Stain-controlling coating composition

Abstract

The present invention relates to a fouling control coating composition comprising (i) a siloxane-modified anionic polymer containing one or more metal cations, and (ii) an amine compound having at least one amine group bonded to a saturated carbon atom, having a boiling point of at least 85°C, and a molecular weight of at least 70. The coating is particularly useful as a self-polishing fouling control coating.

Description

[Technical Field]

[0001] The present invention relates to fouling control coating compositions, substrates or articles coated with such fouling control coating compositions, and methods for controlling aquatic fouling on artificial objects using such coatings. [Background technology]

[0002] Fouling of ship hulls and other floating objects by aquatic organisms is an ongoing problem. Fouling can increase the frictional resistance of boats in the water, potentially increasing fuel costs. In stationary structures, such as drilling rigs, fouling can alter the water flow around support legs, leading to unpredictable and potentially increasing stresses. Fouling can also make inspections more difficult by obscuring defects and cracks. Furthermore, fouling can reduce the flow rate of piping, such as the intakes of cooling water or ballast tanks, by narrowing the cross-sectional area.

[0003] Coatings can be used to reduce fouling. Such coatings may contain biocides to control the growth of aquatic organisms on the surface. Coatings are typically classified into two broad categories: “hard” antifouling coatings, from which biocides gradually leach out over time, and “erosive” antifouling coatings (sometimes called self-polishing coatings), from which the coating gradually erodes to release biocides. However, biocides may pose environmental risks, especially in areas with heavy shipping activity. Therefore, biocides are subject to increasingly stringent environmental legislation.

[0004] Biocide-free coatings are available, including so-called "fouling-removing" coatings, which have a "low surface energy" surface that inhibits the adhesion of fouling organisms and also allow fouling organisms to be washed away more easily from the surface. The fouling control effect can be enhanced by including non-biocidal adhesion-reducing fluids in the formulation. Biocide-free self-polishing coatings, so-called surface-active self-polishing coatings, can also be used, in which gradual abrasion or dissolution is designed to prevent the settlement and growth of biological fouling and continuously present a new, clean surface that promotes its release. Examples are described in International Publication Nos. 2004 / 081121 and International Publication Nos. 2009 / 011332.

[0005] Some fouling control coatings include, for example, Chinese Patent No. 103881576, European Patent No. 0877061, European Patent No. 1036786, European Patent No. 1479737, European Patent No. 2368949, European Patent No. 2489710, European Patent No. 2489711, Japanese Patent No. 3368618, Japanese Patent No. 3774310, Japanese Patent No. 2006077095, Korean Patent No. 101115200, Korean Patent No. 101137 As described in Patent No. 563, Korean Patent No. 101970431, U.S. Patent Publication No. 2003 / 0225184, U.S. Patent Publication No. 2009 / 0042042, U.S. Patent Publication No. 5116407, U.S. Patent No. 5236493, U.S. Patent No. 5298061, International Publication No. 91 / 15546, International Publication No. 96 / 04341, and International Publication No. 2015 / 150249, rosin or rosin derivatives may be included.

[0006] However, there is still a need for further types of fouling control coatings with improved properties. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] International Publication No. 2004 / 081121 [Patent Document 2] International Publication No. 2009 / 011332 [Patent Document 3] Chinese Patent No. 103881576 [Patent Document 4] European Patent No. 0877061 [Patent Document 5] European Patent No. 1036786 [Patent Document 6] European Patent No. 1479737 [Patent Document 7] European Patent No. 2368949 [Patent Document 8] European Patent No. 2489710 [Patent Document 9] European Patent No. 2489711 [Patent Document 10] Japanese Patent No. 3368618 [Patent Document 11] Japanese Patent No. 3774310 [Patent Document 12] Japanese Patent No. 2006077095 [Patent Document 13] Korean Patent No. 101115200 [Patent Document 14] Korean Patent No. 101137563 [Patent Document 15] Korean Patent No. 101970431 [Patent Document 16] U.S. Patent Application Publication No. 2003 / 0225184 [Patent Document 17] U.S. Patent Application Publication No. 2009 / 0042042 [Patent Document 18] U.S. Patent Application Publication No. 5116407 [Patent Document 19] U.S. Patent No. 5,236,493 [Patent Document 20] U.S. Patent No. 5298061 [Patent Document 21] International Publication No. 91 / 15546 [Patent Document 22] International Publication No. 96 / 04341 [Patent Document 23] International Publication No. 2015 / 150249 [Overview of the Initiative] [Means for solving the problem]

[0008] The present invention relates to a fouling control coating composition comprising (i) a siloxane-modified anionic polymer containing one or more metal cations, and (ii) an amine having at least one amine group bonded to a saturated carbon atom, having a boiling point of at least 85°C (at atmospheric pressure), and a molecular weight of at least 70.

[0009] The present invention also relates to a method for controlling aquatic fouling on an artificial object, comprising applying the coating composition to the surface of the artificial structure. The artificial structure is intended to be permanently or intermittently immersed in water, such as seawater, freshwater, or brackish water.

[0010] The present invention further relates to a substrate or article coated with the above-described fouling control coating composition both before and after drying and / or curing.

[0011] The present invention also relates to the use of such coating compositions for controlling aquatic fouling of artificial structures.

[0012] term In the following discussion, references to the amount of components in the overall coating composition refer to the uncured or undried composition unless otherwise specified. Furthermore, unless otherwise specified, the concentrations given are weight percent of the overall coating composition. If the coating composition is provided in separate parts (e.g., a binder-containing portion and a curing agent-containing portion), the amount of components in the overall coating composition is based on the total amount of components in all combined different parts.

[0013] References to “terminal” groups in resins, polymers, or oligomers refer to groups attached to the oligomer / polymer chain or “backbone” at the end (terminal) position. References to “pendant” groups refer to groups attached to the oligomer / polymer chain at positions other than the terminal position.

