Antifouling coating composition, coating film, article, and method for producing antifouling coating composition

Abstract

The present invention relates to an antifouling coating composition containing a water-dispersed elastomer resin and a hydrophilic silicone oil having an HLB of 6 or more. The present invention also relates to a method for producing the antifouling coating composition, the method comprising mixing a first liquid containing at least a water-dispersed elastomer resin with a second liquid containing at least a hydrophilic silicone oil having an HLB of 6 or more.

Description

Antifouling coating composition, coating film, article, and method for producing antifouling coating composition

[0001] The present invention relates to an antifouling coating composition, a coating film, an article, and a method for producing an antifouling coating composition.

[0002] In the areas of underwater structures such as ships that come into contact with water, aquatic organisms such as barnacles, oysters, mussels, hydra, serpula, sea squirts, bryozoans, sea lettuce, green laver, and attached diatoms attach to and multiply, causing undesirable conditions such as increased fluid resistance, reduced thermal conductivity, and other deterioration in equipment and mechanical performance, as well as the spread of attached aquatic organisms overseas. Furthermore, the work of removing attached aquatic organisms requires a great deal of effort and time, resulting in economic losses.

[0003] Similarly, aquatic organisms can attach to and multiply in the areas of textile products used in water, such as fishing nets and ropes. The attached aquatic organisms can clog the mesh of fishing nets, restricting the flow of water, causing oxygen deficiency and resulting in the deaths of large numbers of farmed fish, or the outbreak of infectious diseases that make the products unsuitable for shipment, resulting in significant damage.

[0004] Conventionally, in order to prevent the adhesion of these aquatic organisms, antifouling coating compositions containing copper-based or non-copper-based antifouling agents blended with resins have been used. Furthermore, due to concerns about environmental impact, in recent years, antifouling coating compositions containing bleed-type antifouling components such as silicone oil have been used instead of highly toxic copper-based antifouling agents. For example, Patent Document 1 describes an antifouling coating film formed from a silicone copolymer and an antifouling coating composition containing the copolymer as a vehicle, an underwater structure coated with the antifouling coating film, and a ship whose surface is coated with the above-mentioned antifouling coating film.

[0005] International Publication No. 2011 / 074620

[0006] However, the antifouling coating composition described in Patent Document 1 is a so-called solvent-based antifouling coating composition in which a silicone copolymer is dissolved in an organic solvent, and so there are still concerns about its impact on the environment.Furthermore, there are also concerns about the health of workers because the organic solvent volatilizes when the antifouling coating composition is dried to form a coating film.

[0007] In view of the above, an object of the present disclosure is to provide an antifouling coating composition that exhibits excellent antifouling properties and has no adverse effects on the environment or human body.

[0008] The antifouling coating composition of the present disclosure contains a water-dispersible elastomer resin and a hydrophilic silicone oil having an HLB of 6 or more.

[0009] The present disclosure also provides a coating film formed from the antifouling coating composition.

[0010] The present disclosure also provides an article having the coating film.

[0011] The present disclosure also provides a method for producing an antifouling coating composition, which comprises mixing a first liquid containing at least a water-dispersible elastomer resin with a second liquid containing at least a hydrophilic silicone oil having an HLB of 6 or more.

[0012] The antifouling coating composition of the present disclosure exhibits excellent antifouling properties and has no adverse effects on the environment or the human body, and is therefore useful as an antifouling coating composition.

[0013] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to such embodiments. Furthermore, in this specification, when the expression "to" is used, it is used as an expression including the numerical values ​​or physical property values ​​before and after it. Furthermore, in this specification, various ratios and proportions (parts, percentages, etc.) based on mass are considered to have the same meaning as those based on weight.

[0014] <Antifouling Coating Composition> The antifouling coating composition of this embodiment contains a water-dispersible elastomer resin and a hydrophilic silicone oil having an HLB of 6 or more.

[0015] [Water-Dispersible Elastomer Resin] The antifouling coating composition of this embodiment contains a water-dispersible elastomer resin. Here, the water-dispersible elastomer resin (water-dispersible elastomer resin) can be an elastomer resin dispersed in an aqueous solvent using a dispersant (emulsifier) ​​such as a surfactant (elastomer emulsion resin), or a self-emulsified elastomer resin obtained by introducing an anionic, cationic, or nonionic group, which is a water-dispersible hydrophilic group, into the elastomer resin. Because the antifouling coating composition of this embodiment containing a water-dispersible elastomer resin is aqueous, there is no risk of adverse effects on the environment or the human body.

[0016] The elastomer resin is not particularly limited, and any appropriate elastomer can be used. Examples of the elastomer include silicone elastomers, urethane elastomers, acrylic elastomers, rubber polymers, vinyl chloride elastomers, vinyl acetate elastomers, polyamide elastomers, polyethylene elastomers, styrene elastomers, and butadiene elastomers. The elastomer resins may be used alone or in combination.

[0017] Of these, silicone elastomers, urethane elastomers, acrylic elastomers, vinyl chloride elastomers, vinyl acetate elastomers, styrene elastomers, and polyamide elastomers are preferred, with silicone elastomers being more preferred.

[0018] Examples of silicone elastomers include addition type silicone elastomers, condensation type silicone elastomers, and UV curable type silicone elastomers.

[0019] In this embodiment, among the water-dispersed elastomer resins, an elastomer emulsion resin is preferably used. Here, the elastomer emulsion resin is also referred to as an emulsion-type elastomer resin, and refers to the elastomer resin in an emulsion in which the elastomer resin is dispersed in an aqueous solvent. For example, an emulsion-type silicone elastomer is also referred to as a silicone elastomer emulsion resin. Note that an emulsion in which an elastomer resin is dispersed in an aqueous solvent, i.e., a composition containing an aqueous solvent and an elastomer resin dispersed in the aqueous solvent, is also referred to as an "elastomer emulsion."

[0020] Here, the aqueous solvent refers to water or a mixed solvent containing water as the main component. The solvent other than water contained in the mixed solvent may be one or more selected from various organic solvents (such as lower alcohols) that are uniformly miscible with water. The water content in the aqueous solvent is typically 90% by mass or more, preferably 95% to 100% by mass, and more preferably 100% by mass.

[0021] Among the elastomer emulsions, emulsions of elastomers selected from silicone elastomers, urethane elastomers, acrylic elastomers, vinyl chloride elastomers, vinyl acetate elastomers, styrene elastomers, and polyamide elastomers are preferred, and emulsions of silicone elastomers (silicone elastomer emulsions) are more preferred.

[0022] In one embodiment, a silicone elastomer emulsion (silicone elastomer emulsion) is a one-component emulsion containing a base polymer (silicone elastomer) and a crosslinking agent, and may further contain a catalyst such as a tin compound, if necessary. The base polymer is preferably an organopolysiloxane having at least two curing reactive groups bonded to silicon atoms per molecule, and is emulsified and dispersed in water. Examples of the curing reactive groups include hydrolyzable groups such as hydroxyl groups and alkoxy groups, with alkoxy groups being preferred. Examples of crosslinking agents include ethyl silicate, propyl silicate, methyltrimethoxysilane, and methyltriethoxysilane. A condensation reaction between the base polymer, crosslinking agent, and an optional catalyst proceeds to form a silicone resin. Furthermore, in one embodiment, an elastomer emulsion using an elastomer other than a silicone elastomer also contains a base polymer and a crosslinking agent, and may further contain a catalyst such as a tin compound, if necessary.

