Antifouling agent for inhibiting deposition of aquatic organisms, antifouling agent composition for inhibiting deposition of aquatic organisms, cured product of antifouling agent for inhibiting deposition of aquatic organisms, and antifouling coating film

Abstract

To provide an antifouling agent for inhibiting deposition of aquatic organisms.SOLUTION: Provided is an antifouling agent for inhibiting deposition of aquatic organisms, the agent comprising a titanium oxide composition having a metal compound containing copper supported on titanium oxide particles.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an antifouling agent for suppressing adhesion of aquatic organisms, an antifouling agent composition for suppressing adhesion of aquatic organisms, a cured product of the antifouling agent for suppressing adhesion of aquatic organisms, and an antifouling coating film.

Background Art

[0002] On the surface of a substrate (such as ships, underwater structures, fishing nets, seawater supply and drainage pipes of factories, etc.) that is exposed to water (seas, rivers, lakes, etc.) for a long time in the natural environment, various aquatic organisms tend to adhere. When aquatic organisms adhere to the surface of the substrate, it may damage the appearance and cause various problems. For example, when the substrate is a ship, if aquatic organisms adhere to the ship, the resistance to the adhesion surface by the water flow increases, which may lead to a decrease in the ship speed and an increase in fuel consumption. Also, when the substrate is an underwater structure, the antifouling coating film applied to the surface of the substrate of the underwater structure may be damaged, resulting in damage such as a decrease in strength and function and a significant shortening of the lifespan. In addition, when the substrate is a fishing net such as a culture net or a stationary net, the mesh may be blocked by aquatic organisms, which may cause serious problems such as oxygen deficiency and death of cultured organisms and caught organisms. Also, when aquatic organisms adhere and reproduce in the seawater supply and drainage pipes in factories and thermal power plants and nuclear power plants, it may cause blockage of the supply and drainage pipes and a decrease in the flow rate. In order to prevent the adhesion of aquatic organisms that cause such problems, an antifouling paint is applied to the surface of the substrate to form an antifouling coating film.

[0003] As an antifouling agent used in such antifouling paints, cuprous oxide has been widely used because it can exhibit excellent antifouling performance against the adhesion of aquatic organisms. However, in recent years, alternative substances to cuprous oxide have been studied. For example, in Patent Document 1, the development of an antifouling paint using medetomidine as an antifouling agent has been advanced.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] As substances for antifouling agents to replace cuprous oxide, in addition to the above-mentioned medetomidine, substances such as irgarol (sibutramine) are also being considered. The present inventors have studied antifouling agents that replace the substances used in conventionally known antifouling agents. Therefore, the object of the present invention is to provide an antifouling agent for suppressing the adhesion of aquatic organisms, an antifouling agent composition for suppressing the adhesion of aquatic organisms, a cured product of the antifouling agent for suppressing the adhesion of aquatic organisms, and an antifouling coating film.

Means for Solving the Problems

[0006] As a result of intensive studies to solve the above problems, the present inventors have found that a specific titanium oxide composition is effective as an antifouling agent for suppressing the adhesion of aquatic organisms, and have thus completed the present invention. That is, the gist configuration of the present invention is as follows.

[0007] [1] An antifouling agent for suppressing the adhesion of aquatic organisms, containing a titanium oxide composition in which a metal compound containing copper is supported on titanium oxide particles. An antifouling agent for suppressing the adhesion of aquatic organisms that prevents the adhesion of aquatic organisms.

[0008] [2] The antifouling agent for suppressing the adhesion of aquatic organisms according to [1], wherein the aquatic organisms are barnacles, mussels or oysters.

[0009] [3] The antifouling agent for suppressing the adhesion of aquatic organisms according to [1] or [2], wherein the content ratio of copper (Cu / Ti molar ratio) in the metal compound supported on the titanium oxide particles is 0.1 to 5.0 with respect to 100 of titanium.

[0010] [4] The antifouling agent for suppressing the adhesion of aquatic organisms according to any one of [1] to [3], wherein the content rate (rutile ratio) of rutile-type titanium oxide contained in the titanium oxide particles is 87.2 mol% or more.

[0011] [5] The antifouling agent for suppressing adhesion of aquatic organisms according to any one of [1] to [4], wherein the titanium oxide particles contain zirconium and niobium.

[0012] [6] The antifouling agent for suppressing adhesion of aquatic organisms according to [5], wherein the content ratio of zirconium (Zr / Ti ratio) in the titanium oxide particles is 0.03 to 0.8 with respect to 100 of titanium.

[0013] [7] The antifouling agent for suppressing adhesion of aquatic organisms according to [5], wherein the content ratio of niobium (Nb / Ti ratio) in the titanium oxide particles is 0.05 to 0.8 with respect to 100 of titanium.

[0014] [8] An antifouling agent composition for suppressing adhesion of aquatic organisms, comprising the antifouling agent for suppressing adhesion of aquatic organisms according to any one of [1] to [7] and a solvent.

[0015] [9] The antifouling agent composition for suppressing adhesion of aquatic organisms according to [8], further comprising a binder resin.

[0016]

[10] A cured product of the antifouling agent for suppressing adhesion of aquatic organisms according to [8].

[0017]

[11] An antifouling coating film formed from the cured product of the antifouling agent for suppressing adhesion of aquatic organisms according to

[10] .

[0018]

[12] A substrate with an antifouling coating film, comprising a substrate and the antifouling coating film according to

[11] provided on the surface of the substrate.

[0019]

[13] The substrate with an antifouling coating film according to

[12] , wherein the substrate is at least one selected from ships, underwater structures, fishing materials, and water supply and drainage pipes. [Advantages of the Invention]

[0020] According to the present invention, it is possible to provide an antifouling agent for suppressing adhesion of aquatic organisms that prevents adhesion of aquatic organisms. Further, according to the present invention, it is possible to provide an antifouling agent composition for suppressing adhesion of aquatic organisms. Further, according to the present invention, it is possible to provide a cured product of an antifouling agent for suppressing adhesion of aquatic organisms that prevents adhesion of aquatic organisms. Further, according to the present invention, it is possible to provide an antifouling coating film that prevents adhesion of aquatic organisms. Further, according to the present invention, it is possible to provide a substrate with an antifouling coating film that prevents adhesion of aquatic organisms.

