Coating composition, laminate, resin composition, and molded article

Abstract

The invention relates to a coating composition, a laminate, a resin composition, and a molded article. Provided is a coating composition capable of forming a coating layer that prevents adhesion of microorganisms and inactivates microorganisms. The coating composition contains a block copolymer and titanium dioxide, and the block copolymer has a polymer block (A) containing a polymeric component of a monomer represented by general formula (1), and a polymer block (B) containing a polymeric component of at least one of monomers represented by general formulae (2)-(7).

Description

Technical Field

[0001] This invention relates to coating compositions, laminates, resin compositions, and molded articles. Background Technology

[0002] Due to the COVID-19 pandemic, there has been increasing attention on antibacterial and antiviral agents and processed antibacterial and antiviral products. Previously, antibacterial and antiviral agents and products were primarily used to prevent infection in patients with weakened immune systems, such as those receiving medical care or nursing. However, due to the spread of COVID-19, these agents and products have been widely infiltrated into homes, public transportation, commercial facilities, companies, and factories.

[0003] Most current antibacterial and antiviral processed products damage bacteria and viruses, thus inactivating them. However, the inactivated bacteria and viruses remain directly on the surface of the product. Furthermore, when bacteria and viruses further adhere to the inactivated bacteria and viruses, the following problem arises: because they do not come into contact with the antibacterial and antiviral processed surface, they remain active, proliferate, and form a biofilm.

[0004] To address the aforementioned issues, since microorganisms such as bacteria and viruses are composed of proteins, a method has been proposed that uses a resin that inhibits protein adhesion for coating processing, so that microorganisms such as bacteria and viruses do not adhere at all (e.g., Patent Documents 1-2).

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 7-83923

[0008] Patent Document 2: Japanese Patent Publication No. 7-506138 Summary of the Invention

[0009] The problem the invention aims to solve

[0010] The resins disclosed in Patent Documents 1 and 2 are polymers with phosphorylcholine groups, but they are not effective at inhibiting protein adhesion. Furthermore, they do not have the ability to inactivate microorganisms such as bacteria and viruses, and therefore cannot maintain the hygienic condition of the application site.

[0011] 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 microorganisms.

[0012] The problem to be solved by the present invention is to provide a resin composition capable of forming a molded body that prevents the adhesion of microorganisms and inactivates microorganisms.

[0013] Another problem to be solved by the present invention is to provide a laminate and a molded body that can prevent the adhesion of microorganisms and inactivate microorganisms.

[0014] Solution for solving the problem

[0015] That is, the present invention relates to the following coating compositions, etc.

[0016] 1. A coating composition comprising a block copolymer and titanium dioxide,

[0017] The aforementioned block copolymer is having

[0018] Polymer blocks (A) comprising polymer components of monomers represented by the following general formula (1), and

[0019] Polymer block (B) comprising at least one of the monomers shown in general formulas (2) to (7) below.

[0020] Block copolymers.

[0021]

[0022] (In the aforementioned general formulas (1) to (7),

[0023] R 0 It is an alkyl group having 1 to 6 carbon atoms.

[0024] R 1 It can be a hydrogen atom or a methyl group.

[0025] R 2 It is an alkylene group having 1 to 6 carbon atoms.

[0026] R 3 R 4 R 5 and R 6 Each is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0027] R 7 It is an alkylene group having 1 to 6 carbon atoms.

[0028] X is selected from -CO2 - -SO3 - -OSO3 - -OSO2 - -OP(=O)(OR) 8 )O - -OP(=

[0029] O)(R 8 )O - -P(=O)(OR) 8 )O --P(=O)(R 8 )O - Monovalent anions in

[0030] R 8 It is an alkyl group having 1 to 6 carbon atoms.

[0031] (n is an integer in the range of 1 to 9)

[0032] 2. The coating composition according to 1, wherein the molar ratio of the aforementioned polymer block (A) to the aforementioned polymer block (B) (polymer block (A): polymer block (B)) is in the range of 1:50 to 50:1.

[0033] 3. The coating composition according to 1, wherein the molar ratio of the monomer represented by the aforementioned general formula (1) constituting the aforementioned block copolymer to the monomer represented by the aforementioned general formulas (2) to (7) (molar of the monomer represented by general formula (1) / total molar of the monomer represented by general formulas (2) to (7)) is in the range of 90:10 to 1:99.

[0034] 4. The coating composition according to 1, wherein the aforementioned titanium dioxide comprises rutile titanium dioxide.

[0035] 5. The coating composition according to 1, wherein the aforementioned titanium dioxide is titanium dioxide loaded with a metal compound.

[0036] 6. The coating composition according to claim 5, wherein the aforementioned metal compound is a divalent copper compound.

[0037] 7. The coating composition according to claim 1, wherein the aforementioned titanium dioxide is a titanium dioxide compound containing zirconium and / or niobium.

[0038] 8. The coating composition according to claim 1, wherein the aforementioned titanium dioxide is a zirconium-containing titanium dioxide compound, and the zirconium content relative to titanium 100 in the aforementioned titanium dioxide compound (Zr / Ti ratio) is in the range of 0.03 to 0.8.

[0039] 9. The coating composition according to claim 1, wherein the aforementioned titanium dioxide compound is a titanium dioxide compound containing niobium, and the niobium content ratio (Nb / Ti ratio) of the aforementioned titanium dioxide compound relative to titanium 100 is in the range of 0.05 to 0.8.

[0040] 10. The coating composition according to claim 1, wherein the aforementioned titanium dioxide is contained in the range of 1 to 500 parts by weight relative to 100 parts by weight of the aforementioned block copolymer.

[0041] 11. A laminate having a coating layer and a substrate of any one of the coating compositions described in 1 to 10.

[0042] 12. A method for forming a coating layer by applying the coating composition described in any one of 1 to 10 onto a substrate, thereby preventing the adhesion of bacteria and viruses to the substrate and inactivating the bacteria and viruses.

[0043] The effects of the invention

[0044] According to the present invention, a coating composition capable of forming a coating layer that prevents the adhesion of microorganisms and inactivates microorganisms can be provided.

[0045] According to the present invention, a resin composition capable of forming a molded body that prevents the adhesion of microorganisms and inactivates microorganisms can be provided.

[0046] According to the present invention, laminates and molded bodies that prevent the adhesion of microorganisms and inactivate microorganisms can be provided. Attached Figure Description

[0047] Figure 1 This is a SEM image (500x magnification) showing the state of the layer on which protein adhesion is inhibited in the laminate manufactured in Example 1 during bacterial adhesion evaluation.

[0048] Figure 2 This is a SEM image (10,000x magnification) showing the state of the layer on which protein adhesion is inhibited in the laminate manufactured in Example 1 during bacterial adhesion evaluation.

