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    • 专利摘要:
    A waterborne antifouling coating material composition according to one embodiment of the present invention includes: synthetic resin (A); at least one component (B) selected from a resin acid and a derivative thereof; flaky pigment (C) having an aspect ratio of 5 to 30; antifouling agent (D); and water (E), wherein a mass ratio (A) : (B) between the synthetic resin (A) and the component (B) is l : 0.1 to l : 4.
    公开号:NL2027791A
    申请号:NL2027791
    申请日:2021-03-22
    公开日:2021-10-20
    发明作者:Yamane Kiwamu；Harada Shotaro
    申请人:Chugoku Marine Paints；
    IPC主号:
    专利说明:

    [0001] [0001] One embodiment of the present invention relates to a waterborne antifouling coating material composition, an antifouling coating film, a substrate with an antifouling coating film, or a method for producing a substrate with an antifouling coating film. Description of the Related art
    [0002] [0002] Conventionally, binders for antifouling coating material, including oil resins, vinyl resins, (methjacrylic resins, and chlorinated rubber resins, have been used mainly; however, all of these have been solvent-diluted types. In recent years, from the viewpoint of environmental conservation and improvement of the coating work environment, it has been desired to make the antifouling coating material water-based (refer to, for example, JP $51-014936 A, JP 2009-173914 A, and JP 2003-277680 A). Citation List Patent Literature
    [0003] [0003] Patent Literature 1: JP S51-014936 A Patent Literature 2:JP 2009-173914 A Patent Literature 3: JP 2003-277680 A Summary
    [0004] [0004] Making the antifouling coating material water-based is effective in reducing the amount of volatile organic compounds (VOCs); however, the antifouling coating film formed from the waterborne antifouling coating material has a high affinity with water. Therefore, when such an antifouling coating film is immersed in seawater or fresh water, cracks easily occur, and the coating film finally collapses, making it difficult to exhibit antifouling performance over a long period of time. In order to exhibit sufficient antifouling performance, it is necessary to properly polishing the surface of the coating film and elute an antifouling agent. In addition, when cracks occur in
    [0005] [0005] One embodiment of the present invention provides a waterborne antifouling coating material composition capable of forming an antifouling coating film having excellent crack resistance and antifouling performance over a long period of time.
    [0006] [0006] As a result of intensive investigations to solve the above problem, the present inventors have found that the waterborne antifouling coating material composition described below can solve the above problem. That is, one embodiment of the present invention relates to the following [1] to [8].
    [0007] [0007]
    [1] [1] A waterborne antifouling coating material composition, including: synthetic resin (A); at least one component (B) selected from resin acid and a derivative thereof; flaky pigment (C) having an aspect ratio of 5 to 30; antifouling agent (D); and water (E), wherein a mass ratio between the synthetic resin (A) and the component (B) ((A) : (B))is 1:0.1to 1: 4. {0008] {2] The waterborne antifouling coating material composition according to [1], wherein the synthetic resin (A) is at least one selected from a (meth}acrylic resin, a styrene resin, another vinyl resin, an urethane resin, and a hydrolyzable resin. {0009]
    [3] [3] The waterborne antifouling coating material composition according to [1] or [2], wherein the flaky pigment (C) is mica having an aspect ratio of 5 to 30.
    [4] [4] The waterborne antifouling coating material composition according to any one of [1] to {3], wherein the component (B) is at least one selected from rosin and a derivative thereof.
    [0010] [0010]
    [5] [5] The waterborne antifouling coating material composition according to any one of [1] to {4}, wherein the component (B) is a component other than an alkali metal salt.
    [6] [6] An antifouling coating film formed from the waterborne antifouling coating material composition according to any one of {1} to [5].
    [0011] [0011]
    [7] [7] A substrate with an antifouling coating film, including: a substrate; and the antifouling coating film according to [6] provided on a surface of the substrate.
    [8] [8] A method for producing a substrate with an antifouling coating film, the method including: {1) applying or impregnating to a substrate the waterborne antifouling coating material composition according to any one of [1] to {5] to obtain an applied body or an impregnated body; and {2) drying the applied body or the impregnated body.
    [0012] [0012] One embodiment of the present invention can provide a waterborne antifouling coating material composition capable of forming an antifouling coating film having excellent crack resistance and antifouling performance for a long period of time. Detailed Description of Embodiments
    [0013] [0013] Hereinafter, one embodiment of the present invention will be described in detail. Each component described in the present description may be of a single type, or of two or more types. The term “polymer” means to include homopolymer and copolymer. The term “(meth}acrylate” is a generic term for acrylate and methacrylate. The same applies to, for example, (methacrylic acid.
    [0014] [0014] The term “structural unit derived from XX" means, for example, a structural unit represented by the following formula when XX is represented as A'A’C=CA’A* (C=Cis a polymerizable carbon-carbon double bond, and each of At to A‘ are atoms or groups bonded to the carbon atom).