Mode for Carrying Out the Invention

[0021] Hereinafter, an embodiment of the present invention will be described. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the range that does not impair the effects of the present invention.

[0022] (Antifouling agent for suppressing adhesion of aquatic organisms) The antifouling agent for suppressing adhesion of aquatic organisms according to this embodiment is an antifouling agent for suppressing adhesion of aquatic organisms that contains a titanium oxide composition in which a copper-containing metal compound is supported on titanium oxide particles, and prevents adhesion of aquatic organisms. Thereby, an adhesion suppression effect is exhibited, and it is possible to achieve an effect of suppressing adhesion of aquatic organisms such as animal fouling organisms such as barnacles and mussels, or plant fouling organisms such as seaweeds such as green algae and blue-green algae.

[0023] Here, the above-mentioned aquatic organisms include marine organisms and freshwater organisms, and also include diatoms, seaweeds, shellfish, etc. And the aquatic organisms, in a narrow sense, refer to fouling organisms. Fouling organisms are organisms that form a group on an artificial object placed in water or an artificial object in contact with water (especially its surface), and as a result, the phenomenon of having an unfavorable impact on an artificial structure is called "fouling", and the organisms that form "fouling" are called. The antifouling agent for suppressing adhesion of aquatic organisms of the present invention can specifically suppress the adhesion of organisms that live a floating life in the sea or fresh water during the larval stage and then, when a certain opportunity comes, attach to a suitable substrate and transform into adults and switch to a sedentary life. For example, it can suppress the settlement of barnacles, mussels, hydroids, jellyfish polyps, and barnacle-like organisms.

[0024] The antifouling agent for suppressing adhesion of aquatic organisms of the present invention contains a titanium oxide composition in which a metal compound containing copper is supported on titanium oxide particles. Since this titanium oxide composition has an effect similar to that of titanium oxide as a photocatalyst under light irradiation, namely, a decomposition and sterilization effect on bacteria, viruses, fungi, etc., when aquatic organisms begin to adhere (fixate) to the coating surface using an adhesive component made of protein, it is considered that the adhesion of aquatic organisms to the coating surface can be suppressed by denaturing the protein structure on the surface of this coating. Hereinafter, the details of the antifouling agent for suppressing adhesion of aquatic organisms according to this embodiment will be described.

[0025] <Titanium Oxide Composition> The titanium oxide composition contained in the antifouling agent for suppressing adhesion of aquatic organisms according to this embodiment is a composition in which a metal compound containing copper is supported on titanium oxide particles, and the details thereof will be described below.

[0026] The titanium oxide particles may be pure titanium oxide particles composed only of titanium and oxygen, or may be particles containing a metal element other than titanium in part, and preferably contain zirconium and niobium. And as the titanium oxide particles, those containing rutile-type titanium oxide are included, and as the content (rutile ratio) of the rutile-type titanium oxide, from the viewpoint of obtaining more excellent antimicrobial properties in bright and dark places, decomposability of organic compounds in bright places, and visible light responsiveness, it is preferably 15 mol% or more, more preferably 50 mol% or more, and even more preferably 90 mol% or more.

[0027] As the titanium oxide particles, in addition to the rutile-type titanium oxide, anatase-type titanium oxide, brookite-type titanium oxide, etc. may also be included.

[0028] In the present invention, as the titanium oxide particles, those produced by either a gas phase method or a liquid phase method can be used, but it is preferable to use those produced by the liquid phase method.

[0029] As methods for producing the titanium oxide particles, generally, a liquid phase method and a gas phase method are known. The liquid phase method is a method of obtaining titanium oxide particles by hydrolyzing or neutralizing titanyl sulfate obtained from a solution in which a raw ore such as ilmenite ore is dissolved. The gas phase method is a method of obtaining titanium oxide particles by a gas phase reaction between titanium tetrachloride obtained by chlorinating a raw ore such as rutile ore and oxygen.

[0030] In the present invention, as the raw ore of the titanium oxide particles, ilmenite ore may be used, or titanium slag obtained by metallurgical treatment of ilmenite ore to increase the titanium purity may be used. The content ratio (Cu / Ti molar ratio) of copper in the metal compound supported on the titanium oxide particles is preferably 0.1 or more, more preferably 0.3 or more, still more preferably 0.5 or more, and preferably 5.0 or less, more preferably 3.0 or less, still more preferably 2.0 or less, with respect to 100 of titanium. Any combination of these upper and lower limits may be used.

[0031] In the present invention, by including copper in the above ratio, the titanium oxide composition can obtain more excellent antimicrobial properties in bright and dark places, organic compound decomposability in bright places, and visible light responsiveness. As the main components of conventional antifouling agents, cuprous oxide (Cu 2 O), organotin compounds (TBT, TPT), arsenic-based compounds, mercury-based compounds, etc. have been mainly used. However, organotin compounds (TBT, TPT), arsenic-based compounds, and mercury-based compounds are highly likely to have an adverse effect on the working environment and ecosystem due to the toxicity or low degradability of these compounds. As a result, currently, cuprous oxide (Cu 2The use of the above compounds other than (O) is restricted. Also, regarding Irgarol, at present, a revised proposal to newly add it to the prohibited substances is under consideration by the International Maritime Organization (IMO). However, the antifouling agent for suppressing the adhesion of aquatic organisms of the present invention contains a titanium oxide composition with a significantly reduced amount of copper compound and substantially does not use tin, arsenic, and organotin. Therefore, it is considered that the safety for workers (working environment) and the load on the marine environment can be reduced compared to the conventional antifouling agents.