[0049] Figure 3 This is a SEM image (500x magnification) showing the state of the layer on which the protein adhesion was inhibited in the laminate manufactured in Comparative Example 1 during the bacterial adhesion evaluation.

[0050] Figure 4 This is a SEM image (10,000x magnification) showing the state of the layer on which the protein adhesion was inhibited in the laminate manufactured in Comparative Example 1 during the bacterial adhesion evaluation.

[0051] Figure 5 This is a SEM image (500x magnification) showing the state of the layer on which the protein adhesion was inhibited in the laminate manufactured in Comparative Example 2 during the bacterial adhesion evaluation.

[0052] Figure 6 This is a SEM image (10,000x magnification) showing the state of the layer on which the protein adhesion was inhibited in the laminate manufactured in Comparative Example 2 during the bacterial adhesion evaluation.

[0053] Figure 7 This is a SEM image (500x magnification) showing the state of the layer on which the protein adhesion was inhibited in the laminate manufactured in Comparative Example 3 during the bacterial adhesion evaluation.

[0054] Figure 8This is a SEM image (10,000x magnification) showing the state of the layer on which the protein adhesion was inhibited in the laminate manufactured in Comparative Example 3 during the bacterial adhesion evaluation. Detailed Implementation

[0055] The following describes one embodiment of the present invention. The present invention is not limited to this embodiment, and can be implemented with appropriate modifications without impairing its effects.

[0056] It should be noted that the compounds in this specification may be derived from fossil resources or biological resources.

[0057] [Coating Composition]

[0058] The coating composition of the present invention contains specific block copolymers and titanium dioxide.

[0059] As resins for inhibiting protein adhesion, resins containing phosphorylcholine groups are known, but these resins are susceptible to the effects of 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 effect of inhibiting protein adhesion regardless of pH and salt concentration. Hereinafter, the block copolymer contained in the coating composition of the present invention will sometimes be referred to as "the resin for inhibiting protein adhesion of the present invention".

[0060] By combining titanium dioxide, which has antimicrobial properties that inactivate bacteria and viruses, with the aforementioned resin that inhibits protein adhesion, a coating composition capable of forming a coating layer that prevents microbial adhesion and inactivates microorganisms can be prepared.

[0061] The components contained in the coating composition of the present invention will be described below.

[0062] (Resin that inhibits protein adhesion)

[0063] The resin for inhibiting protein adhesion of the present invention is a block copolymer having: a polymer block (A) comprising a polymer component containing a monomer of the following general formula (1), and a polymer block (B) comprising a polymer component containing at least one of the monomers of the following general formulas (2) to (7).

[0064]

[0065] (In the aforementioned general formulas (1) to (7),

[0066] R 0 It is an alkyl group having 1 to 6 carbon atoms.

[0067] R 1 It can be a hydrogen atom or a methyl group.

[0068] R 2 It is an alkylene group having 1 to 6 carbon atoms.

[0069] R 3 R 4 R 5 and R 6 Each is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0070] R 7 It is an alkylene group having 1 to 6 carbon atoms.

[0071] X is selected from -CO2 - -SO3 - -OSO3 - -OSO2 - -OP(=O)(OR) 8 )O - -OP(=

[0072] O)(R 8 )O - -P(=O)(OR) 8 )O - -P(=O)(R 8 )O - Monovalent anions in

[0073] R 8 It is an alkyl group having 1 to 6 carbon atoms.

[0074] (n is an integer in the range of 1 to 9)

[0075] The monomers represented by the aforementioned general formula (1) constituting the polymer block (A) have the function of guaranteeing the shaping properties of the coating film obtained by the coating composition of the present invention, and can improve the controllability of the coating film thickness, surface smoothness, etc.

[0076] R 0 The alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms.

[0077] 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.

[0078] n is an integer in the range of 1 to 9, preferably an integer in the range of 1 to 6, and more preferably an integer in the range of 1 to 4.

[0079] Specific examples of the monomers represented by the aforementioned general formula (1) include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, methyl carbitol acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, ethyl carbitol acrylate, methoxytriethylene glycol acrylate, ethoxytriethylene glycol acrylate, etc., with 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, and 2-(2-ethoxyethoxy)ethyl acrylate being preferred.

[0080] The polymeric component constituting the polymer block (A) may contain only the monomer shown in the aforementioned general formula (1), and may be substantially formed from the monomer shown in the aforementioned general formula (1). Here, "substantially formed" means that 90% or more, 95% or more, 98% or more, or 100% by mass of the polymeric component constituting the polymer block (A) is the monomer shown in the aforementioned general formula (1).

[0081] When the polymer component constituting the polymer block (A) includes polymer components other than the monomer shown in the aforementioned general formula (1), the polymer component may include the monomer shown in the aforementioned general formulas (2) to (7) and (meth)acrylic acid monomers having functional groups such as hydroxyl, glycidyl, isocyanate, carboxyl, amino, sulfonic acid and so on.

[0082] The protein adhesion-inhibiting resin of the present invention is a copolymer having blocks of (meth)acrylamide derivatives (e.g., (meth)acrylamide, N- or N,N-substituted (meth)acrylamide), wherein the monomers of the aforementioned general formulas (2) to (7) constituting the polymer block (B) can impart the function of inhibiting protein adhesion to the coating film obtained by the coating composition of the present invention.

[0083] R 3 R 4 R 5 R 6 and R 8 It is an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms.

[0084] R 7 The alkylene group having 1 to 6 carbon atoms is preferably an alkylene group having 1 to 3 carbon atoms.

[0085] Specific examples of the monomers shown in the aforementioned general formulas (2) to (7) are (meth)acrylamide, N- or N,N-substituted (meth)acrylamide, and other (meth)acrylamide derivatives.

[0086] The polymeric component constituting the polymer block (B) may contain monomers represented by the aforementioned general formulas (2) to (7), and may be substantially formed from monomers represented by the aforementioned general formulas (2) to (7). Here, "substantially formed" means that 90% or more, 95% or more, 98% or more, or 100% by mass of the polymeric component constituting the polymer block (B) is a monomer represented by the aforementioned general formulas (2) to (7).

[0087] When the polymer component constituting the polymer block (B) includes polymer components other than the monomers shown in the aforementioned general formulas (2) to (7), the polymer components may include the monomers shown in the aforementioned general formula (1), (meth)acrylic acid monomers having anionic groups such as sulfonic acid groups and carboxyl groups, (meth)acrylic acid monomers having cationic groups such as quaternary ammonium groups, (meth)acrylic acid monomers having zwitterionic groups having quaternary ammonium groups and phosphate groups, (meth)acrylic acid monomers having amino acid residues having carboxyl groups and amino groups, (meth)acrylic acid monomers having sugar residues, (meth)acrylic acid monomers having hydroxyl groups, amphiphilic (meth)acrylic acid monomers combining hydrophilic chains such as polyethylene glycol and hydrophobic groups such as nonylphenyl, polyethylene glycol diacrylate, N,N'-methylenebisacrylamide, etc.

