WO2014132607A1

WO2014132607A1 - Liquid dispersion of titanium oxide particles, coating agent composition, and antibacterial/antiviral member

Info

Publication number: WO2014132607A1
Application number: PCT/JP2014/000943
Authority: WO
Inventors: 剛士植田; 絹川　謙作; 大悟山科
Original assignee: パナソニック株式会社
Priority date: 2013-02-27
Filing date: 2014-02-24
Publication date: 2014-09-04
Also published as: JP6347368B2; JPWO2014132607A1

Abstract

　This liquid dispersion of titanium oxide particles contains titanium oxide particles, and a nonionic surfactant in an amount of 5-100 mass parts per 100 mass parts of the titanium oxide particles. Furthermore, this liquid dispersion of titanium oxide particles contains an organic solvent in an amount of 300-2000 mass parts per 100 mass parts of the titanium oxide particles, the organic solvent containing at least 50% by mass of a glycol ether organic solvent. The titanium oxide particles have a mean primary particle size of 2-80 nm and a mean secondary particle size of 50-150 nm, the mean secondary particle size being measured by dynamic light scattering and obtained by cumulant analysis. In addition, the titanium oxide particle content is 10 mass parts or greater in 100 mass parts of the heating residue of the liquid dispersion of titanium oxide particles.

Description

Titanium oxide particle dispersion, coating composition and antibacterial / antiviral member

The present invention relates to a titanium oxide particle dispersion, a coating composition and an antibacterial and antiviral member. In particular, the present invention relates to a titanium oxide particle dispersion and a coating composition capable of obtaining high antibacterial properties, antiviral properties and transparency, and an antibacterial / antiviral component using the coating composition.

With the improvement of consumers' preference for cleanliness, various antibacterial members for reducing microorganisms in the living environment have been developed and commercialized. And the antimicrobial member which provides antimicrobial property with respect to the interior member for houses or vehicles generally contains antimicrobial materials, such as silver and zinc (for example, refer to 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, present in a large amount, and has low ecotoxicity, as an antibacterial material (see, for example, Patent Document 3). Since titanium oxide has photocatalytic activity, an antibacterial action using this photocatalytic activity has attracted attention.

Here, titanium oxide is a white powder as frequently used in pigments of white paints. Therefore, in order to be used in various applications, a technology for securing transparency even when using titanium oxide is required. Specifically, it is necessary to form titanium oxide into fine particles using bottom-up synthesis or various dispersion techniques.

JP 2008-255101 A JP, 2011-42642, A Japanese Patent Laid-Open No. 2003-275601

However, those currently marketed as fine particle dispersions of titanium oxide are mainly aqueous dispersions using repulsion due to charge between particles. Therefore, there is a problem that the transparency is impaired due to the influence of water when a binder in which an acrylic urethane and an isocyanate are combined is used for such an aqueous dispersion of titanium oxide. In addition, when such a binder is used for the aqueous dispersion of titanium oxide, there is also a problem that the pot life becomes extremely short.

Moreover, the conventional fine particle dispersion of titanium oxide has a low concentration of titanium oxide. When the concentration of titanium oxide is low, the coating film becomes thick and problems such as dripping easily occur. Furthermore, the need to increase the drying time and increase the drying temperature arises from the fact that a large amount of solvent is contained.

The present invention has been made in view of the problems of the prior art. And the object of the present invention is titanium oxide particle dispersion liquid and coating agent composition which can obtain a film which has transparency even when titanium oxide concentration is raised and antibacterial property is improved, and the coating agent composition concerned To provide an antibacterial and antiviral material using the

The titanium oxide particle dispersion liquid according to the first aspect of the present invention contains titanium oxide particles and 5 to 100 parts by mass of a nonionic surfactant based on 100 parts by mass of the titanium oxide particles. Furthermore, the titanium oxide particle dispersion liquid contains 300 to 2000 parts by mass of an organic solvent based on 100 parts by mass of titanium oxide particles, containing 50% by mass or more of a glycol ether-based organic solvent. The titanium oxide particles have an average primary particle diameter of 2 to 80 nm, and have an average secondary particle diameter of 50 to 150 nm as measured by a dynamic light scattering method and obtained by a cumulant analysis method. The titanium oxide particles are contained in an amount of 10 parts by mass or more in 100 parts by mass of the heating residue of the titanium oxide particle dispersion.

In the titanium oxide particle dispersion liquid according to the second aspect of the present invention, the above-mentioned nonionic surfactant has a weight average molecular weight of 300 to 10,000.

The coating agent composition which concerns on the 3rd aspect of this invention contains the said titanium oxide particle dispersion liquid and binder resin. The titanium oxide particles in the coating agent composition are 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.

The antibacterial and antiviral member according to the fourth aspect of the present invention has a substrate, and a film provided on the substrate and containing the above-mentioned coating composition.

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

[Titanium oxide particle dispersion]
The titanium oxide particle dispersion liquid according to the embodiment of the present invention contains titanium oxide particles, a nonionic surfactant, and an organic solvent containing 50% by mass or more of a glycol ether-based organic solvent.

