Copper complex titanium oxide dispersion liquid, coating material composition, and antibacterial/antiviral member

The present invention relates to a copper composite titanium oxide dispersion, a coating composition, and an antibacterial / antiviral member. Specifically, the present invention relates to a copper composite titanium oxide dispersion and a coating agent composition that can obtain high antibacterial, antiviral and transparent properties, and an antibacterial / antiviral member using the coating agent composition.

With the improvement of consumers' cleanliness consciousness, various antibacterial members that reduce microorganisms in the living environment have been developed and commercialized. The antibacterial member that imparts antibacterial properties to interior members for houses and automobiles generally contains an antibacterial material such as silver or zinc (see, for example, Patent Documents 1 and 2). However, silver and zinc have problems in terms of price and ecotoxicity.

Therefore, attempts have been made to use titanium oxide, which is inexpensive, abundantly present, and has low ecotoxicity, as an antibacterial material (see, for example, Patent Document 3). Since titanium oxide has photocatalytic activity, antibacterial action using this photocatalytic activity is drawing attention.

Here, titanium oxide is a white powder as is often used as a pigment in white paints. Therefore, a technique for ensuring transparency is required even when titanium oxide is used so that it can be used in various applications. Specifically, it is necessary to make titanium oxide into fine particles by using bottom-up synthesis or various dispersion techniques.

<p num="0005"><patcit num="1"><text>Japanese Unexamined Patent Publication No. 2008-255101</text></patcit><patcit num="2"><text>Japanese Unexamined Patent Publication No. 2011-42642</text></patcit><patcit num="3"><text>Japanese Unexamined Patent Publication No. 2003-275601</text></patcit></p>

However, most of the titanium oxide fine particle dispersions currently on the market are aqueous dispersions that utilize the repulsive action of the charges between the particles. Therefore, if a binder such as a combination of acrylic urethane and isocyanate is used for such an aqueous dispersion of titanium oxide, there is a problem that transparency is impaired by the influence of water. Further, when such a binder is used in the aqueous dispersion of titanium oxide, there is a problem that the pot life becomes extremely short.

Further, the conventional titanium oxide fine particle dispersion has a low titanium oxide concentration. When the titanium oxide concentration is low, the coating film becomes thick and problems such as dripping are likely to occur. Further, since a large amount of solvent is contained, it becomes necessary to lengthen the drying time and raise the drying temperature. Further, in addition to further improving the antibacterial property of the antibacterial material, it is also desired to impart antiviral property.

The present invention has been made in view of the problems of the prior art. An object of the present invention is to provide a copper composite titanium oxide dispersion liquid capable of obtaining a film having transparency while increasing the concentration of an antibacterial material to improve antibacterial properties and also having antiviral properties. To provide a coating composition. Further, an object of the present invention is to provide an antibacterial / antiviral member using the coating agent composition.

The copper composite titanium oxide dispersion according to the first aspect of the present invention contains titanium oxide particles and 0.1 to 20 parts by mass of sub-copper oxide particles with respect to 100 parts by mass of titanium oxide particles. Further, the dispersion liquid contains 5 to 100 parts by mass of a phosphate ester-type anionic surfactant and 100 parts by mass of the titanium oxide particles and the cuprous oxide particles in total with respect to 100 parts by mass of the titanium oxide particles and the cuprous oxide particles. It contains 300 to 2000 parts by mass of an organic solvent. The titanium oxide particles and the cuprous oxide particles have an average primary particle size of 2 to 80 nm, and an average secondary particle size of 50 to 150 nm obtained by a cumulant analysis method measured by a dynamic light scattering method. The titanium oxide particles are contained in 10 parts by mass or more in 100 parts by mass of the heating residue of the copper composite titanium oxide dispersion liquid.

The coating agent composition according to the second aspect of the present invention contains the copper composite titanium oxide dispersion liquid according to the first aspect and the binder resin. The titanium oxide particles in the coating agent composition are contained in 10 to 80 parts by mass in 100 parts by mass of the heating residue of the coating agent composition.

In the coating agent composition according to the third aspect of the present invention, the binder resin contains the chlorinated polyolefin in the coating agent composition according to the second aspect.

The antibacterial / antiviral member according to the fourth aspect of the present invention has a base material and a coating film provided on the base material and containing the coating agent composition according to the second or third aspect.

The antibacterial / antiviral member according to the fifth aspect of the present invention is the antibacterial / antiviral member according to the fourth aspect, and the film has a static contact angle of 30 degrees or less with respect to oleic acid.

Hereinafter, the copper composite titanium oxide dispersion, the coating agent composition, and the antibacterial / antiviral member according to the embodiment of the present invention will be described in detail.

[Copper composite titanium oxide dispersion] The copper composite titanium oxide dispersion according to the embodiment of the present invention contains titanium oxide particles and 0.1 to 20 parts by mass of sub-copper oxide particles with respect to 100 parts by mass of titanium oxide particles. Further, the dispersion liquid contains 5 to 100 parts by mass of the phosphate ester-type anionic surfactant and 100 parts by mass of the titanium oxide particles and the cuprous oxide particles, relative to 100 parts by mass of the titanium oxide particles and the cuprous oxide particles. It contains 300 to 2000 parts by mass of an organic solvent. The titanium oxide particles and the cuprous oxide particles have an average primary particle size of 2 to 80 nm, and an average secondary particle size of 50 to 150 nm obtained by a cumulant analysis method measured by a dynamic light scattering method. The titanium oxide particles are contained in 10 parts by mass or more in 100 parts by mass of the heating residue of the copper composite titanium oxide dispersion liquid.

As the titanium oxide particles, particles made of anatase-type or rutile-type titanium oxide can be used. Further, particles in which anatase-type titanium oxide and rutile-type titanium oxide are mixed can also be used. However, as the titanium oxide particles, it is preferable to use anatase-type titanium oxide particles. This is because the anatase-type titanium oxide has a larger bandgap than the rutile-type titanium oxide and has excellent photocatalytic properties.

The particles of anatase-type titanium oxide may be mixed with titanium oxide having an amorphous shape. However, since the amorphous titanium oxide has poor photocatalytic properties, the mixing amount is preferably as small as possible. Further, in order to improve the photocatalytic activity, particles having iron and copper oxides supported on the surface of the titanium oxide particles may be used.

The average primary particle size of the titanium oxide particles is 2 nm to 80 nm. When the average primary particle size of the titanium oxide particles is less than 2 nm, the surface area of each titanium oxide particle becomes too small, and it may be difficult to exhibit photocatalytic activity. Further, when the average primary particle diameter of the titanium oxide particles exceeds 80 nm, it becomes difficult to sufficiently atomize the titanium oxide particles in the dispersion treatment step described later. As a result, the titanium oxide particles may aggregate during the dispersion treatment step or storage after the dispersion treatment, and may easily precipitate. The average primary particle size of the titanium oxide particles can be determined by measuring the diameters of a plurality of titanium oxide particles using, for example, a transmission electron microscope (TEM).

The average primary particle size of the titanium oxide particles is preferably 5 nm to 50 nm, more preferably 5 nm to 30 nm. With such an average primary particle size, it is possible to highly disperse the titanium oxide particles in an organic solvent while maintaining a high surface area.

Further, the copper composite titanium oxide dispersion of the present embodiment contains cuprous oxide particles in addition to the above-mentioned titanium oxide particles. Here, many copper compounds exhibiting antibacterial activity have been reported in the past, but compared with copper (II) oxide (CuO), copper (I) oxide (copper oxide, Cu) has been reported.₂O) has high antibacterial activity and antiviral activity. That is, since cuprous oxide easily elutes copper ions, when the eluted copper ions come into contact with microorganisms, they bind to enzymes and proteins to reduce their activity and easily inhibit the metabolic function of microorganisms. Furthermore, the catalytic action of the eluted copper ions activates oxygen in the air, making it easier to decompose organic matter of microorganisms. Therefore, it is preferable to use particles made of copper (I) oxide as the cuprous oxide particles.

The average primary particle size of the cuprous oxide particles is 2 nm to 80 nm. When the average primary particle size of the cuprous oxide particles is less than 2 nm, the surface area of each cuprous oxide particle becomes too small, and copper ions may be difficult to elute. Further, when the average primary particle size of the cuprous oxide particles exceeds 80 nm, it becomes difficult to sufficiently atomize the particles in the dispersion treatment step described later. As a result, the cuprous oxide particles may agglomerate during the dispersion treatment step or storage after the dispersion treatment, and may easily precipitate. The average primary particle size of the cuprous oxide particles can be determined by using a transmission electron microscope in the same manner as the titanium oxide particles.

