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

Abstract

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

Description

Technical Field

[0001] This invention relates to antifouling coating compositions, coating films, articles, and methods for manufacturing antifouling coating compositions. Background Technology

[0002] Underwater structures such as ships can harbor and breed aquatic organisms, including barnacles, oysters, mussels, hydroids, slugs, sea squirts, bryozoans, sea lettuce, sea lettuce, and epiphytic diatoms, at their water-contact points. This can lead to several problems: increased fluid resistance and decreased thermal conductivity, resulting in reduced mechanical performance; and the spread of these organisms overseas. Furthermore, removing these organisms requires significant manpower and time, leading to economic losses.

[0003] Similarly, for fibrous products used in water, such as fishing nets and ropes, aquatic organisms sometimes attach to and reproduce at the parts that come into contact with water. Fishing nets may experience the following problems: the mesh of the net may become clogged by the attached aquatic organisms, causing poor water flow, resulting in mass deaths of farmed fish due to lack of oxygen, or infectious diseases that prevent them from being sold, causing serious damage.

[0004] Previously, to prevent the attachment of these aquatic organisms, antifouling coating compositions were used, which incorporated copper-based or non-copper-based antifouling agents into resins. However, due to concerns about environmental impact, in recent years, antifouling coating compositions containing exudative antifouling components such as silicone oil have begun to be used instead of highly toxic copper-based antifouling agents.

[0005] For example, Patent Document 1 describes an organosilicon copolymer and an antifouling coating film formed from an antifouling coating composition containing the copolymer as a paint, an underwater structure covered by the antifouling coating film, and a ship whose surface is covered by such an antifouling coating film.

[0006] Existing technical documents Patent documents Patent Document 1: International Publication No. 2011 / 074620 Summary of the Invention

[0007] The problem that the invention aims to solve However, the antifouling coating composition described in Patent Document 1 is a so-called solvent-based antifouling coating composition formed by dissolving an organosilicon copolymer in an organic solvent, which still raises concerns about its environmental impact. Furthermore, since the organic solvent evaporates during the drying process to form a coating film, there are also concerns about the health of operators.

[0008] In view of the above, one object of this disclosure is to provide a stain-resistant coating composition that exhibits excellent stain resistance and has no adverse effects on the environment or human body.

[0009] Methods for solving problems The antifouling coating composition disclosed herein comprises a water-dispersible elastomer resin and a hydrophilic silicone oil with an HLB of 6 or higher.

[0010] Additionally, according to this disclosure, a coating film formed from the aforementioned antifouling coating composition is provided.

[0011] In addition, articles having the aforementioned coating are provided according to this disclosure.

[0012] In addition, the method for manufacturing the antifouling coating composition of this disclosure is a method for manufacturing the aforementioned antifouling coating composition, which includes mixing a first liquid containing at least a water-dispersible elastomer resin with a second liquid containing at least a hydrophilic silicone oil with an HLB of 6 or more.

[0013] Invention Effects The antifouling coating composition disclosed herein exhibits excellent antifouling properties and has no adverse effects on the environment or human body, and is therefore useful as an antifouling coating composition. Detailed Implementation

[0014] The embodiments of the present invention will be described in detail below, but the present invention is not limited to these embodiments.

[0015] In addition, in this specification, the use of expressions such as "~" is used to express numerical or physical property values ​​that include the values ​​before and after it.

[0016] In addition, in this specification, the various ratios and proportions (parts, percentages, etc.) based on mass have the same meaning as the various ratios and proportions based on weight.

[0017] <Antifouling Coating Composition> The antifouling coating composition of this embodiment comprises a water-dispersible elastomer resin and a hydrophilic silicone oil with an HLB of 6 or higher.

[0018] [Water-dispersible elastomer resin] The antifouling coating composition of this embodiment contains a water-dispersible elastomer resin.

[0019] Here, the water-dispersible elastomer resin (water-dispersible elastomer resin) can be: a resin (elastomer emulsion resin) obtained by dispersing an elastomer resin in an aqueous solvent using a dispersant (emulsifier) ​​such as a surfactant; or a resin obtained by introducing anionic, cationic, or nonionic groups of water-dispersible hydrophilic groups into an elastomer resin to form a self-emulsifier, etc. The antifouling coating composition of this embodiment, which includes a water-dispersible elastomer resin, is water-based, therefore there is no concern about adverse effects on the environment or human health.

[0020] There are no particular restrictions on the elastomer resin used; any suitable elastomer can be used. Examples of elastomers include silicone elastomers, polyurethane elastomers, acrylic elastomers, rubber-like polymers, vinyl chloride elastomers, vinyl acetate elastomers, polyamide elastomers, polyethylene elastomers, styrene elastomers, butadiene elastomers, etc. Elastomer resins can be used alone or in combination.

[0021] Preferably, the elastomer is a silicone elastomer, a polyurethane elastomer, an acrylic elastomer, a vinyl chloride elastomer, a vinyl acetate elastomer, a styrene elastomer, or a polyamide elastomer, and more preferably a silicone elastomer.

[0022] Examples of silicone elastomers include addition-type silicone elastomers, condensation-type silicone elastomers, and UV-curable silicone elastomers.

[0023] In this embodiment, an elastomer emulsion resin is preferably used among water-dispersible elastomer resins.

[0024] Here, elastomeric emulsion resin is also referred to as emulsion-type elastomeric resin, meaning that the elastomeric resin is dispersed in an emulsion in an aqueous solvent. It should be noted that, for example, emulsion-type silicone elastomers are also referred to as silicone elastomer emulsion resins.

[0025] It should be noted 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 called an "elastomer emulsion".

[0026] Here, aqueous solvent refers to water or a mixed solvent with water as the main component. Examples of solvents other than water in the mixed solvent include one or more selected from various organic solvents (such as lower alcohols) that can be uniformly mixed 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.

[0027] The elastomer emulsion is preferably an emulsion of an elastomer selected from silicone elastomers, polyurethane elastomers, acrylic elastomers, vinyl chloride elastomers, vinyl acetate elastomers, styrene elastomers and polyamide elastomers, and more preferably an emulsion of silicone elastomers (silicone elastomer emulsion).

[0028] In one embodiment, the silicone emulsion (silicone emulsion) is a liquid containing a main agent (base polymer, silicone emulsion) and a crosslinking agent, and may also contain a catalyst such as a tin compound if desired. The main agent (base polymer) is an organopolysiloxane having at least two curing reactive groups bonded to silicon atoms in one molecule, preferably emulsified and dispersed in water. Examples of curing reactive groups include hydrolyzable groups such as hydroxyl and alkoxy groups, with alkoxy groups being preferred. Examples of crosslinking agents include ethyl silicate, propyl silicate, methyltrimethoxysilane, and methyltriethoxysilane. Using these main agents (base polymers) and crosslinking agents, and catalysts added as desired, a condensation reaction is carried out to form a silicone resin.