As the titanium oxide particles, particles made of anatase type or rutile type titanium oxide can be used. In addition, particles in which anatase type titanium oxide and rutile type titanium oxide are mixed can also be used. However, as titanium oxide particles, particles of anatase type titanium oxide are preferably used. This is because anatase type titanium oxide has a larger band gap than rutile type titanium oxide and is excellent in photocatalytic property.

In addition, an amorphous titanium oxide may be mixed with particles of anatase type titanium oxide. However, since the amorphous titanium oxide has poor photocatalytic properties, the mixing amount is preferably as small as possible. Moreover, in order to improve the photocatalytic activity, particles of iron oxide and copper oxide supported on the surface of 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 diameter of the titanium oxide particles is less than 2 nm, the surface area of each titanium oxide particle may be too small, which may make it difficult to exhibit the photocatalytic activity. In addition, when the average primary particle diameter of the titanium oxide particles exceeds 80 nm, it is difficult to form fine particles sufficiently in the dispersion treatment step described later. As a result, there is a possibility that the titanium oxide particles may be aggregated and easily precipitated during the dispersion treatment step or storage after the dispersion treatment. The average primary particle size of the titanium oxide particles can be determined, for example, by measuring the diameters of a plurality of titanium oxide particles using a transmission electron microscope (TEM).

The average primary particle diameter of the titanium oxide particles is preferably 5 nm to 50 nm, and more preferably 5 nm to 30 nm. Such an average primary particle size enables high dispersion in an organic solvent while maintaining the surface area of the titanium oxide particles in a high state.

A nonionic surfactant is a surfactant which exhibits surfactant activity without being dissociated into ions in an aqueous solution. By using such a nonionic surfactant, the photocatalytic activity of the titanium oxide particles, that is, the antibacterial property and the antiviral property do not decrease, and furthermore, high dispersion can be achieved in the organic solvent. As the nonionic surfactant, for example, at least one of a polyoxyethylene type, a polyhydric alcohol fatty acid ester type and a type having both of them can be used. However, as a nonionic surfactant, a polyoxyethylene based one is preferable. Examples of polyoxyethylene surfactants include, for example, polyoxyethylene ethers of fatty acids, polyoxyethylene ethers of higher alcohols, alkyl phenols, polyoxyethylene ethers, and the like. There are also polyoxyethylene ethers of sorbitan esters, polyoxyethylene ethers of castor oil, polyoxyethylene ethers of polyoxypropylene and alkylolamides of fatty acids. Examples of polyhydric alcohol fatty acid ester surfactants include monoglycerite surfactants, sorbitol surfactants, soltabine surfactants, and sugar ester surfactants. A nonionic surfactant may be used individually by 1 type, and may be used in combination of 2 or more types.

The weight average molecular weight Mw of the nonionic surfactant is preferably 300 to 10,000. When the weight average molecular weight of the nonionic surfactant is 300 or more, a sufficient viscosity reducing action on the titanium oxide particle dispersion can be obtained, and a transparent film can be obtained. Furthermore, due to the steric hindrance of the nonionic surfactant, the repulsion stability of the titanium oxide particles is improved, and the high dispersibility of the titanium oxide particles is easily maintained. In addition, in the case where the weight average molecular weight of the nonionic surfactant is 10000 or less, the aggregation of particles associated with the binding of the nonionic surfactants after the dispersion treatment is suppressed to maintain the transparency of the film. It becomes possible.

The weight average molecular weight Mw of the nonionic surfactant is more preferably 300 to 5,000. With such a weight average molecular weight, it is possible to further improve the dispersibility of the titanium oxide particles.

As an organic solvent as a dispersion medium of the said titanium oxide particle, the organic solvent containing 50 mass% or more of glycol ether type | system | group organic solvents is used. When a coating agent composition containing the above-mentioned titanium oxide particle dispersion and binder resin is prepared, as described later, by making the glycol ether type organic solvent as the main component, curing inhibition of the composition is hardly caused. It becomes possible. Furthermore, even when titanium oxide particles are contained at a high concentration, the viscosity of the titanium oxide particle dispersion can be reduced, and the efficiency of the coating operation can be improved.

Examples of the glycol ether type organic solvent include diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, hexyl diglycol and the like. One of these glycol ether-based organic solvents may be used alone, or two or more thereof may be used in combination. From among these glycol ether organic solvents, an appropriate solvent can be selected according to the temperature conditions at the time of film formation and the like.

The organic solvent as the dispersion medium in the titanium oxide particle dispersion contains 50% by mass or more of the glycol ether-based organic solvent, preferably 70% by mass or more, and more preferably 90% by mass or more. If the content of the glycol ether-based organic solvent is less than 50% by mass, the viscosity of the dispersion may be increased to lower the efficiency of the coating operation, or the thickness of the film may be excessive. In addition, you may use only a glycol-ether type | system | group organic solvent as a dispersion medium in a titanium oxide particle dispersion liquid.

As the dispersion medium, in addition to the glycol ether type organic solvent, it is possible to mix various organic solvents such as alcohol type and ketone type. Examples of alcohol-based organic solvents include methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, t-butanol, butanediol, 2-ethylhexanol, benzyl alcohol and the like. Moreover, as a ketone system organic solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, diacetone alcohol etc. can be mentioned, for example. These alcohol-based organic solvents and ketone-based organic solvents may be used alone or in combination of two or more.