[0014] References to "aliphatic hydrocarbyl" groups or substituents include saturated and unsaturated hydrocarbyl groups (e.g., alkyl or alkenyl groups), which may be cyclic, linear, or branched, or may include mixtures of cyclic and acyclic portions. Similarly, references to "alkyl" or "alkenyl" groups or substituents include groups that are cyclic, linear, or branched, or mixtures of cyclic and acyclic portions. Unsaturated groups, such as alkenyl groups, have at least two carbon atoms.

[0015] A reference to "aryl" refers to an aromatic hydrocarbon group that may contain one or more aromatic rings. A reference to "heteroaryl" refers to an aromatic group that contains one or more heteroatoms in its aromatic ring, typically selected from oxygen, nitrogen, and sulfur.

[0016] The monomer (or monomer unit) content of a polymer or oligomer is expressed in either weight percent or mole percent, and can be calculated from the weight fraction or mole fraction of the monomer used to prepare the polymer or oligomer, respectively.

[0017] The term "monomer unit" refers to the constituent monomers of a polymer, that is, the portion derived from the monomers after they have been incorporated into the polymer.

[0018] Atmospheric pressure is defined as 1.013 bar-a, where bar-a represents absolute bar, as opposed to gauge bar.

[0019] The term "saturated carbon atom" refers to a carbon atom that has four single covalent bonds with other atoms and no double or triple covalent bonds with other atoms. [Brief explanation of the drawing]

[0020] [Figure 1] The rosinamine selected in the embodiment is a rosinamine. [Modes for carrying out the invention]

[0021] [Anionic polymer] The coating composition comprises one or more binder resins, at least one of which is a siloxane-modified anionic polymer containing one or more metal cations. The anionic polymer can be formed from at least one monomer having an anionic functional group, and one or more metal cations are used to balance the negative charge. In embodiments, it is a thermoplastic polymer.

[0022] Examples of anionic polymers include those having an anionic moiety selected from phosphonates, sulfonates, carboxylates, and carbonates. In embodiments, the anionic moiety, or at least one anionic moiety, is a carboxylate.

[0023] The amount of metal cation-containing siloxane-modified anionic polymer in the coating composition is typically in the range of 20-80% by weight, for example, 20-75% by weight, 25-70% by weight, or 25-60% by weight.

[0024] [Metal cations] The metal cation can be selected from divalent or trivalent metal ions. In embodiments, the metal ion can be selected from alkaline earth metal ions (e.g., Mg, Ca, Sr), transition metals or "d-block" ions (e.g., first-period transition metals, e.g., Ti, Fe, Co, Ni, Cu, Zn), typical "p-block" metals (e.g., Al, Sn), and lanthanides (e.g., La, Ce, Pr). The metal ion can be selected from Mg, Ca, Zn, and Cu, and is typically selected from Cu and Zn.

[0025] The metal cation can be provided in the form of a salt of anionic monomer, for example, as a metal salt of an acrylate monomer, as will be described in more detail below. In other embodiments, it can be provided in the form of another salt, for example, as a carboxylate salt, examples of which will also be described in more detail below.

[0026] The metal cation content of metal cation-containing siloxane-modified anionic polymers is typically in the range of 1–20% by weight, for example, 2–15% by weight, or 2–10% by weight.

[0027] [Siloxane portion] The anionic polymer contains a covalently bonded siloxane moiety. The siloxane moiety may be linear, branched, or cyclic, or may contain a mixture of cyclic and acyclic moieties or regions. In embodiments, the siloxane moiety contains 4 to 150 silicon atoms. In embodiments, the siloxane moiety bonded to the anionic polymer can be represented by formula (1). [ka]

[0028] In embodiments, the siloxane moiety is bonded to the anionic polymer via an oxygen atom or a carbon atom. Typically, the siloxane moiety is bonded to a carbon atom. b is in the range of 3 to 150, for example, 3 to 100 or 8 to 80. c is in the range of 0 to 20, for example, 0 to 10, 0 to 5 or 0 to 3. In embodiments, c is 0.

[0029] Each A is [OSi(R c )2]

[0030] Each R c This is independently, and in some cases, a substituted C 1~20 Aliphatic hydrocarbyl groups, and in some cases substituted C 6~12 An aryl group and one or more C 1~6 C having an alkyl group, and possibly substituted C6~12 It is selected from an aryl group. Optional substituents are further defined below.

[0031] Any alkyl group may be cyclic or acyclic, or may contain cyclic and acyclic moieties. An acyclic alkyl group or substituent may be straight-chain or branched-chain.

[0032] Each R t is independently selected from H, C 1~6 alkyl, and C 1~6 haloalkyl.

[0033] In an embodiment, the siloxane moiety can be represented by formula (2). [Chemical formula]

[0034] In an embodiment, in either formula (1) or (2), there is no halide or halide-containing substituent. In a further embodiment of formula (1) and (2), there is no optional substituent on any R c group.

[0035] In an embodiment, the siloxane moiety is a non-functional dimethylpolysiloxane or methylphenylpolysiloxane, and in formula (2), each R c is unsubstituted methyl or phenyl.

[0036] The amount of polysiloxane in the metal-modified anionic polymer may range from 2 to 70% by weight, for example, from 30 to 65% by weight.

[0037] The molecular weight of the polysiloxane moiety may range from 800 to 6000, for example, from 1000 to 5000, or from 1400 to 3500.

[0038] [Monomer unit of anionic polymer] Anionic polymers are, in embodiments, acrylate polymers or copolymers. Such polymers or copolymers can be obtained by polymerization of a mixture of monomers containing one or more acrylate monomers. Acrylate monomers are monomers having a portion in which a C=C double bond is directly bonded to a carboxyl group, a carboxylate group, or an amide group.

[0039] In the embodiment, the acrylate polymer comprises one or more carboxylate-containing acrylate monomer units represented by formula (3). [ka]

[0040] Each R f H, C 1~20 Aliphatic hydrocarbyl, C 6~12 Aryl, and C 1~6 Alkyl, C(O)O - and C(O)OR t C having one or more substituents selected from 6~12 Selected from the arrows.