The average primary particle size of the cuprous oxide particles is preferably 10 nm to 70 nm, more preferably 30 nm to 60 nm. With such an average primary particle size, it is possible to highly disperse the cuprous oxide particles in an organic solvent while maintaining a high surface area.

The copper composite titanium oxide dispersion of the present embodiment contains a phosphate ester type anionic surfactant in order to improve the dispersibility of the titanium oxide particles and the cuprous oxide particles in the organic solvent. By using the phosphoric acid ester type anionic surfactant, it is possible to enhance the dispersibility while suppressing the deterioration of the antibacterial property and the antiviral property of the titanium oxide particles and the cuprous oxide particles. Examples of the phosphoric acid ester type anionic surfactant include alkyl phosphate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether phosphate and the like. More specifically, alkyl phosphoric acid ester, polyoxyethylene alkyl ether phosphoric acid ester, polyoxyethylene (mono or di) alkyl phenyl ether phosphoric acid ester can be mentioned. Examples thereof include a phosphoric acid ester of a polymer of polyoxyethylene (mono, di or tri) alkyl phenyl ether, and a polyoxyethylene (mono, di or tri) phenyl phenyl ether phosphoric acid ester. Further, polyoxyethylene (mono, di or tri) benzyl phenyl ether phosphoric acid ester and polyoxyethylene (mono, di or tri) styryl phenyl ether phosphoric acid ester can be mentioned. Further, a phosphoric acid ester of a polymer of polyoxyethylene (mono, di or tri) styrylphenyl ether and a phosphoric acid ester of a polyoxyethylene polyoxypropylene block polymer can also be mentioned. Phosphate esters such as phosphatidylcholine, phosphatidylethanolimine and condensed phosphoric acid (eg, tripolyphosphoric acid, etc.) can also be mentioned. Further, the salt of the above-mentioned phosphoric acid ester can be mentioned. One type of phosphoric acid ester type anionic surfactant may be used alone, or two or more types may be used in combination.

The organic solvent as the dispersion medium of the titanium oxide particles and the cuprous oxide particles is not particularly limited, but it is preferable to appropriately select a solvent that easily volatilizes during the formation of the coating film and does not cause curing inhibition during the formation of the coating film. Examples of the organic solvent include aromatic hydrocarbons (toluene, xylene, etc.), alcohols (methanol, ethanol, isopropyl alcohol, etc.), and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Further, aliphatic hydrocarbons (hexane, heptane, etc.), ethers (tetrahydrofuran, etc.), amide solvents (N, N-dimethylformamide (DMF), dimethylacetamide (DMAc), etc.) can be mentioned. Of these, aromatic hydrocarbons and alcohols are preferred. These organic solvents may be used alone or in combination of two or more.

The amount of the sub-copper oxide particles added to the copper composite titanium oxide dispersion can be appropriately adjusted depending on the content of the titanium oxide particles. Specifically, the amount of cuprous oxide particles is 0.1 to 20 parts by mass with respect to 100 parts by mass of titanium oxide particles. If the amount of cuprous oxide particles is less than 0.1 parts by mass, the effect of adding the cuprous oxide particles is not recognized, and the antibacterial property may not be sufficiently improved. Further, when the cuprous oxide particles exceed 20 parts by mass, the hardness of the coating agent composition described later may decrease.

The amount of cuprous oxide particles added is more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of titanium oxide particles. With such an addition amount, high antibacterial and antiviral properties can be exhibited due to the synergistic effect of the titanium oxide particles and the cuprous oxide particles. Further, the dispersibility of the titanium oxide particles and the cuprous oxide particles in the coating agent composition is improved, and the hardness of the coating agent composition can be increased.

The amount of the phosphoric acid ester-type anionic surfactant added to the copper composite titanium oxide dispersion can be appropriately adjusted by the total content of the titanium oxide particles and the cuprous oxide particles. Specifically, the amount of the phosphoric acid ester type anionic surfactant is 5 to 100 parts by mass with respect to 100 parts by mass of the total of the titanium oxide particles and the cuprous oxide particles. If the amount of the phosphoric acid ester type anionic surfactant is less than 5 parts by mass, the titanium oxide particles and / or the cuprous oxide particles may aggregate with each other, and sufficient dispersibility may not be obtained. Further, when the phosphoric acid ester type anionic surfactant exceeds 100 parts by mass, curing inhibition may occur when the film is formed by mixing with the binder resin as described later. Further, if it exceeds 100 parts by mass, the physical characteristics of the film such as film forming property and adhesion may be deteriorated.

The amount of the phosphoric acid ester-type anionic surfactant added is more preferably 5 to 90 parts by mass with respect to 100 parts by mass in total of the titanium oxide particles and the cuprous oxide particles. With such an addition amount, it is possible to suppress deterioration of film physical characteristics while improving the dispersibility of titanium oxide particles and cuprous oxide particles.

The amount of the organic solvent added to the copper composite titanium oxide dispersion can also be appropriately adjusted depending on the total content of the titanium oxide particles and the cuprous copper oxide particles. Specifically, the amount of the organic solvent is 300 to 2000 parts by mass with respect to 100 parts by mass of the total of titanium oxide particles and cuprous oxide particles. If the amount of the organic solvent is less than 300 parts by mass, the dispersibility of the titanium oxide particles and the cuprous copper oxide particles will decrease, and the viscosity of the copper composite titanium oxide dispersion will increase, which may reduce the efficiency of the coating operation. .. Further, when the amount of the organic solvent exceeds 2000 parts by mass, when the film is formed by mixing with the binder resin, the film-forming property (drying property) of the film may be lowered, and the work efficiency may be lowered.

The amount of the organic solvent added is more preferably 500 to 1800 parts by mass with respect to 100 parts by mass in total of the titanium oxide particles and the cuprous oxide particles. With such an addition amount, it is possible to suppress an excessive increase in viscosity while improving the dispersibility of the titanium oxide particles and the cuprous oxide particles.

As will be described later, the copper composite titanium oxide dispersion of the present embodiment becomes a coating agent composition by mixing with a binder resin, and further, by applying the coating agent composition to a base material, antibacterial and antibacterial. It becomes a viral film. From the viewpoint of enhancing the transparency of the coating film, the average secondary particle size of the titanium oxide particles and the sub-copper oxide particles in the copper composite titanium oxide dispersion must be 50 nm to 150 nm. When the average secondary particle size is less than 50 nm, the primary particles whose crystal structure is destroyed and the dispersed secondary particles coexist due to excessive dispersion treatment, and the photocatalytic activity and antibacterial property are deteriorated. It may decrease. Further, when the average secondary particle size exceeds 150 nm, the surface areas of the titanium oxide particles and the cuprous oxide particles may decrease, and the photocatalytic activity and antibacterial properties may decrease. In this specification, the average secondary particle size of the titanium oxide particles and the cuprous oxide particles is measured by a dynamic light scattering method, and the average secondary particle size obtained by a cumulant analysis method is adopted.

Further, in the copper composite titanium oxide dispersion liquid of the present embodiment, 10 parts by mass or more of the titanium oxide particles are contained in 100 parts by mass of the heating residue of the copper composite titanium oxide dispersion liquid. When the content of titanium oxide particles in 100 parts by mass of the total heating residue is less than 10 parts by mass, the solvent component of the coating agent composition becomes excessive when mixed with the binder resin. Therefore, the amount of titanium oxide particles blended in the coating agent composition may decrease, and it may be difficult to ensure high antibacterial properties. Further, if the solvent component becomes excessive, dripping or the like may occur at the time of coating the coating agent composition, resulting in an appearance abnormality, and further, there is a possibility that the physical properties may be deteriorated due to the inability to obtain a sufficient film thickness. The upper limit of the content of titanium oxide particles in the copper composite titanium oxide dispersion is not particularly limited as long as the transparency of the obtained film is ensured. For example, 100 parts by mass of the heating residue of the copper composite titanium oxide dispersion is used. It can be 50 parts by mass or less.

The heating residue in this specification can be measured in accordance with Japanese Industrial Standard JIS K5601-1-2 (Paint component test method-Part 1: General rules-Section 2: Heating residue). Then, the contents of titanium oxide and cuprous oxide can be determined by elemental analysis from the heating residue.