The addition amount of the non-ionic surfactant in the titanium oxide particle dispersion can be appropriately adjusted by the content of the titanium oxide particles. Specifically, the amount of the nonionic surfactant is 5 to 100 parts by mass with respect to 100 parts by mass of the titanium oxide particles. If the amount of the nonionic surfactant is less than 5 parts by mass, titanium oxide particles may be aggregated with each other, and sufficient dispersibility may not be obtained. Moreover, when a nonionic surfactant exceeds 100 mass parts, when mixing with binder resin and forming a film so that it may mention later, there exists a possibility that hardening inhibition may occur. When the amount is more than 100 parts by mass, the physical properties of the film such as film forming ability and adhesion may be deteriorated.

The addition amount of the nonionic surfactant is more preferably 5 to 90 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 a decrease in film physical properties while improving the dispersibility of the titanium oxide particles.

The addition amount of the organic solvent in the titanium oxide particle dispersion can also be appropriately adjusted by the content of the titanium 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 titanium oxide particles. When the amount of the organic solvent is less than 300 parts by mass, the dispersibility of the titanium oxide particles is reduced, and the viscosity of the titanium oxide particle dispersion is increased, which may lower the efficiency of the coating operation. In addition, when 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 working 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 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.

In addition, the titanium oxide particle dispersion liquid of this embodiment becomes a coating agent composition by mixing with binder resin so that it may mention later, and also by apply | coating the said coating agent composition to a base material, antibacterial * antiviral Form a protective coating. Then, from the viewpoint of enhancing the transparency of the film, the average secondary particle diameter of the titanium oxide particles in the titanium oxide particle dispersion needs to be 50 to 150 nm. When the average secondary particle size is less than 50 nm, the crystal structure of the photocatalytic material may be destroyed, and photocatalytic activity (antibacterial and antiviral properties) may be reduced. In addition, when the average secondary particle diameter exceeds 150 nm, the surface area of the titanium oxide particles may be reduced, and the photocatalytic activity may be reduced. In the present specification, the average secondary particle size of the titanium oxide particles is measured by the dynamic light scattering method, and the average secondary particle size obtained by the cumulant analysis method is adopted.

Furthermore, in the titanium oxide particle dispersion liquid of the present embodiment, the titanium oxide particles are contained in an amount of 10 parts by mass or more in 100 parts by mass of the heating residue of the titanium oxide particle dispersion liquid. If the content of the titanium oxide particles in the total heating residue 100 parts by mass 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 compounding quantity of the titanium oxide particle in a coating agent composition may fall, and it may become difficult to ensure high antimicrobial property. In addition, when the solvent component is excessive, liquid dripping or the like occurs during coating of the coating agent composition to cause appearance abnormality, and there is a possibility that physical properties may be lowered due to the fact that a sufficient film thickness can not be obtained. The content of the titanium oxide particles in the titanium oxide particle dispersion is not particularly limited as long as the transparency of the obtained film is secured, but, for example, 50 mass% in 100 parts by mass of the heating residue of the titanium oxide particle dispersion. It can be less than a part. The heating residue in the present specification can be measured in accordance with Japanese Industrial Standard JIS K 5601-1-2 (paint component test method-part 1: general rule-section 2: heating residue).

Thus, the titanium oxide particle dispersion liquid of the present embodiment contains titanium oxide particles and 5 to 100 parts by mass of a nonionic surfactant with respect to 100 parts by mass of the titanium oxide particles. Furthermore, the titanium oxide particle dispersion liquid contains 300 to 2000 parts by mass of an organic solvent based on 100 parts by mass of titanium oxide particles, containing 50% by mass or more of a glycol ether-based organic solvent. The titanium oxide particles have an average primary particle diameter of 2 to 80 nm, and have an average secondary particle diameter of 50 to 150 nm as measured by a dynamic light scattering method and obtained by a cumulant analysis method. The titanium oxide particles are contained in an amount of 10 parts by mass or more in 100 parts by mass of the heating residue of the titanium oxide particle dispersion. With such a configuration, the dispersibility of the titanium oxide particles is improved even when the concentration of the titanium oxide particles in the titanium oxide particle dispersion is increased, so that the transparency of the antibacterial / antiviral film using this is enhanced. It is possible to secure

[Method of producing titanium oxide particle dispersion]
Next, the method for producing the titanium oxide particle dispersion liquid will be described. The titanium oxide particle dispersion liquid can be prepared by mixing the above-mentioned titanium oxide particles, nonionic surfactant and organic solvent and highly dispersing the titanium oxide particles in the organic solvent. Therefore, any method can be used as long as the titanium oxide particles can be highly dispersed.

However, from the viewpoint of enhancing the dispersibility of the titanium oxide particles and making it easy to ensure the transparency of the antibacterial and antiviral coating, it is preferable to divide the titanium oxide particles into a pre-dispersion treatment and a main dispersion treatment. As a result, the surface of the titanium oxide particles gets 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 waste mechanical impact may 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 with reduced stability.