[0088] 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.

[0089] The molar ratio of polymer block (A) to polymer block (B) can be adjusted by the amount of polymer components added to polymer block (A) and polymer block (B).

[0090] 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.

[0091] The number-average molecular weight of the block copolymers 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.

[0092] The weight-average molecular weight and number-average molecular weight were determined by the methods described in the examples.

[0093] The block copolymer of the present invention can be any block copolymer having polymer block (A) and polymer block (B), and there is no particular limitation on the number and bonding order of each polymer block.

[0094] The block copolymers of the present invention are preferably AB-type diblock copolymers, or ABA-type or BAB-type triblock copolymers. The block copolymers of the present invention can be prepared as hyperbranched block copolymers (HBBCPs) using polyfunctional acrylates.

[0095] In the case of the block copolymer of the present invention, for example, a diblock copolymer of polymer block (A) and polymer block (B), the diblock copolymer can be a copolymer in which polymer block (A) and polymer block (B) are directly bonded to each other at their ends, or it can be a copolymer in which polymer block (A) and polymer block (B) are bonded together by spacer groups.

[0096] The same applies when the block copolymer of the present invention is a triblock copolymer or the like.

[0097] The block copolymer of the present invention can be a copolymer having polymer block (A) and polymer block (B), or it can have other polymer blocks besides polymer block (A) and polymer block (B).

[0098] The block copolymer of the present invention is preferably a block copolymer substantially formed from polymer blocks (A) and polymer blocks (B). Here, "substantially formed" means that the total content of polymer blocks (A) and polymer blocks (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.

[0099] (Method for manufacturing resin that inhibits protein adhesion)

[0100] The block copolymers of the present invention can be manufactured by known methods, for example: in the presence of a chain transfer agent such as trithiocarbonate (hereinafter referred to as RAFT agent), using an azo compound and / or an organic peroxide as a free radical polymerization initiator, a method is used to perform living free radical polymerization on one of the polymer components containing monomers of general formula (1) and the polymer components containing monomers of general formulas (2) to (7), and after the living free radical polymerization, another polymer component is subjected to living free radical polymerization; in the presence of an organic halide and a transition metal complex, a method is used to perform free radical polymerization on one of the polymer components containing monomers of general formula (1) and the polymer components containing monomers of general formulas (2) to (7), and then another polymer component is added to perform free radical polymerization, etc.

[0101] The block copolymer of the present invention is preferably manufactured by any of the methods described in (1) to (4) below.

[0102] (1) In the presence of a polymerization initiator, a RAFT agent is polymerized with one of a polymerization component containing monomers of general formula (1) and a polymerization component containing monomers of general formulas (2) to (7), and then separated and purified to synthesize a macromolecular RAFT agent (Macro RAFT agent) formed solely by polymer blocks of that monomer. Then, the macromolecular RAFT agent is polymerized with another polymerization component in the presence of a polymerization initiator to obtain a block copolymer.

[0103] (2) In the presence of an organohalide and a transition metal complex, one of the polymerizing components containing monomers of general formula (1) and the polymerizing components containing monomers of general formulas (2) to (7) is polymerized, and then separated and purified to synthesize a polymeric terminal halide formed solely from the polymer blocks of that one component. Then, in the presence of the transition metal complex, the polymeric terminal halide is polymerized with another polymerizing component to obtain a block copolymer.

[0104] (3) A method of polymerizing a RAFT agent with one of the polymerizing components containing monomers of general formula (1) and the polymerizing components containing monomers of general formulas (2) to (7) in the presence of a polymerization initiator, and then adding another polymerizing component without separation to obtain a block copolymer.

[0105] (4) A method of polymerizing one of the monomers of general formula (1) and the monomers of general formulas (2) to (7) in the presence of organohalides and transition metal complexes, and then adding another polymerizing component without separation to obtain a block copolymer.

[0106] In the cases described in (3) and (4) above, it is not necessary to wait for the former polymer component to be completely consumed before adding the other polymer component; the other polymer component can be added as soon as the conversion rate of the former polymer component reaches, for example, 65% or more. The copolymer obtained at this time is not a complete block copolymer, but a so-called Tapered block copolymer in which the monomers shown in general formula (1) and the monomers shown in general formulas (2) to (7) are partially mixed. However, if the ratio of the monomers shown in general formula (1) to the monomers shown in general formulas (2) to (7) is appropriately selected, a copolymer with the same function as a complete block copolymer can be obtained.

[0107] The method for manufacturing the block copolymer of the present invention has been described using RAFT polymerization as an example, but it is not limited to RAFT polymerization. For example, it can also be manufactured by ATRP (atom transfer radical polymerization), NMP (nitrogen oxide stabilized radical polymerization), etc.

[0108] It should be noted that, in the case of manufacturing by RAFT polymerization, the block copolymer of the present invention is obtained, for example, in the form of a copolymer having a thiocarbonyl sulfide bond (-SC(S)-). This thiocarbonyl sulfide bond can remain in the copolymer, or it can be removed by a process.

[0109] (Titanium dioxide)

[0110] Titanium dioxide has various crystal forms, including rutile titanium dioxide, anatase titanium dioxide, and brookite titanium dioxide. The titanium dioxide of this invention preferably contains rutile titanium dioxide.

[0111] When titanium dioxide contains rutile titanium dioxide, from the viewpoint of antiviral properties in light and dark, decomposition of organic compounds in light, and visible light responsiveness, the content of rutile titanium dioxide (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%.

[0112] 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, for example, it can be 100 mol%.

[0113] The rutile conversion rate of titanium dioxide was confirmed by the method described in the examples.

[0114] The upper limit for the BET specific surface area of ​​titanium dioxide is 200 m². 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 Below / g, the lower limit is 1m 2 / g or more, 2m 2 / g or more, 3m 2 / g or more or 5m 2 / g or more.

[0115] Regarding the BET specific surface area of ​​titanium dioxide, from the perspective of antiviral properties and visible light responsiveness, a combination of upper and lower limits for the BET specific surface area is used, for example, 1–200 m². 2 The range of / g is preferably 3 to 100m. 2 The range of / g is more preferably 5–90m. 2 The range of / g.

[0116] The BET specific surface area of ​​titanium dioxide was determined using the method described in the examples.

[0117] From the viewpoint of visible light responsiveness, the primary particle size of titanium dioxide 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.

[0118] The primary particle size of titanium dioxide was determined using the method described in the examples.

[0119] Titanium dioxide is preferably titanium dioxide loaded with a metal compound. By loading titanium dioxide with a metal compound, its photocatalytic activity in the visible light region can be improved.

