Antifouling paint composition and coating film

Abstract

The present invention provides an antifouling paint composition comprising a curable silicone resin and a surfactant compound, which can form a coating film that exhibits good antifouling properties. [Solution] An antifouling coating composition is provided comprising a curable silicone resin (A), a surfactant compound (B1), and a surfactant compound (B2), wherein when the antifouling correlation hydrophilic-lipophilic balance of surfactant compound (B1) is ARHLB1 and the antifouling correlation hydrophilic-lipophilic balance of surfactant compound (B2) is ARHLB2, the antifouling coating composition satisfies formula [1]:ARHLB1-ARHLB2≧5 and formula [2]:ARHLB2≧2.

Description

Technical Field

[0001] The present invention relates to an antifouling paint composition. The present invention also relates to a coating film formed from the antifouling paint composition, a composite coating film having the coating film, and a ship and an underwater structure provided with the coating film or the composite coating film.

Background Art

[0002] In ships, organisms such as barnacles, mussels, and algae attach to the parts in contact with seawater, which hinders efficient operation and causes problems such as fuel waste. Conventionally, in order to prevent the attachment of organisms, an antifouling paint composition has been applied to the surface of the ship. For example, Japanese Patent Application Laid-Open No. 2023-503512 (Patent Document 1) discloses an adherent peeling coating composition containing a curable polysiloxane-based binder, an antifouling agent, and a nonionic hydrophilic modified polysiloxane.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present invention is to provide an antifouling paint composition containing a curable silicone resin and a surfactant compound, which can form a coating film exhibiting good antifouling properties. Another object of the present invention is to provide a coating film formed from the antifouling paint composition, a composite coating film having the coating film, and a ship and an underwater structure having the coating film or the composite coating film.

Means for Solving the Problems

[0005] The present invention provides the following antifouling paint composition, coating film, composite coating film, ship, and underwater structure. [1] An antifouling coating composition comprising a curable silicone resin (A), a surfactant compound (B1), and a surfactant compound (B2), When the antifouling correlation hydrophilic-lipophilic balance of the surfactant compound (B1) is denoted as ARHLB1 and the antifouling correlation hydrophilic-lipophilic balance of the surfactant compound (B2) is denoted as ARHLB2, the following formulas [1] and [2] are given: ARHLB1-ARHLB2≧5 [1] ARHLB2≧2 [2] A stain-resistant coating composition that satisfies the following conditions. [2] The antifouling paint composition according to [1], further comprising a curing agent (C) for curing the curable silicone resin (A). [3] The antifouling paint composition according to [1] or [2], further comprising an antifouling agent (D). [4] An antifouling coating composition according to any one of [1] to [3], further comprising a non-curing silicone compound (E). [5] An antifouling coating composition according to any one of [1] to [4], further comprising a viscous agent (F). [6] An antifouling coating composition according to any one of [1] to [5], further comprising a friction reducing agent (G). [7] An antifouling coating composition according to any one of [1] to [6], further comprising a salt or acid-base compound (H). [8] An antifouling coating composition according to any one of [2] to [7], further comprising a curing retarder. [9] The antifouling paint composition according to any one of [2] to [7], comprising a first liquid containing the curable silicone resin (A), the surfactant compound (B1), and the surfactant compound (B2), and a second liquid containing the curing agent (C).

[10] A coating film formed by any of the antifouling coating compositions described in [1] to [9].

[11] A composite coating film having a primer coating film formed by a rust-preventive coating composition and a coating film formed by any of the antifouling coating compositions described in [1] to [9] which is laminated on the primer coating film.

[12] A ship having the coating described in

[10] or the composite coating described in

[11] .

[13] An underwater structure having the coating described in

[10] or the composite coating described in

[11] . [Effects of the Invention]

[0006] An antifouling paint composition comprising a curable silicone resin and a surfactant compound can be provided, which can form a coating film that exhibits good antifouling properties. Furthermore, a coating film formed from the antifouling paint composition, a composite coating film having said coating film, and a ship and underwater structure having said coating film or composite coating film can be provided. [Modes for carrying out the invention]

[0007] <Antifouling paint composition> The antifouling coating composition according to the present invention (hereinafter also simply referred to as "coating composition") comprises a curable silicone resin (A), a surfactant compound (B1), and a surfactant compound (B2), wherein when the antifouling correlation hydrophilic-lipophilic balance of surfactant compound (B1) is ARHLB1 and the antifouling correlation hydrophilic-lipophilic balance of surfactant compound (B2) is ARHLB2, the following formulas [1] and [2]: ARHLB1-ARHLB2≧5 [1] ARHLB2≧2 [2] It satisfies the condition.

[0008] According to the antifouling coating composition of the present invention, in an antifouling coating composition using a curable silicone resin (A) as a binder, by containing two surfactant compounds satisfying formulas [1] and [2], namely surfactant compound (B1) and surfactant compound (B2), it is possible to form a coating film that exhibits good antifouling properties. According to the antifouling coating composition of the present invention, it is possible to form a coating film that exhibits good antifouling properties even when the content of the antifouling agent (D) is small, or even when the antifouling agent (D) is not contained.

[0009] Even when the content of antifouling agent (D) is small, or even when antifouling agent (D) is not present at all, the ability to improve antifouling properties by combining specific surfactant compounds that satisfy formulas [1] and [2] and incorporating this combination into a paint composition is an unexpected and unimaginable effect. Although the detailed mechanism is not yet clear, the reason for this unexpected effect is thought to be as follows.

[0010] Since the binder, a curable silicone resin (A), is low polarity, it is presumed that the surfactant compounds tend to concentrate near the interface between the coating film and water during the drying process and after submersion. However, if the coating film contains only one type of surfactant compound, if the surfactant compound is low polarity, the properties of the coating film interface will not change enough to be effective in improving the antifouling properties of the coating film. On the other hand, if the surfactant compound is highly polar, although it is likely to concentrate, it will also be more likely to dissolve into water after concentration, so it is presumed that it will not be possible to secure a concentration large enough to affect the antifouling properties of the coating film.

[0011] As will be explained later, in this invention, instead of using HLB (Hydrophile-Lipophile Balance), which is a value generally known to represent the degree of affinity of a surfactant compound to water and oil (organic compounds insoluble in water), we use an antifouling-related hydrophilic-lipophile balance (ARHLB), which is similar but appropriately defined to obtain a correlation with antifouling properties.