[0029] Alternatively, as an alternative, elastomer emulsions using elastomers other than silicone elastomers may also contain a base agent (basic polymer) and a crosslinking agent, and may also contain catalysts such as tin compounds if necessary.

[0030] The swelling degree of the organosilicon emulsion resin and other 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.

[0031] Here, the swelling degree of the elastomeric emulsion resin is an indicator of the amount of solvent absorbed by the cross-linked elastomeric emulsion resin, and is therefore related to the compatibility between the elastomeric emulsion resin and the silicone oil. When the swelling degree of the elastomeric emulsion resin is 1.1 times or more, the elastomeric emulsion resin and the silicone oil are easily mixed, and this is preferred.

[0032] In addition, there is no particular limit to the upper limit of the swelling degree of elastomeric emulsion resins; for example, it can be less than 50 times, less than 40 times, or less than 30 times.

[0033] It should be noted that the swelling degree (times) of the elastomer emulsion resin is calculated using the following formula.

[0034] Swelling degree (times) = (mass of solvent before drying during gel component determination) ÷ (weight of gel component (mass after drying)) Here, the methods for determining the "mass of the gel component before solvent drying" and the "mass of the gel component (mass after drying)" in the above calculation formula are shown below.

[0035] (Measurement Method) Using a coating applicator, an elastomer emulsion was applied to the surface of a PET film (product name "Lumirror", manufactured by Toray Industries, Inc.) measuring 2 cm long × 2 cm wide × 0.75 cm thick. After standing at 23°C (room temperature) for 3 days, it was dried in an oven at 80°C for 60 minutes to form a coating film. Next, approximately 0.1 g of test piece was collected from the formed coating film, wrapped in a polytetrafluoroethylene porous sheet (average pore size 0.2 μm, trade name "NTF1122", manufactured by Nitto Denko Corporation), and then tied with kite string to obtain the test sample. The mass of the obtained test sample (mass C before impregnation) was then measured. Mass C before impregnation is the total mass of the test piece, the polytetrafluoroethylene porous sheet, and the kite string. Separately, the combined mass of the polytetrafluoroethylene porous sheet and the kite string, i.e., the bag mass B, was measured beforehand. Next, the sample was placed in a 50 mL container filled with toluene and allowed to stand at 23°C for 7 days. After standing, the sample was removed from the container, and the mass D of the sample containing solvent was measured. Then, it was transferred to an aluminum cup and dried in a desiccator at 130°C for 2 hours to remove the toluene. The mass of the dried sample (mass A after impregnation) was then measured.

[0036] Furthermore, the mass obtained by subtracting the "bag mass B" from the "mass D of the sample containing solvent" is set as the "mass of the solvent before drying during gel composition determination".

[0037] In addition, the mass obtained by subtracting the "bag mass B" from the "mass of the dried test sample (mass after impregnation A)" is set as the "mass of the gel component (mass after drying)".

[0038] Examples of 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 WackerAsahikasei Silicone Co., Ltd.; DOWSIL IE-7170 manufactured by Dow Chemical Japan Co., Ltd.; and COATSIL DRI manufactured by Momentive Performance Materials Japan Co., Ltd.

[0039] Regarding the proportion of water-dispersible elastomer resin in the antifouling coating composition of this embodiment, it is preferably 40 to 80% by mass, more preferably 50 to 70% by mass, relative to the total amount of non-volatile components in the antifouling coating composition.

[0040] Furthermore, when the antifouling coating composition of this embodiment contains an elastomer emulsion resin as a water-dispersible elastomer resin, the proportion of the elastomer emulsion resin in the antifouling coating composition is preferably 40 to 80% by mass, more preferably 50 to 70% by mass, relative to the total amount of non-volatile components in the antifouling coating composition.

[0041] Silicone oil Examples of silicone oils include: dimethyl silicone oils in which all substituents bonded to the Si group of a polysiloxane are methyl; methylphenyl silicone oils obtained by replacing some of the methyl groups with phenyl groups; amino-modified silicone oils obtained by replacing monoamines, diamines, or amino-polyether groups; epoxy-modified silicone oils obtained by replacing epoxy groups, alicyclic epoxy groups, epoxy-polyether groups, or epoxy-aryl groups; hydroxymethyl-modified silicone oils obtained by replacing hydroxymethyl groups; mercapto-modified silicone oils obtained by replacing mercapto groups; carboxyl-modified silicone oils obtained by replacing carboxyl groups; methacryl-modified silicone oils obtained by replacing methacryl groups; polyether-modified silicone oils obtained by replacing polyether groups; long-chain alkyl-modified silicone oils obtained by replacing long-chain alkyl groups or long-chain alkyl-aryl groups; higher fatty acid-modified silicone oils obtained by replacing higher fatty acid ester groups; fluoroalkyl-modified silicone oils obtained by replacing fluoroalkyl groups; and so on.

[0042] It should be noted that in this publication, hydrophilic silicone oil refers to silicone oil with an HLB of 1 or higher, and hydrophobic silicone oil refers to silicone oil with an HLB of less than 1.

[0043] HLB refers to the hydrophilic-lipophilic balance, which is a numerical representation of the balance between the hydrophilicity and lipophilicity of an oil. It is short for the Value of Hydrophile and Liophile Balance. Specifically, HLB can be calculated, for example, using the following formula.

[0044] HLB value = (sum of the mass percentage of hydrophilic groups (oxyethylene units, OH groups) in the molecule) / 5 [Hydrophilic silicone oil with an HLB rating of 6 or higher] 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 higher (hereinafter, "also referred to as high HLB hydrophilic silicone oil").

[0045] High HLB hydrophilic silicone oils exhibit high hydrophilicity, thus resulting in high stability when mixed with water-dispersible elastomer resins (in the form of antifouling coating compositions). Consequently, when the antifouling coating composition is dried to form a film, a highly uniform film can be obtained, exhibiting excellent antifouling properties.

[0046] Here, the HLB of the high HLB hydrophilic silicone oil is 6 or more, preferably 7 or more, and even more preferably 8 or more.

[0047] On the other hand, if the HLB of a high-HLB hydrophilic silicone oil becomes too high, the amount of oil seeping out of the coating becomes excessive, which can be detrimental from the perspective of long-term antifouling effect. Therefore, the HLB of a high-HLB hydrophilic silicone oil is preferably 18 or less, more preferably 15 or less, and even more preferably 13 or less.

[0048] As a 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.