[0120] Metals that can be used as metal compounds supported on titanium dioxide include, for example, transition metals such as copper, iron, tungsten, zirconium, and molybdenum; and metals other than transition metals such as zinc, aluminum, antimony, and tin.

[0121] The metal compound supported on titanium dioxide is preferably a copper compound, more preferably a divalent copper compound. Here, "divalent copper compound" can be any type of divalent copper inorganic compound or divalent copper organic compound.

[0122] As the aforementioned divalent copper inorganic compounds, examples include divalent copper inorganic acid salts such as copper sulfate, copper nitrate, copper iodate, copper perchlorate, copper oxalate, copper tetrafluoroborate, copper ammonium sulfate, copper sulfamate, copper ammonium chloride, copper pyrophosphate, and copper carbonate; divalent copper halides such as copper chloride, copper fluoride, and copper bromide; and copper oxide, copper sulfide, azurite, malachite, and copper azide.

[0123] For example, the following divalent copper organic compounds can be used: copper formate, copper acetate, copper propionate, copper butyrate, copper valerate, copper hexanoate, copper heptanoate, copper octanoate, copper nonanoate, copper decanoate, copper myristate, copper palmitate, copper heptadecanate, copper stearate, copper oleate, copper lactate, copper malate, copper citrate, copper benzoate, copper phthalate, copper isophthalate, copper terephthalate, copper salicylate, copper hexabenzoate, copper oxalate, copper malonate, copper succinate, copper glutarate, copper adipic acid, etc. Copper oxyhydroxide, copper glycolate, copper glycerate, copper gluconate, copper tartrate, copper acetylacetone, copper ethyl acetoacetate, copper isovalerate, copper β-resolanoate, copper diacetoacetate, copper formyl succinate, copper salicylamide, copper bis(2-ethylhexanoate), copper sebacic acid, copper naphthenate, copper quinoline (Oxine-copper), copper acetylacetone, copper ethyl acetoacetate, copper trifluoromethanesulfonate, copper phthalocyanine, copper ethoxide, copper isopropoxide, copper methanol, copper dimethyl dithiocarbamate, etc.

[0124] The divalent copper compound supported on titanium dioxide is preferably a compound represented by the following general formula (1).

[0125] CuX2(1)

[0126] (In the aforementioned general formula (1),

[0127] X is a halogen atom, CH3COO, NO3, or (SO4). 1 / 2 .

[0128] X is preferably a halogen atom, and more preferably a chlorine atom.

[0129] When titanium dioxide is loaded with a metal compound, the loading amount of the metal compound is, for example, 0.01 to 20 parts by mass relative to 100 parts by mass of titanium dioxide, 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.

[0130] The loading of the metal compound was determined using the methods described in the examples.

[0131] Metal compounds loaded with titanium dioxide can be used alone or in combination of two or more.

[0132] In the titanium dioxide of the present invention, the titanium dioxide is a titanium dioxide compound containing zirconium and / or niobium, preferably a titanium dioxide compound containing both zirconium and niobium.

[0133] It is speculated that titanium dioxide containing zirconium and / or niobium has low cohesiveness relative to the specific surface area (BET value) of primary particles, which contributes to improved dispersibility of titanium dioxide in the coating composition. It should be noted that it is speculated that in the titanium dioxide compound, both zirconium and niobium are contained in a doped state within the crystal structure of titanium dioxide.

[0134] When the titanium dioxide is a zirconium-containing titanium dioxide compound, the lower limit of the zirconium content relative to titanium 100 (Zr / Ti ratio) 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 relative to titanium 100 (Zr / Ti ratio) in the above-mentioned titanium dioxide 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. These upper and lower limits can be combined arbitrarily.

[0135] The zirconium content relative to titanium 100 in the above-mentioned titanium dioxide 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.

[0136] When the titanium dioxide is a titanium dioxide compound containing niobium, the lower limit of the niobium content relative to titanium 100 (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 niobium content relative to titanium 100 (Nb / Ti ratio) in the above-mentioned titanium dioxide 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. These upper and lower limits can be combined arbitrarily.

[0137] The niobium content relative to titanium 100 in the above-mentioned titanium dioxide compound (Nb / Ti ratio) 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.

[0138] The zirconium content ratio (Zr / Ti ratio) of the titanium dioxide compound to titanium 100 and the niobium content ratio (Nb / Ti ratio) of the titanium dioxide compound to titanium 100 are both fluorescence intensity ratios of the elements in the titanium dioxide compound, and are specifically confirmed by the methods described in the examples.

[0139] (Methods for manufacturing titanium dioxide)

[0140] Titanium dioxide can be manufactured by known methods, including liquid-phase and gas-phase methods. The liquid-phase method involves hydrolyzing or neutralizing titanium oxysulfate obtained from a liquid containing dissolved raw materials such as ilmenite to obtain titanium dioxide compounds. The gas-phase method involves reacting titanium tetrachloride, obtained by chlorinating raw materials such as rutile, with oxygen in the gas phase to obtain titanium dioxide. The titanium dioxide of the present invention is preferably manufactured by the liquid-phase method.

[0141] When titanium dioxide is prepared into a titanium dioxide compound containing zirconium and / or niobium, the desired amounts of zirconium oxide and / or niobium oxide can also be reacted together in the above reaction.

[0142] When loading metal compounds onto titanium dioxide, the loading method can employ well-known techniques.

[0143] Examples include: adding titanium dioxide to a mixture of a metal compound as a support and a solvent, and using the suspended mixture to adsorb the metal compound onto the titanium dioxide; and preparing a mixture of titanium dioxide, a metal compound as a support, a solvent, and an alkaline substance, and reacting the titanium dioxide with the metal compound.

[0144] The concentration of titanium dioxide in the aforementioned mixture can be set, for example, in the range of 3 to 40% by mass. When the titanium dioxide is produced by the aforementioned liquid-phase method, even increasing the concentration of titanium dioxide can produce a well-functioning mixture; for example, the concentration of titanium dioxide can be set in the range of more than 25% by mass and less than 40% by mass.

[0145] The amount of the metal compound used as a load in the aforementioned mixture is, for example, 0.01 to 20 parts by mass relative to 100 parts by mass of titanium dioxide, preferably 0.1 to 15 parts by mass, and more preferably 0.1 to 10 parts by mass.

[0146] By adjusting the amount of metal compound used, the loading of the metal compound can be adjusted.

[0147] Water, organic solvents, or mixtures thereof can be used as solvents for preparing the aforementioned mixture.

[0148] When the aforementioned solvent is a mixed solvent, the mixed solvent is preferably an aqueous solvent with water as the main component. Here, "aqueous solvent with water as the main component" refers to a mixed solvent in which water has the highest content in the total amount of solvent, and preferably a mixed solvent in which the water content is 50% by mass or more.

[0149] When the aforementioned mixed solvent contains an organic solvent, from the viewpoint of reducing environmental impact and improving safety, the content of the organic solvent is preferably 30% by mass or less, more preferably 5% by mass or less.