[0032] Further, the titanium oxide particles preferably contain metal elements such as zirconium and niobium. The content ratio of zirconium to titanium (Zr / Ti ratio) in the titanium oxide particles is preferably 0.03 or more, more preferably 0.04 or more, still more preferably 0.05 or more, and is preferably 0.8 or less, more preferably 0.5 or less, still more preferably 0.3 or less. Any combination of these upper and lower limits may be used. The content ratio of niobium to titanium (Nb / Ti ratio) in the titanium oxide particles is preferably 0.03 or more, more preferably 0.04 or more, still more preferably 0.05 or more, and is preferably 0.8 or less, more preferably 0.5 or less, still more preferably 0.3 or less. Any combination of these upper and lower limits may be used. Titanium oxide particles within the above range have high dispersibility in a solvent, and even when the concentration of the titanium oxide particles is increased, the handling of the mixed solution is good.

[0033] The titanium oxide particles substantially containing the metal element (zirconium and / or niobium) in the present invention have less cohesive force with respect to the specific surface area (BET value) caused by the primary particles and can suppress the viscosity of the mixed solution, and it is presumed that they contribute to the improvement of the concentration of the titanium oxide particles.

[0034] As the BET specific surface area of the titanium oxide particles, a range of 1 to 200 m 2 / g is preferable from the viewpoint of obtaining more excellent antibacterial properties and visible light responsiveness, and 3 to 100 m 2The range of / g is more preferable, 4 to 70 m 2 The range of / g is more preferable, 8 to 50 m 2 The range of / g is even more preferable, and from the point that the productivity of the titanium oxide composition can be further enhanced, it is 7.5 to 9.5 m 2 It is preferably in the range of / g. The BET specific surface area of the titanium oxide composition of the present invention is approximately the same value as the BET specific surface area of the titanium oxide particles before supporting the metal compound, and the measurement method of the BET specific surface area of the titanium oxide particles will be described in the examples described later.

[0035] As the primary particle diameter of the titanium oxide particles, from the point that more excellent antimicrobial properties and visible light responsiveness can be obtained, the range of 0.01 to 0.5 μm is preferable, the range of 0.03 to 0.35 μm is more preferable, and the range of 0.06 to 0.35 μm is even more preferable. The measurement method of the primary particle diameter of the titanium oxide particles is a value measured by a method of directly measuring the size of the primary particles from an electron micrograph using a transmission electron microscope (TEM). Specifically, the minor axis diameter and major axis diameter of each primary particle are measured, and the average is taken as the particle diameter of the primary particle. Next, for 100 or more particles, the volume (weight) of each particle is approximated by the cube of the obtained particle diameter, and the volume average particle diameter is taken as the average primary particle diameter. The primary particle diameter of the titanium oxide composition of the present invention is approximately the same value as the primary particle diameter of the titanium oxide particles before supporting the metal compound.

[0036] <Metal compound> As the metal of the metal compound, it is sufficient to contain at least copper, and in addition, for example, transition metals such as iron, tungsten, zirconium, molybdenum, etc. can be used. As the metal of the metal compound, other metals such as zinc, aluminum, antimony, lanthanum, etc. can also be used according to the desired physical properties. The titanium oxide particles may support an inorganic compound according to the desired physical properties, and for example, silicon may be used.

[0037] As the metal compound containing copper, for example, divalent copper inorganic compounds, divalent copper organic compounds, etc. can be used. Examples of the divalent copper inorganic compound include inorganic acid salts of divalent copper such as copper sulfate, copper nitrate, copper iodate, copper perchlorate, copper oxalate, copper tetraborate, copper ammonium sulfate, copper amidosulfate, copper ammonium chloride, copper pyrophosphate, and copper carbonate; halides of divalent copper such as copper chloride, copper fluoride, and copper bromide; copper oxide, copper sulfide, azurite, malachite, copper azide, etc. These compounds may be used alone or in combination of two or more.

[0038] Examples of the divalent copper organic compound include copper formate, copper acetate, copper propionate, copper butyrate, copper valerate, copper caproate, copper enanthate, copper caprylate, copper pelargonate, copper caprate, copper myristate, copper palmitate, copper margarate, copper stearate, copper oleate, copper lactate, copper malate, copper citrate, copper benzoate, copper phthalate, copper isophthalate, copper terephthalate, copper salicylate, copper mellitate, copper oxalate, copper malonate, copper succinate, copper glutarate, copper adipate, copper fumarate, copper glycolate, copper glycerate, copper gluconate, copper tartrate, copper acetylacetonate, copper ethyl acetoacetate, copper isovalerate, copper β-resorcylate, copper diacetoacetate, copper formylsuccinate, copper salicylamine, copper bis(2-ethylhexanoate), copper sebacate, copper naphthenate, copper oxine, copper acetylacetonate, copper ethyl acetoacetate, copper trifluoromethanesulfonate, copper phthalocyanine, copper ethoxide, copper isopropoxide, copper methoxide, copper dimethyldithiocarbamate, etc. These compounds may be used alone or in combination of two or more.

[0039] Among the above-mentioned ones, those represented by the following general formula (1) are preferably used as the divalent copper compound raw material. CuX 2 (1) (In formula (1), X represents a halogen atom, CH 3 COO, NO 3 , or (SO 4 )1 / 2.)

[0040] As X in the formula (1), a halogen atom is more preferable, and a chlorine atom is even more preferable.

[0041] As a processing method for supporting a supported substance (metal compound or inorganic compound) on the titanium oxide particles, known methods can be used if it is wet. For example, a method of adsorbing with a mixed solution in which titanium oxide particles are suspended in an aqueous solution of a supported substance and a solvent, a method of reacting with a mixed solution of titanium oxide particles, a supported substance, a solvent, and an alkaline substance, etc. can be mentioned. When processing, a mixed solution is prepared. The mixed solution contains at least titanium oxide particles and a solvent.