The pre-dispersion treatment may be stirred using a general dissolver. However, from the viewpoint of making the surface of the titanium oxide particles easy to wet, it is preferable to stir with a high-speed stirrer. As a high-speed stirrer, for example, T.I. K. Homomixer, T.I. K. Robomix and T.K. K. Fillix (trade name, manufactured by Primix Co., Ltd.) can be used. In addition, Creamix (registered trademark) (trade name, manufactured by M. Technique Co., Ltd.) and UltraDispar (trade name, manufactured by Asada Iron Works, Ltd.) can also be used.

As a dispersing apparatus which performs this dispersing process, for example, a kneader, two rolls, three rolls, SS5 (trade name, M. Technique Co., Ltd.), Miracle KCK (registered trademark) (trade name, manufactured by Asada Iron Works Co., Ltd.) Can be used. In addition, ultrasonic dispersion machines, Microfluidizer (trade name, manufactured by Mizuho Kogyo Co., Ltd.) which is a high pressure homogenizer, NanoVeita (registered trademark) (trade name, manufactured by Yoshida Machine Kogyo Co., Ltd.), and the like can also be mentioned. Furthermore, Starburst (registered trademark) (trade name, Sugino Machine Co., Ltd.), G-Smasher (trade name, Lix, Inc.), and the like can also be mentioned. When using bead media such as glass and zircon, ball mills, bead mills, sand mills, horizontal media mills, dispersers, colloid mills, etc. can be used. As media used in a bead mill, bead media having a diameter of 1 mm or less are preferable, and bead media having a diameter of 0.5 mm or less are more preferable. The dispersion time of the pre-dispersion treatment and the main dispersion treatment may be appropriately adjusted depending on each dispersion device or medium so that the titanium oxide particles are highly dispersed in the organic solvent together with the nonionic surfactant.

Also, even when the processing liquid subjected to pre-dispersion processing is supplied to the above-mentioned dispersion apparatus, processing can be performed in a shorter time by supplying while performing sufficient stirring using a high-speed stirrer or the like. is there.

[Coating agent composition]
The coating agent composition which concerns on this embodiment contains the above-mentioned titanium oxide particle dispersion liquid, and binder resin. As described above, since the titanium oxide particle dispersion liquid of the present embodiment improves the dispersibility while improving the titanium oxide concentration, the coating agent composition using such a titanium oxide particle dispersion liquid is antibacterial It is possible to form a coating of high sex, antiviral and transparency.

The binder resin to be mixed with the titanium oxide particle dispersion is not particularly limited as long as the stability, the antimicrobial property and the transparency of the film obtained from the coating agent composition can be ensured. As a binder resin, an alkyd resin, an acrylic resin, a melamine resin, a urethane resin, an epoxy resin, a silicone resin etc. can be used, for example. In addition, polyester resins, polyamide acid resins, polyimide resins, styrene maleic acid resins, styrene maleic anhydride resins, and the like can also be used. Furthermore, various acrylic acid monomers and acrylate monomers are also applicable. Particularly preferable resins as the binder resin and the monomers include urethane resins, acrylic resins, acrylic acid monomers, polyamic acid resins, polyimide resins, styrene maleic acid resins, and styrene maleic anhydride resins. The binder resin may be used alone or in combination of two or more.

Furthermore, the coating agent composition may be added to the titanium oxide particle dispersion liquid and the binder resin, and may contain various additives as long as the photocatalytic activity is not affected. Specifically, dispersants, pigments, fillers, aggregates, thickeners, flow control agents, leveling agents, curing agents, crosslinking agents, curing catalysts and the like can be blended.

The coating agent composition which concerns on this embodiment can be prepared by mixing the above-mentioned titanium oxide particle dispersion liquid and binder resin, and also the said additive as needed. In the mixing step, for example, mixing can be performed using the above-described 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 the titanium oxide particles in the heating residue is less than 10 parts by mass, the antimicrobial properties may be reduced. In addition, the hardness of the coating may be reduced. When the content of the titanium oxide particles exceeds 80 parts by mass, it is possible to obtain sufficient antibacterial properties, but there is a possibility that the film physical properties may deteriorate because the binder resin is insufficient. In addition, the transparency of the film may be reduced.

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

[Antibacterial and antiviral material]
The antibacterial and antiviral member according to the present embodiment has a substrate, and a film provided on the substrate and containing the coating composition. As described above, the coating agent composition of the present embodiment has the high antifungal and antiviral properties attributed to the titanium oxide particles, as well as the antifouling / deodorizing effect. Furthermore, because the titanium oxide particles are highly dispersed in the coating agent composition, the resulting film also has high transparency.

In the present embodiment, the material of the base material may be basically anything, such as organic polymer, ceramic, metal, glass, plastic, decorative plywood or a composite thereof. The shape of the substrate is also not particularly limited. For example, it may be a simple shape or a complicated shape such as a plate, a sphere, a cylinder, a cylinder, a rod, a prism, a hollow prism, etc. Good. Also, the substrate may be a porous body such as a filter.