As described above, the copper composite titanium oxide dispersion of the present embodiment contains titanium oxide particles, cuprous oxide particles, a phosphate ester type anionic surfactant, and an organic solvent. The cuprous oxide particles are contained in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the titanium oxide particles. Further, the phosphate ester type anionic surfactant is contained in an amount of 5 to 100 parts by mass and the organic solvent is contained in an amount of 300 to 2000 parts by mass with respect to 100 parts by mass of the titanium oxide particles and the cuprous oxide particles in total. Further, in the copper composite titanium oxide dispersion, the titanium oxide particles and the cuprous oxide particles have an average primary particle size of 2 nm to 80 nm, and are measured by a dynamic light scattering method and obtained by a cumulant analysis method. Is 50 nm to 150 nm. The titanium oxide particles are contained in 10 parts by mass or more in 100 parts by mass of the heating residue of the copper composite titanium oxide dispersion liquid. With such a configuration, even when the concentrations of titanium oxide particles and cuprous oxide particles are increased, the dispersibility of these particles can be maintained in a high state, and therefore antibacterial and antiviral properties using these particles can be maintained. It is possible to ensure the transparency of the coating film. Further, since it contains not only titanium oxide particles but also cuprous oxide particles, it is possible to obtain high antibacterial and antiviral properties.

[Manufacturing method of copper composite titanium oxide dispersion] Next, a method for producing a copper composite titanium oxide dispersion will be described. The copper composite titanium oxide dispersion liquid is a mixture of the above-mentioned titanium oxide particles, cuprous oxide particles, a phosphate ester type anionic surfactant and an organic solvent, and the titanium oxide particles and the cuprous oxide particles are highly dispersed in the organic solvent. This makes it possible to prepare. Therefore, any method that can highly disperse the titanium oxide particles and the cuprous oxide particles can be used. However, in order to improve the dispersibility of the titanium oxide particles and the cuprous oxide particles, the titanium oxide particle dispersion liquid and the cuprous oxide particle dispersion liquid are individually prepared, and then these dispersions are mixed to obtain copper. It is preferable to obtain a composite titanium oxide dispersion.

&lt;Titanium oxide particle dispersion&gt; The titanium oxide particle dispersion liquid contains the above-mentioned titanium oxide particles, a phosphoric acid ester type anionic surfactant, and an organic solvent. Then, the titanium oxide particle dispersion liquid can be prepared by mixing the above-mentioned titanium oxide particles, the phosphoric acid ester type anionic surfactant and the organic solvent, and highly dispersing the titanium oxide particles in the organic solvent. is there. Therefore, as a method for producing the titanium oxide particle dispersion liquid, any method can be used as long as it is possible to highly disperse the titanium oxide particles.

However, from the viewpoint of enhancing the dispersibility of the titanium oxide particles and facilitating the transparency of the antibacterial / antiviral coating, it is preferable that the dispersal step of the titanium oxide particles is divided into a pre-dispersion treatment and a main dispersion treatment. .. As a result, the surface of the titanium oxide particles becomes wet and the air layer on the surface is replaced with the organic solvent, so that the dispersion proceeds rapidly in the subsequent main dispersion treatment. If this pre-dispersion treatment is insufficient, the progress of dispersion is slow, and there is a risk that unnecessary mechanical impact will be given to the titanium oxide particles. As a result, the crystal structure itself of the titanium oxide particles may be destroyed, resulting in a dispersion having reduced stability.

The pre-dispersion treatment can be performed by stirring with a general dissolver. However, from the viewpoint of making the surface of the titanium oxide particles easy to get wet, it is preferable to stir with a high-speed stirrer. As the high-speed stirrer, for example, TK homomixer, TK Robomix and TK Philmix (trade name, manufactured by Primix Corporation) can be used. In addition, Clairemix (registered trademark) (trade name, manufactured by M-Technique Co., Ltd.) and Ultra Disper (trade name, manufactured by Asada Iron Works Co., Ltd.) can also be used.

Dispersing devices that perform this dispersion processing include, for example, kneader, two-roll, three-roll, SS5 (trade name, M-Technique Co., Ltd.), Miracle KCK (registered trademark) (trade name, manufactured by Asada Iron Works Co., Ltd.). You can use a kneading machine such as. Examples thereof include an ultrasonic disperser, a high-pressure homogenizer Microfluidizer (trade name, manufactured by Mizuho Kogyo Co., Ltd.), and NanoVeta (registered trademark) (trade name, manufactured by Yoshida Kikai Kogyo Co., Ltd.). Further, Starburst (registered trademark) (trade name, Sugino Machine Limited), G-smasher (trade name, RIX Corporation) and the like can be mentioned. For those using bead media such as glass and zircon, ball mills, bead mills, sand mills, horizontal media mill dispersers, colloid mills and the like can be used. As the medium used in the bead mill, bead media having a diameter of 1 mm or less is preferable, and bead media having a diameter of 0.5 mm or less is more preferable. The dispersion time of the pre-dispersion treatment and the main dispersion treatment may be appropriately adjusted by each dispersion device or media so that the titanium oxide particles are highly dispersed in the organic solvent together with the phosphate ester type anionic surfactant.

Further, when the pre-dispersion treatment liquid is supplied to the dispersion device, the treatment can be performed in a shorter time by supplying the treatment liquid with sufficient stirring using a high-speed stirrer or the like. ..

Here, the amount of the phosphoric acid ester-type anionic surfactant added to the titanium oxide particle dispersion can be appropriately adjusted depending on the content of the titanium oxide particles. Specifically, the amount of the phosphoric acid ester type anionic surfactant is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the titanium oxide particles. If the amount of the phosphoric acid ester type anionic surfactant is less than 1 part by mass, the titanium oxide particles may aggregate with each other and sufficient dispersibility may not be obtained. If the amount of the phosphoric acid ester-type anionic surfactant exceeds 30 parts by mass, it may cause hardening inhibition when the film is formed by mixing with the cuprous oxide particle dispersion liquid and the binder resin as described later. .. Further, if it exceeds 30 parts by mass, the physical characteristics of the film such as film forming property and adhesion may be deteriorated.

The amount of the phosphoric acid ester-type anionic surfactant added is more preferably 10 to 25 parts by mass with respect to 100 parts by mass of the titanium oxide particles. With such an addition amount, it is possible to suppress the deterioration of the physical characteristics of the film while improving the dispersibility of the titanium oxide particles.

The amount of the organic solvent added to the titanium oxide particle dispersion can also be appropriately adjusted depending on the content of the titanium oxide particles. Specifically, the amount of the organic solvent is preferably 500 to 2000 parts by mass with respect to 100 parts by mass of the titanium oxide particles. If the amount of the organic solvent is less than 500 parts by mass, the dispersibility of the titanium oxide particles may decrease. Further, when the amount of the organic solvent exceeds 2000 parts by mass, when the film is formed by mixing with the cuprous oxide particle dispersion liquid and the binder resin, the film forming property (drying property) of the film is lowered and the work efficiency is lowered. There is a risk of

The amount of the organic solvent added is more preferably 500 to 1000 parts by mass with respect to 100 parts by mass of the titanium oxide particles. With such an addition amount, it is possible to suppress an excessive increase in viscosity while improving the dispersibility of the titanium oxide particles.

As will be described later, the titanium oxide particle dispersion liquid of the present embodiment becomes a coating agent composition by mixing with the cuprous oxide particle dispersion liquid and the binder resin, and the coating agent composition is further applied to the base material. As a result, it becomes an antibacterial / antiviral coating. From the viewpoint of enhancing the transparency of the coating film, the average secondary particle size of the titanium oxide particles in the titanium oxide particle dispersion liquid needs to be 50 nm to 150 nm. If the average secondary particle size is less than 50 nm, the primary particles whose crystal structure has been destroyed and the dispersed secondary particles coexist due to excessive dispersion treatment, and the photocatalytic activity may decrease. There is. Further, when the average secondary particle size exceeds 150 nm, the surface area of the titanium oxide particles may decrease, and the photocatalytic activity (antibacterial property) may decrease.

Further, in the titanium oxide particle dispersion liquid of the present embodiment, it is preferable that the titanium oxide particles are contained in 10 parts by mass or more in 100 parts by mass of the heating residue of the titanium oxide particle dispersion liquid. When the content of titanium oxide particles in 100 parts by mass of the total heating residue is less than 10 parts by mass, the solvent component of the coating agent composition becomes excessive when mixed with the cuprous oxide particle dispersion liquid and the binder resin. .. Therefore, the amount of titanium oxide particles blended in the coating agent composition may decrease, and it may be difficult to ensure high antibacterial properties. Further, if the solvent component becomes excessive, dripping or the like may occur at the time of coating the coating agent composition, resulting in an appearance abnormality, and further, there is a possibility that the physical properties may be deteriorated due to the inability to obtain a sufficient film thickness. The content of titanium oxide particles in the titanium oxide particle dispersion is not particularly limited as long as the transparency of the obtained film is ensured. For example, 50 mass in 100 parts by mass of the heating residue of the titanium oxide particle dispersion. It can be less than or equal to a part.