[0042] The concentration of the titanium oxide particles in the mixed solution is preferably in the range of 3 to 40% by mass. In the present invention, it is preferable to use titanium oxide particles produced by a liquid phase method, and even if the concentration of the titanium oxide particles is increased, the reaction can be carried out with a well-handling mixed solution. Specifically, even when the concentration of the titanium oxide particles is in the range exceeding 25% by mass and 40% by mass or less, the reaction with a good mixed solution can be carried out.

[0043] The amount of the supported substance raw material used in the mixed solution is preferably in the range of 0.01 to 20 parts by mass, more preferably in the range of 0.1 to 15 parts by mass, and still more preferably in the range of 0.3 to 10 parts by mass with respect to 100 parts by mass of the titanium oxide particles.

[0044] As the solvent, only water may be used, or a mixed solvent of water and an organic solvent may be used. In the case of a mixed solvent, an aqueous solvent mainly composed of water is preferable. Here, the aqueous solvent mainly composed of water means the one having the largest water content in the total amount of the solvent, and preferably 50% by mass or more is water. In the case of a mixed solvent containing an organic solvent, the composition of the organic solvent is determined according to the properties of the desired mixed solution. From the viewpoints of reducing environmental load and improving safety, the mixed solvent preferably contains an organic solvent in 30% by mass or less in the total amount of the solvent, and preferably 5% by mass or less.

[0045] The organic solvents that can be used as the solvent are not particularly limited. For example, organic solvents miscible with water are preferably used. Examples of the organic solvents that can be used as the solvent include monohydric alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, isobutanol, 1-pentanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol, etc.; various diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, propylene glycol, 1,2-butanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, 2-methyl-1,3-propanediol, 1,2-hexanediol, dipropylene glycol, diethylene glycol, etc.; polyhydric alcohols such as glycerin; ketones such as methyl ethyl ketone, methyl isobutyl ketone, etc.; dimethylformamide, tetrahydrofuran, bisphenol A, aromatic diols that are adducts of bisphenol A with alkylene oxides having 2 or 3 carbon atoms (average addition mole number is 1 or more and 16 or less), alicyclic diols such as hydrogenated bisphenol A, polyoxypropylene-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene-2,2-bis(4-hydroxyphenyl)propane, cyclohexanediol, ethylene glycol monomethyl ether, ethylene glycol mono-isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-isobutyl ether, diethylene glycol monomethyl ether, diethylene glycol mono-isopropyl ether, diethylene glycol monobutyl ether, diethylene glycol mono-isobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, ethyl carbitol, γ-butyrolactone, and the like.These may be used singly or in combination of two or more, without limitation. Among them, 1-butanol, isobutanol, 1-pentanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol, methyl ethyl ketone, methanol, ethanol, n-propyl alcohol (NPA), isopropyl alcohol (IPA), propylene glycol, propylene glycol monomethyl ether (1-methoxy-2-propanol) (PGM), and ethylene glycol are preferred.

[0046] Examples of the alkaline substance include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, trimethylamine, ammonia, basic surfactants, etc., and it is preferable to use sodium hydroxide.

[0047] From the viewpoint of easy reaction control, the alkaline substance is preferably added as a solution. The concentration of the alkaline solution to be added is preferably in the range of 0.1 to 5 mol / L, more preferably in the range of 0.3 to 4 mol / L, and still more preferably in the range of 0.5 to 3 mol / L.

[0048] Next, the method of supporting a divalent copper compound on titanium oxide particles, which is the most preferred embodiment, will be described.

[0049] The mixed solution may be prepared by mixing the titanium oxide particles, the divalent copper compound raw material, the solvent, and the alkaline substance. For example, first, the titanium oxide particles are mixed with water and stirred as necessary, then the divalent copper compound raw material is mixed and stirred, and then the alkaline substance is added and stirred. By this mixed solution, the divalent copper compound derived from the divalent copper compound raw material is supported on the titanium oxide particles.

[0050] As the total stirring time of the mixed solution, for example, 5 to 120 minutes can be mentioned, preferably 10 to 60 minutes. As the reaction temperature of the mixed solution, for example, the range from room temperature to 70 °C can be mentioned.

[0051] From the point that the loading of the divalent copper compound on the titanium oxide particles is good, as the pH of the mixed solution after mixing and stirring the titanium oxide particles, the divalent copper compound raw material, and water, and then mixing and stirring the alkaline substance, it is preferably in the range of 6 to 12, more preferably in the range of 7.5 to 10.5.

[0052] After the reaction in the mixed solution is completed, the solid content can be separated. Examples of the method for performing the separation include filtration, sedimentation separation, centrifugal separation, evaporation to dryness, etc., but filtration is preferred. The separated solid content may then be washed with water, crushed, classified, etc. as necessary.

[0053] After obtaining the solid content, it is preferable to heat-treat the solid content from the point that the divalent copper compound derived from the divalent copper compound raw material supported on the titanium oxide particles can be more firmly bonded. As the heat treatment temperature, it is preferably in the range of 150 to 600 °C, more preferably in the range of 250 to 450 °C. Also, the heat treatment time is preferably 1 to 10 hours, more preferably 2 to 5 hours.

[0054] By the above method, a titanium oxide composition in which a divalent copper compound is supported on titanium oxide particles is obtained. From the point of photocatalytic activity including antibacterial properties, the loading amount of the divalent copper compound in the titanium oxide composition is preferably in the range of 0.01 to 20% by mass with respect to the titanium oxide composition. The loading amount of the divalent copper compound can be adjusted by the usage amount of the divalent copper compound raw material in the mixed solution. The measurement method of the loading amount of the divalent copper compound will be described in the examples described later.

[0055] The mixture may contain other components as long as the effects of the present invention can be obtained. Examples of other components include pigments, leveling agents, defoaming agents, plasticizers, infrared absorbers, ultraviolet absorbers, fragrances, flame retardants, and the like. Further, the mixture in the present invention is a dispersion of a titanium oxide composition and can also be used as an antimicrobial agent, a coating agent, a coloring agent, and the like. Examples of coloring agents include general inks, paints, and recording agents.

