KR20150088998A - Antimicrobial and antiviral composition, and method of producing the same - Google Patents

Abstract

The present invention provides antibacterial and antiviral materials, antibacterial and antiviral compositions and methods for their production, and dispersions of antibacterial and antiviral compositions that can exhibit excellent antibacterial and antiviral properties for a long period of time in various applications. Wherein the antibacterial and antiviral material comprises copper oxide particles and at least a part of the silica coating layer on the surface of the copper oxide particles, the content of the silica coating layer is 5 to 20 parts by mass with respect to 100 parts by mass of the copper oxide particles, The BET specific surface area of the copper oxide particles coated with the copper oxide particles is 5 to 100 m < 2 > / g.

Description

TECHNICAL FIELD [0001] The present invention relates to an antimicrobial and antiviral composition,

The present invention relates to an antibacterial and antiviral material, an antibacterial and antiviral composition and a preparation method thereof, a dispersion of an antibacterial and antiviral composition, an antibacterial and antiviral material, Coatings containing the active ingredients, antibacterial and antiviral membranes, and antibacterial and antiviral products.

Copper (II) ions are known as effective components for antibacterial and antiviral properties. For example, Patent Document 1 discloses an antimicrobial and antiviral polymer material having microscopic particles of ionic copper encapsulated therein and protruding from the surface.

Patent Documents 2 to 4 disclose copper (I) compounds having superior antibacterial and antiviral performance over copper (II) compounds. Patent Document 5 discloses nanoparticles formed from a mixed composition of copper, copper (II) oxide and / or cuprous oxide having excellent antibacterial and antiviral performance.

In the synthesis of copper oxide, it is widely known to use a saccharide having a reducing aldehyde group represented by glucose or the like as a reducing agent. For example, Patent Documents 6 to 8 disclose the synthesis of various forms of micronized copper oxide using a reducing sugar such as glucose.

Further, researches for supporting antibacterial and antiviral performance by supporting a copper compound on a photocatalyst material are also known. For example, Patent Document 9 discloses an inactive agent for phage virus which is formed of copper oxide (II) supported on titanium oxide and inactivates virus under ultraviolet irradiation.

Patent Document 10 discloses titanium oxide supported on copper (I) oxide exhibiting antiviral performance. Patent Document 11 discloses copper (I) oxide exhibiting high antibacterial and antiviral performance.

As copper (I) compounds exhibiting excellent antibacterial and antiviral properties, copper oxide is known. However, nanoparticles of pure copper oxide are unstable in the atmosphere. Copper oxide is slowly oxidized to copper (II) oxide, and its antibacterial and antiviral performance is weakened. However, Patent Documents 1 to 4 do not disclose such a problem that antibacterial and antiviral properties are reduced.

Patent Document 5 does not disclose the evaluation of only nanoparticles of copper oxide or the problem that antibacterial and antiviral properties are deteriorated by copper oxide nanoparticles which are easily oxidized in the atmosphere.

In Patent Documents 6 to 8, the reducing agent is removed after synthesizing copper oxide. Copper oxysulfide obtained by the methods described in these documents can also be easily oxidized in the atmosphere, resulting in reduced antibacterial and antiviral properties. In addition, the copper oxide of micron size obtained by the methods described in these documents may have a reduced specific surface area, which may degrade the antibacterial and antiviral performance.

Patent Document 9 does not disclose that copper oxide has a very high antibacterial and antiviral performance. It is considered desirable that the state of copper oxide (II) is maintained on the surface of titanium oxide for antibacterial and antiviral purposes. In addition, when copper oxide nanoparticles are oxidized in the air to form copper oxide (II), the reduction of copper oxide with copper by a photocatalyst is advantageous for the continuation of antibacterial and antiviral effects, but there is no description about them.

Patent Document 10 does not disclose that titanium oxide supported on copper (I) oxide is easily oxidized in the atmosphere. Antibacterial and antiviral properties may be reduced for the same reasons as in other documents.

In Patent Document 11, copper (I) oxide is easily oxidized in the atmosphere, and antibacterial and antiviral performance may be deteriorated. In this respect, Patent Document 11 does not disclose a method for suppressing the oxidation of copper (I) oxide.

