Antifouling coating for ship bottom, method for producing the same, and ship

Abstract

To provide a water-based antifouling coating which considers the health of employees involved in coating operations and the surrounding environment, and which enables further reduction of frictional resistance between seawater and a hull surface.SOLUTION: An antifouling coating for ship bottoms comprises the following components (A) to (F): (A) carboxyl group-containing cellulose fiber; (B) amino-modified silicone; (C) silicone oil (excluding the component (B)); (D) (meth)acrylic polymer compound; (E) urethane-modified polyether-based thickener; and (F) water.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a ship bottom paint. The present invention also relates to a method for producing a ship bottom paint and a ship. [Background technology]

[0002] The resistance acting on a ship sailing in calm water can be classified into friction resistance, form pressure resistance, wave resistance, etc. Of these, friction resistance accounts for a large proportion of total resistance, at 50-80%, so reducing friction resistance is important for saving energy on ships. For this reason, ship bottom paints that reduce friction resistance are being developed.

[0003] Furthermore, because ship bottoms are exposed to seawater for long periods of time, marine organisms such as barnacles often attach to them. The attachment of such marine organisms increases the frictional resistance between the seawater and the surface of the ship's hull, which is thought to be one of the causes of poor fuel economy. In order to prevent the attachment of such marine organisms, antifouling paints are applied to the ship bottom (Patent Document 1). The main antifouling paints hydrolyze on contact with seawater, releasing antifouling agents as they hydrolyze, thereby preventing the attachment of marine organisms. However, since many antifouling paints use large amounts of organic solvents, sufficient consideration must be given to the health of employees involved in the application and the surrounding environment. For this reason, water-based antifouling paints have been developed in recent years (Patent Documents 2 to 4). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Unexamined Patent Publication No. 51-14936 [Patent Document 2] Japanese Patent Application Laid-Open No. 2003-277680 [Patent Document 3] Japanese Patent Application Laid-Open No. 2009-173914 [Patent Document 4] Japanese Patent Publication No. 2021-155719 Summary of the Invention [Problem to be solved by the invention]

[0005] As mentioned above, in recent years, there has been progress in the development of water-based antifouling paints that are health- and environmentally friendly, but there is also an increasing demand for reduced frictional resistance. Therefore, further improvements in ship bottom paints that can achieve both of these goals are required.

[0006] Therefore, the present invention relates to providing a water-based antifouling paint that is considerate of the health of employees involved in the application and the surrounding environment, and that can further reduce frictional resistance between seawater and the surface of a ship's hull, a method for producing the same, and a ship. [Means for solving the problem]

[0007] The present invention relates to the following [1] to [8]. [1] A ship bottom paint containing the following components (A) to (F): (A) Carboxy group-containing cellulose fiber (B) Amino-modified silicone (C) Silicone oil (excluding component (B) above) (D) (Meth)acrylic polymer compound (E) Urethane-modified polyether thickener (F)Water [2] The ship bottom paint according to the above [1], further comprising one or more components selected from the group consisting of the following components (G), (H), (I) and (J): (G) Wetting agent (H) Solvent (I) Pigments (J) Antifouling agent [3] The paint for ship bottoms according to [1] or [2] above, wherein the content ratio of component (D) to component (A) is 2 or more and 20 or less. [4] The paint for ship bottoms according to any one of the above [1] to [3], wherein the content ratio of component (E) to component (A) is 0.05 or more and 0.5 or less. [5] A method for manufacturing a ship bottom paint, comprising the following steps: Step 1: Mixing the components (A), (B), (C), and (F) Step 2: Mixing the mixture obtained in step 1 with component (D) and component (E). [6] A friction resistance reducer for ships containing the above components (A) to (F). [7] A ship having a bottom coated with the ship bottom paint according to any one of [1] to [4], the ship bottom paint produced by the production method according to [5], or the ship friction resistance reducer according to [6]. [Effects of the Invention]

[0008] The present invention can provide a water-based antifouling paint that is considerate of the health of employees involved in the application and the surrounding environment, and that can further reduce frictional resistance between seawater and the surface of a ship's hull, as well as a method for producing the same and a ship. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is a schematic diagram showing the schematic configuration of an experimental device used in a test for evaluating the friction resistance of a ship bottom paint. [Figure 2] This is a graph for determining the equivalent sand roughness (Ks) corresponding to the friction resistance coefficient (Cf) acting on each cylinder. [Figure 3] This is a graph for determining the equivalent sand roughness (Ks) of each cylinder at the same roughness (Rz). DETAILED DESCRIPTION OF THE INVENTION

[0010] As a result of the inventors' investigations, they discovered that by applying a composition containing specific cellulose fibers to the bottom of a ship as a ship bottom paint, a coating film with lubricating properties can be formed on the bottom of the ship, thereby further reducing the frictional resistance between seawater and the surface of the ship's hull, and thus completed the present invention.

[0011] 1.Bottom paint The ship bottom paint of the present invention is mainly applied to the ship bottom, which in the present invention means the area below the summer load waterline of the ship. The ship bottom paint of the present invention contains the following components (A) to (F).

[0012] <Component (A)> Component (A) is a carboxy group-containing cellulose fiber. Carboxy group-containing cellulose fibers are cellulose fibers that have been chemically modified to contain carboxy groups. Component (A), alone or in combination with other components, is presumed to function as an emulsifier that emulsifies water and hydrophobic components (e.g., components (B) and (C)).

[0013] The carboxyl group-containing cellulose fibers have a cellulose type I crystal structure derived from the raw cellulose fibers. From the viewpoint of the stability of the coating material of the present invention, the crystallinity of the carboxyl group-containing cellulose fibers is preferably 10% or more, more preferably 15% or more, and even more preferably 20% or more. From the viewpoint of raw material availability, the crystallinity is preferably 90% or less, more preferably 85% or less, even more preferably 80% or less, and even more preferably 75% or less.

[0014] In this specification, the crystallinity of various cellulose fibers refers to the cellulose type I crystallinity calculated from the diffraction intensity value obtained by X-ray diffraction, and can be measured according to the method described in the Examples below. Cellulose type I refers to the crystalline form of natural cellulose, and cellulose type I crystallinity refers to the proportion of crystalline regions in the entire cellulose fiber. The presence or absence of a cellulose type I crystalline structure can be determined by the presence of a peak at 2θ = 22.6° in X-ray diffraction measurement.

[0015] Examples of counter ions to the carboxyl groups in carboxyl group-containing cellulose fibers include metal ions such as sodium ions, potassium ions, calcium ions, and aluminum ions that are generated in the presence of alkali during production, and protons that are generated by substituting these metal ions with acids.

[0016] The carboxy group content of the carboxy group-containing cellulose fiber is preferably 0.1 mmol / g or more, more preferably 0.4 mmol / g or more, even more preferably 0.6 mmol / g or more, and even more preferably 0.8 mmol / g or more, from the viewpoint of bonding with component (B). Furthermore, from the viewpoint of improving handleability, it is preferably 3 mmol / g or less, more preferably 2 mmol / g or less, and even more preferably 1.8 mmol / g or less. The "carboxy group content" refers to the total amount of carboxy groups in the cellulose constituting the cellulose fiber, and is specifically measured by the method described in the Examples below.

[0017] The average fiber diameter of the carboxyl group-containing cellulose fibers is preferably 0.1 nm or more, more preferably 1.0 nm or more, and even more preferably 2.0 nm or more from the viewpoint of handleability, and is preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less from the viewpoint of film strength. In this specification, carboxyl group-containing cellulose fibers having an average fiber diameter on the nm scale may be referred to as "micronized carboxyl group-containing cellulose fibers." The average fiber diameter of the carboxyl group-containing cellulose fibers is measured by the method described in the Examples below.