&lt;Copper oxide particle dispersion&gt; The cuprous oxide particle dispersion liquid contains the above-mentioned cuprous oxide particles, a phosphoric acid ester type anionic surfactant, and an organic solvent. Then, the cuprous oxide particle dispersion liquid is prepared by mixing the above-mentioned cuprous oxide particles, a phosphoric acid ester type anionic surfactant and an organic solvent, and highly dispersing the cuprous oxide particles in the organic solvent. Is possible. Therefore, any method that can highly disperse the cuprous oxide particles can be used. However, from the viewpoint of enhancing the dispersibility of the cuprous oxide particles and facilitating the transparency of the antibacterial / antiviral coating, the dispersion step of the cuprous oxide particles is a pre-dispersion treatment similar to the titanium oxide particle dispersion. It is preferable to perform this dispersion processing separately. As a result, the surface of the cuprous oxide particles becomes wet and the air layer on the surface is replaced with the organic solvent, so that the dispersion proceeds rapidly in the subsequent main dispersion treatment.

Here, the amount of the phosphoric acid ester-type anionic surfactant added to the cuprous oxide particle dispersion can be appropriately adjusted depending on the content of the cuprous oxide particles. Specifically, the amount of the phosphoric acid ester type anionic surfactant is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the cuprous oxide particles. If the amount of the phosphoric acid ester type anionic surfactant is less than 10 parts by mass, the cuprous oxide particles may aggregate with each other and sufficient dispersibility may not be obtained. If the amount of the phosphate ester-type anionic surfactant exceeds 100 parts by mass, it may cause curing inhibition when mixed with the titanium oxide particle dispersion and the binder resin to form a film. Further, if it exceeds 100 parts by mass, the physical characteristics of the film such as film forming property and adhesion may be deteriorated.

The amount of the phosphoric acid ester-type anionic surfactant added is more preferably 20 to 90 parts by mass and particularly preferably 30 to 70 parts by mass with respect to 100 parts by mass of the cuprous oxide particles. With such an addition amount, it is possible to suppress the deterioration of the film physical properties while improving the dispersibility of the cuprous oxide particles.

The amount of the organic solvent added to the cuprous oxide particle dispersion can also be appropriately adjusted depending on the content of the cuprous oxide particles. Specifically, the amount of the organic solvent is preferably 500 to 10000 parts by mass with respect to 100 parts by mass of the cuprous oxide particles. If the amount of the organic solvent is less than 500 parts by mass, the dispersibility of the cuprous oxide particles is lowered, and the viscosity of the cuprous oxide particle dispersion is increased, which may lower the efficiency of the coating operation. Further, when the amount of the organic solvent exceeds 10,000 parts by mass, when the film is formed by mixing with the titanium oxide particle dispersion liquid and the binder resin, the film forming property (drying property) of the film is lowered and the work efficiency is lowered. There is a fear.

The amount of the organic solvent added is more preferably 1000 to 5000 parts by mass with respect to 100 parts by mass of the cuprous oxide particles. With such an addition amount, it is possible to suppress an excessive increase in viscosity while improving the dispersibility of the cuprous oxide particles.

As will be described later, the cuprous oxide particle dispersion liquid of the present embodiment becomes a coating agent composition by mixing with the titanium oxide particle dispersion liquid and the binder resin, and further, by applying the coating agent composition to the base material. , Antibacterial and antiviral coating. From the viewpoint of enhancing the transparency of the coating film, the average secondary particle size of the cuprous oxide particles in the cuprous oxide particle dispersion liquid needs to be 50 nm to 150 nm. If the average secondary particle size is less than 50 nm, the primary particles whose crystal structure has been destroyed due to excessive dispersion treatment and the dispersed secondary particles coexist, which may reduce antibacterial properties. There is. Further, when the average secondary particle size exceeds 150 nm, the surface area of the cuprous oxide particles may decrease, and the antibacterial property may decrease.

&lt;Copper composite titanium oxide dispersion&gt; The copper composite titanium oxide dispersion liquid of the present embodiment can be obtained by mixing the titanium oxide particle dispersion liquid and the cuprous copper oxide particle dispersion liquid obtained as described above so as to have the above-mentioned addition amounts. .. When mixing the titanium oxide particle dispersion liquid and the cuprous oxide particle dispersion liquid, the above-mentioned high-speed stirrer can be used.

[Coating agent composition] The coating agent composition according to the present embodiment contains the above-mentioned copper composite titanium oxide dispersion and a binder resin. As described above, in the copper composite titanium oxide dispersion liquid of the present embodiment, titanium oxide and cuprous oxide coexist, and their dispersibility is further enhanced. Therefore, a coating agent composition using such a copper composite titanium oxide dispersion can form a film having high antibacterial / antiviral properties and high transparency.

The binder resin mixed with the copper composite titanium oxide dispersion is not particularly limited as long as the stability, antibacterial / antiviral property and transparency of the film obtained from the coating agent composition are ensured. As the binder resin, for example, an alkyd resin, an acrylic resin, a melamine resin, a urethane resin, an epoxy resin, a silicon resin, or the like can be used. Further, polyester resin, polyamic acid resin, polyimide resin, styrene maleic acid resin, styrene maleic anhydride resin and the like can also be used. Further, various acrylic acid-based monomers and acrylate-based monomers can also be applied. Particularly preferable resins and monomers as the binder resin include urethane resin, acrylic resin, acrylic monomer, polyamic acid resin, polyimide resin, styrene maleic acid resin, and styrene maleic anhydride resin. As the binder resin, one type may be used alone, or two or more types may be used in combination.

Further, the binder resin preferably has at least one of an alkyl group having 5 to 23 carbon atoms and an aromatic ring as a functional group. When a binder resin having such a functional group is used, lipophilicity can be imparted to the film surface of the antibacterial / antiviral member. As a result, when a lipid component such as a fingerprint adheres to the coating film, the lipid component easily diffuses on the interface of the lipophilic coating surface. As a result, the stains caused by the attached lipid component can be made inconspicuous, or the stains can be made inconspicuous.

As described above, when the binder resin has an alkyl group, the alkyl group preferably contains 5 to 23 carbon atoms. Even if the number of carbon atoms is out of this range, lipophilicity can be imparted and the above effects can be exhibited. However, if the alkyl group has less than 5 carbon atoms, the lipophilicity may be slightly insufficient. Further, when the number of carbon atoms exceeds 23, the handleability of the binder resin deteriorates, and it may be difficult to obtain a coating agent composition having stable performance. When the binder resin has an aromatic ring as a functional group, the aromatic ring is not particularly limited, and a phenyl group, an aminophenyl group, or the like can be used.

Further, the binder resin may contain chlorinated polyolefin in addition to the above resin. As will be described later, the base material on which the coating agent composition is applied is not particularly limited. However, since polyolefins such as polyethylene and polypropylene have low surface free energy, the adhesiveness of the coating film made of the above coating agent composition may decrease. However, by containing the chlorinated polyolefin as the binder resin, it is possible to improve the adhesiveness to the polyolefin substrate.

The content of the chlorinated polyolefin is preferably 20 to 50 parts by mass, more preferably 30 to 40 parts by mass in 100 parts by mass of the binder component. When the content of the chlorinated polyolefin is within this range, it is possible to enhance the long-term storage stability of the coating agent composition and the mechanical strength and adhesion of the coating film composed of the coating agent composition.

Here, the chlorine content in 100 parts by mass of the chlorinated polyolefin is preferably 20 to 30 parts by mass, and more preferably 25 to 30 parts by mass. When an acrylic resin and a chlorinated polyolefin are used as the binder resin, the chlorine content is within the above range, so that the viscosity does not increase or gelled products are less likely to be formed during storage, and a stable coating agent composition is obtained. It becomes possible to obtain things. In addition, there is a tendency for the adhesion performance to polyolefins such as polyethylene and polypropylene to be improved.

Examples of the chlorinated polyolefin that can be contained in the binder resin include chlorinated polyethylene, chlorinated polypropylene, chlorinated polybutadiene, chlorinated ethylene-propylene copolymer, and chlorinated ethylene-vinyl acetate copolymer. These chlorinated polyolefins may be used alone or in combination of two or more.

Further, the coating agent composition may contain various additives in addition to the copper composite titanium oxide dispersion and the binder resin as long as the antibacterial activity is not affected. Specifically, a dispersant, a pigment, a filler, an aggregate, a thickener, a flow control agent, a leveling agent, a curing agent, a cross-linking agent, a curing catalyst and the like can be blended.

The coating agent composition according to the present embodiment can be prepared by mixing the above-mentioned copper composite titanium oxide dispersion and the binder resin, and if necessary, the above-mentioned additives. In the mixing step, for example, it is possible to mix using the above-mentioned dissolver or high-speed stirrer.