    [0015] [0015] [Chemical Formula 1]
    [0016] [0016] [Waterborne antifouling coating material composition] The waterborne antifouling coating material composition of the present embodiment
    [0017] [0017] <Synthetic resin (A}> Examples of synthetic resin (A) include (meth)acrylic resin, styrene resin, other vinyl resin, urethane resin, and hydrolyzable resin. From the viewpoints such as easily forming an antifouling coating film having excellent crack resistance and antifouling performance over a long period of time, (meth)acrylic resin, styrene resin, other vinyl resin, and hydrolyzable resin are preferable, and (meth)acrylic resin, styrene resin, and hydrolyzable resin are more preferable. In addition, from the viewpoints such as allowing easy formation of an antifouling coating film having excellent crack resistance and easy availability as synthetic resin (A), (methacrylic resin and styrene resin are preferable.
    [0018] [0018] Examples of the (methacrylic resin include a homopolymer or copolymer of at least one monomer selected from (methacrylic acid and an ester thereof (hereinafter, also referred to as “{meth)acrylic monomer”), and a copolymer of the (meth}acrylic monomer and a monomer copolymerizable therewith (hereinafter, also referred to as “comonomer”).
    [0020] [0020] Examples of the comonomer include styrene, a-methylstyrene, vinyltoluene, vinyl acetate,
    [0021] [0021] When the {methjacrylic resin is a copolymer of a (meth)acrylic monomer and a comonomer, the amount of the structural unit derived from the (methacrylic monomer is preferably 20% by mass or more, more preferably 40% by mass or more, still more preferably 55% by mass or more, preferably 99.9% by mass or less, and more preferably 99.5% by mass or less; the amount of the structural unit derived from the comonomer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, preferably 80% by mass or less, more preferably 60% by mass or less, and still more preferably 45% by mass or less, based on the amount of all of the structural unit in the (meth)acrylic resin. The amount of each of the structural unit can be determined by, for example, nuclear magnetic resonance spectroscopy (NMR), pyrolysis gas chromatography mass spectrometry (Pyro-GC/MS).
    [0022] [0022] The (meth)acrylic resin is produced by appropriately selecting a (meth)acrylic monomer and, as necessary, a comonomer in consideration of, for example, the structural unit and weight average molecular weight, and then using a known method, for example, a solution radical polymerization method.
    [0023] [0023] Examples of the styrene resin include a homopolymer of styrene or a copolymer of styrene and a monomer copolymerizable therewith. Examples of the monomer copolymerizable with styrene include the above (meth)acrylic monomer, a-methylstyrene, vinyltoluene, vinyl acetate, vinyl propionate, maleic acid, itaconic acid, (meth)acrylic acid amide, acrylonitrile, methacrylonitrile, and butadiene. The copolymer of a (meth}acrylic monomer and styrene is classified as styrene resin when the amount of the structural unit derived from styrene is larger than the amount of the structural unit derived from the (meth)acrylic monomer, and is classified as a (methjacrylic resin when the amount of the structural unit derived from the (meth)acrylic monomer is equal to or larger than the amount of the structural unit derived from styrene, based onthe amount of all of the structural unit in the resin (based on % by mass). The same applies to other resins.
    [0024] [0024] Examples of other vinyl resins include a homopolymer or copolymer of a vinyl compound such as vinyl chloride, vinyl acetate, and vinyl propionate, and a copolymer of the vinyl compound
    [0026] [0026] (Meth)acrylic resins, styrene resins, other vinyl resins, and urethane resins are typically insoluble resins that do not hydrate or undergo chemical reactions in seawater or fresh water (resins other than hydrolyzable resins).
    [0027] [0027] The silyl ester polymer is preferably, for example, a silyl ester polymer having structural unit (a-1) derived from polymerizable monomer (al) represented by Formula (al). Structural unit (a-1) included in the silyl ester polymer may be of a single type, or of two or more types.
    [0028] [0028] [Chemical Formula 2] RY RZ 3 | | | = ie Es (al) 0 R° R°
    [0029] [0029] Each of symbol in Formula (al) will be described below.
    [0030] [0030] Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group, and a 2-ethylhexyl group, and the isopropyl group is preferable.