[0012] When there is only one type of surfactant compound contained in the coating film, by combining two surfactant compounds with moderately different ARHLBs, interactions occur between surfactant compounds with different properties (polar interactions in the coating film and hydrophobic interactions on the water surface). The elution of the surfactant compound with a higher ARHLB into water is suppressed by the surfactant compound with a lower ARHLB, and it is considered that a specific structure in which the surfactant compound with a higher ARHLB extends from the coating film surface into seawater is likely to be formed at a high concentration and is also likely to be retained. Thus, it is presumed that a surface that is difficult for marine organisms to adhere to is formed by the formation of a composite surfactant compound layer (a layer containing a combination of two surfactant compounds) that is hydrophobic and likely to be retained at a high concentration at the interface.

[0013] The reason for the above unexpected effect is probably based on the mechanism that hydrophobic biological probes or adhesion surfaces are enveloped by the composite surfactant compound and lose their activity, hydrophilic biological probes or adhesion surfaces cannot cause adhesion interactions with the coating film surface or within the coating film because the binder is hydrophobic, and electrostatic biological probes or adhesion surfaces cannot adhere due to the shielding of electrostatic interactions by the highly polar composite surfactant compound layer. In contrast, in the case of a coating composition containing only one type of surfactant compound, it is considered that the concentration of the surfactant compound in the surface layer cannot be sufficiently ensured due to the balance between the concentration of the surfactant compound in the surface layer of the coating film and the solubility of the surfactant compound, and the above effect is small and may not be substantially effective. Also, for example, even if there is an effect at the very initial stage of the immersion of the coating film, it is considered that the layer of the surfactant compound may be depleted immediately and may not be substantially effective. By combining two surfactant compounds with moderately different ARHLBs, it is presumed that a composite surfactant compound layer is unevenly distributed in the surface layer of the coating film with sufficient concentration and retention, and persistent and substantially effective antifouling properties are exhibited.

[0014] It is presumed that the antifouling coating composition of the present invention containing the curable silicone resin (A) and a combination of surfactant compounds with moderately different ARHLBs can exhibit the above unexpected effect for the above reasons. The components contained or that can be contained in the coating composition will be described in detail below.

[0015] [a] Curable silicone resin (A) The curable silicone resin (A) is a binder component. The curable silicone resin (A) is a silicone resin that cures at room temperature (for example, 1 to 30 °C) or slightly elevated temperature (for example, 30 to 40 °C) or by heating. The curable silicone resin (A) may be an organopolysiloxane having at least two curable reactive groups bonded to silicon atoms in one molecule, for example, an organopolysiloxane having curable reactive groups at both ends of the molecular chain. The coating composition can contain one or more kinds of the curable silicone resin (A).

[0016] Examples of the curable reactive groups that the organopolysiloxane can have include a hydroxyl group, an amino group, a primary amino group, a secondary amino group, a tertiary amino group, a carbinol group, a hydrazide group, an epoxy group, an isocyanate group, a carboxyl group, a (meth)acryloyl group, a thiol group, an aldehyde group, a silane group, a vinyl group, an allyl group, an alkenyl group, and a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group having 1 to 8 carbon atoms such as a methoxy group, an ethoxy group, and a propoxy group; an alkoxyalkoxy group such as a methoxyethoxy group, an ethoxyethoxy group, and a methoxypropoxy group; an acyloxy group such as an acetoxy group, an octanoyloxy group, and a benzoyloxy group; an alkenyloxy group such as a vinyloxy group, an isopropenyloxy group, and a 1-ethyl-2-methylvinyloxy group; a ketoxime group such as a dimethylketoxime group, a methylethylketoxime group, and a diethylketoxime group; an aminoxy group such as a dimethylaminoxy group and a diethylaminoxy group; an amide group such as an N-methylacetamide group, an N-ethylacetamide group, and an N-methylbenzamide group. The curable reactive group is preferably a hydroxyl group, a carbinol group, an epoxy group, an isocyanate group, or a hydrolyzable group, and more preferably a hydroxyl group or a hydrolyzable group. The hydrolyzable group is preferably an alkoxy group.

[0017] Groups other than the curing-reactive group that organopolysiloxanes may have include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and octadecyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; aryl groups such as phenyl, tolyl, xylyl, and α-,β-naphthyl groups; aralkyl groups such as benzyl, 2-phenylethyl, and 3-phenylpropyl groups; substituted ester groups having substituents selected from the group consisting of alkyl, cycloalkyl, aryl, and aralkyl groups; and groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms, cyano groups, etc. The groups other than the curing-reactive group are preferably methyl, ethyl, and phenyl groups, and more preferably methyl groups.

[0018] The organopolysiloxane is preferably a diorganopolysiloxane such as dimethylpolysiloxane having hydroxyl groups or the above-mentioned hydrolyzable groups at both ends of the molecular chain, and more preferably a dimethylpolysiloxane having hydroxyl groups or alkoxy groups having 1 to 8 carbon atoms at both ends of the molecular chain.

[0019] The curable silicone resin (A) preferably has a viscosity at 23°C of 20 to 1,000,000 mPa·s, more preferably 100 to 500,000 mPa·s, and even more preferably 1,000 to 50,000 mPa·s. The viscosity can be measured by a rotational viscometer. In this specification, when a mixture of two or more curable silicone resins (A) is used, the viscosity refers to the viscosity of the mixture.

[0020] [b] Surface active compound (B) The paint composition comprises a curable silicone resin (A) as a binder, and two surfactant compounds (B1) and (B2). Both surfactant compounds (B1) and (B2) are nonionic surfactant compounds. Surfactant compounds (B1) and (B2) are different surfactant compounds. When the antifouling correlation hydrophilicity-lipophilicity balance of surfactant compound (B1) is ARHLB1 and the antifouling correlation hydrophilicity-lipophilicity balance of surfactant compound (B2) is ARHLB2, surfactant compounds (B1) and (B2) satisfy formulas [1] and [2]. ARHLB1-ARHLB2≧5 [1] ARHLB2≧2 [2]

[0021] When a paint composition contains two types of surfactant compounds, according to formula [1], the surfactant compound having a greater antifouling correlation hydrophilic-lipophilic balance ARHLB is defined as surfactant compound (B1). That is, ARHLB1 is greater than ARHLB2.

[0022] As previously described, by including a curable silicone resin (A) and a combination of surfactant compounds with appropriately different ARHLB values ​​in the paint composition, the antifouling paint composition can exhibit the above-mentioned unexpected effects and form a coating film that exhibits good antifouling properties. Here, "appropriately different ARHLB values" means that the difference between ARHLB1 and ARHLB2 is 5 or more, as shown in formula [1]. From the viewpoint of improving the antifouling properties of the coating film, the difference is preferably 5.5 or more, more preferably 6.0 or more, and may be 6.5 or more, 7.0 or more, 7.5 or more, 8.0 or more, 8.5 or more, or 9.0 or more. The difference is usually 15 or less, and may be 14 or less, 12 or less, or 11 or less.