[0049] Examples of hydrophilic silicone oils include silicone oils that are co-modified with hydrophilic groups and hydrophobic groups such as alkyl groups (polyether-modified silicone oil, polyglycerol-modified silicone oil, polyether, etc.). In these hydrophilic silicone oils, the hydrophilic groups of polyether-modified silicone oil, polyglycerol-modified silicone oil, and polyether can be terminally capped with hydroxyl groups or alkyl ester groups such as methyl or methyl ester groups.

[0050] 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 with siloxane bonds in their main chain and one or more polyoxyalkylene groups as substituents. The main chain can also form rings.

[0051] The polyoxyalkylene groups in polyether-modified silicone oils can be bonded at any suitable position. For example, the polyoxyalkylene groups can be bonded to both ends of the main chain, to a single end of the main chain, or to a side chain. From the viewpoint of antifouling, polyether-modified silicone oils with polyoxyalkylene groups bonded to side chains (side-chain type polyether-modified silicone oils) are preferred.

[0052] Examples of polyoxyalkylene compounds include polyoxyethylene (PEO), polyoxypropylene (PPO), and polyoxybutylene (PBO). From the viewpoint of antifouling properties, polyoxyethylene (PEO) and polyoxypropylene (PPO) are preferred, and polyoxyethylene (PEO) is more preferred.

[0053] The polyoxyalkylene bonds to polysiloxanes can have identical or different structures within the molecule.

[0054] In side-chain polyether-modified silicone oils, the number of repetitions of the polyoxyalkylene oxides in the side chains is preferably 1 to 300, more preferably 1 to 250, even more preferably 1 to 200, even more preferably 1 to 100, and particularly preferably 1 to 50.

[0055] From the viewpoint of oil penetration, 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 penetration, 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.

[0056] As a 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.

[0057] It should be noted that the weight-average molecular weight (Mw) of hydrophilic silicone oils can be determined using GPC (gel permeation chromatography). The specific apparatus and conditions for GPC determination are shown below.

[0058] Sample preparation: The sample was prepared into a 0.5 wt% THF eluent and allowed to stand overnight. The solution was filtered through a 0.45 μm membrane filter, and the filtrate was subjected to GPC analysis.

[0059] • Apparatus: Waters, Alliance • Column: TSKgel SuperHZM-H ×2 Column temperature: 40℃ • Elution buffer: THF • Flow rate: 0.2 mL / min Injection volume: 30μL • Detector: Differential Refractive Index (RI) • Standard sample: Agilent, polystyrene (PS) As a high HLB hydrophilic silicone oil, an appropriate silicone oil with an HLB value of 6 or higher can be selected from the above-mentioned hydrophilic silicone oils. It should be noted that the high HLB hydrophilic silicone oil used can be a single type or two or more.

[0060] As a high HLB hydrophilic silicone oil, a polyether-modified silicone oil with an HLB of 6 or higher is preferred. Examples of polyether-modified silicone oils with an HLB of 6 or higher include those manufactured by Shin-Etsu Chemical Industry 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: 7.0), "KF353" (HLB: 10.0), "KF354L" (HLB: 16.0), "KF355A" (HLB: 12.0), "KF615A" (HLB: 10.0), "KF-64 0" (HLB: 14.0), "KF-642" (HLB: 12.0), "KF-643" (HLB: 14.0), "KF-644" (HLB: 11.0), "KF-6204" (HLB: 10.0), Dow Side-chain (linear) polyether modified silicone oils such as "DOWSIL SH 3746" (HLB: 16.0), "VORASURF SH 193Fluid" (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, and "WACKER L 066" (HLB: 13.6) manufactured by Wacker Asahikasei Silicone Co., Ltd.

[0061] In the antifouling coating composition of this embodiment, the content ratio of high HLB hydrophilic silicone oil relative to 100 parts by weight of water-dispersible elastomer resin (hereinafter, the mass of the solid component of the water-dispersible elastomer resin is converted to 100 parts by weight) is preferably 1 to 30 parts by weight, more preferably 3 to 20 parts by weight, and even more preferably 5 to 15 parts by weight. When the content ratio of high HLB hydrophilic silicone oil is within the above range, the antifouling effect of the antifouling coating composition can be more fully presented.

[0062] [Hydrophilic silicone oil with an HLB value of 1 or higher and less than 6] Furthermore, the antifouling coating composition of this embodiment preferably includes, in addition to a hydrophilic silicone oil with an HLB value of 6 or higher (high HLB hydrophilic silicone oil), a hydrophilic silicone oil with an HLB value of 1 or higher but less than 6 (hereinafter also referred to as "low HLB hydrophilic silicone oil"). By including both high HLB hydrophilic silicone oil and low HLB hydrophilic silicone oil in the antifouling coating composition, the stability of the coating film formed using this antifouling coating composition is improved. Furthermore, this is also preferred from the viewpoint of long-term sustainability of the antifouling effect.

[0063] As a low-HLB hydrophilic silicone oil, an appropriate amount of silicone oil with an HLB value of 1 or higher and less than 6 can be selected from the above-mentioned hydrophilic silicone oils. It should be noted that the low-HLB hydrophilic silicone oil used can be a single type or two or more types.

[0064] In addition, the HLB content of low HLB hydrophilic silicone oil is preferably 2 or more, and more preferably 4 or more.

[0065] As a low-HLB hydrophilic silicone oil, a polyether-modified silicone oil with an HLB value of 1 or higher and less than 6 is preferred. Examples of polyether-modified silicone oils with an HLB value of 1 or higher and less than 6 include, for example, those manufactured by Shin-Etsu Chemical Industry Co., Ltd. under the trade names "KF-6020" (HLB: 4.0), "KF-6015" (HLB: 5.0), "KF-6017" (HLB: 5.0), "KF945" (HLB: 4.0), "X-22-4515" (HLB: 5.0), etc., and those manufactured by Dow Chemical Japan Co., Ltd., such as "DOWSIL FZ-5609" (HLB: 4.0) and "DOWSIL Y-7006" (HLB: 2.0).

[0066] In the antifouling coating composition of this embodiment, from the viewpoint of coating stability and long-term sustainability of antifouling effect, the content ratio of low HLB hydrophilic silicone oil relative to 100 parts by weight of water-dispersible elastomer resin (hereinafter, the mass of the solid component of the water-dispersible elastomer resin is converted to 100 parts by weight) is preferably 1 to 30 parts by weight, more preferably 3 to 20 parts by weight, and even more preferably 5 to 15 parts by weight.

[0067] Furthermore, when using both high-HLB hydrophilic silicone oil and low-HLB hydrophilic silicone oil, from the viewpoint of coating stability and long-term sustainability of antifouling effect, the preferred ratio of the two components, based on mass, is high-HLB hydrophilic silicone oil / low-HLB hydrophilic silicone oil = 5 / 25 to 25 / 5, more preferably 10 / 20 to 20 / 10.