[0023] The swelling degree of elastomer emulsion resins, such as silicone elastomer emulsion resins, in toluene is preferably 1.1 times or more, more preferably 2 times or more, even more preferably 5 times or more, even more preferably 7 times or more, and particularly preferably 10 times or more. The swelling degree of the elastomer emulsion resin is an indicator of the amount of solvent trapped in the crosslinked elastomer emulsion resin, and is therefore related to the compatibility of the elastomer emulsion resin with silicone oil. A swelling degree of 1.1 times or more is preferred because it facilitates mixing of the elastomer emulsion resin with silicone oil. The upper limit of the swelling degree of the elastomer emulsion resin is not particularly limited, but may be, for example, 50 times or less, 40 times or less, or 30 times or less.

[0024] The swelling degree (times) of the elastomer emulsion resin is calculated by the following formula: Swelling degree (times) = (mass before drying of the solvent when measuring the gel content) / (gel content weight (mass after drying)).

[0025] The methods for measuring the "mass before drying of the solvent when measuring the gel content" and the "mass of the gel content (mass after drying)" in the above formula are described below. (Measurement Method) The elastomer emulsion was applied with an applicator to the surface of a 2 cm x 2 cm x 0.75 cm thick PET film (product name "Lumirror", manufactured by Toray Industries, Inc.), left to stand at 23°C (room temperature) for 3 days, and then dried in an oven at 80°C for 60 minutes to form a coating film. Next, an approximately 0.1 g test piece was taken from the formed coating film, wrapped in a polytetrafluoroethylene porous sheet (average pore size 0.2 μm, product name "NTF1122", manufactured by Nitto Denko Corporation), and tied with kite string to obtain a measurement sample. Next, the mass of the obtained measurement sample (mass before immersion C) was measured. The mass before immersion C was the total mass of the test piece, the polytetrafluoroethylene porous sheet, and the kite string. Separately, the envelope mass B, which is the total mass of the polytetrafluoroethylene porous sheet and kite string, is measured. Next, the measurement sample is placed in a 50 mL container filled with toluene and left to stand at 23 ° C for 7 days. After standing, the measurement sample is removed from the container and the mass D of the sample containing the solvent is measured. Then, the sample is transferred to an aluminum cup and dried in a dryer at 130 ° C for 2 hours to remove the toluene. The mass of the measurement sample after drying (mass A after immersion) is measured. Then, the mass obtained by subtracting the "envelope mass B" from the "mass D of the sample containing the solvent" is defined as the "mass before drying of the solvent when measuring the gel content." In addition, the mass obtained by subtracting the "envelope mass B" from the "mass A of the measurement sample after drying (mass A after immersion)" is defined as the "gel content mass (mass after drying)."

[0026] Examples of silicone elastomer emulsions (silicone elastomer emulsions) include POLON-MF-56, KM-9771, KM-9774, KM-2002-T, KM-2002-L-1, and KM-9772 manufactured by Shin-Etsu Chemical Co., Ltd., SILRES BS 45 manufactured by Wacker Asahi Kasei Silicones Co., Ltd., DOWSIL IE-7170 manufactured by Dow Chemical Japan, Ltd., and COATSIL DRI manufactured by Momentive Performance Materials Japan, LLC.

[0027] The proportion of the water-dispersible elastomer resin in the antifouling coating composition of this embodiment is preferably 40 to 80 mass %, more preferably 50 to 70 mass %, based on the total amount of nonvolatile content of the antifouling coating composition. Furthermore, when the antifouling coating composition of this embodiment contains an elastomer emulsion resin as the water-dispersible elastomer resin, the proportion of the elastomer emulsion resin in the antifouling coating composition is preferably 40 to 80 mass %, more preferably 50 to 70 mass %, based on the total amount of nonvolatile content of the antifouling coating composition.

[0028] [Silicone Oil] Examples of silicone oils include dimethylsilicone oils in which all of the substituents bonded to Si in the polysiloxane are methyl groups, methylphenylsilicone oils in which some of the methyl groups of these dimethylsilicone oils have been substituted with phenyl groups, amino-modified silicone oils substituted with monoamine, diamine, or amino-polyether groups, epoxy-modified silicone oils substituted with epoxy, alicyclic epoxy, epoxy-polyether, or epoxy-aralkyl groups, carbinol-modified silicone oils substituted with carbinol groups, mercapto-modified silicone oils substituted with mercapto groups, carboxyl-modified silicone oils substituted with carboxyl groups, methacrylic-modified silicone oils substituted with methacrylic groups, polyether-modified silicone oils substituted with polyethers, long-chain alkyl-modified silicone oils substituted with long-chain alkyl or long-chain alkyl-aralkyl groups, higher fatty acid-modified silicone oils substituted with higher fatty acid ester groups, and fluoroalkyl-modified silicone oils substituted with fluoroalkyl groups. In the present disclosure, hydrophilic silicone oil refers to a silicone oil whose HLB is 1 or more, and hydrophobic silicone oil refers to a silicone oil whose HLB is less than 1. HLB refers to the hydrophilic-lipophilic balance that numerically indicates the balance between the hydrophilicity and lipophilicity of an oil, and is an abbreviation for Value of Hydrophile and Liophile Balance. Specifically, HLB can be calculated, for example, by the following formula: HLB value = (sum of mass % values ​​of hydrophilic groups (oxyethylene units, OH groups) in the molecule) / 5

[0029] [Hydrophilic Silicone Oil with HLB of 6 or More] Here, the antifouling coating composition of this embodiment contains, in addition to a water-dispersible elastomer resin, a hydrophilic silicone oil with an HLB of 6 or more (hereinafter also referred to as a "high HLB hydrophilic silicone oil"). The high HLB hydrophilic silicone oil has high hydrophilicity, and therefore increases the stability of the liquid (antifouling coating composition) when mixed with the water-dispersible elastomer resin. Therefore, when the antifouling coating composition is dried to form a film, a highly uniform film is obtained, demonstrating high antifouling properties. Here, the HLB of the high HLB hydrophilic silicone oil is 6 or more, preferably 7 or more, and more preferably 8 or more.

[0030] On the other hand, if the HLB of the high HLB hydrophilic silicone oil is too high, the amount of oil bleeding from the coating film will be excessive, which may be disadvantageous from the viewpoint of long-term durability of the antifouling effect. Therefore, the HLB of the high HLB hydrophilic silicone oil is preferably 18 or less, more preferably 15 or less, and even more preferably 13 or less. In one preferred embodiment, the HLB of the high HLB hydrophilic silicone oil is preferably 6 to 18, more preferably 7 to 15, and even more preferably 8 to 13.