[0056] The antifouling agent for suppressing adhesion of aquatic organisms of the present invention contains a titanium oxide composition. The titanium oxide composition contained in the antifouling agent for suppressing adhesion of aquatic organisms may be a single type or two or more types of titanium oxide compositions having different structures from each other, and may also contain any other components.

[0057] The antifouling agent for suppressing adhesion of aquatic organisms of the present invention only needs to contain a titanium oxide composition. For example, the antifouling agent for suppressing adhesion of aquatic organisms of the present invention consists essentially of a titanium oxide composition, or the antifouling agent for suppressing adhesion of aquatic organisms of the present invention is a titanium oxide composition. Here, "consisting essentially of" means that the proportion of the titanium oxide composition in the antifouling agent for suppressing adhesion of aquatic organisms of the present invention is 90% by mass or more, 95% by mass or more, or 99% by mass or more.

[0058] The above titanium oxide composition can be obtained by supporting a metal compound containing copper on titanium oxide particles by any of the above-described wet methods, and can also be produced by any known method, and commercially available products may be used.

[0059] (Antifouling agent composition for suppressing adhesion of aquatic organisms) The antifouling agent composition for suppressing adhesion of aquatic organisms of the present invention contains the antifouling agent for suppressing adhesion of aquatic organisms of the present invention and a solvent. Further, preferably, in addition to the antifouling agent for suppressing adhesion of aquatic organisms of the present invention and the solvent, it further contains a binder resin.

[0060] The content of the antifouling agent for suppressing the adhesion of aquatic organisms in the antifouling agent composition for suppressing the adhesion of aquatic organisms of the present invention is not particularly limited. For example, it may be contained in an amount of 1% by mass or more, preferably 5% or more, more preferably 10% or more, and even more preferably 30% or more based on the total mass of the antifouling agent composition for suppressing the adhesion of aquatic organisms.

[0061] The antifouling agent for suppressing the adhesion of aquatic organisms contained in the antifouling agent composition for suppressing the adhesion of aquatic organisms of the present invention may be used alone or in combination of two or more.

[0062] The solvent contained in the antifouling agent composition for suppressing the adhesion of aquatic organisms is added for the purpose of adjusting the viscosity of the antifouling agent composition for suppressing the adhesion of aquatic organisms, and may be either an aqueous medium or an oily medium.

[0063] Specific examples of the solvent include water, monohydric alcohols such as 1-butanol, isobutanol, 1-pentanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol, methyl ethyl ketone, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, etc., polyhydric alcohols such as various diols and glycerin, diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, propylene glycol, 1,2-butanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, 2-methyl-1,3-propanediol, 1,2-hexanediol, dipropylene glycol, diethylene glycol, etc., aromatic diols which are adducts of bisphenol A and alkylene oxides having 2 or 3 carbon atoms (average addition mole number is 1 or more and 16 or less) of bisphenol A, alicyclic diols such as hydrogenated bisphenol A, hydrocarbons such as toluene, xylene, normal hexane, isohexane, cyclohexane, ethylcyclohexane, methylcyclohexane, normal heptane, isooctane, normal decane, normal pentane, isopentane, solvent naphtha, etc., ketones such as acetone, MEK, MIBK, DIBK, MIPK, cyclohexanone, diacetone alcohol, etc., esters such as ethyl acetate, butyl acetate, methoxybutyl acetate, amyl acetate, normal propyl acetate, isopropyl acetate, methyl lactate, ethyl lactate, butyl lactate, etc., methyl cellosolve, ethyl cellosolve, butyl cellosolve, polyoxypropylene-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene-2,2-Bis(4-hydroxyphenyl)propane, cyclohexanediol, ethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, ethyl carbitol, γ-butyrolactone, various fatty acids, etc. are included.,

[0064] The solvent contained in the antifouling agent composition for suppressing adhesion of aquatic organisms of the present invention may be a single kind or two or more kinds.,

[0065] The content of the solvent in the antifouling agent composition for suppressing adhesion of aquatic organisms of the present invention is not particularly limited, and for example, it may be appropriately set so that the solid content concentration of the antifouling agent composition for suppressing adhesion of aquatic organisms is in the range of 1 to 100% by mass.,

[0066] When the antifouling agent composition for suppressing adhesion of aquatic organisms of the present invention contains a binder resin, the content of the antifouling agent for suppressing adhesion of aquatic organisms of the present invention is not particularly limited. For example, it may contain the antifouling agent for suppressing adhesion of aquatic organisms in the range of 0.5 to 200 parts by mass with respect to 100 parts by mass of the resin solid content, preferably in the range of 1 to 100 parts by mass with respect to 100 parts by mass of the resin solid content, and more preferably in the range of 10 to 70 parts by mass with respect to 100 parts by mass of the resin solid content. Here, the "resin solid content" means the total amount of the solid content such as the binder resin contained in the antifouling agent composition for suppressing adhesion of aquatic organisms.,

[0067] The binder resin contained in the antifouling agent composition for suppressing adhesion of aquatic organisms of the present invention is not particularly limited, and for example, any type of emulsion resin, latex resin, thermosetting resin, or active energy ray-curable resin can be used.

[0068] The binder resin may be either a water-soluble resin or a water-insoluble resin (solvent-based resin). In the present application, the "water-soluble resin" means that the amount of water required to dissolve 1 g of the resin at 20°C is less than 10 ml. The "water-insoluble resin" refers to a resin other than the above-mentioned "water-soluble resin".

[0069] Specific examples of the binder resin include acrylic resin, vinyl acetate resin, styrene resin, vinyl chloride resin, olefin resin, urethane resin, urea resin, urethane urea resin, acrylic urethane resin, epoxy resin, melamine resin, phenol resin, polyester resin, alkyd resin, silicone resin, polyphenylene sulfide resin, acrylonitrile / styrene copolymer resin, acrylonitrile / butadiene copolymer resin, and acrylonitrile / butadiene / styrene copolymer (ABS) resin, etc. In particular, it is preferable to use a resin that is known as an antifouling paint such as a ship bottom paint and has physical properties such as hydrolyzability, abrasiveness, and suppression of adhesion of aquatic organisms in the binder resin itself. The binder resin also includes those obtained by modifying the above resins. For example, in the case of a phenol resin, it includes a rosin-modified phenol resin.