As the base material, building materials such as ceiling materials, tiles, glass, wallpaper, wall materials, floors and construction materials, interior materials for automobiles (instrument panels, sheets, ceiling materials), household appliances such as refrigerators and air conditioners, clothes Textile products such as curtains and the like, industrial equipment, medical equipment and the like are preferable. Furthermore, as the base material, for example, a door, a door handle, a pull handle, a handrail, an interior counter, furniture, a kitchen, a toilet, a bath, a lighting fixture, a touch panel, a switch, a sheet used for these, etc. are preferable. The coating formed of the coating composition of the present embodiment has high antibacterial and antiviral properties, and thus is particularly effective for such a surface that the human body etc. frequently contacts.

The antibacterial and antiviral members 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 it reduces the risk of infection with bacteria and viruses by being used not only at homes, but also at hospitals and elderly facilities and places used by unspecified people such as public transport such as trains, buses and planes. It is possible and useful.

The antimicrobial / antiviral member according to the present embodiment can be obtained by applying a coating composition to a substrate and drying it. The coating method and drying conditions at this time are not particularly limited. As a method of applying the coating composition to at least a part of the substrate, 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.

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

Thus, the antibacterial and antiviral member of the present embodiment has a substrate and a film provided on the substrate and containing a coating composition. And, in the coating agent composition, nano level titanium oxide particles are dispersed at a high concentration. Therefore, it is possible to ensure high antibacterial and antiviral properties due to the photocatalytic activity of the titanium oxide particles and to obtain transparency.

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited to these examples.

Example 1
First, ST-01 (average primary particle diameter: 7 nm, crystal structure: anatase) manufactured by Ishihara Sangyo Co., Ltd. was prepared as titanium oxide particles, and diethylene glycol monomethyl ether (DEGME) was prepared as an organic solvent. Furthermore, Uniol (registered trademark) TG-1000 (polyoxypropylene glyceryl ether, weight average molecular weight Mw: 1000) manufactured by NOF Corporation was prepared as a nonionic surfactant.

Next, 100 parts by mass of the titanium oxide, 500 parts by mass of diethylene glycol monomethyl ether, and 30 parts by mass of the nonionic surfactant were mixed, and stirring was performed at 8,000 rpm for 30 minutes using a stirrer as predispersion treatment. In addition, the stirrer is T.M. K. I used Robomix.

Thereafter, 1 L of the treatment liquid obtained by the pre-dispersion treatment is stirred at 3000 rpm using a stirrer (TK Robotix manufactured by Primix, Inc.), and then a dispersing machine (Picomill manufactured by Asada Iron Works, Ltd.) This distributed processing was performed using this. In addition, the dispersion process was performed by circulating for 2 hours using the zirconia bead of 0.3 mm as a dispersion medium of a dispersion machine. Thus, a titanium oxide particle dispersion liquid of the present example having a titanium oxide concentration of 16% by mass was prepared. Furthermore, 13 parts by mass of the obtained titanium oxide particle dispersion and 10 parts by mass of a binder resin were mixed to prepare a coating agent composition of this example. In addition, the following resin was used as binder resin.

First, Acrydic (registered trademark) A801 (made by DIC Corporation) and Duranate (registered trademark) TPA 100 (made by Asahi Kasei Chemicals Corporation) as an acrylic resin for isocyanate curing are used, and the isocyanate group and the hydroxyl group are NCO / OH = 1. Mixed to become. Next, a binder resin was prepared by diluting this mixture with methyl ethyl ketone so that the heating residue became 20% by mass.

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, 500 parts by mass of diethylene glycol monomethyl ether, and 6 parts by mass of nonionic surfactant were mixed. The titanium oxide concentration in the titanium oxide particle dispersion of this example was 17% by mass.

Furthermore, in the same manner as Example 1, 12 parts by mass of the obtained titanium oxide particle dispersion liquid and 10 parts by mass of a binder resin were mixed to prepare a coating agent composition of this example.

[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, 500 parts by mass of diethylene glycol monomethyl ether, and 90 parts by mass of nonionic surfactant were mixed. The titanium oxide concentration in the titanium oxide particle dispersion of this example was 14% by mass.

Furthermore, in the same manner as in Example 1, 14 parts by mass of the obtained titanium oxide particle dispersion liquid and 10 parts by mass of a binder resin were mixed to prepare a coating agent composition of this example.

Example 4
A titanium oxide particle dispersion was prepared in the same manner as in Example 1 except that 100 parts by mass of titanium oxide, 350 parts by mass of diethylene glycol monomethyl ether, and 30 parts by mass of the nonionic surfactant were mixed. The titanium oxide concentration in the titanium oxide particle dispersion of this example was 21% by mass.

Furthermore, similarly to Example 1, 10 parts by mass of the obtained titanium oxide particle dispersion liquid and 10 parts by mass of a binder resin were mixed to prepare a coating agent composition of this example.

[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, 900 parts by mass of diethylene glycol monomethyl ether, and 30 parts by mass of a nonionic surfactant were mixed. The titanium oxide concentration in the titanium oxide particle dispersion liquid of this example was 10% by mass.

Furthermore, in the same manner as in Example 1, 39 parts by mass of the obtained titanium oxide particle dispersion liquid and 10 parts by mass of a binder resin were mixed to prepare a coating agent composition of this example.