[0041] Each R g These are, independently, H, and C 1~20 Aliphatic hydrocarbyl (e.g., alkyl), C 6~12 Aryl, and one or more (e.g., 1 to 4) C 1~6 C substituted with an aliphatic hydrocarbyl group 6~12 Selected from the alphabet. f and R g Each aliphatic hydrocarbyl substituent, aliphatic hydrocarbyl group, and aryl group in the compound may be substituted as described below.

[0042] In the explicit section, C 1~20 Aliphatic hydrocarbils are C 1~10 or C 1~6 Aliphatic hydrocarbyl groups, for example, C 1~10 or C1~6 It can be selected from alkyl groups. In this embodiment, each R g This is selected from hydrogen and methyl.

[0043] In one embodiment, R g The groups are H and unsubstituted C, independently. 1~6 Alkyl, for example, H and C 1~4 Alkyl, for example, selected from H and methyl. In one embodiment, R f H, -C(O)O-, -C(O)OR t , and -C(O)O - and -C(O)OR t C which may be replaced by one or more groups selected from 1~6 Selected from alkyl groups. f In some cases, C is replaced. 1~6 In embodiments where the alkyl group is one optional -C(O)O - or -C(O)OR t Only substituents are present.

[0044] In some embodiments, the acrylate polymer is a copolymer comprising one or more further monomer units. In one embodiment, the one or more further monomer units can be selected from those represented by formula (4). [ka]

[0045] R f and R g This is defined as above. Z is -OR h and -N(R h ) Selected from 2.

[0046] In this embodiment, base Z is OR h For example, OR t Selected from.

[0047] Z is N(R h In the embodiment where Rf and R g In all cases, the carbonyl-containing portion is -C(O)O - , -C(O)OR t or -C(O)NR t It does not contain 2.

[0048] Each R h Independently, H, and C which is substituted in some cases, as further described below. 1~20 Selected from alkyl groups. In an embodiment, C 1~20 Alkyl is C 1~10 or C 1~6 It is alkyl.

[0049] In embodiments, the monomer of formula (3) may be based on acrylate, methacrylate, itaconate, maleate, or crotonate. These also apply to the monomer of formula (4), but may include acrylamide and methacrylamide. In embodiments, the monomer of formula (3) is based on acrylate or methacrylate, and the monomer of formula (4) is based on acrylate, methacrylate, acrylamide, or methacrylamide.

[0050] In one embodiment, R h There is at least one monomer unit of formula (4) containing a siloxane moiety as a substituent on the group, for example Z is OR h The siloxane portion may be as follows: [ka]

[0051] In such an embodiment, R h is C 1~6 You can choose from alkyl groups.

[0052] Other types of comonomers (i.e., non-acrylate monomers) that can form part of anionic polymers include those having polymerizable unsaturated carbon-carbon bonds, for example, those represented by formula (5). [ka]

[0053] Each R j These are independently H, a halide (e.g., selected from F and Cl), and C 1~6 Selected from alkyl groups. k R j , C 2~6 Alkenil, C 6~12 Aryl, and one or more C 1~6 C substituted with an aliphatic hydrocarbyl group 6~12 It can be selected from the alphabet. In this embodiment, R j and R k Only one of them may be a halide, or it may contain a halide-containing substituent. In the embodiment, R k is C 6~12 Contains an aryl compound. In the embodiment, the comonomer is R h and R g As shown below, it may contain one or more optional substituents.

[0054] The average number of monomer units in an acrylate-based anionic polymer can range from 5 to 500, for example, from 10 to 300.

[0055] In the embodiment, the optionally substituted group may include 1 to 4 substituents, for example, 1 or 2 substituents.

[0056] In the embodiment, the viscosity of the siloxane-modified anionic polymer is in the range of 3 to 100 poise, for example, 5 to 50 poise, when measured at 25°C.

[0057] In embodiments, metal cation-containing siloxane-modified anionic polymers are prepared, for example, by using anionic monomers in their acidic form, i.e., protonated form, where the monomer unit is of formula (4) where Z is OH, and then exchanging one or more H ions with metal cations.

[0058] When preparing siloxane-modified anionic polymers, the proportion of anionic monomers (or protonated forms of anionic monomers) in the monomer mixture is typically in the range of 0.5 to 20% by weight, for example, 1 to 12% by weight, or for example, 2 to 10% by weight.

[0059] In some embodiments, the anionic monomer is an acrylate-based anionic monomer containing at least 80% of monomer units according to formulas (3) and (4) on a molar basis. In further embodiments, this amount is at least 90% or at least 95% on a molar basis. In further embodiments, all monomer units are according to formulas (3) and (4).

[0060] In embodiments, in an anionic polymer, the amount of metal cation relative to the anionic monomer units in the polymer is at least 80 mol%, for example, at least 90 mol% or at least 95 mol%. In this sense, monomer units containing an acidic group, for example, monomer units of formula (4) where Z is -OH, are considered to be anionic monomer units. Otherwise, anionic polymers may become excessively soluble and decompose excessively rapidly when in contact with water.

[0061] In the embodiment, anionic monomer units that are not charge-equalized by a metal cation can be charge-equalized by another cation, such as a proton or an amine cation. In the embodiment, substantially all anionic monomer units are charge-equalized by a metal cation.

[0062] [Optional substituents] R c and Rh The optional substituent is a halide, -OR t , and -N(R t )2 selected from.

[0063] R h and R g The optional substituent is a halide, -OR t , -N(R t )2, the siloxane moiety defined above, -OC(O)R t , -C(O)N(R t )2 and -OC(O)N(R t )2 can be selected from. Further optional substituents include polyethers, polyamines, and -([CR t 2] j E-) p R t and -E-([CR t 2] j E-) p R t selected polyether / amine groups. Each E is independently selected from O and NR t . j may be from 1 to 6, for example 2 to 4, and p may be from 1 to 20. For R f , the same optional substituents apply, and further optional substituents are selected from -C(O)O - , and -C(O)OR t .