In the coating agent composition, the titanium oxide particles are preferably contained in an amount of 10 to 80 parts by mass in 100 parts by mass of the heating residue of the coating agent composition. If the content of titanium oxide particles in the heating residue is less than 10 parts by mass, the antibacterial property may decrease. In addition, the hardness of the coating film may decrease. When the content of the titanium oxide particles exceeds 80 parts by mass, it is possible to obtain sufficient antibacterial properties, but the physical properties of the film may deteriorate due to the lack of the binder resin. In addition, the transparency of the coating may be reduced.

The content of titanium oxide particles in the coating agent composition is more preferably 30 to 70 parts by mass, particularly preferably 40 to 60 parts by mass in 100 parts by mass of the heating residue of the coating agent composition. preferable. When the content of the titanium oxide particles is within this range, it is possible to suppress the deterioration of the physical characteristics of the film and ensure high transparency while having sufficient antibacterial and antiviral properties.

The content of the cuprous oxide particles in the coating agent composition is more preferably 0.1 to 10 parts by mass, particularly preferably 0.1 to 5 parts by mass in 100 parts by mass of the heated residue of the coating agent composition. .. When the content of the cuprous oxide particles is within this range, the synergistic effect with the titanium oxide particles provides sufficient antibacterial and antiviral properties, while suppressing deterioration of the physical properties of the film and ensuring high transparency. It becomes possible to do.

[Antibacterial / antiviral member] The antibacterial / antiviral member according to the present embodiment has a base material and a coating film provided on the base material and containing the coating agent composition. As described above, the coating agent composition of the present embodiment has antifouling and deodorant effects as well as high antibacterial and antiviral properties due to the titanium oxide particles and cuprous oxide particles. Further, since the titanium oxide particles and the cuprous oxide particles are highly dispersed in the coating agent composition, the obtained coating film also has high transparency.

In the present embodiment, the material of the base material may be basically anything such as an organic polymer, ceramic, metal, glass, plastic, decorative plywood or a composite thereof. The shape of the base material is also not particularly limited, and may be a simple shape or a complicated shape such as a plate-shaped object, a spherical object, a columnar object, a cylindrical object, a rod-shaped object, a prismatic object, or a hollow prismatic object. Good. Further, the base material may be a porous material such as a filter.

Base materials include ceiling materials, tiles, glass, wallpaper, wall materials, floor and construction materials and other building materials, automobile interior materials (instrument panels, seats, ceiling materials), home appliances such as refrigerators and air conditioners, and clothing. , Textile products such as curtains, industrial equipment, medical equipment, etc. are preferable. Further, as the base material, for example, doors, door handles, pullers, handrails, interior counters, furniture, kitchens, toilets, baths, lighting fixtures, touch panels, switches, and sheets used for these purposes are also preferable. Since the coating film made of the coating agent composition of the present embodiment has high antibacterial and antiviral properties, it is particularly effective for such surfaces that the human body or the like frequently comes into contact with.

Further, the antibacterial / antiviral member according to the present embodiment can also be applied as, for example, a filter for an air purifier or a filter for an air conditioner. And by using it not only in houses but also in hospitals and facilities for the elderly, and in places used by an unspecified number of people such as public transportation such as trains, buses and airplanes, the risk of infection with bacteria and viruses is reduced. It is possible and useful.

The antibacterial / antiviral member according to the present embodiment can be obtained by applying a coating agent composition to a base material and drying it. The coating method and drying conditions at this time are not particularly limited. As a method of applying the coating agent composition to at least a part of the base material, methods such as screen printing, spin coating, dip coating, roll coating, brush coating, spray coating, and inkjet can be used. The drying conditions are not particularly limited as long as the organic solvent is removed.

If necessary, after the coating agent composition has dried, further ultraviolet irradiation may be performed. This makes it possible to cure the obtained film and increase its hardness.

The thickness of the coating film of the coating agent composition is preferably 2 μm to 15 μm, more preferably 4 μm to 13 μm as the film thickness after curing. When the film thickness of the film after curing is within this range, it is possible to improve the adhesion while improving the surface hardness of the film.

As described above, the antibacterial / antiviral member of the present embodiment has a base material and a coating film provided on the base material and containing the coating agent composition. Then, in the coating agent composition, nano-level titanium oxide particles and cuprous oxide particles are dispersed at a high concentration. Therefore, it is possible to secure high antibacterial and antiviral properties due to the titanium oxide particles and cuprous oxide particles, and also to obtain transparency.

Further, the binder resin contained in the coating film of the antibacterial / antiviral member may have at least one of an alkyl group having 5 to 23 carbon atoms and an aromatic ring as a functional group. When the binder resin has such a lipophilic group, stains caused by lipid components such as fingerprints can be made inconspicuous or stains can be made inconspicuous, and an antibacterial / antiviral member having excellent fingerprint resistance. Can be provided. In this case, the film preferably has a static contact angle with respect to oleic acid of 30 degrees or less, and particularly preferably 15 degrees or less. The lower limit of the static contact angle with respect to oleic acid is not particularly limited, but is preferably 1 degree or more.

Further, the binder resin contained in the coating film of the antibacterial / antiviral member may contain chlorinated polyolefin. By containing the chlorinated polyolefin, it is not necessary to perform a pretreatment such as coating a primer or the like on a base material such as polyolefin having poor adhesion, and the coating agent composition is directly applied to the base material. It becomes possible.