[0023] From the viewpoint of improving the antifouling properties of the coating film, ARHLB1 of the surfactant compound (B1) is preferably 7 or more and less than 20, more preferably 8 to 19, and even more preferably 9 to 18. ARHLB2 of the surfactant compound (B2) is 2 or more, as shown in formula [2]. If ARHLB2 is less than 2, the significance of using a combination of the two surfactant compounds diminishes, and the effect of improving the antifouling properties of the coating film becomes insufficient. From the viewpoint of improving the antifouling properties of the coating film, ARHLB2 is preferably 2 to 14, more preferably 2.2 to 12, and even more preferably 2.3 to 11.

[0024] In the present invention, the ARHLB of the surfactant compound is calculated according to the following formula (I). ARHLB = 20 × (sum of formula weights of hydrophilic parts) / (molecular weight of surfactant) (I)

[0025] The proportionality constant in equation (I) is the same value as in the equation based on Griffin's model, which is generally known as a value representing the degree of affinity of a surfactant compound to water and oil (Reference: Griffin, WC Calculation of HLB values ​​of non-ionic surfactants, J. Soc. Cosmet. Chem. 1954, 5, 249-256). However, in ARHLB, the definitions other than the proportionality constant are similar to those in HLB, but are appropriately defined to obtain a correlation with antifouling properties. This is because, in the inventors' studies, it became clear that the correlation between the antifouling properties of a coating film formed from a coating composition containing a curable silicone resin (A) as a binder and a surfactant compound (B), and the HLB presented by the manufacturer or supplier of the surfactant compound (B), or the HLB of the surfactant compound (B) according to Griffin's model, was not always good, and that the above correlation could be sufficiently improved by appropriately defining the hydrophilic portion and handling the non-hydrophilic portion. It has been pointed out that Griffin's definition of HLB is ambiguous (Reference: Ricardo C. Pasquali, Melina P. Taurozzi, Carlos Bregni, Some considerations about the hydrophilic-lipophilic balance system, Int. J. Pharm. 2008, 356, 44-51), and the formula for calculating HLB presented by the manufacturer or supplier of the surfactant compound (B) is often not disclosed. ARHLB is an index related to surfactant compounds that specifically concerns the antifouling properties of coating films formed from paint compositions containing a curable silicone resin (A) and a surfactant compound (B).

[0026] In calculating ARHLB, the hydrophilic area is defined as follows: 1) Hydroxyl group (-OH) and -O-(CH2) n We consider the structural part of -O-[n is an integer less than or equal to 2] as the hydrophilic part. 2) -O-(CR1R2) present in the cyclic structure of surfactant compounds m -(CR3R4) nThe -O- structural part [m and n are each independent integers from 0 to 2, and m+n is 1 or 2] is considered hydrophilic including the H (hydrogen atom) or O (oxygen atom) contained in R1 to R4 if at least one of R1 to R4 is H (hydrogen atom) or OR5 [R5 is a group other than a hydrogen atom], otherwise it is considered hydrophilic excluding R1 to R4.

[0027] Examples of structural parts considered hydrophilic in ARHLB are shown below. For example, the hydrophilic portion of triethylene glycol monododecyl ether is as follows: [ka]

[0028] The hydrophilic portion of sorbitan monopalmitate is as follows: [ka]

[0029] The hydrophilic portion of DBE-712 (manufactured by Gelest, Inc., dimethylsiloxane-(60-70% ethylene oxide) block copolymer) is as follows: [ka]

[0030] Regarding 1) and 2) above, the difference from HLB based on Griffin's model is that the hydroxyl group is considered the hydrophilic part, -O-(CR1R2) m -(CR3R4) n The structural part of a compound having an -O- structure that is considered hydrophilic is specifically defined. Our research has shown that by defining the hydrophilic part as described in 1) and 2) above, the correlation can be significantly improved compared to evaluation using general HLB. Furthermore, in 2) above, -O-(CR1R2) m -(CR3R4) nThe -O- structural portion is considered a hydrophobic portion if it is in a linear structure rather than a cyclic structure and does not fall under category 1) above. This is because, when the above structural portion is in a cyclic structure, the range of movement of atoms in and near the cyclic structure is restricted, making the lone pair of electrons of oxygen atoms in the cyclic structure less susceptible to steric hindrance and more likely to undergo hydrophilic interactions. On the other hand, when the above structural portion is in a linear structure, it is less likely to undergo the above hydrophilic interactions.

[0031] In calculating ARHLB, structural parts and elements other than those described in 1) and 2) above are considered hydrophobic (not hydrophilic). Therefore, for example, the siloxane structural part is considered hydrophobic. On the other hand, in the case of a Si-OH structural part as described in 1) above, the -OH part is considered hydrophilic.

[0032] For surfactant compounds with a molecular weight distribution, or surfactant compounds with repeating units and a distribution in the number of repeating units, the ARHLB is determined using the average value of the molecular weight or the number of repeating units. For example, for repeating units such as EO (ethylene oxide), the average value of the number of repeating units is used. Note that if commercially available surfactant compounds (B1) and (B2) have different average values ​​for the number of repeating units, these average values ​​are not averaged.

[0033] The surfactant compounds (B1) and (B2) are not particularly limited as long as they are nonionic surfactant compounds and a combination of surfactant compounds that satisfy formulas [1] and [2], but examples include non-silicone surfactant compounds and silicone surfactant compounds, respectively. When surfactant compound (B1) is a non-silicone surfactant compound, surfactant compound (B1) usually has a polyoxyalkylene group with 3 or more repeating units containing alkylene groups with 3 or more carbon atoms, and / or a hydrocarbon group with 10 or more carbon atoms. The same applies to surfactant compound (B2). Surfactant compounds (B1) and (B2) usually do not have curing reactive groups. A hydrocarbon group with 10 or more carbon atoms includes the case where the non-silicone surfactant compound has 2 or more hydrocarbon groups and the total number of carbon atoms of these 2 or more hydrocarbon groups is 10 or more. Examples of non-silicone surfactant compounds include polyoxyethylene alkyl ethers having 10 or more C10 alkyl groups, polyoxyethylene alkylphenol ethers having 4 or more C10 alkyl groups, polyoxyethylene distyleninated phenyl ethers, alkyl glucosides having 10 or more C10 alkyl groups, polyoxyethylene fatty acid esters having 10 or more C10 alkyl groups, sucrose fatty acid esters having 10 or more C10 alkyl groups, sorbitan fatty acid esters having 10 or more C10 alkyl groups, polyoxyethylene sorbitan fatty acid esters having 10 or more C10 alkyl groups, fatty acid alkanolamides having 10 or more C10 alkyl groups, polyoxyethylene polyoxypropylene glycols with 3 or more repeating polyoxypropylene groups, polyoxyethylene polyoxypropylene alkyl ethers having 10 or more C10 alkyl groups and / or polyoxypropylene groups with 3 or more repeating polyoxybutylene groups and / or polyoxybutylene polyoxypropylene glyceryl ethers with 3 or more repeating polyoxybutylene groups.

