Titanium oxide composition, coating composition, antibacterial / antiviral fiber body, and antibacterial / antiviral film

Abstract

The purpose of the present disclosure is to provide a titanium oxide composition, a coating composition, an antibacterial / antiviral fabric, and an antibacterial / antiviral film that exhibit excellent dark activity and high antibacterial / antiviral properties. The present disclosure is a titanium oxide composition that includes: rutile-type titanium oxide; and two or more copper atom-containing nanoclusters containing copper atoms and provided on the surface of the rutile-type titanium oxide. The titanium oxide composition contains, as the two or more copper atom-containing nanoclusters, a first nanocluster containing copper atoms and chlorine atoms.

Description

Titanium dioxide composition, coating composition, antibacterial and antiviral fiber, and antibacterial and antiviral film

[0001] This disclosure relates to titanium dioxide compositions, coating compositions, antimicrobial and antiviral fibers, and antimicrobial and antiviral films.

[0002] Efforts to impart antibacterial or antiviral properties to products (textiles, films, painted boards) that people touch in living spaces have been underway for some time, but the outbreak of the novel coronavirus has further increased interest in antiviral properties. As a result, there is a growing global need to make products that people touch "antibacterial and antiviral" to reduce the possibility of infection by pathogens or viruses. Since such "antibacterial and antiviral" effects are obtained by controlling the structure and function of the material surface of things present in the living environment, material design mainly involves mechanisms such as the generation and utilization of reactive oxygen species and control of hydrophobicity / hydrophilicity, surface charge, and pH. For example, metals such as silver, copper, and zinc, which are inorganic materials mainly used as "antibacterial and antiviral" materials, utilize reactive oxygen species and free radicals (e.g., hydroxyl radicals, superoxide anion radicals) to cause chain-reaction oxidation reactions that destroy or render functional cell membranes, proteins, or nucleic acids. Photocatalytic semiconductors such as titanium dioxide are also known to exert "antibacterial and antiviral" effects through a similar mechanism, although they require ultraviolet irradiation.

[0003] In particular, photocatalysts using titanium dioxide are being investigated as antiviral agents because they possess high photocatalytic activity, including antiviral properties, and are harmless to the human body. For example, Patent Document 1 describes a titanium dioxide composition that substantially contains at least one metal element selected from the group consisting of zirconium and niobium, which exhibits antiviral properties.

[0004] International Publication No. 2022 / 138187

[0005] The technology described in Patent Document 1 above can provide a titanium dioxide composition with excellent antibacterial and antiviral properties, but its dark-time activity has not been investigated. Therefore, this disclosure aims to provide a titanium dioxide composition and a coating composition with excellent dark-time activity, antibacterial properties, and antiviral properties, as well as antibacterial and antiviral fibers and antibacterial and antiviral films supported by these compositions.

[0006] In order to solve the above problems, the inventors of the present invention have conducted extensive research and have found that by preparing a titanium dioxide composition having a specific composition ratio and a specific morphology, excellent dark-activity, antibacterial properties, and antiviral properties can be achieved, and have completed the present invention as shown in any of the following [1] to

[14] .

[0007] [1] A titanium oxide composition comprising rutile-type titanium oxide and two or more copper atom-containing nanoclusters provided on the surface of the rutile-type titanium oxide, wherein the two or more copper atom-containing nanoclusters include a first nanocluster containing copper atoms and chlorine atoms.

[0008] [2] The titanium oxide composition according to [1], wherein the total amount of copper atoms contained in the copper atom-containing nanocluster is 0.4 parts by mass to 10 parts by mass relative to the entire titanium oxide composition.

[0009] [3] The titanium oxide composition according to [1] or [2], wherein the amount of chlorine atoms contained in the copper atom-containing nanoclusters is 0.01 parts by mass to 2 parts by mass relative to the entire titanium oxide composition.

[0010] [4] The titanium oxide composition according to any one of [1] to [3], wherein the first nanocluster has an atacamite-based structure.

[0011] [5] The titanium oxide composition according to [4], wherein the atacamite-based structure is one or more selected from the group consisting of atacamite (Cu2Cl(OH)3, space group; Orth. Mmm (2 / m2 / m2 / m): Pnma), botalachite (Cu2Cl(OH)3, space group; Mon. 2 / m: P21 / m), and clinoatacamite (Cu2Cl(OH)3, space group; Mon. 2 / m).

[0012] [6] The titanium oxide composition according to any one of [1] to [5], containing rutile-type titanium oxide as a reaction raw material.

[0013] [7] The titanium oxide composition according to any one of [1] to [4] is a fired body, and the fired body is the titanium oxide composition according to any one of [1] to [6], using an atacamite-based structure as a reaction raw material.

[0014] [8] The rutile-type titanium oxide is rutile-type titanium oxide derived from a liquid phase method and contains at least one metal element selected from the group consisting of zirconium and niobium. The titanium oxide composition according to any one of [1] to [7].

[0015] [9] The average particle diameter of the copper atom-containing nanocluster is in the range of 0.2 nm to 500 nm. The titanium oxide composition according to any one of [1] to [8].

[0016]

[10] The BET specific surface area is 1 m ２ / g to 200 m ２ / g. The titanium oxide composition according to any one of [1] to [9].

[0017]

[11] A coating composition containing the titanium oxide composition according to any one of [1] to

[10] and a binder resin.

[0018]

[12] An antibacterial and antiviral fibrous body having a fibrous body main body and a coating layer made of the coating composition of

[11] attached to the fibrous body main body.

[0019]

[13] A titanium oxide composition-containing antibacterial and antiviral fibrous body in which the titanium oxide composition according to any one of [1] to

[10] is contained inside the fiber.

[0020]

[14] An antibacterial and antiviral film having a base film and a coating layer made of the coating composition of

[11] provided on at least one surface of the base film.

[0021] This disclosure provides titanium dioxide compositions and coating compositions that exhibit excellent dark-activity, antibacterial properties, and antiviral properties, as well as antibacterial and antiviral fibers and antibacterial and antiviral films supported by these compositions.

[0022] Figure 1 shows the EDS elemental mapping analysis results of the titanium oxide composition (4) obtained in Example 4. Figure 2 shows the EDS elemental mapping analysis results of the titanium oxide composition (6) obtained in Example 6. Figure 3 shows the LAADF-STEM image of the titanium oxide composition (4) from Example 4. Figure 4 shows the HAADF-STEM image of the titanium oxide composition (4) from Example 4. Figure 5 shows the crystal structure analysis results of sample 1) prepared in Example 1 by powder X-ray diffraction (instrument name: Rigaku, SmartLab 9kW, measurement conditions: 2θ method, 2θ = 1 to 70 deg., speed = 1.0 deg. / min, analysis software ReciPro). Figure 6 shows the results of the crystal structure analysis of sample 2) prepared in Example 1 using powder X-ray diffraction (instrument name: Rigaku, SmartLab 9kW, measurement conditions: 2θ method, 2θ = 1 to 70 deg., speed = 1.0 deg. / min, analysis software: ReciPro).

[0023] The embodiments of this disclosure (hereinafter referred to as "this embodiment") will be described in detail below, but this disclosure is not limited to the following description and can be implemented in various modifications within the scope of its gist. In this specification, A (numerical value) to B (numerical value) means A or more and B or less. [Titanium Dioxide Composition] The titanium dioxide composition of this disclosure comprises rutile-type titanium dioxide and two or more copper atom-containing nanoclusters containing copper atoms provided on the surface of the rutile-type titanium dioxide, wherein the two or more copper atom-containing nanoclusters include a first nanocluster containing copper atoms and chlorine atoms. It is believed that this makes it possible to exhibit excellent dark-activity, antibacterial and antiviral effects with a titanium dioxide composition having a specific composition ratio and a specific morphology.

[0024] (Terminology) In this disclosure, "antibacterial" encompasses effects such as reducing the number of bacteria and inhibiting bacterial growth. Similarly, in this invention, "antiviral" encompasses effects such as reducing the number of viruses, inactivating viruses, and reducing the infectivity of viruses. In this disclosure, the bacteria targeted for antibacterial treatment are not particularly limited and may include either bacteria or fungi. Examples of bacteria include Gram-negative bacteria such as Escherichia coli, Pseudomonas aeruginosa, Salmonella, Moraxella, and Legionella; and Gram-positive bacteria such as Staphylococcus aureus and Clostridium. Examples of fungi include yeasts such as Candida, Rhodotorula, and baker's yeast; and molds such as Red mold and Black mold. In this disclosure, the viruses targeted for antiviral treatment are not particularly limited and may include either known enveloped viruses (viruses with an envelope) or non-enveloped viruses (viruses without an envelope). Examples of enveloped viruses include coronavirus, influenza virus, rubella virus, Ebola virus, measles virus, varicella-zoster virus, herpes virus, mumps virus, arbovirus, RSV virus, SARS virus, hepatitis viruses (e.g., hepatitis A virus, hepatitis B virus, hepatitis C virus, hepatitis D virus, hepatitis E virus, etc.), yellow fever virus, HIV, rabies virus, hantavirus, dengue virus, nipah virus, lyssavirus, etc. Examples of non-enveloped viruses include adenovirus, norovirus, rotavirus, human papillomavirus, poliovirus, enterovirus, coxsackievirus, human parvovirus, encephalomyocarditis virus, polyomavirus, BK virus, rhinovirus, feline calicivirus, etc. The components of the titanium dioxide composition of this embodiment will be described below.

[0025] (Rutile Titanium Dioxide) The titanium dioxide composition of this embodiment contains rutile titanium dioxide as an essential component. This allows it to exhibit antibacterial and antiviral properties. Generally, the photocatalytic effect of titanium dioxide such as rutile titanium dioxide is due to excited electrons and holes generated by ultraviolet light absorption forming on the crystal surface. ２ and H２ Singlet oxygen, which is a reactive oxygen species, interacts with oxygen. ２ －The photocatalytic reaction occurs when reactive oxygen species (superoxide ions), hydrogen peroxide, or •OH (hydroxyl radicals) are formed, and these reactive oxygen species react with organic compounds. Since the first step in this series of elementary processes is the interaction between photoexcited carriers and adsorbed chemical species, the dynamics of these photoexcited carriers can be one of the important factors determining photocatalytic activity. Furthermore, there are three types of crystalline structures for titanium dioxide: the high-temperature rutile type, which belongs to the tetragonal system; the low-temperature anatase type; and the orthorhombic brookite type. Among these, the most common crystalline structure is the tetragonal system, and it is known that anatase-type titanium dioxide is superior to rutile-type titanium dioxide in terms of photocatalytic activity. One reason for this is the difference in their energy structures (band gap of approximately 3.2 eV for anatase-type and approximately 3.0 eV for rutile-type). Furthermore, mixed titanium dioxide of anatase and rutile forms may exhibit even higher photocatalytic activity than anatase-type titanium dioxide (T. Ohno et al., Appl. Catal. A 244, 383–391 (2003); YK Kho et al., J. Phys. Chem. C 114, 2821–2829 (2010); R. Suet al., J. Phys. Chem. C 115, 24287–24292 (2011)). Therefore, it is thought that the synergistic effect of such material mixing is manifested by the promotion of charge separation between electrons and holes at the anatase / rutile junction interface, and the dynamics of photoexcited carriers greatly influence photocatalytic activity. Considering that the photocatalytic reaction of titanium dioxide proceeds on the crystal surface of the titanium dioxide, the potential barrier formed on the crystal surface can be one of the important factors determining photocatalytic activity. Similarly, by adding a metal compound that functions as a co-catalyst to a photocatalyst such as titanium dioxide, charge separation between electrons and holes is promoted in specific combinations, resulting in a synergistic effect that can become one of the important factors determining photocatalytic activity.Furthermore, it is known that reducing the size of the co-catalyst particles allows the charge separation of electrons and holes generated on the co-catalyst to proceed to the photocatalytic reaction faster than it can be recombined, thereby increasing photocatalytic activity. This can be one of the important factors determining photocatalytic activity. Therefore, although the detailed mechanism is unknown, in this disclosure, it is thought that the presence of two or more copper atom-containing nanoclusters containing copper atoms, as described later, on the surface of rutile-type titanium oxide enables efficient interfacial charge transfer between these two or more copper atom-containing nanoclusters and titanium oxide, thereby improving photocatalytic activity. In addition, it is thought to have the effect of stabilizing the first nanocluster containing chlorine.

[0026] The rutile-type titanium dioxide referred to in this disclosure is titanium dioxide in which the proportion of rutile-type crystal structure is 50% or more. In the titanium dioxide composition of this embodiment, the proportion of rutile-type crystal structure (=rutile rate) in the total titanium dioxide contained in the titanium dioxide composition is preferably 50% to 100%, more preferably 80% to 100%, and even more preferably 90% to 100%. The rutile rate is a value calculated from the X-ray diffraction peak, and the details are described in the examples.

[0027] In the titanium dioxide composition of this embodiment, the content of rutile-type titanium dioxide is preferably 45% to 99.6% by mass, more preferably 70% to 99.6% by mass, even more preferably 80% to 99.6% by mass, even more preferably 90% to 99.6% by mass, and even more preferably 95% to 99.6% by mass, relative to the total titanium dioxide composition. When the content of rutile-type titanium dioxide in the titanium dioxide composition of this embodiment is within the above range, superior dark-area activity, antibacterial properties, and antiviral properties can be exhibited.

[0028] The titanium dioxide composition of this embodiment may further contain anatase-type titanium dioxide and / or brookite-type titanium dioxide, if necessary. In the titanium dioxide composition of this embodiment, the content of anatase-type titanium dioxide is preferably 0% to 50% by mass, more preferably 0% to 25% by mass, even more preferably 0% to 15% by mass, even more preferably 0% to 10% by mass, and even more preferably 0% to 5% by mass, based on the total titanium dioxide composition. In the titanium dioxide composition of this embodiment, the content of brookite-type titanium dioxide is preferably 0% to 50% by mass, more preferably 0% to 25% by mass, even more preferably 0% to 15% by mass, even more preferably 0% to 10% by mass, and even more preferably 0% to 5% by mass, based on the total titanium dioxide composition. The anatase-type titanium dioxide of this disclosure refers to titanium dioxide in which the proportion of anatase-type crystalline structure is 50% or more. Furthermore, brookite-type titanium oxide refers to titanium oxide in which the proportion of brookite-type crystal structure is 50% or more. This proportion is calculated from the X-ray diffraction peak, and the details are described in the examples.

[0029] A preferred embodiment of this product is a titanium dioxide composition in which the proportion of rutile-type crystal structures in the total titanium dioxide contained in the titanium dioxide composition is 50% to 100%, the proportion of anatase-type crystal structures in the total titanium dioxide is 0% or more and less than 50%, and the proportion of brookite-type crystal structures in the total titanium dioxide is 0% or more and less than 50%. A more preferred embodiment is a titanium dioxide composition in which the proportion of rutile-type crystal structures in the total titanium dioxide contained in the titanium dioxide composition is more than 90% and 100% or less, the proportion of anatase-type crystal structures is 0% or more and less than 10%, and the proportion of brookite-type crystal structures is 0% or more and less than 10%. When the relative abundance of each crystal structure of rutile-type, anatase-type, and brookite-type in the total titanium dioxide contained in the titanium dioxide composition is within the above range, a synergistic effect is more easily achieved in combination with the presence of two or more copper atom-containing nanoclusters containing copper atoms, enabling more efficient interfacial charge transfer and further improving photocatalytic activity.