[0070] The binder resin contained in the antifouling agent composition for suppressing adhesion of aquatic organisms of the present invention may be used alone or in combination of two or more.

[0071] The antifouling agent composition for suppressing adhesion of aquatic organisms of the present invention only needs to contain the antifouling agent for suppressing adhesion of aquatic organisms of the present invention and a solvent, and may contain a binder resin and other additives as long as the effects of the present invention are not impaired. Examples of the other additives include pigments, matting agents, curing agents, curing accelerators, plasticizers, defoamers, dispersants, leveling agents, thickeners, antioxidants, weathering agents, flame retardants, antistatic agents, lubricants, preservatives, and the like. Further, the antifouling agent composition for suppressing adhesion of aquatic organisms of the present invention may further contain other antifouling agents such as cuprous oxide, and by using it in combination with the antifouling agent for suppressing adhesion of aquatic organisms of the present invention, the usage amount of the other antifouling agents can be reduced, leading to a reduction in the environmental load.

[0072] (Hardened product of antifouling agent for suppressing adhesion of aquatic organisms) By applying the antifouling agent composition for suppressing adhesion of aquatic organisms of the present invention to the surface of a substrate and applying a curing method (such as heat curing or active energy ray curing) suitable for the antifouling agent composition for suppressing adhesion of aquatic organisms to the obtained coating film, a hardened product of the antifouling agent for suppressing adhesion of aquatic organisms can be formed.

[0073] (Antifouling coating film) Regarding the coating method of the antifouling agent composition for suppressing adhesion of aquatic organisms, any known and publicly used coating method can be used. For example, roll coaters, electrostatic coating, bar coaters, gravure coaters, knife coaters, dipping coating, spray coating such as airless spray coating and air spray coating, shower, brush coating, roller coating, and other conventionally known methods can be mentioned.

[0074] (Substrate with antifouling coating film) In the substrate with an antifouling coating film, the substrate to be coated is not particularly limited. For example, in the case of substrates such as ships, FRP, steel, wood, and aluminum alloys can be mentioned. Particularly in the case of steel ships and aluminum ships, the surface may be a surface coated with a primer, an anticorrosive paint, and, if necessary, a binder paint. In addition, as general substrates, paper, synthetic paper, steel plates, aluminum foils, glass, wood, woven fabrics, knitted fabrics, non-woven fabrics, gypsum boards, wooden boards, resin substrates, and the like can be mentioned.

[0075] Specific examples of the resin base material include polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: low-density polyethylene film, HDPE: high-density polyethylene film), polypropylene film (CPP: unoriented polypropylene film, OPP: biaxially oriented polypropylene film), polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, polycarbonate film, polyethylene terephthalate film, polymethyl methacrylate film, polystyrene film, polyester film, polyolefin film, epoxy resin film, melamine resin film, triacetyl cellulose resin film, polyvinyl alcohol film, ABS resin film, norbornene resin film, cyclic olefin resin film, polyimide resin film, polyvinyl fluoride resin film, polyvinylidene fluoride resin film, ethylene-vinyl acetate copolymer film, and the like. The resin base material to be used may be subjected to surface treatment such as corona treatment.

[0076] The antifouling agent composition for suppressing aquatic organism adhesion obtained by using the antifouling agent for suppressing aquatic organism adhesion of the present invention, the cured product of the antifouling agent for suppressing aquatic organism adhesion obtained by using the antifouling agent for suppressing aquatic organism adhesion of the present invention, the antifouling coating film obtained by using the antifouling agent for suppressing aquatic organism adhesion of the present invention, and the base material with the antifouling coating film can be suitably used as a base material having antifouling properties for suppressing aquatic organism adhesion. In addition to ships, at least a part of the outer surface of underwater structures such as wave-dissipating blocks, breakwaters, coastal roads, submarine tunnels, port facilities, canals, waterways, quay walls, and parts of bridges is placed or installed in water, fishing nets, ropes, floats, buoys, and other fishing materials, seawater supply and drainage pipes, water intake facilities, and cooling conduits in factories, thermal power plants, nuclear power plants, etc., industrial water systems, and submarine bases. It can be used in a wide range of applications.

Examples

[0077] Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. Note that the present invention is not limited to the following Examples.

[0078] (Synthesis Example 1: Preparation of Titanium Oxide Composition (Cu: 0.5%)) (1) Titanium Oxide Particles According to the general sulfuric acid method, sulfuric acid, water, and iron were added to a mixture of ilmenite ore, niobium pentoxide, and zirconium dioxide and dissolved to obtain a solution mainly composed of titanium sulfate and iron sulfate. Impurities such as iron sulfate were removed, and thermal hydrolysis was performed to obtain a hydrated titanium hydroxide composition. The titanium hydroxide composition was washed and calcined at 900 °C, and the obtained solid was pulverized to obtain titanium oxide particles having the following characteristics. a) Crystalline Rutile-Type Titanium Oxide b) Physical Property Values · BET Specific Surface Area: 9.0 m 2 / g · Rutile Conversion Rate: 95.4% · Primary Particle Size: 0.18 μm · Zr / Ti Ratio: 0.05 · Nb / Ti Ratio: 0.17

[0079] (2) Titanium Oxide Composition (Cu: 0.5%) a) Mixing Step (Reaction Step) 600 parts by mass of the titanium oxide particles, 8 parts by mass of copper (II) chloride dihydrate, and 900 parts by mass of water were mixed in a stainless steel container. Subsequently, while continuously stirring the obtained mixture with a stirrer ("Robomix" manufactured by Tokushu Kika Kogyo Co., Ltd.), a 1 mol / L aqueous sodium hydroxide solution was added dropwise until the pH of the liquid in the mixture reached 10. b) Dehydration Step Vacuum filtration was performed using qualitative filter paper (5C) to separate the solid content from the mixed solution, and further washing was carried out with ion-exchanged water. Subsequently, the washed solid was dried at 120 °C for 12 hours to remove moisture. After drying, a powdery titanium oxide composition was obtained with a mill ("Mill Sir" manufactured by Iwatani Sangyo Co., Ltd.). c) Heat Treatment Step The powdery titanium oxide composition obtained in the dehydration step of b) was heat-treated at 450 °C for 3 hours in the presence of oxygen using a precision thermostat ("DH650" manufactured by Yamato Scientific Co., Ltd.) to obtain a titanium oxide composition according to Synthesis Example 1 in which a divalent copper compound was supported on titanium oxide particles (Cu: 0.5%).