[0034] Examples of silicone-based surfactants include polysiloxane-based surfactants having a structure in which polysiloxane is introduced to the terminal and / or side chain and / or main chain of the above-mentioned non-silicone-based surfactant; polysiloxane-based surfactants having a structure in which one or more repeating ethylene oxide chains are introduced to the terminal and / or side chain and / or main chain of polysiloxane; polysiloxane-based surfactants having a structure in which one or more glycerol residues and / or sorbitol residues and / or anhydrosorbitol residues are introduced to the terminal and / or side chain and / or main chain of polysiloxane; and silicone-based surfactants having a structure in which an alkylene oxide having three or more C1 alkylene groups is further introduced to the terminal and / or side chain and / or main chain of the above-mentioned polysiloxane-based surfactant.

[0035] Furthermore, silicone-based components that do not fall under either surfactant compound (B1) or surfactant compound (B2) but have a curing reactive group are included in curable silicone resin (A) insofar as they satisfy the definition of curable silicone resin (A) described above.

[0036] The paint composition may contain three or more nonionic surfactant compounds with different ARHLB values. In this case, the nonionic surfactant compound with the highest ARHLB value is defined as surfactant compound (B1), and the nonionic surfactant compound with the lowest ARHLB value is defined as surfactant compound (B2).

[0037] The content of nonionic surfactant compounds in the paint composition (when the nonionic surfactant compounds consist of two types, surfactant compound (B1) and surfactant compound (B2), or when they consist of three or more types of nonionic surfactant compounds, the total amount thereof) is preferably 0.5 to 40 parts by mass, more preferably 1 to 30 parts by mass, even more preferably 3 to 25 parts by mass, and particularly preferably 4 to 22 parts by mass per 100 parts by mass of curable silicone resin (A), from the viewpoint of improving the stain resistance of the coating film. The content of surfactant compound (B1) and surfactant compound (B2) in the paint composition is preferably 0.3 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, even more preferably 1 to 13 parts by mass, and particularly preferably 2 to 11 parts by mass, respectively, per 100 parts by mass of curable silicone resin (A).

[0038] From the viewpoint of improving the antifouling properties of the coating film, the ratio of surfactant compound (B1) to surfactant compound (B2) in the coating composition is preferably 1 / 9 to 9 / 1 by mass, more preferably 3 / 17 to 17 / 3, and even more preferably 1 / 4 to 4 / 1 (for example, 5 / 5).

[0039] [c] Hardener (C) The paint composition may contain a curing agent (C) for curing a curable silicone resin (A). Here, "curing" means initiating curing or accelerating curing. The paint composition may contain one or more curing agents (C).

[0040] For example, the hardening agent (C) is: Organic titanium compounds such as tetrabutyl titanate, tetra-2-ethylhexyl titanate, tetraoctyl titanate, triethanolamine titanate, tetra(isopropenyloxy) titanate, organosiloxy titanium, diisopropoxy titanium bis(ethylacetoacetate), titanium tetra(acetylacetonate), titanium tris(dodecylbenzenesulfonic acid) isopropoxide, titanium octylene glycolate, titanium lactate, and butyl titanate dimer; Organic germanium compounds such as germanium tetraethoxide, germanium tetraisopropoxide, germanium n-butoxide, germanium acetate, and bis(2-carboxyethylgermanium sesquioxide); Organoaluminum compounds such as aluminum secondary butoxides, aluminum trisacetylacetonate, aluminum monoacetylacetonate bis(ethylacetoacetate), and ethylacetoacetate aluminum diisopropylate; Organic silane compounds such as tetraalkoxysilanes (ethyl silicate, etc.), vinyltris(methylethylketoxime)silane, tetramethylguanidylpropyltrimethoxysilane, tetramethylguanidylpropylmethyldimethoxysilane, and tetramethylguanidylpropyltris(trimethylsiloxy)silane; Organotin compounds such as tin naphthenate, tin caprylate, tin oleate, dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin dioleate, diphenyltin diacetate, dibutyltin oxide, dibutyltin dimethoxide, dibutylbis(triethoxysiloxy)tin, and dibutyltin benzylmalate; Examples of organozirconium compounds include n-propyl zirconate, n-butyl zirconate, zirconium monoacetylacetonate, zirconium tetraacetylacetonate, zirconium ethyl acetate, bis(2-ethylhexanoic acid) zirconium oxide, and zirconium lactate ammonium salt. Among these, organometallic compounds having one or more alkoxides as ligands are among the preferred curing agents.

[0041] When the paint composition contains a curing agent (C), the content of the curing agent (C) in the paint composition is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and even more preferably 0.3 to 15 parts by mass, per 100 parts by mass of the curable silicone resin (A), from the viewpoint of achieving both curability and paintability of the paint composition.

[0042] [d] Antifouling agent (D) The paint composition may contain an antifouling agent (D). Since the coating film formed from the paint composition of the present invention can exhibit good antifouling properties even without containing an antifouling agent (D), it is not necessarily required to contain an antifouling agent (D). However, to further enhance antifouling properties or to improve the long-term durability of antifouling properties, an antifouling agent (D) may be included in the paint composition as needed. Known antifouling agents can be used, such as inorganic compounds, organic compounds containing metals, and organic compounds that do not contain metals. The paint composition may contain one or more antifouling agents (D).