[0030] The rutile-type titanium dioxide in this embodiment may be either rutile-type titanium dioxide produced by a liquid-phase method or rutile-type titanium dioxide produced by a gas-phase method, but rutile-type titanium dioxide produced by a liquid-phase method is more preferred. This is because, although rutile-type titanium dioxide produced by a gas-phase method has the advantage of being able to produce uniform particle sizes, secondary aggregates are less likely to form, which is thought to increase the apparent specific surface area and thus increase the viscosity of the mixed solution during the reaction process. In contrast, rutile-type titanium dioxide produced by a liquid-phase method is thought to be able to produce loose secondary aggregates during the calcination process, and the cohesive force is less than that of the specific surface area (BET value) caused by the primary particles, making it possible to suppress the viscosity of the mixed solution, which is thought to contribute to improving the productivity of the titanium dioxide composition in this embodiment. In other words, the rutile-type titanium dioxide in this embodiment is preferably rutile-type titanium dioxide derived by a liquid-phase method. The preferred rutile-type titanium dioxide in this embodiment is rutile-type titanium dioxide derived by a liquid-phase method and titanium dioxide in which the proportion of rutile-type crystal structure is 50% or more. The content of the rutile-type titanium oxide is 45% to 99.6% by mass relative to the total titanium oxide composition (100% by mass). The characteristics of rutile-type titanium oxide derived from the liquid phase method are that it contains one or more elements selected from the group consisting of zirconium and niobium, as will be described later. The zirconium content in the rutile-type titanium oxide derived from the liquid phase method is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, relative to the total titanium oxide composition (100% by mass), and there is no upper limit, but it may be 1% by mass or less. The niobium content in the rutile-type titanium oxide derived from the liquid phase method is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, relative to the total titanium oxide composition (100% by mass), and there is no upper limit, but it may be 1% by mass or less. On the other hand, rutile-type titanium oxide derived from the vapor phase method is characterized by being substantially free of one or more elements selected from the group consisting of zirconium and niobium. The above phrase "substantially free of elements" means that the elements are below the detection limit.For example, when the intensity ratio (Zr / Ti ratio or Nb / Ti ratio) of the fluorescence intensity (cps) described below is 0.02 or less, it is assumed that Zr or Nb is not substantially contained.

[0031] As the BET specific surface area of the rutile-type titanium oxide of the present embodiment, from the viewpoint of obtaining more excellent antiviral properties and visible light responsiveness, 1 m ２ / g to 200 m ２ / g is preferable, 3 m ２ / g to 100 m ２ / g is more preferable, 4 to 70 m ２ / g is more preferable, 6 m ２ / g to 50 m ２ / g is even more preferable, and from the viewpoint of further enhancing the productivity of the antiviral agent, 7.5 m ２ / g to 9.5 m ２ / g is preferably in the range. The method for measuring the BET specific surface area of the rutile-type titanium oxide will be described in the examples described later.

[0032] As the primary particle diameter of the rutile-type titanium oxide of the present embodiment, from the viewpoint of obtaining more excellent antiviral properties and visible light responsiveness, a range of 0.01 μm to 0.5 μm is preferable, a range of 0.03 μm to 0.35 μm is more preferable, and a range of 0.06 μm to 0.35 μm is even more preferable. The method for measuring the primary particle diameter of the rutile-type titanium oxide is a value measured by a method of directly measuring the size of the primary particles from an electron micrograph using a transmission electron microscope (TEM). Specifically, the minor axis diameter and major axis diameter of the primary particles of each rutile-type titanium oxide are measured, and the average of 200 is taken as the particle diameter of the primary particles. Next, for 100 or more titanium oxide particles, the volume (weight) of each particle is approximated by a cube of the obtained particle diameter, and the volume average particle diameter is taken as the average primary particle diameter.

[0033] Further, the rutile-type titanium oxide of the present embodiment may be surface-treated or surface-supported as necessary. Examples of the surface treatment or surface support include alumina (Al ２ O ３ ), silica (SiO ２ ), zirconium oxide (ZrO ２Examples of treatments include forming zinc oxide (ZnO) or the like on the surface of rutile-type titanium oxide. For example, when wettability and durability of titanium oxide are important, silica-alumina treated rutile-type titanium oxide is preferred. In the case of silica-alumina treatment, for example, the mass of silica and alumina present together with the rutile-type titanium oxide can be measured using fluorescent X-rays. Silica and alumina are present on the surface of titanium oxide, and some of them may also exist as free particles, so the total amount can be measured by measuring with fluorescent X-rays. For quantitative analysis using fluorescent X-rays, analytical methods using calibration curves with standard samples have been established.

[0034] Generally, two methods are known for producing the rutile-type titanium oxide composition: the liquid-phase method and the gas-phase method. The liquid-phase method involves hydrolyzing or neutralizing titanyl sulfate, obtained from a solution of raw material ore such as ilmenite, to obtain titanium oxide. The gas-phase method involves a gas-phase reaction between titanium tetrachloride, obtained by chlorinating raw material ore such as rutile, and oxygen. A method for distinguishing between titanium oxide produced by both methods is to compare and analyze the titanium (Ti) content and the content of metallic elements using an X-ray fluorescence analyzer or the like.

[0035] The rutile-type titanium oxide preferably contains metallic elements such as zirconium and niobium. Titanium oxide containing metallic elements such as zirconium and niobium can also be called a titanium oxide composition.

[0036] In this disclosure, ilmenite ore may be used as the raw material ore for rutile-type titanium oxide, or titanium slag obtained by metallurgizing ilmenite ore to increase its titanium purity may be used. The rutile-type titanium oxide produced by the liquid-phase method contains metallic elements such as zirconium and niobium derived from ilmenite ore in its products. The zirconium content ratio (Zr / Ti ratio) to titanium 100 in the titanium oxide produced by the liquid-phase method may be 0.03 or higher, 0.04 or higher, 0.05 or higher, 0.8 or lower, 0.5 or lower, or 0.3 or lower. Any combination of these upper and lower limits is acceptable. The zirconium content ratio (Zr / Ti ratio) to titanium 100 in the titanium oxide may be 0.03 to 0.8, 0.04 to 0.5, or 0.05 to 0.3. The niobium content ratio (Nb / Ti ratio) to titanium 100 in the titanium oxide produced by the liquid-phase method described above may be 0.05 or higher, 0.08 or higher, 0.1 or higher, 0.8 or lower, 0.5 or lower, or 0.3 or lower. Any combination of these upper and lower limits is acceptable. The niobium content ratio (Nb / Ti ratio) to titanium 100 in the titanium oxide may be 0.05 to 0.8, 0.08 to 0.5, or 0.10 to 0.3. If the titanium oxide is within the above range, a mixture with high dispersibility in the solvent and good handling even when the concentration of rutile-type titanium oxide is increased can be obtained. In a titanium oxide composition obtained with titanium oxide within the above range, the content ratio of metal elements (zirconium and / or niobium) to titanium 100 in the titanium oxide composition will be the same as the above range. In contrast, the gas phase method refines titanium tetrachloride, so these metal elements (zirconium and / or niobium) are substantially absent from titanium oxide. Here, "substantially absent from titanium oxide" means that the content ratio of metal elements in titanium oxide is less than 0.02 per 100 units of titanium. Conversely, "substantially present in titanium oxide with metal elements (zirconium and / or niobium)" means that the content ratio of metal elements in titanium oxide is 0.02 or more per 100 units of titanium.Rutile-type titanium oxide obtained from titanium oxide substantially containing metallic elements (zirconium and / or niobium) substantially contains metallic elements (zirconium and / or niobium).

[0037] The titanium oxide substantially containing metal elements (zirconium and / or niobium) in this disclosure has low cohesive force relative to the specific surface area (BET value) caused by primary particles, which can suppress the viscosity of the mixture and is presumed to contribute to improving the concentration of rutile-type titanium oxide.

[0038] The rutile-type titanium oxide of this embodiment may be synthesized by the liquid-phase or gas-phase method described above, or a commercially available product may be used. Examples of such commercially available products include Typake R-820, Typake R-830, Typake R-930, Typake R-550, Typake R-630, Typake R-680, Typake R-670, Typake R-680, Typake R-670, Typake R-780, Typake R-850, Typake CR-50, Typake CR-57, Typake CR-Super70, Typake CR- 80, Typeque CR-90, Typeque CR-93, Typeque CR-95, Typeque CR-97, Typeque CR-60, Typeque CR-63, Typeque CR-67, Typeque CR-58, Typeque CR-85, Typeque UT771, CR-EL, PT-401L, PT-401M, PT-501R (manufactured by Ishihara Sangyo Co., Ltd.), Typeque R-100, Typeque R-101, Typeque R-102, TyPure R-103, TyPure R-104, TyPure R-105, TyPure R-108, TyPure R-900, TyPure R-902, TyPure R-960, TyPure R-706, TyPure R-931 (manufactured by DuPont), R-25, R-21, R-32, R-7E, R-5N, R-61N, R-62N, R-42, R-45M, R-44, R-49S, GTR-10 You can use 0, GTR-300, D-918, TCR-29, TCR-52, FTR-700, STR-100N, STR-100W (manufactured by Sakai Chemical Industry Co., Ltd.), JR, JR-403, JR-605, JR-806, JR-701, JR-805, JR-701, JR-800, JR-405, MT200B, MT500B, MT600B, MT-700B, MT150W (manufactured by Teika Co., Ltd.), etc.

[0039] (Copper Atom-Containing Nanoclusters) The titanium dioxide composition of this embodiment contains two or more copper atom-containing nanoclusters (hereinafter simply referred to as copper atom-containing nanoclusters). The copper atom-containing nanoclusters include a first nanocluster (hereinafter simply referred to as the first nanocluster) containing copper atoms and chlorine atoms. The copper atom-containing nanoclusters and the first nanocluster are attached to the surface of rutile-type titanium dioxide. As a result, the presence of the copper atom-containing nanoclusters and / or the first nanocluster changes the potential barrier formed on the surface of the rutile-type titanium dioxide, making it possible to efficiently transfer interfacial charge between these nanoclusters and the rutile-type titanium dioxide, thereby improving photocatalytic activity. Furthermore, rutile-type titanium dioxide can not only kill bacteria but also decompose their remains, so it can decompose toxins such as endotoxins produced when E. coli is killed, or verotoxins produced when E. coli O-157 is killed. Furthermore, copper atoms present on the surface of multiple or numerous copper atom-containing nanoclusters (one or more selected from the group consisting of the first nanocluster, second nanocluster, and third nanocluster described later) tend to have dangling bonds, thus exhibiting a higher bactericidal effect. As a result, bacteria killed by the copper atom-containing nanoclusters are completely decomposed by rutile-type titanium dioxide present in the vicinity of the copper atom-containing nanoclusters, thus exhibiting extremely high antibacterial and antiviral properties.

[0040] In this embodiment, it has been confirmed that the titanium dioxide composition contains two or more types of copper atom-containing nanoclusters. As will be described in the examples below, the existence of a first nanocluster containing copper and chlorine atoms, and a second nanocluster containing copper atoms but not chlorine atoms (or in which the presence of chlorine atoms cannot be observed) has been confirmed. Furthermore, it is suggested that there may also be nanoclusters (referred to as third nanoclusters) from which chlorine atoms are thought to have been released from the first nanoclusters. However, it is technically difficult to measure not only the amount of chlorine atoms present in the nanoclusters from which chlorine atoms are thought to have been released from the first nanoclusters (= third nanoclusters), but also the amount of chlorine atoms present in the second nanoclusters, making it difficult to distinguish between the third nanoclusters and the second nanoclusters. In the manufacturing method described in the examples section below, for example, after the second nanocluster is formed, the second nanocluster becomes saturated and the first nanocluster is formed. Then, as the number of first nanoclusters increases, it is thought that nanoclusters from which chlorine is released from the first nanoclusters (= third nanoclusters) are formed.

[0041] In this specification, "nanocluster" refers to a granular mass of nano-order size (average particle size of approximately 500 nm or less) formed by an aggregate of atoms, regardless of its internal structure; it may be an aggregate of crystalline structures or an amorphous aggregate. Furthermore, "nanocluster" means an aggregate formed by several to several hundred atoms selected from the group consisting of atoms (e.g., copper atoms, chlorine atoms, oxygen atoms), monovalent copper compounds, and divalent copper compounds. Therefore, the copper atom-containing nanoclusters in this specification include a first nanocluster containing copper atoms and chlorine atoms, a second nanocluster containing copper atoms but not chlorine atoms (or in which the presence of chlorine atoms cannot be observed), and a nanocluster (third nanocluster) from which chlorine atoms are thought to have been released from the first nanocluster.

[0042] In the titanium oxide composition of this embodiment, two or more copper atom-containing nanoclusters are formed (e.g., supported or impregnated) on the surface of rutile-type titanium oxide, and one of them is a first nanocluster containing copper atoms and chlorine atoms. The size (average particle diameter) of the copper atom-containing nanoclusters (including at least two of the first nanoclusters, the second nanoclusters and the third nanoclusters described later) is preferably about 0.2 nm to 500 nm. The size (average particle diameter) of the first nanocluster is preferably about 0.2 nm to 500 nm. In this embodiment, it is preferable that the copper atom-containing nanoclusters include a first nanocluster containing copper atoms and chlorine atoms, and a second nanocluster containing copper atoms but not chlorine atoms. This is thought to enable more efficient interfacial charge transfer between these nanoclusters and rutile-type titanium oxide, thereby improving photocatalytic activity. The size (average particle diameter) of the second nanocluster is preferably about 0.2 to 5 nm.

