Coating composition, laminate, resin composition and molded article

Abstract

Provided is a coating composition capable of forming a coating layer that prevents the adhesion of microorganisms and inactivates them. [Solution] The coating composition contains a block copolymer and titanium oxide, the block copolymer having polymer block (A) of polymerization components containing an acrylate monomer represented by a specific chemical structural formula and polymer block (B) of polymerization components containing at least one monomer represented by several specific chemical structural formulas different from the above. Specifically, for example, the acrylate monomer constituting polymer block (A) is 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, etc., and the monomer constituting polymer block (B) is a (meth)acrylamide derivative such as (meth)acrylamide or N- or N,N-substituted (meth)acrylamide.

Description

[Technical Field]

[0001] The present invention relates to a coating composition, a laminate, a resin composition, and a molded article. [Background technology]

[0002] The COVID-19 pandemic has led to growing interest in antibacterial and antiviral agents and processed products. Previously, antibacterial and antiviral agents and processed products were mainly used to prevent infection in patients with weakened resistance, such as those in medical and nursing care settings, but with the spread of COVID-19, they have become widely used in ordinary homes, public transportation, commercial facilities, companies, and factories.

[0003] Most current antibacterial and antiviral processed products inactivate bacteria and viruses by damaging them, but the inactivated bacteria and viruses remain on the product surface.If additional bacteria or viruses adhere to the inactivated bacteria or viruses, they will remain active and multiply, forming a biofilm, because they do not come into contact with the antibacterial and antiviral processed surface.

[0004] To solve the above problems, methods have been proposed in which microorganisms such as bacteria and viruses are composed of proteins, and thus a coating process is performed with a protein adhesion-inhibiting resin to prevent the adhesion of microorganisms such as bacteria and viruses in the first place (e.g., Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 7-83923 [Patent Document 2] Special Publication No. 7-506138 Summary of the Invention [Problem to be solved by the invention]

[0006] The resins disclosed in Patent Documents 1 and 2 are polymers having phosphorylcholine groups, but they are insufficient in their effect of inhibiting protein adhesion and lack the ability to inactivate microorganisms such as bacteria and viruses, making it impossible to maintain hygienic conditions at the application site.

[0007] The problem to be solved by the present invention is to provide a coating composition capable of forming a coating layer that prevents the adhesion of microorganisms and inactivates them. The problem to be solved by the present invention is to provide a resin composition capable of forming a molded article that prevents the adhesion of microorganisms and inactivates microorganisms. Another problem to be solved by the present invention is to provide a laminate and a molded article that prevent the adhesion of microorganisms and inactivate microorganisms. [Means for solving the problem]

[0008] That is, the present invention relates to the following coating composition, etc. 1. A coating composition containing a block copolymer and titanium oxide, The coating composition is a block copolymer having a polymer block (A) of polymerization components containing a monomer represented by the following general formula (1) and a polymer block (B) of polymerization components containing at least one of the monomers represented by the following general formulas (2) to (7): [ka] (In the general formulas (1) to (7), R 0 is an alkyl group having 1 to 6 carbon atoms, R 1 is a hydrogen atom or a methyl group, R 2 is an alkylene group having 1 to 6 carbon atoms, R 3 , R 4 , R 5 and R 6are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 7 is an alkylene group having 1 to 6 carbon atoms, X is -CO2 - , -SO3 - , -OSO3 - , -OSO2 - ,-OP(=O)(OR 8 )O - , -OP(=O)(R 8 )O - , -P(=O)(OR 8 )O - , -P(=O)(R 8 )O - is a monovalent anion selected from R 8 is an alkyl group having 1 to 6 carbon atoms, n is an integer ranging from 1 to 9. 2. The coating composition according to 1, wherein the molar ratio of the polymer block (A) to the polymer block (B) (polymer block (A):polymer block (B)) is in the range of 1:50 to 50:1. 3. The coating composition according to 1, wherein the molar ratio of the monomer represented by general formula (1) to the monomers represented by general formulas (2) to (7) constituting the block copolymer (moles of the monomer represented by general formula (1) / total moles of the monomers represented by general formulas (2) to (7)) is in the range of 90:10 to 1:99. 4. The coating composition according to 1, wherein the titanium oxide comprises rutile titanium oxide. 5. The coating composition according to 1, wherein the titanium oxide is titanium oxide supporting a metal compound. 6. The coating composition according to 5, wherein the metal compound is a divalent copper compound. 7. The coating composition according to 1, wherein the titanium oxide is a titanium oxide compound containing zirconium and / or niobium. 8. The coating composition according to 1, wherein the titanium oxide is a titanium oxide compound containing zirconium, and the content ratio of zirconium to 100 of titanium in the titanium oxide compound (Zr / Ti ratio) is in the range of 0.03 to 0.8. 9. The coating composition according to 1, wherein the titanium oxide compound contains niobium, and the content ratio of niobium to titanium (Nb / Ti ratio) in the titanium oxide compound is in the range of 0.05 to 0.8. 10. The coating composition according to 1, wherein the titanium oxide is contained in an amount ranging from 1 to 500 parts by mass per 100 parts by mass of the block copolymer. 11. A laminate having a substrate and a coating layer of the coating composition according to any one of 1 to 10. 12. A method for preventing adhesion of bacteria and viruses to a substrate and inactivating bacteria and viruses, comprising applying the coating composition according to any one of 1 to 10 onto the substrate to form a coating layer. [Effects of the Invention]

[0009] The present invention provides a coating composition that can form a coating layer that prevents the adhesion of microorganisms and inactivates them. According to the present invention, a resin composition can be provided that can form a molded article that prevents the adhesion of microorganisms and inactivates microorganisms. The present invention can provide a laminate and a molded article that prevent and inactivate microorganisms. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is an SEM image (500x magnification) showing the state of the protein adhesion-inhibitory layer of the laminate produced in Example 1 in the bacterial adhesion evaluation. [Figure 2] 1 is an SEM image (10,000x magnification) showing the state of the protein adhesion-inhibiting layer of the laminate produced in Example 1 in a bacterial adhesion evaluation. [Figure 3]1 is an SEM image (500x magnification) showing the state of the protein adhesion-inhibitory layer of the laminate produced in Comparative Example 1 in the evaluation of bacterial adhesion. [Figure 4] 1 is an SEM image (10,000x magnification) showing the state of the protein adhesion-inhibitory layer of the laminate produced in Comparative Example 1 in the evaluation of bacterial adhesion. [Figure 5] 1 is an SEM image (500x magnification) showing the state of the protein adhesion-inhibitory layer of the laminate produced in Comparative Example 2 in the evaluation of bacterial adhesion. [Figure 6] 1 is an SEM image (10,000x magnification) showing the state of the protein adhesion-inhibitory layer of the laminate produced in Comparative Example 2 in the bacterial adhesion evaluation. [Figure 7] 1 is an SEM image (500x magnification) showing the state of the protein adhesion-inhibitory layer of the laminate produced in Comparative Example 3 in the evaluation of bacterial adhesion. [Figure 8] 1 is an SEM image (10,000x magnification) showing the state of the protein adhesion-inhibitory layer of the laminate produced in Comparative Example 3 in the bacterial adhesion evaluation. DETAILED DESCRIPTION OF THE INVENTION

[0011] An embodiment of the present invention will be described below. The present invention is not limited to the following embodiment, and can be implemented by making appropriate modifications within the scope that does not impair the effects of the present invention. The compounds in this specification may be derived from fossil resources or biological resources.