[0031] Examples of hydrophilic silicone oils include polyether-modified silicone oils, polyglycerin-modified silicone oils, silicone oils co-modified with hydrophilic groups such as polyether and hydrophobic groups such as alkyl, etc. In these hydrophilic silicone oils, the hydrophilic groups of the polyether-modified silicone oils, polyglycerin-modified silicone oils, polyether, etc. may be terminated with a hydroxyl group, or may be capped with an alkyl group such as a methyl group or an alkyl ester group such as a methyl ester group.

[0032] Among hydrophilic silicone oils, polyether-modified silicone oils are preferred from the viewpoint of antifouling properties and their durability. Polyether-modified silicone oils are polysiloxanes whose main chains have siloxane bonds and have one or more polyoxyalkylene groups as substituents. The main chains may form rings.

[0033] The bonding position of the polyoxyalkylene group in the polyether-modified silicone oil can be any suitable bonding position.For example, the polyoxyalkylene group may be bonded to both ends of the main chain, or may be bonded to one end of the main chain, or may be bonded to a side chain.Among them, from the viewpoint of antifouling property, polyether-modified silicone oil in which the polyoxyalkylene group is bonded to a side chain (side chain type polyether-modified silicone oil) is preferred.Examples of the polyoxyalkylene group include polyoxyethylene group (PEO), polyoxypropylene group (PPO) and polyoxybutylene group (PBO).From the viewpoint of antifouling property, polyoxyethylene group (PEO) and polyoxypropylene group (PPO) are preferred, and polyoxyethylene group (PEO) is more preferred.The polyoxyalkylene groups bonded to the polysiloxane may all have the same structure within the molecule, or may be different. In the side chain type polyether modified silicone oil, the number of repeating polyoxyalkylene groups in the side chain is preferably 1 to 300, more preferably 1 to 250, even more preferably 1 to 200, particularly preferably 1 to 100, and particularly preferably 1 to 50.

[0034] From the viewpoint of oil-bleeding, the weight-average molecular weight (Mw) of the hydrophilic silicone oil is preferably 200 or more, more preferably 400 or more, and even more preferably 600 or more. Furthermore, from the viewpoint of oil-bleeding, the weight-average molecular weight (Mw) of the hydrophilic silicone oil is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 40,000 or less. In one preferred embodiment, the weight-average molecular weight (Mw) of the hydrophilic silicone oil is preferably 200 to 100,000, more preferably 400 to 50,000, and even more preferably 600 to 40,000. The weight-average molecular weight (Mw) of the hydrophilic silicone oil can be measured by gel permeation chromatography (GPC). Specific embodiments of the GPC measurement device and measurement conditions are described below. Sample preparation: The sample is prepared in a 0.5 wt % THF eluent and allowed to stand overnight. This solution is filtered through a 0.45 μm membrane filter, and the filtrate is subjected to GPC measurement. Apparatus: Alliance, manufactured by Waters; Column: TSKgel SuperHZM-H x 2; Column temperature: 40°C; Eluent: THF; Flow rate: 0.2 mL / min; Injection volume: 30 μL; Detector: Refractive index (RI); Standard sample: Polystyrene (PS), manufactured by Agilent.

[0035] The high HLB hydrophilic silicone oil can be appropriately selected from the above-mentioned hydrophilic silicone oils and used from those having an HLB of 6 or more. The high HLB hydrophilic silicone oil used may be one type only, or two or more types.

[0036] As the high HLB hydrophilic silicone oil, a polyether-modified silicone oil having an HLB of 6 or more is preferred. Examples of polyether-modified silicone oils having an HLB of 6 or more include those manufactured by Shin-Etsu Chemical Co., Ltd. under the trade names "KF-6011" (HLB: 12.0), "KF-6011P" (HLB: 14.5), "KF-6012" (HLB: 7.0), "KF-6013" (HLB: 10.0), "KF-6043" (HLB: 14.5), "KF-6004" (HLB: 9.0), "KF351A" (HLB: 12.0), and "KF352A" (HLB: 10.0). : 7.0), "KF353" (HLB: 10.0), "KF354L" (HLB: 16.0), "KF355A" (HLB: 12.0), "KF615A" (HLB: 10.0), "KF-640" (HLB: 14.0), "KF-642" (HLB: 12.0), "KF-643" (HLB: 14.0), "KF-644" (HLB: 11.0), "KF-6204" (HLB: 10.0), "DOWSIL" manufactured by Dow Chemical Japan Co., Ltd. Examples of the side chain type (linear type) polyether-modified silicone oil include "DOWSIL SH 3746" (HLB: 16.0), "VORASURF SH 193 Fluid" (HLB: 15.0), "DOWSIL L-7604" (HLB: 13.0), "DOWSIL SH 8400" (HLB: 8.0), "DOWSIL SH 8700" (HLB: 7.0), "DOWSIL SF 8410" (HLB: 6.0), "COATOSIL 7602" (HLB: 9.3) manufactured by Momentive Performance Materials Japan LLC, and "WACKER L 066" (HLB: 13.6) manufactured by Wacker Asahi Kasei Silicones Co., Ltd.

[0037] In the antifouling coating composition of this embodiment, the content of the high HLB hydrophilic silicone oil relative to 100 parts by mass of the water-dispersible elastomer resin (hereinafter, calculated assuming the resin solids mass of the water-dispersible elastomer resin is 100 parts) is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, and even more preferably 5 to 15 parts by mass. If the content of the high HLB hydrophilic silicone oil is within the above range, the antifouling effect of the antifouling coating composition can be more fully exhibited.

[0038] [Hydrophilic silicone oil having an HLB of 1 or more and less than 6] Furthermore, the antifouling coating composition of this embodiment preferably further contains a hydrophilic silicone oil having an HLB of 1 or more and less than 6 (hereinafter also referred to as a "low HLB hydrophilic silicone oil") in addition to a hydrophilic silicone oil having an HLB of 6 or more (high HLB hydrophilic silicone oil). When the antifouling coating composition contains a low HLB hydrophilic silicone oil in addition to a high HLB hydrophilic silicone oil, the stability of the coating film when formed by the antifouling coating composition is improved. This is also preferable from the viewpoint of long-term durability of the antifouling effect.

[0039] As the low HLB hydrophilic silicone oil, one having an HLB of 1 or more and less than 6 can be appropriately selected from the above-mentioned hydrophilic silicone oils. The low HLB hydrophilic silicone oil used may be one type only, or two or more types. The HLB of the low HLB hydrophilic silicone oil is preferably 2 or more, and more preferably 4 or more.

[0040] The low HLB hydrophilic silicone oil is preferably a polyether-modified silicone oil having an HLB of 1 or more and less than 6. Examples of polyether-modified silicone oils having an HLB of 1 or more and less than 6 include trade names "KF-6020" (HLB: 4.0), "KF-6015" (HLB: 5.0), "KF-6017" (HLB: 5.0), "KF945" (HLB: 4.0), and "X-22-4515" (HLB: 5.0), all manufactured by Shin-Etsu Chemical Co., Ltd., and "DOWSIL FZ-5609" (HLB: 4.0) and "DOWSIL Y-7006" (HLB: 2.0), all manufactured by Dow Chemical Japan Ltd.