[0018] [Method for producing carboxyl group-containing cellulose fibers] The carboxy group-containing cellulose fibers used in the present invention can be obtained by subjecting raw cellulose fibers to an oxidation treatment or a treatment for adding carboxy groups, thereby introducing one or more carboxy groups per glucose residue.

[0019] The cellulose fibers to be introduced with carboxyl groups, i.e., the cellulose fibers used as the raw material for carboxyl group-containing cellulose fibers, are preferably natural cellulose fibers from an environmental perspective, and examples thereof include wood pulps such as softwood pulp and hardwood pulp; cotton pulps such as cotton linter and cotton lint; non-wood pulps such as straw pulp and bagasse pulp; and bacterial cellulose, and these may be used alone or in combination of two or more.

[0020] The average fiber diameter of the raw material cellulose fibers is preferably 1 μm or more, and preferably 300 μm or less, from the viewpoints of handling and cost. Moreover, from the viewpoints of availability and cost, the average fiber length of the raw cellulose fibers is preferably 100 μm or more and preferably 5,000 μm or less. The average fiber diameter and average fiber length of the raw cellulose fibers can be measured according to the method described in the Examples below. From the viewpoint of dispersibility, it is preferable to use raw cellulose fibers that have been subjected to a fiber shortening treatment such as alkaline hydrolysis or acid hydrolysis, and have an average fiber length of 1 μm or more and 1,000 μm or less.

[0021] Methods for introducing carboxy groups into cellulose fibers include, for example, a method of converting hydroxy groups of cellulose into carboxy groups by oxidation, and a method of reacting the hydroxy groups of cellulose with one or more compounds selected from the group consisting of compounds having carboxy groups, acid anhydrides of compounds having carboxy groups, and derivatives thereof.

[0022] The hydroxyl groups of the cellulose can be oxidized, for example, by reacting an oxidizing agent such as sodium hypochlorite with a bromide such as sodium bromide using 2,2,6,6-tetramethyl-1-piperidine-N-oxyl (TEMPO) as a catalyst. For more details, known methods, such as those described in JP 2011-140632 A, can be used.

[0023] By subjecting cellulose fibers to oxidation treatment using TEMPO as a catalyst, the hydroxymethyl group (-CHOH) at the C6 position of the cellulose structural unit is selectively converted to a carboxy group. This method is particularly advantageous in that it has excellent selectivity for the hydroxy group at the C6 position, which is the target of oxidation on the surface of the raw cellulose fiber, and the reaction conditions are mild. Therefore, a preferred embodiment of the carboxy group-containing cellulose fiber of the present invention is a cellulose fiber in which the C6 position of the cellulose structural unit is a carboxy group. In this specification, cellulose fibers obtained by oxidizing hydroxy groups in cellulose structural units are sometimes referred to as "oxidized cellulose fibers," and cellulose fibers obtained by oxidizing cellulose fibers using TEMPO as a catalyst and having a carboxy group at the C6 position of the cellulose structural units are sometimes referred to as "TEMPO-oxidized cellulose fibers." Oxidized cellulose fibers, and particularly TEMPO-oxidized cellulose fibers, are preferred because they are easier to prepare than other carboxyl group-containing cellulose fibers.

[0024] By further subjecting the oxidized cellulose fibers to a further oxidation treatment or reduction treatment, it is possible to prepare oxidized cellulose fibers from which the remaining aldehyde groups have been removed.

[0025] <Ingredient (B)> Component (B) is an amino-modified silicone. Component (B) may be used alone or in combination of two or more. In the present invention, the amino group refers to a monovalent functional group obtained by removing one hydrogen atom from ammonia, a primary amine, or a secondary amine.

[0026] The silicone has a polysiloxane structure with a siloxane bond as the main chain, which may further include an alkylene group. The polysiloxane structure may have a substituent, which will be described later.

[0027] Examples of the substituent include alkoxy groups having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, an isopentyloxy group, and a hexyloxy group; a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, and the like. alkoxycarbonyl groups having 1 to 6 carbon atoms in the alkoxy group, such as a carboxyl group, a tert-butoxycarbonyl group, a pentyloxycarbonyl group, or an isopentyloxycarbonyl group; halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; acyl groups having 1 to 6 carbon atoms, such as an acetyl group or a propionyl group; aralkyl groups; aralkyloxy groups; alkylamino groups having 1 to 6 carbon atoms; and dialkylamino groups having an alkyl group with 1 to 6 carbon atoms.

[0028] From the viewpoint of strength during film formation, the weight average molecular weight of the amino-modified silicone is preferably 2,000 or more, more preferably 5,000 or more, and even more preferably 8,000 or more, and from the same viewpoint, it is preferably 1,000,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.

[0029] As an amino-modified silicone, the kinematic viscosity at 25°C is 10mm 2 / s or more 20,000mm 2 Further, amino-modified silicones having an amino equivalent of 400 g / mol or more and 16,000 g / mol or less are preferred.

[0030] The kinematic viscosity at 25°C can be determined using an Ostwald viscometer. From the viewpoint of film strength, it is more preferable to use a viscosity of 20 mm. 2 / s or more, more preferably 50 mm 2 / s or more, and from the viewpoint of handling, 10,000 mm 2 / s or less, more preferably 5,000 mm 2 / s or less.

[0031] From the viewpoint of film strength, the amino equivalent is preferably 400 g / mol or more, more preferably 600 g / mol or more, and even more preferably 800 g / mol or more, and from the viewpoint of ease of bonding to carboxy group-containing cellulose fibers, it is preferably 16,000 g / mol or less, more preferably 14,000 g / mol or less, and even more preferably 12,000 g / mol or less. The amino equivalent is the molecular weight per nitrogen atom, and can be determined by quantifying the amount of nitrogen atoms in a sample by elemental analysis and calculating the mass of the sample containing 1 mole of nitrogen atoms.

[0032] Specific examples of amino-modified silicones include compounds represented by general formula (a1).

[0033] [ka]

[0034] [In the formula, R 1a R represents a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxy group, an alkoxy group having 1 to 3 carbon atoms, or a hydrogen atom, and is preferably a methyl group or a hydroxy group from the viewpoint of synovial properties. 2a is a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxy group, or a hydrogen atom, and from the same viewpoint, is preferably a methyl group or a hydroxy group. B represents a side chain having at least one amino group, and R 3a represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. x and y each represent an average degree of polymerization, and are selected so that the kinematic viscosity at 25°C and amino equivalent of the compound fall within the above-mentioned ranges. 1a , R 2a , R 3a may be the same or different, and multiple R 2a may be the same or different.

[0035] In the compound of general formula (a1), from the viewpoint of synovial properties, x is preferably a number of 10 or more and 10,000 or less, more preferably a number of 20 or more and 5,000 or less, and even more preferably a number of 30 or more and 3,000 or less. y is preferably a number of 1 or more and 1,000 or less, more preferably a number of 1 or more and 500 or less, and even more preferably a number of 1 or more and 200 or less. From the viewpoint of strength during film formation, the weight-average molecular weight of the compound of general formula (a1) is preferably 2,000 or more, more preferably 5,000 or more, and even more preferably 8,000 or more, and from the same viewpoint, it is preferably 1,000,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.

[0036] In the general formula (a1), examples of the side chain B having an amino group include the following. -C3H6-NH2 -C3H6-NH-C2H4-NH2 -C3H6-NH-[C2H4-NH] e -C2H4-NH2 -C3H6-NH(CH3) -C3H6-NH-C2H4-NH(CH3) -C3H6-NH-[C2H4-NH] f -C2H4-NH(CH3) -C3H6-N(CH3)2 -C3H6-N(CH3)-C2H4-N(CH3)2 -C3H6-N(CH3)-[C2H4-N(CH3)] g -C2H4-N(CH3)2 -C3H6-NH-cyclo-C5H 11 (where e, f, and g are numbers from 1 to 30.)