<p num="0077"> Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.</p><p num="0078">[Example 1] &lt;Preparation of titanium oxide particle dispersion&gt; First, ST-01 (average primary particle size: 7 nm, crystal structure: anatase) manufactured by Ishihara Sangyo Co., Ltd. was prepared as titanium oxide particles, and methyl ethyl ketone (MEK) was prepared as an organic solvent. Furthermore, DISPARLON (registered trademark) PW-36 manufactured by Kusumoto Kasei Co., Ltd. was prepared as a phosphoric acid ester type anionic surfactant.</p><p num="0079"> Next, 100 parts by mass of the titanium oxide particles, 800 parts by mass of methyl ethyl ketone, and 10 parts by mass of the phosphate ester type anionic surfactant were mixed, and as a predispersion treatment, stirring was performed at 8000 rpm for 30 minutes using a stirrer. As the stirrer, TK Robomix manufactured by Primix Corporation was used.</p><p num="0080"> After that, 1 L of the treatment liquid obtained by the pre-dispersion treatment was stirred at 3000 rpm using a stirrer (TK Robomix manufactured by Primix Corporation), and then subsequently, the book was prepared using a disperser (Picomill manufactured by Asada Iron Works Co., Ltd.). Distributed processing was performed. As the dispersion medium of the disperser, 0.3 mm zirconia beads were used, and the dispersion treatment was performed by circulating for 2 hours. As a result, a titanium oxide particle dispersion having a titanium oxide concentration of 11% by mass was prepared.</p><p num="0081"> &lt;Preparation of cuprous oxide particle dispersion&gt; First, cuprous oxide (average primary particle size: 50 nm, CuO reduction) manufactured by Sigma Aldrich Co., Ltd. was prepared as the cuprous oxide particles, and methyl ethyl ketone (MEK) was prepared as the organic solvent. Furthermore, DISPARLON PW-36 manufactured by Kusumoto Kasei Co., Ltd. was prepared as a phosphoric acid ester type anionic surfactant.</p><p num="0082"> Next, 100 parts by mass of the above cuprous oxide particles, 2500 parts by mass of methyl ethyl ketone, and 50 parts by mass of the phosphate ester type anionic surfactant were mixed, and as a predispersion treatment, stirring was performed at 8000 rpm for 30 minutes using a stirrer. .. As the stirrer, TK Robomix manufactured by Primix Corporation was used.</p><p num="0083"> After that, 1 L of the treatment liquid obtained by the pre-dispersion treatment was stirred at 3000 rpm using a stirrer (TK Robomix manufactured by Primix Corporation), and then subsequently, the book was prepared using a disperser (Picomill manufactured by Asada Iron Works Co., Ltd.). Distributed processing was performed. As the dispersion medium of the disperser, 0.3 mm zirconia beads were used, and the dispersion treatment was performed by circulating for 2 hours. As a result, a cuprous oxide particle dispersion having a cuprous oxide concentration of 4% by mass was prepared.</p><p num="0084"> &lt;Preparation of coating agent composition&gt; Then, 455 parts by mass of the obtained titanium oxide particle dispersion, 27 parts by mass of the cuprous oxide particle dispersion, and 245 parts by mass of the binder resin are mixed and stirred using a stirrer to form the coating agent composition of this example. The thing was prepared. The following resin was used as the binder resin.</p><p num="0085"> First, Acrydic (registered trademark) A801 (manufactured by DIC Corporation) and Duranate (registered trademark) TPA100 (manufactured by Asahi Kasei Chemicals Co., Ltd.) as acrylic resins for isocyanate curing are used, and the isocyanate group and hydroxyl group are NCO / OH = 1. It was mixed so as to be. Next, a binder resin was prepared by diluting this mixture with methyl ethyl ketone so that the heating residue was 20% by mass.</p><p num="0086">[Example 2] A titanium oxide particle dispersion was prepared in the same manner as in Example 1 except that 100 parts by mass of titanium oxide particles, 1800 parts by mass of methyl ethyl ketone, and 10 parts by mass of a phosphate ester type anionic surfactant were mixed. The titanium oxide concentration in the titanium oxide particle dispersion was 5% by mass.</p><p num="0087"> Further, 955 parts by mass of the titanium oxide particle dispersion, 27 parts by mass of the cuprous oxide particle dispersion obtained in Example 1, and 245 parts by mass of the binder resin were mixed in the same manner as in Example 1 to obtain the present example. A coating composition was prepared.</p><p num="0088">[Example 3] A titanium oxide particle dispersion was prepared in the same manner as in Example 1 except that 100 parts by mass of titanium oxide particles, 300 parts by mass of methyl ethyl ketone, and 10 parts by mass of a phosphate ester type anionic surfactant were mixed. The titanium oxide concentration in the titanium oxide particle dispersion was 24% by mass.</p><p num="0089"> Further, 205 parts by mass of the titanium oxide particle dispersion, 27 parts by mass of the cuprous oxide particle dispersion obtained in Example 1, and 245 parts by mass of the binder resin were mixed in the same manner as in Example 1 to obtain the present example. A coating composition was prepared.</p><p num="0090">[Example 4] A cuprous oxide particle dispersion was prepared in the same manner as in Example 1 except that 100 parts by mass of copper peroxide particles, 10,000 parts by mass of methyl ethyl ketone, and 50 parts by mass of a phosphate ester-type anionic surfactant were mixed. The copper oxide concentration in the cuprous oxide particle dispersion was 1% by mass.</p><p num="0091"> Further, 455 parts by mass of the titanium oxide particle dispersion obtained in Example 1, 102 parts by mass of the sub-copper oxide particle dispersion, and 245 parts by mass of the binder resin were mixed in the same manner as in Example 1 to obtain the present example. A coating composition was prepared.</p><p num="0092">[Example 5] A cuprous oxide particle dispersion was prepared in the same manner as in Example 1 except that 100 parts by mass of copper peroxide particles, 800 parts by mass of methyl ethyl ketone, and 50 parts by mass of a phosphate ester-type anionic surfactant were mixed. The copper oxide concentration in the cuprous oxide particle dispersion was 11% by mass.</p><p num="0093"> Further, 455 parts by mass of the titanium oxide particle dispersion obtained in Example 1, 10 parts by mass of the sub-copper oxide particle dispersion, and 245 parts by mass of the binder resin were mixed in the same manner as in Example 1 to obtain the present example. A coating composition was prepared.</p><p num="0094">[Example 6] A titanium oxide particle dispersion was prepared in the same manner as in Example 1 except that 100 parts by mass of titanium oxide particles, 800 parts by mass of methyl ethyl ketone, and 25 parts by mass of a phosphate ester type anionic surfactant were mixed. The titanium oxide concentration in the titanium oxide particle dispersion was 11% by mass.</p><p num="0095"> Further, 453 parts by mass of the titanium oxide particle dispersion, 27 parts by mass of the cuprous oxide particle dispersion obtained in Example 1, and 245 parts by mass of the binder resin were mixed in the same manner as in Example 1 to obtain the present example. A coating composition was prepared.</p><p num="0096">[Example 7] A titanium oxide particle dispersion was prepared in the same manner as in Example 1 except that 100 parts by mass of titanium oxide particles, 800 parts by mass of methyl ethyl ketone, and 5 parts by mass of a phosphate ester type anionic surfactant were mixed. The titanium oxide concentration in the titanium oxide particle dispersion was 11% by mass.</p><p num="0097"> Further, 453 parts by mass of the titanium oxide particle dispersion, 27 parts by mass of the cuprous oxide particle dispersion obtained in Example 1, and 245 parts by mass of the binder resin were mixed in the same manner as in Example 1 to obtain the present example. A coating composition was prepared.</p><p num="0098">[Example 8] A cuprous oxide particle dispersion was prepared in the same manner as in Example 1 except that 100 parts by mass of copper peroxide particles, 2500 parts by mass of methyl ethyl ketone, and 70 parts by mass of a phosphoric acid ester type anionic surfactant were mixed. The copper oxide concentration in the cuprous oxide particle dispersion was 4% by mass.</p><p num="0099"> Further, 455 parts by mass of the titanium oxide particle dispersion obtained in Example 1, 27 parts by mass of the sub-copper oxide particle dispersion, and 245 parts by mass of the binder resin were mixed in the same manner as in Example 1 to obtain the present example. A coating composition was prepared.</p><p num="0100">[Example 9] A cuprous oxide particle dispersion was prepared in the same manner as in Example 1 except that 100 parts by mass of copper peroxide particles, 2500 parts by mass of methyl ethyl ketone, and 20 parts by mass of a phosphoric acid ester type anionic surfactant were mixed. The copper oxide concentration in the cuprous oxide particle dispersion was 4% by mass.</p><p num="0101"> Further, 455 parts by mass of the titanium oxide particle dispersion obtained in Example 1, 26 parts by mass of the sub-copper oxide particle dispersion, and 245 parts by mass of the binder resin were mixed in the same manner as in Example 1 to obtain the present example. A coating composition was prepared.</p><p num="0102">[Example 10] The coating agent composition of this example was prepared in the same manner as in Example 1 except that 182 parts by mass of the titanium oxide particle dispersion, 27 parts by mass of the cuprous oxide particle dispersion, and 245 parts by mass of the binder resin were mixed. ..</p><p num="0103">[Example 11] The coating agent composition of this example was prepared in the same manner as in Example 1 except that 819 parts by mass of the titanium oxide particle dispersion, 27 parts by mass of the cuprous oxide particle dispersion, and 45 parts by mass of the binder resin were mixed. ..</p><p num="0104">[Example 12] The coating agent composition of this example was prepared in the same manner as in Example 1 except that 455 parts by mass of the titanium oxide particle dispersion, 13 parts by mass of the cuprous oxide particle dispersion, and 248 parts by mass of the binder resin were mixed. ..</p><p num="0105">[Example 13] The coating agent composition of this example was prepared in the same manner as in Example 1 except that 455 parts by mass of the titanium oxide particle dispersion, 212 parts by mass of the cuprous oxide particle dispersion, and 210 parts by mass of the binder resin were mixed. ..