[0064] Any halide substituent or any halide in any substituent is typically selected from F and Cl.

[0065] [Other organic anions] The coating composition can include one or more further organic anions. They can be ionically bonded to the polymer, for example, as counterions of an anionic polymer having divalent or trivalent metal ions.

[0066] In embodiments, further organic anions are selected from carboxylate anions having at least one carboxylate group. Organic anions typically contain a total of 2 to 50 carbon atoms.

[0067] The organic ion consists of at least one carboxyl group and a halide (typically selected from F and Cl), R t OR as defined above t and N(R t )C having one or more additional substituents of any choice selected from 2 2~50 It may be a hydrocarbyl group. In embodiments, it is unsubstituted except having at least one carboxyl group, for example, one or two carboxyl groups. In embodiments, there is only one carboxyl group.

[0068] The hydrocarbyl group is a C4-C group selected from aliphatic, aromatic, or aliphatic-substituted aromatic groups. 20 A hydrocarbyl group may also be used.

[0069] In embodiments, the organic ion includes fatty acids, naphthenic acids, and versatic acids, aliphatic groups such as saturated aliphatic groups, such as C4-C 20 Alkyl alkyl groups or C6-C 20 Selected from carboxyl-containing compounds selected from alkyl groups.

[0070] The organic ions may be part of the carboxyl-containing compounds present in the rosin, selected from, for example, gum rosin, wood rosin, and tall oil rosin. In embodiments, the rosin may be hydrogenated or disproportionated rosin.

[0071] [Amine compounds] The coating composition contains an amine compound having a boiling point of at least 85°C (at atmospheric pressure). In embodiments, the boiling point is at least 100°C, for example, at least 200°C or at least 250°C. Furthermore, the boiling point is typically 800°C or less, for example, 600°C or less.

[0072] The amine compound has a molecular weight of at least 70, for example, in the range of 70 to 10000. In embodiments, the molecular weight is at least 100, for example, at least 200 or at least 250. In embodiments, the molecular weight is 500 or less, for example, 350 or less.

[0073] In embodiments, the amine compound has at least one primary or secondary amine group, i.e., an amine group containing at least one NH bond. The primary or secondary amine group (or at least one of the primary or secondary amine groups) is bonded to a saturated carbon atom, i.e., not directly bonded to an unsaturated or aromatic carbon atom.

[0074] A primary or secondary amine group is represented by R in the formula. t As defined above, formula -NHR t It can be selected from those. In the embodiment, in the case of a secondary amine, R t C 1~4 -Alkyl or C 1~2 Alkyl is also acceptable.

[0075] In the embodiment, the amine group is R in the formula v C 1~6 Alkyl and C 1~6 Formula selected from haloalkyls - NR v It is a tertiary amine group of 2. In further embodiments, one or both R v The base is C 1~4 Alkyl and C 1~2 You can choose from alkyl groups.

[0076] In embodiments, one or more amine groups are bonded to a hydrocarbon skeleton having 4 to 50 carbon atoms, which may be optionally substituted. In embodiments, the hydrocarbon skeleton may be linear, branched, or cyclic, or may consist of a mixture of cyclic and acyclic portions. The skeleton may contain one or more aromatic rings. One or more optional substituents are halides, where Rt is as defined above - OR t and -N(R t )2 can be selected. If present, the halide can be selected from F and Cl, but in this embodiment, no halide substituent is present.

[0077] In other embodiments, the amine compound is a polyamine and a polyalcoholamine, for example, formula R t E-([CR t 2] j E-) p R t You can choose from, and in the formula, R t E, j, and p are as defined above, such that at least one E group is NH, and the entire molecule meets the above boiling point and molecular weight requirements. In embodiments, all E are NR t That is the case.

[0078] Typically, there are no halides or halide-containing substituents. In embodiments, any substituent other than the amine substituent is C 1~6 Alkyl, for example, C 1~4 Selected from alkyl groups.

[0079] In embodiments, the amine compound comprises a single amine group which may be a primary, secondary, or tertiary amine group. This avoids potentially excessive viscosity increases or gelation resulting from increased crosslinking.

[0080] In the embodiment, the amine compound includes an alicyclic ring, such as rosinamine or pyrrolidine.

[0081] In embodiments, the source of one or more amine compounds is a rosinamine. Rosinamines are commercially available. Rosinamines are typically derived from an acidic rosin, i.e., a rosin containing one or more carboxyl groups, by a suitable reaction in which the corresponding amide is formed by reaction with, for example, ammonia or an amine, and then converted to an amine by reduction or Hoffmann rearrangement.

[0082] In embodiments, the rosinamine compound comprises, for example, a diterpenoid "skeleton" containing three rings. The rings may be saturated, unsaturated, aromatic, or any mixture thereof.

[0083] In the embodiment, the rosinamine compound may be of formula (6). [ka]

[0084] Ring A is an alicyclic C6 ring or an aromatic C6 ring. An alicyclic C6 ring contains 0, 1, or 2 C=C double bonds.

[0085] Ring B is an alicyclic C6 ring having zero or one C=C double bond.

[0086] Ring A and base R x The bond between them may be a single bond or a double bond.

[0087] R x C 1~20 Selected from aliphatic hydrocarbyls, halides (typically from F and Cl), -OR t and -N(R t ) optionally substituted with one or more substituents selected from 2. In embodiments, R x In the formula, each R t is H or unsubstituted aliphatic hydrocarbyl, for example, C 1~6 Alkyl -C(R t )3 units or =C(R t There are two of them.

[0088] R y In the formula, R t Furthermore, j and p are as defined above - ([CR t 2] j NR t -) p It is H.

[0089] In some cases, the ring in formula (6) is a halide (typically selected from F and Cl), OR t , N(R t )2 and R x It may have one or more substituents selected from. In embodiments, the compound of formula (6) does not have a halide or a halide-containing substituent. In embodiments, C 1~20 Aliphatic hydrocarbyl groups are sometimes substituted with C 1~6 Alkyl or C 1~6 It is an alkenyl group.