[0037] The amino-modified silicone used in the present invention can be produced, for example, by hydrolyzing an organoalkoxysilane represented by general formula (a2) with excess water to obtain a hydrolyzate, and then heating the resulting hydrolyzate with dimethylcyclopolysiloxane in the presence of a basic catalyst such as sodium hydroxide to 80 to 110°C to cause an equilibrium reaction, and then neutralizing the basic catalyst with an acid when the reaction mixture reaches the desired viscosity (see JP 53-98499 A). H2N(CH2)2NH(CH2)3Si(CH3)(OCH3)2(a2)

[0038] Furthermore, from the viewpoint of strength during film formation, the amino-modified silicone is preferably at least one selected from the group consisting of monoamino-modified silicones having one amino group in one of the side chains B and diamino-modified silicones having two amino groups in one of the side chains B, and more preferably at least one selected from the group consisting of compounds in which the side chain B having an amino group is represented by -C3H6-NH2 [hereinafter referred to as component (a1-1)] and compounds in which the side chain B having an amino group is represented by -C3H6-NH-C2H4-NH2 [hereinafter referred to as component (a1-2)].

[0039] The amino-modified silicones used in the present invention may be selected from the following in terms of performance: TSF4703 (kinematic viscosity: 1000, amino equivalent: 1600) and TSF4708 (kinematic viscosity: 1000, amino equivalent: 2800) manufactured by Momentive Performance Materials; SS-3551 (kinematic viscosity: 1000, amino equivalent: 1700), FZ-3710 (kinematic viscosity: 1000, amino equivalent: 1700), SF8457C (kinematic viscosity: 1200, amino equivalent: 1800), SF8417 (kinematic viscosity: 1200, amino equivalent: 1700), SF8452C (kinematic viscosity: 600, amino equivalent: 6400), BY16-209 (kinematic viscosity: 500, amino equivalent: 1800), and BY16-209 (kinematic viscosity: 500, amino equivalent: 1800) manufactured by Dow-Toray Industries, Inc. -892 (kinematic viscosity: 1500, amino equivalent: 2000), BY16-898 (kinematic viscosity: 2000, amino equivalent: 2900), FZ-3760 (kinematic viscosity: 220, amino equivalent: 1600), BY16-213 (kinematic viscosity: 55, amino equivalent: 2700), Shin-Etsu Chemical Co., Ltd.'s KF-8002 (kinematic viscosity: 1100, amino equivalent: 1700 ), KF-8004 (kinematic viscosity: 800, amino equivalent: 1500), KF-8005 (kinematic viscosity: 1200, amino equivalent: 11000), KF-867 (kinematic viscosity: 1300, amino equivalent: 1700), KF-864 (kinematic viscosity: 1700, amino equivalent: 3800), KF-859 (kinematic viscosity: 60, amino equivalent: 6000). In parentheses, kinematic viscosity is measured at 25°C (unit: mm 2 / s), and the unit of amino equivalent is g / mol.

[0040] As the component (a1-1), BY16-213 (kinematic viscosity: 55, amino equivalent: 2700) and BY16-853U (kinematic viscosity: 14, amino equivalent: 450) are more preferred.

[0041] As the (a1-2) component, SF8417 (kinematic viscosity: 1200, amino equivalent: 1700), BY16-209 (kinematic viscosity: 500, amino equivalent: 1800), FZ-3760 (kinematic viscosity: 220, amino equivalent: 1600), SF8452C (kinematic viscosity: 600, amino equivalent: 6400), KF-8002 (kinematic viscosity: 1100, amino equivalent: 1700), SS-3551 (kinematic viscosity: 1000, amino equivalent: 1700), and FZ-3710 (kinematic viscosity: 1000, amino equivalent: 1700) are more preferred.

[0042] <Ingredient (C)> Component (C) in the present invention is a silicone oil, except for those that fall under the category of component (B).

[0043] The solubility of component (C) in water is preferably 10 g or less, more preferably 1 g or less, per 100 g of water at 25°C. From the viewpoint of the stability of the coating material of the present invention, the weight average molecular weight of component (C) is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 10,000 or less, and from the same viewpoint, it is preferably 100 or more, more preferably 200 or more.

[0044] Examples of silicone oils include dimethylpolysiloxane, methylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane.

[0045] From the viewpoint of the stability of the coating material of the present invention, component (C) preferably has an SP value of 10 or less, more preferably 9.5 or less, even more preferably 9.0 or less, and even more preferably 8.5 or less, and from the same viewpoint, preferably 6.0 or more, more preferably 6.5 or more. For example, those having an SP value of 10 or less, as described below, can be exemplified as being preferable.

[0046] The SP value in this specification refers to the solubility parameter calculated by the Fedors method (unit: (cal / cm 3 ) 1 / 2) and are described in, for example, references such as "SP Value Basics, Applications and Calculation Methods" (Johokikansha, 2005) and Polymer Handbook Third Edition (A Wiley-Interscience publication, 1989).

[0047] Examples of silicone oils having an SP value of 10 or less that are suitable for use in the present invention include KF96-1cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96-10cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96-50cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96-100cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96-1000cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), and KF-96H-10,000cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3).

[0048] <Ingredient (D)> Component (D) in the present invention is a (meth)acrylic polymer compound, which acts as a membrane reinforcing agent that improves the durability of the membrane's synovial properties.

[0049] The weight-average molecular weight of the polymer compound is preferably 10,000 or more, more preferably 20,000 or more, and even more preferably 30,000 or more, from the viewpoint of obtaining a film that has excellent synovial fluid retention, and from the same viewpoint, is preferably 5 million or less, more preferably 1 million or less, and even more preferably 500,000 or less.

[0050] Examples of (meth)acrylic polymers include methacrylic or acrylic polymers having an ester group or an amide group in the side chain, and more specific examples include polyalkyl(meth)acrylates such as polymethyl(meth)acrylate, polyethyl(meth)acrylate, and polybutyl(meth)acrylate; copolymers with acrylic such as acrylic styrene and urethane acrylic; and poly(meth)acrylamides such as poly(meth)acrylamide, poly-N-methyl(meth)acrylamide, poly-N,N-dimethyl(meth)acrylamide, and poly-N-phenyl(meth)acrylamide.

[0051] Specific examples of polymer compounds that can be preferably used as component (D) include the DAOTAN series (e.g., DAOTAN TW 6495 / 35WA, DAOTAN TW 6464 / 36WA, etc.), the VIACRYL series (e.g., VIACRYL VSC 6286w / 45WA, VIACRYL SC 6828w / 45WA, etc.), and the VISCOPOL series (e.g., VISCOPOL 6191, etc.) manufactured by Daicel Allnex Corporation, and the NeoCryl series (e.g., NeoCryl XK-188, NeoCryl A-1127, etc.) manufactured by DSM.

[0052] <Ingredient (E)> The component (E) in the present invention is a urethane-modified polyether thickener. By using the component (E) as a thickener, the synovial fluid retention of the membrane can be improved.

[0053] Examples of urethane-modified polyether thickeners include urethane-modified polyethers having urethane bonds and polyether chains in the molecule and having hydrophobic groups at the ends. Such urethane-modified polyether thickeners are commercially available, and examples thereof include SN Thickener 660T, SN Thickener 621N, and SN Thickener 623N manufactured by San Nopco; the ADEKA NOL series, such as ADEKA NOL UH-814N, UH-752, UH-756VF, UH-420, and UH-462 manufactured by ADEKA; RHEOLATE 244 and RHEOLATE 278 manufactured by Elementis Japan; and COAPUR 2025, COAPUR 2501, COAPUR 3025, COAPUR 520W, COAPUR 830W, COAPUR XS22, COAPUR XS71, and COAPUR XS83 manufactured by ARKEMA.