[0012] [Coating composition] The coating composition of the present invention contains a specific block copolymer and titanium oxide. Resins containing phosphorylcholine groups are known as protein adhesion-inhibiting resins, but these resins have the problem of being easily affected by pH and salt concentration. The block copolymer contained in the coating composition of the present invention does not contain phosphorylcholine groups and can exhibit a stable protein adhesion-inhibiting effect without being affected by pH or salt concentration. Hereinafter, the block copolymer contained in the coating composition of the present invention may be referred to as the "protein adhesion-inhibiting resin of the present invention." By combining the above-mentioned protein adhesion-inhibiting resin with titanium oxide, which has antimicrobial properties that inactivate bacteria and viruses, it is possible to obtain a coating composition that can form a coating layer that prevents the adhesion of microorganisms and inactivates them. Each component contained in the coating composition of the present invention will be described below.

[0013] (Protein adhesion inhibitor resin) The protein adhesion-inhibiting resin of the present invention is a block copolymer having a polymer block (A) of polymerization components containing a monomer represented by the following general formula (1) and a polymer block (B) of polymerization components containing at least one of the monomers represented by the following general formulas (2) to (7).

[0014] [ka] (In the general formulas (1) to (7), R 0 is an alkyl group having 1 to 6 carbon atoms, R 1 is a hydrogen atom or a methyl group, R 2 is an alkylene group having 1 to 6 carbon atoms, R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 7 is an alkylene group having 1 to 6 carbon atoms, X is -CO2- , -SO3 - , -OSO3 - , -OSO2 - ,-OP(=O)(OR 8 )O - , -OP(=O)(R 8 )O - , -P(=O)(OR 8 )O - , -P(=O)(R 8 )O - is a monovalent anion selected from R 8 is an alkyl group having 1 to 6 carbon atoms, n is an integer ranging from 1 to 9.

[0015] The monomer represented by the general formula (1) constituting the polymer block (A) has the function of ensuring the molding performance of the coating film obtained from the coating composition of the present invention, and can improve the controllability of the thickness of the coating film, the surface smoothness, etc.

[0016] R 0 The alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms.

[0017] R 2 The alkylene group having 1 to 6 carbon atoms is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms.

[0018] n is an integer ranging from 1 to 9, preferably an integer ranging from 1 to 6, and more preferably an integer ranging from 1 to 4.

[0019] Specific examples of the monomer represented by the general formula (1) include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, methyl carbitol acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, ethyl carbitol acrylate, methoxytriethylene glycol acrylate, and ethoxytriethylene glycol acrylate, and preferred are 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, and 2-(2-ethoxyethoxy)ethyl acrylate.

[0020] The polymerization components constituting polymer block (A) may contain a monomer represented by general formula (1) above, and may consist essentially of the monomer represented by general formula (1). Here, "consist essentially of" means that 90% by mass or more, 95% by mass or more, 98% by mass or more, or 100% by mass of the polymerization components constituting polymer block (A) are the monomer represented by general formula (1).

[0021] When the polymerization components constituting the polymer block (A) contain a polymerization component other than the monomer represented by the general formula (1), examples of the polymerization component include the monomers represented by the general formulae (2) to (7) and (meth)acrylic monomers having functional groups such as a hydroxyl group, a glycidyl group, an isocyanato group, a carboxyl group, an amino group, and a sulfonic acid group.

[0022] The protein adhesion-inhibiting resin of the present invention is a copolymer having a block of a (meth)acrylamide derivative (e.g., (meth)acrylamide, N- or N,N-substituted (meth)acrylamide), and the monomers represented by the general formulae (2) to (7) constituting the polymer block (B) can impart protein adhesion-inhibiting properties to the coating film obtained from the coating composition of the present invention.

[0023] R 3 , R 4 , R 5 , R 6 and R 8 It is an alkyl group having 1 to 6 carbon atoms, and preferably an alkyl group having 1 to 3 carbon atoms. R 7 The alkylene group having 1 to 6 carbon atoms is preferably an alkylene group having 1 to 3 carbon atoms.

[0024] Specific examples of the monomers represented by the general formulas (2) to (7) are (meth)acrylamide derivatives such as (meth)acrylamide and N- or N,N-substituted (meth)acrylamides.

[0025] The polymerization components constituting the polymer block (B) may contain the monomers represented by the general formulas (2) to (7), and may consist essentially of the monomers represented by the general formulas (2) to (7). Here, "consist essentially of" means that 90% by mass or more, 95% by mass or more, 98% by mass or more, or 100% by mass of the polymerization components constituting the polymer block (B) are the monomers represented by the general formulas (2) to (7).

[0026] When the polymerization components constituting the polymer block (B) contain polymerization components other than the monomers represented by the general formulae (2) to (7), examples of the polymerization components include monomers represented by the general formulae (1) to (7), (meth)acrylic monomers having an anionic group such as a sulfonic acid group or a carboxyl group, (meth)acrylic monomers having a cationic group such as a quaternary ammonium group, (meth)acrylic monomers having a zwitterionic group having a quaternary ammonium group and a phosphate group, (meth)acrylic monomers having an amino acid residue having a carboxyl group and an amino group, (meth)acrylic monomers having a sugar residue, (meth)acrylic monomers having a hydroxyl group, amphiphilic (meth)acrylic monomers having both a hydrophilic chain such as polyethylene glycol and a hydrophobic group such as a nonylphenyl group, polyethylene glycol diacrylate, and N,N'-methylenebisacrylamide.

[0027] In the copolymer of the present invention, the molar ratio of polymer block (A) to polymer block (B) (polymer block (A):polymer block (B)) is preferably in the range of 1:50 to 50:1, more preferably in the range of 1:20 to 20:1, and even more preferably in the range of 1:20 to 1:1. The molar ratio of polymer block (A) to polymer block (B) can be adjusted by the amount of each of the polymerization components of polymer block (A) and polymer block (B) charged.

[0028] The weight average molecular weight of the block copolymer of the present invention is, for example, in the range of 1,000 to 1,000,000, preferably in the range of 10,000 to 500,000, and more preferably in the range of 50,000 to 500,000. The number average molecular weight of the block copolymer of the present invention is, for example, in the range of 1,000 to 500,000, preferably in the range of 10,000 to 300,000, and more preferably in the range of 20,000 to 300,000. The weight average molecular weight and number average molecular weight are measured by the method described in the Examples.