[0043] Examples of antifouling agents (D) include zinc oxide; cuprous oxide; manganese ethylene bisdithiocarbamate; zinc dimethyl dithiocarbamate; 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine; 2,4,5,6-tetrachloroisophthalonitrile; zinc ethylene bisdithiocarbamate; rhodane copper (cuprous thiocyanate); 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (4,5,-dichloro-2- n-Octyl-3(2H)isothiazolone; N-(fluorodichloromethylthio)phthalimide; N,N'-dimethyl-N'-phenyl-(N'-fluorodichloromethylthio)sulfamide; pyrithione metal salts such as 2-pyridinethiol-1-oxide zinc salt (zinc pyrithione) or copper salt (copper pyrithione); tetramethylthiuram disulfide; 2,4,6-trichlorophenylmaleimide; 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridin n; 3-iodo-2-propynylbutylcarbamate; diiodomethylparatolylsulfone; phenyl(bispyridyl)bismuth dichloride; 2-(4-thiazolyl)-benzimidazole; triphenylborone pyridine salt; stearylamine-triphenylborone; laurylamine-triphenylborone; bisdimethyldithiocarbamoylzinc ethylenebisdithiocarbamate; 1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N- Examples include phenylmethanesulfenamide; 1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-(4-methylphenyl)methanesulfenamide; N-(3,4-dichlorophenyl)-N',N'-dimethylurea; 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile; and 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (generic name: medetomidine).

[0044] In particular, the antifouling agent (D) is preferably at least one selected from the group consisting of cuprous oxide, pyrithione metal salt, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, N-(3,4-dichlorophenyl)-N',N'-dimethylurea, bisdimethyldithiocarbamoylzinc ethylenebisdithiocarbamate, and medetomidine.

[0045] If the paint composition contains an antifouling agent (D), the content of the antifouling agent (D) in the paint composition is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass, but may be 0.5 parts by mass or more, 1 part by mass or more, or 5 parts by mass or more, per 100 parts by mass of the curable silicone resin (A). The content of the antifouling agent (D) in the paint composition is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, even more preferably 60 parts by mass or less, but may be 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, 10 parts by mass or less, or 5 parts by mass or less, per 100 parts by mass of the curable silicone resin (A). When the content of the antifouling agent (D) is within the above range, the antifouling properties can be further enhanced without adversely affecting the various properties of the resulting coating film, or the long-term durability of the antifouling properties can be further enhanced.

[0046] [e] Non-curing silicone compound (E) The paint composition may contain a non-curing silicone compound (E). Further inclusion of a non-curing silicone compound (E) in the paint composition can further improve the stain resistance of the coating film. The paint composition may contain one or more non-curing silicone compounds (E).

[0047] Examples of non-curable silicone compounds (E) include silicone compounds that do not have any of the hydroxyl groups, ethylene oxide groups, glycerol residues, sorbitan residues, anhydrosorbitol residues, or the hydrolyzable groups mentioned above. More specifically, examples of silicone oils that do not have any of the hydroxyl groups, ethylene oxide groups, glycerol residues, sorbitan residues, anhydrosorbitol residues, or the hydrolyzable groups mentioned above include dimethyl silicone oil, methylphenyl silicone oil, alkyl-modified silicone oil, aralkyl-modified silicone oil, fluoroalkyl-modified silicone oil, fatty acid-modified silicone oil, fatty acid amide-modified silicone oil, and polyether epoxy-modified silicone oil (the polyether portion has 3 or more carbon atoms).

[0048] When the paint composition contains a non-curable silicone compound (E), the content of the non-curable silicone compound (E) in the paint composition is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, even more preferably 1 to 15 parts by mass, and particularly preferably 2 to 10 parts by mass, per 100 parts by mass of the curable silicone resin (A), from the viewpoint of improving the physical properties of the coating film.

[0049] [f] Viscosity agent (F) The paint composition may contain a viscous agent (F). The viscous agent (F) can be used as a viscosity modifier, anti-sagging agent, anti-settlement agent, etc., in the paint composition. By including a viscous agent (F) in the paint composition, the storage stability and / or paintability of the paint composition can be improved. The paint composition may contain one or more types of viscous agents (F).

[0050] Examples of viscous agents (F) include amide-based viscous agents, urethane-based viscous agents, cellulose-based viscous agents, bentonite-based viscous agents, polyethylene waxes such as oxidized polyethylene wax, hydrogenated castor oil wax, long-chain fatty acid ester polymers, polycarboxylic acids, and silica fine particle-based viscous agents. Examples of amide-based viscous agents include fatty acid amide waxes and polyamide waxes. Examples of fatty acid amide waxes include stearic acid amide wax and oleic acid amide wax.

[0051] If the paint composition contains a viscous agent (F), the content of the viscous agent (F) in the paint composition is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, even more preferably 0.5 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass, per 100 parts by mass of the curable silicone resin (A), from the viewpoint of improving the storage stability and / or paintability of the paint composition.

[0052] [g] Friction reducing agent (G) The paint composition may contain a friction reducing agent (G). Further inclusion of a friction reducing agent (G) in the paint composition can improve the low-friction performance of the coating film. When the low-friction performance of the coating film is good, for example, when the coating film is formed on the surface of a ship, the frictional resistance with water can be reduced by the coating film while the ship is underway. This can lead to reduced fuel consumption and energy savings for the ship's operation. The paint composition may contain one or more types of friction reducing agents (G).

[0053] Examples of friction reducing agents (G) include polymer particles described in Japanese Patent Publication No. 2006-328244, Japanese Patent Publication No. 2007-169628, and International Publication No. 2010 / 038692. The polymer constituting the particles may be a natural polymer or a synthetic polymer. The friction reducing agent (G) may also be a whisker described in Japanese Patent Publication No. 2018-035227, for example. The whisker may be tetrapod-shaped or needle-shaped.

[0054] When the paint composition contains a friction reducing agent (G), the amount of friction reducing agent (G) in the paint composition is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, even more preferably 1 to 15 parts by mass, and particularly preferably 1.5 to 10 parts by mass, per 100 parts by mass of curable silicone resin (A), from the viewpoint of improving the low friction performance of the coating film. When whiskers are used as the friction reducing agent (G), the amount may be 20 to 200 parts by mass per 100 parts by mass of curable silicone resin (A).

[0055] [h] Salt or acid-base compound (H) The paint composition may contain a salt or acid-base compound (H). Further inclusion of a salt or acid-base compound (H) in the paint composition may improve the curability and / or storage stability of the paint composition. Alternatively, the salt or acid-base compound (H) may also act as a curing retarder, as described later. The paint composition may contain one or more salts or acid-base compounds (H). In this specification, an acid-base compound means a compound having one or both of an acidic group and a basic group. A salt means a neutralized product of an acid and a base.