[0150] There are no particular limitations on the organic solvents that can be used as solvents; for example, organic solvents that are mixed with water are preferred. Examples of organic solvents that can be used as solvents 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; 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, and diethylene glycol; polyols such as glycerol; ketones such as methyl ethyl ketone and methyl isobutyl ketone; and bisphenol A, etc. Aromatic diols of epoxides with 2 or 3 carbon atoms (average addition molar number 1 or more and 16 or less); alicyclic diols such as hydrogenated bisphenol A; 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 diethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, ethyl carbitol, γ-butyrolactone, etc.

[0151] The aforementioned organic solvents are preferably 1-butanol, isobutanol, 1-pentanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol, methyl ethyl ketone, methanol, ethanol, n-propanol (NPA), isopropanol (IPA), propylene glycol, propylene glycol monomethyl ether (1-methoxy-2-propanol) (PGM), and ethylene glycol.

[0152] It should be noted that one type of organic solvent can be used alone, or two or more types can be used in combination.

[0153] When the aforementioned alkaline substance is used in the manufacture of titanium dioxide loaded with metal compounds, such alkaline substance may be sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, trimethylamine, ammonia, alkaline surfactant, etc., with sodium hydroxide being preferred.

[0154] From the viewpoint of easy reaction control, the aforementioned alkaline substance is preferably added in the form of an aqueous solution of the alkaline substance. The concentration of the alkaline substance in the aqueous 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.

[0155] Hereinafter, a method for manufacturing titanium dioxide loaded with divalent copper compounds will be described as one embodiment.

[0156] First, water and titanium dioxide are stirred and mixed as needed. Then, a divalent copper compound is added to the mixture and stirred. Next, an alkaline substance is added and the prepared mixture is stirred, thereby producing titanium dioxide loaded with a divalent copper compound.

[0157] The overall stirring time in the aforementioned method for manufacturing titanium dioxide loaded with divalent copper compounds can be, for example, in the range of 5 to 120 minutes, preferably in the range of 10 to 60 minutes. The reaction temperature of the aforementioned mixture can be, for example, in the range of room temperature (25°C) to 70°C.

[0158] From the viewpoint that divalent copper compounds can be well loaded on titanium dioxide, the pH of the mixture after adding alkaline substances is preferably in the range of 8 to 11, and more preferably in the range of 9.0 to 10.5.

[0159] After the reaction in the aforementioned mixture is completed, the solid components can be separated. Methods for performing this separation include, for example, filtration, sedimentation, centrifugation, and evaporation drying, with filtration being preferred. The separated solid components can then be washed, crushed, or graded as needed.

[0160] After obtaining the aforementioned solid components, from the viewpoint of enabling a more robust bond between the aforementioned divalent copper compound supported on the aforementioned titanium dioxide, it is preferable to subject the reacted titanium dioxide loaded with the divalent copper compound to heat treatment. The heat treatment temperature is preferably in the range of 150–600°C, more preferably in the range of 250–450°C. Furthermore, the heat treatment time is preferably in the range of 1–10 hours, more preferably in the range of 2–5 hours.

[0161] The content of titanium dioxide in the coating composition of the present invention is not particularly limited. For example, it may contain 1 to 500 parts by weight relative to 100 parts by weight of the resin that inhibits protein adhesion, preferably 1.5 to 250 parts by weight relative to 100 parts by weight of the resin that inhibits protein adhesion, and more preferably 3 to 200 parts by weight relative to 100 parts by weight of the resin that inhibits protein adhesion.

[0162] The coating composition of the present invention may contain only a resin that inhibits protein adhesion, or it may contain other binder components other than the resin that inhibits protein adhesion.

[0163] Other adhesive components mentioned above can be any of the following: water-based resin, non-water-soluble resin (solvent-based resin), or inorganic adhesive.

[0164] It should be noted that, in this application, "water-soluble resin" refers to resin for which less than 10 ml of water is required to dissolve 1 g of resin at 20°C. "Insoluble resin" refers to resin that is not the aforementioned "water-soluble resin".

[0165] Specific examples of other adhesive components include acrylic resins, vinyl acetate resins, styrene resins, vinyl chloride resins, olefin resins, urethane resins, urea-formaldehyde resins, polyurethane urea-formaldehyde resins, acrylic polyurethane resins, epoxy resins, melamine resins, phenolic resins, polyester resins, alkyd resins, silicone resins, polyphenylene sulfide resins, acrylonitrile / styrene copolymer resins, acrylonitrile / butadiene copolymer resins and acrylonitrile / butadiene / styrene copolymer (ABS) resins, alkaline silicates, colloidal silica, organometallic silanolates, dihydrogen phosphates, polyvalent metal alkoxides, organosilicon, alkyl silicates, alumina sols, cement, etc.

[0166] Other binder components also include those modified from the above components, such as rosin-modified phenolic resin if it is a phenolic resin.

[0167] The other binder components contained in the coating composition of the present invention may be a single type or two or more types.

[0168] In the coating composition of the present invention, the proportion of the resin that inhibits protein adhesion in the binder component 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. If the proportion of the resin that inhibits protein adhesion is 50% by mass or more, the effect of inhibiting protein adhesion can be sufficiently obtained.

[0169] There is no particular upper limit to the proportion of resin that inhibits protein adhesion in the adhesive component, for example, it may be less than 100% by mass.

[0170] The content of binder components (e.g., resins and other binder components that inhibit protein adhesion) in the coating composition of the present invention is not particularly limited, and can be appropriately set in the range of 0.02 to 99.9% by mass of the total solid components of the coating composition.

[0171] The coating composition of the present invention may further contain a dispersion medium. The dispersion medium is added to adjust the viscosity of the coating composition and may be either an aqueous medium or an oil-based medium.

[0172] Specific examples of dispersion media include: water, 1-butanol, isobutanol, 1-pentanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol, methanol, ethanol, n-propanol, isopropanol, and other monofunctional alcohols; various glycols; polyols such as glycerol; 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, and other glycols; bisphenol A; and glycols with 2 or 3 carbon atoms in bisphenol A. Aromatic diols of epoxide adducts (average addition molar number 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 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 diethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, ethyl carbitol, γ-butyrolactone, methyl ethyl ketone, various fatty acids, etc.

[0173] The dispersion medium contained in the coating composition of the present invention may be a single type or two or more types.

[0174] The content of the dispersion medium in the coating composition of the present invention is not particularly limited, and can be appropriately set, for example, so that the concentration of the solid components of the coating composition is in the range of 0.01 to 80% by mass.

[0175] The coating composition of the present invention may further contain a plasticizer.

[0176] By adding plasticizers to the coating composition, the resulting coating layer can be made flexible and its conformability to the substrate can be improved.