[0029] The block copolymer of the present invention may be a block copolymer having polymer block (A) and polymer block (B), and the number and bonding order of each polymer block are not particularly limited. The block copolymer of the present invention is preferably an AB type diblock copolymer or an ABA type or BAB type triblock copolymer. The block copolymer of the present invention may be a multi-branched block copolymer using a multifunctional acrylate.

[0030] When the block copolymer of the present invention is, for example, a diblock copolymer of polymer block (A) and polymer block (B), the diblock copolymer may be a copolymer in which polymer block (A) and polymer block (B) are directly bonded to each other at their terminals, or may be a copolymer in which polymer block (A) and polymer block (B) are bonded to each other via a spacer. The above also applies when the block copolymer of the present invention is a triblock copolymer or the like.

[0031] The block copolymer of the present invention may be any copolymer having polymer block (A) and polymer block (B), and may have polymer blocks other than polymer block (A) and polymer block (B).

[0032] The block copolymer of the present invention is preferably a block copolymer essentially consisting of polymer block (A) and polymer block (B). Here, "essentially consisting of" means that the total content of polymer block (A) and polymer block (B) in the block copolymer of the present invention is 90% by mass or more, 95% by mass or more, 99% by mass or more, or 100% by mass.

[0033] (Method of manufacturing protein adhesion inhibiting resin) The block copolymer of the present invention can be produced by known methods, such as a method of performing living radical polymerization of one of the polymerization components containing a monomer represented by general formula (1) and the polymerization components containing monomers represented by general formulas (2) to (7) using an azo compound and / or organic peroxide as a radical polymerization initiator in the presence of a chain transfer agent (hereinafter referred to as a RAFT agent) such as trithiocarbonate, and then performing living radical polymerization of the other polymerization component after the living radical polymerization; or a method of performing radical polymerization of one of the polymerization components containing a monomer represented by general formula (1) and the polymerization components containing monomers represented by general formulas (2) to (7) in the presence of an organic halide and a transition metal complex, and then adding the other polymerization component to perform radical polymerization.

[0034] The block copolymer of the present invention is preferably produced by any one of the following methods (1) to (4). (1) In the presence of a polymerization initiator, a RAFT agent is polymerized with either a polymerization component containing a monomer represented by general formula (1) or a polymerization component containing a monomer represented by general formulas (2) to (7), followed by isolation and purification to synthesize a macro RAFT agent consisting of only one polymer block. The macro RAFT agent is then polymerized with the other polymerization component in the presence of a polymerization initiator to obtain a block copolymer. (2) In the presence of an organic halide and a transition metal complex, one of the polymerization components containing a monomer represented by general formula (1) and the polymerization components containing monomers represented by general formulas (2) to (7) is polymerized, followed by isolation and purification to synthesize a polymer end halide consisting of only one polymer block, and then the other polymerization component is polymerized with the polymer end halide in the presence of a transition metal complex to obtain a block copolymer. (3) A method in which, in the presence of a polymerization initiator, a RAFT agent and one of the polymerization components containing the monomer represented by general formula (1) and the polymerization components containing the monomers represented by general formulas (2) to (7) are polymerized, and then the other polymerization component is added without isolation to obtain a block copolymer. (4) A method in which one of a polymerization component containing a monomer represented by general formula (1) and a polymerization component containing a monomer represented by general formulas (2) to (7) is polymerized in the presence of an organic halide and a transition metal complex, and then the other polymerization component is added without isolation to obtain a block copolymer.

[0035] In the above methods (3) and (4), it is not necessary to wait until one polymerization component is completely consumed before adding the other polymerization component; the other polymerization component can be added when the conversion of one polymerization component reaches, for example, 65% or more. The copolymer obtained in this case is not a complete block copolymer, but a so-called tapered block copolymer in which a monomer represented by general formula (1) and a monomer represented by general formulas (2) to (7) are mixed in part. However, by appropriately selecting the ratio of the monomer represented by general formula (1) to the monomer represented by general formulas (2) to (7), a copolymer with the same functionality as a complete block copolymer can be obtained.

[0036] The method for producing the block copolymer of the present invention has been described using RAFT polymerization as an example, but the present invention is not limited to RAFT polymerization, and the block copolymer can also be produced by other methods, such as ATRP (atom transfer radical polymerization) and NMP (nitroxide-mediated radical polymerization). When produced by RAFT polymerization, the block copolymer of the present invention is obtained as a copolymer having, for example, a thiocarbonylthio bond (-SC(S)-). The thiocarbonylthio bond may be left as it is in the copolymer, or a treatment for removing the thiocarbonylthio bond may be performed.

[0037] (Titanium oxide) The crystalline form of titanium oxide includes rutile type titanium oxide, anatase type titanium oxide, brookite type titanium oxide, etc., but the titanium oxide of the present invention preferably includes rutile type titanium oxide.

[0038] When the titanium oxide contains rutile-type titanium oxide, the content of the rutile-type titanium oxide (rutile content) is, for example, 15 mol% or more, 50 mol% or more, 75 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or more than 95 mol% from the viewpoints of antiviral activity in bright and dark places, organic compound decomposition ability in bright places, and visible light responsiveness. The rutile content is preferably 75 mol % or more, more preferably 80 mol % or more, and even more preferably 90 mol % or more. There is no particular upper limit to the rutile content, but it is, for example, 100 mol %. The rutile content of titanium oxide is confirmed by the method described in the examples.

[0039] The upper limit of the BET specific surface area of ​​titanium oxide is 200m 2 / g or less, 100m 2 / g or less, 90m 2 / g or less, 70m 2 / g or less, 40m 2 / g or less, 30m 2 / g or less or 20m 2 / g or less, with a lower limit of 1m 2 / g or more, 2m 2 / g or more, 3m 2 / g or more or 5m 2 / g or more. From the viewpoint of antiviral properties and visible light responsiveness, the BET specific surface area of ​​titanium oxide is, for example, 1 to 200 m as a combination of the upper and lower limits of the BET specific surface area. 2 / g, preferably 3 to 100m 2 / g, more preferably 5 to 90 m 2 / g range. The BET specific surface area of ​​titanium oxide is confirmed by the method described in the Examples.

[0040] From the viewpoint of visible light responsiveness, the primary particle diameter of titanium oxide is, for example, in the range of 0.01 to 0.5 μm, preferably in the range of 0.01 to 0.35 μm, and more preferably in the range of 0.02 to 0.35 μm. The primary particle size of titanium oxide is confirmed by the method described in the examples.

[0041] The titanium oxide is preferably titanium oxide supporting a metal compound, which can improve photocatalytic activity in the visible light region.

[0042] Examples of the metal of the metal compound supported on titanium oxide include transition metals such as copper, iron, tungsten, zirconium, and molybdenum; and metals other than transition metals such as zinc, aluminum, antimony, and tin.