[0068] [Hydrophobic silicone oil] Furthermore, the antifouling coating composition of this embodiment preferably includes both a hydrophilic silicone oil with an HLB value of 6 or higher (high HLB hydrophilic silicone oil) and a hydrophobic silicone oil. By including both high HLB hydrophilic silicone oil and hydrophobic silicone oil in the antifouling coating composition, the oil exudation from the coating film formed by the antifouling coating composition in water is promoted. Alternatively, in this case, the antifouling coating composition may also include a hydrophilic silicone oil with an HLB value of 1 or higher but less than 6 (low HLB hydrophilic silicone oil).

[0069] Examples of hydrophobic silicone oils include non-reactive silicone oils such as polysiloxanes, whose main chain is formed by siloxane bonds. These oils may contain substituents, and the main chain may form rings. Examples include linear silicone oils and modified silicone oils (excluding polyether-modified silicone oils). The substituents in linear silicone oils are preferably alkyl or phenyl groups.

[0070] Specifically, examples include dimethyl silicone oils containing terminal hydroxyl groups (either at one or both ends of the polysiloxane), dimethyl silicone oils where all substituents bonded to the Si of the polysiloxane are methyl, phenylmethyl silicone oils (phenyl-modified silicone oils) obtained by replacing some of the methyl groups with phenyl groups, amino-modified silicone oils, epoxy-modified silicone oils, and long-chain alkyl-modified silicone oils. It should be noted that the hydrophobic silicone oil used can be a single type or two or more.

[0071] In this embodiment, an emulsion-type hydrophobic silicone oil (hydrophobic silicone oil emulsion) can be used as the hydrophobic silicone oil. Here, emulsion-type hydrophobic silicone oil refers to an emulsion in which the hydrophobic silicone oil is dispersed in water. Emulsion-type hydrophobic silicone oil has the advantage of being easily mixed with elastomer emulsions.

[0072] Examples of hydrophobic silicone oils include "KF-96-100CS" manufactured by Shin-Etsu Chemical Industry Co., Ltd., and "WACKER AK100" manufactured by Wacker Asahikasei Silicone Co., Ltd.

[0073] 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 Industry Co., Ltd.

[0074] In the antifouling coating composition of this embodiment, from the viewpoint of appropriate oil penetration, the content ratio of hydrophobic silicone oil (solid component mass) relative to 100 parts by mass of water-dispersible elastomer resin (hereinafter, the resin solid component mass of water-dispersible elastomer resin is converted to 100 parts by mass) 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.

[0075] Furthermore, when using hydrophilic silicone oil and hydrophobic silicone oil, the content ratio of the two components, based on the mass of the solid components, is preferably 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).

[0076] [water] The antifouling coating composition of this embodiment typically contains water. For example, an elastomer emulsion is a form in which an elastomer resin is dispersed in water. By incorporating the elastomer emulsion into the antifouling coating composition, the water in the elastomer emulsion is contained within the antifouling coating composition. Furthermore, when a hydrophobic silicone oil emulsion is incorporated into the antifouling coating composition, the water in the hydrophobic silicone oil emulsion is contained within the antifouling coating composition. Additionally, water may be further added to the antifouling coating composition of this embodiment.

[0077] [Other ingredients] The antifouling coating composition according to this embodiment may contain any other suitable additives without impairing the effects of this disclosure. Such other additives include, for example, various components commonly used in conventional coating compositions, such as ultraviolet absorbers (as weathering agents), antifouling agents, plasticizing resins, surface conditioners, surfactants, thixotropic agents, coloring pigments, extender pigments, and other film-forming components. Furthermore, the antifouling coating composition according to this embodiment may contain resins other than the aforementioned water-dispersible elastomer resins and oils other than the aforementioned silicone oils, without impairing the effects of this disclosure.

[0078] The antifouling coating composition involved in this embodiment preferably includes a surfactant, preferably including at least one of anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.

[0079] As an anionic surfactant, any suitable anionic surfactant may be used within the scope of not impairing the effects of the present invention. Examples of such anionic surfactants include, for instance, alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, polyoxyalkylene alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, α-olefin sulfonates, α-sulfonyl fatty acids or esters, alkyl sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, amino acid surfactants, N-acyl amino acid surfactants, alkyl or alkenyl phosphates or their salts, etc. There may be only one anionic surfactant or two or more.

[0080] As a nonionic surfactant, any suitable nonionic surfactant may be used within the scope that does not impair the effects of the present invention. Examples of such nonionic surfactants include, for instance, polyoxyalkylene alkyl or alkenyl ethers, polyoxyethylene alkylphenyl ethers, higher fatty acid alkanolamides or their epoxy alkyl adducts, sucrose fatty acid esters, alkyl glycosides, fatty acid glycerol monoesters, alkylamine oxides, etc. There may be only one nonionic surfactant or two or more.

[0081] As a cationic surfactant, any suitable cationic surfactant can be used within the scope of not impairing the effects of the present invention. Examples of such cationic surfactants include quaternary ammonium salts. There may be only one cationic surfactant or two or more.

[0082] As an amphoteric surfactant, any suitable amphoteric surfactant can be used within the scope of not impairing the effects of the present invention. Examples of such amphoteric surfactants include carboxyl-type or sulfobetaine-type amphoteric surfactants. There may be only one amphoteric surfactant or two or more.

[0083] As a surfactant, anionic surfactants or nonionic surfactants are preferred. Specifically, examples of anionic surfactants and nonionic surfactants can be cited below.

[0084] <Anionic Surfactants> Alkyl sulfate salts: Emal 10PT • Polyoxyethylene alkyl ether sulfate salt: Latemul E-118B Alkylbenzene sulfonates: Neopelex GS • Polyoxyalkylene ether ammonium sulfate: Latemul PD-104 <Nonionic Surfactants> • Polyoxyethylene alkyl ether: EMULGEN 1150S-60 • Polyoxyethylene alkylene alkyl ethers: EMULGEN LS-114 • Polyoxyethylene styrene phenyl ether: EMULGEN B-66 • Polyoxyethylene polyoxypropylene glycol: EMULGEN PP-290 • Polyoxyethylene glycerol ether: EMULGEN GE-1 Polyoxyethylene diglyceride: EMULGEN G2E-4 • Polyoxyalkylene ether: Latemul PD-430 Sorbitol fatty acid esters: 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.

[0085] When the antifouling coating composition of this embodiment contains a surfactant, the surfactant content relative to 100 parts by weight of the water-dispersible resin (hereinafter, the mass of the solid component of the water-dispersible resin is converted to 100 parts by weight) is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more. Furthermore, the surfactant content is preferably 5 parts by weight or less, more preferably 1 part by weight or less.