[0090] In the embodiment, the amine compound (or at least one amine compound) is a compound of formula (7). [ka]

[0091] In equation (7), r may be 1 to 6, for example, 1 to 2, and is 1 in the embodiment.

[0092] In this embodiment, rosinamine or at least one of rosinamines is selected from those shown in Figure 1.

[0093] One or more amine compounds can be used. For example, when rosinamine is used, commercial sources often contain two or more amine moieties of formula (6) or (7). In embodiments, the amine or at least one amine is abiethylamine or dehydroabiethylamine.

[0094] The coating composition may contain one or more amine compounds in an amount ranging from 0.1 to 30% by weight, for example, 0.5 to 30% by weight, 1 to 30% by weight, or 1 to 25% by weight.

[0095] The use of amine compounds as described above helps to avoid cracking of the coating film (after application and drying or curing) and improve mechanical integrity, thus reducing or eliminating the need to add plasticizers to the formulation. In embodiments, the coating composition contains less than 2% by weight of plasticizer, for example, less than 1% by weight or less than 0.5% by weight.

[0096] [Additional ingredients] The coating composition may optionally contain one or more other components selected from, for example, curable resins, crosslinking agents, reactive diluents, corrosion inhibitors, pigments, gloss additives, waxes, rosins, fillers and extenders, thixotropic agents, plasticizers, inorganic and organic dehydrating agents (stabilizers), UV stabilizers, defoamers, and any combination thereof. These components are well known to those skilled in the art.

[0097] The total amount of such further optional components may be in the range of 0 to 65% by weight, typically 50% or less by weight of the coating composition, for example, 35% or less by weight, based on the total content of the coating composition.

[0098] Except for organic solvents, marine biocides, pigments, fillers, and extenders, which are discussed further below, the coating composition may contain a total of less than 5% by weight or less than 3% by weight of any further optional components.

[0099] The coating composition may contain small amounts of non-volatile and non-reactive oligomers or polymer fluids (e.g., polysiloxane oil or fluoropolymers, e.g., perfluoropolyethers), or hydrocarbon waxes or oil mixtures (e.g., petrolatum), or it may not contain such non-volatile and non-reactive fluids. For example, their content may be 5% by weight or less, e.g., 3% by weight or less, 1% by weight or less, or 0.1% by weight or less.

[0100] [organic solvent] The composition may contain one or more organic solvents. These organic solvents are typically organic liquids that have a boiling point of 250°C or less at atmospheric pressure (i.e., 101.3 kPa or 1.013 bar-a) and evaporate from the coating composition during the drying and curing process.

[0101] The organic solvent can be selected from hydrocarbon compounds and heteroatom-containing organic compounds, where the heteroatom is selected from O, S, and N, for example, O.

[0102] Examples of organic solvents include alkyl aromatic hydrocarbons (e.g., xylene, toluene, and trimethylbenzene) and aliphatic hydrocarbons (e.g., C 4~20 Cyclic and acyclic hydrocarbons selected from alkanes, or mixtures of any two or more thereof), alcohols (e.g., benzyl alcohol, octylphenol, resorcinol, n-butanol, isobutanol, and isopropanol), ethers (e.g., methoxypropanol), glycol ethers (e.g., phenyl, benzyl, or C of ethylene glycol, diethylene glycol, propylene glycol, or dipropylene glycol). 1~4 Examples include alkyl ethers or diethers, ketones (e.g., methyl ethyl ketone, methyl isobutyl ketone, and methyl isopentyl ketone), and esters (e.g., butyl acetate). In embodiments, the organic solvent contains 2 to 20 carbon atoms, for example, 3 to 15 carbon atoms. A mixture of any two or more organic solvents can be used.

[0103] The total amount of organic solvent can be up to 80% by weight of the total weight of the coating composition, for example, in the range of 10-80% by weight, 20-80% by weight, or 25-65% by weight.

[0104] The organic solvent content is separate from the water content. Coating compositions are typically non-aqueous compositions. Water may be present, but typically at low concentrations. If present, the water concentration is typically 5% by weight or less, for example, 1% by weight or less.

[0105] [Marine biological agents] The coating composition may, in some embodiments, contain one or more marine biocides. Marine biocides are chemical substances known to have chemical or biological bactericidal activity against marine or freshwater organisms.

[0106] The coating compositions described herein do not require any additional marine biocides, but may incorporate them as needed. In embodiments where marine biocides are present, the marine biocides may be present in concentrations of up to 50% by weight, for example, up to 30% by weight or up to 10% by weight. However, in embodiments, the amount of marine biocides is limited, for example, 1% by weight or less of the total coating composition, for example, 0.5% by weight or less or 0.1% by weight or less. In embodiments, the coating composition does not contain marine biocides.

[0107] If used, suitable marine biological agents are well known in this art and include inorganic, organometallic, metal-organic, or organic biocides.

[0108] Examples of inorganic biocides include copper compounds, such as copper oxide, copper thiocyanate, copper bronze, copper carbonate, copper chloride, copper-nickel alloys, and silver salts, such as silver chloride or silver nitrate.

[0109] Examples of organometallic biocides and metal-organic biocides include zinc pyrithione (zinc salt of 2-pyridinethiol-1-oxide), copper pyrithione, bis(N-cyclohexyl-diazenium dioxy)copper, zinc ethylene-bis(dithiocarbamate) (i.e., zineb), zinc dimethyldithiocarbamate (dilam), and manganese ethylene-bis(dithiocarbamate) (i.e., mancozeb) complexed with a zinc salt.