    [0031] [0031] nis an integer of 0 or 1 or more, preferably 0. The upper limit of n may be, for example,
    [0032] [0032] The polymerizable monomer (al) is preferably trialkylsilyl (meth}acrylate, alkyldiarylsilyl (methacrylate, and aryldialkylsilyl (meth)acrylate, and more preferably trialkylsilyl (meth)acrylate. Examples of the trialkylsilyl (methacrylate include trimethylsilyl (meth)acrylate, triethylsily! (meth)acrylate, tripropylsilyl (meth}acrylate, triisopropyisilyl (meth)acrylate, tributylsilyl (methjacrylate, triisobutylsilyl (methacrylate, tri-sec-butylsilyl (meth)acrylate, tri-2-ethylhexylsilyl (meth)acrylate, and butyldiisopropylsilyl (methacrylate. In addition, examples of polymerizable monomer (al) include a polymerizable monomer having n of 2 or more in Formula (al) such as 1- (meth)acryloyloxynonamethyltetrasiloxane. Of these, from the viewpoints such as allowing easy formation of an antifouling coating film having crack resistance and antifouling property in an excellent balance, a trialkylsilyl (meth)acrylate having a branched alkyl group is preferable, a triisopropylsilyl (meth)acrylate is more preferable, and triisopropylsilyl methacrylate is particularly preferable.
    [0033] [0033] The silyl ester polymer can further have structural unit (a-2) derived from another ethylenically unsaturated monomer (hereinafter, also referred to as “monomer (a2)").
    [0034] [0034]
    [0036] [0036] The ratio of the structural unit (a-2) in the silyl ester polymer is preferably 20% by mass or more, more preferably 25% by mass or more, still more preferably 30% by mass or more, preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 55% by mass or less.
    [0037] [0037] Zinc (meth)acrylic resin is represented by Formula (a21) or Formula (a22). The zinc (meth)acrylic resin is a salt formed by zinc and an organic, and is a resin having a structure formed by combining zinc and carboxylic acid.
    [0038] [0038] Formula (a21): R*-CO0-Zn-00C-R Formula (a22): R3-COO-Zn-OOC-RP In Formula (a21) and Formula (a22), R3 each independently represents a base resin and R® each independently represents a monovalent organic group having 1 to 20 carbon atoms. in addition, instead of Zn, those including polyvalent metals such as Cu, Ca, Mg, Fe, and Ni may be used in combination.
    [0039] [0039] Base resin R , which is the base of the zinc (meth)acrylic resin, is a resin having an acid value of typically about 1 to 300 mgKOH/g. In order to produce the zinc (meth)acrylic resin represented by Formula (a21) and Formula (322) by using such a base resin, for example, a divalent metal (Zn) oxide or hydroxide may be reacted in an amount of about 0.1 to 1 mol with 1 mol of a resin having a carboxy group in the molecule in the presence of a small amount of water.
    [0040] [0040] Examples of the resin having a carboxy group in the molecule include polyester,
    [0041] [0041] Specific examples of the zinc (meth)acrylic resin and the production method thereof include the specific examples and the production method described in JP HO8-209005 A and JP HO5-171066 A.
    [0042] [0042] From the viewpoint of obtaining an antifouling coating material composition having excellent film-forming property, the weight average molecular weight (Mw) of synthetic resin (A} is preferably 1,000 or more, more preferably 2,000 or more, preferably 1,000,000 or less, and more preferably 700,000 or less. Mw can be measured by gel permeation chromatography (GPC). When the aqueous dispersion of synthetic resin (A) is a so-called self-crosslinking resin that becomes high molecular weight in evaporating a solvent, the upper limit of the above Mw is not limited.
    [0043] [0043] From the viewpoints such as easy formation of an antifouling coating film having crack resistance and antifouling property in a good balance, the glass transition temperature (Tg} of synthetic resin (A) is preferably -50°C or more, preferably 90°C or less, more preferably 60°C or less, and still more preferably 40°C or less. Tg can be measured by a differential scanning calorimetry (DSC).
    [0044] [0044] One or more of synthetic resin (A} can be used.
    [0045] [0045] The solid content of the composition (I) and each component (for example, aqueous dispersion) means the heating residue after drying in an incubator at 108°C for 3 hours.
    [0046] [0046] The aqueous dispersion of synthetic resin (A) is a dispersion in which synthetic resin (A) is dispersed in a dispersion medium including water (hereinafter, also referred to as “aqueous medium”). The aqueous medium is not particularly limited as long as it includes water; however, the content of water in the aqueous medium is preferably 50 to 100% by mass, and more preferably 60 to 100% by mass.
    [0047] [0047] The aqueous medium may include a medium other than water, and examples of such a medium include acetone, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyt alcohol, n- butyl alcohol, isobutyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 1-methoxy- 2-propanol, 1-ethoxy-2-propanol, diacetone alcohol, dioxane, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monohexyl ether. One or more of these can be used.
    [0048] [0048] An aqueous emulsion of synthetic resin (A) can be prepared by emulsifying synthetic resin (A} with a surfactant to form an emulsion. In addition, an emulsion can be directly prepared by emulsion polymerization of the monomer forming synthetic resin (A). The surfactant is not particularly limited, and can be appropriately selected from a cationic surfactant, an anionic surfactant, and a nonionic surfactant.