[0086] As a preferred embodiment, the surfactant content relative to 100 parts by weight of the water-dispersible resin is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 1 parts by weight.

[0087] It should be noted that the antifouling coating composition according to this embodiment may contain the above-mentioned additives, but depending on the application of the antifouling coating composition and from the viewpoint of reducing environmental impact, it is sometimes preferable not to include them, depending on the type of additive. For example, from the viewpoint of reducing environmental impact, it is preferable not to include the above-mentioned antifouling agents.

[0088] Furthermore, the antifouling coating composition according to this embodiment preferably does not contain organic solvents, and more preferably does not contain organic solvents. It should be noted that "substantially does not contain organic solvents" means that the content of organic solvents relative to the total amount of the antifouling coating composition is less than 1% by mass.

[0089] The antifouling coating composition according to this embodiment preferably contains emulsion particles. From the viewpoint of antifouling properties and liquid stability, the average particle size (D50) of the emulsion particles is preferably 0.01 μm or more, more preferably 0.1 μm or more. In addition, from the viewpoint of antifouling properties and liquid stability, the average particle size (D50) of the emulsion particles is preferably 200 μm or less, more preferably 100 μm or less.

[0090] As a preferred embodiment, the average particle size (D50) of the emulsion particles is preferably 0.01 to 200 μm, more preferably 0.1 to 100 μm.

[0091] Furthermore, from the viewpoint of antifouling and liquid stability, the average particle size (D90) of the emulsion particles is preferably 0.01 μm or more, more preferably 0.1 μm or more. Additionally, from the viewpoint of antifouling 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.

[0092] As 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 even more preferably 0.1 to 100 μm.

[0093] It should be noted that, in this specification, emulsion particles refer to the dispersed phase in the emulsion. Furthermore, the average particle size of the emulsion particles refers to the median particle size (D50) based on volume, determined using laser diffraction and scattering. D50 refers to the diameter of the total 50% of particles smaller than this value, and D90 refers to the diameter of the total 90% of particles smaller than this value.

[0094] Examples of emulsion particles included in the antifouling coating composition according to this embodiment include emulsion particles containing a water-dispersible resin dispersed in an aqueous solvent (typically particles containing a water-dispersible resin and a dispersant such as a surfactant), and emulsion particles containing hydrophobic silicone oil and hydrophilic silicone oil (typically particles containing a hydrophobic silicone oil, a hydrophilic silicone oil and a dispersant such as a surfactant).

[0095] Regarding the antifouling coating composition according to this embodiment, from the viewpoint of achieving excellent antifouling properties and easy cleaning, the water contact angle of the coating film formed by the antifouling coating composition is preferably 70° or less, more preferably 60° or less, and even more preferably 55° or less. There is no particular limitation on the lower limit of the water contact angle of the coating film; it can be 0° or more, 10° or more, 20° or more, or 25° or more.

[0096] The water contact angle of the coating film formed by the antifouling coating composition according to this embodiment was determined by the following method: using an applicator, the antifouling coating composition was applied to the surface of a PET film (product name "Lumirror", manufactured by Toray Industries, Inc.) with a length of 30cm × width of 25cm × thickness of 0.75cm, and allowed to dry to form a coating film with a thickness of 100μm. A test sample was prepared, and 2μl of water droplets were added to the surface of the coating film. The water contact angle of the coating film surface was measured after 5 minutes using a contact angle meter (DropMaster, manufactured by Kyowa Interface Science Co., Ltd.) based on the static drop method of JIS R3257.

[0097] <Coating> The coating of this embodiment is formed from the above-described antifouling coating composition, which is useful for preventing the attachment of aquatic organisms.

[0098] For example, on a suitable article as the substrate, the coating composition of this embodiment is applied by a known coating method such as spraying, brushing, rolling, spraying, roller, dipping, or coating machine. For example, it is 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, thereby forming a coating on the surface of the article.

[0099] The coating thickness can be any appropriate thickness depending on the application and operating environment. The preferred coating thickness is 10 μm to 5000 μm. By keeping the coating thickness within this range, the antifouling effect can be fully and effectively maintained over a long period. If the coating thickness is thinner than 10 μm, the effective antifouling period will be shorter, which may render it impractical. If the coating thickness is thicker than 5000 μm, the coating preparation will be time-consuming, which may also render it impractical.

[0100] <Items> The article of this embodiment has a coating film formed by the above-described antifouling coating composition.

[0101] As an item, there are no particular limitations; for example, examples include underwater structures, fishing nets, or ropes and other fibrous products.

[0102] As fiber products, examples include silk, ropes, cables, nets, fishing nets, fish traps and other fishing gear, woven fabrics, knitted fabrics, non-woven fabrics and other textiles used in underwater structures.

[0103] In addition, examples of underwater structures include ships, buoys, port equipment, offshore oilfield equipment, waterways for power plant cooling water, floating debris passages, sluice gates, underwater sensors, underwater cameras, underwater lighting, underwater pumps, underwater piping, underwater power generation equipment (e.g., tidal power generation equipment, ocean current power generation equipment, wave power generation equipment, offshore wind power generation equipment), underwater rotating bodies such as propellers, and various underwater mooring devices such as underwater cables.

[0104] <Method for manufacturing antifouling coating composition> The method for manufacturing the antifouling coating composition of this embodiment is not particularly limited. For example, it can be manufactured by mixing a first liquid containing at least a water-dispersible elastomer resin with a second liquid containing at least a hydrophilic silicone oil with an HLB of 6 or more.

[0105] Here, the first liquid, which at least contains a water-dispersible elastomer resin, is, for example, an elastomer emulsion in which the elastomer resin is dispersed in an aqueous solvent by a dispersant (emulsifier); or a liquid formed by dispersing a self-emulsifier of the elastomer resin in an aqueous solvent. Additionally, if the antifouling coating composition contains a hydrophobic silicone oil, the first liquid is, for example, a mixture of an elastomer emulsion and a hydrophobic silicone oil emulsion.

[0106] Furthermore, the second liquid, which contains at least a hydrophilic silicone oil with an HLB value of 6 or higher (high HLB hydrophilic silicone oil), may be formed solely from the high HLB hydrophilic silicone oil, or it may contain other components besides the high HLB hydrophilic silicone oil. Examples of other components include, for instance, hydrophilic silicone oils with an HLB value of 1 or higher but less than 6 (low HLB hydrophilic silicone oil). Additionally, the second liquid may also contain a hydrophobic silicone oil.

[0107] The following describes the specific methods for manufacturing the antifouling coating composition of this embodiment, namely manufacturing method A and manufacturing method B.

[0108] In manufacturing method A and manufacturing method B, the first liquid is, for example, an aqueous liquid, and the second liquid is, for example, a non-aqueous liquid.