[0177] As a plasticizer, there are no particular limitations. Examples include phthalates, non-aromatic diesters, aliphatic esters, esters of polyalkylene glycols, phosphate esters, trimellitates, chlorinated paraffins, hydrocarbon oils, process oils, polyethers, epoxy plasticizers, polyester plasticizers, etc., with phthalates being preferred.

[0178] 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, benzyl epoxidized stearate, etc.

[0179] The plasticizer contained in the coating composition of the present invention may be a single type or two or more types.

[0180] The content of plasticizer in the coating composition of the present invention is not particularly limited, and can be appropriately set in the range of 0.1 to 50 parts by weight relative to 100 parts by weight of the resin solids component of the coating composition.

[0181] The coating composition of the present invention only needs to contain the titanium dioxide of the present invention, the resin of the present invention that inhibits protein adhesion, any other binder component, any dispersion medium, and any plasticizer. Other additives may be included without impairing the effects of the present invention. Examples of such other additives include: pigments, matting agents, curing agents, curing accelerators, defoamers, dispersants, leveling agents, thickeners, antioxidants, weathering agents, flame retardants, antistatic agents, lubricants, preservatives, and anti-biofilm agents (e.g., isothiazolinite compounds, thiazoline compounds, thiazolite compounds, triazine compounds, urea compounds, imidazole compounds, benzimidazole compounds, pyridine compounds, zinc pyridinethione compounds, phenylphenol compounds), etc.

[0182] The coating layer of the coating composition of the present invention can be a cured coating film formed by curing the coating composition, or it can be an uncured coating film of the coating composition.

[0183] When the coating layer is a cured coating film of the coating composition, the coating composition of the present invention can be applied to the surface of the substrate, and the resulting coating film can be cured by a curing method suitable for the adhesive components (thermal curing, active energy radiation curing, etc.).

[0184] Regarding the coating method of the coating composition, any well-known and commonly used coating method can be used, such as: roller coating, electrostatic coating, bar coating, gravure coating, doctor blade coating, dip coating, spray coating, etc.

[0185] There are no particular limitations on the substrate to be coated. Examples include: paper, synthetic paper, steel plate, aluminum foil, glass, wood, woven fabric, knitted fabric, non-woven fabric, gypsum board, wood board, resin substrate, etc.

[0186] Specific examples of the aforementioned resin substrates 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 resin film, cyclic olefin resin film, polyimide resin film, polyvinyl fluoride resin film, polyvinylidene fluoride resin film, ethylene-vinyl acetate copolymer film, etc.

[0187] The resin substrate used can undergo surface treatments such as corona treatment.

[0188] [Resin Composition]

[0189] The resin composition of the present invention contains the protein adhesion-inhibiting resin of the present invention and the titanium dioxide of the present invention.

[0190] The resin composition containing the protein adhesion inhibitor of the present invention and the titanium dioxide of the present invention is not only used for coating purposes, but can also be molded into a molded body that prevents the adhesion of microorganisms containing bacteria and viruses and inactivates microorganisms containing bacteria and viruses by molding it itself.

[0191] The resin components contained in the resin compositions of the present invention may be the same as those described in the coating compositions of the present invention. Furthermore, the resin compositions of the present invention may contain the same components as those that may be contained in the coating compositions of the present invention.

[0192] The molding method of the resin composition of the present invention can be any molding method suitable for the resin used, such as injection molding, extrusion molding, compression molding, pneumatic molding, vacuum molding, melt molding, and casting.

[0193] 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 to prevent the adhesion of microorganisms containing bacteria and viruses and to inactivate microorganisms containing bacteria and viruses (antibacterial / antiviral material).

[0194] It should be noted that the above-mentioned "inactivation" refers to the state in which any one or more of the harmful properties of microorganisms (bacteria, viruses, proteins derived from animals and plants, etc.) such as pathogenicity, allergenicity, infectivity, and proliferative capacity cannot be expressed.

[0195] The anti-biofilm properties 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 are also expected.

[0196] Biofilms are three-dimensional aggregates formed by microorganisms attached to the surface of a substance and the extracellular matrix produced by these microorganisms; for example, they correspond to the slimy substances produced in bathrooms and kitchens. Biofilm formation begins with suspended cells attaching to a solid surface. Irreversible bacteria proliferate on the solid surface, forming microcolonies and producing extracellular polymeric substances (EPS). EPS are known to include extracellular polysaccharides, extracellular DNA, and proteins. Therefore, by inhibiting the attachment of microorganisms themselves, and also inhibiting the proliferation of a small number of attached microorganisms, it is possible to inhibit the formation of microcolonies and, consequently, the attachment of EPS. It is considered that biofilms are extremely difficult to form on the surfaces of coatings obtained using the coating composition of the present invention and molded articles obtained using the resin composition of the present invention.

[0197] Microorganisms that form biofilms include, for example, *Rhizobium*, *Pseudomonas*, *Sphingomonas*, *Sphingopyxis*, *Sphingobium*, *Brevundimonas*, *Blastomonas*, *Stenotrophomonas*, *Porphyromonas*, *Aeromonas*, *Klebsiella*, *Flavobacterium*, *Ochrobactrum*, *Methylobacterium*, *Fusobacterium*, *Brevibacterium*, *Burkholderia*, *Enterobacter*, and *Acinetobacter*. Gram-negative bacteria include *Citrobacter*, *Aggregatibacter*, *Rhodobacter*, *Erwinia*, *Escherichia*, *Ralstonia*, *Salmonella*, *Serratia*, *Yersinia*, *Acidovorax*, *Prevotella*, *Tannerella*, and *Alcaligenes*; and Gram-positive bacteria include *Staphylococcus* (commonly known as "Staphylococcus"), *Streptococcus*, *Enterococcus*, *Bacillus*, *Lactobacillus*, and *Deinococcus*.

[0198] 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 such as home kitchens and central kitchens; drainage components such as drain plugs, drain pipes, and drain channels; water storage / water system equipment such as water tanks, water troughs, pools, artificial pools, and cooling circulating water systems; air conditioning devices such as heat exchangers and drip trays; outdoor equipment such as signs, logos, and railings; textile products such as clothing and towels; and medical equipment.

[0199] Example

[0200] The present invention will now be described in detail through examples and comparative examples.

[0201] It should be noted that the present invention is not limited to the following embodiments.

[0202] (Synthetic Example 1: Preparation of Resin P1 for Inhibiting Protein Adhesion)

[0203] 5.84 g of 2-methoxyethyl acrylate (MEA; manufactured by Toa Synthetic Co., Ltd.), 0.0254 g of the following compound (2-(1-carboxy-1-methylethylsulfanylthiocarbonylsulfanyl)-2-methylpropionic acid, 2-(1-Carboxy-1-methylethylsulfanylthiocarbonylsulfanyl)-2-methylpropionicacid) as a RAFT agent, 0.0014 g of 2,2'-azobisisobutyronitrile, 25.4 g of tert-butanol and 3.8 g of water were stirred and bubbled under nitrogen for 1 hour. The reaction was then carried out under nitrogen flow at 70°C for 20 hours to obtain a polymer block (polyMEA) solution of 2-methoxyethyl acrylate.