</p><p num="0106">[Example 14] 455 parts by mass of the titanium oxide particle dispersion and 27 parts by mass of the cuprous oxide particle dispersion obtained in Example 1 were mixed with 245 parts by mass of the binder resin. Next, this mixed solution was diluted with methyl ethyl ketone so that the heating residue was 20% by mass, and the mixture was stirred with a stirrer to prepare the coating agent composition of this example. As the binder resin, a mixture of 100 parts by mass of UV curable resin beam set 1461 manufactured by Arakawa Chemical Industry Co., Ltd. and 15 parts by mass of the photopolymerization initiator IRGACURE184 (manufactured by BASF) was used.</p><p num="0107">[Example 15] First, 15 parts by mass of Hardlen (registered trademark) 13-LP (manufactured by Toyo Boseki Co., Ltd., chlorine content: 26% by mass, solid content: 100%) as a chlorinated polyolefin and 85 parts by mass of methyl ethyl ketone as a solvent. The mixture was mixed to obtain a chlorinated polyolefin solution.</p><p num="0108"> Next, in addition to 455 parts by mass of the titanium oxide particle dispersion liquid of Example 1, 27 parts by mass of the cuprous oxide particle dispersion liquid, and 122.5 parts by mass of the binder resin, 122.5 parts by mass of the chlorinated polyolefin solution was mixed and stirred. Was stirred using. As a result, the coating agent composition of this example was prepared.</p><p num="0109">[Comparative example 1] A titanium oxide particle dispersion was prepared in the same manner as in Example 1 except that 100 parts by mass of titanium oxide particles, 2500 parts by mass of methyl ethyl ketone, and 10 parts by mass of a phosphate ester type anionic surfactant were mixed. The titanium oxide concentration in the titanium oxide particle dispersion was 4% by mass.</p><p num="0110"> Further, 1305 parts by mass of the titanium oxide particle dispersion liquid, 27 parts by mass of the cuprous oxide particle dispersion liquid obtained in Example 1, and 245 parts by mass of the binder resin were mixed in the same manner as in Example 1 to obtain the present example. A coating composition was prepared.</p><p num="0111">[Comparative example 2] First, titanium oxide particles, methyl ethyl ketone, and a phosphate ester-type anionic surfactant were prepared in the same manner as in Example 1. Next, 100 parts by mass of the titanium oxide particles, 800 parts by mass of methyl ethyl ketone, and 100 parts by mass of the phosphate ester type anionic surfactant were mixed, and as a predispersion treatment, stirring was performed at 8000 rpm for 30 minutes using a stirrer. As the stirrer, TK Robomix manufactured by Primix Corporation was used.</p><p num="0112"> Then, 1 L of the treatment liquid obtained by the pre-dispersion treatment was stirred at 3000 rpm using a stirrer (TK Robomix manufactured by Primix Corporation), and then subsequently, the book was prepared using a disperser (Picomill manufactured by Asada Iron Works Co., Ltd.). I tried to perform distributed processing. However, since the viscosity of the treatment liquid obtained by the pre-dispersion treatment did not decrease to the extent that it could be supplied to the disperser, the present dispersion treatment could not be carried out. Therefore, the titanium oxide particle dispersion cannot be prepared, and the coating agent composition of this example cannot be obtained.</p><p num="0113">[Comparative example 3] A cuprous oxide particle dispersion was prepared in the same manner as in Example 1 except that 100 parts by mass of copper peroxide particles, 15,000 parts by mass of methyl ethyl ketone, and 50 parts by mass of a phosphate ester-type anionic surfactant were mixed. The copper oxide concentration in the cuprous oxide particle dispersion was 1% by mass.</p><p num="0114"> Further, 455 parts by mass of the titanium oxide particle dispersion obtained in Example 1, 152 parts by mass of the sub-copper oxide particle dispersion, and 245 parts by mass of the binder resin were mixed in the same manner as in Example 1 to obtain the present example. A coating composition was prepared.</p><p num="0115">[Comparative example 4] First, as in Example 1, cuprous oxide particles, methyl ethyl ketone and a phosphate ester type anionic surfactant were prepared. Next, 100 parts by mass of the above cuprous oxide particles, 100 parts by mass of methyl ethyl ketone, and 50 parts by mass of the phosphate ester type anionic surfactant were mixed, and a stirrer (TK Robomix manufactured by Primix Corporation) was used as a predispersion treatment. Stirring was performed at 8000 rpm for 30 minutes.</p><p num="0116"> After that, 1 L of the treatment liquid obtained by the pre-dispersion treatment was stirred at 3000 rpm using a stirrer (TK Robomix manufactured by Primix Corporation), and then subsequently, the book was prepared using a disperser (Picomill manufactured by Asada Iron Works Co., Ltd.). I tried to perform distributed processing. However, since the viscosity of the treatment liquid obtained by the pre-dispersion treatment did not decrease to the extent that it could be supplied to the disperser, the present dispersion treatment could not be carried out. Therefore, the cuprous oxide particle dispersion could not be prepared, and the coating agent composition of this example could not be obtained.</p><p num="0117">[Comparative example 5] A titanium oxide particle dispersion was prepared in the same manner as in Example 1 except that 100 parts by mass of titanium oxide particles, 800 parts by mass of methyl ethyl ketone, and 50 parts by mass of a phosphate ester type anionic surfactant were mixed. The titanium oxide concentration in the titanium oxide particle dispersion was 11% by mass.</p><p num="0118"> Further, 475 parts by mass of the titanium oxide particle dispersion, 27 parts by mass of the cuprous oxide particle dispersion obtained in Example 1, and 245 parts by mass of the binder resin were mixed in the same manner as in Example 1 to obtain the present example. A coating composition was prepared.</p><p num="0119">[Comparative example 6] First, titanium oxide particles, methyl ethyl ketone, and a phosphate ester-type anionic surfactant were prepared in the same manner as in Example 1. Next, 100 parts by mass of the titanium oxide particles, 800 parts by mass of methyl ethyl ketone, and 0.5 parts by mass of the phosphate ester type anionic surfactant were mixed, and as a predispersion treatment, stirring was performed at 8000 rpm for 30 minutes using a stirrer. As the stirrer, TK Robomix manufactured by Primix Corporation was used.</p><p num="0120"> Then, 1 L of the treatment liquid obtained by the pre-dispersion treatment was stirred at 3000 rpm using a stirrer (TK Robomix manufactured by Primix Corporation), and then subsequently, the book was prepared using a disperser (Picomill manufactured by Asada Iron Works Co., Ltd.). I tried to perform distributed processing. However, since the viscosity of the treatment liquid obtained by the pre-dispersion treatment did not decrease to the extent that it could be supplied to the disperser, the present dispersion treatment could not be carried out. Therefore, the titanium oxide particle dispersion cannot be prepared, and the coating agent composition of this example cannot be obtained.</p><p num="0121">[Comparative example 7] A cuprous oxide particle dispersion was prepared in the same manner as in Example 1 except that 100 parts by mass of copper peroxide particles, 2500 parts by mass of methyl ethyl ketone, and 200 parts by mass of a phosphoric acid ester type anionic surfactant were mixed. The copper oxide concentration in the cuprous oxide particle dispersion was 4% by mass.</p><p num="0122"> Further, 455 parts by mass of the titanium oxide particle dispersion obtained in Example 1, 28 parts by mass of the sub-copper oxide particle dispersion, and 245 parts by mass of the binder resin were mixed in the same manner as in Example 1 to obtain the present example. A coating composition was prepared.</p><p num="0123">[Comparative example 8] First, as in Example 1, cuprous oxide particles, methyl ethyl ketone and a phosphate ester type anionic surfactant were prepared. Next, 100 parts by mass of the above cuprous oxide particles, 2500 parts by mass of methyl ethyl ketone, and 5 parts by mass of the phosphate ester type anionic surfactant were mixed, and a stirrer (TK Robomix manufactured by Primix Corporation) was used as a predispersion treatment. Stirring was performed at 8000 rpm for 30 minutes.</p><p num="0124"> After that, 1 L of the treatment liquid obtained by the pre-dispersion treatment was stirred at 3000 rpm using a stirrer (TK Robomix manufactured by Primix Corporation), and then subsequently, the book was prepared using a disperser (Picomill manufactured by Asada Iron Works Co., Ltd.). I tried to perform distributed processing. However, since the viscosity of the treatment liquid obtained by the pre-dispersion treatment did not decrease to the extent that it could be supplied to the disperser, the present dispersion treatment could not be carried out. Therefore, the cuprous oxide particle dispersion could not be prepared, and the coating agent composition of this example could not be obtained.</p><p num="0125">[Comparative example 9] The coating agent composition of this example was prepared by mixing 27 parts by mass of the cuprous oxide particle dispersion obtained in Example 1 and 495 parts by mass of a binder resin and stirring with a stirrer. That is, in this example, the titanium oxide particle dispersion was not used.</p><p num="0126">[Comparative example 10] The coating agent composition of this example was prepared in the same manner as in Example 1 except that 865 parts by mass of the titanium oxide particle dispersion, 27 parts by mass of the cuprous oxide particle dispersion, and 20 parts by mass of the binder resin were mixed. ..</p><p num="0127">[Comparative example 11] The coating agent composition of this example was prepared by mixing 455 parts by mass of the titanium oxide particle dispersion obtained in Example 1 and 250 parts by mass of a binder resin and stirring with a stirrer. That is, in this example, the cuprous oxide particle dispersion was not used.</p><p num="0128">[Comparative example 12] The coating agent composition of this example was prepared in the same manner as in Example 1 except that 455 parts by mass of the titanium oxide particle dispersion, 530 parts by mass of the cuprous oxide particle dispersion, and 250 parts by mass of the binder resin were mixed. ..</p><p num="0129">[Comparative example 13] The coating agent composition of this example was prepared in the same manner as in Example 1 except that DISPERBYK (registered trademark) -111 (ionic surfactant) manufactured by Big Chemie Japan Co., Ltd. was used as the surfactant.