[0043] The metal compound supported on titanium oxide is preferably a copper compound, more preferably a divalent copper compound. Here, the "divalent copper compound" may be, for example, either an inorganic divalent copper compound or an organic divalent copper compound.

[0044] Examples of the divalent copper inorganic compound that can be used include inorganic acid salts of divalent copper such as copper sulfate, copper nitrate, copper iodate, copper perchlorate, copper oxalate, copper tetraborate, ammonium copper sulfate, copper amidosulfate, ammonium copper chloride, copper pyrophosphate, and copper carbonate; divalent copper halides such as copper chloride, copper fluoride, and copper bromide; copper oxide, copper sulfide, azurite, malachite, and copper azide.

[0045] Examples of the divalent copper organic compounds include copper formate, copper acetate, copper propionate, copper butyrate, copper valerate, copper caproate, copper enanthate, copper caprylate, copper pelargonate, copper caprate, copper myristic acid, 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 mellitic acid, copper oxalate, copper malonate, copper succinate, copper glutarate, copper adipate, copper fumarate, glycol Examples of copper nitrate that can be used include copper nitrate, copper glycerate, copper gluconate, copper tartrate, copper acetylacetonate, copper ethylacetoacetate, copper isovalerate, copper β-resorcylate, copper diacetoacetate, copper formylsuccinate, copper salicylamine, copper bis(2-ethylhexanoate), copper sebacate, copper naphthenate, copper oxine, copper acetylacetonate, copper ethylacetoacetate, copper trifluoromethanesulfonate, copper phthalocyanine, copper ethoxide, copper isopropoxide, copper methoxide, and copper dimethyldithiocarbamate.

[0046] The divalent copper compound supported on titanium oxide is preferably a compound represented by the following general formula (1). CuX2(1) (In the general formula (1), X is a halogen atom, CH3COO, NO3 or (SO4) 1 / 2 is. X is preferably a halogen atom, more preferably a chlorine atom.

[0047] When titanium oxide supports a metal compound, the amount of the metal compound supported is, for example, in the range of 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass, per 100 parts by mass of titanium oxide. The amount of the metal compound supported is confirmed by the method described in the Examples.

[0048] The metal compounds supported on titanium oxide may be one type alone or two or more types in combination.

[0049] The titanium oxide of the present invention is a titanium oxide compound containing zirconium and / or niobium, and preferably a titanium oxide compound containing both zirconium and niobium. Titanium oxide containing zirconium and / or niobium has a small cohesive force relative to the specific surface area (BET value) resulting from the primary particles, and is presumed to contribute to improving the dispersibility of titanium oxide in the coating composition. In addition, it is presumed that both zirconium and niobium are contained in the titanium oxide crystal in a doped state in the titanium oxide compound.

[0050] When the titanium oxide is a titanium oxide compound containing zirconium, the lower limit of the zirconium content ratio (Zr / Ti ratio) relative to 100 titanium is, for example, 0.02 or more, preferably 0.03 or more, more preferably 0.04 or more, and even more preferably 0.05 or more. Similarly, the upper limit of the zirconium content ratio (Zr / Ti ratio) relative to 100 titanium in the titanium oxide compound is, for example, 1.0 or less, preferably 0.8 or less, more preferably 0.5 or less, and even more preferably 0.3 or less. Any combination of these upper and lower limits is acceptable. The content ratio of zirconium to titanium (100) in the titanium oxide compound (Zr / Ti ratio) is preferably in the range of 0.03 to 0.8, more preferably in the range of 0.04 to 0.5, and even more preferably in the range of 0.05 to 0.3.

[0051] When the titanium oxide is a titanium oxide compound containing niobium, the lower limit of the content ratio of niobium to 100 titanium (Nb / Ti ratio) is, for example, 0.02 or more, preferably 0.05 or more, more preferably 0.08 or more, and even more preferably 0.1 or more. Similarly, the upper limit of the content ratio of niobium to 100 titanium (Nb / Ti ratio) in the titanium oxide compound is, for example, 1.0 or less, preferably 0.8 or less, more preferably 0.5 or less, and even 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 compound is preferably in the range of 0.05 to 0.8, more preferably in the range of 0.08 to 0.5, and even more preferably in the range of 0.10 to 0.3.

[0052] The zirconium content ratio (Zr / Ti ratio) relative to 100% titanium in the titanium oxide compound and the niobium content ratio (Nb / Ti ratio) relative to 100% titanium in the titanium oxide compound are both fluorescence intensity ratios of the respective elements in the titanium oxide compound, and are specifically confirmed by the method described in the Examples.

[0053] (Method of manufacturing titanium oxide) Titanium oxide can be produced by known methods, including a liquid phase method and a gas phase method. The liquid phase method is a method in which titanyl sulfate obtained from a solution in which a raw ore such as ilmenite is dissolved is hydrolyzed or neutralized to obtain a titanium oxide compound. The gas phase method is a method in which titanium oxide is obtained by a gas phase reaction between oxygen and titanium tetrachloride obtained by chlorinating a raw ore such as rutile. The titanium oxide of the present invention is preferably produced by a liquid phase method.

[0054] When titanium oxide is to be a titanium oxide compound containing zirconium and / or niobium, a desired amount of zirconium oxide and / or niobium oxide may also be reacted in the above reaction.

[0055] When a metal compound is supported on titanium oxide, a known method can be used as the supporting method. Examples of such methods include a method in which titanium oxide is further added to a mixture of a metal compound (support) and a solvent, and the metal compound is adsorbed onto the titanium oxide in the resulting suspension; and a method in which a mixture of titanium oxide, a metal compound (support), a solvent, and an alkaline substance is prepared, and the titanium oxide and the metal compound are reacted with each other.

[0056] The concentration of titanium oxide in the mixed solution may be, for example, in the range of 3 to 40% by mass. When the titanium oxide is titanium oxide produced by the liquid phase method, the mixed solution can be easy to handle even if the concentration of titanium oxide is increased, and the concentration of titanium oxide can be, for example, in the range of more than 25% by mass to 40% by mass or less.

[0057] The amount of the metal compound used as the supported material in the mixed solution is, for example, in the range of 0.01 to 20 parts by mass, preferably in the range of 0.1 to 15 parts by mass, and more preferably in the range of 0.1 to 10 parts by mass, per 100 parts by mass of titanium oxide. The amount of the metal compound supported can be adjusted by adjusting the amount of the metal compound used.

[0058] The solvent for the mixed solution may be water, an organic solvent, or a mixed solvent thereof. When the solvent is a mixed solvent, the mixed solvent is preferably an aqueous solvent containing water as the main component. Here, "aqueous solvent containing water as the main component" refers to a mixed solvent in which the water content is the highest in the total amount of solvent, and preferably a mixed solvent in which the water content is 50 mass % or more.

[0059] When the mixed solvent contains an organic solvent, the content of the organic solvent is preferably 30% by mass or less, and more preferably 5% by mass or less, from the viewpoint of reducing the environmental load and improving safety.