[0056] The salt or acid-base compound (H) may be one or more compounds selected from the group consisting of inorganic salts, inorganic acids, inorganic bases, organic salts, organic acids, and organic bases. Examples of inorganic salts include sodium chloride, calcium chloride, magnesium sulfate, and zeolite compounds. Examples of inorganic acids include hydrochloric acid, boric acid, phosphoric acid, and thiosulfate. Examples of inorganic bases include ammonium hydroxide, sodium hydroxide, calcium hydroxide, and barium hydroxide. Examples of organic salts include salt compounds having an organic cationic group and / or an organic anionic group. Examples of organic acids include acetic acid, oleic acid, succinic acid, toluenesulfonic acid, and triphenylborane. Examples of organic bases include ethanolamine, diethanolamine, triethanolamine, triethylenetetramine, quinoline, triphenylphosphine, 2,2'-bipyridine, and 1,4-diazabicyclo[2.2.2]octane.

[0057] Examples of salt compounds having an organic cationic group include quaternary ammonium salts such as alkylbenzyldimethylammonium bromide, benzyltrimethylammonium bromide, benzalkonium chloride, and hexadecyltrimethylammonium bromide; sulfonium salts such as trimethylsulfonium chloride; and phosphonium salts such as methyltriphenylphosphonium bromide. The number of carbon atoms in the quaternary ammonium group is preferably 8 or more. Examples of salt compounds having an organic anionic group include sulfonate salts, phenate salts, salicylate salts, carboxylate salts, naphthenate salts, and phosphonate salts.

[0058] When the paint composition contains a salt or acid-base compound (H), the content of the salt or acid-base compound (H) in the paint composition is preferably 0.001 to 20 parts by mass, more preferably 0.01 to 15 parts by mass, even more preferably 0.05 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass, per 100 parts by mass of the curable silicone resin (A), from the viewpoint of improving the curability and / or storage stability of the paint composition.

[0059] [i] Other components that the paint composition may contain The paint composition may contain one or more other components besides those mentioned above. Examples include additives such as defoamers, plasticizers, color separation inhibitors, coating wear regulators, UV absorbers, leveling agents, pigment dispersants, and curing retarders, as well as pigments and organic solvents. These additives, pigments, and organic solvents may be used individually or in combination of two or more.

[0060] Examples of pigments include extender pigments such as precipitated barium, talc, kaolin, clay, gypsum, chalk, feldspar, silica white, alumina white, colloidal silica, bentonite, calcium carbonate, magnesium carbonate, silicic acid, silicates, aluminum oxide hydrate, calcium sulfate, wollastonite, and diatomaceous earth; and coloring pigments such as titanium dioxide, zircon oxide, basic lead sulfate, tin oxide, carbon black, white lead, graphite, zinc sulfide, zinc oxide, chromium oxide, yellow nickel titanium, yellow chromium titanium, yellow iron oxide, red iron oxide (red iron oxide), black iron oxide, azo-based red and yellow pigments, chromium yellow, phthalocyanine green, phthalocyanine blue, ultramarine blue, and quinacridone.

[0061] Examples of plasticizers include phthalate esters such as dioctyl phthalate (DOP), dimethyl phthalate, dicyclohexyl phthalate, and diisodecyl phthalate (DIDP); aliphatic dibasic acid esters such as diisobutyl adipate and dibutyl sebacate; glycol esters such as diethylene glycol dibenzoate and pentaerythritol alkyl ester; phosphate esters such as tricresyl phosphate, triaryl phosphate, and trichloroethyl phosphate; epoxy compounds such as epoxy soybean oil and epoxy octyl stearate; polyvinyl compounds such as polyvinyl acetate, polyvinyl chloride, and polyethyl vinyl ether; and trioctyl trimellitic acid and triacetylene.

[0062] Examples of organic solvents include hydrocarbons such as toluene, xylene, benzene, ethylbenzene, isopropylbenzene, trimethylbenzene, naphthalene, cyclopentane, octane, heptane, nonane, cyclohexane, petroleum naphtha, aromatic naphtha, and white spirits; Ethers such as dioxane, tetrahydrofuran, diethyl ether, dipropyl ether, butyl ethyl ether, dibutyl ether, ethylene glycol dibutyl ether, diethylene glycol dibutyl ether, and propylene glycol dibutyl ether; Esters having hydrocarbon groups with 9 or fewer carbon atoms, such as butyl acetate, propyl acetate, ethyl acetate, benzyl acetate, dimethyl succinate, dimethyl glutarate, and dimethyl adipate; Ether esters having hydrocarbon groups with 9 or fewer carbon atoms, such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, ethyl-3-ethoxypropionate, and 3-methoxy-3-methyl-1-butyl acetate; Ketones such as acetone, methyl ethyl ketone, ethyl isobutyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-methoxy-1-phenylethanone; Alcohols having hydrocarbon groups with 9 or fewer carbon atoms, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-octanol, 2-ethylhexanol, benzyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and 3-methoxy-3-methyl-1-butanol; Amides such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-ethyl-2-pyrrolidone, and N-methylcaprolactam; Halogenated hydrocarbons such as chloroform, dichloroethane, trichloroethane, and tetrachloroethylene; Examples include sulfoxides such as dimethyl sulfoxide, diethyl sulfoxide, and dipropyl sulfoxide.

[0063] The paint composition preferably contains a first organic solvent that is compatible with (a good solvent for) the curable silicone resin (A), and a second organic solvent that is compatible with (a good solvent for) the surfactant compound. Examples of the first organic solvent include the hydrocarbons, esters, ketones, halogenated hydrocarbons, etc. Examples of the second organic solvent include the ethers, ether esters, alcohols, amides, sulfoxides, etc.

[0064] The solubility parameter (SP) value of the first organic solvent is preferably 10 or less, more preferably 7 to 9.5, from the viewpoint of affinity to the curable silicone resin (A). The solubility parameter (SP) value of the second organic solvent is preferably 8 to 15, more preferably 8.5 to 12, from the viewpoint of affinity to the surfactant compound. The SP values ​​of the organic solvents can be adopted from literature such as Burke, J. Solubility Parameters: Theory and Application, The Book and Paper Group Annual, Vol. 3, 1984.

[0065] The content of organic solvents in the paint composition is, for example, 5 to 80% by mass, preferably 7 to 75% by mass, more preferably 10 to 70% by mass, and even more preferably 15 to 60% by mass. That is, the content of solids in the paint composition may be 20 to 95% by mass, 25 to 93% by mass, 30 to 90% by mass, or 40 to 85% by mass. Solids refer to the total amount of components other than solvents contained in the paint composition.