[0110] Organic biocides include formaldehyde, dodecylguanidine monohydrochloride, thiabendazole, medetomidine, N-trihalomethylthiophthalimide, trihalomethylthiosulfamide, N-arylmaleimide, such as N-(2,4,6-trichlorophenyl)maleimide, 3-(3,4-dichlorophenyl)-1,1-dimethylurea (diurone), 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, and 2-methylthio-4-butyl Amino-6-cyclopropylamino-s-triazine, 3-benzo[b]thienyl-5,6-dihydro-1,4,2-oxathiazidine-4-oxide, 4,5-dichloro-2-(n-octyl)-3(2H)-isothiazolone, 2,4,5,6-tetrachloroisophthalonitrile, tolylfluanide, diclofluanide, diiodomethyl-p-tosylsulfone, capsaicin and substituted capsaicin, N-cyclopropyl-N'-(1,1-dimethyl Ethyl)-6-(methylthio)-1,3,5-triazine-2,4-diamine, 3-iodo-2-propynylbutylcarbamate, medetomidine, 1,4-dithiaanthraquinone-2,3-dicarbonitrile (dithianone), borane, e.g., pyridinetriphenylborane, 2-trihalogenomethyl-3-halogeno-4-cyanopyrrole derivatives substituted at position 5 and possibly at position 1, e.g., 2-(p-chlorophenyl)-3-cyano-4 Examples include bromo-5-trifluoromethylpyrrole (tralopyryl), furanones, such as 3-butyl-5-(dibromomethylidene)-2(5H)-furanone, macrocyclic lactones, such as avermectin, such as avermectin B1, ivermectin, doramectin, abamectin, amamectin, and selamectin, and quaternary ammonium salts, such as didecyldimethylammonium chloride and alkyldimethylbenzylammonium chloride.

[0111] Biocides may, in embodiments, be encapsulated, adsorbed, captured, supported, or bound. Certain biocides are advantageously difficult or hazardous to handle and are used in encapsulated, captured, absorbed, supported, or bound forms. Encapsulation, capture, absorption, support, or binding of biocides can provide secondary mechanisms for controlling biocide leaching from coating systems to achieve slower release and sustained effects. The methods of encapsulating, capturing, adsorbing, supporting, or binding biocides are not particularly limited. Examples include the use of single-layer and double-layer amino-formaldehyde, or hydrolyzed polyvinyl acetate-phenol resin capsules or microcapsules as described in International Publication No. 2006 / 032019. An example of a suitable encapsulated biocide is encapsulated 4,5-dichloro-2-(n-octyl)-3(2H)-isothiazolon, commercially available from Dow Microbial Control as Sea-Nine CR2 Marine Antifouling Agent. Examples of methods by which absorbed, supported, or conjugated biocides may be prepared include the use of host-guest complexes, e.g., clathrate as described in European Patent No. 0709358, phenolic resin as described in European Patent No. 0880892, carbon-based adsorbents, e.g., those described in European Patent No. 1142477, or microporous inorganic carriers, e.g., amorphous silica, amorphous alumina, pseudoboehmite, or zeolite as described in International Publication No. 00 / 11949.

[0112] [Pigments, fillers, and corrosion inhibitors] In embodiments, one or more pigments, fillers, and anticorrosive agents may be included in the coating composition.

[0113] Examples of suitable fillers include zinc oxide, barium sulfate, calcium sulfate, calcium carbonate, silica, or silicates (e.g., talc, feldspar, and clay) (such as calcined silica, bentonite, and other clays). Some fillers (e.g., fumed silica) may have a thixotropic effect on the coating composition.

[0114] The proportion of filler may range from 0 to 25% by weight based on the total weight of the coating composition. If clay is present, the amount of clay is up to 1% by weight, e.g., 0.1 to 1% by weight, based on the total weight of the coating composition. If thixotrope is present, the amount of thixotrope is up to 5% by weight, e.g., 0.1 to 5% by weight, based on the total weight of the coating composition.

[0115] Examples of pigments include black iron oxide, red iron oxide, yellow iron oxide, titanium dioxide, carbon black, graphite, red molybdate, yellow molybdate, zinc sulfide, antimony oxide, sodium aluminum sulfosilicate, quinacridone, phthalocyanine blue, phthalocyanine green, indanthron blue, aluminum cobalt oxide, carbazole dioxazine, chromium oxide, isoindoline orange, bis-acetoaceto-tolidiole, benzimidazolone, quinafthron yellow, isoindoline yellow, tetrachloroisoindolinone, quinophthalone yellow, and metal flake materials, such as aluminum flakes.

[0116] Examples of corrosion inhibitors include zinc powder and zinc alloys, as well as so-called lubrication pigments, such as graphite, molybdenum disulfide, tungsten disulfide, and boron nitride. If present, the corrosion inhibitor may be present in an amount of up to 25% by weight of the entire coating composition, for example, in the range of 0.1 to 25% by weight.

[0117] In embodiments including any pigments, fillers, or anticorrosive agents, they may together constitute up to 50% by weight, for example up to 40% by weight, of the coating composition based on the total weight of the coating composition. In embodiments, there may be at least 0.1% by weight, for example at least 5% by weight, at least 10% by weight, or at least 20% by weight of these components. Exemplary ranges include 0.1–50% by weight, 0.1–40% by weight, 5–50% by weight, 5–40% by weight, 10–50% by weight, 10–40% by weight, 20–50% by weight, and 20–40% by weight.

[0118] [Properties of the coating composition] In the embodiments, the coating composition has a non-volatile substance content of 35% by weight or more, based on the total weight of the coating composition. In further embodiments, the non-volatile substance content is 50% by weight or more, for example, 70% by weight or more. In embodiments, the non-volatile substance content is 85% by weight or less. The non-volatile substance content can be determined according to ASTM D2697, for example, D2697-03 (2014).

[0119] In the embodiment, the touch-dry time of the coating composition at 23°C and 50% relative humidity is in the range of 0.1 to 4 hours, for example, in the range of 0.2 to 3 hours. The touch-dry time is the time after which the coating is not sticky when lightly pressed with a finger and no marks are left on the coating.

[0120] In the embodiment, the hard-dry time is 1 to 30 hours, for example, 2 to 20 hours, at 23°C and 50% relative humidity. The hard-dry time is the time it takes for no film damage or marks to occur when a thumb is pressed firmly against the surface and twisted 180°.