[0043] In this embodiment, the first nanocluster is a copper atom-containing nanocluster containing copper atoms and chlorine atoms, and preferably has an average particle size of approximately 0.2 to 500 nm. On the other hand, the second nanocluster has a different composition from the first nanocluster, and the presence of chlorine atoms is not confirmed by measurement (below the detection limit, or does not contain chlorine atoms). Therefore, it contains copper atoms (for example, only copper atoms other than unavoidable impurities), and preferably has an average particle size of approximately 0.2 to 5 nm. In the second nanocluster, oxygen atoms and / or hydrogen atoms may coexist as part of the copper oxide or hydroxide in the second nanocluster. The presence of the first nanocluster was confirmed from the HR-TEM images of the titanium oxide compositions of Examples 4 and 6 described later. Specifically, as shown in Figures 1 and 2, which display HR-TEM images of the titanium oxide compositions of Examples 4 and 6 described later, the surface of the titanium oxide composition was observed, and EDS elemental mapping confirmed the presence of copper atoms and chlorine atoms on the surface of the rutile-type titanium oxide. Their diameter was approximately several hundred nm. Furthermore, when titanium oxide compositions were prepared by changing the amount of copper compound from 0.4 mass% to 2 mass%, the presence of copper atoms and chlorine atoms was similarly confirmed. Therefore, considering the detection limits of the measuring instruments, it is considered highly probable that the first nanocluster will be formed if the amount of copper atoms supported on the rutile-type titanium oxide in the titanium oxide composition (the total amount of copper atoms in the entire composition) is 0.4 mass% or more. Similarly, the presence of the second nanocluster was confirmed from the STEM image of the titanium oxide composition of Example 4 described later. Specifically, as shown in Figure 3, which displays the LAADF-STEM image of the titanium dioxide composition of Example 4 described later, and Figure 4, which displays the HAADF-STEM image of the titanium dioxide composition of Example 4 described later, atomic decomposition observation of the surface of the titanium dioxide composition revealed the presence of copper particles composed of copper atoms on the surface of the rutile-type titanium dioxide. These were clusters with a diameter of approximately several nanometers and consisting of 150 to 250 atoms.In the titanium oxide composition of this embodiment, the ratio of Cu to Cl (Cl / Cu) in the first nanocluster is preferably in the range of 0.15 to 0.65, more preferably in the range of 0.3 to 0.6, and even more preferably in the range of 0.4 to 0.55. On the other hand, in the titanium oxide composition of this embodiment, the ratio of Cu to Cl (Cl / Cu) in the second nanocluster is preferably below the detection limit, for example, 0.001 or less. This makes it possible to perform interfacial charge transfer between these nanoclusters and rutile-type titanium oxide more efficiently, and is thought to improve photocatalytic activity in the dark. In this specification, the average particle size of each nanocluster and the presence of chlorine atoms are calculated by the method described in the examples below. Furthermore, the ratio of Cu to Cl in the nanocluster is calculated by extracting an EDS spectrum from the measurement area of ​​one particle by EDS mapping analysis, as described in the examples section below, and calculating the ratio of Cu to Cl from the Ratio method.

[0044] (Preferred form of the first nanocluster) The first nanocluster of this embodiment preferably has an atacamite-based structure. This is thought to result in superior antibacterial and antiviral properties because chloride ions in the atacamite-based structure can be released and react with new copper components or other atoms.

[0045] Examples of the atacamite-type structures in this embodiment include the so-called atacamaite group. In particular, the atacamite-type structure is defined by the following general formula (1): [Chemical Formula 1] Cu ｍ M ｎ Cl ｐ (OH) ｑ[In the above general formula (1), M represents a divalent cation, and is preferably a divalent cation of one or more metals selected from the group consisting of magnesium, nickel, cobalt, zinc, and manganese, m is greater than 0 and less than 3, n is 0 or greater and 2 or less, p is 1 or greater and 2 or less, q is 2.5 or greater and 6 or less, and 2m + 2n = p + q.] It is preferably represented by the composition of the above general formula (1) and has an orthorhombic (ortho.), monoclinic (mon.), triclinic (tric.), or trigonal (trig.) crystal structure. More specifically, the atacamite structure represented by general formula (1) is Cu ２－ｘ M ｘ Cl(OH) ３ The composition is represented by [0 ≤ x < 2, M represents a divalent cation], or Cu ３－ｙ M ｙ Cl ２ (OH) ６ It is preferable that the composition be expressed as [0 ≤ y ≤ 1, where M represents a divalent cation]. Examples of the former composition include para-atacamalite type, botalakite type, or monoclinic atacamalite type. On the other hand, examples of the latter composition include para-atacamalite type, Harvardsmithite type, or capellasite type.

[0046] Preferred atacamite-based structures in this embodiment include atacamite (Cu2Cl(OH)3, space group; Orth.mmm(2 / m2 / m2 / m):Pnma), botalachite (Cu2Cl(OH)3, space group; Mon.2 / m:P21 / m), clinoatacamite (Cu2Cl(OH)3, space group; Mon.2 / m), gillardite (Cu3NiCl2(OH)6, space group; Trig.3(-)m(3(-)2 / m):R3(-)m), haydeeite (Cu3MgCl2(OH)6, space group; Trig. Trig. 3(-)m(3(-)2 / m):P3(-)m1), and herbertsmithite (Cu3ZnCl2(OH)6, space group; Trig. 3(-) m(3(-) 2 / m):R3(-)m), Iyoite (MnCuCl(OH)3, space group; Mon.2 / m:P21 / m), Kapelasite (Cu3ZnCl2(OH)6, space group; Trig. Trig. 3(-) m(3(-) 2 / m):P3(-)m1), Leverettite (Cu3CoCl2(OH)6, space group; Trig. 3(-):R3(-)), Misakiite (Cu3MnCl2(OH)6, space group; Trig. 3(-)m(3(-) 2 / m):P3(-)m1), Paratacamite (Cu3(Cu,Zn)Cl2(OH)6, space group; Trig. Examples include 3(-):R3(-)), paraatacamite-(Mg) (Cu3(Mg,Cu)Cl2(OH)6, space group; Trig. 3(-):R3(-)), paraatacamite-(Ni) (Cu3(Ni,Cu)Cl2(OH)6, space group; Trig.3(-):R3(-)), tondite (Cu3MgCl2(OH)6, space group; Trig.3(-)m(3(-) 2 / m):R3(-)m), and Cu-Zn chloride hydroxide (CuZnCl(OH)3, space group; Mon. 2 / m : P21 / m).In particular, the atacamite-based structure of this embodiment is more preferably one or more selected from the group consisting of atacamite (Cu2Cl(OH)3, space group; Orth.mmm(2 / m2 / m2 / m):Pnma), botalacite (Cu2Cl(OH)3, space group; Mon.2 / m:P21 / m), and clinoatacamite (Cu2Cl(OH)3, space group; Mon.2 / m). In the space group, when the figure overlaps the original figure by inversion following a rotation of 2π / n, this axis is called the n-fold inversion axis and is represented by the symbol "n(-)". Originally, the n-fold inversion axis is written with a minus sign directly above the n, but due to the limitations of permissible characters in patent applications, it is written as "n(-)". Therefore, the above "3(-)" means the 3-fold inversion axis.

[0047] The first nanocluster of this embodiment may contain copper atoms and chlorine atoms, and preferably oxygen atoms and / or hydrogen atoms. By including the atacamite-based structure in the first nanocluster, a titanium oxide composition with superior dark-activated activity, antibacterial properties, and antiviral properties can be obtained. Furthermore, from the viewpoint of stability, clinoatacamite, atacamite, and botalakite are preferred as the atacamite-based structure. When the titanium oxide composition contains a stable atacamite-based structure, chloride ions in the atacamite-based structure can be released and react with new copper components and other atoms, which is thought to result in superior antibacterial and antiviral properties.

[0048] Furthermore, the first nanocluster of this embodiment coexists in close proximity with copper atom-containing nanoclusters that substantially do not contain chlorine atoms, such as the second or third nanocluster. Therefore, the reaction in which chloride ions in the atacamite-based structure are released and react with copper atoms in the second or third nanocluster to produce new copper chloride can be repeated. For this reason, it is considered that the copper atom-containing nanoclusters of this embodiment, in combination with the first and second nanoclusters (or in combination with the first nanocluster, the second nanocluster, and / or the third nanocluster), can maintain high activity over time.

[0049] In this embodiment, controlling the pH during the manufacturing process is considered to be one of the important factors for forming the first nanocluster having an atacamite-like structure. More specifically, if the pH is raised too high during the alkali compound addition step in the manufacturing process (for example, pH 12 or higher) when preparing the slurry, chlorine atoms tend to be removed, making it impossible to form the atacamite-like structure. Other requirements for forming the first nanocluster having an atacamite-like structure include the concentration of copper ions and chloride ions, the calcination temperature, and the calcination time. That is, if the concentrations of copper ions and chloride ions are insufficient, only the second nanocluster will be formed on the titanium oxide surface during the alkali compound addition step, and the atacamite-like structure will not be formed. If the concentrations of copper ions and chloride ions are sufficiently high, it is thought that copper ions attracted to the second nanocluster on the titanium oxide surface react with chloride ions to form a chlorine-containing copper compound, i.e., the first nanocluster. Furthermore, it is thought that a stable atacamite structure can be formed by setting the calcination temperature to 150-600°C and the calcination time to 1 hour or more. Even if the concentrations of copper ions and chloride ions are sufficiently high, if the pH is raised too much in the alkali compound addition step, it is thought that chlorine will be detached from the generated first nanoclusters, changing to botalac, then copper hydroxide, and then copper oxide, thereby transforming into third nanoclusters. The atacamite-based structure in this embodiment may be a product or a precursor to the calcined body. That is, if the titanium oxide composition in this embodiment is a non-calcined body, the titanium oxide composition may be a composition containing the atacamite-based structure before calcination (i.e., before the heat treatment step described later). On the other hand, if the titanium oxide composition in this embodiment is a calcined body, the composition containing the atacamite-based structure may be a precursor to the calcined body.

[0050] (Preferred Embodiment of Titanium Dioxide Composition) In the titanium dioxide composition of this embodiment, as described above, when the first nanoclusters and optionally contained second nanoclusters and / or third nanoclusters are formed on the surface of rutile-type titanium dioxide (particularly when the first nanoclusters and the second nanoclusters and / or third nanoclusters are formed on the surface of rutile-type titanium dioxide), it has been confirmed that the reaction endpoint pH is important in the manufacturing process of the titanium dioxide composition. <Reaction Endpoint pH> In the titanium dioxide composition of this embodiment, by carrying out the reaction step of an alkali compound in the presence of titanium dioxide, copper ions and chloride ions, the first nanoclusters and optionally contained second nanoclusters and / or third nanoclusters are formed on the surface of the titanium dioxide. With chloride ions and copper ions readily adsorbed on the titanium dioxide, by reacting the alkali compound stepwise from an acidic region to a weakly acidic region, and then from a weakly acidic region to a neutral to alkaline region, the second nanoclusters and / or third nanoclusters that do not contain chlorine atoms (or whose presence of chlorine atoms cannot be confirmed) and the first nanoclusters that contain chlorine atoms tend to be formed on the surface of the titanium dioxide. The reaction endpoint upon addition of the alkali compound is preferably neutral to alkaline, more preferably pH 6 to 11, even more preferably pH 7 to 10, and even more preferably pH 7.5 to 9.5. If the reaction endpoint pH exceeds 11, the chlorine atoms contained in the formed first nanoclusters gradually dissolve, and the total chlorine atom content in the titanium dioxide composition decreases. Furthermore, if the reaction endpoint pH exceeds 11, too many chlorine atoms are removed, making it difficult to maintain the first nanoclusters having an atacamite-like structure. Moreover, if the chlorine atoms contained in the first nanoclusters gradually dissolve and the total chlorine atom content in the titanium dioxide composition decreases, it is considered that a second nanocluster containing copper atoms and not containing chlorine atoms (or in which the presence of chlorine atoms cannot be observed) and / or a third nanocluster from which chlorine atoms have been released from the first nanocluster are formed.

[0051] Based on the above, it is preferable that the copper atom-containing nanoclusters of this embodiment are composed of a first nanocluster containing copper atoms and chlorine atoms, and a second nanocluster and / or a third nanocluster that substantially does not contain chlorine atoms and contains copper atoms. Accordingly, the preferred titanium oxide composition of this embodiment includes rutile-type titanium oxide and a first nanocluster containing copper atoms and chlorine atoms, and a second nanocluster substantially does not contain chlorine atoms and contains copper atoms, provided on the surface of the rutile-type titanium oxide. Furthermore, although it is difficult to distinguish from the second nanocluster from the viewpoint of measurement technology, the surface of the rutile-type titanium oxide may include a third nanocluster containing copper atoms, from which chlorine atoms have been released in the first nanocluster. This is thought to enable more efficient interfacial charge transfer between these nanoclusters and rutile-type titanium oxide, thereby improving photocatalytic activity. Furthermore, if the copper atom-containing nanoclusters or the first nanoclusters contain a stable atacamite-based structure, chloride ions in the atacamite-based structure can be released and react with new copper components or other atoms, thus resulting in superior antibacterial and antiviral properties. In particular, the titanium dioxide composition of this embodiment has at least two types of copper atom-containing nanoclusters: a first nanocluster containing copper atoms and chlorine atoms, and a second nanocluster that is virtually chlorine-free and contains copper atoms. Therefore, if the first nanocluster contains an atacamite-based structure, chloride ions in the atacamite-based structure can be released and react with copper atoms in the nearby second nanocluster to form new copper chlorides, thus maintaining chloride ions with high reactivity over time. As a result, it is thought to have the effect of maintaining high photocatalytic activity over time. Note that "virtually chlorine-free" means that the presence of chlorine atoms cannot be confirmed by measurement.

[0052] In this embodiment, the lower limit of the total copper atom content (i.e., copper load) included in the copper atom-containing nanoclusters is preferably 0.4 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 0.8 parts by mass or more, and even more preferably 1 part by mass or more, based on 100 parts by mass of the entire titanium oxide composition. The upper limit of the total copper atom content (i.e., copper load) included in the copper atom-containing nanoclusters is preferably 10 parts by mass or less, more preferably 6 parts by mass or less, even more preferably 4 parts by mass or less, even more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less, based on 100 parts by mass of the entire titanium oxide composition. The upper and lower limits of the copper atom content can be combined arbitrarily. In this embodiment, the method for measuring the total copper content contained in the copper atom-containing nanoclusters is as follows, as described in the Examples section below: the titanium oxide composition is completely dissolved in a hydrofluoric acid solution, and the copper content (parts by mass) per 100 parts by mass of the copper compound-supported titanium oxide composition is quantified by analyzing it with an ICP emission spectrometer.

[0053] In this embodiment, the lower limit of the total chlorine atom content (i.e., chlorine content) in the copper atom-containing nanoclusters, more specifically in the first nanocluster, is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, and even more preferably 0.2 parts by mass or more, based on 100 parts by mass of the entire titanium oxide composition. The upper limit of the chlorine atom content in the copper atom-containing nanoclusters, more specifically in the first nanocluster, is preferably 2 parts by mass or less, more preferably 1 part by mass or less, even more preferably 0.6 parts by mass or less, even more preferably 0.5 parts by mass or less, and even more preferably 0.4 parts by mass or less, based on 100 parts by mass of the entire titanium oxide composition. The upper and lower limits of the chlorine atom content can be arbitrarily combined. In this embodiment, the method for measuring the total chlorine content in copper atom-containing nanoclusters, more specifically, in the first nanocluster, is as described in the Examples section below. A combustion-chromatographic analyzer was used to quantify the chlorine content (parts by mass) per 100 parts by mass of the titanium oxide composition under combustion conditions of 1100°C.

[0054] (Method for producing titanium dioxide composition) The method for producing the titanium dioxide composition of this embodiment is not particularly limited as long as it is a method for producing a titanium dioxide composition comprising rutile-type titanium dioxide, which is the object of this disclosure, and two or more copper atom-containing nanoclusters containing copper atoms provided on the surface of the rutile-type titanium dioxide, wherein the two or more copper atom-containing nanoclusters include a first nanocluster containing copper atoms and chlorine atoms. For example, a titanium dioxide composition can be produced by the following method. The method for producing the titanium dioxide composition of this embodiment preferably comprises a mixing step of preparing a mixed solution by mixing 30 to 1000 parts by mass of raw material titanium dioxide (a) (for example, titanium dioxide (a1) to (a3)) and 40 to 1600 parts by mass of an aqueous solvent in the presence of copper ions and chloride ions, and a dehydration step of separating the solid content from the mixed solution and drying the solid content under conditions of 30 to 200°C for 0.5 to 72 hours to perform a dehydration treatment. Furthermore, a preferred embodiment of the method for producing the titanium oxide composition of this embodiment is to include, if necessary, a heat treatment step after the dehydration step, in which the solid content after the dehydration treatment is heat-treated at 300°C to 580°C for 0.5 hours to 12 hours in the presence of oxygen. Also, if necessary, the above-mentioned atacamite-based structure (preferably powder of the atacamite-based structure) may be mixed into the mixed solution or the solid content in the mixing step and / or dehydration step.