    [0049] [0049] <Component (B)> Component (B) is at least one selected from the resin acid and derivatives thereof. The component (B} contributes to, for example, the adjustment of the polishing rate of an antifouling coating film obtained and the improvement of long-term antifouling property. {0050] Examples of derivatives of the resin acid include hydrogenated bodies, disproportionated bodies, and metal salts of the resin acid. Examples of the metal salt include alkali metal salts such as sodium salt and potassium salt, zinc salt, copper salt, aluminum salt, magnesium salt, calcium
    [0051] [0051] Examples of the component (B) include rosins such as gum rosin, wood rosin, and tall oil rosin; rosin derivatives such as hydrogenated rosin, disproportionated rosin, and rosin metal salt; and copal resin and derivatives thereof. In addition, a rosin resin acid that is a component included in rosin, a copal resin acid that is a component included in copal resin, and derivatives thereof may be used as component (B). Examples of the rosin resin acid and their derivatives include abietic acid, neoavietic acid, dehydroabietic acid, secodehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, pimaric acid, isopimaric acid, levopimaric acid, paramatrinic acid, and sandara-copimaric acid. Examples of the copal resin acid and derivatives thereof include agathene dicarboxylic acid and agathene dicarboxylic acid monoalkyl ester. At least one selected from rosin and a derivative thereof (rosin derivative) is preferable as component (B). {0052] In order to develop antifouling performance, it is effective to add at least one component (B) selected from the resin acid and a derivative thereof, and particularly of components (B), selecting components other than alkali metal salts can exhibit more excellent antifouling performance. When synthetic resin (A) is a hydrolyzable resin, of components (B), a metal salt other than the alkali metal salt is preferable. {0053] One or more of components (B} can be used.
    [0054] [0054] In composition (1), the mass ratio between synthetic resin (A} to component (B) ((A) : (B)) is1:0.1to 1:4, preferably 1:0.4to1:3.8, and more preferably 1: 0.8 to 1: 3.5. Composition (I) including synthetic resin (A) and component (B) in the mass ratio described above and including flaky pigment (C) having an aspect ratio in the range described later can form an antifouling coating film that is particularly excellent in crack resistance and long-term antifouling property (particularly long-term dynamic antifouling property). In the evaluation of antifouling property, in the case of the static antifouling property test, cracks occur in the coating film, peeling does not easily occur, and the antifouling property may not deteriorate; however, in the case of the dynamic antifouling property test, cracks occur in the coating film, peeling easily occurs, and the
    [0055] [0055] In the production of the composition {I}, an aqueous dispersion of component (B}, particularly an aqueous emulsion is preferably used. The content of the solid content of component (B} in the aqueous dispersion is preferably 20% by mass or more, more preferably 35% by mass or more, preferably 80% by mass or less, and more preferably 65% by mass or less, from the viewpoint of workability in the production of coating material composition.
    [0056] [0056] The aqueous dispersion of the component (B) is a dispersion in which component (B) is dispersed in an aqueous medium. The aqueous medium is not particularly limited as long as it includes water; however, the content of water in the aqueous medium is preferably 50 to 100% by mass, and more preferably 60 to 100% by mass. Specific examples of media other than water in the aqueous medium are as described above.
    [0057] [0057] <Flaky pigment (C)> Flaky pigment (C) is a pigment having an aspect ratio of 5 to 30. The aspect ratio of flaky pigment (C) is preferably 7 or more, more preferably 10 or more, preferably 27 or less, and more preferably 25 or less. Using flaky pigment (C} having an aspect ratio in this range improves the crack resistance of the antifouling coating film that has been immersed in seawater or fresh water, and thereby peeling of the coating film hardly occurs and stable antifouling performance can be exhibited for a long period of time. It is assumed that flaky pigment (C) in the coating film prevents the infiltration of water and relaxes the internal stress of the coating film to improve the crack resistance.
    [0058] [0058] The aspect ratio of flaky pigment (C) can be calculated by measuring the thickness of flaky pigment (C) and the maximum length on the main surface thereof for any 100 pieces and by determining the average value of these ratios (maximum length on the main surface / thickness) with using a scanning electron microscope (SEM), for example, “TM 3030 Plus Miniscope” (manufactured by Hitachi High-Technologies Corporation, desktop SEM).
    [0059] [0059] The thickness of flaky pigment (C) can be measured by observing the horizontal direction
    [0060] [0060] The median diameter (d50) of flaky pigment {C) is preferably 1 um or more, more preferably 10 um or more, preferably 100 um or less, and more preferably 60 um or less. The median diameter can be measured by using a laser scattering diffraction type particle size distribution measuring device, for example, “SALD 2200” (manufactured by Shimadzu Corporation).
    [0061] [0061] Flaky pigment {C} is not particularly limited, examples thereof include inorganic pigments having a plate-shaped structure having the above aspect ratio, specific examples thereof include mica, glass flakes, and aluminum flakes, and the mica is particularly preferable.