JP 2003-528975 T JP 2006-506105 T JP 2007-504291 T JP 2008-518712 T JP 2009-526828 T JP 4401197 B JP 4401198 B JP 4473607 B JP 4646210 B CN 101322939 A JP 2011-153163 A

It is an object of the present invention to provide antibacterial and antiviral materials, antibacterial and antiviral compositions capable of exhibiting excellent antibacterial and antiviral properties for a long period of time for various uses, a method for producing the same, and a dispersion of antibacterial and antiviral compositions . It is also an object of the present invention to provide coatings, antibacterial and antiviral membranes, and antibacterial and antiviral products containing an antibacterial and antiviral composition capable of exhibiting excellent antibacterial and antiviral properties for a long period of time.

The present inventors have found that it is important to coat the copper oxide particles with a specific amount of silica in order to stably present copper oxide particles exhibiting excellent antibacterial and antiviral properties without being oxidized with copper (II) oxide in the atmosphere. That is, it has been found that the presence of a certain amount of the silica coating layer can inhibit the oxidation of copper oxide to copper (II) oxide, and the excellent antibacterial and antiviral properties of the copper oxide are retained for a long time. In addition, by combining with a photocatalyst material, copper (II) oxide is oxidized from copper oxide and loses antimicrobial and antiviral properties. Therefore, it can be reduced to copper oxide by the reduction action of the photocatalyst under light irradiation, found.

Specifically, the present invention is as follows.

[1] An antibacterial and antiviral material comprising copper oxide particles and at least a silica coating layer on the surface of the copper oxide particles,

Wherein the content of the silica coating layer is 5 to 20 parts by mass based on 100 parts by mass of the copper oxide particles, and the BET specific surface area of the silica coated copper oxide particles is 5 to 100 m < 2 > / g. material.

[2] An antimicrobial and antiviral composition comprising the antibacterial and antiviral material according to [1].

[3] The antimicrobial and antiviral composition according to [2], further comprising a photocatalytic substance.

[4] The antimicrobial and antiviral composition according to [3], wherein the content of the photocatalyst material is 70 to 99.9 mass% with respect to the total amount of the antibacterial and antiviral material and the photocatalyst material.

[5] The antibacterial and antiviral composition according to [3] or [4], wherein the photocatalytic material comprises at least one species selected from titanium oxide and tungsten oxide.

[6] The photocatalytic substance according to [3] or [4], wherein the substrate containing at least one selected from titanium oxide and tungsten oxide is at least one selected from copper (II) Wherein the photocatalyst is a visible light-responsive photocatalyst modified by the photocatalyst.

[7] The substrate according to [6], wherein the substrate comprises at least one selected from titanium oxide doped with at least one of a transition metal and a non-metal, and tungsten oxide doped with at least one of a transition metal and a non- Gt; antiviral < / RTI >

[8] The antibacterial and antiviral material according to any one of [2] to [7], wherein the L * a * b * color system according to JIS Z8701 has an L * value of 50 or more, 0.0 > b * < / RTI > of at least 20.

[9] A process for producing a non-aqueous organic solvent, which comprises 1 to 30 mass% of the antimicrobial and antiviral composition according to any one of [2] to [8], 40 to 98.98 mass% And 0.01 to 10% by mass of the antimicrobial and antiviral composition.

[10] The dispersion of an antibacterial and antiviral composition according to [9], further comprising 0.01 to 20% by mass of a surfactant soluble in the non-aqueous organic solvent.

[11] A coating agent containing an antibacterial and antiviral composition, which comprises a dispersion of the antibacterial and antiviral composition according to [9] or [10], and a binder component curable in an environment of 10 to 120 캜 .

[12] An antibacterial and antiviral membrane characterized by applying a coating agent containing the antibacterial and antiviral composition according to [11] and then curing.

[13] An antibacterial and antiviral product characterized by comprising an antibacterial and antiviral membrane according to claim 12 at least in part of the outermost side.

[14] A method for producing an antibacterial and antiviral material according to [1]

(1) a step of synthesizing copper oxide particles by adding a basic substance, a particle growth inhibitor and a reducing agent to an aqueous solution of a copper (II) compound;

(2) Copper oxide particles are mixed with silica in a solvent to hydrolyze the silica source, and the copper oxide particles are coated with silica so that the content of silica is 5 to 20 parts by mass with respect to 100 parts by mass of the copper oxide particles ; And

(3) a step of separating the solid component and then pulverizing the separated solid component.

(Effects of the Invention)

The present invention can provide antimicrobial and antiviral materials, antimicrobial and antiviral compositions and methods for their production, and dispersions of antimicrobial and antiviral compositions that can exhibit excellent antibacterial and antiviral properties for a long period of time for various uses . In addition, it is possible to provide coatings, antibacterial and antiviral membranes, and antibacterial and antiviral products containing an aqueous antibacterial and antiviral composition which can exhibit excellent antibacterial and antiviral properties for a long period of time.