[0041] In the antifouling coating composition of this embodiment, the content ratio of the low HLB hydrophilic silicone oil relative to 100 parts by mass of the water-dispersible elastomer resin (hereinafter, calculated assuming that the mass of the resin solid content of the water-dispersible elastomer resin is 100 parts) is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, and even more preferably 5 to 15 parts by mass, from the viewpoints of coating film stability and long-term durability of the antifouling effect.

[0042] Furthermore, when a high HLB hydrophilic silicone oil and a low HLB hydrophilic silicone oil are used in combination, the content ratio of the two components is preferably high HLB hydrophilic silicone oil / low HLB hydrophilic silicone oil=5 / 25 to 25 / 5, and more preferably 10 / 20 to 20 / 10, on a mass basis, from the viewpoint of the stability of the coating film and the long-term durability of the antifouling effect.

[0043] [Hydrophobic Silicone Oil] The antifouling coating composition of this embodiment preferably further contains a hydrophobic silicone oil in addition to a hydrophilic silicone oil having an HLB of 6 or more (high HLB hydrophilic silicone oil). When the antifouling coating composition contains a hydrophobic silicone oil in addition to a high HLB hydrophilic silicone oil, bleeding of the oil in water from a coating film formed by the antifouling coating composition is promoted. In this case, the antifouling coating composition may further contain a hydrophilic silicone oil having an HLB of 1 or more and less than 6 (low HLB hydrophilic silicone oil).

[0044] Examples of hydrophobic silicone oils include non-reactive silicone oils such as polysiloxanes whose main chains are formed by siloxane bonds, which may have a substituent, and the main chain may form a ring. Examples include straight silicone oils and modified silicone oils (excluding polyether-modified silicone oils). The substituents in straight silicone oils are preferably alkyl groups or phenyl groups. Specific examples include terminal hydroxyl group-containing dimethyl silicone oils in which both or one end of the polysiloxane is a hydroxyl group, dimethyl silicone oils in which all of the substituents bonded to the Si of the polysiloxane are methyl groups, phenylmethyl silicone oils (phenyl-modified silicone oils) in which some of the methyl groups of these dimethyl silicone oils are replaced with phenyl groups, amino-modified silicone oils, epoxy-modified silicone oils, and long-chain alkyl-modified silicone oils. The hydrophobic silicone oils used may be one type only, or two or more types.

[0045] In this embodiment, the hydrophobic silicone oil may be an emulsion-type hydrophobic silicone oil (hydrophobic silicone oil emulsion). Here, the emulsion-type hydrophobic silicone oil refers to an emulsion in which the hydrophobic silicone oil is dispersed in water. The emulsion-type hydrophobic silicone oil has the advantage of being easily mixed with the elastomer emulsion.

[0046] Examples of hydrophobic silicone oils include "KF-96-100CS" manufactured by Shin-Etsu Chemical Co., Ltd. and "WACKER AK100" manufactured by Wacker Asahi Kasei Silicones Co., Ltd. Examples of emulsion-type hydrophobic silicone oils include "KM-860A," "KM-9782," "KM-9739," "KM-9771," and "X-51-1264" manufactured by Shin-Etsu Chemical Co., Ltd.

[0047] In the antifouling coating composition of this embodiment, the content ratio of the hydrophobic silicone oil (by mass of solid content) relative to 100 parts by mass of the water-dispersible elastomer resin (hereinafter, calculated assuming that the mass of the resin solid content of the water-dispersible elastomer resin is 100 parts) is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and even more preferably 40 to 60 parts by mass, from the viewpoint of appropriate oil-bleeding properties.

[0048] Furthermore, when a hydrophilic silicone oil and a hydrophobic silicone oil are used in combination, the content ratio of the two components, based on the solid content mass, is preferably hydrophilic silicone oil / hydrophobic silicone oil = 1 / 20 (0.05) to 20 / 20 (1.0), more preferably 10 / 50 (0.2) to 20 / 25 (0.8), and even more preferably 10 / 40 (0.25) to 30 / 60 (0.5).

[0049] [Water] The antifouling coating composition of this embodiment usually contains water. For example, an elastomer emulsion is a form in which an elastomer resin is dispersed in water, and by blending an elastomer emulsion into an antifouling coating composition, the water in the elastomer emulsion is included in the antifouling coating composition. Furthermore, when a hydrophobic silicone oil emulsion is blended into the antifouling coating composition, the water in the hydrophobic silicone oil emulsion is included in the antifouling coating composition. Furthermore, water may be further added to the antifouling coating composition of this embodiment.

[0050] [Other Components] The antifouling coating composition according to this embodiment may contain any other appropriate additives as long as the effects of the present disclosure are not impaired. Examples of such other additives include various components used in general coating compositions, such as weathering agents, ultraviolet absorbers, antifouling agents, plastic resins, surface conditioners, surfactants, thixotropic agents, coloring pigments, extender pigments, and other coating film-forming components. Furthermore, the antifouling coating composition according to this embodiment may contain resins other than the above-described water-dispersible elastomer resins and oils other than the above-described silicone oils as long as the effects of the present disclosure are not impaired.

[0051] In particular, the antifouling coating composition according to this embodiment preferably contains a surfactant, and more preferably contains at least one of an anionic surfactant (anionic surfactant), a nonionic surfactant (nonionic surfactant), a cationic surfactant, and an amphoteric surfactant.

[0052] As the anionic surfactant, any appropriate anionic surfactant can be used as long as it does not impair the effects of the present invention. Examples of such anionic surfactants include alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, polyoxyalkylene alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, α-olefin sulfonates, α-sulfofatty acid or ester salts, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, amino acid surfactants, N-acylamino acid surfactants, alkyl or alkenyl phosphate esters or salts thereof, and the like. The anionic surfactant may be used alone or in combination of two or more types.

[0053] As the nonionic surfactant, any suitable nonionic surfactant can be used as long as it does not impair the effects of the present invention. Examples of such nonionic surfactants include polyoxyalkylene alkyl or alkenyl ethers, polyoxyethylene alkylphenyl ethers, higher fatty acid alkanolamides or their alkylene oxide adducts, sucrose fatty acid esters, alkylglycoxides, fatty acid glycerin monoesters, and alkylamine oxides. The nonionic surfactant may be used alone or in combination of two or more types.

[0054] As the cationic surfactant, any appropriate cationic surfactant can be used as long as it does not impair the effects of the present invention. Examples of such cationic surfactants include quaternary ammonium salts. The cationic surfactant may be one type or two or more types.

[0055] As the amphoteric surfactant, any appropriate amphoteric surfactant can be used as long as it does not impair the effects of the present invention. Examples of such amphoteric surfactants include carboxy-type and sulfobetaine-type amphoteric surfactants. Only one type of amphoteric surfactant may be used, or two or more types may be used.