[Example 6]
A titanium oxide particle dispersion was prepared in the same manner as in Example 1 except that 250 parts by mass of diethylene glycol monomethyl ether and 250 parts by mass of methyl ethyl ketone (MEK) were used as the organic solvent. The titanium oxide concentration in the titanium oxide particle dispersion of this example was 16% by mass.

Furthermore, in the same manner as in Example 1, 13 parts by mass of the obtained titanium oxide particle dispersion and 10 parts by mass of a binder resin were mixed to prepare a coating agent composition of this example.

[Example 7]
A titanium oxide particle dispersion was prepared in the same manner as in Example 1 except that Uniol TG-330 (polyoxypropylene glyceryl ether, weight average molecular weight Mw: 330) manufactured by NOF Corporation was used as the nonionic surfactant. did. The titanium oxide concentration in the titanium oxide particle dispersion of this example was 16% by mass.

[Example 8]
A titanium oxide particle dispersion was prepared in the same manner as in Example 1 except that Uniol TG-4000 (polyoxypropylene glyceryl ether, weight average molecular weight Mw: 4000) manufactured by NOF Corporation was used as the nonionic surfactant. did. The titanium oxide concentration in the titanium oxide particle dispersion of this example was 16% by mass.

[Example 9]
A titanium oxide particle dispersion was prepared in the same manner as in Example 1 except that ST-21 (average primary particle diameter: 20 nm, crystal structure: anatase) manufactured by Ishihara Sangyo Co., Ltd. was used as the titanium oxide particles. The titanium oxide concentration in the titanium oxide particle dispersion of this example was 16% by mass.

[Example 10]
Twenty-nine parts by mass of the titanium oxide particle dispersion obtained in Example 1 and 10 parts by mass of a binder resin were mixed to prepare a coating agent composition of this example. The resin described in Example 1 was used as the binder resin.

[Example 11]
Two parts by mass of the titanium oxide particle dispersion obtained in Example 1 and 10 parts by mass of a binder resin were mixed to prepare a coating agent composition of this example. The resin described in Example 1 was used as the binder resin.

Comparative Example 1
First, ST-01 (average primary particle diameter: 7 nm, crystal structure: anatase) manufactured by Ishihara Sangyo Co., Ltd. was prepared as titanium oxide particles, and diethylene glycol monomethyl ether was prepared as an organic solvent.

Next, 100 parts by mass of the above titanium oxide and 500 parts by mass of diethylene glycol monomethyl ether were mixed, and as a pre-dispersion treatment, stirring was performed for 30 minutes at 8000 rpm using a stirrer (TK. .

Thereafter, 1 L of the treatment liquid obtained by the pre-dispersion treatment is stirred at 3000 rpm using a stirrer (TK Robotix manufactured by Primix, Inc.), and then a dispersing machine (Picomill manufactured by Asada Iron Works, Ltd.) We tried to use this for distributed processing. However, since the viscosity of the treatment liquid obtained by the pre-dispersion treatment did not decrease to such an extent that it can be supplied to the disperser, this dispersion treatment could not be carried out.

Comparative 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, 500 parts by mass of diethylene glycol monomethyl ether, and 150 parts by mass of a nonionic surfactant were mixed. The titanium oxide concentration in the titanium oxide particle dispersion liquid of the present comparative example was 13% by mass.

Furthermore, similarly to Example 1, 15 parts by mass of the obtained titanium oxide particle dispersion liquid and 10 parts by mass of a binder resin were mixed to prepare a coating agent composition of the present comparative example.

Comparative 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, 4000 parts by mass of diethylene glycol monomethyl ether, and 150 parts by mass of a nonionic surfactant were mixed. The titanium oxide concentration in the titanium oxide particle dispersion liquid of the present comparative example was 2% by mass.

Furthermore, in the same manner as in Example 1, 83 parts by mass of the obtained titanium oxide particle dispersion and 10 parts by mass of a binder resin were mixed to prepare a coating agent composition of this comparative example.

Comparative Example 4
First, ST-01 (average primary particle diameter: 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, Uniol TG-1000 (polyoxypropylene glyceryl ether, weight average molecular weight Mw: 1000) manufactured by NOF Corporation was prepared as a nonionic surfactant.

Next, 100 parts by mass of the above-mentioned titanium oxide, 500 parts by mass of methyl ethyl ketone and 150 parts by mass of non-ionic surfactant are mixed, and as a pre-dispersion treatment, using a stirrer (TK Robomix manufactured by Primix, Inc.) The mixture was stirred for 30 minutes.

Comparative Example 5
First, ST-01 (average primary particle diameter: 7 nm, crystal structure: anatase) manufactured by Ishihara Sangyo Co., Ltd. was prepared as titanium oxide particles, and diethylene glycol monomethyl ether was prepared as an organic solvent. Furthermore, Uniloop 70 DP-600B (weight-average molecular weight Mw: 13000) manufactured by NOF Corporation was prepared as a nonionic surfactant.