[0109] When mixing the first liquid and the second liquid, for example, the second liquid can be added dropwise to the first liquid to mix them (this method is referred to as "manufacturing method A"). In manufacturing method A, it is preferable to add the second liquid dropwise while stirring the first liquid.

[0110] Alternatively, when mixing the first liquid and the second liquid, the first liquid can be added dropwise to the second liquid to achieve mixing (this method is referred to as "manufacturing method B"). In manufacturing method B, it is preferable to add the first liquid dropwise while stirring the second liquid.

[0111] Furthermore, although the detailed reasons are not yet certain, from the viewpoint of the antifouling properties of the coating film formed by the manufactured antifouling coating composition, manufacturing method A is preferred over manufacturing method A and manufacturing method B.

[0112] Next, another specific method for manufacturing the antifouling coating composition of this embodiment, namely manufacturing method C, will be described.

[0113] In manufacturing method C, the first liquid and the second liquid are, for example, aqueous liquids.

[0114] Furthermore, in manufacturing method C, the second liquid can be an emulsified liquid. The antifouling coating composition of this embodiment can also be manufactured by mixing the first liquid with the emulsified second liquid (this method is referred to as "manufacturing method C"). In manufacturing method C, the first liquid can be mixed by adding the second liquid dropwise, or the second liquid can be mixed by adding the first liquid dropwise. When mixing the first liquid by adding the second liquid dropwise, it is preferable to add the second liquid dropwise while stirring the first liquid. Similarly, when mixing the second liquid by adding the first liquid dropwise, it is preferable to add the first liquid dropwise while stirring the second liquid.

[0115] In manufacturing method C, when preparing the second liquid, for example, hydrophilic silicone oil is added dropwise to water or water containing a dispersant (emulsifier) ​​such as a surfactant and mixed to emulsify it, thereby obtaining the second liquid. The dropwise addition of the hydrophilic silicone oil is preferably carried out in the presence of stirred water or water containing a dispersant.

[0116] Alternatively, if the second liquid contains both hydrophobic and hydrophilic silicone oil, for example, hydrophobic silicone oil can be added dropwise to the second liquid containing hydrophilic silicone oil and mixed to emulsify it. The addition of the hydrophobic silicone oil is preferably carried out while the second liquid containing hydrophilic silicone oil is being stirred.

[0117] As hydrophobic silicone oil, hydrophilic silicone oil, and surfactant, the descriptions of the hydrophobic silicone oil, hydrophilic silicone oil, and surfactant in the above-mentioned antifouling coating composition can be directly cited.

[0118] As explained above, the following matters are described in this instruction manual.

[0119] (1) An antifouling coating composition comprising a water-dispersible elastomer resin and a hydrophilic silicone oil with an HLB of 6 or higher.

[0120] (2) The antifouling coating composition as described in (1), wherein the aforementioned water-dispersible elastomer resin comprises an elastomer emulsion resin.

[0121] (3) The antifouling coating composition as described in (2), wherein the aforementioned elastomeric emulsion resin comprises an organosilicon elastomer.

[0122] (4) The antifouling coating composition as described in (1), wherein the weight-average molecular weight of the aforementioned hydrophilic silicone oil with an HLB of 6 or higher is 200 to 100,000.

[0123] (5) The antifouling coating composition as described in (1), wherein the aforementioned hydrophilic silicone oil with an HLB of 6 or higher is contained in a polyether-modified silicone oil having a polyoxyalkylene side chain.

[0124] (6) The antifouling coating composition as described in any one of (1) to (5) further comprises a hydrophilic silicone oil having an HLB of 1 or more and less than 6.

[0125] (7) The antifouling coating composition as described in (6), wherein the weight-average molecular weight of the aforementioned hydrophilic silicone oil having an HLB of 1 or more and less than 6 is 200 to 100,000.

[0126] (8) The antifouling coating composition as claimed in (6) or (7), wherein the aforementioned hydrophilic silicone oil with an HLB of 1 or more and less than 6 is contained in a polyether-modified silicone oil having a polyoxyalkylene side chain.

[0127] (9) The antifouling coating composition as described in any one of (1) to (8) further comprises a hydrophobic silicone oil.

[0128] (10) The antifouling coating composition as described in any one of (1) to (9), wherein the antifouling coating composition contains emulsion particles having an average particle size D50 of 0.01 to 200 μm.

[0129] (11) A coating film formed from any one of (1) to (10) antifouling coating compositions.

[0130] (12) An article having the coating described in (11).

[0131] (13) The article as described in (12), wherein the aforementioned article is a fiber product.

[0132] (14) A method for manufacturing an antifouling coating composition, wherein the method is the same as that for manufacturing any one of (1) to (10) antifouling coating compositions. The method includes 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 higher.

[0133] (15) A method for manufacturing an antifouling coating composition as described in (14), wherein the aforementioned second liquid further comprises a hydrophobic silicone oil.

[0134] (16) A method for manufacturing an antifouling coating composition as described in (14) or (15), wherein the first liquid is added dropwise to the second liquid and mixed.

[0135] (17) A method for manufacturing an antifouling coating composition as described in (14) or (15), wherein the first liquid is added dropwise to the second liquid and mixed.

[0136] (18) The method of manufacturing the antifouling coating composition as claimed in (14) or (15), wherein the aforementioned second liquid is an emulsified liquid.

[0137] Example The present invention will be specifically described below through examples, but the present invention is not limited to these examples in any way.

[0138] (Example 1) The following specifies the proportions of each component when the mass of the solid resin component in the silicone elastomer emulsion is set to 100 parts by mass. Furthermore, the proportions of the hydrophobic silicone oil emulsion, calculated based on the mass of the solid component, are specified. The same applies to the examples and comparative examples other than Example 1 described below.

[0139] Five parts by weight of polyether-modified silicone oil (trade name "KF-6020", HLB: 4.0, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and 15 parts by weight of polyether-modified silicone oil (trade name "KF-6011", HLB: 12.0, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) were placed in a container and stirred for 5 minutes at room temperature (23°C) using a homogenizer to obtain liquid mixture 1A. Next, 100 parts by weight of silicone elastomer emulsion (self-crosslinking silicone resin, trade name "KM-9772", manufactured by Shin-Etsu Chemical Industry Co., Ltd.) (the solid component mass of the resin is set as 100 parts by weight) and 50 parts by weight of dimethyl silicone oil emulsion (trade name "KM-860A", manufactured by Shin-Etsu Chemical Industry Co., Ltd.) (converted to solid component mass) were placed in another container and stirred for 5 minutes at room temperature (23°C) using a homogenizer to obtain liquid mixture 1B. Next, while stirring liquid mixture 1A in the container, liquid mixture 1B is added and dissolved and dispersed uniformly to obtain the antifouling coating composition of Example 1. The antifouling coating composition of Example 1 is manufactured using manufacturing method B described above.