For example, by applying a coating agent containing the antimicrobial and antiviral composition of the present invention to an article or portion contacted by an unspecified large number of people, the risk of spread of bacteria and virus infection to other people through the surface of the article Can be expected to be reduced.

Fig. 1 shows a TEM photograph of the cuprous oxide particles obtained in Example 1. Fig.
2 is a diagram showing an X-ray diffraction pattern of the antibacterial and antiviral material obtained in Example 1. Fig.
3 is a graph showing the virus inactivation ability of the antimicrobial and antiviral composition obtained in Example 5. Fig.

1. Antimicrobial and antiviral material

The antibacterial and antiviral material of the present invention comprises at least a part of the silica coating layer on the surface of the copper oxide particles and the copper oxide particles and the content of the silica coating layer is 5 to 20 parts by mass relative to 100 parts by mass of the copper oxide particles , And the BET specific surface area of the silica-coated copper oxide particles is 5 to 100 m 2 / g.

The copper oxide particles have high antimicrobial and antiviral properties, but are highly inversely oxidized, making it difficult to maintain excellent antimicrobial and antiviral properties for a long period of time. In the present invention, a silica coating layer was formed on the surface of the copper oxide particles to maintain excellent antibacterial and antiviral properties of the copper oxide particles. However, if the silica coating layer is kept too low, the inverse oxidation of the copper oxide particles can not be suppressed. If the silica coating layer is maintained too much, the antibacterial and antiviral properties of the copper oxide particles can be suppressed. In the present invention, the content of the silica coating layer is adjusted to 5 to 20 parts by mass with respect to 100 parts by mass of the copper oxide particles, thereby suppressing the inversion of the copper oxide particles and achieving excellent antibacterial and antiviral properties.

The copper oxide particles may be coated with silica at least a part of the surface, but it is preferable that the entire surface is coated with the silica coating layer.

Copper oxide particles

Copper oxide particles used in the present invention is represented by the formula of Cu ₂ O. The shape of the cuprous oxide observed with an electron microscope is not particularly limited. However, some of the copper oxide particles are spherical, amorphous, and nearly spherical. In the present invention, these shape crystals may be present singly or in combination.

The smaller the particle size of copper oxide, the greater the antibacterial and antiviral performance. It is also known that the color of copper oxide is blurred by the quantum size effect when pulverized. In this case, the antimicrobial and antiviral performance also increases and the amount of usage can be reduced. This leads to reduced coloration. Therefore, copper oxide as an antibacterial and antiviral material is preferably in the form of a small pore microparticle. However, copper oxide particles tend to be oxidized in the atmosphere as the particle diameter is smaller. Copper (II) oxide is known to be blackish, causing damage to the design of articles coated with copper (II) oxide. In addition, copper (II) oxide degrades antibacterial and antiviral performance.

Therefore, the average primary particle diameter determined from the maximum particle diameter measured by an electron microscope with respect to the particle diameter of the cuprous oxide particles is preferably within a range of 1 to 400 nm, more preferably 5 to 150 nm, and more preferably 10 to 50 nm More preferable.

Silica coating layer

In the present invention, the silica coating layer coated on the surface of the copper oxide particles can be formed by attaching a silica source to the surface of the copper oxide particles and hydrolyzing the silica source. The silica source is not particularly limited as long as it can generate silica by hydrolysis. Examples of the silica source include tetraethoxysilane, tetramethoxysilane, and silicon tetrachloride. Of these, tetraethoxysilane and tetramethoxysilane are more preferable, and tetraethoxysilane (hereinafter sometimes referred to as "TEOS ") is most preferable in consideration of availability and cost.

The silica coating layer of the present invention is preferably formed of an amorphous silica film. The thickness of the silica film is preferably in the range of 1 to 20 nm, more preferably 3 to 15 nm, and further preferably 5 to 10 nm.

The silica coating layer may contain a substance other than silica, so long as the effect of the present invention is not impaired. However, the content of the silica component in the silica coating layer is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 99% by mass or more, and most preferably 99.9% by mass or more.