[0080] (Synthesis Example 2: Preparation of titanium oxide composition (Cu: 1.0%)) In Synthesis Example 1, a titanium oxide composition (Cu: 1.0%) in which a divalent copper compound was supported on titanium oxide particles was obtained in the same manner as in Example 1, except that the amount of copper(II) chloride dihydrate used was changed from 8 parts by mass to 16 parts by mass.

[0081] (Synthesis Example 3: Preparation of titanium oxide composition (Fe: 2.0%)) In Synthesis Example 1, a titanium oxide composition (Fe: 2.0%) in which an iron compound was supported on titanium oxide particles was obtained in the same manner as in Example 1, except that 58 parts by mass of iron(III) chloride hexahydrate was mixed instead of 8 parts by mass of copper(II) chloride dihydrate being mixed.

[0082] [Method for measuring BET specific surface area] Using a fully automatic BET specific surface area measuring device "MacSORB HM model - 1208" manufactured by Mountech Co., Ltd., measurement was performed by specific surface area measurement (BET one-point method).

[0083] [Method for measuring rutile ratio] Using an X-ray diffractometer "XRD - 6100" manufactured by Shimadzu Corporation, the peak height ratio corresponding to the rutile-type crystal was calculated from the peak heights corresponding to the crystals of the entire titanium oxide (rutile type, brookite type, anatase type).

[0084] [Calculation method for Zr / Ti ratio and Nb / Ti ratio] Using the fluorescent X-ray analyzer "SEA1200VX" manufactured by Seiko Instruments Inc., metal element composition analysis was performed by the bulk fundamental parameter (bulk FP) method. For the fluorescence intensity (cps: count per second) of each metal element obtained by measuring a titanium oxide sample, when the fluorescence intensity (cps) of titanium was set to 100, the intensity ratio of the fluorescence intensity (cps) of zirconium or niobium was calculated as the Zr / Ti ratio or Nb / Ti ratio, respectively.

[0085] [Method for measuring metal loading amount] The titanium oxide composition was completely dissolved in a hydrofluoric acid solution, and the extract was analyzed by an ICP emission spectrometer to quantify the metal loading amount (mass%) with respect to the titanium oxide composition.

[0086] (Examples 1, 2) 2.0 g of the titanium oxide composition (Cu: 0.5%) prepared in Synthesis Example 1 above (the addition amount with respect to the binder resin was 50 wt%), 1.64 g of a synthetic resin (product name: V343-306SA (manufactured by DIC Graphics Co., Ltd., solid content concentration: 25%, weight ratio of solvent: methyl ethyl ketone / ethyl acetate / toluene = 35 / 20 / 20), 5.30 g of a polyurethane resin as a binder resin (product name: Sample IB-D12 (manufactured by Sanyo Chemical Industries, Ltd., solid content concentration: 30%, weight ratio of solvent: methyl ethyl ketone / isopropanol = 47 / 23), 8.85 g of methyl ethyl ketone (manufactured by Kanto Chemical Co., Inc.), 8.85 g of toluene (manufactured by Kanto Chemical Co., Inc.), and 80 g of 1 / 8-inch steel beads were placed in a poly bottle and shaken for 30 minutes with a paint conditioner to obtain an antifouling agent composition for suppressing aquatic organism adhesion according to Example 1. Then, the prepared antifouling agent composition for suppressing aquatic organism adhesion was applied onto a PET film substrate with a thickness of 188 μm using a bar coater so that the wet film thickness became 37 μm. After that, the obtained substrate was dried at room temperature for 12 hours and further dried at 150°C for 15 minutes to produce a substrate coated with the antifouling agent composition for suppressing aquatic organism adhesion and used as a test piece. And in Example 2, instead of the titanium oxide composition (Cu: 0.5%) of Synthesis Example 1 in Example 1, the titanium oxide composition (Cu: 1.0%) synthesized in Synthesis Example 2 was used to produce an antifouling agent composition for suppressing the adhesion of aquatic organisms and used as a test piece.

[0087] (Comparative Examples 1 to 3) In Examples 1 and 2, the titanium oxide compositions of Synthesis Examples 1 and 2 were used respectively, while in Comparative Example 1, the titanium oxide composition of Synthesis Example 3 was used as a test piece. In Comparative Example 2, a blank test piece consisting only of a binder resin without a titanium oxide composition was prepared, and in Comparative Example 3, a test piece consisting only of a glass piece was used.

[0088] [Antifouling Property Evaluation of Antifouling Agent for Suppressing the Adhesion of Aquatic Organisms] Using the test pieces obtained in Examples 1 and 2 and Comparative Examples 1 to 3 above, the antifouling property evaluation of the antifouling agent for suppressing the adhesion of aquatic organisms was carried out. The results are shown in Table 1. The antifouling property was evaluated by observing the state of barnacles. The outline is described below.

[0089] [Antifouling Property Evaluation Method] The method for evaluating the antifouling property follows the following procedures (1) to (3).

[0090] (1) First, in a test container, a test piece coated with the antifouling agent composition for suppressing the adhesion of aquatic organisms prepared in the example and a certain number (about 100 in this test) of Cypris larvae are placed, and the number of Cypris larvae is measured. Here, the "Cypris larvae" refers to the larvae in the attachment period of barnacles.