[0121] [Preparation of coating composition] The coating composition can be prepared by mechanical mixing of components using conventional means and apparatus, such as stirring mixers, including anchor, paddle, propeller, turbine, and helical mixers.

[0122] In embodiments, the composition is prepared and provided in separate parts, for example, in a two-pack or two-component (2K) system. However, typically, the coating composition is a one-pack (1K) composition, i.e., the formulation is provided in a single pack so that mixing of separate curing and binder components is not required at the time of application.

[0123] The coating composition can achieve highly effective fouling control without the need for marine biocides. The combination of siloxane-modified anionic polymers and amine compounds can also, surprisingly, contribute to lower viscosity, thus reducing the need for organic solvents.

[0124] The use of amine compounds in combination with siloxane-modified anionic polymers also allows for the achievement of a good combination of flexible yet rigid coatings. This is advantageous because increasing the flexibility of the coating often decreases its hardness, and vice versa. The coating also exhibits reduced cracking without the need to add plasticizers to the composition.

[0125] In the embodiment, the coating is a so-called self-polishing coating, that is, designed to gradually wear or erode over time. Continuous erosion of the surface prevents the adhesion of fouling organisms, or at least shortens the adhesion period. The self-polishing rate of the coating composition has been found to have good long-term consistency in polishing rate, as well as good crack resistance.

[0126] [Application of coating composition] The coating composition can be applied to the substrate by known methods, such as conventional air spraying, or by airless spraying or air mix spraying equipment. Alternatively, for example, when used as a stripe coat, or for smaller vessels such as yachts, it can be applied using a brush or roller. The composition can be applied under ambient conditions without preheating. For spray application, conventional pressures, such as 3-6 bara (absolute bar), can be used.

[0127] The coating is typically applied to achieve a total dry film thickness of 100–1000 μm, for example, 100–500 μm or 150–350 μm. The applied film thickness may vary depending on the properties of the substrate to be coated and the environment to which it will be exposed.

[0128] [Coating type] The coating composition can be used alone or as part of a coating system comprising multiple coating compositions. The coating composition can be applied directly to a substrate surface or a pre-coated surface. For example, it can be applied over a primer or intermediate coat, such as a tie coat.

[0129] A particular advantage of the coating composition described above is its ability to combine desirable attributes such as good adhesion to an undercoat or tiecoat, while still possessing highly effective fouling control properties.

[0130] In one embodiment, the coating composition is applied directly to the undercoated surface. In a further embodiment, the coating composition is applied to a tie coat layer. The tie coat may be on top of the primer layer or directly on the substrate surface.

[0131] In some embodiments, the coating composition is applied directly to a bare substrate. In other embodiments, the coating composition is applied to a pre-coated substrate so as to include one or more existing pre-cured and / or dried coating layers.

[0132] In the embodiment, the coating composition is applied to a primer layer on a substrate. The origin of the primer layer is not particularly limited, but in the embodiment, the primer is an epoxy resin-based primer.

[0133] In the embodiment, the coating composition is applied to a tie coat layer on a substrate, and the tie coat layer may optionally be on a primer layer on the substrate.

[0134] In one embodiment, the coating composition forms part of a multi-coat system that additionally includes a primer and / or tie coat.

[0135] In some embodiments, a tie coat layer can be applied on top of the primer layer to aid in bonding between the coating composition and the primer layer. However, in some embodiments, the tie coat is not required.

[0136] [Base material] The substrate to which the coating is applied may be intended to be permanently or intermittently immersed in water. Examples of substrates include metal, concrete, wood, or polymer surfaces.

[0137] The polymer surface includes polyvinyl chloride (PVC) or a fiber-reinforced resin composite material. It also includes a flexible polymer carrier foil, such as a PVC carrier foil, where the uncoated side is or may be bonded to a different surface.

[0138] In the embodiment, the substrate is a surface that may be submerged in water, selected from, for example, one or more of the hull (or at least the waterline portion of the hull), propeller, and rudder. [Examples]

[0139] Next, the present invention will be described with reference to the following non-limiting embodiments.

[0140] [Siloxane-modified acrylate polymer containing metal cations] Table 1 lists the amounts (by weight) of materials used in the preparation of the metal cation-containing siloxane-modified acrylate polymers.

[0141] Approximately 75% (by weight) of the total solvent was added to the polymerization reaction vessel and heated to 100°C. The monomer and "azo" initiator were dissolved in 10% solvent and then added dropwise to the polymerization vessel with constant stirring over 5 hours. After the addition, the peroxide solution in the remaining 15% solvent was added over 30 minutes. The reaction was maintained for 90 minutes, after which it was cooled to room temperature.

[0142] Next, the resulting resin solution was mixed with zinc oxide and naphthenic acid, heated at 105°C for 10 hours with constant stirring, and then cooled to room temperature.

[0143] [Table 1]

[0144] [Base composition] Using the obtained polymer solution, amine-free base formulations were prepared in parts by weight according to the components listed in Table 2.

[0145] Next, coating compositions were prepared by adding various amine compounds, the boiling points and molecular weights of which are listed in Table 3, to these base compositions. The amounts of materials used in preparing the coating compositions are listed in Table 4.

[0146] [Table 2]

[0147] [Table 3]

[0148] [Table 4]

[0149] [Anti-fouling activity] The coating was applied to plywood test panels in a 6x6 "Latin grid" arrangement. The panels were immersed in seawater from Singapore or the northeast coast of the UK, and biofouling was checked periodically. The degree of observed fouling was assigned on a scale of 1 to 10, with 1 representing very low fouling and 10 representing very high fouling. The results are shown in Tables 5-9.

[0150] [Table 5]

[0151] [Table 6]

[0152] [Table 7]

[0153] [Table 8]

[0154] [Table 9]

[0155] These results generally indicate that the coating compositions described herein exhibit fouling control activity comparable to that of commercially available fouling control coating compositions.