The content of the silica coating layer is 5 to 20 parts by mass with respect to 100 parts by mass of the copper oxide particles. When the content is less than 5 parts by mass, the antioxidant effect is insufficient. On the other hand, when the content is 20 parts by mass or more, the antibacterial and antiviral performance is lowered. The content of the surfactant is preferably from 6.0 to 15% by mass, more preferably from 7.0 to 14% by mass, still more preferably from 7.0 to 13% by mass, and most preferably from 8.0 to 12% by mass.

The silica-coated copper oxide particles (antibacterial and antiviral material) have a BET specific surface area of 5 to 100 m 2 / g, preferably 10 to 50 m 2 / g, calculated by the nitrogen adsorption method (BET method) More preferably 40 m < 2 > / g. The copper oxide particles having a BET specific surface area of 5 to 100 m 2 / g can exhibit excellent antibacterial and antiviral properties. However, copper oxide particles having a BET specific surface area of 100 m < 2 > / g or more are difficult to synthesize and recover. This makes it possible to produce copper oxide particles which are difficult to handle. On the other hand, the following problems arise. The cuprous oxide particles having a specific surface area of less than 5 m < 2 > / g have a small contact point with bacteria or viruses, and their antibacterial and antiviral effects are reduced. On the other hand, the obtained copper oxide particles become dark orange brown under the influence of the own color of copper oxide. If these particles are used as antibacterial and antiviral coatings, the design of the articles coated with such coatings is impaired.

In order to adjust the BET specific surface area to fall within the above-mentioned range, it is necessary to reduce the crushing energy in the step of crushing the silica coated copper oxide particles, to adjust the coating amount of silica to fall within the above- (BET specific surface area is typically reduced by coating) such that the BET specific surface area of the cuprous oxide particles is controlled to be within or within the above-mentioned range.

The antibacterial and antiviral material preferably has an L * value of 50 or more, an a * value of 8 or less, and a b * value of 20 or more in the L * a * b * color system according to JIS Z8701. Compared to commercially available copper oxide, the antimicrobial and antiviral materials of the present invention are brightened by having a large L * value, a small a * value, and a large b * value to provide an excellent design by becoming reddish and more yellowish.

L * a * b * color system represents object color, L * represents brightness, and a * and b * represent color tone and intensity. The larger L * indicates brighter. a * and b * denote the direction of the color. Specifically, a * indicates a red direction, -a * indicates a green direction, b * indicates a yellow direction, and -b * indicates a blue direction. The intensity c * is expressed as ((a *) ² + (b *) ² ) ^1/2 .

2. Method for producing antimicrobial and antiviral material

The antibacterial and antiviral material of the present invention comprises (1) synthesizing copper oxide particles by adding a basic substance, a particle growth inhibitor and a reducing agent to an aqueous solution of copper (II) compound;

(2) Copolymerizing the copper oxide particles with silica so that the silica source is hydrolyzed by mixing the copper oxide particles and the hydrolyzable silica source in a solvent so that the content of silica is 5 to 20 mass parts relative to 100 mass parts of the copper oxide fair; And

(3) a step of separating the solid component and then pulverizing the separated solid component.

Each step will be described below.

(1) Process for synthesizing copper oxide particles

The water-soluble copper (II) compound includes copper (II) sulfate, copper (II) chloride, copper (II) chloride, copper (II) acetate and copper (II) hydroxide. Copper (II) sulfate is preferred. The concentration of the copper (II) compound in the aqueous copper solution used for synthesis is preferably 0.05 to 1 mol / L, more preferably 0.1 to 0.5 mol / L from the viewpoint of copper (II) ion.

When the concentration of the copper (II) compound is 0.05 mol / L or less, it is not economical from the viewpoint of mass production. If the concentration of the copper (II) compound is 1 mol / L or more, the concentration of copper ions in the solution becomes too high, which is disadvantageous for the synthesis of copper oxide particles.

The basic substance may be any one of organic and inorganic materials, and includes sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, triethylamine and tetrabutylammonium hydroxide. Of these, sodium hydroxide and tetrabutylammonium hydroxide are preferred. The amount of the basic substance to be added is preferably 0.5 to 5 times, more preferably 1 to 3 times, the number of moles of copper (II) ions.

If the added amount of the basic substance is less than 0.5 times the mole number of the copper (II) ion, the basic environment for sufficiently reducing copper (II) to copper (I) can not be made. The addition amount of the basic substance having a molar number of 5 or more is disadvantageous for the precipitation of copper (I) oxide, since the extra hydroxyl group is coordinated with the copper (II) ion.