[0204] 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 above polyMEA solution, and the mixture was stirred at 70°C for 24 hours to obtain a solution of ABA-type block copolymer (resin P1 for inhibiting protein adhesion) formed by polyMEA and polyDMAA (MEA 500 mol, DMAA 1, 500 mol).

[0205]

[0206] The above-mentioned protein-inhibiting resin P1 was dissolved in tetrahydrofuran and analyzed by gas chromatography (GC; Agilent Technologies 7890B GC system) equipped with a Phenomenex ZB-WAX column (30m in length, 0.25mm in inner diameter, and 0.25μm in film thickness). The structure of the protein-inhibiting resin P1 was identified as follows.

[0207]

[0208] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the obtained resin P1 that inhibits protein adhesion were determined by gel permeation chromatography (GPC; HLC-8220GPC system manufactured by Tosoh Corporation). The results showed that the weight-average molecular weight was 110,000 and the number-average molecular weight was 50,000.

[0209] (Synthetic Example 2: Preparation of copper-loaded titanium dioxide compound M1)

[0210] Sulfuric acid, water, and iron are added to a mixture of ilmenite, niobium pentoxide, and zirconium oxide and dissolved to obtain a solution mainly composed of titanium sulfate and ferrous sulfate. Impurities such as ferrous sulfate are removed, and the mixture is subjected to hot water hydrolysis to obtain a hydrated titanium hydroxide composition. The titanium hydroxide composition is washed, calcined at 900°C, and the resulting solid is pulverized to obtain a titanium dioxide compound as crystalline rutile titanium dioxide.

[0211] The obtained titanium dioxide compounds were evaluated for various physical properties using the methods described later.

[0212] The results are shown below:

[0213] BET specific surface area: 9.0 m² 2 / g

[0214] Rutile conversion rate: 95.4%

[0215] Primary particle size: 0.18 μm

[0216] Zr / Ti ratio: 0.05

[0217] Nb / Ti ratio: 0.17

[0218] (Method for determining the BET specific surface area of ​​titanium dioxide compounds)

[0219] The determination was performed using the fully automated BET surface area measuring device "Macsorb HM model-1208" manufactured by Mounttech Co., Ltd., based on the surface area measurement (BET 1-point method).

[0220] (Method for determining the primary particle size of titanium dioxide compounds)

[0221] The primary particle size of titanium dioxide compounds is determined by directly measuring the size of the primary particles based on electron microscope images. Specifically, the minor axis diameter and major axis diameter of each titanium dioxide primary particle are measured under the following conditions, and the average is taken as the particle size of that primary particle. Then, for more than 100 titanium dioxide particles, the volume (weight) of each particle is approximated as a cube of the calculated particle size, and the volume-average particle size is taken as the average primary particle size.

[0222] Measurement conditions for transmission electron microscopy (TEM)

[0223] Device Name: JEM-1400Flash (Manufactured by Nippon Electronics Co., Ltd.)

[0224] Accelerating voltage: 120kV

[0225] Multiplier: 20K

[0226] (Method for determining the rutile content of titanium dioxide compounds)

[0227] Using the X-ray diffraction apparatus "XRD-6100" manufactured by Shimadzu Corporation, the peak height ratio corresponding to the rutile crystal was calculated from the peak height corresponding to the overall titanium dioxide crystal (rutile, brookite, anatase).

[0228] (Calculation methods for Zr / Ti ratio and Nb / Ti ratio)

[0229] Metal elemental composition analysis based on the Bulk Fundamental Parameter (bulk FP) method was performed using a Seiko Instruments SEA1200 VX fluorescence X-ray analyzer. Specifically, for each metal element, the fluorescence intensity (cps: count per second) was calculated, and the fluorescence intensity (cps) of zirconium or niobium was recorded as the Zr / Ti ratio or Nb / Ti ratio when the fluorescence intensity (cps) of titanium was set to 100.

[0230] The obtained titanium dioxide compound is subjected to the following steps (a) to (c) to prepare a copper-loaded titanium dioxide compound:

[0231] a) Mixing process (reaction process)

[0232] 600 parts by mass of the aforementioned titanium dioxide compound, 8 parts by mass of copper(ii) dihydrate, and 900 parts by mass of water were mixed in a stainless steel container. Next, the mixture was stirred using a mixer (ROBO MICS, manufactured by Tokusho Keika Kogyo Co., Ltd.), and a 1 mol / L sodium hydroxide aqueous solution was added dropwise until the pH of the mixture reached 10.

[0233] b) Dehydration process

[0234] The solid components were separated from the mixture by vacuum filtration using qualitative filter paper (5C), and then washed with deionized water. The washed solids were then dried at 120°C for 12 hours to remove moisture. After drying, a powdered titanium dioxide compound was obtained using a mill (MILLSER, manufactured by Iwatani Sangyo Co., Ltd.).

[0235] c) Heat treatment process

[0236] For the powdered titanium dioxide compound obtained in the dehydration process of b), a precision thermostat (manufactured by Yamato Scientific Co., Ltd., "DH650") was used to heat-treat at 450°C for 3 hours in the presence of oxygen to obtain a titanium dioxide compound loaded with divalent copper, namely copper-loaded titanium dioxide compound M1.

[0237] The obtained copper-loaded titanium dioxide compound was completely dissolved in hydrofluoric acid solution, and the extract was analyzed using ICP emission spectroscopy. The results showed that the copper loading of the copper-loaded titanium dioxide compound was 0.5 parts by mass per 100 parts by mass of titanium dioxide.

[0238] (Example 1: Preparation and evaluation of the coating composition)

[0239] 100 parts by mass of the protein adhesion inhibitory resin P1 prepared in Synthesis Example 1 were diluted in a solvent of water / ethanol = 1 / 9 so that the resin solids concentration was 0.2% by mass.

[0240] 25 parts of the copper-loaded titanium dioxide compound M1 prepared in Synthesis Example 2, 75 parts of water, and 8 parts of a wetting and dispersing agent (acid value 75 mg KOH / g, BYK-Chemie Co., Ltd. "DISPERBYK-194N") were mixed and stirred. The mixture was then added... One hundred parts of ceramic beads were ground in a sand mill for 4 hours to prepare a dispersion of copper-loaded titanium dioxide compound M1. After grinding, the beads were separated from the dispersion and diluted with a solvent of water / ethanol = 75 / 25 to achieve a solid content concentration of 0.2% by mass.