[0060] The organic solvent usable as the solvent is not particularly limited, but for example, an organic solvent miscible with water is preferably used. Examples of the organic solvent usable as the solvent include monofunctional alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, isobutanol, 1-pentanol, 2-methyl-2-pentanol, and 3-methyl-3-pentanol; 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, and propylene glycol. Various diols such as coal, 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 and methyl isobutyl ketone; aromatic diols which are adducts of bisphenol A and bisphenol A with alkylene oxides having 2 or 3 carbon atoms (average number of added moles: 1 to 16); and fats such as hydrogenated bisphenol A. Cyclic diols; dimethylformamide, tetrahydrofuran, 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, and γ-butyrolactone.

[0061] The organic solvent is preferably 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), ethylene glycol. The organic solvent may be used alone or in combination of two or more kinds.

[0062] When the alkaline substance is used in producing titanium oxide carrying a metal compound, examples of the alkaline substance that can be used include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, trimethylamine, ammonia, and basic surfactants, and sodium hydroxide is preferred.

[0063] The alkaline substance is preferably added as an aqueous alkaline substance solution, from the viewpoint of easy reaction control. The concentration of the alkaline substance in the aqueous alkaline substance solution is, for example, in the range of 0.1 to 5 mol / L, preferably in the range of 0.3 to 4 mol / L, and more preferably in the range of 0.5 to 3 mol / L.

[0064] A method for producing titanium oxide carrying a divalent copper compound will be described below as one embodiment. First, water and titanium oxide are mixed by stirring as needed, then a divalent copper compound is added to this mixture and stirred, and then an alkaline substance is added to prepare a mixed liquid, which is then stirred, thereby producing titanium oxide supported with a divalent copper compound.

[0065] The total stirring time in the method for producing titanium oxide supporting a divalent copper compound is, for example, in the range of 5 to 120 minutes, and preferably in the range of 10 to 60 minutes. The reaction temperature of the mixed solution is, for example, in the range of room temperature (25°C) to 70°C.

[0066] In order to ensure good support of the divalent copper compound on titanium oxide, the pH of the mixed solution after the addition of the alkaline substance is preferably in the range of 8 to 11, and more preferably in the range of 9.0 to 10.5.

[0067] After the reaction in the mixed solution is completed, the solid content can be separated. Examples of the separation method include filtration, sedimentation, centrifugation, and evaporation / drying, with filtration being preferred. The separated solid content may then be washed with water, crushed, classified, etc., as necessary.

[0068] After obtaining the solid content, the divalent copper compound-supported titanium oxide after the reaction is preferably heat-treated, since this allows the divalent copper compound supported on the titanium oxide to be more firmly bound. The heat treatment temperature is preferably in the range of 150 to 600° C., more preferably in the range of 250 to 450° C. The heat treatment time is preferably in the range of 1 to 10 hours, more preferably in the range of 2 to 5 hours.

[0069] The content of titanium oxide in the coating composition of the present invention is not particularly limited, and may be, for example, in the range of 1 to 500 parts by mass per 100 parts by mass of the protein adhesion-inhibiting resin, preferably in the range of 1.5 to 250 parts by mass per 100 parts by mass of the protein adhesion-inhibiting resin, and more preferably in the range of 3 to 200 parts by mass per 100 parts by mass of the protein adhesion-inhibiting resin.

[0070] The coating composition of the present invention only needs to contain a protein adhesion-inhibiting resin, and may also contain other binder components in addition to the protein adhesion-inhibiting resin. The other binder components may be any of aqueous resins, non-water-soluble resins (solvent-based resins), and inorganic binders. In this application, the term "water-soluble resin" means that the amount of water required to dissolve 1 g of resin at 20° C. is less than 10 ml. The term "water-insoluble resin" refers to a resin that is not one of the aforementioned "water-soluble resins."

[0071] Specific examples of other binder components 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, acrylonitrile / butadiene / styrene copolymer (ABS) resin, alkali silicate, colloidal silica, organic metal siliconate, heavy phosphate, polyvalent metal alcoholate, silicone, alkyl silicate, alumina sol, cement, etc. Other binder components include those obtained by modifying the above components, and for example, in the case of phenolic resin, this also means that it includes rosin-modified phenolic resin.

[0072] The other binder components contained in the coating composition of the present invention may be one type alone or two or more types.

[0073] The proportion of the protein adhesion-inhibiting resin in the binder component of the coating composition of the present invention is, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. When the proportion of the protein adhesion-inhibiting resin is 50% by mass or more, a sufficient protein adhesion-inhibiting effect can be obtained. There is no particular upper limit to the proportion of the protein adhesion inhibiting resin in the binder component, but it is, for example, 100% by mass or less.

[0074] The content of binder components (e.g., protein adhesion inhibiting resin and other binder components) in the coating composition of the present invention is not particularly limited, and may be appropriately set within the range of, for example, 0.02 to 99.9 mass % of the total solid content of the coating composition.

[0075] The coating composition of the present invention may further contain a dispersion medium. The dispersion medium is added for the purpose of adjusting the viscosity of the coating composition, and may be either an aqueous medium or an oil-based medium.

[0076] Specific examples of the dispersion medium include water, monofunctional alcohols such as 1-butanol, isobutanol, 1-pentanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol, methyl ethyl ketone, methanol, ethanol, n-propyl alcohol, and isopropyl alcohol, various diols, polyhydric alcohols such as glycerin, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, and 1,9- Diols such as 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, and diethylene glycol; aromatic diols which are adducts of bisphenol A with alkylene oxides having 2 or 3 carbon atoms (average number of added moles: 1 to 16); and hydrogenated bisphenol A. alicyclic diols such as 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, and various fatty acids.

[0077] The dispersion medium contained in the coating composition of the present invention may be one type alone or two or more types.

[0078] The content of the dispersion medium in the coating composition of the present invention is not particularly limited, and may be appropriately set so that the solid content of the coating composition is in the range of 0.01 to 80% by mass, for example.

[0079] The coating composition of the present invention may further contain a plasticizer. By adding a plasticizer to the coating composition, flexibility can be imparted to the resulting coating layer, and conformability to the substrate can be improved.

[0080] The plasticizer is not particularly limited, and examples thereof include phthalate esters, non-aromatic dibasic acid esters, aliphatic esters, esters of polyalkylene glycols, phosphate esters, trimellitate esters, chlorinated paraffins, hydrocarbon oils, process oils, polyethers, epoxy plasticizers, and polyester plasticizers, with phthalate esters being preferred. Specific examples of plasticizers include dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, dioctyl phthalate, dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate, tricresyl phosphate, tributyl phosphate, epoxidized soybean oil, and benzyl epoxy stearate.

[0081] The coating composition of the present invention may contain one type of plasticizer alone or two or more types of plasticizers.