Particle growth inhibitors include glucose, PVP, PVA, gelatin and amino acids. Of these, glucose is preferable. The addition amount of the particle growth inhibitor is preferably 0.1 to 5 times, more preferably 0.3 to 3 times, the number of moles of copper (II) ions.

If the addition amount of the particle growth inhibitor is less than 0.1 times the mole number of the copper (II) ion, the effect of inhibiting grain growth is not obtained. If the addition amount of the particle growth inhibitor is 5 times or more the mole number of the copper (II) ion, it is not economical from the viewpoint of cost.

The reducing agent includes aqueous solutions of hydroxylamine sulfate, hydroxylamine hydrochloride, sodium sulfite, sodium hydrogen sulfite, sodium aditate, hydrazine sulfate, hydrazine and sodium phosphite. Of these, a hydrazine aqueous solution is preferable. The amount of the reducing agent to be added is preferably 0.1 to 1 times, more preferably 0.2 to 0.5 times the number of moles of copper (II) ions.

If the addition amount of the reducing agent is 0.1 times or less, the copper (II) ion can not be sufficiently reduced with copper (I) oxide. If the addition amount of the reducing agent is more than 1 time, the amount of the reducing agent is too much so that the copper (II) ion is reduced to copper metal.

In the synthesis of the copper oxide particles, the temperature is preferably 10 to 90 占 폚, more preferably 30 to 60 占 폚.

When the temperature is 10 ° C or lower, the reaction rate is slowed, which is not preferable from the viewpoint of synthesis efficiency. When the temperature is 90 DEG C or higher, heat supply is increased, which is not preferable from the viewpoint of cost. The reaction time for synthesizing the copper oxide particles is preferably about 0.5 to 5 minutes. If the reaction time is less than 0.5 minutes, the copper (II) ion can not be completely reduced. The reaction time of 5 minutes or more is not necessary because it is not preferable from the viewpoint of cost. The silica-coated copper oxide particles can be filtered through a membrane filter.

(2) Coating of copper oxide particles with a silica coating layer

In this step, the obtained copper oxide particles are mixed with a hydrolyzable silica source in a solvent, and the hydrolysis of the silica source to form copper oxide particles so that the content of silica is 5 to 20 parts by mass relative to 100 parts by mass of copper oxide Coat with silica.

In this method, the silica coating layer is an amorphous silica film formed by hydrolysis of a silica source. The silica source includes the silica source (tetraethoxysilane and the like) described above. The solvent is not particularly limited, but it is preferable to include an alcohol. Especially, ethanol is more preferable.

It is preferable to prepare a dispersion of copper oxide before the copper oxide particles are mixed with the silica source. The copper oxide dispersion can be obtained by adding the copper oxide particles obtained in the step (1) to a solvent such as ethanol, if necessary, and dispersing the dispersion in a ball mill.

Preferably, in the hydrolysis process, the silica source is added to the dispersion of copper oxide and stirred for 2 hours, ammonia water is added, and the silica source is hydrolyzed. During the hydrolysis, a catalyst such as hydrochloric acid can be used.

The total amount of the silica source to be added is set so that the content of the silica coating layer is 5 to 20 mass parts relative to 100 mass parts of the copper oxide particles in the antibacterial and antiviral material finally obtained after hydrolysis. The total amount of the silica source to be added is generally about 5 to 35 parts by mass (in terms of silica) based on 100 parts by mass of the copper oxide particles. The hydrolysis time is usually about 9 to 15 hours.

(3) Grinding process

After the step (2), the solid content is dried, separated and pulverized to obtain the antimicrobial and antiviral material of the present invention.

Filtration by a membrane filter can be employed for separating solid components. The separated solids are dried at 50-80 占 폚 as needed before grinding. For pulverizing, a pulverizer such as a ball mill, a mixer and a pot mill; Inducing and blocking; . Preferably, the crushing means illustrated here is easy to adjust with a small crushing energy, so that the BET specific surface area of the antibacterial and antiviral material is within the range of 5 to 100 m 2 / g. Fragments of silica may be mixed during various pulverization.

3. Antimicrobial and antiviral composition

The antimicrobial and antiviral composition of the present invention contains the above-described antimicrobial and antiviral materials of the present invention. Such an antibacterial and antiviral composition preferably contains a photocatalyst material in addition to an antibacterial and antiviral material. (Copper (I) oxide) under irradiation with light because it contains antimicrobial and antiviral properties after being changed from copper (I) oxide to copper (II) oxide by containing a photocatalyst material. As a result, antimicrobial and antiviral performance can be almost permanently sustained.