[0056] The surfactant is preferably an anionic surfactant or a nonionic surfactant, and specific examples thereof include the following anionic surfactants and nonionic surfactants. <Anionic surfactants> ・Alkyl sulfate ester salt: EMAL 10PT ・Polyoxyethylene alkyl ether sulfate ester salt: LATEMUL E-118B ・Alkylbenzene sulfonate: NEOPELEX GS ・Polyoxyalkylene alkenyl ether ammonium sulfate: LATEMUL PD-104 <Nonionic surfactants> ・Polyoxyethylene alkyl ether: EMULGEN 1150S-60 ・Polyoxyethylene alkylene alkyl ether: EMULGEN LS-114 ・Polyoxyethylene distyrenated phenyl ether: EMULGEN B-66 ・Polyoxyethylene polyoxypropylene glycol: EMULGEN PP-290 ・Polyoxyethylene glyceryl ether: EMULGEN GE-1 ・Polyoxyethylene diglyceryl ether: EMULGEN G2E-4 ・Polyoxyalkylene alkenyl ether: LATEMUL PD-430 ・Sorbitan fatty acid ester: RHEODOL SP-L10 Polyoxyethylene sorbitan fatty acid ester: Rheodol TW-L120 Polyoxyethylene fatty acid ester: Emanon 4110 These are all surfactants manufactured by Kao Corporation.

[0057] When the antifouling coating composition of this embodiment contains a surfactant, the content ratio of the surfactant relative to 100 parts by mass of the water-dispersible resin (hereinafter, calculated assuming the mass of the resin solids content of the water-dispersible resin is 100 parts) is preferably 0.1 parts by mass or more, and more preferably 0.2 parts by mass or more. The content ratio of the surfactant is preferably 5 parts by mass or less, and more preferably 1 part by mass or less. In one preferred embodiment, the content ratio of the surfactant relative to 100 parts by mass of the water-dispersible resin is preferably 0.1 to 5 parts by mass, and more preferably 0.2 to 1 parts by mass.

[0058] The antifouling coating composition according to this embodiment may contain the above-mentioned additives, but depending on the application of the antifouling coating composition, it may be better not to include certain types of additives from the viewpoint of reducing the environmental load. For example, it is preferable not to include the above-mentioned antifouling agents from the viewpoint of reducing the environmental load. Furthermore, the antifouling coating composition according to this embodiment preferably does not contain substantially any organic solvent, and more preferably does not contain any organic solvent. Note that "substantially does not contain any organic solvent" means that the content of the organic solvent relative to the total amount of the antifouling coating composition is less than 1 mass%.

[0059] The antifouling coating composition according to this embodiment preferably contains emulsion particles, and the emulsion particles preferably have an average particle size (D50) of 0.01 μm or more, more preferably 0.1 μm or more, from the viewpoints of antifouling properties and liquid stability. Furthermore, the emulsion particles preferably have an average particle size (D50) of 200 μm or less, more preferably 100 μm or less, from the viewpoints of antifouling properties and liquid stability. In one preferred embodiment, the emulsion particles have an average particle size (D50) of 0.01 to 200 μm, more preferably 0.1 to 100 μm.

[0060] The average particle size (D90) of the emulsion particles is preferably 0.01 μm or more, and more preferably 0.1 μm or more, from the viewpoints of antifouling properties and liquid stability. The average particle size (D90) of the emulsion particles is preferably 600 μm or less, more preferably 300 μm or less, and even more preferably 100 μm or less, from the viewpoints of antifouling properties and liquid stability. In a preferred embodiment, the average particle size (D90) of the emulsion particles is preferably 0.01 to 600 μm, more preferably 0.1 to 300 μm, and more preferably 0.1 to 100 μm. In this specification, emulsion particles refer to the dispersoid in the emulsion. The average particle size of emulsion particles refers to the volume-based median diameter (D50) measured by laser diffraction / scattering. D50 refers to the diameter below which 50% of the population is located, and D90 refers to the diameter below which 90% of the population is located.

[0061] Examples of emulsion particles contained in the antifouling coating composition according to this embodiment include emulsion particles dispersed in an aqueous solvent, which contain a water-dispersible resin (typically, particles containing a water-dispersible resin and a dispersant such as a surfactant), and emulsion particles containing a hydrophobic silicone oil and a hydrophilic silicone oil (typically, particles containing a hydrophobic silicone oil, a hydrophilic silicone oil, and a dispersant such as a surfactant).

[0062] From the viewpoint of achieving excellent antifouling properties and easy cleaning, the antifouling coating composition according to this embodiment preferably has a water contact angle of 70° or less, more preferably 60° or less, and even more preferably 55° or less of a coating film formed from the antifouling coating composition. There is no particular restriction on the lower limit of the water contact angle of the coating film, and it may be 0° or more, 10° or more, 20° or more, or 25° or more.

[0063] The water contact angle of a coating film formed from the antifouling coating composition according to this embodiment can be determined by applying the antifouling coating composition with an applicator to the surface of a PET film (product name "Lumirror", manufactured by Toray Industries, Inc.) measuring 30 cm long x 25 cm wide x 0.75 cm thick, and drying the film to form a coating film with a thickness of 100 μm, preparing a measurement sample, dropping 2 μl of water onto the coating film surface, and measuring the water contact angle of the coating film surface after 5 minutes using a contact angle meter (DropMaster, manufactured by Kyowa Interface Science Co., Ltd.) by the sessile drop method according to JIS R3257.

[0064] <Coating Film> The coating film of this embodiment is a coating film formed from the antifouling coating composition described above, and is useful for preventing the adhesion of aquatic organisms. For example, the coating film-forming composition of this embodiment can be applied to an appropriate article to be adhered by a known application method such as spraying, brushing, roller application, curtain flow application, roll application, dipping, or coater, and then dried at a temperature of 0°C to 250°C (preferably, room temperature to 180°C, more preferably, room temperature to 160°C) for, for example, 2 minutes to 12 hours, to form a coating film on the surface of the article.

[0065] The thickness of the coating film can be any appropriate thickness depending on the application, usage environment, etc. The thickness of the coating film is preferably 10 μm to 5000 μm. When the thickness of the coating film falls within the above range, the antifouling effect works effectively for a sufficiently long period of time. If the thickness of the coating film is thinner than 10 μm, the period during which the antifouling effect works effectively may be shortened, making it impractical. If the thickness of the coating film is thicker than 5000 μm, it may take too long to prepare the coating film, making it impractical.

[0066] <Article> The article of this embodiment has a coating film formed from the antifouling coating composition described above. Examples of the article include, but are not limited to, underwater structures and textile products such as fishing nets and ropes. Examples of textile products include fishing gear such as threads, ropes, cables, nets, fishing nets, and fish pens used in underwater structures, and fabrics such as woven fabrics, knitted fabrics, and nonwoven fabrics. Examples of underwater structures include ships, buoys, port facilities, offshore oil field facilities, waterways for power plant cooling water, floating walkways on water, sluice gates, underwater sensors, underwater cameras, underwater lights, underwater pumps, underwater piping, underwater power generation facilities (e.g., tidal power generation facilities, ocean current power generation facilities, wave power generation facilities, and offshore wind power generation facilities), underwater rotating bodies such as propellers, and various underwater mooring devices such as underwater wires.

[0067] <Method for producing antifouling coating composition> The method for producing the antifouling coating composition of the present embodiment is not particularly limited, but the composition can be produced, for example, by mixing a first liquid containing at least a water-dispersible elastomer resin with a second liquid containing at least a hydrophilic silicone oil having an HLB of 6 or more.