[0140] It should be noted that, regarding "KM-9772" used as an organosilicon elastomer emulsion, the swelling degree in toluene calculated under the above conditions is 10.4 times.

[0141] (Examples 2-3) Except for changing the ratio of polyether-modified silicone oil (trade name "KF-6020", HLB: 4.0, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) to polyether-modified silicone oil (trade name "KF-6011", HLB: 12.0, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as shown in Table 1, the same procedure was followed as in Example 1 to obtain the antifouling coating compositions of Examples 2 and 3. The antifouling coating compositions of Examples 2 and 3 were manufactured using manufacturing method B described above.

[0142] (Example 4) 100 parts by weight of a silicone elastomer emulsion (self-crosslinking silicone resin, trade name "KM-9772", manufactured by Shin-Etsu Chemical Industry Co., Ltd.) (the solid component mass of the resin is set as 100 parts by weight) and 50 parts by weight of a dimethyl silicone oil emulsion (trade name "KM-860A", manufactured by Shin-Etsu Chemical Industry Co., Ltd.) (converted to solid component mass) were placed in a container and stirred for 5 minutes at room temperature (23°C) using a homogenizer to obtain liquid mixture 4A. Next, 15 parts by weight of a polyether modified silicone oil (trade name "KF-6020", HLB: 4.0, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and 5 parts by weight of a polyether modified silicone oil (trade name "KF-6011", HLB: 12.0, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) were placed in another container and stirred for 5 minutes at room temperature (23°C) using a homogenizer to obtain liquid mixture 4B. Next, while stirring liquid mixture 4A in the container, liquid mixture 4B is added dropwise and allowed to dissolve and disperse uniformly, thereby obtaining the antifouling coating composition of Example 4. The antifouling coating composition of Example 4 was manufactured using manufacturing method A described above.

[0143] (Example 5) Except for using 20 parts by weight of polyether-modified silicone oil (trade name "KF-6024", HLB: 10.0, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) instead of liquid mixture 1A, the same procedure as in Example 1 was followed to obtain the antifouling coating composition of Example 5. The antifouling coating composition of Example 5 was manufactured using the manufacturing method B described above.

[0144] (Example 6) Except for using 20 parts by weight of polyether-modified silicone oil (trade name "KF-6011", HLB: 12.0, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) instead of liquid mixture 1A, the same procedure as in Example 1 was followed to obtain the antifouling coating composition of Example 6. The antifouling coating composition of Example 6 was manufactured using the manufacturing method B described above.

[0145] (Example 7) Except for replacing 50 parts by weight (based on solid component weight) of dimethyl silicone oil emulsion (trade name "KM-860A", manufactured by Shin-Etsu Chemical Industry Co., Ltd.), 50 parts by weight of dimethyl silicone oil emulsion (trade name "KM-9782", manufactured by Shin-Etsu Chemical Industry Co., Ltd.) were used, the same procedure as in Example 4 was followed to obtain the antifouling coating composition of Example 7. The antifouling coating composition of Example 7 was manufactured using the manufacturing method A described above.

[0146] (Example 8) Except for replacing 50 parts by weight (based on solid component weight) of dimethyl silicone oil emulsion (trade name "KM-860A", manufactured by Shin-Etsu Chemical Industry Co., Ltd.) with 50 parts by weight of phenyl-modified silicone oil emulsion (trade name "KM-9739", manufactured by Shin-Etsu Chemical Industry Co., Ltd.), the same procedure as in Example 4 was followed to obtain the antifouling coating composition of Example 8. The antifouling coating composition of Example 8 was manufactured using the manufacturing method A described above.

[0147] (Example 9) Except for replacing 50 parts by weight (based on solid component weight) of dimethyl silicone oil emulsion (trade name "KM-860A", manufactured by Shin-Etsu Chemical Industry Co., Ltd.) with 50 parts by weight (based on solid component weight), the same procedure as in Example 4 was followed to obtain the antifouling coating composition of Example 9. The antifouling coating composition of Example 9 was manufactured using the manufacturing method A described above.

[0148] (Example 10) Except for replacing 50 parts by weight (based on solid component weight) of dimethyl silicone oil emulsion (trade name "KM-860A", manufactured by Shin-Etsu Chemical Industry Co., Ltd.) with 50 parts by weight (based on solid component weight), the same procedure as in Example 4 was followed to obtain the antifouling coating composition of Example 10. The antifouling coating composition of Example 10 was manufactured using the manufacturing method A described above.

[0149] (Example 11) Add 75 parts by weight of ion-exchanged water and 0.5 parts by weight of anionic surfactant (trade name "Latemul E-118B", manufactured by Kao Corporation) to a container, and stir for 5 minutes at room temperature (23°C) using a homogenizer to obtain water containing surfactant.

[0150] Next, while stirring the water containing the surfactant in a container at room temperature (23°C) using a homogenizer, 20 parts by weight of polyether modified silicone oil (trade name "DOWSIL SH 8400", HLB: 8.0, manufactured by Dow Chemical Japan Co., Ltd.) were added dropwise and dissolved and dispersed uniformly to obtain a liquid mixture.

[0151] Next, while stirring the above liquid mixture in the container, 50 parts by weight of dimethyl silicone oil (trade name "KF-96-100CS", manufactured by Shin-Etsu Chemical Industry Co., Ltd.) were added dropwise and emulsified to obtain liquid mixture 11A.

[0152] Next, while stirring the liquid mixture 11A in a container using a homogenizer, 100 parts by weight of an organosilicon elastomer emulsion (self-crosslinking organosilicon resin, trade name "KM-9772", manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was added dropwise (the mass of the solid resin component is set as 100 parts by weight) and allowed to dissolve and disperse uniformly, thereby obtaining the antifouling coating composition of Example 11. The antifouling coating composition of Example 11 was manufactured using the manufacturing method C described above.

[0153] (Example 12) to (Example 15) Except for changing the types of silicone elastomer emulsion, dimethyl silicone oil, and polyether-modified silicone oil as described in Table 2, the antifouling coating compositions of Examples 12 to 15 were obtained by operating in the same manner as in Example 11. The antifouling coating compositions of Examples 12 to 15 were manufactured using the manufacturing method C described above.

[0154] It should be noted that in Examples 12 and 14, the swelling degree in toluene of COATSIL DRI manufactured by Momentive Performance Materials Japan Co., Ltd., used as a silicone elastomer emulsion, was 4.8 times under the above conditions.

[0155] In addition, in Example 13, the swelling degree in toluene of SILRES BS 45 manufactured by Wacker AsahikaseiSilicone Co., Ltd., which was used as a silicone elastomer emulsion, was calculated to be 10.8 times under the above conditions.