Photocatalyst material

The photocatalyst material should be capable of reducing copper (II) oxide to copper (I) oxide under light irradiation, and preferably contains a photocatalyst as a main component. Here, the "main component" means that the photocatalyst material contains a photocatalyst in an amount of 60 mass% or more.

The photocatalyst includes a compound semiconductor such as a metal oxide and a metal oxynitride. Of these, titanium oxide or tungsten oxide is preferable from the viewpoint of versatility, and titanium oxide is particularly preferable.

It is known that titanium oxide has a crystalline form of rutile, anatase, and brookite, but can be applied without particular limitation. The present inventors believe that the rutile type having antimicrobial and antiviral properties has comparatively high performance. Since the rutile type has a large specific gravity, it is difficult to disperse in a solution, and it is difficult to obtain a transparent coating agent. From the viewpoint of practical use, it is important to use an anatase type or a brookite type for the coating agent having high transparency through the anatase type and the brookite type, which has a slightly poor antifungal and antiviral performance against the rutile type. Therefore, the crystal structure of titanium oxide can be selected according to productivity and use.

When it is assumed to be used indoors, the photocatalyst material is preferably a visible light-responsive photocatalyst.

The photocatalyst material is more preferably a visible light-responsive photocatalyst in which the surface of the substrate containing at least one kind selected from titanium oxide and tungsten oxide is modified with at least one kind selected from copper (II) ions and iron (III) ions . The base material of the visible light-responsive photocatalyst is a titanium oxide doped with at least one of a transition metal and a non-metal, from the viewpoint of increasing the light absorption amount; And tungsten oxide doped with at least one of a transition metal and a nonmetal.

As the visible light-responsive photocatalyst, titanium oxide is not particularly limited. For example, single crystal amorphous titanium oxide each having a single crystal structure of an anatase, rutile or broucite type and having two or more kinds of these crystal structures can be used. As the visible light responsive photocatalyst, tungsten oxide is not particularly limited. For example, tungsten oxide having a triple crystal structure, a monoclinic crystal structure, and a tetragonal crystal structure may be used.

As the visible light responsive photocatalyst, copper (II) ion and iron (III) ion are not particularly limited as long as they can be modified with a photocatalyst and improve photocatalytic activity under visible light irradiation. For example, the copper (II) ion and the iron (III) ion modified by the photocatalyst include oxides, hydroxides, chlorides, nitrates, sulfates and acetic acid salts or organic complexes of copper (II) Respectively. Of these, oxides and hydroxides are preferable.

As the visible light responsive photocatalyst, there is no particular limitation so long as the transition metal and the non-metal can be doped with titanium oxide to increase the impurity level and increase absorption of visible light. For example, the transition metal includes vanadium, chromium, iron, copper, ruthenium, rhodium, tungsten, gallium and indium. Nonmetals include carbon, nitrogen and sulfur. In the titanium oxide or the tungsten oxide crystal, a plurality of transition metals, or a transition metal and a nonmetal can be co-doped to maintain charge balance.

As these catalysts, copper (II) ion-modified titanium oxide is exemplified in paragraphs [0029] to [0032] of JP 2011-079713 A. Copper (II) ion-modified tungsten oxide is exemplified in paragraphs [0028] to [0031] of JP 2009-226299 A. Copper (II) ion-modified exemplified titanium oxide that is co-doped with a tungsten and gallium is illustrated in paragraphs [0013] to [0021] of JP 2011-031139 A.

The photocatalyst material preferably has a high crystallinity, and specifically has a crystallinity of at least 60%. High crystallinity can inhibit the binding of electrons and holes generated by photoexcitation from binding. This improves the probability of copper (II) receiving electrons and improves the reduction suitability.

The photocatalyst material preferably has a small average particle diameter, and is specifically 500 nm or less, more preferably 300 nm or less, and further preferably 100 nm or less. When the average particle diameter is small, the time for electrons generated by photoexcitation to reach the surface of the photocatalyst material can be shortened. This improves the probability of copper (II) receiving electrons and improves the reduction suitability.

The ratio of the photocatalyst material in the total amount of the ordinary photocatalyst material and the total amount of the antibacterial and antiviral material is preferably 70 to 99.9 mass% from the viewpoint of balance between the antimicrobial and antiviral performance due to the reducing ability and the initial antimicrobial and antiviral performance By mass, more preferably 80 to 99% by mass, and still more preferably 90 to 98% by mass.