[0068] Here, the first liquid containing at least a water-dispersible elastomer resin is, for example, an elastomer emulsion in which an elastomer resin is dispersed in an aqueous solvent with a dispersant (emulsifier), or a self-emulsified elastomer resin dispersed in an aqueous solvent. In addition, when a hydrophobic silicone oil is contained in the antifouling coating composition, the first liquid is, for example, a mixture of an elastomer emulsion and a hydrophobic silicone oil emulsion.

[0069] Furthermore, the second liquid containing at least a hydrophilic silicone oil having an HLB of 6 or more (high HLB hydrophilic silicone oil) may consist solely of the high HLB hydrophilic silicone oil, or may contain other components in addition to the high HLB hydrophilic silicone oil. Examples of other components include a hydrophilic silicone oil having an HLB of 1 or more and less than 6 (low HLB hydrophilic silicone oil). Furthermore, the second liquid may further contain a hydrophobic silicone oil.

[0070] Hereinafter, Production Method A and Production Method B, which are specific embodiments of the method for producing the antifouling coating composition of this embodiment, will be described. In Production Method A and Production Method B, the first liquid is, for example, an aqueous liquid, and the second liquid is, for example, a non-aqueous liquid. When mixing the first liquid and the second liquid, for example, the second liquid may be added dropwise to the first liquid (this embodiment is referred to as "Production Method A"). In Production Method A, it is preferable to add the second liquid dropwise while the first liquid is being stirred. Alternatively, when mixing the first liquid and the second liquid, it is also possible to add the first liquid dropwise to the second liquid (this embodiment is referred to as "Production Method B"). In Production Method B, it is preferable to add the first liquid dropwise while the second liquid is being stirred.

[0071] Furthermore, although the detailed reason is not clear, from the viewpoint of the antifouling properties of the coating film formed from the antifouling coating composition produced, of Production Methods A and B, Production Method A is preferred.

[0072] Next, Production Method C, which is another specific embodiment of the method for producing the antifouling coating composition of this embodiment, will be described. In Production Method C, the first liquid and the second liquid are, for example, aqueous liquids. Furthermore, in Production Method C, the second liquid may be an emulsified liquid. The antifouling coating composition of this embodiment can also be produced by mixing the first liquid with an emulsified second liquid (this embodiment is referred to as "Production Method C"). In Production Method C, the second liquid may be added dropwise to the first liquid to mix them, or the first liquid may be added dropwise to the second liquid to mix them. When adding the second liquid dropwise to mix the first liquid, it is preferable to add the second liquid dropwise while stirring the first liquid. When adding the first liquid dropwise to mix the second liquid, it is preferable to add the first liquid dropwise while stirring the second liquid.

[0073] In manufacturing method C, when preparing the second liquid, for example, hydrophilic silicone oil is dropped into water or water containing a dispersant (emulsifier) ​​such as a surfactant, mixed, and emulsified to obtain the second liquid.The dropping of hydrophilic silicone oil is preferably carried out while stirring water or water containing a dispersant.In addition, when the second liquid contains hydrophobic silicone oil in addition to hydrophilic silicone oil, for example, the hydrophobic silicone oil can be dropped into the second liquid containing the hydrophilic silicone oil, mixed, and emulsified.The dropping of hydrophobic silicone oil is preferably carried out while stirring the second liquid containing hydrophilic silicone oil.

[0074] As for the hydrophobic silicone oil, hydrophilic silicone oil, and surfactant, the descriptions of the hydrophobic silicone oil, hydrophilic silicone oil, and surfactant in the antifouling coating composition described above can be used as is.

[0075] As explained above, the present specification describes the following: (1) An antifouling coating composition comprising a water-dispersible elastomer resin and a hydrophilic silicone oil having an HLB of 6 or more. (2) The antifouling coating composition according to (1), in which the water-dispersible elastomer resin comprises an elastomer emulsion resin. (3) The antifouling coating composition according to (2), in which the elastomer emulsion resin comprises a silicone elastomer. (4) The antifouling coating composition according to (1), in which the hydrophilic silicone oil having an HLB of 6 or more has a weight-average molecular weight of 200 to 100,000. (5) The antifouling coating composition according to (1), in which the hydrophilic silicone oil having an HLB of 6 or more comprises a polyether-modified silicone oil having a polyoxyalkylene group in its side chain. (6) The antifouling coating composition according to any one of (1) to (5), further comprising a hydrophilic silicone oil having an HLB of 1 or more but less than 6. (7) The antifouling coating composition according to (6), wherein the hydrophilic silicone oil having an HLB of 1 or more and less than 6 has a weight-average molecular weight of 200 to 100,000. (8) The antifouling coating composition according to claim (6) or (7), wherein the hydrophilic silicone oil having an HLB of 1 or more and less than 6 comprises a polyether-modified silicone oil having a polyoxyalkylene group in a side chain. (9) The antifouling coating composition according to any one of (1) to (8), further comprising a hydrophobic silicone oil. (10) The antifouling coating composition according to any one of (1) to (9), wherein the antifouling coating composition contains emulsion particles, and the average particle size D50 of the emulsion particles is 0.01 to 200 μm. (11) A coating film formed from the antifouling coating composition according to any one of (1) to (10). (12) An article having the coating film according to (11). (13) The article according to (12), wherein the article is a textile product. (14) A method for producing the antifouling coating composition according to any one of (1) to (10), comprising mixing a first liquid containing at least a water-dispersible elastomer resin with a second liquid containing at least a hydrophilic silicone oil having an HLB of at least 6. (15) The method for producing the antifouling coating composition according to (14), wherein the second liquid further contains a hydrophobic silicone oil.(16) The method for producing an antifouling coating composition according to (14) or (15), wherein the second liquid is added dropwise to the first liquid and mixed. (17) The method for producing an antifouling coating composition according to (14) or (15), wherein the first liquid is added dropwise to the second liquid and mixed. (18) The method for producing an antifouling coating composition according to claim (14) or (15), wherein the second liquid is an emulsified liquid.

[0076] The present invention will be specifically explained below with reference to examples, but the present invention is not limited to these examples in any way.

[0077] (Example 1) In the following, the proportion of each component is specified when the mass of the resin solid content of the silicone elastomer emulsion is 100 parts by mass. Furthermore, for the hydrophobic silicone oil emulsion, the proportion is specified in terms of its solid content mass. The same applies to each example and comparative example other than Example 1 described below.

[0078] Five parts by mass of polyether-modified silicone oil (trade name "KF-6020", HLB: 4.0, manufactured by Shin-Etsu Chemical Co., Ltd.) and 15 parts by mass of polyether-modified silicone oil (trade name "KF-6011", HLB: 12.0, manufactured by Shin-Etsu Chemical Co., Ltd.) were placed in a container and mixed by stirring for 5 minutes using a homomixer at room temperature (23°C) to obtain Liquid Mixture 1A. Subsequently, 100 parts by mass (based on 100 parts by mass of resin solids) of silicone elastomer emulsion (self-crosslinking silicone resin, trade name "KM-9772", manufactured by Shin-Etsu Chemical Co., Ltd.) and 50 parts by mass (based on solids mass) of dimethyl silicone oil emulsion (trade name "KM-860A", manufactured by Shin-Etsu Chemical Co., Ltd.) were placed in another container and mixed by stirring for 5 minutes using a homomixer at room temperature (23°C) to obtain Liquid Mixture 1B. Next, while Liquid Mixture 1A was being stirred in a container, Liquid Mixture 1B was added dropwise to dissolve and disperse uniformly, thereby obtaining the antifouling coating composition of Example 1. The antifouling coating composition of Example 1 was produced by the above-mentioned Production Method B. The degree of swelling of "KM-9772" used as the silicone elastomer emulsion in toluene, calculated under the above-mentioned conditions, was 10.4 times.