[0054] <Component (F)> Component (F) in the present invention is water. Water serves as a medium and as one of the constituents of the paint of the present invention.

[0055] <Additional Ingredients> The paint for ship bottoms of the present invention may contain one or more components selected from the group consisting of component (G), component (H), component (I) and component (J). (G) Wetting agent (H) Solvent (I) Pigments (J) Antifouling agent

[0056] [Component (G)] Wetting agents are effective in increasing the wettability of various surfaces, allowing the ship bottom paint of the present invention to be applied to the metal surface of the hull or the surface of the base material without being repelled, so it is preferable to contain or incorporate such components.

[0057] Wetting agents that can be used in the present invention include those used in water-containing products such as water-based paints, water-based inks, daily necessities, and cosmetics, and preferred examples thereof include polyether-modified silicones; water-miscible organic solvents such as ethanol and isopropanol; and surfactants such as sodium dodecyl sulfate. Among these, polyether-modified silicones are preferred from the viewpoint of improving the durability of the synovial properties of the film.

[0058] Examples of polyether-modified silicones include compounds having a methyl silicone chain as the main chain and a polyoxyethylene group as the side chain, and specific examples include compounds represented by the following general formula:

[0059] [ka]

[0060] In the formula, R 1 is a methylene group, an ethylene group, or a trimethylene group, and R 2 represents an alkyl group having 1 to 4 carbon atoms, m represents an integer of 0 to 50, n represents an integer of 1 to 10, p represents an integer of 1 to 50, and q represents an integer of 0 to 50. 1 (C2H4O) p (C3H6O) q R 2In the group represented by (C2H4O) p and (C3H6O) q can be random or block.

[0061] The HLB value of the polyether-modified silicone is preferably within a specific range from the viewpoint of the synovial fluid durability of the film obtained by drying the coating material of the present invention and the stability of the coating material of the present invention; specifically, it is preferably 1 or more, more preferably 5 or more, and even more preferably 10 or more, and is preferably 18 or less, more preferably 16 or less.

[0062] When two or more polyether-modified silicones with different HLB values ​​are used as wetting agents, the weighted average of the HLB values ​​of the wetting agents should fall within the above range. The HLB value is an index that represents the balance between hydrophilicity and lipophilicity, and in the present invention refers to the value calculated using the Griffin formula below. HLB value = 20 × total molecular weight of hydrophilic groups / molecular weight

[0063] The kinematic viscosity of the polyether-modified silicone at 25°C is preferably within a specific range from the viewpoint of the synovial fluid durability of the film obtained by drying the coating material of the present invention, and specifically, is preferably 1 mm 2 / s or more, preferably 5 mm 2 / s or more, more preferably 10 mm 2 / s or more, preferably 1000 mm 2 / s or less, preferably 500 mm 2 / s or less, more preferably 200 mm 2 / s or less, more preferably 100 mm 2 / s or less.

[0064] The weight average molecular weight of the polyether-modified silicone is preferably 300 or more, more preferably 500 or more, from the viewpoint of improving the synovial fluid durability of the film obtained by drying the coating material of the present invention, and from the same viewpoint, is preferably 9,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.

[0065] Polyether-modified silicone compounds that can be preferably used as wetting agents are commercially available, and examples of commercially available products include KF-615A, KF-640, KF-642, KF-643, KF-644, KF-351A, KF-354L, KF-355A, KF-6011, KF-6012, KF-6015, KF-6016, KF-6017, KF-6020, and KF-6043 manufactured by Shin-Etsu Chemical Co., Ltd. From the viewpoint of the synovial fluid durability of the film obtained by drying the coating material of the present invention, KF-640, KF-642, KF-643, KF-351A, KF-354L, and KF-355A can be preferably used. Commercially available products having structures that do not fall within the general formula (for example, KF-6028 and KF-6038 manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as wetting agents.

[0066] [Component H] The solvent is preferably an organic solvent. Examples of solvents include methanol, ethanol, benzyl alcohol, N,N-dimethylformamide (DMF), isopropanol (IPA), dimethyl sulfoxide (DMSO), N,N-dimethylacetamide, hexane, dioxane, tetrahydrofuran (THF), 1-methyl-2-pyrrolidone (NMP), cyclohexanone, diester of succinic acid and triethylene glycol monomethyl ether, acetone, methyl ethyl ketone (MEK), acetonitrile, dichloromethane, chloroform, toluene, xylene, acetic acid, methyl acetate, ethyl acetate, butyl acetate, and the like.

[0067] [Component (I)] The pigment that can be used in the present invention is not particularly limited as long as it is known in the field of paints, and may be either an inorganic pigment or an organic pigment. Specific examples of inorganic pigments include metal oxides such as carbon black, titanium oxide, iron oxide, red iron oxide, and chromium oxide, and pearlescent pigments. Specific examples of organic pigments include azo pigments such as azo lake pigments, insoluble monoazo pigments, insoluble disazo pigments, and chelate azo pigments; and polycyclic pigments such as phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, benzimidazolone pigments, and threne pigments. The pigments can be used alone or in combination of two or more.

[0068] [Component (J)] The antifouling agent that can be used in the present invention is not particularly limited as long as it is known in the field of ship bottom paints.

[0069] Specific examples of such antifouling agents include copper or copper compounds (excluding pyrithione compounds) such as cuprous oxide, metallic copper powder, and cuprous thiocyanate (copper rhodanide), metal pyrithiones (pyrithione compounds) such as copper pyrithione and zinc pyrithione, tetraalkylthiuram disulfides such as tetramethylthiuram disulfide, carbamate compounds such as zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, and bisdimethyldithiocarbamoylzinc ethylenebisdithiocarbamate, maleimide compounds such as 2,4,6-triphenylmaleimide, 2,3-dichloro-N-(2',6'-diethylphenyl)maleimide, and 2,3-dichloro-N-(2'-ethyl-6'-methylphenyl)maleimide, Examples include 4,5,6-tetrachloroisophthalonitrile, N,N-dimethyldichlorophenylurea, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2-methylthio-4-tert-butylamino-6-cyclopropyl-S-triazine, chloromethyl-n-octyl disulfide, N',N'-dimethyl-N-phenyl-(N-fluorodichloromethylthio)sulfamide, N',N'-dimethyl-N-tolyl-(N-fluorodichloromethylthio)sulfamide, amine-organoborane complexes such as pyridinetriphenylborane and 4-isopropylpyridinediphenylmethylborane, and (+ / -)-4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (medetomidine).

[0070] <Other ingredients> In addition to the above components, the coating material of the present invention may contain antibacterial compounds (e.g., organic synthetic antibacterial agents, natural antibacterial agents, and inorganic antibacterial agents), plasticizers, nucleating agents, fillers (inorganic fillers, organic fillers), hydrolysis inhibitors, flame retardants, antioxidants, lubricants such as hydrocarbon waxes and anionic surfactants, UV absorbers, antistatic agents, antifogging agents, light stabilizers, foaming agents, surfactants; polysaccharides such as starches and alginic acid; natural proteins such as gelatin, glue, and casein; tannins, zeolites, ceramics, fragrances; flow control agents; leveling agents; conductive agents; UV dispersants; deodorizers, etc., within the range that does not impair the effects of the present invention. Similarly, other polymeric materials and other compositions may also be added within the range that does not impair the effects of the present invention.