[0082] The content of the plasticizer in the coating composition of the present invention is not particularly limited, and may be appropriately set within the range of, for example, 0.1 to 50 parts by mass per 100 parts by mass of the resin solid content of the coating composition.

[0083] The coating composition of the present invention may contain the titanium oxide of the present invention, the protein adhesion-inhibiting resin of the present invention, any other binder component, any dispersion medium, and any plasticizer, and may also contain other additives to the extent that the effects of the present invention are not impaired. Examples of such other additives include pigments, matting agents, curing agents, curing accelerators, antifoaming agents, dispersants, leveling agents, thickeners, antioxidants, weathering agents, flame retardants, antistatic agents, lubricants, preservatives, and anti-biofilm agents (e.g., isothiazolinone compounds, thiazolinone compounds, thiazole compounds, triazine compounds, urea compounds, imidazole compounds, benzimidazole compounds, pyridine compounds, zinc pyrithione compounds, and phenylphenol compounds).

[0084] The coating layer of the coating composition of the present invention may be a cured film obtained by curing the coating composition, or may be an uncured film of the coating composition. When the coating layer is a cured coating film of a coating composition, the coating composition of the present invention may be applied to the surface of a substrate, and the resulting coating film may be cured by a method suitable for the binder component (thermal curing, active energy ray curing, etc.).

[0085] The coating composition can be applied by any known and commonly used coating method, such as a roll coater, electrostatic coating, bar coater, gravure coater, knife coater, dipping coating, or spray coating.

[0086] The substrate to be coated is not particularly limited, and examples thereof include paper, synthetic paper, steel plate, aluminum foil, glass, wood, woven fabric, knitted fabric, nonwoven fabric, gypsum board, wooden board, and resin substrate.

[0087] Specific examples of the resin substrate include polyethylene terephthalate (PET) film, polyethylene naphthalate (PEN) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: low-density polyethylene film, HDPE: high-density polyethylene film), polypropylene film (CPP: unstretched polypropylene film, OPP: biaxially oriented polypropylene film), polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, polycarbonate film, polymethyl methacrylate film, polyester film, polyolefin film, epoxy resin film, melamine resin film, triacetyl cellulose resin film, ABS resin film, norbornene-based resin film, cyclic olefin-based resin film, polyimide resin film, polyvinyl fluoride resin film, polyvinylidene fluoride resin film, ethylene-vinyl acetate copolymer film, etc. The resin substrate to be used may be subjected to a surface treatment such as a corona treatment.

[0088] [Resin composition] The resin composition of the present invention contains the protein adhesion-inhibiting resin of the present invention and the titanium oxide of the present invention. The protein adhesion-inhibiting resin of the present invention and the resin composition containing titanium oxide of the present invention can be used not only for coating applications, but also for molding into molded articles that prevent the adhesion of microorganisms, including bacteria and viruses, and inactivate microorganisms, including bacteria and viruses.

[0089] The resin component contained in the resin composition of the present invention can be the same as the resin component described in the coating composition of the present invention. In addition, the resin composition of the present invention can contain the same components as those that can be contained in the coating composition of the present invention.

[0090] The resin composition of the present invention can be molded by any molding method suitable for the resin used, including melt molding methods such as injection molding, extrusion molding, pressure molding (press molding), compressed air molding, and vacuum molding, and casting methods.

[0091] The coating layer obtained using the coating composition of the present invention and the molded article obtained using the resin composition of the present invention can be used as a material (antibacterial / antiviral material) that prevents adhesion of microorganisms including bacteria and viruses and inactivates microorganisms including bacteria and viruses. The term "inactivation" as used above means rendering a microorganism (bacteria, viruses, animal and plant-derived proteins, etc.) in a state in which it is unable to express one or more of the harmful properties of the microorganism, such as pathogenicity, allergenicity, infectivity, proliferation, etc.

[0092] The coating layer obtained using the coating composition of the present invention and the molded article obtained using the resin composition of the present invention are also expected to have anti-biofilm properties. Biofilms are three-dimensional aggregates formed from microorganisms attached to the surface of a material and the extracellular matrix they produce. Examples of such aggregates include the slimy substance found in bathrooms and kitchens. Biofilm formation begins with the attachment of planktonic cells to a solid surface. The irreversibly attached bacteria grow on the surface, forming microcolonies and producing extracellular polymers (EPS). Known EPS include extracellular polysaccharides, extracellular DNA, and proteins. Therefore, by inhibiting the attachment of microorganisms and even the growth of even slightly attached microorganisms, it is possible to inhibit the formation of microcolonies and EPS adhesion. It is believed that the coating layer obtained using the coating composition of the present invention and the surface of a molded article obtained using the resin composition of the present invention are highly resistant to biofilm formation.

[0093] Examples of microorganisms that form biofilms include Rhizobium, Pseudomonas, Sphingomonas, Sphingopyxis, Sphingobium, Brevundimonas, Blastomonas, Stenotrophomonas, and Porphyromonas. onas, Aeromonas, Klebsiella, Flavobacterium, Ochrobactrum, Methylobacterium, Fusobacterium, Brevibacterium, Burkholderia, Enterobacter, Acinetobacter Acinetobacter, Citrobacter, Aggregatibacter, Rhodobacter, Erwinia, Escherichia, Ralstonia, Salmonella, Serratia, Yersinia, Acidovorax, Prevotella Known examples of bacteria include gram-negative bacteria such as Staphylococcus (commonly known as "staphylococcus"), Streptococcus, Enterococcus, Bacillus, Lactobacillus, and Deinococcus.

[0094] Applications of the coating layer obtained using the coating composition of the present invention and the molded article obtained using the resin composition of the present invention include bathroom components such as bathtubs, bathroom walls, and faucets; sanitary components such as washbasins, wash basins, and toilet bowls; cooking components for kitchens and galleys; drainage components such as drain plugs, drain pipes, and drain ditches; water storage and water channel equipment such as water storage tanks, cisterns, swimming pools, artificial ponds, and cooling circulating water channels; air conditioning devices such as heat exchangers and drain pans; outdoor equipment such as signs, labels, and guardrails; textile products such as clothing and towels, and medical equipment. [Example]

[0095] The present invention will be specifically described below with reference to examples and comparative examples. The present invention is not limited to the following examples.

[0096] (Synthesis Example 1: Preparation of Protein Adhesion Inhibitory Resin P1) 5.84 g of 2-methoxyethyl acrylate (MEA; manufactured by Toagosei Co., Ltd.), 0.0254 g of the following compound (2-(1-Carboxy-1-methylethylsulfanylthiocarbonylsulfanyl)-2-methylpropionic acid) as a RAFT agent, 0.0014 g of 2,2'-azobisisobutyronitrile, 25.4 g of tert-butanol, and 3.8 g of water were mixed together and nitrogen was bubbled through for 1 hour while stirring, followed by reaction for 20 hours at 70°C under a nitrogen stream to obtain a solution of a 2-methoxyethyl acrylate polymer block (polyMEA). Next, 13.3 g of N,N-dimethylacrylamide (DMAA; KJ Chemicals Co., Ltd.), 57.9 g of tert-butanol, and 8.6 g of water were added to the polyMEA solution, and the mixture was further stirred at 70°C for 24 hours to obtain a solution of an ABA-type block copolymer (protein adhesion inhibitor resin P1) consisting of polyMEA and polyDMAA (500 mol of MEA, 1,500 mol of DMAA).