    [0062] [0062] One or more of flaky pigment (C) can be used. For example, a flaky pigment having an aspect ratio of 5 to 30 measured in advance may be blended in producing composition (1).
    [0063] [0063] <Antifouling agent (D)> Antifouling agent (D) may be any of organic and inorganic antifouling agents.
    [0064] [0064] Examples of the organic antifouling agent include: metal pyrithione (pyrithione compounds) such as copper pyrithione and zinc pyrithione; tetraalkylthiuramdisulfide such as tetramethylthiuramdisulfide; carbamate compounds such as zinc dimethyl dithio carbamate, zinc ethylene bisdithiocarbamate, and bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate;
    [0065] [0065] One or more of antifouling agents (D) can be used.
    [0066] [0066] <Water (E}> Composition (1) is a waterborne antifouling coating material composition. The “waterborne composition” refers to a composition including water. The content of water in composition (I} is preferably 5% by mass or more, more preferably 10% by mass or more, preferably 50% by mass or less, and more preferably 45% by mass or less.
    [0067] [0067] <Other components> As necessary, composition (I) may contain additives such as pigments other than flaky pigment (C) having an aspect ratio in the above range (for example, extender pigments and coloring pigments), pigment dispersing agent, antifoaming agent, thickening agent, antisettling agent, and film-forming agent, as long as the effect of the present invention is not impaired. One or more of the additives can be used.
    [0068] [0068] Examples of extender pigments include zinc oxide, talc, silica, mica, clay, potash feldspar,
    [0069] [0069] Various conventionally known organic and inorganic pigments can be used as the coloring pigment. Examples of the organic pigment include naphthol red and phthalocyanine blue. Examples of the inorganic pigment include carbon black, red iron oxide, titanium white (titanium oxide) and yellow iron oxide. The content of the coloring pigment is preferably 0.01 to 50% by mass, and more preferably 0.01 to 30% by mass, in 100% by mass of the solid content of composition (1).
    [0071] [0071] The antifoaming agent is preferably a material capable of suppressing the generation of foam during the production and/or coating application of the coating material composition, or a material capable of breaking the foam generated in the coating material composition. Examples of the antifoaming agent include silicone antifoaming agents and mineral oil antifoaming agents. The content of the antifoaming agent is preferably 0.01 to 2% by mass in 100% by mass of the solid content of composition (I).
    [0072] [0072] For example, a commercially available product that is generally marketed as a thickening agent can be used as the thickening agent. The commercially available product is not particularly limited, and examples thereof include an alkali thickening agent, a nonionic association thickening agent, a water-soluble polymer thickening agent, and a polyamide thickening agent. The content of the thickening agent is preferably 0.01 to 10% by mass in 100% by mass of the solid content of composition (I).
    [0073] [0073] The antisettling agent is preferably a material capable of suppressing pigment settling in
    [0074] [0074] Examples of the film-forming agent include conventionally known alcohols, glycol ethers, and esters, and examples thereof include alcohols such as alcohol having 1 to 3 carbon atoms such asisopropyl alcohol, and 2,2,4-trimethylpentanediol; glycol ethers such as ethylene glycol monobutyl ether, ethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol diethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol n-butyl ether; and esters such as 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate. The content of the film-forming agent is preferably 0.1 to 15% by mass, and more preferably 0.1 to 5% by mass, in 100% by mass of the total amount of composition (1). {0075] <Method for producing waterborne antifouling coating material composition> Composition (1) can be produced by appropriately using a known method. For example, the production can be performed by adding synthetic resin (A), component (B}, flaky pigment (C), antifouling agent (D), and the above other components as necessary to a mixing container at once or in any order, mixing each component by a known stirring/mixing means, and by dispersing or dissolving in water (E).
    [0076] [0076] In the production of composition {1}, the aqueous dispersion of synthetic resin (A) and the aqueous dispersion of component (B} are preferably used, from the viewpoint of workability in the production of the coating material composition.
    [0078] [0078] Composition (1) is preferably a low VOC coating material composition.
    [0079] [0079] The VOC content in the composition can be calculated from the following Formula (1) by using the following values of composition specific gravity and the heating residue. VOC content (g/L) = composition specific gravity x 1000 x (100 - heating residue - moisture content) / 100 … (1)
    [0080] [0080] Composition specific gravity (g/mL): a value calculated by filling a specific gravity cup having an internal volume of 100 mL with the composition under a temperature condition of 23°C and by weighing the composition.
    [0082] [0082] [Use of waterborne antifouling coating material composition] The antifouling coating film of the present embodiment (hereinafter, also referred to as “antifouling coat (J)") is formed from composition (I). The substrate with the antifouling coating film (hereinafter, also referred to as “antifouling substrate (K}”) of the present embodiment has a substrate and antifouling coat (J) provided on the surface of the substrate.