[0066] [j] Form of paint composition The paint composition may be a one-component antifouling paint composition comprising a curable silicone resin (A), a surfactant compound (B1), a surfactant compound (B2), and other components as needed. Alternatively, the paint composition may be a two-component antifouling paint composition comprising, for example, a first liquid comprising a curable silicone resin (A), a surfactant compound (B1), and a surfactant compound (B2), and a second liquid comprising a curing agent (C). The first and second liquids may each contain an organic solvent.

[0067] If the paint composition is a one-component antifouling paint composition, the paint composition may further contain one or more curing retarders from the viewpoint of improving the pot life or storage stability of the paint composition. Even if the paint composition is a two-component antifouling paint composition, the paint composition may further contain one or more curing retarders. In this case, the curing retarder may be contained in the first component, in the second component, or in both.

[0068] Examples of curing retarders include β-ketoesters such as methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, isopropyl acetoacetate, butyl acetoacetate, isobutyl acetoacetate, tert-butyl acetoacetate, octyl acetoacetate, 2-ethylhexyl acetoacetate, oleyl acetoacetate, lauryl acetoacetate, and stearyl acetoacetate; and β-diketones such as acetylacetone, 2,4-hexanedione, and benzoylacetone. Hydroxyketones having a hydrocarbon group with 9 or fewer carbon atoms, such as hydroxyacetone, 2-hydroxy-3-pentanone, diacetone alcohol, and 1-(2-furanyl)-2-hydroxyethanone; Hydroxycarboxylic acids such as 3-hydroxypropionic acid, 3-hydroxybutyric acid, hydroxyethylethylenediaminetriacetic acid, hydroxyethyliminodiacetic acid, dihydroxyethylglycine, 1,3,-diamino-2-hydroxypropanetetraacetic acid, and gluconic acid, or their neutralized salts; Carboxylic acids such as butyric acid, caproic acid, 2-ethylhexanoic acid, octanoic acid, lauric acid, malonic acid, methylmalonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, and citric acid, or their neutralized salts; Phosphonic acids such as hydroxyethylidene diphosphonic acid, aminotrismethylenephosphonic acid, phosphonobutanetricarboxylic acid, and ethylenediaminetetramethylenephosphonic acid, or their neutralized salts; aminocarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid, 1,3-propanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, L-glutamic acid diacetic acid, ethylenediamine disuccinic acid, and cyclohexanediaminetetraacetic acid, and their neutralized salts These are some examples.

[0069] If the paint composition contains a curing retarder, the content of the curing retarder in the paint composition is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, even more preferably 0.1 to 4 parts by mass, and particularly preferably 0.2 to 3 parts by mass, per 100 parts by mass of the curable silicone resin (A).

[0070] If the paint composition is a two-component antifouling paint composition, other components that are added as needed may be contained in the first component, the second component, or both. For example, an antifouling agent (D), a non-curing silicone compound (E), a viscosity agent (F), a friction reducer (G), a salt compound (H), and a pigment may be contained in the first component.

[0071] In preparing the paint composition, mixing of the first and second liquids, as well as mixing of the first and second liquids, can be performed using a disperser, SG mill, ball mill, roll mill, colloid mill, mortar mixer, paint shaker, homogenizer, planetary mixer, ultrasonic disperser, etc.

[0072] <Coating films and composite coating films> The coating film according to the present invention (hereinafter also simply referred to as "coating film") is a coating film formed from the antifouling paint composition according to the present invention. The coating film is an antifouling coating film having antifouling properties. Because the coating film is formed from the antifouling paint composition according to the present invention, it can exhibit excellent antifouling properties.

[0073] The coating film can be formed by applying the above-mentioned coating composition to the surface of the object to be coated according to a conventional method, and then drying and curing the applied coating composition. Examples of conventional methods for applying the coating composition include airbrush coating, air spray coating, airless spray coating, brush coating, flow coating, roller coating, dipping coating, curtain coating, electrostatic coating, and electrodeposition coating. The drying and curing of the applied coating composition can be carried out at a temperature of, for example, 1 to 40°C, preferably 5 to 35°C. If necessary, drying and curing may be carried out while heating. The thickness of the coating film after drying and curing is, for example, 30 μm to 600 μm, preferably 40 μm to 400 μm.

[0074] Examples of objects to be coated include underwater moving bodies such as ships and underwater structures. Examples of underwater structures include various fishing nets and other fishing gear such as aquaculture nets; port facilities; oil fences; water intake facilities for power plants, etc.; piping such as cooling water conduits; bridges; buoys; industrial water systems; and underwater bases.

[0075] The painted surface of the object to be painted may be pre-treated as necessary, and a composite coating may be formed by forming a coating film made of the coating composition of the present invention on a primer coating film formed of other coating compositions such as rust-preventive coating compositions (corrosion-preventive coating compositions) or adhesion coating compositions formed on the object to be painted.

[0076] The paint composition of the present invention exhibits excellent antifouling performance, making it possible to eliminate or reduce the amount of separately formulated antifouling agents. Therefore, the paint composition of the present invention makes it possible to form an antifouling coating film that transmits electromagnetic waves such as visible light. When forming an antifouling coating film that transmits electromagnetic waves such as visible light, it can be suitably applied to electromagnetic wave-transmitting substrates such as windows in or near the water surface. [Examples]

[0077] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited thereto.

[0078] <Examples 1-1 to 1-35, 2-1 to 2-4, 3-1 to 3-15, and Comparative Examples 1-0 to 1-8, 2-0 to 2-4, 3-0 to 3-14> 1. Preparation of ingredients (1) Surface active compound Tables 1 to 3 show the formulations of the prepared surfactant compounds, S-1 to S-19 and S-C1 to SC12. The amounts in the tables are parts by mass per 100 parts by mass of curable silicone resin (A). "ΔARHLB" in the tables represents the difference between ARHLB1 and ARHLB2.

[0079] [Table 1]

[0080] [Table 2]

[0081] [Table 3]

[0082] Details of surfactant compounds 1-22 are shown in Table 4. The ARHLB values ​​calculated according to the above definition are also shown in Table 4. Surfactant compounds 1-22 have an active ingredient content of 100% by mass.

[0083] [Table 4]

[0084] (2) Pigments and antifouling agents The prepared pigment and antifouling agent formulations P-1 to P-15 are shown in Tables 5 and 6. Formulation P-8 further includes a salt or acid-base compound in addition to the pigment and antifouling agent. The amounts in the table are parts by mass per 100 parts by mass of curable silicone resin (A).

[0085] [Table 5]

[0086] [Table 6]

[0087] Details of pigments 1-11, salts or acid-base compounds, and antifouling agents 1-8 are shown in Table 7. The active ingredient content of antifouling agent 4 is 30% by mass, while pigments 1-11, salts or acid-base compounds 1, and antifouling agents 1-3 and 5-8 contain 100% by mass of active ingredients.