</p><p num="0130"> Tables 1 and 2 show the amount of titanium oxide particles added to the titanium oxide particle dispersion, the amount of organic solvent added, the amount of surfactant added, and the concentration of titanium oxide particles in the titanium oxide particle dispersion in Examples and Comparative Examples. Shown. Further, the amount of cuprous oxide particles added in the cuprous oxide particle dispersion in Examples and Comparative Examples, the amount of organic solvent added, the amount of surfactant added, and the concentration of cuprous oxide particles in the cuprous oxide particle dispersion. Is also shown in Tables 1 and 2. Further, the mixed amounts of the titanium oxide particle dispersion liquid, the cuprous oxide particle dispersion liquid and the binder resin in the coating agent composition are also shown in Tables 1 and 2.</p><p num="0131"><tables num="1"><img id="000002" he="230" wi="159" file="JP5914890B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0132"><tables num="2"><img id="000003" he="230" wi="159" file="JP5914890B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0133"> The following evaluation tests were carried out on the titanium oxide particle dispersion, the cuprous oxide particle dispersion and the coating agent composition obtained in the above Examples and Comparative Examples. The results of the evaluation test are shown in Tables 3 and 4.</p><p num="0134">[Appropriate dispersion] After performing the pre-dispersion treatment using a stirrer, when the main dispersion treatment is performed using a disperser, the treatment liquid that could be sent from the stirrer to the disperser using a liquid feed pump is marked with "". evaluated. However, those that could not be sent because the viscosity of the treatment liquid was too high were evaluated as "x". As the liquid feed pump, a MASTER FLEX liquid feed pump manufactured by MASTER FLEX equipped with a PTFE pump head was used.</p><p num="0135">[Average secondary particle size] The titanium oxide particle dispersion and the cuprous oxide particle dispersion obtained in each example were measured by a dynamic light scattering method and cumulant analysis was performed to determine the average secondary particle size of the titanium oxide particles and the cuprous oxide particles. It was measured. A concentrated particle size analyzer FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) was used to measure the particle size.</p><p num="0136">[transparency] The titanium oxide particle dispersions obtained in each example were adjusted to a titanium oxide concentration of 1% by mass using methyl ethyl ketone. Next, the diluted titanium oxide particle dispersion was applied onto a glass plate using bar coater # 10. Further, the obtained coating film was dried at 50 ° C. for 30 minutes. The degree of cloudiness of the thin film obtained after drying was measured using a haze meter NDH4000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.), and a degree of cloudiness of 3 or less was evaluated as "" and a degree of cloudiness of 3 or more was evaluated as "x". did. Similarly, the transparency of the cuprous oxide particle dispersion was evaluated.</p><p num="0137">[Antibacterial] Antibacterial properties were evaluated using Escherichia coli in accordance with JIS R1702 (Fine Ceramics-Antibacterial Test Method / Antibacterial Effect of Photocatalytic Antibacterial Processed Products). As for the light irradiation conditions, irradiation was performed for 1 hour at 1000 Lx of total light of a fluorescent lamp. An antibacterial activity value of 3 or more per hour was evaluated as "", 0.5 or more and less than 3 was evaluated as "Δ", and less than 0.5 was evaluated as "x".</p><p num="0138">[Antiviral] Anti-viral evaluation is carried out in accordance with JIS R 1756 (Fine Ceramics-Anti-viral test method for visible light responsive photocatalytic materials-Method using bacteriophage Qβ), which has been established as an alternative evaluation method for antiviral tests. did. As for the light irradiation conditions, irradiation was performed for 1 hour at 1000 Lx of total light of a fluorescent lamp. An antibacterial activity value of 3 or more per hour was evaluated as "", 0.5 or more and less than 3 was evaluated as "Δ", and less than 0.5 was evaluated as "x".</p><p num="0139">[Film filmability] The coating agent compositions of Examples 1 to 14 and Comparative Examples 1 to 13 were applied onto a glass plate having a thickness of 2 mm and a size of 10 cm × 10 cm using a bar coater # 10. Then, the coating film of each example was prepared by drying at 100 ° C. for 30 seconds. In Example 14, the obtained film was further subjected to 800 mJ / cm using an ultraviolet irradiator.²The film was cured by irradiating with ultraviolet rays.</p><p num="0140"> Further, the coating agent composition of Example 15 was applied to a polypropylene base material using a bar coater # 10. Then, the coating film of Example 15 was prepared by drying at 80 ° C. for 3 hours. As the polypropylene base material, Takiron Co., Ltd., product name: PP1300 PP plate (polypropylene) / press natural was used.</p><p num="0141"> Next, the dryness to the touch of the coating film of each obtained example was evaluated. Specifically, the center of the coating film of each example was touched with a finger, and those in which fingerprint marks could not be visually confirmed were evaluated as "", and those in which fingerprint marks could be confirmed were evaluated as x.</p><p num="0142">[Adhesion (adhesiveness)] Adhesion was evaluated for the coating films of each Example and Comparative Example obtained in the film formation property evaluation at a cut interval of 1 mm in accordance with the cross-cut method in JIS K5600 (general paint test method). At this time, those without peeling were evaluated as "", and those with peeling were evaluated as "x".</p><p num="0143">[Pencil hardness] The coating films of each Example and Comparative Example obtained in the film formation evaluation were evaluated in accordance with the scratch hardness (pencil method) in JIS K5600 (general paint test method).</p><p num="0144">[Scratch resistance] 100 g / cm using steel wool (grade: # 0000) for the coating films of each Example and Comparative Example obtained in the film formation evaluation.²Rubbed 50 times with the load of. After rubbing, the surface of the coating was examined for scratches. Those in which scratches could not be visually confirmed were evaluated as "", and those in which scratches could be confirmed were evaluated as "x".</p><p num="0145">[Contact angle] The static contact angle was measured 5 seconds after dropping 0.3 mg of oleic acid onto the coating films of the Examples and Comparative Examples obtained in the film formation evaluation. The static contact angle was measured using a contact angle meter (CA-DT manufactured by Kyowa Interface Science Co., Ltd.).</p><p num="0146"><tables num="3"><img id="000004" he="213" wi="159" file="JP5914890B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0147"><tables num="4"><img id="000005" he="212" wi="159" file="JP5914890B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0148"> As shown in Table 3, the copper composite titanium oxide dispersions of Examples 1 to 15 showed good results in the dispersion proper evaluation, and the obtained coating agent composition was also transparent, antibacterial, and antiviral. Good results were shown in each evaluation of film formation property, adhesion, pencil hardness, and scratch resistance. Further, in Example 14, the oleic acid contact angle was 10 °, and good results were also shown for fingerprint resistance. Further, in Example 15, good adhesion was shown even with a poorly adherent substrate such as polypropylene.</p><p num="0149"> On the other hand, as shown in Table 4, in Comparative Example 1 and Comparative Example 3 in which the amount of the organic solvent was excessive, the film properties such as film forming property, pencil hardness and scratch resistance were deteriorated. Further, in Comparative Example 2 in which the amount of the surfactant was excessive and Comparative Example 6 in which the amount of the surfactant was insufficient, the viscosity of the dispersion liquid increased, and the titanium oxide particle dispersion liquid could not be prepared. Further, in Comparative Example 4 in which the amount of the organic solvent was too small, the viscosity of the dispersion liquid increased, and the cuprous oxide particle dispersion liquid could not be prepared. In Comparative Example 7 in which the amount of the surfactant was excessive, the scratch resistance was lowered, and the antibacterial and antiviral properties were also insufficient. In Comparative Example 8 in which the amount of the surfactant was too small, the viscosity of the dispersion liquid increased, and the cuprous oxide particle dispersion liquid could not be prepared.</p><p num="0150"> In Comparative Example 9 which did not contain titanium oxide particles and Comparative Example 11 which did not contain cuprous oxide particles, the antibacterial and antiviral properties were insufficient. In Comparative Example 10 in which the amount of cuprous oxide particles was too small, the antibacterial and antiviral properties were insufficient. In Comparative Example 12 in which the amount of cuprous oxide particles was excessive, the film properties such as pencil hardness and scratch resistance were deteriorated. In Comparative Example 13 in which a surfactant other than the phosphoric acid ester-type anionic surfactant was used, the dispersibility of the particles was high, but the antibacterial and antiviral properties were lowered.</p><p num="0151"> Japanese Patent Application No. 2013-050239 (Filing Date: March 13, 2013), Japanese Patent Application No. 2013-094288 (Filing Date: April 26, 2013), and Japanese Patent Application No. 2013-257283 (Filing Date: December 2013) The entire contents of (March 12) are incorporated here.</p><p num="0152"> Although the contents of the present invention have been described above with reference to Examples, it is obvious to those skilled in the art that the present invention is not limited to these descriptions and various modifications and improvements are possible.</p>

The copper composite titanium oxide dispersion of the present invention can maintain the dispersibility of these particles in a high state even when the concentrations of the titanium oxide particles and the cuprous copper oxide particles are increased. As a result, it becomes possible to improve the transparency of the coating agent composition containing these particles and the antibacterial / antiviral member using the coating agent composition. Further, since the coating agent composition and the antibacterial / antiviral member contain not only titanium oxide particles but also cuprous oxide particles, high antibacterial and antiviral properties can be exhibited.