[0055] In the mixing step, the concentration of titanium oxide (a) in the mixture is preferably about 1% to 55% by mass, and more preferably about 3% to 50% by mass.

[0056] In the mixing step, the presence of copper ions and chloride ions means that the copper ion concentration in the mixture is preferably in the range of 0.002 mol / L to 0.8 mol / L, more preferably 0.01 mol / L to 0.22 mol / L, and even more preferably 0.02 mol / L to 0.12 mol / L, and the chloride ion concentration in the mixture is preferably in the range of 0.004 mol / L to 1.6 mol / L, even more preferably 0.03 mol / L to 0.45 mol / L, and even more preferably 0.04 mol / L to 0.24 mol / L. Furthermore, the method and means of adding copper ions and chloride ions are not limited. Therefore, the copper atoms and chlorine atoms may be contained in the same compound, or in different compounds. For this reason, the copper ions may be ions derived from a copper compound containing copper atoms, or they may be compounds containing copper atoms and chlorine atoms (= copper atom and chlorine atom containing compounds). Similarly, the chloride ions may be ions derived from a chlorine compound containing chlorine atoms, or they may be derived from a copper atom and a chlorine atom-containing compound. For example, when using a copper atom and a chlorine atom-containing compound to prepare a mixture in the presence of copper ions and chloride ions, the amount of the copper atom and chlorine atom-containing compound is preferably 1 to 27 parts by mass, more preferably 1.3 to 16 parts by mass, per 100 parts by mass of titanium dioxide (a). Alternatively, the copper atom and chlorine atom-containing compound may be added to an aqueous solvent beforehand, and the resulting aqueous solution containing the copper atom and chlorine atom-containing compound may be mixed with the titanium dioxide (a) and the aqueous solvent. Furthermore, for example, when using a copper compound and a chlorine compound respectively in the presence of copper ions and chloride ions, the amount of the copper compound is preferably 1.5 to 40 parts by mass, more preferably 1.9 to 24 parts by mass, per 100 parts by mass of titanium dioxide (a). On the other hand, the amount of chlorine compound added is preferably 1.3 to 25 parts by mass, more preferably 1.6 to 42 parts by mass, per 100 parts by mass of titanium dioxide (a). Alternatively, the copper compound and / or the chlorine compound may be added to an aqueous solvent beforehand, and the resulting aqueous solution containing the copper compound and / or the chlorine compound may be mixed with the titanium dioxide (a) and the aqueous solvent.

[0057] In the above mixing step, it is preferable to further carry out an alkali compound addition step in which an alkali compound is added to the mixed solution. This makes it easier to adjust the reaction endpoint by adding the alkali compound to neutral to alkaline (for example, pH 6 to 11), thereby making it easier to form first nanoclusters containing copper atoms and chlorine atoms, preferably second nanoclusters and / or third nanoclusters containing the first nanoclusters and copper atoms but not chlorine atoms, on the surface of rutile-type titanium dioxide. Furthermore, it is preferable to add the alkali compound to the mixed solution in one or two or more steps in the alkali compound addition step. This makes it possible to change the pH stepwise from the acidic region to weakly acidic, and then from weakly acidic to neutral to alkaline, so that chloride ions and copper ions are more easily adsorbed on the titanium dioxide. A preferred mixing step in this embodiment may be a step of mixing 30 to 1000 parts by mass of titanium dioxide (a) and 40 to 1600 parts by mass of an aqueous solvent in the presence of copper ions and chloride ions, and further adding an alkali compound to prepare a mixed solution with a pH of 6 to 11. Furthermore, it is even more preferable that the step of further adding the alkali compound comprises a first alkali compound addition step of adding the alkali compound to control the pH of the mixed solution within the range of 4 to 7, and a second alkali compound addition step of further adding the alkali compound to the mixed solution with a pH of 4 to 7 to control the pH within the range of 7 to 10. This allows the pH to be changed stepwise from the acidic region to weakly acidic, and then from weakly acidic to neutral to alkaline, making it easier for chloride ions and copper ions to be adsorbed onto the titanium dioxide, and thus making it easier to form first nanoclusters containing copper atoms and chlorine atoms on the surface of the rutile-type titanium dioxide. In addition, when the step of further adding the alkali compound comprises a first alkali compound addition step of adding the alkali compound to control the pH of the mixed solution within the range of 4 to 7, and a second alkali compound addition step of further adding the alkali compound to the mixed solution with a pH of 4 to 7 to control the pH within the range of 7 to 10, the resulting precursor tends to contain a large amount of atacamite-type structures.

[0058] Examples of the copper and chlorine atom-containing compounds mentioned above include copper(I) chloride (cuprous chloride) and copper(II) chloride (cupric chloride), as well as their hydrates. Alternatively, a mixture of the copper and chlorine compounds described later may also be used.

[0059] In the above mixing step, divalent copper compounds are preferred as copper compounds, and for example, divalent copper inorganic compounds, divalent copper organic compounds, etc., can be used. Examples of the divalent copper inorganic compounds include divalent copper inorganic salts such as copper sulfate, copper nitrate, copper iodate, copper perchlorate, copper oxalate, copper tetraborate, copper ammonium sulfate, copper amidosulfate, copper ammonium chloride, copper pyrophosphate, and copper carbonate; divalent copper halides such as copper chloride, copper fluoride, and copper bromide; and copper oxide, copper sulfide, azurite, malachite, and copper azide. These compounds may be used individually or in combination of two or more. Examples of the aforementioned divalent copper organic compounds include copper formate, copper acetate, copper propionate, copper butyrate, copper valerate, copper caproate, copper enantate, copper caprylate, copper pelargonate, copper caprate, copper myristicate, 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 melitate, copper oxalate, copper malonate, copper succinate, copper glutarate, copper adipate, copper fumarate, and glycol. Copper oxide, copper glycerate, copper gluconate, copper tartrate, copper acetylacetone, copper ethylacetoacetate, copper isovalerate, copper β-resorsylate, copper diacetoacetate, copper formylsuccinate, copper salicylate, copper bis(2-ethylhexanoate), copper sebacate, copper naphthenate, copper oxyne, copper acetylacetone, copper ethylacetoacetate, copper trifluoromethanesulfonate, copper phthalocyanine, copper ethoxide, copper isopropoxide, copper methoxide, copper dimethyldithiocarbamate, etc. can be used. These compounds may be used individually or in combination of two or more.

[0060] Examples of the chlorine compound include chlorides of Group 1 elements of the periodic table, such as one or more chlorides selected from the group consisting of sodium chloride, potassium chloride, rubidium chloride, and cesium chloride.

[0061] The above-mentioned aqueous solvent may contain 90% by mass or more of water relative to the total aqueous solvent, and may be water alone or a known buffer solution, or may contain other solvents as needed. Examples of the other solvents include alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; and dimethylformamide and tetrahydrofuran. These solvents may be used alone or in combination of two or more.

[0062] Examples of the alkali compound include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, trimethylamine, ammonia, and basic surfactants, with sodium hydroxide being preferred. The alkali compound is preferably added as a solution for easier control of the reaction, and the concentration of the added alkali solution is preferably in the range of 0.1 to 5 mol / L, more preferably in the range of 0.3 to 4 mol / L, and even more preferably in the range of 0.5 to 3 mol / L.

[0063] The total stirring time in the mixing step can be, for example, 5 to 120 minutes, preferably 10 to 60 minutes. The temperature during the mixing step can be, for example, in the range of room temperature to 70°C.

[0064] After the mixing step is completed, the mixture can be separated into solid components. In the dewatering step, methods for separating the solid components include, for example, filtration, sedimentation, centrifugal separation, and evaporation drying, but filtration is preferred. The separated solid components may then be washed, crushed, classified, etc., as necessary.

[0065] After obtaining the solid content, it is preferable to heat-treat the solid content in order to more firmly bond the nanoclusters supported on the titanium oxide (a). The heat treatment temperature is preferably in the range of 150 to 600°C, and more preferably in the range of 250 to 450°C. The heat treatment time is preferably 1 to 10 hours, and more preferably 2 to 5 hours. By heat-treating the solid content separated from the mixed liquid obtained in the above mixing step at the heat treatment temperature (for example, in the range of 150 to 600°C), a calcined titanium oxide composition is obtained. By the above manufacturing method, a titanium oxide composition containing titanium oxide with nanoclusters supported on titanium oxide (a) is obtained.

[0066] The titanium dioxide composition of this embodiment may be in any form that includes rutile-type titanium dioxide and two or more copper-containing nanoclusters (a first nanocluster containing copper atoms and chlorine atoms, and other copper-containing nanoclusters (e.g., a second nanocluster and / or a third nanocluster)), and may be a mixture of rutile-type titanium dioxide and two or more copper-containing nanoclusters, or a calcined body.

[0067] The titanium dioxide composition of this embodiment is preferably a composition containing rutile-type titanium dioxide as a reaction material, and more preferably a composition containing rutile-type titanium dioxide, a copper compound and a chlorine compound or a compound containing copper atoms and chlorine atoms, and an aqueous solvent (or water) as reaction materials. Furthermore, the reaction materials may also contain an atacamite-type structure. If the titanium dioxide composition of this embodiment is a calcined body, it may also be a composition containing an atacamite-type structure as a reaction material. This makes it easier to retain the atacamite-type structure in two or more copper-containing nanoclusters contained in the target titanium dioxide composition. An example of a method for producing a composition using rutile-type titanium dioxide as a reaction material, and a composition using an atacamite-type structure as a reaction material, will be described below. As a method for producing the composition using rutile-type titanium dioxide as a reaction material, a titanium dioxide composition can be produced using rutile-type titanium dioxide, a copper compound and a chlorine compound or a compound containing copper atoms and chlorine atoms, and an aqueous solvent (or water) as reaction materials by following the conditions (amount of ingredients, temperature, etc.) described in the section (Method for producing a titanium dioxide composition) above. Furthermore, in this embodiment, a method for producing an atacamite-based structure is to perform an alkali compound addition step in which an alkali compound is added in the presence of copper ions and chloride ions, using a copper compound and a chlorine compound, respectively. Atacamite-based structures such as atacamaite obtained as a natural mineral can also be used. When the target product is a titanium oxide composition which is a calcined body, it is preferable to heat-treat the atacamite-based structure obtained above as a so-called intermediate. The heat treatment temperature for heat-treating the solid content of the atacamite-based structure 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 1 to 10 hours, more preferably 2 to 5 hours.

[0068] In this specification, "reaction raw materials" refer to compounds used to obtain a target compound through chemical reactions such as bonding, decomposition, or calcination, and which partially constitute the chemical structure of the target compound. Substances that act as aids to chemical reactions, such as solvents and catalysts, are excluded. Specifically in this specification, "reaction raw materials" refer to precursors for obtaining the target titanium dioxide composition through chemical reactions, and intermediates of the titanium dioxide composition are also included as reaction raw materials. Therefore, rutile-type titanium dioxide and atacamite-based structures can serve as reaction raw materials for titanium dioxide compositions.

[0069] [Coating Composition] The coating composition of this embodiment contains the above-mentioned titanium dioxide composition and a binder resin. In addition to the titanium dioxide composition and the binder resin, the coating composition of this embodiment may further contain any optional additive components as needed. Examples of such optional additive components include one or more selected from the group consisting of solvents, dispersants, and additives. Because the coating composition of this embodiment contains a titanium dioxide composition, it may be a coating composition that exhibits antibacterial and antiviral properties.

[0070] The lower limit of the titanium dioxide composition content, which is an essential component of the coating composition of this embodiment, is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 1% by mass or more, and even more preferably 5% by mass or more, based on the total amount (100% by mass) of the coating composition. The upper limit of the titanium dioxide composition content may be preferably 60% by mass or less, more preferably 30% by mass or less, and even more preferably 10% by mass or less, based on the total amount of the coating composition. The upper and lower limits of the titanium dioxide composition content can be combined as appropriate. After explaining the terms used in this specification, the binder resin and any additional components (solvents, dispersants, etc.) that may be included in the coating composition of this embodiment will be described below. When the coating composition of this embodiment is used as a so-called coating composition for forming a coating layer on the surface of a fibrous body, fabric, or substrate, the coating composition will also be referred to as an antibacterial and antiviral coating composition. Furthermore, since the solvents volatilize in the coating layer made from the antibacterial and antiviral coating composition, the coating layer contains the titanium dioxide composition and the binder resin.

[0071] (Binder Resin) The coating composition of this embodiment contains a binder resin. By incorporating a binder resin, the titanium dioxide composition can be fixed onto the substrate. The binder resin of this embodiment is not particularly limited and can be any type, such as emulsion resins, latex resins, thermosetting resins, or active energy ray curing resins. Specific examples of binder resins include organic binder resins such as acrylic resins, vinyl acetate resins, styrene resins, vinyl chloride resins, olefin resins, urethane resins, urea resins, urethane urea resins, acrylic urethane resins, epoxy resins, melamine resins, phenolic resins, polyester resins, alkyd resins, polyphenylene sulfide resins, acrylonitrile / styrene copolymer resins, acrylonitrile / butadiene copolymer resins, and acrylonitrile / butadiene / styrene copolymer (ABS) resins, as well as inorganic binders that use metal alkoxides such as silicone resins or polysiloxane compounds as reaction raw materials. The term "binder resin" also includes modified versions of the above resins; for example, phenolic resin includes rosin-modified phenolic resin. The binder resin used in this embodiment may be a single type or two or more types.

[0072] The inorganic binder is a metal alkoxide represented by the following general formula (1): M-(OR １ ) ｎ (In the above general formula (1), M represents an n-valent metal atom, preferably Si, Ti, Al, or Zr, and R １ It is preferable to use a metal alkoxide (Si(OC)) as a reaction raw material. A specific example of the metal alkoxide is tetraethyl orthosilicate (Si(OC) ２ H ５ ) ４ ), triisopropylaluminum (Al(OC) ３ H ７ ) ３Examples include the following. If necessary, the inorganic binder may be blended with a known silane coupling agent or a catalyst for controlling the reaction of the inorganic binder. The silane coupling agent is preferably one of the following functional groups: vinyl, epoxy, styryl, methacrylic, acrylic, amino, ureido, mercapto, sulfide, or isocyanate.

[0073] The lower limit of the binder resin content, which is an essential component of the coating composition of this embodiment, is preferably 7% by mass or more, more preferably 26% by mass or more, and even more preferably 49 parts by mass or more, based on the total amount (100% by mass) of the titanium dioxide composition in the coating composition. The upper limit of the binder resin content when it is included is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, and even more preferably 99% by mass or less, based on the total amount (100% by mass) of the coating composition. The upper and lower limits of the binder resin content can be combined as appropriate.