[0088] [Table 7]

[0089] (3) Other main ingredients Tables 8 to 10 show the formulations M-1 to M-22 of the other main components that were prepared. Of the formulations M-1 to M-22, M-12 and M-13 were used to prepare a one-component antifouling paint composition. The other formulations were used to prepare a two-component antifouling paint composition. The amounts in the tables are parts by mass per 100 parts by mass of curable silicone resin (A).

[0090] [Table 8]

[0091] [Table 9]

[0092] [Table 10]

[0093] Table 11 details the curable silicone resins 1-5, viscous agents, organic solvents 1-6, curing retarders, curing agents 1-3, non-curable silicone compounds 1-3, friction reducers 1-4, and salts or acid-base compounds 2-3. The active ingredient content of each compound is also shown in the same table.

[0094] [Table 11]

[0095] (4) Curing agent composition Table 12 shows the formulations H-1 to H-6 for the prepared curing agent compositions (the second component of the two-component antifouling paint composition). Note that formulations H-1 to H-6 were not used in Examples 1-29 and 1-30, which will be described later, as they were one-component antifouling paint compositions. The amounts in the table are parts by mass per 100 parts by mass of curable silicone resin (A).

[0096] [Table 12]

[0097] Details of the hardeners 1-6, organic solvents 1 and 3, and curing retarders are shown in Table 13. The hardeners 1-6 and curing retarders contain 100% by mass of the active ingredients.

[0098] [Table 13]

[0099] 2. Preparation of antifouling paint composition (1) In all examples except Examples 1-29 and 1-30, and in all comparative examples, a two-component antifouling paint composition was prepared. Specifically, the main component composition (the first component of the two-component antifouling paint composition) was prepared by weighing the predetermined components (parts by mass per 100 parts by mass of curable silicone resin (A)) into a container according to the formulation of the surfactant compound, the formulation of the pigment and antifouling agent, and the formulation of other main components in predetermined amounts (parts by mass per 100 parts by mass of curable silicone resin (A)) into a container and then mixing and dispersing them using a high-speed disperser. In addition, the curing agent composition (the second component of the two-component antifouling paint composition) was prepared by weighing the predetermined components (parts by mass per 100 parts by mass of curable silicone resin (A)) into a separate container and then mixing them using a disperser. In the antifouling performance evaluation tests described below, the antifouling paint composition was prepared by mixing the main component composition and the curing agent composition using a disperser immediately before painting. Tables 14 to 16 show the various formulations used in each example and comparative example.

[0100] (2) In Examples 1-29 and 1-30, one-component antifouling paint compositions were prepared. Specifically, predetermined formulations of surfactant compounds, pigments and antifouling agents, and other main components were weighed into a container in predetermined amounts (parts by mass per 100 parts by mass of curable silicone resin (A)), and then mixed and dispersed using a high-speed disperser to prepare the antifouling paint composition. In the antifouling performance evaluation tests described below, the mixing and dispersion was performed immediately before painting. The various formulations used in Examples 1-29 and 1-30 are shown in Table 14.

[0101] [Table 14]

[0102] [Table 15]

[0103] [Table 16]

[0104] [Evaluation of stain resistance] A surface-polished vinyl chloride board measuring 300 mm x 20 mm x 2 mm (thickness) was uniformly coated with a primer to a thickness of 100 μm to ensure adhesion, and then dried. One of the antifouling paint compositions prepared in the examples and comparative examples was then uniformly applied to the surface of this primer to a thickness of 100 μm and dried to obtain test specimens. The obtained test specimens were immersed in a water channel with a constant flow of natural seawater. The water channel was positioned facing south, ensuring ample sunlight on sunny days. In Examples 3-1 to 3-15 and Comparative Examples 3-0 to 3-14, which included antifouling agents, an air pump was installed upstream of the water channel to continuously supply bubbles to the natural seawater, promoting the growth of organisms. The test specimens were removed one month after immersion in the water channel. The area of ​​organism attachment on the test specimen surface was determined by visual inspection and touch, and the antifouling performance was evaluated according to the following criteria. The results are shown in Tables 14 to 16. A rating of 3 or higher is preferred. 5: Biotope area is less than 10% 4: Biotope area is 10% or more but less than 20% 3: Biotope area is between 20% and 40% 2: Biotope area is between 40% and 70% 1: Biotope attachment area is 80% or more

[0105] The antifouling paint compositions of the examples employing combinations of surfactant compounds that satisfy formulas [1] and [2] exhibit superior antifouling properties compared to comparative examples that do not contain surfactant compounds, comparative examples that contain only one surfactant compound, and comparative examples that employ combinations of surfactant compounds but do not satisfy formula [1].

Claims

1. An antifouling coating composition comprising a curable silicone resin (A), a surfactant compound (B1), and a surfactant compound (B2), When the antifouling-correlated hydrophilic-lipophilic balance of the surfactant compound (B1) is ARHLB1 and the antifouling-correlated hydrophilic-lipophilic balance of the surfactant compound (B2) is ARHLB2, the following formulas [1] and [2] are given: ARHLB1-ARHLB2≧5 [1] ARHLB2 ≥ 2 [2] A stain-resistant coating composition that satisfies the following conditions.

2. The antifouling paint composition according to claim 1, further comprising a curing agent (C) for curing the curable silicone resin (A).

3. The antifouling paint composition according to claim 1, further comprising an antifouling agent (D).

4. The antifouling coating composition according to claim 1, further comprising a non-curing silicone compound (E).

5. The antifouling coating composition according to claim 1, further comprising a viscous agent (F).

6. The antifouling coating composition according to claim 1, further comprising a friction reducing agent (G).

7. The antifouling coating composition according to claim 1, further comprising a salt or acid-base compound (H).

8. The antifouling coating composition according to claim 2, further comprising a curing retarder.

9. The antifouling paint composition according to claim 2, comprising a first liquid containing the curable silicone resin (A), the surfactant compound (B1), and the surfactant compound (B2), and a second liquid containing the curing agent (C).

10. A coating film formed by the antifouling coating composition described in claim 1.

11. A composite coating film having a primer coating film formed by a rust-preventive coating composition and a coating film formed by the antifouling coating composition according to claim 1, which is laminated on the primer coating film.

12. A ship having the coating film described in claim 10 or the composite coating film described in claim 11.

13. An underwater structure having the coating film described in claim 10 or the composite coating film described in claim 11.

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