[0071] <Properties of ship bottom paint> The ship bottom paint of the present invention contains the above-mentioned components (A), (B), (C), (D), (E), and (F) and water as essential components, and may be an emulsified composition. The emulsified state is determined by visually observing the composition, and if it is cloudy, it is considered to be in an emulsified state. When the ship bottom paint of the present invention is an emulsified composition, it may be either an O / W type emulsion or a W / O type emulsion, but is preferably an O / W type emulsion.

[0072] The content ratio of component (D) to component (A) in the ship bottom paint or during preparation of the ship bottom paint (i.e., D / A) is, in terms of mass ratio, preferably 2 or more, more preferably 5 or more, and even more preferably 8 or more, from the viewpoint of film strength, while, in terms of mass ratio, it is preferably 20 or less, more preferably 16 or less, and even more preferably 12 or less, from the viewpoint of synovial properties.

[0073] The content ratio of component (E) to component (A) in the ship bottom paint or during preparation of the ship bottom paint (i.e., E / A) is, from the viewpoint of the synovial fluid durability of the film, preferably 0.05 or more, more preferably 0.1 or more, and even more preferably 0.15 or more, in mass ratio, while from the viewpoint of synovial fluid properties, it is preferably 0.5 or less, more preferably 0.4 or less, and even more preferably 0.3 or less, in mass ratio.

[0074] The content or blending amount of component (A) in the ship bottom paint or when preparing the ship bottom paint is, from the viewpoint of preparing the paint of the present invention as an emulsion composition, preferably 0.02 mass% or more, more preferably 0.1 mass% or more, and even more preferably 0.4 mass% or more, while from the viewpoint of handleability, it is preferably 15 mass% or less, more preferably 10 mass% or less, even more preferably 5 mass% or less, and even more preferably 2 mass% or less.

[0075] The content or blending amount of component (B) in the ship bottom paint or during the preparation of the ship bottom paint is, from the viewpoint of emulsion stability when the paint of the present invention is obtained as an emulsion composition, preferably 0.5 equivalents or more, more preferably 1 equivalent or more, and even more preferably 1.5 equivalents or more, relative to the carboxy groups of component (A); and from the same viewpoint, it is preferably 3 equivalents or less, more preferably 2.5 equivalents or less, and even more preferably 2 equivalents or less.

[0076] The content or blending amount of component (C) in the ship bottom paint or when preparing the ship bottom paint is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, from the viewpoint of exhibiting synovial properties, and is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, from the viewpoint of film-forming properties.

[0077] The content or blending amount of component (F) in the ship bottom paint or during preparation of the ship bottom paint is, from the viewpoint of maintaining an emulsified state, preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, and from the viewpoint of the effective amount, is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.

[0078] In the present invention, it is preferable to contain or incorporate component (G) from the viewpoint of improving wettability to the surface of the ship bottom member and the surface of the base material. The content or blending amount of component (G) in the ship bottom paint or when preparing the ship bottom paint is, from the viewpoint of exerting the above-mentioned effects, preferably 0.01 mass % or more, more preferably 0.1 mass % or more, and even more preferably 0.2 mass % or more, while, from the viewpoint of the water resistance of the film, it is preferably 2 mass % or less, more preferably 1 mass % or less, and even more preferably 0.7 mass % or less.

[0079] In the present invention, from the viewpoint of film-forming properties, it is preferable to contain or incorporate component (H). The content or blending amount of component (H) in the ship bottom paint or when preparing the ship bottom paint is, from the viewpoint of exerting the above-mentioned effects, preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, while, from the viewpoint of paint stability, it is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0080] In the present invention, it is preferable to contain or incorporate component (I) from the viewpoint of the appearance of the film. The content or blending amount of component (I) in the ship bottom paint or when preparing the ship bottom paint is, from the viewpoint of exerting the above-mentioned effects, preferably 0.1 mass % or more, more preferably 0.3 mass % or more, and even more preferably 0.5 mass % or more, while, from the viewpoint of film-forming properties, it is preferably 5 mass % or less, more preferably 3 mass % or less, and even more preferably 1.5 mass % or less.

[0081] The viscosity of the ship bottom paint of the present invention is set at 25°C, a shear rate of 1 s, from the viewpoint of improving the synovial fluid durability of the formed film. -1 The viscosity at 1000 mPa·s is preferably 1,000 mPa·s or more, more preferably 2,000 mPa·s or more, even more preferably 5,000 mPa·s or more, and even more preferably 10,000 mPa·s or more. On the other hand, from the viewpoint of handling, the viscosity is preferably 100,000 mPa·s or less, more preferably 50,000 mPa·s or less, and even more preferably 30,000 mPa·s or less. The viscosity at 25°C of the ship bottom paint of the present invention is measured by the method described in the examples below.

[0082] <Friction resistance reducer for ships> A coating film is formed by applying the above-mentioned ship bottom paint of the present invention. In the coating film, the carboxy group of component (A) and the amino group of component (B) form a salt. Such a coating film exhibits the synovial surface properties shown in the literature (Technology of Super Water-Repellent, Super Oil-Repellent, and Synovial Surfaces / Publisher: Hiroshi Motoki / Publisher: Science & Technology Co., Ltd. / Published January 28, 2016). The ship bottom paint of the present invention described above has lubricating surface properties, and when applied to the bottom of a ship, it can reduce the frictional resistance between seawater and the surface of the hull. Therefore, the above-mentioned composition, i.e., a composition containing components (A) to (F), and further a composition further containing one or more selected from the group consisting of components (G), (H), (I), and (J), can be used as a frictional resistance reducer for ships.

[0083] 2. Manufacturing method of ship bottom paint The method for producing a ship bottom paint of the present invention is a method comprising the steps of: mixing the aforementioned components (A), (B), (C), and (F) (step 1); and mixing the mixture obtained in step 1 (referred to herein as the "emulsified mixture") with the aforementioned components (D) and (E) (step 2).

[0084] The entire amount of component (F) does not need to be blended in step 1; a portion of it may be blended in step 2. Component (G), component (H), component (I) and / or component (J) can be added at any time in step 2.

[0085] Mixing the components causes emulsification, resulting in the production of a ship bottom paint. For the mixing treatment in step 1 or step 2, a magnetic stirrer, mechanical stirrer, homomixer, vacuum emulsifier, low-pressure homogenizer, high-pressure homogenizer, grinder, cutter mill, ball mill, jet mill, single-screw extruder, twin-screw extruder, ultrasonic agitator, household juicer mixer, or the like can be used. The mixing treatment may be performed by combining two or more types of operations.

[0086] The temperature and time for mixing the components in step 1 or step 2 are not particularly limited, but are preferably within the temperature range of 5 to 50°C and within the range of 1 minute to 3 hours, for example.

[0087] The preferred ranges of the content of each component and the ratio between components in each step are the same as those preferred ranges for the paint for ship bottoms of the present invention described above.

[0088] At any stage in the process of producing a ship bottom paint, for example, before step 1, simultaneously with step 2, after step 1, simultaneously with step 2, and / or after step 2, components or compositions containing carboxy group-containing cellulose fibers can be subjected to a micronization treatment, thereby reducing the average fiber diameter of the carboxy group-containing cellulose fibers to the nanometer scale, thereby improving the stability of the ship bottom paint and the strength of the film when formed, and therefore it is preferable to carry out such a micronization treatment step.