[0074] In this embodiment, when curing the coating composition, the binder resin may be cured by irradiation with active energy rays such as UV light. Therefore, the coating composition may contain a photopolymerization initiator. Examples of the photopolymerization initiator include one or more selected from the group consisting of alkylphenone initiators, benzophenone initiators, acylphosphine oxide initiators, intramolecular hydrogen abstraction initiators, and oxime ester initiators. The polymerization initiator may be used to reduce the copper compound.

[0075] Examples of the alkylphenone-based polymerization initiators mentioned above include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morphonyl)phenyl]-1-butanone.

[0076] Examples of the above-mentioned acylphosphine oxide polymerization initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0077] Examples of the intramolecular hydrogen abstraction type polymerization initiators mentioned above include phenylglyoxylic acid methyl ester, oxyphenylsaxane, 2-[2-oxo-2-phenylacetoxyethoxy]ethyl ester, a mixture of oxyphenylacetic acid and 2-(2-hydroxyethoxy)ethyl ester, and the like.

[0078] Examples of the above-mentioned oxime ester polymerization initiators include 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)], etanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime), and the like.

[0079] (Optional Additives) The coating composition of this embodiment essentially contains the above titanium dioxide composition and the above binder resin, and may further contain optional additives as needed. Examples of optional additives include solvents, dispersants, surfactants, thickeners, dispersion aids, pH adjusters, preservatives, fungicides, corrosion inhibitors, viscosity modifiers, chelating agents, defoaming agents, or antioxidants. In the coating composition of this embodiment, the lower limit of the content of the optional additives is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more, based on the total amount (100% by mass) of the coating composition. The upper limit of the content of additives other than the binder resin is preferably 30% by mass or less, more preferably 15% by mass or less, and even more preferably 5% by mass or less, based on the entire coating composition. The upper and lower limits of the content of the additives can be combined as appropriate.

[0080] <Solvent> The solvent in this embodiment is preferably one selected from the group consisting of aqueous solvents (A) and organic solvents (B). <<Aqueous Solvent (A)>> In this specification, aqueous solvent (A) means water or a solvent mainly composed of water. Therefore, aqueous solvent (A) may contain water and components other than water (organic solvents, buffer solutions, salts, etc.). Furthermore, "solvent mainly composed of water" means a solvent in which the water content in aqueous solvent (A) is 50% by mass or more of the total amount of aqueous solvent (A). Examples of water that can be used as aqueous solvent (A) in this embodiment include pure water, ultrapure water, RO water (water passed through a reverse osmosis membrane), deionized water (water from which ions have been removed using an ion exchange resin, etc.), distilled water (water distilled in a distillation apparatus), etc. Furthermore, in the aqueous solvent (A) of this embodiment, components other than water include, as non-limiting examples, ketones such as acetone, lower alcohols such as methanol, ethanol, n-propyl alcohol, and isopropyl alcohol, mixtures of water-compatible organic solvents such as acetonitrile and tetrahydrofuran with water, buffer solutions such as potassium bis(oxalic acid) aqueous solution, potassium hydrogen phthalate aqueous solution, potassium dihydrogen phosphate / disodium hydrogen phosphate aqueous solution, sodium tetraborate aqueous solution, sodium bicarbonate / sodium carbonate aqueous solution, sodium chloride, potassium chloride, ammonium chloride, sodium bromide, bromide Examples include aqueous solutions of inorganic and organic salts such as potassium and ammonium bromide; aqueous solutions of sugars containing monosaccharides, oligosaccharides, and polysaccharides, such as allose, altrose, glucose, mannose, gulose, idos, galactose, talose, ribose, arabinose, xylose, lyxose, erythrose, threose, psicose, fructose, sorbose, tagatose, fucose, deoxy sugars, amino sugars, uronic acid, sulfur sugars, algitol, cyclitol, urose, branched sugars, glucose, starch, heparin, and heparan sulfate; aqueous solutions of proteins; aqueous solutions of DNA and RNA; liquid culture media; and mixtures thereof. It may also include substances that do not dissolve in the aqueous solvent (A) but are dispersed. Examples, not limited to, include minerals such as clay, metal nanoparticles such as gold nanoparticles, polymer nanoparticles such as polystyrene beads and latex particles, animal cells, plant cells, microorganisms, viruses, etc., or mixtures thereof.

[0081] When the coating composition of this embodiment contains an aqueous solvent (A), the upper limit of the content of the aqueous solvent (A) is preferably 95% by mass or less, more preferably 93% by mass or less, even more preferably 90% by mass or less, 88% by mass or less, and 87% by mass or less, relative to the entire coating composition (100% by mass). The lower limit of the content of the aqueous solvent (A) is preferably 20% by mass or more, 22% by mass or more, 24% by mass or more, 25% by mass or more, and 26% by mass or more, relative to the entire coating composition (100% by mass). The upper and lower limits of the content of the aqueous solvent (A) can be combined arbitrarily.

[0082] <<Organic solvent (B)>> In the coating composition of this embodiment, the upper limit of the content of organic solvent (B) is preferably 60% by mass or less, 55% by mass or less, 45% by mass or less, and 40% by mass or less, in that order, relative to the entire coating composition (100% by mass). The lower limit of the content of organic solvent (B) is preferably 0.5% by mass or more, 1% by mass or more, 2% by mass or more, and 3% by mass or more, in that order, relative to the entire coating composition (100% by mass). The upper and lower limits of the content of organic solvent (B) can be combined arbitrarily. A range of 3 to 40% by mass for the content of organic solvent (B) is preferable from the viewpoint of facilitating the preparation and handling of metal compounds.

[0083] The organic solvent (B) in this embodiment is preferably one or more selected from the group consisting of hydrocarbon solvents such as ketones, esters, alcohols, fatty acids, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, petroleum hydrocarbons and waxes; silicone solvents; chlorine solvents; and fluorine solvents. Examples of ketones include ketones having 4 to 20 carbon atoms, with ketones having 9 to 20 carbon atoms being preferred. Specifically, examples include diisobutyl ketone, acetophenone, propiophenone, benzophenone, methyl ethyl ketone, methyl isopropyl ketone, and methyl isobutyl ketone. Examples of esters include esters having 4 to 20 carbon atoms, with esters having 6 to 20 carbon atoms being preferred. Specifically, examples include ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, allyl acetate, isoamyl propionate, benzyl propionate, ethyl phenylacetate, dimethyl malonate, and diethyl malonate. Examples of the above alcohols include linear or branched saturated alcohols having 5 to 22 carbon atoms, and linear or branched unsaturated alcohols having 12 to 22 carbon atoms, with linear or branched saturated alcohols having 8 to 22 carbon atoms and linear or branched unsaturated alcohols having 16 to 22 carbon atoms being preferred. Specifically, examples include oleyl alcohol, lauryl alcohol, myristyl alcohol, stearyl alcohol, linolyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, etc. The alkyl group having 1 to 21 carbon atoms may be a linear alkyl group, a branched alkyl group, or may contain an alicyclic structure.The above fatty acids include linear or branched saturated fatty acids having 5 to 22 carbon atoms, and linear or branched unsaturated fatty acids having 12 to 22 carbon atoms. Examples of such fatty acids include pentanoic acid, hexanoic acid, 2-ethylbutyric acid, heptanoic acid, octanoic acid, acrylic acid, methacrylic acid, 2-ethylhexanoic acid (octylic acid), neodecanoic acid, naphthenic acid residues, isononanoic acid, tung oil acid, tall oil fatty acid, coconut oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, safflower oil fatty acid, dehydrated castor oil fatty acid, tuni oil fatty acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, and oleic acid. The alkyl group having 1 to 21 carbon atoms may be a linear alkyl group, a branched alkyl group, or may contain an alicyclic structure. The above-mentioned aromatic hydrocarbons include aromatic hydrocarbons having 6 to 20 carbon atoms, specifically benzene, toluene, xylene, styrene, mesitylene, cumene, indene, naphthalene, anthracene, and triphenylene. The above-mentioned aliphatic hydrocarbons include saturated or unsaturated aliphatic hydrocarbons having 5 to 18 carbon atoms, specifically pentane, hexane, heptane, octane, tridecane, tetradecane, pentadecane, and 2,4-heptadiene. The above-mentioned alicyclic hydrocarbons include alicyclic hydrocarbons (naphthenic saturated hydrocarbons) having 6 to 20 carbon atoms, specifically cyclohexane, cyclohexene, methylcyclohexane, cyclooctane, and cyclodecane. The above-mentioned petroleum hydrocarbons include mineral spirits, gasoline, coal tar naphtha, petroleum ether, petroleum naphtha, petroleum benzine, and turpentine. Examples of the above-mentioned waxes include plant-based waxes (such as sumac wax and lacquer wax), animal-based waxes (such as beeswax and whale wax), mineral waxes (such as montan wax), petroleum-based waxes (such as paraffin wax), and synthetic waxes.Examples of the above-mentioned silicone-based solvents include straight silicone oils and modified silicone oils such as dimethyl silicone, methyl hydrogen silicone, methylphenyl silicone, cyclic dimethyl silicone, fluoroalkyl-modified silicone, and carboxy-modified silicone. In the case of modified silicone oils, examples include side-chain type modified silicone oil, double-ended type modified silicone oil, single-ended type modified silicone oil, and side-chain double-ended type modified silicone oil. Examples of the above-mentioned chlorine-based solvents include 1,2-dichloroethylene, trichloroethylene, and tetrachloroethylene. Examples of the above-mentioned fluorine-based solvents include hydrofluorocarbon (HFC) solvents, hydrofluoroether (HFE) solvents, perfluorocarbon (PFC) solvents, and hydrochlorofluorocarbon (HCFC) solvents.

[0084] Furthermore, other forms of the organic solvent (B) in this embodiment include, for example, ester solvents such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, butyl acetate, ethyl acetate, isobutyl acetate, carbonate solvents such as ethylene carbonate, propylene carbonate, glycol solvents such as diethylene glycol dimethyl ether, triethylene glycol, triethylene glycol dimethyl ether, phenol solvents such as phenol, m-cresol, p-cresol, o-cresol, 3-chlorophenol, 4-chlorophenol, ketone solvents such as cyclopentanone, cyclohexanone, acetone, methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, diethoxyethane, dibutyl ether, benzene, toluene, xylene, trimethyl Examples of solvents include aromatic hydrocarbon solvents such as benzene, naphthalene, ethylbenzene, and tetralin; hydrocarbon solvents such as n-heptane, n-hexane, n-octane, cycloalkanes (e.g., cyclohexane, methylcyclohexane, cyclopentane, methylcyclopentane), methylpentane, 2-ethylpentane, isoparaffinic hydrocarbons, liquid paraffin, decane, undecane, and dodecane; and other general-purpose solvents such as N-methyl-2-pyrrolidone (NMP), acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, chloroform, butanol, ethanol, chlorobenzene, turpentine, mineral spirits, and petroleum naphtha-based solvents. These may be used individually or in mixtures of two or more types.

[0085] <Dispersant> The coating composition of this embodiment may contain a dispersant. The dispersant is not particularly limited, but from the viewpoint of dispersion stability, the acid value of the dispersant is preferably 5 mg KOH / g or more and 160 mg KOH / g or less, and more preferably 7 mg KOH / g or more and 120 mg KOH / g or less. Furthermore, from the viewpoint of dispersion stability, an acidic dispersant with a pH of less than 7 is preferred.

[0086] Examples of dispersants usable in this disclosure include, specifically, acrylic polymers, styrene-acrylic polymers, maleic acid polymers, styrene-maleic acid polymers, α-olefin-maleic acid polymers, urethane polymers, ester resin polymers, sulfonic acid polymers, phosphate polymers, and the like. For example, commercially available products include Disperbyk-102, Disperbyk-111, Disperbyk-190, Disperbyk-191, Disperbyk-194N, Disperbyk-2010, Disperbyk-2012, and Disperbyk-2015 from BIC Chemie Japan, TEGO Dispers-715N, TEGO Dispers-750W, and TEGO Dispers-755W from Evonik Japan, and Efka6230 from BASF. The above dispersants may be used individually or in combination.

[0087] If the coating composition of this embodiment contains a dispersant, the lower limit of the dispersant content is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more, per 100 parts by mass of the titanium oxide composition in the coating composition. The upper limit of the dispersant content may be preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less, per 100 parts by mass of the titanium oxide composition in the coating composition. The upper and lower limits of the dispersant content can be combined as appropriate.

[0088] <Surfactants> The coating composition of this embodiment preferably contains, in addition to the titanium dioxide composition, one or more selected from the group consisting of surfactants and thickeners. The surfactant can be any ionic (including anionic, cationic, and amphoteric) or nonionic surfactant, but an anionic surfactant exhibiting anionic properties, a cationic surfactant exhibiting cationic properties, or a nonionic surfactant exhibiting nonionic properties is preferred.

[0089] In the coating composition of this embodiment, the upper limit of the surfactant content is preferably 20% by mass or less, 15% by mass or less, 12.5% ​​by mass or less, and 10% by mass or less, in that order, relative to the entire coating composition (100% by mass). The lower limit of the surfactant content is preferably 0.5% by mass or more, 1% by mass or more, 2% by mass or more, and 3% by mass or more, in that order, relative to the entire coating composition (100% by mass). The upper and lower limits of the surfactant content can be combined arbitrarily.

[0090] <<Anionic Surfactants>> The anionic surfactants in this embodiment are not particularly limited and include carboxylic acid-based anionic surfactants such as N-acyl amino acid salts, fatty acid salts, alkyl ether carboxylates, fatty acid amide ether carboxylates, fatty acid amide ether carboxylic acids, and acyl lactates; phosphoric acid-based anionic surfactants such as alkyl phosphates, polyoxyethylene alkyl ether phosphates, alkylaryl ether phosphates, and fatty acid amide ether phosphates; sulfonic acid-based anionic surfactants such as alkanesulfonates, α-olefin sulfonates, α-sulfo fatty acid methyl ester salts, acyl isethionates, alkyl glycidyl ether sulfonates, alkyl sulfosuccinates, alkyl sulfoacetates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, and N-acylmethyl taurates; and sulfate-based anionic surfactants such as alkyl sulfates, alkyl ether sulfates, alkylaryl ether sulfates, fatty acid alkanolamide sulfates, and fatty acid monoglyceride sulfates.

[0091] <<Cationic surfactants>> The cationic surfactants in this embodiment are not particularly limited and include alkyltrimethylammonium salts, alkoxyalkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylamidealkyltrimethylammonium salts, alkyldimethylamines and their salts, alkoxyalkyldimethylamines and their salts, and (vii)alkylamidealkyldimethylamines and their salts.

[0092] <<Nonionic Surfactants>> The nonionic surfactant in this embodiment is not particularly limited and may be of the ester type, ether type, ester-ether type, or any other type, and examples include polyoxyalkylene polyhydric alcohol ethers, polyoxyalkylene polyhydric alcohol fatty acid esters, polyoxyalkylene aliphatic alcohol ethers, fatty acid esters of polyalkylene glycols, and polyhydric alcohol fatty acid esters.