    [0083] [0083] The method for producing antifouling substrate (K} has a step (1} of applying or impregnating composition (1) to the substrate (object or object to be coated) to obtain an applied body or an impregnated body, and a step (2) of drying the applied body or the impregnated body.
    [0084] [0084] For example, a known method such as an air spray, an airless spray, a brush coating application, and a roller coating application can be used for applying.
    [0088] [0088] In producing antifouling substrate (K}, when the substrate is a fishing net or a steel plate, composition (I) may be directly applied to the surface of the substrate. When the substrate is a fishing net, the surface thereof may be impregnated with composition {I}. When the substrate is a steel plate, an undercoating material such as a rust inhibitor and/or a primer is applied to the surface of the substrate in advance to form a base layer, and then composition (I) may be applied to the surface of the base layer. In addition, for the purpose of repair, antifouling coat (J) may be further formed on the surface of the substrate on which antifouling coat (J) or the conventional antifouling coating film is formed, such as a steel plate having a deteriorated antifouling coating film.
    [0089] [0089] The thickness of antifouling coat (J) is not particularly limited, but is, for example, about 30 to 1000 um. When forming antifouling coat (J), there is a method in which the thickness of the antifouling coating film formed by once coating application is preferably 10 to 300 um, more preferably 30 to 200 um, and the number of applying times is once to multiple.
    [0091] [0091] Hereinafter, the present invention will be described in more detail based on examples and comparative examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, “parts” indicates “parts by mass”.
    [0092] [0092]
    [0093] [0093] <Aspect ratio of pigment> The aspect ratio of the pigment was calculated by using a scanning electron microscope (SEM) “TM 3030 Plus Miniscope” (manufactured by Hitachi High-Technologies Corporation, desktop SEM} to measure the thickness and the maximum length on the main surface for any 100 pieces of the pigment and to determine the average value of these ratios (maximum length on the main surface / thickness).
    [0094] [0094] The thickness of the pigment was measured by observing the horizontal direction of the main surface (the surface having the largest area} of the pigment, and the maximum length on the main surface of the pigment means the length of the diagonal line when the main surface is square, the diameter when the main surface is circular, and the length of the major axis when the main surface is elliptical.
    [0095] [0095] <Solid content> The solid content of the composition and each component mean the heating residue when dried in an incubator at 108°C for 3 hours. From this heating residue, the solid content (% by mass) of the composition and each component was calculated.
    [0096] [0096] [Production example 1] 53 parts of xylene were charged into a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen introduction tube, and a dropping funnel, and was heated under normal pressure until the temperature of xylene reached 85°C while xylene was stirred in a nitrogen atmosphere with a stirrer. A monomer mixture consisting of 60 parts of triisopropylsilylmethacrylate (TIPSMA), 20 parts of 2-methoxyethyl methacrylate (MEMA), 10 parts of methyl methacrylate (MMA), 10 parts of butyl acrylate (BA), and a part of 2,2'-azobis (2- methylbutyronitrile) (AMBN) was added dropwise into the reaction vessel over 2 hours by using a dropping funnel while maintaining the temperature of xylene in the reaction vessel at 85°C.
    [0097] [0097] Then, 0.5 parts of t-butyl peroxyoctoate was further added to the reaction vessel, the mixture was stirred with a stirrer for 2 hours under normal pressure while maintaining the liquid temperature in the reaction vessel at 85°C, the liquid temperature in the vessel was raised from 85°Cto 110°C and heated for 1 hour, 14 parts of xylene was added into the reaction vessel to lower the liquid temperature in the reaction vessel, stirring was stopped at the liquid temperature of 40°C, and thus a hydrolyzable polymer solution including a hydrolyzable copolymer was prepared.
    [0098] [0098] 200 parts of the hydrolyzable polymer solution that had been heated to 30°C and held were charged into a 500 ml plastic container, 14 parts of the heat-melted emulsifier (polyoxyethylene lauryl ether} was added thereto while stirring with a disperser, and dissolved and mixed uniformiy.
    [0099] [0099] Then, while stirring the obtained solution with a disperser, 60 parts of ion-exchanged water was added dropwise into the solution from the dropping funnel over 30 minutes and mixed uniformly. Moreover, while stirring the obtained solution with a disperser, 120 parts of ion- exchanged water was added dropwise into the solution from the dropping funnel over 1 hour, uniformly mixed, and subjected to phase inversion emulsification to provide emulsion 1 having a solid content of 45%.
    [0101] [0101]
    [0103] [0103] {Preparation of antifouling coating material composition] [Example 1] The antifouling coating material composition was prepared as follows.