[0091] (2) After a certain period of time (12 days after the start of the test in this test), the state of barnacles on the test piece and at each location other than the test piece (inside the test container) is observed, and the number of individuals in each state is measured accordingly.

[0092] (3) From the number of each individual measured at the end of the test, it is classified into attachment, non - attached survival, and death on the test piece, and the probabilities of each are obtained.

[0093] [Test Container and Each Condition] The test pieces obtained in Examples 1 and 2 and Comparative Examples 1 to 3 were placed statically on the bottom surface of the test container, and seawater and settlement-stage larvae were introduced. The test was carried out under the following conditions for the test container and each condition.

[0094] - Test container - Material: Polypropylene Dimensions: 111 mm in length, 81 mm in width, 46 mm in depth

[0095] - Seawater - Natural seawater collected from the coast of Himeji City was filtered using a mixed cellulose membrane filter with a pore size of 0.45 μm (manufactured by Toyo Roshi Kaisha, Ltd.) and used. The salt concentration was 3.11%, the pH was 8.14, and the water temperature was 20°C.

[0096] - Light irradiation conditions - Light irradiation: 12 hours (per day) Dark room: 12 hours (per day)

[0097] <State of barnacles> Each state of the barnacles when observed in the antifouling evaluation test is described below.

[0098] - Swimming - The state in which the cypris larvae of barnacles swim and survive without attaching to either the test container or the sample surface.

[0099] - Exploration and primary attachment (sample surface) - The state in which the cypris larvae are walking on the sample surface by the first tactile sense, or the state in which primary attachment to the sample surface by the first tactile sense and walking are repeated.

[0100] - Attachment to the test container - The state in which it has metamorphosed from cypris larvae, shed its carapace, and attached to the test container other than the sample surface of the test piece.

[0101] - During metamorphosis (sample surface) - A state in which a Cypris larva adheres to the sample surface and is in the process of becoming a young barnacle (larva of a barnacle).

[0102] ―Young barnacle (sample surface)― Those that have metamorphosed from Cypris larvae and are attached to the test piece sample surface in a state where they have molted their carapaces.

[0103] ―Rolling·Thoracic limb movement― In a state where the thoracic limbs are moving while rolling. Dying state.

[0104] ―Thoracic limb protrusion·Non-responsive― A state with no response or a state where tissue disintegration has started.

[0105] Among these states, the states of swimming and exploration·Primary attachment, and attachment to the test container are classified as non-attached survival, the states of metamorphosis and young barnacles are classified as attached, and the states of rolling·Thoracic limb movement and thoracic limb protrusion·Non-responsive are classified as dead. The number of each state measured in the test pieces after 12 days was evaluated, and the toxicity and antifouling properties were evaluated based on this non-attached survival rate and attachment rate. The state and number of barnacles in each test piece are shown in Table 1.

[0106]

Table 1

[0107] From Table 1, compared with Comparative Examples 1 to 3 that do not contain an antifouling agent for suppressing the attachment of aquatic organisms (Comparative Example 2 has only a binder resin on the substrate), in Examples 1 to 2 of the present invention, by adding the antifouling agent for suppressing the attachment of aquatic organisms of the present invention, the final attachment rate of barnacles is lowered, and it was found that antifouling properties are obtained. Also, in Example 2 where the amount of copper supported is 1.0%, it was found that it is particularly excellent in antifouling properties. Also, Examples 1 to 2 have a low attachment rate and excellent antifouling properties, while also having a low mortality rate, and it was confirmed that they have high aquatic organism repellency and low toxicity.

Claims

1. A titanium oxide composition in which a copper-containing metal compound is supported on titanium oxide particles. An antifouling agent for inhibiting the adhesion of aquatic organisms, preventing the adhesion of aquatic organisms.

2. 2. The antifouling agent for inhibiting adhesion of aquatic organisms according to claim 1, wherein the aquatic organisms are barnacles, mussels or limnoperna species.

3. 2. The antifouling agent for suppressing adhesion of aquatic organisms according to claim 1, wherein the copper content (Cu / Ti molar ratio) in the metal compound supported on the titanium oxide particles is 0.1 to 5.0 per 100 of titanium.

4. 2. The antifouling agent for suppressing adhesion of aquatic organisms according to claim 1, wherein the content of rutile-type titanium oxide (rutile ratio) contained in the titanium oxide particles is 87.2 mol % or more.

5. 2. The antifouling agent for suppressing adhesion of aquatic organisms according to claim 1, wherein the titanium oxide particles contain zirconium and niobium.

6. 6. The antifouling agent for suppressing adhesion of aquatic organisms according to claim 5, wherein the zirconium content (Zr / Ti ratio) in the titanium oxide particles is 0.03 to 0.8 per 100 of titanium.

7. The antifouling agent for suppressing adhesion of aquatic organisms according to claim 5, wherein the niobium content (Nb / Ti ratio) in the titanium oxide particles is 0.05 to 0.8 relative to 100% titanium.

8. An antifouling composition for suppressing adhesion of aquatic organisms, comprising the antifouling agent for suppressing adhesion of aquatic organisms according to any one of claims 1 to 7 and a solvent.

9. The antifouling composition for suppressing adhesion of aquatic organisms according to claim 8, further comprising a binder resin.

10. A cured antifouling agent for suppressing adhesion of aquatic organisms, obtained by curing the antifouling agent composition for suppressing adhesion of aquatic organisms according to claim 8.

11. An antifouling coating film formed from the cured product of the antifouling agent for suppressing adhesion of aquatic organisms according to claim 10.

12. A substrate with an antifouling coating film, comprising: a substrate; and the antifouling coating film according to claim 11 provided on a surface of the substrate.

13. The substrate with an antifouling coating film according to claim 12, wherein the substrate is at least one selected from ships, underwater structures, fishing materials, and water supply and drainage pipes.

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