[0097] [ka]

[0098] The protein adhesion-inhibiting resin P1 was dissolved in tetrahydrofuran, and the structure of the protein adhesion-inhibiting resin P1 was identified as follows by gas chromatography (GC; 7890B GC system, manufactured by Agilent Technologies) equipped with a ZB-WAX column (length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm) manufactured by Phenomenex.

[0099] [ka]

[0100] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained protein adhesion inhibitor resin P1 were measured using gel permeation chromatography (GPC; Tosoh Corporation HLC-8220GPC system), and the weight average molecular weight was found to be 110,000 and the number average molecular weight was 50,000.

[0101] (Synthesis Example 2: Preparation of copper-supported titanium oxide compound M1) Sulfuric acid, water, and iron were added to a mixture of ilmenite, niobium pentoxide, and zirconium oxide, and dissolved to obtain a solution mainly composed of titanium sulfate and iron sulfate. Impurities such as iron sulfate were removed, and the mixture was subjected to thermal hydrolysis to obtain a hydrous titanium hydroxide composition. The titanium hydroxide composition was washed and calcined at 900°C, and the resulting solid was pulverized to obtain a titanium oxide compound, which is crystalline rutile titanium oxide.

[0102] The obtained titanium oxide compound was evaluated for various physical properties by the methods described below. The results are shown below: BET specific surface area: 9.0m 2 / g Rutile rate: 95.4% Primary particle size: 0.18μm Zr / Ti ratio: 0.05 Nb / Ti ratio: 0.17

[0103] (Method for measuring the BET specific surface area of ​​titanium oxide compounds) The specific surface area was measured (BET single point method) using a fully automatic BET specific surface area measuring device "Macsorb HM model-1208" manufactured by Mountech Co., Ltd.

[0104] (Method for measuring primary particle size of titanium oxide compound) The primary particle size of the titanium oxide compound was measured by directly measuring the size of the primary particles from an electron microscope photograph. Specifically, the minor axis and major axis diameters of each titanium oxide primary particle were measured under the following conditions, and the average was taken as the particle size of the primary particle. Next, the volume (weight) of each of 100 or more titanium oxide particles was calculated by approximating it to the cube of the calculated particle diameter, and the volume-average particle size was taken as the average primary particle size. <Transmission electron microscope (TEM) measurement conditions> Device name: JEM-1400Flash (manufactured by JEOL Ltd.) Acceleration voltage: 120kv Magnification: 20K

[0105] (Method for measuring the rutile content of titanium oxide compounds) Using an X-ray diffractometer "XRD-6100" manufactured by Shimadzu Corporation, the peak height ratio corresponding to rutile crystals was calculated from the peak heights corresponding to all titanium oxide crystals (rutile, brookite, and anatase).

[0106] (Calculation method for Zr / Ti ratio and Nb / Ti ratio) Metal element composition analysis was performed using the bulk fundamental parameter (bulk FP) method using an X-ray fluorescence analyzer "SEA1200VX" manufactured by Seiko Instruments Inc. Specifically, for the fluorescence intensity (cps: counts per second) of each metal element, the intensity ratio of the fluorescence intensity (cps) of zirconium or niobium, when the fluorescence intensity (cps) of titanium was set to 100, was calculated as the Zr / Ti ratio or Nb / Ti ratio, respectively.

[0107] The obtained titanium oxide compound was subjected to the following steps (a) to (c) to prepare a copper-supported titanium oxide compound: a) Mixing process (reaction process) 600 parts by mass of the titanium oxide compound, 8 parts by mass of copper(II) chloride dihydrate, and 900 parts by mass of water were mixed in a stainless steel container. The mixture was then stirred with a mixer ("Robomix" manufactured by Tokushu Kika Kogyo Co., Ltd.), and a 1 mol / L aqueous sodium hydroxide solution was added dropwise until the pH of the mixture reached 10. b) Dehydration process The mixture was filtered under reduced pressure using qualitative filter paper (5C) to separate the solid matter from the mixture, and then washed with ion-exchanged water. The washed solid matter was then dried at 120°C for 12 hours to remove moisture. After drying, a powdery titanium oxide compound was obtained using a mill (Iwatani Sangyo Co., Ltd.'s "Miller"). c) Heat treatment process The powdered titanium oxide compound obtained in the dehydration step b) was heat-treated in the presence of oxygen at 450°C for 3 hours using a precision incubator ("DH650" manufactured by Yamato Scientific Co., Ltd.) to obtain copper-supported titanium oxide compound M1, which is a titanium oxide compound supported with a divalent copper compound.

[0108] The obtained copper-supported titanium oxide compound was completely dissolved in a hydrofluoric acid solution, and the resulting extract was analyzed using an ICP emission spectrometer. As a result, it was found that the amount of copper supported in the copper-supported titanium oxide compound was 0.5 parts by mass per 100 parts by mass of titanium oxide.

[0109] Example 1: Preparation and evaluation of coating compositions 100 parts by mass of the protein adhesion-inhibiting resin P1 prepared in Synthesis Example 1 was diluted with a solvent of water / ethanol=1 / 9 so that the resin solids concentration was 0.2% by mass. 25 parts of the copper-supported titanium oxide compound M1 prepared in Synthesis Example 2, 75 parts of water, and 8 parts of a wetting dispersant (acid value 75 mgKOH / g, "DISPERBYK-194N" manufactured by BYK-Chemie Co., Ltd.) were mixed and stirred. 100 parts of 1.0 mm diameter ceramic beads were added to this mixture and ground with a sand grinder for 4 hours to obtain a dispersion of copper-supported titanium oxide compound M1. After grinding, the beads and the dispersion were separated and then diluted with a solvent of water / ethanol = 75 / 25 so that the solids concentration was 0.2 mass%. The 0.2 mass % diluted solution of P1 and the 0.2 mass % diluted solution of M1 prepared above were mixed and stirred in a ratio of 1:1 to prepare coating composition A. The obtained coating composition A was thinly applied by dipping to a PEN (polyethylene naphthalate) film (manufactured by Teijin DuPont, thickness 125 μm) that had been sterilized in advance using a UV ozone cleaner (manufactured by Filgen), and then dried for 4 hours in a clean bench to produce a laminate A consisting of a protein adhesion-inhibiting layer and a PEN substrate layer.