[0241] The 0.2% by mass dilution of P1 and the 0.2% by mass dilution of M1 prepared above were mixed and stirred at a ratio of 1:1 to prepare coating composition A.

[0242] The obtained coating composition A was thinly coated onto a PEN (polyethylene naphthalate) film (125 μm thick, manufactured by Teijin-DuPont) that had been sterilized using a UV ozone cleaner (manufactured by Filgen) by means of an impregnation method. The film was then dried in a clean bench for 4 hours to produce a laminate A consisting of a protein adhesion inhibition layer and a PEN substrate layer.

[0243] (Evaluation of bacterial adhesion)

[0244] 100 μl of the protein adhesion-inhibiting layer of the manufactured laminate was suspended in LB medium (manufactured by NACALAITESQUE Co., Ltd., product name: LB medium, Miller) to prepare a 1×10⁻⁶ plate.6 Bacteria (E. coli) at concentrations of 1 / ml were cultured and removed after 24 hours. After washing with physiological saline, the bacteria were immobilized in glutaraldehyde solution for 1 hour. Following immobilization, the bacteria were washed with pure water, and SEM images of the bacteria attached to the protein-inhibiting layer were prepared. For bacterial adhesion evaluation, images observed at 500x magnification (…) Figure 1 The evaluation was conducted visually according to the following criteria. The results are shown in Table 1. It should be noted that SEM images were also prepared at 10,000x magnification. Figure 2 Also observe whether the E. coli on the surface is inactivated.

[0245] 〇: Almost no E. coli attachment was identified on the layer of the laminate that inhibits protein attachment.

[0246] ×: A large amount of E. coli was found attached to the layer of the laminate that inhibits protein attachment.

[0247] It should be noted that the above-mentioned glutaraldehyde solution was prepared using glutaraldehyde (manufactured by Kanto Chemical, glutaraldehyde solution, 25%, for electron microscope) with phosphate-buffered saline (manufactured by Fujifilm and Kouichi Pharmaceutical, D-PBS(-)) to a concentration of 1%.

[0248] <Measurement conditions for scanning electron microscopy (SEM)>

[0249] Device: TM4000PlusII (Made by Hitachi High Technology Co., Ltd.)

[0250] Measurement conditions: Charge reduction mode, secondary electron detector

[0251] Multipliers: 500x and 10,000x

[0252] (Antibacterial performance evaluation)

[0253] For the manufactured laminates, the antimicrobial efficacy was evaluated based on JIS Z 2801:2010. The results are shown in Table 1. It should be noted that the test conditions are as follows.

[0254] Bacterial strain: Escherichia coli (Strain number NBRC3972)

[0255] Inoculation volume: 0.4 mL

[0256] Covering film: Additive-free polyethylene film

[0257] The antibacterial activity value R is calculated as follows: viable count Ut - viable count At. Here, viable count Ut represents the average of the logarithmic values ​​of the viable count of the PEN film (without a layer that inhibits protein adhesion) after 24 hours, and viable count At represents the average of the logarithmic values ​​of the viable count of the antibacterial processing test piece (laminate A) after 24 hours.

[0258] (Comparative Example 1: Preparation and Evaluation of Coating Compositions)

[0259] Copper-loaded titanium dioxide compound M1 was not used. Otherwise, the laminate was fabricated in the same manner as in Example 1, and bacterial adhesion and antibacterial activity were evaluated. The results are shown in Table 1. Furthermore, SEM images of bacteria attached to the surface of the layer inhibiting protein adhesion are presented, with 500x magnification used as the reference image. Figure 3 Using 10,000 times the image as Figure 4 .

[0260] (Comparative Example 2: Preparation and Evaluation of Coating Compositions)

[0261] A general-purpose resin (waterborne urethane resin, "HYDRAN WLS-210" manufactured by DIC Corporation) was used instead of the protein adhesion-inhibiting resin P1. Otherwise, the laminate was manufactured in the same manner as in Example 1, and bacterial adhesion and antibacterial activity were evaluated. The results are shown in Table 1. Furthermore, SEM images of bacteria attached to the surface of the protein adhesion-inhibiting layer are presented at 500x magnification. Figure 5 Using 10,000 times the image as Figure 6 .

[0262] (Comparative Example 3: Evaluation of PEN Thin Films)

[0263] Bacterial adhesion was evaluated on the PEN film. The results are shown in Table 1. Furthermore, SEM images of bacteria attached to the surface of the layer inhibiting protein adhesion were presented, with 500x magnification used as the baseline. Figure 7 Using 10,000 times the image as Figure 8 .

[0264] [Table 1]

[0265]

[0266] The results in Table 1 show that the combination of a resin that inhibits protein adhesion and titanium dioxide can achieve both prevention of bacterial adhesion and antibacterial properties. In Comparative Example 1, since the coating layer did not contain titanium dioxide, although the amount was trace, *E. coli* adhered in a viable state. Furthermore, the antibacterial data showed that the bacteria exhibited growth / proliferation / toxicity. On the other hand, in Comparative Example 2, since the coating layer did not contain a resin that inhibits protein adhesion, although an antibacterial effect was achieved using titanium dioxide, the SEM images showed that viable *E. coli* bacteria adhered to the inactivated *E. coli*.

Claims

1. A coating composition comprising a block copolymer and titanium dioxide, The block copolymer is having Polymer blocks (A) comprising polymer components of monomers represented by the following general formula (1), and A block copolymer comprising a polymer block (B) of at least one of the monomers shown in general formulas (2) to (7) below. In the general formulas (1) to (7), R 0 It is an alkyl group having 1 to 6 carbon atoms. R 1 It can be a hydrogen atom or a methyl group. R 2 It is an alkylene group having 1 to 6 carbon atoms. R 3 R 4 R 5 and R 6 Each is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R 7 It is an alkylene group having 1 to 6 carbon atoms. X is selected from -CO2 - -SO3 - -OSO3 - -OSO2 - -OP(=O)(OR) 8 )O - -OP(= O)(R 8 )O - -P(=O)(OR) 8 )O - -P(=O)(R 8 )O - Monovalent anions in R 8 It is an alkyl group having 1 to 6 carbon atoms. n is an integer in the range of 1 to 9.

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

99.

4. The coating composition according to claim 1, wherein, The titanium dioxide comprises rutile titanium dioxide.

5. The coating composition according to claim 1, wherein, The titanium dioxide is titanium dioxide loaded with a metal compound.

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

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

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

8.

9. The coating composition according to claim 1, wherein, The titanium dioxide compound is a titanium dioxide compound containing niobium, and the niobium content relative to titanium 100 in the titanium dioxide compound (Nb / Ti ratio) is in the range of 0.05 to 0.

8.

10. The coating composition according to claim 1, wherein, The titanium dioxide is contained in the range of 1 to 500 parts by mass relative to 100 parts by mass of the block copolymer.

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

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

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