[0079] Examples 2 to 3 Antifouling coating compositions of Examples 2 to 3 were obtained in the same manner as in Example 1, except that the ratio of polyether-modified silicone oil (trade name "KF-6020", HLB: 4.0, manufactured by Shin-Etsu Chemical Co., Ltd.) to polyether-modified silicone oil (trade name "KF-6011", HLB: 12.0, manufactured by Shin-Etsu Chemical Co., Ltd.) was changed as shown in Table 1. The antifouling coating compositions of Examples 2 and 3 were produced by Production Method B described above.

[0080] Example 4: 100 parts by mass of a silicone elastomer emulsion (self-crosslinking silicone resin, trade name "KM-9772", manufactured by Shin-Etsu Chemical Co., Ltd.) (based on 100 parts by mass of the resin solids) and 50 parts by mass of a dimethyl silicone oil emulsion (trade name "KM-860A", manufactured by Shin-Etsu Chemical Co., Ltd.) (based on solids mass) were placed in a container and mixed by stirring using a homomixer at room temperature (23°C) for 5 minutes to obtain a liquid mixture 4A. Subsequently, 15 parts by mass of a polyether-modified silicone oil (trade name "KF-6020", HLB: 4.0, manufactured by Shin-Etsu Chemical Co., Ltd.) and 5 parts by mass of a polyether-modified silicone oil (trade name "KF-6011", HLB: 12.0, manufactured by Shin-Etsu Chemical Co., Ltd.) were placed in a separate container and mixed by stirring using a homomixer at room temperature (23°C) for 5 minutes to obtain a liquid mixture 4B. Next, while Liquid Mixture 4A was being stirred in a container, Liquid Mixture 4B was added dropwise to dissolve and disperse uniformly, thereby obtaining the antifouling coating composition of Example 4. The antifouling coating composition of Example 4 was produced by the above-mentioned Production Method A.

[0081] Example 5 An antifouling coating composition of Example 5 was obtained in the same manner as in Example 1, except that 20 parts by mass of polyether-modified silicone oil (trade name "KF-6024", HLB: 10.0, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of Liquid Mixture 1A. The antifouling coating composition of Example 5 was produced by Production Method B described above.

[0082] Example 6 An antifouling coating composition of Example 6 was obtained in the same manner as in Example 1, except that 20 parts by mass of polyether-modified silicone oil (trade name "KF-6011", HLB: 12.0, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of Liquid Mixture 1A. The antifouling coating composition of Example 6 was produced by Production Method B described above.

[0083] Example 7 An antifouling coating composition of Example 7 was obtained in the same manner as in Example 4, except that 50 parts by mass (solid content mass equivalent) of dimethyl silicone oil emulsion (trade name "KM-9782", manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of 50 parts by mass (solid content mass equivalent) of dimethyl silicone oil emulsion (trade name "KM-860A", manufactured by Shin-Etsu Chemical Co., Ltd.). The antifouling coating composition of Example 7 was produced by Production Method A described above.

[0084] Example 8 An antifouling coating composition of Example 8 was obtained in the same manner as in Example 4, except that 50 parts by mass (solid content mass equivalent) of phenyl-modified silicone oil emulsion (trade name "KM-9739", manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of 50 parts by mass (solid content mass equivalent) of dimethyl silicone oil emulsion (trade name "KM-860A", manufactured by Shin-Etsu Chemical Co., Ltd.). The antifouling coating composition of Example 8 was produced by Production Method A described above.

[0085] Example 9 An antifouling coating composition of Example 9 was obtained in the same manner as in Example 4, except that 50 parts by mass (solid content mass equivalent) of an amino-modified silicone oil emulsion (trade name "KM-9771", manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of 50 parts by mass (solid content mass equivalent) of a dimethyl silicone oil emulsion (trade name "KM-860A", manufactured by Shin-Etsu Chemical Co., Ltd.). The antifouling coating composition of Example 9 was produced by Production Method A described above.

[0086] Example 10 An antifouling coating composition of Example 10 was obtained in the same manner as in Example 4, except that 50 parts by mass (solid content mass equivalent) of an epoxy-modified silicone oil emulsion (trade name "X-51-1264", manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of 50 parts by mass (solid content mass equivalent) of a dimethyl silicone oil emulsion (trade name "KM-860A", manufactured by Shin-Etsu Chemical Co., Ltd.). The antifouling coating composition of Example 10 was produced by Production Method A described above.

[0087] (Example 11) 75 parts by mass of ion-exchanged water and 0.5 parts by mass of an anionic surfactant (trade name "Latemul E-118B", manufactured by Kao Corporation) were added to a container and stirred for 5 minutes using a homomixer at room temperature (23 ° C.) to obtain water containing a surfactant. Next, while stirring the water containing the surfactant in a container using a homomixer at room temperature (23 ° C.), 20 parts by mass of polyether-modified silicone oil (trade name "DOWSIL SH 8400", HLB: 8.0, manufactured by Dow Chemical Japan Co., Ltd.) was added dropwise and uniformly dissolved and dispersed to obtain a liquid mixture. Next, while stirring the liquid mixture in the container, 50 parts by mass of dimethyl silicone oil (trade name "KF-96-100CS", manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise and emulsified to obtain a liquid mixture 11A. Next, while the liquid mixture 11A was being stirred in a container using a homomixer, 100 parts by mass (mass of resin solids taken as 100 parts by mass) of a silicone elastomer emulsion (self-crosslinking silicone resin, product name "KM-9772", manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise and uniformly dissolved and dispersed, thereby obtaining the antifouling coating composition of Example 11. The antifouling coating composition of Example 11 was produced by the above-mentioned Production Method C.

[0088] Examples 12 to 15 The antifouling coating compositions of Examples 12 to 15 were obtained in the same manner as Example 11, except that the types of silicone elastomer emulsion, dimethyl silicone oil, and polyether-modified silicone oil were changed as shown in Table 2. The antifouling coating compositions of Examples 12 to 15 were produced by Production Method C described above. In Examples 12 and 14, the silicone elastomer emulsion used, COATSIL DRI manufactured by Momentive Performance Materials Japan, LLC, had a swelling degree in toluene calculated under the conditions described above of 4.8 times. In Example 13, the silicone elastomer emulsion used, SILRES BS 45 manufactured by Wacker Asahi Kasei Silicone Co., Ltd., had a swelling degree in toluene calculated under the conditions described above of 10.8 times.

