage 4: >15% barnacle coverage

[0131] The rating scale is 100-150cm 2 The test is valid only for the test area of ​​the PVC panel. The edge effect of the PVC panel is excluded when evaluating the coating film, as specified in ASTM D6990-05, Section 7.5.

[0132] Preparation procedure for copolymer solutions S1 and S9 53 parts by weight of xylene is charged to a temperature-controlled reactor equipped with an agitator, condenser, nitrogen inlet, and material inlet. The reactor is heated to and maintained at a reaction temperature of 85°C. A premix is ​​prepared by premixing triisopropylsilyl methacrylate, 2-methoxyethyl methacrylate, n-butyl acrylate, and methyl methacrylate in the proportions listed in Table 1 with 1.0 part 2,2'-azobis(2-methylbutyronitrile). This premix is ​​charged to the reactor at a constant rate over a two-hour period under a nitrogen atmosphere. 0.5 parts tert-butyl peroxy-2-ethylhexanoate are then added. The reactor is maintained at the reaction temperature for an additional two hours. The reactor is then heated to 110°C and maintained at this temperature for an additional one hour. 30 parts xylene is added for dilution, and the reactor is cooled to room temperature.

[0133] General procedure for preparing copolymer solutions S2-S8 and comparative copolymer solutions CS3-CS4 A predetermined amount of solvent is charged to a temperature-controlled reactor equipped with an agitator, condenser, nitrogen inlet, and material inlet. The reactor is heated to and maintained at the reaction temperature listed in Table 1. A premix of monomer, initiator, solvent, and optional chain transfer agent is prepared. This premix is ​​charged to the reactor at a constant rate over a two-hour period under a nitrogen atmosphere. Thirty minutes later, a boost initiator solution is added. The reactor is maintained at the reaction temperature for an additional two hours. The reactor is then heated to 110°C and maintained at this temperature for one hour. Additional solvent is added for dilution, and the reactor is cooled to room temperature.

[0134] Preparation procedure for comparative copolymer solution CS1 Preparation Example 4 for producing the silyl ester copolymer (a3-1) described in Patent Document 35 was repeated to prepare a comparative copolymer solution CS1.

[0135] A temperature-controlled reactor equipped with a stirrer, a condenser, a nitrogen inlet, and a material inlet was charged with 100 parts by weight of xylene, and heated and stirred under a nitrogen stream at 85°C. While maintaining this temperature, a mixture of 60 parts of triisopropylsilyl acrylate, 40 parts of methyl methacrylate, and 0.3 parts of 2,2'-azobis(isobutyronitrile) was charged into the reactor over 2 hours. Stirring was then continued at this temperature for 4 hours, and then 0.4 parts of 2,2'-azobis(isobutyronitrile) was added, followed by further stirring at this temperature for 4 hours, yielding a colorless, transparent reaction mixture containing a silyl ester copolymer.

[0136] Preparation procedure for comparative copolymer solution CS2 Copolymer solution CS2 was prepared using the procedure described for the preparation of copolymer solution CS1. The components of copolymer solution CS2 were used in the proportions listed in Table 1.

[0137] [Table 1]

[0138]

Table 2

[0139]

Table 3

[0140] Table 4A

[0141] Table 4B

[0142]

Table 5

[0143] Table 6A

[0144] Table 6B

[0145] Table 7A

[0146] Table 7B

[0147]

Table 8

[0148]

Table 9

Claims

1. 1. An antifouling coating composition comprising: (i) a silyl ester copolymer and (ii) medetomidine; The silyl ester copolymer is (a) triisopropylsilyl methacrylate; (b) A compound represented by the following formula (I): 【Chemical 1】 In formula (I), R １ is hydrogen or methyl, and R ２ is a cyclic ether (for example, oxolane, oxane, dioxolane, or dioxane substituted or unsubstituted with an alkyl group), and X is a C1-C4 alkylene; and / or a compound represented by the following formula (II): 【Chemistry 2】 In formula (II), R ３ is hydrogen or methyl, and R ４ is a C3-C18 substituent having at least one oxygen or nitrogen atom, preferably at least one oxygen atom; Further optionally, (c) one or more comonomers represented by formula (III): 【Chemistry 3】 In formula (III), R ５ is hydrogen or methyl, and R ６ is a C1 to C8 hydrocarbyl; and 1. An antifouling coating composition comprising:

2. 2. The antifouling coating composition of claim 1, wherein the amount of component (b) in the silyl ester copolymer is in the range of 2 to 50 wt %, preferably in the range of 2 to 40 wt %, more preferably in the range of 5 to 35 wt %.

3. 3. The method of claim 1, wherein the amount of (a) in the silyl ester copolymer is in the range of 5 to 80 wt %, preferably 25 to 75 wt %, especially 30 to 70 wt % of the copolymer. The antifouling coating composition according to any one of the preceding claims.

4. In formula (II), R ４ is the formula -(CH ２ CH ２ O) ｍ -R ７ is a group represented by R ７ An antifouling coating composition according to any one of claims 1 to 3, wherein is a C1-C10 alkyl substituent or a C6-C10 aryl substituent, and m is an integer ranging from 1 to 6, preferably from 1 to 3.

5. R ４ is the formula -(CH ２ CH ２ O) ｍ -R ７ is a group of R ７ The antifouling coating composition of claim 4, wherein is a C1 to C10 alkyl substituent, preferably methyl or ethyl, and m is an integer ranging from 1 to 3, preferably 1 or 2.

6. 6. The antifouling coating composition of any one of claims 1 to 5, wherein component (b) comprises one or more of 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-(2-ethoxyethoxy)ethyl acrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, tetrahydrofurfuryl acrylate, and tetrahydrofurfuryl methacrylate.

7. One or more non-hydrophilic comonomers represented by formula (III): 【Chemistry 4】 In formula (III), R ５ is hydrogen or methyl, and R ６ The antifouling coating composition of any one of claims 1 to 6, comprising one or more non-hydrophilic comonomers, wherein is a C1 to C8 hydrocarbyl substituent.

8. The antifouling coating composition of any one of claims 1 to 7, comprising one or more of methyl methacrylate and n-butyl acrylate.

9. An antifouling coating composition according to any one of claims 1 to 8, comprising methyl methacrylate as a comonomer in an amount of 2 to 60 wt%, preferably 5 to 50 wt%.

10. An antifouling coating composition according to any one of claims 1 to 9, comprising n-butyl acrylate as a comonomer in an amount of 1 to 30 wt%, preferably 2 to 25 wt%.

11. The antifouling coating composition according to claim 1 , comprising rosin or a derivative thereof.

12. 12. The antifouling coating composition according to any one of claims 1 to 11, which is free of inorganic copper compounds.

13. 13. The antifouling coating composition of any one of claims 1 to 12, wherein the biocide comprises cuprous oxide and / or copper pyrithione.

14. 14. An antifouling coating composition according to any one of claims 1 to 13, comprising a silane such as tetraethoxysilane.

15. 15. An antifouling coating composition according to any one of claims 1 to 14, comprising a silane such as tetraethoxysilane and rosin or a derivative thereof.

16. A process for protecting an object from adhesion, comprising: Coating at least a portion of the object to which adhesion is possible with the antifouling coating composition according to any one of claims 1 to 15. The process includes:

17. An object coated with the antifouling coating composition according to any one of claims 1 to 15.

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