[0093] <Thickening Agent> As the thickening agent in this embodiment, materials known for use in water-based coatings can be used. Examples include association-type thickening agents, cellulose-based thickening agents, (meth)acrylic acid-based thickening agents, polyurethane-based thickening agents, polyacrylamide-based thickening agents, vinyl ether-based thickening agents, mineral-based thickening agents, or polysaccharide-based thickening agents. In the coating composition of this embodiment, the upper limit of the thickening agent content is preferably 20% by mass or less, 15% by mass or less, 12.5% ​​by mass or less, and 10% by mass or less, in that order, relative to the entire coating composition (100% by mass). The lower limit of the thickening agent content is preferably 0.5% by mass or more, 1% by mass or more, 2% by mass or more, and 3% by mass or more, in that order, relative to the entire coating composition (100% by mass). The upper and lower limits of the thickening agent content can be arbitrarily combined. Furthermore, commercially available thickeners can be used, such as Adekanol® UH series manufactured by ADEKA Corporation, SN Thickener series manufactured by Sunopco Corporation, Aron® Thickener series manufactured by Toagosei Co., Ltd., and BYK Co., Ltd.'s (trademark registered) OPTIFLO series. The content of the thickener is 0.01 to 10 parts by mass per 100 parts by mass of solids in the surfactant mixture. The thickener may be used alone or in combination of two or more types. Examples of the dispersion aid include high-molecular-weight dispersants such as polycarboxylic acids, naphthalene sulfonic acid formalin condensates, and their salts. Examples of the dispersion aid include condensed phosphates such as pyrophosphates and hexametaphosphates. Examples of the preservative include sodium hypochlorite. Examples of the antifungal agent include oxazolidine-2,5-dione and other oxazolines. Examples of the above-mentioned corrosion inhibitors include amines, pyridines, tetraphenylphosphonium salts, benzotriazoles, triazoles, tetrazoles, and benzoic acid. Examples of the above-mentioned thickeners include hydrated aluminum silicate, dimethyloctadecyl salt of montmorillonite clay, alkali-soluble acrylic polymers, colloidal silica, alumina sol, heavy metal soaps, polyvinyl alcohol, carboxymethylcellulose, and xanthan gum. Examples of the above-mentioned viscosity modifiers include:

[0094] <Chelating Agents> Examples of the above chelating agents include carboxylic acid chelating agents such as gluconic acid; amine chelating agents such as ethylenediamine, diethylenetriamine, and trimethyltetraamine; polyaminopolycarboxylic acid chelating agents such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, triethylenetetraminehexaacetic acid, and diethylenetriaminepentaacetic acid; organic phosphonic acid chelating agents such as 2-aminoethylphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, methanehydroxyphosphonic acid, and 1-phosphonovutane-2,3,4-tricarboxylic acid; phenol derivatives; and 1,3-diketones. If such additive components overlap with the above-mentioned other components, they shall be used as those components and not exceed that range. In the coating composition of this embodiment, the content of the additive component is preferably 0.1 to 20% by mass relative to the total coating composition (100% by mass).

[0095] In embodiments of the coating composition of the present disclosure, which contains a titanium dioxide composition, a binder resin, a solvent, a dispersant, and any additive components other than the solvent and the dispersant, the total amount of the titanium dioxide composition, binder resin, solvent, dispersant, and any additive components other than the solvent and the dispersant is preferably 0.1 to 100% by mass, more preferably 0.5 to 90% by mass, even more preferably 1 to 80% by mass, even more preferably 1.5 to 70% by mass, and particularly preferably 2 to 50% by mass, relative to the entire coating composition (100% by mass). In embodiments of the coating composition of the present disclosure, which contains a titanium dioxide composition, a binder resin, a solvent, and a dispersant, the total amount of the titanium dioxide composition, binder resin, solvent, and dispersant is preferably 0.1 to 100% by mass, more preferably 0.5 to 90% by mass, even more preferably 1 to 80% by mass, even more preferably 1.5 to 70% by mass, and particularly preferably 2 to 50% by mass, relative to the entire coating composition (100% by mass).

[0096] (Physical properties of the coating composition) When the coating composition of this embodiment is in solution form, the viscosity is preferably 10 to 100,000 mPa·s, and more preferably 100 to 50,000 mPa·s, from the viewpoint of dispersion stability and handling. The viscosity can be measured by adjusting the temperature of the solution-type coating composition to 25°C and using a Brookfield viscometer (B8L type viscometer, manufactured by Tokimec Co., Ltd.). When the coating composition of this embodiment is a solution-type coating composition containing an aqueous solvent (A), the pH of the solution coating composition is preferably 3 to 11, more preferably 4 to 10, and even more preferably 4.5 to 9.5.

[0097] [Method for Manufacturing the Coating Composition] The method for manufacturing the coating composition of this disclosure is not particularly limited, and a method that allows for the uniform mixing of the titanium dioxide composition, the binder resin, and, if necessary, a photoinitiator and / or any additional components (dispersant, solvent, etc.) as essential components is appropriately employed. As long as the above-mentioned components are included, there are no particular restrictions on the method of mixing the components or the order in which they are mixed, and an appropriate known kneading method or known mixing method can be selected considering the type of each component used, but examples include the following methods.

[0098] For example, the coating composition can be manufactured by kneading the titanium dioxide composition and a binder resin as described above. A kneading method using a stirring and mixing device (e.g., a roll mill) is one example. Specifically, the desired coating composition can be obtained by preparing a binder resin and, if necessary, a solvent, blending the titanium dioxide composition into the prepared mixture, pre-mixing with a stirrer, and then kneading with a three-roll mill. Depending on the type of binder resin used or the mixing ratio of the solvent, the coating composition can be liquid or paste-like (semi-solid).

[0099] For example, if the coating composition contains a solvent, the titanium dioxide composition, the binder resin, and, if necessary, a photoinitiator and / or any additional components (dispersant, solvent, etc.) are mixed and stirred. At this time, beads are added to the mixture, and the slurry, which is a mixture of powder and liquid, and the beads are stirred in a bead mill to grind the material particles. After grinding is complete, the beads are separated from the mixture to obtain a dispersion. Another method is to mix the obtained dispersion with any additional components as necessary.

[0100] The antibacterial and antiviral coating composition of this embodiment can be applied to the surface of a substrate such as a film, and a coating layer can be formed by applying a curing method suitable for the dispersion (drying, heating, thermosetting, active energy ray curing, etc.) to the resulting coating film. Furthermore, any known and publicly available coating method can be used for applying the antibacterial and antiviral coating composition, such as roll coaters, electrostatic coating, bar coaters, gravure coaters, knife coaters, dipping coatings, and spray coatings. The substrate to be coated is not particularly limited and can be, for example, paper, synthetic paper, steel plates, aluminum foil, glass, wood, woven fabrics, knitted fabrics, nonwoven fabrics, gypsum boards, wood-based boards, resin substrates, etc. Specific examples of the above-mentioned resin substrates include polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: low-density polyethylene film, HDPE: high-density polyethylene film), polypropylene film (CPP: unoriented polypropylene film, OPP: biaxially oriented polypropylene film), polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, polycarbonate film, polyethylene terephthalate film, polymethyl methacrylate film, polystyrene film, polyester film, polyolefin film, epoxy resin film, melamine resin film, triacetylcellulose resin film, polyvinyl alcohol 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 above-mentioned resin substrates used may be subjected to surface treatments such as corona treatment.

[0101] (Antibacterial and Antiviral Fiber) The antibacterial and antiviral fiber of this embodiment may be any embodiment that includes the above-mentioned titanium dioxide composition or antibacterial and antiviral coating composition. Specifically, it is preferable that the above-mentioned titanium dioxide composition or antibacterial and antiviral coating composition is incorporated into the fibers constituting the fiber, or attached to the surface of the fiber body. When incorporating the above-mentioned titanium dioxide composition or antibacterial and antiviral coating composition into the fibers or on the fiber surface, one or more types of fibers selected from the group consisting of synthetic fibers, natural fibers, cellulose fibers, and inorganic fibers are impregnated with the above-mentioned titanium dioxide composition or antibacterial and antiviral coating composition, or the above-mentioned titanium dioxide composition or antibacterial and antiviral coating composition is kneaded into the fiber-forming resin that forms the fibers in advance.Therefore, it is preferable that the antibacterial and antiviral fiber of this embodiment has a fiber body and the above-mentioned titanium dioxide composition or antibacterial and antiviral coating composition impregnated into or kneaded into the fiber body.

[0102] When impregnating the fibers or the fiber surface with the titanium dioxide composition or antimicrobial antiviral coating composition, the fibers or fiber body can be impregnated with the titanium dioxide composition or antimicrobial antiviral coating composition by treating the fibers or fiber body in a dispersion of the titanium dioxide composition or antimicrobial antiviral coating composition in a predetermined solvent after the fibers or fiber body have been formed. On the other hand, when kneading the titanium dioxide composition or antimicrobial antiviral coating composition into the fibers, fibers can be obtained in which a specific amount of the titanium dioxide composition or antimicrobial antiviral coating composition is impregnated by melt spinning while blending the titanium dioxide composition or antimicrobial antiviral coating composition to a predetermined amount with the fiber forming resin, or by melt spinning using a fiber resin composition that already contains the titanium dioxide composition or antimicrobial antiviral coating composition and the fiber forming resin. When the fibers contain the titanium dioxide composition or antimicrobial antiviral coating composition, the average content (amount per unit length) of the fibers is set as appropriate, but when converted to the amount of titanium dioxide composition, it is approximately 0.2 to 5 g / m ２ Preferably, the concentration is 0.5 to 2 g / m ２It is preferable that this be the case.

[0103] The antibacterial and antiviral fiber of this embodiment is characterized in that a coating layer containing the above-mentioned titanium dioxide composition or antibacterial and antiviral coating composition is laminated or attached to the fiber body. The coating layer may be laminated or attached to all or part of the surface of the fiber body.

[0104] In this specification, "fibrous body" refers to short fibers (staples), long fibers (filaments), and various processed yarns made from these fibers (filament yarns and spun yarns, etc.), and broadly includes these. Examples of the fibrous body include synthetic fibers mainly composed of polymer materials such as polyester, polyamide, acrylic, polyolefin, or nylon; natural fibers such as cotton; cellulosic fibers such as rayon; inorganic fibers such as glass fiber; or composite fibrous bodies thereof. These fibrous bodies may be a blend of two or more types, or a blend of synthetic fibers and natural fibers. Of these, the present invention is particularly useful for fibrous bodies using single fibers of synthetic fibers such as polyester fibers, nylon fibers, polyamide fibers, or acrylic fibers, or single fibers of natural fibers such as cotton. In the fibrous body of this embodiment, a material with an average thickness of 1 to 100 dtex (decitex) of single fibers is preferred, more preferably 1 to 50 dtex (decitex), and even more preferably 1 to 10 dtex (decitex). If the fiber diameter is thinner than 1 dtex, the fiber strength will be insufficient, and it will be difficult to coat its surface with a coating layer containing the titanium oxide composition. On the other hand, if the fiber diameter is thicker than 100 dtex, the antibacterial and antiviral fiber itself will become hard and tend to lose its flexibility. Furthermore, known methods can be applied as the method for forming the fiber. For example, the resin that forms the fiber (fiber-forming resin) can be melt-extruded using a single-screw or twin-screw extruder, extruded through a nozzle with a diameter of 0.1 to 10.0 mm to form a fibrous material, and then wound up the fibrous material at 300 to 3000 m / min to obtain the fibers of 1 to 100 dtex.

[0105] The average coating amount (amount per unit length) of the above coating layer is set as appropriate, but when converted to the amount of titanium dioxide composition, it is approximately 0.2 g / m ２ ~5g / m ２ Preferably, it is 0.5 g / m ２ ~2g / m 、 It is preferable that this be the case.

[0106] In this embodiment, specific applications of the antibacterial and antiviral fiber include antibacterial and antiviral socks, underwear, jackets, lab coats, bedding, sheets, towels, napkins, gloves, hats, shirts, handkerchiefs, trousers, carpets, mats, curtains, or work clothes. Furthermore, the antibacterial and antiviral fiber of this embodiment is not limited to fabric materials, but can be used as a substitute material for general processed yarns by utilizing its antibacterial and antiviral properties. It can also be used as a reinforcing material for fiber-reinforced plastics, etc.

[0107] (Antibacterial and antiviral fabric) The antibacterial and antiviral fabric of this embodiment comprises a fabric and a coating layer attached to the fabric, which is made from an antibacterial and antiviral coating composition. In other words, the antibacterial and antiviral fabric of this embodiment comprises a fabric and a coating layer attached to the fabric, and the coating layer contains the titanium dioxide composition and the dispersant described above. The method for producing the antibacterial and antiviral fabric of this embodiment comprises the following steps: (I) preparing an aqueous coating by mixing 0.01 to 5 parts by mass of an adhesive such as ethylcellulose for adjusting the viscosity of the coating material, 0.01 to 20 parts by mass of a dispersant such as an aqueous acrylic resin, 1 to 60 parts by mass of the above-mentioned coating composition, and 15 to 99 parts by mass of an aqueous solvent (A) added as needed; (II) preparing an aqueous processing solution by mixing 1 to 50 parts by mass of the aqueous coating with 50 to 99 parts by mass of an aqueous solvent (A) added as needed; (III) applying or immersing a substrate (e.g., fabric) in the aqueous processing solution; and (IV) drying the fabric coated with the aqueous processing solution at 20 to 180°C for 1 minute to 48 hours. The average coating amount of the above coating layer is set as appropriate, but is generally 0.01 to 10 g / m when converted to the amount of metal in the metal compound (B). ２It is preferable that the above-mentioned adhesive is a water-soluble polymer. The water-soluble polymer may be a natural polymer or a synthetic polymer. Examples of the aqueous polymer include known natural aqueous polymers such as starch substances such as corn and wheat, cellulosic substances such as carboxymethylcellulose, methylcellulose, ethylcellulose, and hydroxyethylcellulose, polysaccharides such as sodium alginate, gum arabic, locust bean gum, tranto gum, guar gum, and tamarind seed, protein substances such as gelatin and casein, tannin substances, and lignin substances. Examples of synthetic aqueous polymers include known polyvinyl alcohol compounds, polyethylene oxide compounds, acrylic acid aqueous polymers, and maleic anhydride aqueous polymers. Among these, polysaccharide polymers and cellulosic polymers are preferred. Furthermore, the antibacterial and antiviral fabric of this embodiment can be obtained, for example, using the above-mentioned fibers or fibrous material, and any type of fabric such as woven fabric, knitted fabric, or nonwoven fabric can be obtained.

[0108] (Antibacterial and Antiviral Film) The antibacterial and antiviral film of this embodiment comprises a base film and a coating layer provided on at least one surface of the base film, the coating layer being made from an antibacterial and antiviral coating composition. In other words, the antibacterial and antiviral film of this embodiment comprises a base film and a coating layer attached to the base film, the coating layer containing the titanium oxide composition and the dispersant described above. The method for producing the antibacterial and antiviral film of this embodiment comprises the steps of: (I) preparing an aqueous coating by mixing 1 to 99 parts by mass of a dispersant such as an aqueous acrylic resin, 1 to 50 parts by mass of the coating composition described above, and 0 to 98 parts by mass of an aqueous solvent (A) added as needed; (II) applying the aqueous coating to a substrate (for example, a base film such as a PET film); and (III) drying the substrate coated with the aqueous coating at 20 to 180°C for 1 minute to 48 hours. The average thickness of the coating layer is set as appropriate, but is preferably about 1 to 50 μm. Furthermore, the haze value of the coating layer is preferably 10% or less, more preferably 7% or less, even more preferably 5% or less, and most preferably 3% or less. The haze value was measured in accordance with the JIS K7136:2000 standard, as described in the examples below.