[0156] (Comparative Example 1) Except for using 20 parts by weight of polyether-modified silicone oil (trade name "KF-6017", HLB: 5.0, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) instead of liquid mixture 1A, the same procedure as in Example 1 was followed to obtain the antifouling coating composition of Comparative Example 1. The antifouling coating composition of Comparative Example 1 was manufactured using the manufacturing method B described above.

[0157] (Comparative Example 2) Except for using 20 parts by weight of polyether-modified silicone oil (trade name "KF-6020", HLB: 4.0, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) instead of liquid mixture 1A, the same procedure as in Example 1 was followed to obtain the antifouling coating composition of Comparative Example 2. The antifouling coating composition of Comparative Example 2 was manufactured using the manufacturing method B described above.

[0158] (Comparative Example 3) Except for using 20 parts by weight of polyether-modified silicone oil (trade name "KF-6015", HLB: 5.0, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) instead of liquid mixture 1A, the same procedure as in Example 1 was followed to obtain the antifouling coating composition of Comparative Example 3. The antifouling coating composition of Comparative Example 3 was manufactured using the manufacturing method B described above.

[0159] (Average particle size of emulsion particles) The average particle size of the emulsion particles contained in the antifouling coating compositions of the Examples and Comparative Examples was determined using a laser scattering diffraction particle size distribution measuring device “MT3300EX II” manufactured by MicrotracBEL Co., Ltd.

[0160] (Evaluation of stain resistance) The antifouling coating compositions of the examples and comparative examples were applied to polyethylene fishing nets and dried at room temperature for 24 hours. The fishing nets were fixed to a 45×35cm frame and immersed in seawater using a raft in Mikawa Bay, Aichi Prefecture, a water area with active aquatic life, for a field seawater test. Additionally, for blank correction described later, fishing nets not treated with the antifouling coating composition were also subjected to the same field seawater test. It should be noted that the test periods differed in the examples shown in Table 1 and Table 2.

[0161] After 3 months of field seawater trials, photographs of the fishing nets were taken from above, and the percentage of aquatic organisms attached to the nets was visually evaluated. A value of 0% for aquatic organisms attached to the nets was set as 20, and a value of 100% (attached to the entire net) was set as 0, with 20 levels of evaluation.

[0162] Depending on the season and duration of the experiment, the ease with which aquatic organisms attach to the fishing nets varies; therefore, the antifouling performance is evaluated using blank-corrected values. First, the values ​​of the fishing net (A) coated with the antifouling paint composition and the fishing net (B) not treated with the antifouling paint composition are evaluated using the aforementioned 20 levels. Then, the blank-corrected values ​​are calculated using the following formula.

[0163] (Value after blank correction) = (Value of A) - (Value of B) It should be noted that the closer the blank-corrected value is to 20, the higher the stain resistance; the closer it is to 0, the lower the stain resistance.

[0164] It should be noted that the examples shown in Table 1 are also evaluated (judged) according to the following criteria.

[0165] ◎: The attachment area of ​​aquatic organisms is 0%. ○: The surface area of ​​aquatic organisms attached to the surface is greater than 0 and less than 10%. △: The attachment area of ​​aquatic organisms exceeds 10% but is less than 50%. ×: The attachment area of ​​aquatic organisms is more than 50%. The composition and evaluation results of the antifouling coating compositions of the Examples and Comparative Examples are summarized in Tables 1 and 2.

[0166] It should be noted that, as mentioned above, the table shows the proportions of each component when the mass of the solid resin component of the silicone elastomer emulsion is set to 100 parts by mass. Additionally, for hydrophobic silicone oil emulsions, the proportions are shown based on the mass of their solid components.

[0167] Additionally, blank columns in the table indicate that the corresponding ingredients are not present or that the corresponding items have not been measured.

[0168] [Table 1] [Table 2] The polyether-modified silicone oils used in the examples and comparative examples are shown in Table 3. It should be noted that "-" in the table indicates that details of the corresponding item are unknown.

[0169] [Table 3] As shown in Tables 1 and 2, antifouling coating compositions of Examples 1 to 15, which contain an elastomeric emulsion resin as a water-dispersible elastomeric resin and a hydrophilic silicone oil with an HLB value of 6 or higher, can yield coatings with excellent long-term antifouling properties. Furthermore, the antifouling coating compositions of Examples 1 to 15 do not use solvent-based resins, and there are no concerns about adverse effects on the environment or human health.

[0170] On the other hand, the antifouling coating compositions of Comparative Examples 1 to 3, which contain elastomeric emulsion resin but not hydrophilic silicone oil with an HLB of 6 or higher, have poor long-term antifouling durability of the resulting coating film.

[0171] Industrial availability According to the present invention, a nonfouling coating composition that exhibits excellent antifouling properties and has no adverse effects on the environment or human body can be provided.

[0172] The present invention has been described in detail with reference to specific embodiments, but 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 invention.

[0173] This application is based on Japanese patent application No. 2024-051861 filed on March 27, 2024 and Japanese patent application No. 2024-232381 filed on December 27, 2024, 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 with an HLB of 6 or higher.

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 an organosilicon elastomer.

4. The antifouling coating composition according to claim 1, wherein, The weight-average molecular weight of the hydrophilic silicone oil with an HLB of 6 or higher is 200 to 100,000.

5. The antifouling coating composition according to claim 1, wherein, The hydrophilic silicone oil with an HLB of 6 or higher is a polyether-modified silicone oil having polyoxyalkylene side chains.

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

7. The antifouling coating composition of claim 6, wherein, The weight-average molecular weight of the hydrophilic silicone oil with an HLB of 1 or higher and less than 6 is 200 to 100,000.

8. The antifouling coating composition of claim 6, wherein, The hydrophilic silicone oil with an HLB of 1 or higher and less than 6 is included in polyether-modified silicone oils with polyoxyalkylene side chains.

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

10. The antifouling coating composition of claim 1, wherein, The antifouling coating composition contains emulsion particles with an average particle size D50 of 0.01 to 200 μm.

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

12. An article having the coating as claimed in claim 11.

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

14. A method for manufacturing an antifouling coating composition, wherein the method comprises manufacturing the antifouling coating composition according to any one of claims 1 to 10. The method includes 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 higher.

15. The method for manufacturing the antifouling coating composition as described in claim 14, wherein, The second liquid also contains hydrophobic silicone oil.

16. The method for manufacturing the antifouling coating composition as described in claim 14, wherein, The second liquid is added dropwise to the first liquid and mixed.

17. The method for manufacturing the antifouling coating composition as described in claim 14, wherein, The first liquid is added dropwise to the second liquid and mixed.

18. The method for manufacturing the antifouling coating composition as described in claim 14, wherein, The second liquid is an emulsified liquid.

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