[0089] Comparative Example 1 An antifouling coating composition of Comparative Example 1 was obtained in the same manner as in Example 1, except that 20 parts by mass of polyether-modified silicone oil (trade name "KF-6017", HLB: 5.0, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of Liquid Mixture 1A. The antifouling coating composition of Comparative Example 1 was produced by Production Method B described above.

[0090] Comparative Example 2 An antifouling coating composition of Comparative Example 2 was obtained in the same manner as in Example 1, except that 20 parts by mass of polyether-modified silicone oil (trade name "KF-6020", HLB: 4.0, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of Liquid Mixture 1A. The antifouling coating composition of Comparative Example 2 was produced by Production Method B described above.

[0091] Comparative Example 3 An antifouling coating composition of Comparative Example 3 was obtained in the same manner as in Example 1, except that 20 parts by mass of polyether-modified silicone oil (trade name "KF-6015", HLB: 5.0, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of Liquid Mixture 1A. The antifouling coating composition of Comparative Example 3 was produced by Production Method B described above.

[0092] (Average particle size of emulsion particles) The average particle size of the emulsion particles contained in each antifouling coating composition of the Examples and Comparative Examples was measured using a laser scattering diffraction particle size distribution analyzer "MT3300EX II" manufactured by Microtrac Bell Corporation.

[0093] (Evaluation of Antifouling Properties) Each of the antifouling coating compositions of the Examples and Comparative Examples was applied to a polyethylene fishing net by dip coating and allowed to dry at room temperature for 24 hours. The fishing net was fixed to a 45 x 35 cm frame and immersed in the underwater portion of a raft in Mikawa Bay, Aichi Prefecture, an area of ​​seawater with high aquatic life activity, for a real seawater test. Furthermore, for blank correction, as described below, a fishing net not treated with the antifouling coating composition was also subjected to the same real seawater test. Note that the test periods for each example shown in Table 1 and each example shown in Table 2 differ.

[0094] After the test period in actual seawater (3 months), photographs of the fishing nets were taken from above, and the adhesion area (%) of aquatic organisms on the fishing nets was visually evaluated. Evaluation was performed on a 20-point scale, with 20 representing an adhesion area of ​​0% of the fishing net by aquatic organisms and 0 representing 100% (adhesion to the entire fishing net). Because the ease with which aquatic organisms adhere to fishing nets varies depending on the season and period of the test, the antifouling properties were evaluated using blank-corrected values. First, the values ​​of a fishing net (A) dip-coated with the antifouling coating composition and a fishing net (B) not treated with the antifouling coating composition were evaluated on the 20-point scale, and then the blank-corrected value was calculated using the following formula: (blank-corrected value) = (value of A) - (value of B). The closer the blank-corrected value is to 20, the higher the antifouling properties, and the closer it is to 0, the lower the antifouling properties.

[0095] Each example shown in Table 1 was also evaluated (judged) according to the following criteria: ⊚: Area of ​​adhesion of aquatic organisms is 0% ◯: Area of ​​adhesion of aquatic organisms is more than 0 and less than 10% △: Area of ​​adhesion of aquatic organisms is more than 10 and less than 50% ×: Area of ​​adhesion of aquatic organisms is 50% or more

[0096] The compositions and evaluation results of the antifouling coating compositions of the Examples and Comparative Examples are summarized in Tables 1 and 2. As mentioned above, the tables show the proportion of each component when the resin solid content mass of the silicone elastomer emulsion is taken as 100 parts by mass. For the hydrophobic silicone oil emulsion, the proportion is shown converted to its solid content mass. Blank spaces in the tables indicate that the corresponding component was not included or that the corresponding item was not measured.

[0097]

[0098]

[0099] The polyether-modified silicone oils used in the examples and comparative examples are shown in Table 3. Note that "-" in the table indicates that the details of the corresponding item are unknown.

[0100]

[0101] As shown in Tables 1 and 2, the antifouling coating compositions of Examples 1 to 15, which contained an elastomer emulsion resin that is a water-dispersible elastomer resin and a hydrophilic silicone oil having an HLB of 6 or more, produced coating films with excellent long-lasting antifouling properties. Furthermore, the antifouling coating compositions of Examples 1 to 15 did not use a solvent-based resin, and therefore there were no concerns about adverse effects on the environment or human body. On the other hand, the antifouling coating compositions of Comparative Examples 1 to 3, which contained an elastomer emulsion resin but no hydrophilic silicone oil having an HLB of 6 or more, produced coating films with poor long-lasting antifouling properties.

[0102] According to the present invention, it is possible to provide an antifouling coating composition that exhibits excellent antifouling properties and has no adverse effects on the environment or human body.

[0103] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on Japanese patent applications filed on March 27, 2024 (Patent Application No. 2024-051861) and December 27, 2024 (Patent Application No. 2024-232381), the contents of which are incorporated herein by reference.

Claims

1. An antifouling coating composition comprising a water-dispersible elastomer resin and a hydrophilic silicone oil having an HLB of 6 or more.

2. The antifouling coating composition according to claim 1, wherein the water-dispersible elastomer resin comprises an elastomer emulsion resin.

3. The antifouling coating composition according to claim 2, wherein the elastomer emulsion resin contains a silicone elastomer.

4. The antifouling coating composition according to claim 1, wherein the hydrophilic silicone oil having an HLB of 6 or more has a weight average molecular weight of 200 to 100,000.

5. The antifouling coating composition according to claim 1, wherein the hydrophilic silicone oil having an HLB of 6 or more includes a polyether-modified silicone oil having a polyoxyalkylene group in the side chain.

6. The antifouling coating composition according to claim 1, further comprising a hydrophilic silicone oil having an HLB of 1 or more and less than 6.

7. The antifouling coating composition according to claim 6, wherein the hydrophilic silicone oil having an HLB of 1 or more but less than 6 has a weight average molecular weight of 200 to 100,000.

8. The antifouling coating composition according to claim 6, wherein the hydrophilic silicone oil having an HLB of 1 or more and less than 6 includes a polyether-modified silicone oil having a polyoxyalkylene group in the side chain.

9. The antifouling coating composition of claim 1, further comprising a hydrophobic silicone oil.

10. The antifouling coating composition according to claim 1, which contains emulsion particles, the average particle size D50 of which is 0.01 to 200 μm.

11. A coating film formed from the antifouling coating composition according to any one of claims 1 to 10.

12. An article having the coating film of claim 11.

13. The article of claim 12, wherein the article is a textile.

14. A method for producing the antifouling coating composition according to any one of claims 1 to 10, comprising mixing a first liquid containing at least a water-dispersible elastomer resin with a second liquid containing at least a hydrophilic silicone oil having an HLB of 6 or more.

15. The method for producing an antifouling coating composition according to claim 14, wherein the second liquid further comprises a hydrophobic silicone oil.

16. The method for producing an antifouling coating composition according to claim 14, wherein the second liquid is added dropwise to the first liquid and mixed.

17. The method for producing an antifouling coating composition according to claim 14, wherein the first liquid is added dropwise to the second liquid and mixed.

18. The method for producing an antifouling coating composition according to claim 14, wherein the second liquid is an emulsified liquid.

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