The antimicrobial and antiviral composition may contain solids other than the antibacterial and antiviral material and the photocatalytic material, so long as the effect of the present invention is not impaired. The total amount of the antibacterial and antiviral material and the photocatalyst material in the antibacterial and antiviral composition is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 99.9% by mass or more from the viewpoint of the solid content . When the antibacterial and antiviral composition does not contain a photocatalyst material, the proportion of the antibacterial and antiviral material in the antibacterial and antiviral composition is preferably 90% by mass or more, more preferably 95% by mass or more, More preferably 99.9% by mass or more.

The antibacterial and antiviral composition containing the photocatalyst material and the antibacterial and antiviral material can be obtained by mixing the antibacterial and antiviral material of the present invention or a dispersion thereof with the above-described dispersion of the photocatalyst material.

4. Dispersions of antimicrobial and antiviral compositions

The dispersion of the antibacterial and antiviral composition of the present invention (hereinafter sometimes referred to as "dispersion of the present invention") may be prepared by mixing 1 to 30% by mass of the antibacterial and antiviral composition of the present invention, By mass of a basic substance soluble in a non-aqueous organic solvent, and 0.01 to 10% by mass of a basic substance soluble in a non-aqueous organic solvent.

In the dispersion of the present invention, by adjusting the content ratio as described above, the antibacterial and antiviral composition can be uniformly dispersed and stably stored.

The antimicrobial and antiviral composition contained in an amount of 1% by mass or less may exhibit antibacterial and antiviral properties. The antimicrobial and antiviral composition contained in an amount of 30 mass% or less can be stably stored in the dispersion of the present invention, thereby improving the convenience. The concentration of the antibacterial and antiviral composition in the dispersion of the antibacterial and antiviral composition is preferably 2 to 20% by mass, more preferably 3 to 10% by mass.

A non-aqueous organic solvent containing a concentration of 40% by mass can stably preserve the antimicrobial and antiviral composition. A concentration of 98.98 mass% or less can ensure antimicrobial and antiviral performance by securing the amount of the antimicrobial and antiviral composition. The concentration of the non-aqueous organic solvent is preferably 58 to 97.90 mass%, more preferably 75 to 96.84 mass%.

A basic substance soluble in a non-aqueous organic solvent having a concentration of not less than 0.01% by mass can inhibit the dissolution of the copper oxide particles because the dispersion of the present invention becomes basic. In addition, a basic substance having a concentration of 10% by mass or less can reduce the residual amount of a basic substance in the film formed from the dispersion of the present invention to maintain the antibacterial and antiviral performance of the copper oxide particles. The concentration of the basic substance in the dispersion of the antibacterial and antiviral composition is preferably 0.05 to 7% by mass, and more preferably 0.08 to 5% by mass.

The non-aqueous organic solvent is an organic solvent other than water and includes ethanol, methanol, 2-propanol, denatured alcohol, methyl ethyl ketone (MEK), and n-propyl acetate (NPAC).

The reason for using the non-aqueous organic solvent is that the copper oxide is easily oxidized into divalent copper in water but is not easily oxidized in the non-aqueous solvent. Therefore, it is preferable that the amount of water in the non-aqueous organic solvent is 0.5% by mass or less based on the amount of the non-aqueous solvent.

The basic substance soluble in the non-aqueous organic solvent may be any one of organic or inorganic materials and includes sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, triethylamine and tetrabutylammonium hydroxide. Of these, sodium hydroxide and tetrabutylammonium hydroxide are preferred. The solubility of the basic substance is preferably 0.05 g or more per 100 g of the non-aqueous organic solvent.

If the solubility of the basic substance is 0.05 g or less based on 100 g of the non-aqueous organic solvent, the dispersion of the present invention can not be sufficiently retained in a basic environment and is dissolved by acidity when mixed with copper (I) oxide.

The dispersion of the present invention preferably further contains a surfactant soluble in a non-aqueous organic solvent. By containing the surfactant, the dispersion can be stabilized by reducing the intergranular aggregation of the antibacterial and antiviral composition to give steric hindrance.

The surfactant is preferably contained in an amount of 0.01 to 20% by mass in the dispersion of the antibacterial and antiviral composition. When the content of the surfactant is 0.01 mass% or more, the dispersibility of the dispersion becomes good, and the antibacterial and antiviral composition can be prevented from the precipitation. By setting the content of the surfactant to 20% by mass or less, the amount of the surfactant remaining in the film formed from the dispersion can be reduced to prevent the antibacterial and antiviral performance of the film from deteriorating. The content of the surfactant is preferably 0.05 to 15 mass%, more preferably 0.08 to 10 mass%.