[0109] In a preferred embodiment of the antimicrobial and antiviral film of this embodiment, it is preferable that the difference between the haze value of a blank film having a base film and a reference coating layer provided on one side of the base film and the haze value of the antimicrobial and antiviral film having a base film and the coating layer provided on one side of the base film is 10% or less. The reference coating layer may be formed from a reference composition obtained by removing the metal compound (B) from the antimicrobial and antiviral coating composition. More specifically, the reference composition, which is the raw material for the reference coating layer, essentially contains water and a dispersant. The content of the dispersant in the reference composition can be determined by referring to the numerical range of the content of the dispersant in the antimicrobial and antiviral coating composition.

[0110] "Molded Article" The antibacterial and antiviral curing composition of this embodiment contains a titanium dioxide composition and a resin. The antibacterial and antiviral curing composition is prepared by blending the titanium dioxide composition and the resin, mixing or melt-kneading them according to the type of resin while heating to room temperature (20 to 30°C) or a predetermined temperature (for example, more than 30°C and 150°C or less), and then curing and molding the antibacterial and antiviral curing composition itself to obtain a molded article exhibiting antibacterial and antiviral properties in which the titanium dioxide composition is dispersed with the resin as a matrix. The term "curing" may mean either that a thermosetting resin or its initial condensate becomes insoluble and infusible by crosslinking due to heat, a catalyst, etc., or that a thermoplastic resin that has softened and flowed due to heating solidifies due to cooling. The antibacterial and antiviral curing composition can also be prepared by first making a masterbatch containing a high concentration of titanium dioxide composition, and then diluting it with a resin before use.

[0111] From the viewpoint of providing excellent dispersibility in the matrix and excellent antibacterial and antiviral properties in the antibacterial and antiviral curing composition of this embodiment, the composition ratio of the titanium dioxide composition and the resin is preferably 1% by mass or more, more preferably 5% by mass or more, preferably 50% by mass or less, and more preferably 20% by mass or less, based on 100% by mass of the total of the titanium dioxide composition and the resin in the antibacterial and antiviral curing composition of this embodiment. In the embodiment in which the antibacterial and antiviral curing composition of this embodiment contains the titanium dioxide composition and the resin, the total amount of the titanium dioxide composition and the resin components is preferably 40% by mass or more, more preferably 45% by mass or more, even more preferably 50% by mass or more, particularly preferably 95% by mass or more, preferably 100% by mass or less, more preferably 99.9% by mass or less, even more preferably 99.5% by mass or less, and particularly preferably 99% by mass or less, based on 100% by mass or less of the entire antibacterial and antiviral curing composition (100% by mass).

[0112] The resin contained in the antibacterial and antiviral curing composition of this embodiment may be the same resin as the dispersant contained in the antibacterial and antiviral coating composition, but is not limited to that, and known thermosetting resins and / or thermoplastic resins may be used. As such thermosetting resins, any thermosetting resin used as a conventional molding material can be selected. Such resins are not particularly limited, but examples include epoxy resins, phenolic resins, furan resins, urea resins, melamine resins, unsaturated polyester resins, silicon resins, etc. On the other hand, as thermoplastic resins, any thermoplastic resin used as a conventional molding material can be selected. Such materials are not particularly limited, but include, for example, polyolefin resins such as polyethylene, polypropylene, poly(4-methyl-1-pentene), and poly(1-butene); polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyamide resins such as polyamide-6 (nylon-6), polyamide-66 (nylon-66), and polymetaxylene adipamide; ethylene-unsaturated ester copolymers such as ethylene-vinyl ester copolymers and ethylene-unsaturated carboxylic acid copolymers; and ethylene-unsaturated carboxylic acid copolymers or their ionomer resins. Examples include: poly(meth)acrylic resins such as poly(meth)acrylic acid ester resins; chlorine-based resins such as polyvinyl chloride and polyvinylidene chloride; fluorine-based resins such as polytetrafluoroethylene, ethylenetetrafluoroethylene copolymer, polyvinylidene fluoride, and polyvinyl fluoride; polystyrene resins; polyether-based resins such as polyether ether ketone resins and polyether ketone resins; polycarbonate resins; polyphenylene-based resins such as polyphenylene oxide resins and polyarylene sulfide resins represented by polyphenylene sulfide resins; polyvinyl acetate resins; polyacrylonitrile resins; and thermoplastic elastomers. These thermosetting resins and thermoplastic resins may be used individually or in combination of two or more types.

[0113] Furthermore, the antibacterial and antiviral curing composition of this embodiment may contain the same additive components as those contained in the aforementioned antibacterial and antiviral coating composition as optional components. In addition, curing agents, curing accelerators, initiators, catalysts, etc. may be added as optional reaction raw material components. Moreover, depending on the application, various additive components, such as known plasticizers (mineral oil, silicone oil, etc.), lubricants, dispersants, stabilizers, UV absorbers, mold release agents, colorants, inorganic fillers, organic fillers, flame retardants, antibacterial agents, antiviral agents, etc., may also be added as optional components.

[0114] In the antibacterial and antiviral curing composition of this embodiment, the lower limit of the content of the above-mentioned arbitrary component is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, relative to the entire antibacterial and antiviral curing composition. The upper limit of the content of the above-mentioned arbitrary component is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 15% by mass or less, and particularly preferably 5% by mass or less, relative to the entire antibacterial and antiviral curing composition. The upper and lower limits of the content of the above-mentioned arbitrary component can be combined as appropriate.

[0115] The molding method for the antibacterial and antiviral curing composition of the present invention can be any molding method suitable for the resin used, and examples include injection molding, extrusion molding including sheet molding and film molding, pressure molding (press molding), pressure molding and vacuum molding, melt molding methods such as melt spinning, casting, multilayer extrusion, and composite spinning. Among these, multilayer extrusion and composite spinning are preferred when emphasis is placed on uneven distribution of the titanium oxide composition within the molded product. The coating layer obtained using the antibacterial and antiviral coating composition of this disclosure and the molded article obtained using the antibacterial and antiviral curing composition of the present invention can be suitably used as a material with antibacterial and antiviral activity in areas that are touched by human hands. Applicable uses include a wide range of applications such as smartphone casings, personal computer casings, touch panels, handrails, doorknobs, washbasins, push buttons such as elevator buttons, interior furnishings (wallpaper, flooring, etc.), various packaging materials, various textile products, and medical equipment (medical gloves, medical glasses, etc.).

[0116] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way to the examples described below. Also, in the following, "parts" and "%" are based on mass unless otherwise specified.

[0117] (Evaluation Method) 1. [Method for Measuring the Antiviral Properties of Titanium Dioxide Compositions] 25 parts of the titanium dioxide composition from the example described below, 25 parts of the composition prepared in the comparative example, 75 parts of water, and 4 parts of a dispersant (DISPERBY K-194N manufactured by BIC Chemie Co., Ltd.) were mixed and stirred. 100 parts of 1.0 mmφ ceramic beads were added, and the mixture was ground in a sand grinder for 4 hours. After grinding, the ceramic beads and the dispersion were separated to obtain a copper compound-supported titanium dioxide composition dispersion. 3.2 parts of the dispersion and 100 parts of urethane resin (Hydran WLS-210 manufactured by DIC Corporation, resin solids content: 35% by mass) were mixed to form a coating composition. This composition was applied to a PET film (ACL-250 manufactured by Panac) using a piano wire bar coater (No. 4), dried at 120°C for 5 minutes, and a film for evaluation was obtained. JIS R An antiviral test was conducted using bacteriophage Qβ in accordance with 1756:2020 (film contact method). Antiviral activity was evaluated by the degree of inactivation, calculated using the following formula (1), when the evaluation film was subjected to 2 or 4 hours under 500 lux illuminance using a light source with wavelengths below 400 nm filtered by an N-113 filter, and under 2 or 4 hours under dark conditions. Degree of inactivation = log(N / N) ０ ) (Formula (1)) In the above formula (1), N represents the infectious titer of the sample after the reaction, N ０ The value represents the infectivity titer of the inoculated phage. "Inactivation degree -1" indicates 90% inactivation, "Inactivation degree -2" indicates 99% inactivation, and "Inactivation degree -3" indicates 99.9% inactivation. A "-" indicates that antiviral testing was not performed.

[0118] 2. "Method for measuring the BET specific surface area of ​​titanium dioxide raw materials and titanium dioxide compositions" The specific surface area was measured using the "MacSORBHM model-1208" fully automatic BET specific surface area measuring device manufactured by Mountec Co., Ltd. (BET single-point method).

[0119] 3. "Method for measuring the rutile content of titanium dioxide raw material" Using the X-ray diffractometer "XRD-6100" manufactured by Shimadzu Corporation, the peak height ratio corresponding to rutile-type crystals was calculated from the peak heights corresponding to the crystals of titanium dioxide as a whole (rutile-type, brookite-type, anatase-type).

[0120] 4. "Method for Measuring the Primary Particle Size of Titanium Dioxide as a Raw Material" In this example and comparative example, the primary particle size of the titanium dioxide raw material is shown as a value measured by directly measuring the size of the primary particles from electron microscope images using a transmission electron microscope (TEM). Specifically, the short axis diameter and long axis diameter of each primary titanium dioxide particle were measured, and the average of 200 particles was taken as the particle size of that primary particle. Then, for 100 or more titanium dioxide particles, the volume (weight) of each particle was approximated to a cube of the calculated particle size, and the volume-average particle size was taken as the average primary particle size.

[0121] 5. "Method for Calculating the Zr / Ti Ratio and Nb / Ti Ratio of the Raw Material Titanium Oxide" Metal element composition analysis was performed using the bulk fundamental parameter (bulk FP) method with the SEA1200VX X-ray fluorescence analyzer manufactured by Seiko Instruments Inc. For the fluorescence intensity (cps: count per second) of each metal element obtained by measuring the titanium oxide sample, the intensity ratio of the fluorescence intensity (cps) of zirconium or niobium, with the fluorescence intensity (cps) of titanium set to 100, was calculated as the Zr / Ti ratio or Nb / Ti ratio, respectively.

[0122] 6. "Method for measuring the amount of copper supported in a titanium dioxide composition (copper content in the entire copper-containing nanocluster)" The titanium dioxide composition of the example or the composition of the comparative example was completely dissolved in a hydrofluoric acid solution, and the copper content (parts by mass) per 100 parts by mass of the titanium dioxide composition or the composition was quantified by analysis using an ICP emission spectrometer.

[0123] 7. "Method for Measuring the Chlorine Content of Titanium Dioxide Compositions" The titanium dioxide compositions of the examples or the comparative examples were subjected to combustion under combustion conditions of 1100°C using a combustion-chromatographic analyzer, and the chlorine content (parts by mass) per 100 parts by mass of the titanium dioxide composition or the composition was quantified. In ICP analysis, the measured values ​​can be approximately ±0.02% for low chlorine content and approximately within ±0.05% for high chlorine content.

[0124] 8. [Method for Observing Copper Nanoclusters in Titanium Dioxide Compositions] The titanium dioxide compositions prepared in this example were observed using an atomic resolution electron microscope with the following configuration: HAADF-STEM observation. Based on the observation, clusters consisting of copper compounds containing chlorine were observed as having a first cluster, and clusters consisting of copper atoms with an average particle size of 0.26 to 5 nm were observed as having a second cluster. Furthermore, the ratio of Cu to Cl in the first and second clusters was determined by EDS mapping analysis. An EDS spectrum was extracted from the measurement area of ​​a single particle, and the ratio of Cu to Cl was calculated using the Ratio method. <Hardware used in the above HAADF-STEM observation> JEM-ARM300F D configuration, atomic resolution electron microscope (JEOL Ltd.) EDS JED-2300 dual detector configuration, energy dispersive X-ray analyzer (JEOL Ltd.) <Software used in the above HAADF-STEM observation> TEMCenter ver. 2.14.4.2362 (Thermo Fisher Scientific Inc.) Digital Micrograph ver. 3.21.1374.0 (Gatan Inc.) Analysis Station ver. 4.16.0.82 (JEOL Ltd.) NSS4 ver. 4.1.95.190 (Thermo Fisher Scientific Inc.) <HAADF-STEM Measurement Conditions> HAADF-STEM observation acceleration voltage: 80kV, 300kV Irradiation current: 5-115pA

[0125] 9. [Method for Measuring the Average Amount of Copper Dissolved from Titanium Dioxide Compositions] The amount of copper dissolved in water from titanium dioxide compositions (1) to (14) prepared in this example and comparative example was measured according to the following procedure. 0.015 g of each titanium dioxide composition from the example and comparative example and 30 g of deionized water were placed in a glass bottle, the lid was closed and shaken thoroughly, and then left to stand for 72 hours at 20°C and 50°C. After standing, 1.5 ml of the supernatant was placed in a dedicated pack test cup WAK-CC10 (manufactured by Kyoritsu Chemical Laboratory), and colorimetric quantification was performed using Pack Test Copper Wak-Cu (manufactured by Kyoritsu Chemical Laboratory), and the amount of copper dissolved in water was measured using Digital Pack Test Copper The amount of copper ions eluted was measured using DPM2-Cu (manufactured by Kyoritsu Chemical Laboratory). The detection range for the eluted amount is 0.10 to 4.00 mg / L. For levels exceeding 4.00 mg / L, the supernatant was arbitrarily diluted with deionized water to bring it within the detection range, and the measured value was multiplied by the dilution factor to obtain the eluted amount. For each titanium dioxide composition, the eluted amount was measured at 20°C and 50°C, and the average of the eluted amounts under the two conditions was taken as the "copper eluted amount." Furthermore, in the above pack test, the total copper ions are quantified by first reducing all monovalent and divalent copper ions to monovalent. Therefore, the above total copper ions are detected as the sum of monovalent and divalent copper ions.