    [0104] [0104] After dispersion, glass beads were removed from the mixture through a filtration net (opening: 80 mesh) to obtain a filtrate, and into the filtrate, 28 parts of New Coat TS-100 (synthetic resin, manufactured by Shin-Nakamura Chemical Co., Ltd.)}, 14 parts of Harsize NES-500 (resin acid, manufactured by Harima Chemicals, inc.), 0.5 parts of Adekanol UH-752 (thickening agent, manufactured by ADEKA Corporation), 2 parts of Kyowanol M (film-forming agent, manufactured by KH Neochem Co, Ltd.), and 0.5 parts of Butyl Cellosolve (film-forming agent, manufactured by KH Neochem Co. Ltd.) were added, and dispersed by using a disperser for 20
    [0105] [0105] [Examples 2 to 16 and Comparative Examples 1 to 6] An antifouling coating material composition was prepared in the same manner as in Example 1 except that the type and blending amount of each component were changed as shown in Table 1 and Table 3.
    [0106] [0106] [Evaluation of physical properties of antifouling coating material composition] The physical properties of the coating film formed by using the antifouling coating material compositions obtained in Examples and Comparative Examples were evaluated as follows. The results obtained are shown in Table 1 to Table 3.
    [0107] [0107] <Static antifouling property test> Epoxy anticorrosion coating material (trade name “Banno 500”, manufactured by Chugoku Marine Paints Ltd.) was applied onto a sandblasted steel plate (300 mm x 100 mm x 2.3 mm) by using an applicator, so that the dry film thickness was 150 um, and dried to form a cured coating film. Then, onto the cured coating film, epoxy binder coating material (trade name “Banno 500N”, manufactured by Chugoku Marine Paints Ltd.) was applied so that the dry film thickness was 100 um, and dried at 23°C for 1 day to produce a test plate.
    [0108] [0108] Then, onto the test plate (on the surface of the cured coating film of the epoxy binder coating material}, each antifouling coating material composition of examples or comparative examples shown in Table 1 to Table 3 was applied by using an applicator so that the dry film thickness was 150 um, dried at 23°C for 7 days to form an antifouling coating film, and thus test plate 1 with an antifouling coating film was produced.
    [0109] [0109] This test plate 1 with an antifouling coating film was suspended and immersed at a position about 2 m below the sea level off the coast of Hatsukaichi, Hiroshima prefecture, and placed in a stationary condition. 3 months and 12 months after the start of immersion, the area of marine organisms adhered on the antifouling coating film when the total area (test surface} of the antifouling coating film on the constantly submerged part of the test plate was 100% was measured, and the static antifouling property was evaluated based on the following evaluation criteria 1 and/or evaluation criteria 2.
    [0110] [0110]
    [0111] [0111] (Evaluation criteria 2) 3: area of marine organisms adhered was less than 35% with respect to the test surface. 2: area of the same was 35% or more and less than 80% with respect to the test surface. 1: area of the same was 80% or more with respect to the test surface.
    [0112] [0112] <Coating film crack resistance (water resistance} test> Test plate 2 with an antifouling coating film was produced in the same manner as test plate 1 with an antifouling coating film for the static antifouling property test, except that sandblasted steel plate (150 mm x 70 mm x 2.3 mm) was used instead of sandblasted steel plate (300 mm x 100 mm x 2.3 mm). Test plate 2 with an antifouling coating film was immersed in artificial seawater at 50°C, and 6 months after the start of immersion, the crack resistance of the coating film was evaluated based on the following evaluation criteria. {0113] (Evaluation criteria) 0: no coating films peeled off and there were no cracks. A: peeling was observed in small portions. X: peeling was observed in most portions.
    [0114] [0114] {Table 1]
    [0115] [0115] {Table 2] eee A a (A) [PRIMALTX-100 [| [| | | | | UltrasolN80 | [| [| | | (B) |HarsizeNES-745 | | [| | | | Hariestersk-37o0N [| [| | | | Formula) py [Zinebt | 4 | 4 | 4 [4 | | | tion Copper OmadinePowder | [| LL 13 [| 3 | (parts Selektope® LLL 04 | by mass) NovepermRedF5RK | 06 | 06 | 06 | 06 | 06 | 06 | femelle EE LL Calculat uy mass) # 8 5 eee [ian [ta [to [enen (mass ratio) Result months) evaluation criteria 1 months) evaluation criteria 1
    [0117] [0117] The details of the components used in the examples and comparative examples are as follows.