Next, 100 parts by mass of the above-mentioned titanium oxide, 500 parts by mass of methyl ethyl ketone and 30 parts by mass of nonionic surfactant are mixed, and as a pre-dispersion treatment, using a stirrer (TK Robomix manufactured by Primix Co., Ltd.) The mixture was stirred for 30 minutes.

Comparative Example 6
A titanium oxide particle dispersion was prepared in the same manner as in Example 1 except that DISPERBYK (registered trademark) -111 (ionic surfactant) manufactured by BIC-Chemie Japan Ltd. was used as a surfactant. The titanium oxide concentration in the titanium oxide particle dispersion liquid of the present comparative example was 16% by mass.

Furthermore, in the same manner as Example 1, 13 parts by mass of the obtained titanium oxide particle dispersion liquid and 10 parts by mass of a binder resin were mixed to prepare a coating agent composition of this comparative example.

Comparative Example 7
First, TTO-50 (average primary particle diameter: 10 nm, crystal structure: rutile) manufactured by Ishihara Sangyo Co., Ltd. was prepared as titanium oxide particles, and diethylene glycol monomethyl ether was prepared as an organic solvent. Furthermore, Uniol TG-1000 (polyoxypropylene glyceryl ether, weight average molecular weight Mw: 1000) manufactured by NOF Corporation was prepared as a nonionic surfactant.

Next, 100 parts by mass of the above titanium oxide, 500 parts by mass of diethylene glycol monomethyl ether, and 30 parts by mass of nonionic surfactant are mixed, and pre-dispersion treatment is performed using a stirrer (TK Robomix manufactured by Primix, Inc.) at 8,000 rpm. Stirring was performed for 30 minutes.

Thereafter, 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, Inc.) to obtain a titanium oxide dispersion. Thereby, the titanium oxide particle dispersion liquid of this comparative example whose titanium oxide concentration is 16 mass% was prepared. In the present example, this dispersion processing using a dispersing machine was not performed.

Furthermore, 2 parts by mass of the obtained titanium oxide particle dispersion and 10 parts by mass of a binder resin were mixed to prepare a coating agent composition of this comparative example. The compound described in Example 1 was used as the binder resin.

Comparative Example 8
71 parts by mass of the titanium oxide particle dispersion obtained in Example 1 and 10 parts by mass of a binder resin were mixed to prepare a coating agent composition of this comparative example. The resin described in Example 1 was used as the binder resin.

Comparative Example 9
One part by mass of the titanium oxide particle dispersion obtained in Example 1 and 10 parts by mass of a binder resin were mixed to prepare a coating agent composition of this comparative example. The resin described in Example 1 was used as the binder resin.

Table 1 shows the additive amount and average primary particle diameter of titanium oxide particles, the additive amount of an organic solvent, the additive amount and weight average molecular weight of a surfactant, and the titanium oxide particle concentration in the titanium oxide particle dispersion in Examples and Comparative Examples. Shown in 2. Further, the mixing amounts of the titanium oxide particle dispersion and the binder resin in the coating agent composition are also shown in Tables 1 and 2.

The following evaluation test was implemented with respect to the titanium oxide particle dispersion liquid and coating agent composition which were obtained by the said Example and comparative example. The results of the evaluation test are shown in Tables 3 and 4.

[Distribution appropriate]
After the pre-dispersion treatment using a stirrer, when performing the main dispersion treatment using a disperser, "○" indicates that the treatment liquid can be transferred from the stirrer to the disperser using a liquid feed pump. evaluated. However, the viscosity of the processing liquid was too high, and what was not able to be sent was evaluated as "x". As a liquid transfer pump, a MASTER FLEX liquid transfer pump manufactured by MASTER FLEX Co., Ltd. equipped with a PTFE pump head was used.

[Average secondary particle size measurement]
The titanium oxide particle dispersion obtained in each example was measured by a dynamic light scattering method, and cumulant analysis was performed to measure the average secondary particle size of the titanium oxide particles. A concentrated particle size analyzer FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) was used to measure the particle size.

[transparency]
The titanium oxide particle dispersion liquid obtained in each example was adjusted using methyl ethyl ketone so that the titanium oxide concentration was 1% by mass. Next, the diluted titanium oxide particle dispersion was applied onto a glass plate using a bar coater # 10. Further, the obtained coating was dried at 50 ° C. for 30 minutes. The haze of the thin film obtained after drying is measured using a haze meter NDH4000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.), and the haze of 3 or less is evaluated as "o", and 3 or more is evaluated as "x". did.

[Antibacterial]
Antibacterial evaluation was carried out using E. coli according to JIS R 1702 (Fine ceramics-Antibacterial test method for antibacterially processed products of photocatalysts and antibacterial effect). In addition, the conditions of light irradiation performed irradiation for 1 hour by 1000 Lx of total lights of a fluorescent lamp. An antimicrobial activity value of 3 or more per hour was evaluated as “o”, and 0.5 or more and less than 3 were evaluated as “Δ”, and less than 0.5 was evaluated as “x”.