[0089] A known dispersing machine is preferably used as the apparatus used in the micronization treatment. For example, a disintegrator, a beater, a low-pressure homogenizer, a high-pressure homogenizer, a grinder, a cutter mill, a ball mill, a jet mill, a single-screw extruder, a twin-screw extruder, an ultrasonic agitator, a household juicer mixer, etc. can be used. In addition, the solid content of the target material in the micronization treatment is preferably 50% by mass or less. The operating conditions of the apparatus during the micronization treatment can be appropriately set by a person skilled in the art based on known operating conditions or the operating conditions described in the instruction manual for each apparatus.

[0090] 3.Ship The ship of the present invention is a ship whose bottom is coated with the above-mentioned ship bottom paint of the present invention, the ship bottom paint produced by the above-mentioned production method of the present invention, or the above-mentioned ship frictional resistance reducer for ships of the present invention.Since such a ship has reduced frictional resistance between seawater and the hull surface, improved fuel efficiency can be expected. [Example]

[0091] The present invention will be specifically described below with reference to examples. Note that the following examples are merely illustrative of the present invention and are not intended to limit the scope of the present invention. Note that "normal pressure" refers to 101.3 kPa, and "normal temperature" refers to 25°C.

[0092] [Carboxy group content of carboxy group-containing cellulose fiber] A 100 mL beaker is filled with 0.5 g of dry cellulose fiber to be measured, and deionized water or a 2:1 methanol / water mixture is added to make a total volume of 55 mL. 5 mL of 0.01 M sodium chloride aqueous solution is then added to prepare a dispersion. The dispersion is stirred until the cellulose fiber to be measured is fully dispersed. 0.1 M hydrochloric acid is added to the dispersion to adjust the pH to 2.5-3. Using an automatic titrator (DKK-TOA Corporation, AUT-701), 0.05 M sodium hydroxide aqueous solution is added dropwise to the dispersion with a waiting time of 60 seconds, and the conductivity and pH values ​​are measured every minute. Measurements are continued until the pH reaches approximately 11, and a conductivity curve is obtained. The sodium hydroxide titration amount is determined from this conductivity curve, and the carboxyl group content of the cellulose fiber to be measured is calculated using the following formula: Carboxylic group content (mmol / g) = [sodium hydroxide titration amount × sodium hydroxide aqueous solution concentration (0.05M)] / [mass of cellulose fiber to be measured (0.5g)]

[0093] [Solid content in dispersion] The measurement is performed using an infrared moisture meter (Shimadzu Corporation, MOC-120H). Measurements are performed every 30 seconds on 1 g of sample at a constant temperature of 150°C, and the value when the mass loss is 0.1% or less of the initial amount of the sample is taken as the solid content.

[0094] [Average fiber diameter, average fiber length and average aspect ratio of various cellulose fibers] Depending on the size of the cellulose fiber to be measured, one of the following two measurement methods is selected for measurement. (1) Deionized water or N,N-dimethylformamide (DMF) is added to the cellulose fibers to be measured to prepare a dispersion with a content of 0.0001% by mass. The dispersion is dropped onto mica and dried to form an observation sample. The fiber height (height difference between where fibers are present and where fibers are absent) of the cellulose fibers in the observation sample is measured using an atomic force microscope (AFM) (Nanoscope II Tapping mode AFM manufactured by Digital Instruments; the probe used is Point Probe (NCH) manufactured by Nanosensors). 100 cellulose fibers are extracted from a microscopic image in which the cellulose fibers can be seen, and the average fiber diameter is calculated from their fiber height. The average fiber length is calculated from the distance in the fiber direction. The average aspect ratio is calculated by dividing the average fiber length by the average fiber diameter. The height analyzed in the AFM image is considered to be the fiber diameter. (2) Deionized water is added to the cellulose fibers to be measured to prepare a dispersion with a cellulose content of 0.01% by mass. This dispersion is measured using a wet dispersion type image analysis particle size distribution analyzer (IF-3200, manufactured by Jusco International) under the following conditions: front lens: 2x, telecentric zoom lens: 1x, image resolution: 0.835 μm / pixel, syringe inner diameter: 6515 μm, spacer thickness: 500 μm, image recognition mode: ghost, threshold: 8, analysis sample volume: 1 mL, and sampling: 15%. The cellulose fibers are then approximated as a rectangle, with the length of the minor axis being the fiber diameter and the length of the major axis being the fiber length. Each value is measured for 100 cellulose fibers, and the average value is calculated.

[0095] [Confirmation of crystalline structure in various cellulose fibers] The crystalline structure of various cellulose fibers is confirmed by measurement using an X-ray diffractometer (MiniFlexII, manufactured by Rigaku Corporation) under the following conditions. The measurement conditions were as follows: X-ray source: Cu / Kα-radiation, tube voltage: 30 kV, tube current: 15 mA, measurement range: diffraction angle 2θ = 5 to 45°, X-ray scan speed: 10° / min. The measurement sample had an area of ​​320 mm 2 The cellulose is compressed into a pellet with a thickness of 1 mm. The degree of crystallinity of the cellulose type I crystal structure is calculated from the obtained X-ray diffraction intensity according to the following formula A.

[0096] <Formula A> Cellulose type I crystallinity (%) = [(I 22.6 -I 18.5 ) / I 22.6 ] x 100 [In the formula, I 22.6 is the diffraction intensity of the lattice plane (002 plane) (diffraction angle 2θ = 22.6°) in X-ray diffraction, I 18.5 indicates the diffraction intensity of the amorphous part (diffraction angle 2θ = 18.5°).

[0097] On the other hand, if the crystallinity obtained by the above formula A is 35% or less, it is preferable to calculate it based on the following formula B in accordance with the description on pages 199-200 of the "Wood Science Experiment Manual" (edited by the Japan Wood Research Society; published in April 2000) in order to improve calculation accuracy. Therefore, when the crystallinity obtained by the above formula A is 35% or less, the value calculated based on the following formula B can be used as the crystallinity.

[0098] <Formula B> Cellulose type I crystallinity (%) = [A c / (A c +A a )] x 100 [In the ceremony, A c is the sum of the peak areas of the lattice planes (002 plane) (diffraction angle 2θ = 22.6°), (011 plane) (diffraction angle 2θ = 15.1°), and (0-11 plane) (diffraction angle 2θ = 16.2°) in X-ray diffraction, Aa indicates the peak area of ​​the amorphous portion (diffraction angle 2θ = 18.5°), and each peak area is determined by fitting the obtained X-ray diffraction chart with a Gaussian function.

[0099] [Measurement of viscosity of paints and various mixtures] Measurement was performed using an E-type viscometer (manufactured by Anton Paar, MCR300) and a measuring jig: CP50-1 at a measurement temperature of 25°C as follows: shear rate: 0.1 s -1 From the 7000s -1 The viscosity of the paint to be measured was measured while gradually increasing the shear rate up to 7000s. -1 to 0.1 seconds -1 Measure the viscosity while gradually decreasing the shear rate to 0.1 s. -1 From the 7000s -1 The viscosity was measured while gradually increasing the shear rate from 1 s to 1 s. -1 The viscosity at this point is taken as the viscosity of the paint.

[0100] [Measurement of emulsion droplet size by laser diffraction method] The particle size of the emulsified droplets is measured by laser diffraction using an LA-960 manufactured by Horiba Ltd. Measurement conditions: Add water to the measurement cell, and measure the volume particle size distribution and volume median particle size (D 50 The relative refractive index is 1.4, the temperature is 25°C, the circulation pump is ON, the circulation speed is 5, and the stirring speed is 5.

[0101] [Glucose moieties in cellulose fibers with chemical modifications] With regard to the mass of glucose moieties in chemically modified cellulose fibers such as carboxy group-containing cellulose fibers and modified cellulose fibers, the "mass of glucose moieties" refers to the entire glucose unit including the glucose unit and the carboxy group bound to the glucose unit, i.e., the "mass of glucose moieties" includes not only unmodified glucose units but also glucose units in which the hydroxymethyl group has been converted to a carboxy group.