[0126] (Preparation of Titanium Dioxide Composition) [Example 1] (1-1) Preparation of Titanium Dioxide (a1) Titanium dioxide (a1) having the following characteristics (i) to (iii) was prepared. (i) Crystalline rutile-type titanium dioxide (ii) Manufacturing method: Liquid phase method (sulfuric acid method) (iii) Physical properties and BET specific surface area: 9.1 m² ２ / g • Rutile content: 95.4% • Primary particle size: 165 nm • Zr / Ti ratio: 0.05% • Nb / Ti ratio: 0.17%

[0127] (1-2) Method for producing titanium dioxide composition a) Mixing step (reaction step) 600 parts by mass of titanium dioxide (a1) and 900 parts by mass of water prepared above were mixed in a stainless steel container and stirred for 10 minutes with a stirrer (Robomix, manufactured by Tokushu Kika Kogyo Co., Ltd.) to prepare a titanium dioxide (a1)-containing mixture. Next, an aqueous copper(II) chloride solution, in which 16 parts by mass of copper(II) chloride dihydrate and 80 parts by mass of water were dissolved, was added to the titanium dioxide (a1)-containing mixture and mixed with a stirrer for 10 minutes to prepare a mixed solution. The pH of the mixed solution at this time was 2.8. As the first alkali compound addition step, a 1 mol / L aqueous sodium hydroxide solution was added dropwise to this mixed solution over 15 minutes until the pH of the mixed solution reached 6.0, and the mixture was thoroughly mixed for 15 minutes. Furthermore, as the second alkali compound addition step, the solution was added dropwise over 30 minutes until the pH of the mixed solution reached 8.0, and this was the reaction endpoint. After reaching the reaction endpoint, the mixture was stirred for 30 minutes. Prior to this, copper(II) chloride was dissolved in water to an appropriate concentration and then mixed with titanium dioxide and thoroughly mixed again. This created a state where chloride ions and copper ions could be easily adsorbed onto the surface of titanium dioxide (a1). By reacting the alkali compound step by step, it was confirmed that a second nanocluster containing copper atoms and no chlorine, and a first nanocluster compound containing chlorine atoms and copper atoms were formed on the surface of titanium dioxide (a1). b) Dehydration process The mixture was subjected to reduced pressure filtration using qualitative filter paper (5C) to separate the solid components, and then washed with deionized water. Next, the washed solid was dried at 120°C for 12 hours to remove moisture. After drying, a powdered copper compound containing titanium dioxide and nanoclusters containing copper atoms and chlorine atoms (hereinafter referred to as nanocluster-containing titanium dioxide composition) was obtained using a mill ("Millser" manufactured by Iwatani Industries Co., Ltd.). The powdered copper compound obtained in this dehydration process (=Sample 1) was subjected to powder X-ray diffraction (instrument name: Rigaku, SmartLab 9kW, measurement conditions: 2θ method, 2θ = 1 to 70 deg., speed = 1.0 deg. / min, analysis software: ReciPro) to identify its crystal structure. The results are shown in Figure 5.As shown in Figure 5, a clino-atacamite structure was confirmed in the obtained nanocluster-containing titanium oxide composition. Therefore, the presence of a first nanocluster containing an atacamite-type structure was confirmed by the above method. The titanium oxide composition containing the first and second nanoclusters obtained above was subjected to a heat treatment step by the following method to prepare a calcined titanium oxide composition (1). c) Heat treatment step The nanocluster-containing titanium oxide composition obtained in the dehydration step of b) above was heat-treated at 450°C for 3 hours in the presence of oxygen using a precision constant temperature oven (DH650 manufactured by Yamato Scientific Co., Ltd.) to obtain the target first and second nanocluster-containing titanium oxide compositions (calcined bodies). The total copper content of the first and second nanoclusters in the first and second nanoclusters-containing titanium oxide compositions was 0.5% by mass in terms of copper atoms relative to titanium oxide. The first and second nanocluster-containing titanium oxide compositions (=Sample 2), which are the sintered bodies obtained in this heat treatment process, had their crystal structures identified by powder X-ray diffraction (instrument name: Rigaku X-ray analyzer SmartLab 9kW, measurement conditions: 2θ method, 2θ = 1 to 70 deg., step = 0.02 deg., speed = 1.0 deg. / min.) and by HR-TEM crystal lattice imaging (instrument name: JEOL JRM-ARM300F, measurement conditions accelerating voltage: 200kV, analysis instrument: ReciPro). The results are shown in Figure 6. As shown in Figure 6, the obtained sintered bodies, the first and second nanocluster-containing titanium oxide compositions, have an atacamite crystal structure ((Cu. ２ Cl(OH) ３ )) was confirmed. Therefore, the existence of the first nanocluster containing the atacamite-based structure was confirmed by the above method.

[0128] [Examples 2-3, 5-6 and 10-11] Methods for producing titanium dioxide compositions (2)-(3), (5)-(6) and (10)-(11) The target first and second nanocluster-containing titanium dioxide compositions (2)-(3), (5)-(6) and (10)-(11) were produced in the same manner as described in the section "(1-2) Method for producing titanium dioxide compositions" above.

[0129] [Example 4] Method for producing titanium oxide composition (4) The target first and second nanocluster-containing titanium oxide compositions were produced using the same procedure and conditions as in Example 1, except that the "c) heat treatment step" was omitted from the method described in the section "(1-2) Method for producing titanium oxide composition" above.

[0130] Then, various evaluations were performed on the obtained titanium oxide compositions (2) to (6) and (10) to (11). The composition ratios, such as the total copper content of the first and second nanoclusters, and the experimental results for the first and second nanocluster-containing titanium oxide compositions (2) to (6) and (10) to (11) are shown in Table 1. Figure 1 shows the EDS elemental mapping analysis results for titanium oxide composition (4) obtained in Example 4 (see Figure 1). The copper loading amount (1.0%) in Figure 1 is a value that includes the total amount of copper atoms in the entire titanium oxide composition, and includes all of the first, second, and third clusters. Similarly, Figure 2 shows the EDS elemental mapping analysis results for titanium oxide composition (6) obtained in Example 6 (see Figure 2). The copper loading amount (2.0%) in Figure 2 is a value that includes the total amount of copper atoms in the entire titanium oxide composition, and includes all of the first, second, and third clusters. Figure 3 shows the HAADF-STEM image and secondary electron image of the titanium oxide composition obtained in Example 4, and Figure 4 shows a magnified image of the HAADF-STEM image in Figure 3. From these experimental results in Figures 1 and 3-4, the presence of first nanoclusters containing copper atoms and chlorine atoms and second nanoclusters containing copper atoms was confirmed. In addition, similar to Example 1, atacamite crystal structures (Cu) were found in the nanoclusters contained in titanium oxide compositions (2)-(6) and (10)-(11). ２ Cl(OH) ３ The existence of ) was confirmed.

[0131] [Example 7] (2-1) Preparation of Titanium Oxide (a2) Titanium oxide (a2) having the following characteristics (i) to (iii) was prepared. (i) Crystalline rutile-type titanium oxide (ii) Manufacturing method: Liquid phase method (sulfuric acid method) (iii) Physical properties and BET specific surface area: 66.2 m² ２ / g ・Rutile rate: >99.9% ・Primary particle size: 20 nm ・Zr / Ti ratio: 0.05% ・Nb / Ti ratio: 0.22% (2-2) Method for producing titanium oxide composition (7) The target first and second nanocluster-containing titanium oxide composition (7) was obtained in the same manner as described in the section "(1-2) Method for producing titanium oxide composition" above. The obtained titanium oxide composition (7) was then evaluated in various ways. The composition ratios of the total copper content of the first and second nanoclusters and experimental results in the first and second nanocluster-containing titanium oxide composition (7) are shown in Table 1. In addition, the titanium oxide composition (7) also contains an atacamite crystal structure (Cu) in the nanoclusters, similar to Example 1. ２ Cl(OH) ３ The existence of ) was confirmed.

[0132] [Example 8] (3-1) Preparation of Titanium Oxide (a3) ​​Titanium oxide (a3) ​​having the following characteristics (i) to (iii) was prepared. (i) Crystalline rutile-type titanium oxide (ii) Manufacturing method: Liquid phase method (sulfuric acid method) (iii) Physical properties and BET specific surface area: 35.2 m² ２ / g ・Rutile rate: >99.9% ・Primary particle size: 35 nm ・Zr / Ti ratio: 0.05% ・Nb / Ti ratio: 0.26% (3-2) Method for producing titanium oxide composition (a3) ​​The target first and second nanocluster-containing titanium oxide composition (8) was obtained in the same manner as described in the section "(1-2) Method for producing titanium oxide composition" above. The obtained titanium oxide composition (8) was then evaluated in various ways. The composition ratios of the total copper content of the first and second nanoclusters and experimental results in the first and second nanocluster-containing titanium oxide composition (8) are shown in Table 1. In addition, the titanium oxide composition (8) also contains an atacamite crystal structure (Cu) in the nanoclusters, similar to Example 1. ２ Cl(OH) ３ The existence of ) was confirmed.

[0133] [Example 9] (4-1) Preparation of Titanium Oxide (a4) Titanium oxide (a4) having the following characteristics (i) to (iii) was prepared. (i) Crystalline rutile-type titanium oxide (ii) Manufacturing method: Liquid phase method (sulfuric acid method) (iii) Physical properties and BET specific surface area: 23.8 m² ２ / g ・Rutile rate: >99.9% ・Primary particle size: 50 nm ・Zr / Ti ratio: 0.05% ・Nb / Ti ratio: 0.22% (4-2) Method for producing titanium oxide composition (9) The target first and second nanocluster-containing titanium oxide composition (9) was obtained in the same manner as described in the section "(1-2) Method for producing titanium oxide composition" above. The obtained titanium oxide composition (9) was then evaluated in various ways. The composition ratios of the total copper content of the first and second nanoclusters and experimental results in the first and second nanocluster-containing titanium oxide composition (9) are shown in Table 1. In addition, the titanium oxide composition (9) also contains an atacamite crystal structure (Cu) in the nanoclusters, similar to Example 1. ２ Cl(OH) ３ The existence of ) was confirmed.

[0134] [Example 12] 25 parts by mass of the titanium oxide composition (1) obtained in Example 1, 73.5 parts by mass of water, and 1.5 parts by mass of a dispersant (DISPERBIK 190 manufactured by BIC Chemie) were dispersed in a sand grinder to prepare a paint composition (1) which is an aqueous slurry.

[0135] [Example 13] 35 parts by mass of the obtained paint composition (1), 5 parts by mass of acrylic resin binder ("RYUDYE-W FIXER 254PK" manufactured by DIC Corporation), and 60 parts by mass of O / W type emulsion (an emulsion of 5 parts "RYUDYE-W REDUCER CONC 720ENF" manufactured by DIC Corporation, 45 parts of water, and 50 parts of mineral spirits) were mixed and applied to cotton broadcloth fabric (122.5 g / m2) using an auto screen printing machine (manufactured by Tsujii Dyeing Machinery Co., Ltd.) with a pre-drying coating amount of 100 g / m². ２ The material was printed in this manner and dried in a hot air circulating dryer at 150°C for 2 minutes to produce an antibacterial and antiviral fiber (1).

[0136] Next, the fabricated antibacterial and antiviral fiber (1) was subjected to an antiviral test using bacteriophage Qβ in accordance with JIS R 1756:2020 (glass contact method). The antiviral activity was evaluated by the following formula (1) when the antibacterial and antiviral fiber (1) was subjected to light under 500 lux for 4 hours under light conditions and under dark conditions for 4 hours using a light source with wavelengths below 400 nm cut off by an N-113 filter. The value obtained was then evaluated as the degree of inactivation. Degree of inactivation = log(N / N) ０ ) (Formula (1)) In the above formula (1), N represents the infectious titer of the sample after the reaction, N ０ The value represents the infectivity titer of the inoculated phage. "Inactivation degree -1" indicates 90% inactivation, "Inactivation degree -2" indicates 99% inactivation, and "Inactivation degree -3" indicates 99.9% inactivation. The antibacterial and antiviral fiber (1) showed an inactivation degree of -2.5 after 4 hours under an illumination of 500 lux and an inactivation degree of -2.0 after 4 hours under dark conditions.

[0137] (Comparative Example 1) The titanium dioxide (a1) prepared to prepare the titanium dioxide composition of the example was used as is as the titanium dioxide composition (12), and various evaluations were performed. As a result, it was confirmed that there were no trace amounts of total copper supported or total chlorine atoms. Therefore, it is considered that the first nanocluster and the second nanocluster do not exist.

[0138] (Comparative Example 2) A titanium dioxide composition (13) for Comparative Example 2 was prepared in the same manner as in Example 1, except that the amount of copper(II) chloride dihydrate added in "a) Mixing step (reaction step)" was 6.4 parts by mass, according to the formulation shown in Table 1. No traces of chlorine atoms were observed in either the EDS mapping image or the measurement results of the total chlorine atom content of the produced titanium dioxide composition (13). Therefore, the presence of the first nanocluster could not be confirmed.

[0139] (Comparative Example 3) As the second alkali compound addition step in "a) Mixing step (reaction step)" described above, the mixture was added dropwise over 30 minutes until the pH of the mixture reached 12.0, which served as the reaction endpoint. In the same manner as in Example 1, a titanium dioxide composition (14) was prepared according to the formulation shown in Table 1. As the pH approached 12 in the second alkali compound addition step, the color of the mixture changed from greenish-white to reddish-white, and no trace of chlorine atoms was observed in either the EDS mapping image or the measurement results of the total chlorine atom content of the produced titanium dioxide composition (14). Therefore, the presence of the first nanocluster could not be confirmed.

[0140] This application claims priority based on Japanese Patent Application No. 2024-195472, filed with the Japan Patent Office on November 7, 2024, and includes the entire contents of that Japanese Patent Application.

[0141]

Claims

1. A titanium dioxide composition comprising rutile-type titanium dioxide and two or more copper atom-containing nanoclusters provided on the surface of the rutile-type titanium dioxide, wherein the two or more copper atom-containing nanoclusters include a first nanocluster containing copper atoms and chlorine atoms.

2. The titanium oxide composition according to claim 1, wherein the total copper atom content in the copper atom-containing nanocluster is 0.4 parts by mass to 10 parts by mass relative to the entire titanium oxide composition.

3. The titanium oxide composition according to claim 1, wherein the amount of chlorine atoms contained in the copper atom-containing nanoclusters is 0.01 parts by mass to 2 parts by mass relative to the entire titanium oxide composition.

4. The titanium oxide composition according to claim 1, wherein the first nanocluster has an atacamite-based structure.

5. The titanium oxide composition according to claim 4, wherein the atacamite-based structure is one or more selected from the group consisting of atacamite (Cu2Cl(OH)3, space group; Orth. Mmm (2 / m2 / m2 / m): Pnma), botalachite (Cu2Cl(OH)3, space group; Mon. 2 / m: P21 / m), and clinoatacamite (Cu2Cl(OH)3, space group; Mon. 2 / m).

6. The titanium dioxide composition according to claim 1, comprising rutile-type titanium dioxide as a reaction raw material.

7. The titanium oxide composition according to claim 1, wherein the rutile-type titanium oxide is rutile-type titanium oxide derived by a liquid-phase method and contains at least one metal element selected from the group consisting of zirconium and niobium.

8. The titanium oxide composition according to claim 1, wherein the average particle size of the copper atom-containing nanoclusters is in the range of 0.2 nm to 500 nm.

9. The BET specific surface area is 1 m² ２ / g to 200m ２ The titanium dioxide composition according to claim 1, wherein the amount is / g.

10. A coating composition comprising a titanium dioxide composition according to any one of claims 1 to 9 and a binder resin.

11. An antibacterial and antiviral fiber comprising a fibrous body and a coating layer attached to the fibrous body, the coating layer being made from the coating composition of claim 10.

12. A titanium dioxide composition-containing antibacterial and antiviral fiber in which the titanium dioxide composition according to any one of claims 1 to 9 is contained inside the fiber.

13. An antibacterial and antiviral film comprising a base film and a coating layer provided on at least one surface of the base film, the coating layer being made from the coating composition of claim 10.

Images