[0156] [Microhardness, viscosity, and flexibility] Measurements were collected using a Fischer microhardness tester and a Sheen cone-plate viscometer. Tests were performed on coated glass panels, with a wet film thickness of 200 μm. Viscometer experiments were conducted at 750 rpm for 15 seconds at 25°C.

[0157] The panels were dried at ambient temperature for one week before testing. Table 10 shows the results of comparing the amounts of different anionic polymers and resins. Table 11 shows the results collected separately using different amine compounds.

[0158] [Table 10]

[0159] [Table 11]

[0160] These results demonstrate that the coating composition has a sufficiently low viscosity to be applied using airless spray technology. They also highlight the advantages of amine compounds in achieving generally lower viscosity in coating compositions. However, the amount added should not be excessive to avoid viscosity increases if the amine has a high intrinsic viscosity.

[0161] [Flexibility] Flexibility tests were performed using a conical mandrel according to ASTM D522. The results are shown in Table 12. High mm values ​​indicate low flexibility, while low values ​​indicate good flexibility. Samples were tested 1 day and 8 days after coating the substrate, and the samples were kept at ambient temperature throughout.

[0162] [Table 12]

[0163] These results indicate that coating compositions within the above-mentioned range (i.e., having a boiling point of at least 85°C, a molecular weight of at least 70, and an amine bonded to a saturated carbon atom) are more flexible than compositions with amines having different properties. While ammonia helps achieve good flexibility, the coatings tend to have poor long-term mechanical performance (see wet / dry cycle results below). The results also demonstrate the flexibility advantage of siloxane groups compared to silyl groups on anionic polymers. [Wet / Dry Cycle]

[0164] [Table 13]

[0165] The experiment was conducted by spreading a test coating onto a primer-coated steel panel and allowing it to dry. The panel was then circulated between a warm seawater environment and a cold, dry environment, with each immersion lasting 24 hours. The degree of cracking between cycles was evaluated on a scale of 1 to 5, where 5 = no cracking and 1 = severe cracking. The results are shown in Table 13.

[0166] This effect indicates that when the composition contains an amine compound having an anionic siloxane-modified polymer, resistance to cracking is improved even in the absence of a plasticizer. However, when using low-boiling point materials, such as ammonia, the effect is very short-lived.

[0167] [Polishing speed] The substrate used in these experiments was a 23 cm diameter Perspex disk pre-coated with a layer of Intergard® 263 epoxy tie coat. The test coat was applied using a 600 μm drawdown cube and dried under ambient conditions for two weeks. Five replication experiments were performed for each test coating.

[0168] [Table 14]

[0169] The substrate was immersed in seawater and rotated at 700 rpm. A laser surface shape analyzer was used to measure the film thickness at periodic intervals, and film loss was calculated. The results are shown in Table 14.

[0170] These results indicate that the self-polishing performance of amine-containing coatings is more stable over the long term compared to amine-free compositions (base compositions), which tend to degrade more rapidly after about 100 days due to mechanical fracture and cracking.

Claims

1. A fouling control coating composition comprising (i) a siloxane-modified anionic polymer containing one or more metal cations, and (ii) an amine compound having at least one amine group bonded to a saturated carbon atom, having a boiling point of at least 85°C, and a molecular weight of at least 70.

2. The fouling control coating composition according to claim 1, which is a self-polishing fouling control coating composition.

3. The fouling control coating composition according to claim 1 or claim 2, wherein the siloxane-modified anionic polymer is a polymer made from one or more acrylate monomers.

4. The fouling control coating composition according to claim 3, comprising one or more anionic acrylate monomers.

5. The contamination control composition according to claim 3 or 4, comprising one or more acrylate monomers containing a polysiloxane substituent.

6. The contamination control composition according to claim 4, wherein the polysiloxane substituent is a polydimethylsiloxane substituent.

7. The contamination control composition according to any one of claims 1 to 6, wherein the siloxane-modified anionic polymer is a thermoplastic polymer.

8. below (i) The amine compound contains only one amine group, (ii) The amine compound contains at least one primary or secondary amine group, (iii) The amine compound comprises a diterpenoid skeleton substituted with one or more amine substituents, (iv) The contamination control composition according to any one of claims 1 to 7, wherein one or more of the following are applicable: the molecular weight of the amine compound is 500 or less or 350 or less.

9. below (i) The amine compound is R in the formula ｔ H, C １～６ - Alkyl and C １～６ Formula selected from haloalkyls - NHR ｔ It contains at least one primary or secondary amine group, (ii) the amine compound, wherein R ｖ is C １～６ alkyl and C １～６ haloalkyl, and the tertiary amine group of the formula -NR ｖ ２ is included, and one or more of the above are applied. The fouling control composition according to any one of claims 1 to 8.

10. The contamination control composition according to any one of claims 1 to 8, wherein the amine compound or at least one amine compound is selected from the following: 【Chemistry 1】

11. The contamination control composition according to claim 10, wherein the source of the amine compound is rosinamine.

12. The fouling control coating composition according to any one of claims 1 to 11, wherein the metal cation is selected from Mg, Ca, Zn, and Cu.

13. A method for controlling aquatic fouling on an artificial object, comprising the step of applying a fouling control coating composition according to any one of claims 1 to 12 to the surface of the artificial structure, wherein the artificial structure is a structure intended to be permanently or intermittently immersed in water.

14. A substrate or article coated before or after curing using the fouling control coating composition according to any one of claims 1 to 11.

15. Use of the coating composition according to any one of claims 1 to 11 for controlling aquatic fouling on artificial structures.

16. The use of an amine compound having at least one amine group bonded to a saturated carbon atom, a boiling point of at least 85°C, and a molecular weight of at least 70 in the fouling control coating composition according to any one of claims 1 to 12, wherein the amine compound is as follows: (i) To reduce the viscosity of the contamination control composition, (ii) To increase the flexibility of the contamination control composition, (iii) To improve the crack resistance of the contamination control composition, (iv) Use for one or more of the following: improving the long-term stability of the self-polishing rate of the fouling control composition.

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