[0110] (Bacterial adhesion evaluation) The protein adhesion-inhibiting layer of the laminate was then coated with 1 × 10 6 100 μl of bacteria (E. coli) adjusted to cells / ml was placed on the plate, and the medium was removed after 24 hours. After washing with physiological saline, a glutaraldehyde solution was placed on the plate and left to stand for 1 hour for fixation. After fixation, the plate was washed with pure water, and SEM images of the bacteria adhering to the surface of the protein adhesion-inhibiting layer were prepared. Bacterial adhesion was evaluated by visual inspection of images observed at 500x magnification (Figure 1) according to the following criteria. The results are shown in Table 1. SEM images at 10,000x magnification (Figure 2) were also prepared and observed to determine whether the E. coli on the surface had been inactivated. ◯: Almost no adhesion of E. coli was observed on the protein adhesion-inhibiting layer of the laminate. ×: A large number of E. coli bacteria were observed adhering to the protein adhesion-inhibiting layer of the laminate.

[0111] The glutaraldehyde solution was prepared by using glutaraldehyde (Kanto Chemical Co., Ltd., glutaraldehyde solution, 25%, for electron microscopy) and adjusting the concentration to 1% in phosphate-buffered saline (Fujifilm Wako Pure Chemical Industries, Ltd., D-PBS(-)).

[0112] <Scanning electron microscope (SEM) measurement conditions> Equipment: TM4000PlusII (Hitachi High-Tech Corporation) Measurement conditions: Charge reduction mode, secondary electron detector Magnification: 500x and 10,000x

[0113] (Antibacterial evaluation) The antibacterial effect of the produced laminate was evaluated in accordance with JIS Z2801:2010. The results are shown in Table 1. The test conditions were as follows: Bacterial species: Escherichia coli (E. coli, strain number NBRC3972) Bacterial solution inoculation amount: 0.4mL Cover film: additive-free polyethylene film The antibacterial activity value R was determined by calculating the following: antibacterial activity value R = viable bacteria count Ut - viable bacteria count At. Here, the viable bacteria count Ut is the average logarithm of the viable bacteria count on the PEN film (without a protein adhesion-inhibitory layer) after 24 hours, and the viable bacteria count At is the average logarithm of the viable bacteria count on the antibacterial treated test piece (laminate A) after 24 hours.

[0114] Comparative Example 1: Preparation and Evaluation of Coating Composition A laminate was produced in the same manner as in Example 1, except that copper-supported titanium oxide compound M1 was not used, and bacterial adhesion and antibacterial properties were evaluated. The results are shown in Table 1. SEM images of bacteria adhering to the surface of the protein adhesion-inhibitory layer are shown in Figure 3 at 500x magnification and in Figure 4 at 10,000x magnification.

[0115] Comparative Example 2: Preparation and Evaluation of Coating Composition A laminate was produced in the same manner as in Example 1, except that a general-purpose resin (aqueous urethane resin, "Hydran WLS-210" manufactured by DIC Corporation) was used instead of the protein adhesion-inhibiting resin P1, and the bacterial adhesion and antibacterial properties were evaluated. The results are shown in Table 1. Figure 5 shows SEM images of bacteria adhering to the surface of the protein adhesion-inhibiting layer at 500x magnification, and Figure 6 shows images at 10,000x magnification.

[0116] (Comparative Example 3: Evaluation of PEN film) The PEN film was evaluated for bacterial adhesion. The results are shown in Table 1. Figure 7 shows SEM images of bacteria adhering to the surface of the protein adhesion-inhibiting layer at 500x magnification, and Figure 8 shows images at 10,000x magnification.

[0117] [Table 1]

[0118] The results in Table 1 show that the combination of protein adhesion-inhibiting resin and titanium oxide makes it possible to achieve both bacterial adhesion and antibacterial properties. In Comparative Example 1, the coating layer does not contain titanium oxide, so a small amount of live E. coli adheres to the surface, and the antibacterial data shows that the bacteria are able to grow, multiply, and become toxic. On the other hand, in Comparative Example 2, the coating layer does not contain protein adhesion-inhibiting resin, so although the titanium oxide provides an antibacterial effect, the SEM image shows that live E. coli adheres to the inactivated E. coli.

Claims

1. A coating composition comprising a block copolymer and titanium oxide, The block copolymer is a coating composition which is a block copolymer having a polymer block (A) of polymerization components containing a monomer represented by the following general formula (1) and a polymer block (B) of polymerization components containing at least one of the monomers represented by the following general formulas (2) to (7): 【Chemistry 1】 (In the general formulas (1) to (7), R ０ is an alkyl group having 1 to 6 carbon atoms, R １ is a hydrogen atom or a methyl group, R ２ is an alkylene group having 1 to 6 carbon atoms, R ３ , R ４ , R ５ and R ６ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ７ is an alkylene group having 1 to 6 carbon atoms, X is -CO ２ － , -SO ３ － , -OSO ３ － , -OSO ２ － , -OP(=O)(OR ８ ) O － , -OP(=O)(R ８ ) O － , -P(=O)(OR ８ ) O － , -P(=O)(R ８ ) O － is a monovalent anion selected from R ８ is an alkyl group having 1 to 6 carbon atoms, n is an integer ranging from 1 to 9.

2. 2. The coating composition according to claim 1, wherein the molar ratio of the polymer block (A) to the polymer block (B) (polymer block (A):polymer block (B)) is in the range of 1:50 to 50:

1.

3. 2. The coating composition according to claim 1, wherein the molar ratio of the monomer represented by general formula (1) to the monomers represented by general formulas (2) to (7) constituting the block copolymer (moles of the monomer represented by general formula (1) / total moles of the monomers represented by general formulas (2) to (7)) is in the range of 90:10 to 1:

99.

4. 2. The coating composition of claim 1, wherein the titanium oxide comprises rutile titanium oxide.

5. 2. The coating composition according to claim 1, wherein the titanium oxide is titanium oxide supporting a metal compound.

6. 6. The coating composition according to claim 5, wherein the metal compound is a divalent copper compound.

7. 2. The coating composition according to claim 1, wherein the titanium oxide is a titanium oxide compound containing zirconium and / or niobium.

8. 2. The coating composition according to claim 1, wherein the titanium oxide is a titanium oxide compound containing zirconium, and the content ratio of zirconium to 100 of titanium in the titanium oxide compound (Zr / Ti ratio) is in the range of 0.03 to 0.

8.

9. 2. The coating composition according to claim 1, wherein the titanium oxide compound contains niobium, and the content ratio of niobium to titanium (Nb / Ti ratio) in the titanium oxide compound is in the range of 0.05 to 0.

8.

10. 2. The coating composition according to claim 1, wherein the titanium oxide is contained in an amount ranging from 1 to 500 parts by mass relative to 100 parts by mass of the block copolymer.

11. A laminate having a substrate and a coating layer of the coating composition according to any one of claims 1 to 10.

12. A method for preventing adhesion of bacteria and viruses to a substrate and inactivating bacteria and viruses, comprising applying the coating composition according to any one of claims 1 to 10 onto the substrate to form a coating layer.

Images