[Antiviral]
Performs antiviral evaluation in accordance with JIS R 1756 (Fine ceramics-Method of testing antiviral materials for visible light responsive photocatalyst materials-Method using bacteriophage Qβ) established as an alternative evaluation method for antiviral tests did. In addition, the conditions of light irradiation performed irradiation for 1 hour by 1000 Lx of total lights of a fluorescent lamp. An antimicrobial activity value of 3 or more per hour was evaluated as “o”, and 0.5 or more and less than 3 were evaluated as “Δ”, and less than 0.5 was evaluated as “x”.

[Film forming ability]
The coating agent compositions of the respective examples and comparative examples were coated on a glass plate having a thickness of 2 mm and a size of 10 cm × 10 cm using a bar coater # 10. Next, the coating of each example was prepared by drying at 100 ° C. for 30 seconds.

Next, the touch to dryness of the coating obtained in each example was evaluated. Specifically, the center of the film of each example is touched with a finger, those which can not confirm a fingerprint mark visually are evaluated as "○", and those which have no fingerprint mark but have adhesiveness are evaluated as "Δ". , Those which can confirm the fingerprint mark were evaluated as "x".

[Adhesiveness (adhesiveness)]
With respect to the films of the respective Examples and Comparative Examples obtained in the film formation evaluation, the adhesion was evaluated at a cut interval of 1 mm in accordance with the cross cut method in JIS K5600 (paint general test method). Under the present circumstances, the thing in which peeling is not seen was evaluated as "(circle)", and the thing in which peeling is seen was evaluated as "x".

[Pencil hardness]
It evaluated based on the scratch hardness (pencil method) in JISK5600 (paint general test method) with respect to the film of each Example and comparative example obtained in film-forming evaluation.

As shown in Table 3, the titanium oxide particle dispersions of Examples 1 to 11 show good results in the dispersion adequacy evaluation, and the obtained coating agent composition is also transparent, antibacterial, antiviral, synthetic. Good results were obtained in each evaluation of film properties, adhesion and pencil hardness.

On the other hand, as shown in Table 4, in Comparative Example 1 in which the surfactant is not contained, Comparative Example 4 in which the organic solvent consists only of MEK, and Comparative Example 5 in which the weight average molecular weight of the surfactant is too large, The viscosity of the solution increased, and a titanium oxide particle dispersion could not be prepared. In addition, in Comparative Example 2 in which the amount of surfactant is excessive, film properties such as film forming property, adhesion property and pencil hardness decrease, and accordingly, the antibacterial property and the antiviral property also become insufficient results. In addition, in Comparative Example 3 in which the surfactant and the organic solvent were excessive, the film forming property was lowered. Furthermore, when the surfactant is an ionic surfactant as in Comparative Example 6 or when the average secondary particle size of the titanium oxide particles is too large as in Comparative Example 7, the photocatalytic performance is lowered, Along with that, the antibacterial and antiviral properties also decreased. And, as in Comparative Example 7, when the average secondary particle diameter of the titanium oxide particles is too large, the transparency is also lowered.

In addition, as a result of investigating the heating residue in the coating agent composition of Comparative Example 8, in 100 parts by mass of the heating residue of the coating agent composition, the titanium oxide particles exceeded 80 parts by mass. Therefore, the result was a decrease in transparency. Moreover, as a result of investigating the heating residue in the coating agent composition of Comparative Example 9, the titanium oxide particles were less than 10 parts by mass in 100 parts by mass of the heating residue of the coating agent composition. Therefore, the surface hardness of the film decreased.

The entire contents of Japanese Patent Application No. 2013-036788 (filing date: February 27, 2013) are incorporated herein by reference.

Although the contents of the present invention have been described above according to the embodiments, the present invention is not limited to these descriptions, and it is obvious to those skilled in the art that various modifications and improvements are possible.

The titanium oxide particle dispersion liquid of the present invention can maintain the dispersibility of the titanium oxide particles in a high state even when the concentration of the titanium oxide particles is increased. As a result, it becomes possible to improve the transparency of the coating agent composition containing the titanium oxide particles and the antibacterial and antiviral member using the coating agent composition. Furthermore, the coating composition and the antibacterial and antiviral member have high content of titanium oxide particles and thus have high antibacterial and antiviral properties.

Claims

Titanium oxide particles,
5 to 100 parts by mass of a nonionic surfactant with respect to 100 parts by mass of the titanium oxide particles,
300 to 2000 parts by mass of an organic solvent containing 50% by mass or more of a glycol ether-based organic solvent with respect to 100 parts by mass of the titanium oxide particles,
Contains
The titanium oxide particles have an average primary particle size of 2 to 80 nm, and have an average secondary particle size of 50 to 150 nm as measured by a dynamic light scattering method and obtained by a cumulant analysis method.
The titanium oxide particle dispersion liquid contains 10 parts by mass or more in 100 parts by mass of the heating residue of the titanium oxide particle dispersion liquid.
The titanium oxide particle dispersion liquid according to claim 1, wherein the weight average molecular weight of the nonionic surfactant is 300 to 10,000.
A titanium oxide particle dispersion liquid according to claim 1 or 2, and a binder resin,
The coating agent composition, wherein the titanium oxide particles are 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.
A substrate,
A film provided on the substrate and containing the coating composition according to claim 3;
Antibacterial and antiviral material having