    -928- {Table 4] Acrylic acid ester copolymer emulsion, manufactured New Coat TS-100 by Shin-Nakamura Chemical Co, Ltd., solid content 50%, Tg: -35°C . Acrylic emulsion, manufactured by Dow Inc., solid IMAL TX-100 (A) Syihetic PRIMAL TX-10 content 46%, Tg: 28°C Ultrasol N-80 Acrylic emulsion, manufactured by Aica Kogyo Co, Ltd. solid content 45%, Tg: 80°C Emulsion 1 Emulsion of silyl ester copolymer, solid content 45%, Tg: 39.4°C . Modified rosin emulsion, manufactured by Harima Harsize NES-500 Chemicals, Inc., solid content 50.4% Resin acid Special dified rosi Isi f . pecial modified rosin emulsion, manufactured by (B) and Harsize NES-745 Harima Chemicals, Inc., solid content 50.3% derivative Hariester SK-370N Rosinized emulsion, manufactured by Harima thereof Chemicals, Inc., solid content 50.5% Rosin zinc salt emulsion, solid content 50%, Tg: 57.9°C i f d k Tal ., Ltd.
    Mica Powder 325mesh Mica, manufactured by Fukuoka Talc Co., Ltd., aspect raio 16.2 : ; ning Inc. : (©) Flaky Suzolite Mica 200-HK Mica, manufactured by Suzorite Mining Inc., aspec pigment ratio 18.3 Mica powder 100 Mica, manufactured by Fukuoka Talc Co, Ltd., aspect mesh raio 20.5 Cuprous oxide NC-301 |Cuprous oxide, manufactured by NC Tech Co., Ltd.
    Zineb TC Zinc ethylene bisdithiocarbamate, manufactured by (D) Antifouling Cerexagri S.A. agent Copper Omadine Copper pyrithion, manufactured by Arch UK Biocides Powder Ltd.
    Selektope® Medetomidine, manufactured by ITECH AB Extender Talc, manufactured by Takehara Chemical Industry . TTK Talc . pigment Co, Ltd., aspect ratio 3 MIO-NM Ferric oxide, manufactured by Nippon Inorganic Colour & Chemical Co, Ltd., aspect ratio 3.2 Coloring Noveperm Red F5RK |Naphthol red, manufactured by Clariant Japan K.K. : . Titanium dioxide, manufactured by Ishihara Sangyo pigment _ Tipaque R-930 Kaisha, Ltd.
    Redi 7 : shite B Red iron oxide No.404 ed iron oxide, manufactured by Morishita Bengara Kogyo Co., Lid.
    Dispersin Solution of high molecular weight block copolymer > at 8 Disperbyk-190 having pigment affinity group, manufactured by BYK- g Chemie Japan Co., Ltd., solid content 40% . . Mixture of defoaming polysiloxane and hydrophobic Antifoarming BYK-018 particles, manufactured by BYK-Chemie Japan Co., g Ltd. solid content 97% Thickening Polyether polyol urethane polymer, manufactured by agent Adekanol UH-752 ADEKA Corporation, solid content 28%
    -29- Antisettling Hectorite clay, 1-hydroxyethylidene-1,1-tetrasodium Benton DE disulfonate mixture, manufactured by Elementis agent us Specialties Inc.
    Kvowanol M 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, Film-forming Y manufactured by KH Neochem Co, Ltd. agent Butyl Cellosolve Ethylene glycol monobutyl ether, manufactured by KH Neochem Co., Ltd.
    权利要求:
    Claims (8)
    [1]
    A waterborne antifouling coating material composition comprising: synthetic resin {A}; at least one component (B} selected from a resinous acid and a derivative thereof; flocculent pigment {C} having an aspect ratio of 5 to 30; antifouling agent (D); and water (E), wherein a mass ratio (A): {B} between the synthetic resin (A) and the component (B) is 1:0.1 to 1:4.
    [2]
    The waterborne antifouling coating material composition according to claim 1, wherein the synthetic resin (A) is at least one selected from a (meth)acrylic resin, a styrene resin, another vinyl resin, a urethane resin, and a hydrolyzable resin.
    [3]
    The waterborne antifouling coating material composition according to claims 1 or 2, wherein the flocculent pigment (C) is mica having an aspect ratio of 5 to 30.
    [4]
    The waterborne antifouling coating material composition according to any one of claims 1 to 3, wherein the component (B) is at least one selected from rosin and a derivative thereof.
    [5]
    The waterborne antifouling coating material composition according to any one of claims 1 to 4, wherein the component (B) is a component other than an alkali metal salt.
    [6]
    An antifouling coating film formed from the waterborne antifouling coating material composition according to any one of claims 1 to 5.
    [7]
    A substrate having an antifouling coating film, comprising: a substrate; and the antifouling coating film of claim 6 provided on a surface of the substrate.
    -31-
    [8]
    A method for producing a substrate having an antifouling coating film, the method comprising: (1} applying to a substrate of, or impregnating it with, the waterborne antifouling coating material composition according to any one of claims 1 to 5 around an applied body or impregnated body, and {2) drying the applied body or impregnated body.
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    同族专利:
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    NO20210360A1|2021-09-27|
    JP2021155719A|2021-10-07|
    US20210301153A1|2021-09-30|
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