[0102] [Carboxy group-containing cellulose fiber] As the carboxyl group-containing cellulose fiber, carboxyl group-containing cellulose fiber 1 having the physical properties shown in Table 1 was used.

[0103] [Table 1]

[0104] Such carboxyl group-containing cellulose fibers can be prepared, for example, by the method described in the TEMPO oxidation treatment below.

[0105] [TEMPO oxidation treatment] 10 g of bleached softwood kraft pulp fiber (natural cellulose fiber) and 990 g of deionized water were weighed into a 2-L polypropylene beaker equipped with a mechanical stirrer and impeller and stirred at 25°C and 100 rpm for 30 minutes. Next, 0.13 g of 2,2,6,6-tetramethyl-1-piperidine-N-oxyl (TEMPO), 1.3 g of sodium bromide, and 35.5 g of 10.5% by weight sodium hypochlorite solution were added to the 10 g of pulp fiber in this order. Next, pH stat titration was performed using an automatic titrator, and 0.5 M sodium hydroxide solution was added dropwise to maintain the pH at 10.5. The reaction was carried out at 25°C for 120 minutes with stirring at 100 rpm.

[0106] Next, 1 M hydrochloric acid is added to the suspension while stirring to adjust the pH of the suspension to 2. The solids are then separated by suction filtration. The solids are dispersed in deionized water and the solids are separated by suction filtration. This procedure is repeated until the conductivity of the filtrate reaches 200 μs / cm or less. The resulting solids are then dehydrated to obtain carboxyl group-containing cellulose fibers.

[0107] Preparation Example 1 [Preparation of finely divided carboxyl group-containing cellulose fibers] [Preparation of dispersion of finely divided carboxyl group-containing cellulose fibers 1] Deionized water was added to the carboxyl group-containing cellulose fiber 1 to prepare 100 g of a suspension (solid content: 2.0% by mass). A 0.5 M aqueous solution of sodium hydroxide was added to the suspension to adjust the pH to 8, and deionized water was added to make a total of 200 g. This suspension was subjected to a micronization treatment three times at 150 MPa using a high-pressure homogenizer (NanoVeita L-ES, manufactured by Yoshida Kikai Kogyo Co., Ltd.) to obtain a dispersion (solid content: 1.0% by mass). 182 g of the resulting dispersion was weighed out and added with deionized water to a total of 400 g. 1.2 mL of 0.1 M aqueous sodium hydroxide and 120 mg of sodium borohydride were added and stirred at 25°C for 4 hours. Next, 9 mL of 1 M hydrochloric acid was added and stirred to perform protonation. After stirring, the solids in the dispersion were filtered off by suction. The solids were then dispersed in deionized water and the procedure of filtering off the solids by suction was repeated until the conductivity of the filtrate reached 50 μS / cm or less, yielding a dispersion of micronized carboxyl group-containing cellulose fiber 1 in deionized water (solid content: 0.9% by mass). The carboxyl group content of the resulting cellulose fiber was 1.45 mmol / g.

[0108] Preparation Example 2 [Preparation of Emulsified Mixture 1] A beaker was mixed with 667 g of the above-mentioned dispersion of finely divided carboxyl group-containing cellulose fibers 1 in deionized water (solid content: 0.9% by mass), 60 g of silicone oil, and 25.9 g of amino-modified silicone as a modifying compound (equivalent to 1.75 equivalents of the carboxyl groups in the carboxyl group-containing cellulose fibers, assuming the molar mass of amino groups in the amino-modified silicone is 1). Deionized water was then added to make a total of 1000 g. This dispersion was stirred with a mechanical stirrer at room temperature for 5 minutes and then subjected to 10 passes at 150 MPa in a high-pressure homogenizer (Yoshida Kikai Kogyo Co., Ltd., Nanovaita L-ES) to obtain emulsified mixture 1 (solid content: 9.2% by mass). The resulting mixture 1 was a cloudy white liquid. Oil droplets dispersed in water were observed under an optical microscope, confirming its emulsification. The average particle size of the emulsified droplets was 300 nm as determined by laser diffraction. The viscosity of the mixture at 25 °C was 10 mPa·s.

[0109] Preparation Example 3 [Preparation of Emulsified Mixture 2] Emulsified mixture 1 was concentrated using a rotary evaporator (Tokyo Rikakikai, N-2110) under conditions of a hot bath of 40°C, 15 Torr, and a rotation speed of 80 rpm. Next, it was subjected to two passes at 150 MPa in a high-pressure homogenizer (Yoshida Kikai Kogyo, Nanovaita L-ES) to obtain emulsified mixture 2 (solid content 29.9% by mass).

[0110] Preparation Example 4 [Preparation of Pigment Dispersion 1] 50 g of zirconia balls (Nikkato Corporation, YTZ, φ0.3 mm) were weighed and placed in a 100 mL plastic bottle. 37.5 g of SN Dispersant 5029 (manufactured by San Nopco, active ingredient: 25% by mass) was diluted with ion-exchanged water to a concentration of 0.5% by mass, and added to the plastic bottle. 25 g of red iron oxide (manufactured by Toda Kogyo Co., Ltd., 140ED) was also added to the plastic bottle. Next, the plastic bottle was subjected to vibration stirring at room temperature for 2 hours using a paint shaker (manufactured by Asada Iron Works, vibration frequency: 643 rpm) to obtain a 40 mass % aqueous red iron oxide dispersion, which was designated as Pigment Dispersion 1.

[0111] Example 1 [Preparation of ship bottom paint] Components (G), (D), (H), (I), and (E) were added to emulsified mixture 2 in this order to obtain the composition shown in Table 2, and the mixture was stirred and mixed using a planetary centrifugal mixer (Thinky Corporation, Awatori Rentaro, ARE-310). After stirring for 20 minutes, the mixture was degassed for 2 minutes to prepare a ship bottom paint. The viscosity of the resulting ship bottom paint was 7,100 mP·s.

[0112] [Table 2]

[0113] Details of the representative components used in the examples are summarized below. Note that the numbers marked with * in Table 2 are the amount of active ingredient (or pigment itself), not the amount of product. [Component (B)] Amino-modified silicone: Dow Toray, DOWSIL TM FZ-3710 (Kinematic viscosity: 1,000, Amino equivalent: 1,700) [Component (C)] Silicone oil: Shin-Etsu Chemical Co., Ltd., KF-96-100cs (SP value: 7.3) [Component (D)] (Meth)acrylic polymer compound: Neocryl XK-188 (acrylic styrene copolymer, solid content concentration 44.5% by mass, viscosity: 400 mPa·s (GAP0020)), manufactured by DSM [Component (E)] Urethane-modified polyether thickener: San Nopco SN Thickener 660T (solids concentration: 20% by mass) [Component (G)] Wetting agent: Polyether-modified silicone, manufactured by Shin-Etsu Chemical Co., Ltd., KF-642 (HLB: 12, kinematic viscosity (25 °C): 50 mm 2 / s) [Component (H)] Solvent: Fujifilm Wako Pure Chemical Industries, Ltd., 1-methyl-2-pyrrolidone (NMP) (Wako special grade)

[0114] Comparative Example 1 In Comparative Example 1, SEAFLONEO SL Z manufactured by Chugoku Paint Co., Ltd. was used as existing ship bottom paint 1.

[0115] Test Example 1 [Cylinder production and Rz measurement] (Coating on cylinders) A PVC cylinder with an outer diameter of 150 mm and a length of 150 mm was prepared. A hole was drilled in the center of the cylinder to attach the rotating shaft of a rotating cylinder-type friction resistance measuring device. The circumferential surface of this cylinder was painted as follows. (For Example 1) (1) Three cylinders were prepared. The circumferential surfaces of these cylinders were sprayed with a primer coat of Banno 500 (manufactured by Chugoku Paint Co., Ltd.) and then allowed to dry. (2) Next, the ship bottom paint of Example 1 was spray-painted as follows, and then dried to prepare three types of cylinders each having a different surface roughness. Cylinder 1-1: No additional coating was applied. Cylinder 1-2: Repainted 1 hour after painting. Cylinder 1-3: Two hours after painting, another coat was applied, one hour later, and one hour later.

[0116] (For Comparative Example 1) (1) Three cylinders were prepared. The circumferential surfaces of these cylinders were sprayed with a primer coat of Banno 1500RZ (manufactured by Chugoku Paint Co., Ltd.) and then allowed to dry. (2) Existing ship bottom paint 1 was spray painted as shown below, and then dried to create three types of cylinders with different surface roughness. Cylinder 2-1: No additional coating was applied. Cylinder 2-2: Repainted 2 minutes after painting. Cylinder 2-3: Repainted 10 minutes after painting.

[0117] (Measurement of cylinder roughness (Rz)) Using a surface roughness measuring instrument (Mitutoyo Corporation, SJ-210), the maximum height roughness (Rz) of the surface roughness of the paint applied to each cylinder was determined as follows. The surface roughness Rz was measured along the length of the cylinder at positions 37.5 mm, 75 mm, and 112.5 mm from the top end (a total of three points).Furthermore, the surface roughness Rz was measured similarly at positions 37.5 mm, 75 mm, and 112.5 mm from the top end of the cylinder (a total of three points) when the cylinder was rotated 90°, 180°, and 270° from these measurement positions. The average value of the surface roughness Rz obtained from these surface roughness measurements at a total of 12 points per cylinder was taken as the representative value of the surface roughness Rz of the paint on that cylinder. The representative values ​​of the surface roughness Rz for each cylinder are shown in Table 3.

[0118] [Table 3]

[0119] Test Example 2 [Measurement of equivalent sand roughness] (Rotating cylinder test) The frictional resistance acting on the painted cylindrical surface was evaluated using a rotating cylinder frictional resistance measuring device. Using this device, it is possible to evaluate the frictional resistance between seawater and the hull surface that occurs when a ship is sailing.

[0120] The outline of this test equipment is shown in Figure 1, and the measurement and analysis methods were carried out in accordance with Document 1. Material 1: The influence of coating surface characteristics on frictional resistance, Toshio Tanaka, Yasuyuki Toda, Kiyoaki Higo; Kazuharu Yamashita, Journal of the Kansai Shipbuilding Association, No. 239 (2003)

[0121] As shown in Figure 1, the cylinder was double-layered, with the inner cylinder 1 being the one produced in Example 1 and Comparative Example 1 above, and the outer cylinder 2 (diameter 450 mm) being used as a water tank. Horizontal plates 11 and 12 were installed at the top and bottom ends of cylinder 1 to eliminate the resistance and free surface effect caused by the ends of cylinder 1. The inner cylinder 1 was rotated at a specified rotation speed by a motor 3, and the torque acting on the rotating shaft 4 was measured by a sensor 5. Measurements were performed by varying the rotation speed in increments of 2 rps from 2 rps to 34 rps. After the torque stabilized at the specified rotation speed, torque data was collected for 30 seconds, and the time-averaged value was used as the torque acting on the cylinder for analysis. The water temperature during the test was also measured to obtain the water's physical properties (density, dynamic viscosity coefficient). Tap water was used as the water in the tank. The motor 3 used here was a Yaskawa Electric SGMSH-40ACA21, and the sensor 5 was a Kyowa Electric TP-1KMCB.

[0122] (Test analysis method and test results) An overview of the test analysis method is provided below. (1) The Reynolds number Rn and the resistance coefficient Ct acting on the cylinder surface during measurement were calculated according to the following formula. Rn=UL / ν Ct=Q / (D / 2) / (1 / 2ρU 2 S) U=πDn L=πD S=πDH D: Cylindrical diameter (m) n: rotation speed (rps) Q: Measurement torque (N m) ρ: density of water (kg / m 3 ) ν: Dynamic viscosity of water (m 2 / s) H: Cylinder height (m)

[0123] (2) The resistance of the smooth cylinder was measured, and the components other than the frictional resistance acting on the cylinder were calculated in the form of a shape influence coefficient. Using this shape influence coefficient, the frictional resistance coefficient Cf was calculated from the total resistance coefficient acting on each cylinder calculated in (1). (3) A theoretical solution that fits the measured Cf was obtained, and the equivalent sand roughness was calculated from the resistance coefficient acting on each cylinder (Fig. 2). (4) Based on the relationship between the roughness of the cylinder and the equivalent sand roughness calculated in (3), the equivalent sand roughness (Ks) between paints with the same roughness was compared (Fig. 3). Since the equivalent sand roughness indirectly indicates the magnitude of frictional resistance, the smaller the equivalent sand roughness, the smaller the frictional resistance.

[0124] Table 4 shows the equivalent sand roughness of each paint at any Rz obtained from the above test analysis.

[0125] [Table 4]

[0126] The difference in friction resistance due to the difference in Ks was evaluated. 6 ), the friction resistance coefficient Cf of Example 1 was found to be approximately 1.61 × 10 -3 , and Cf of Comparative Example 1 is about 1.67 × 10 -3 It was found that the friction resistance of Example 1 was approximately 3.5% lower.

[0127] [Table 5] [Industrial Applicability]

[0128] The ship bottom paint of the present invention not only has a smooth coating surface but also is capable of preventing adhesion of marine organisms, and therefore can be used in the field of ship bottom paints. [Explanation of symbols]

[0129] 1 (inner) cylinder 2 (outer) cylinder 3 motors 4 rotation axes 5 sensors 11 horizontal plate 12 horizontal plate

Claims

1. A paint for ship bottoms containing the following components (A) to (F): (A) Carboxy group-containing cellulose fiber (B) Amino-modified silicone (C) Silicone oil (excluding the component (B)). (D) (Meth)acrylic polymer compound (E) Urethane-modified polyether thickener (F) Water

2. The ship bottom paint according to claim 1, further comprising one or more components selected from the group consisting of the following components (G), (H), (I) and (J): (G) Wetting agent (H) Solvent (I) Pigment (J) Antifouling agent

3. 3. The paint for ship bottoms according to claim 1 or 2, wherein the content ratio of component (D) to component (A) is 2 or more and 20 or less.

4. 3. The ship bottom paint according to claim 1 or 2, wherein the content ratio of component (E) to component (A) is 0.05 or more and 0.5 or less.

5. A method for producing a ship bottom paint comprising the following steps: Step 1: A step of mixing the following components (A), (B), (C), and (F): Step 2: Mixing the mixture obtained in Step 1 with the following component (D) and the following component (E): (A) Carboxy group-containing cellulose fiber (B) Amino-modified silicone (C) Silicone oil (excluding the component (B)). (D) (Meth)acrylic polymer compound (E) Urethane-modified polyether thickener (F) Water

6. A friction resistance reducer for ships containing the following components (A) to (F): (A) Carboxy group-containing cellulose fiber (B) Amino-modified silicone (C) Silicone oil (excluding the component (B)). (D) (Meth)acrylic polymer compound (E) Urethane-modified polyether thickener (F) Water

7. A ship having a bottom coated with the ship bottom paint according to claim 1 or 2, the ship bottom paint produced by the production method according to claim 5, or the ship friction resistance reducer according to claim 6.

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