The surfactant which is soluble in the non-aqueous organic solvent is preferably a nonionic surfactant, and examples thereof include esters such as glycerin fatty acid esters, sorbitan fatty acid esters and sucrose fatty acid esters, fatty acid alcohol ethoxylates, polyoxyethylene alkylphenyl ethers, And ethers such as phenoxy polyethoxy ethanol (Triton 占 X-100) and alkyl glycosides. Of these, octylphenoxy polyethoxy ethanol is preferred.

5. Coatings containing antibacterial and antiviral compositions, antibacterial and antiviral membranes, and antimicrobial and antiviral products

Coatings containing the antimicrobial and antiviral compositions of the present invention include dispersions of the antimicrobial and antiviral compositions of the present invention, depending on the binder component that can be cured under an environment of 10 to 120 캜. As the binder component, any one of an inorganic binder and an organic binder may be used. From the viewpoint of decomposition of the binder by the photocatalyst material, an inorganic binder is preferable. The kind of the binder is not particularly limited and includes, for example, a silica binder, a zirconia binder, an alumina binder and a titania binder, and combinations thereof. Among these, a silica binder or a zirconia binder is preferable.

The content of the binder is preferably 0.5 to 10% by mass, and more preferably 1 to 8% by mass in the coating agent containing the antibacterial and antiviral composition. By setting the content of the binder to the above range, the coating agent can be stably dispersed, the coating agent can be coated on the coating agent, and the coating agent can be easily and uniformly formed by curing the coating agent and the coating adhesion to the coating agent can be improved .

The antibacterial and antiviral membrane of the present invention is formed by applying and curing a coating agent containing the antibacterial and antiviral composition of the present invention. Coatings for coatings containing antibacterial and antiviral compositions of the present invention include metals, ceramics, glass, fibers, nonwoven fabrics, films, plastics, rubbers, paper and wood. The surface of the coating body may be subjected to this bonding process or the like. The coating method is not particularly limited. As the coating method, a spin coating method, a dip coating method, a spray coating method, or the like can be applied.

The curing temperature after application of the coating agent is preferably about 20 to 80 캜, although it depends on the binder component to be used. The thickness of the antibacterial and antiviral film of the present invention obtained by curing is preferably 0.05 to 1 mu m, more preferably 0.1 to 0.5 mu m.

If the film thickness is 0.05 탆 or less, the amount of the antibacterial and antiviral composition becomes small, and the antibacterial and antiviral performance can not be sufficiently exhibited by the material. If the film thickness is 1 탆 or more, the amount of the antimicrobial and antiviral composition increases, so that the material can sufficiently exhibit antibacterial and antiviral performance, but the hardness and durability of the film are reduced.

The antimicrobial and antiviral products of the present invention have antibacterial and antiviral membranes of the present invention in at least a part of the outermost side (for example, a part where human contact is made), and they can be used for building construction materials, sanitary articles, .

(Example)

The present invention will be described in detail with reference to the following examples.

The examples and comparative examples were measured and evaluated as follows.

XRD measurement

The crystal peak attribution of the copper oxide particles of the antibacterial and antiviral composition obtained in each Example was measured by XRD measurement. In the XRD measurement, Cu-K? 1 line was used as the copper target, the tube voltage was 45 kV, the tube current was 40 mA, the measurement range was 2? = 20 to 80 deg, the sampling width was 0.0167 deg, Min. For this measurement, X'PertPRO from Panalytical B. V. was used.

BET specific surface area

The BET specific surface area of the antibacterial and antiviral material obtained in each of the examples and the comparative examples was measured by using the method of Mountech Co., Ltd. Quot; Macsorb, HM model-1208 ".

Mass of the silica coating layer

The mass of the silica coating layer of the antibacterial and antiviral material obtained in each of the Examples and Comparative Examples was measured by the following procedure. Silica-coated copper oxide particles (0.1 g), Na ₂ CO ₃ (2 g) and H ₃ BO ₃ (1 g) were added to the platinum crucible and alkali melting was performed. After allowing to stand and cooling, the molten mixture was mixed with a nitric acid solution to obtain a mixed solution. The obtained solution was measured with an ICP emission spectrophotometer (product name: ICPS-7500, manufactured by Shimadzu Corporation). The calibration curve was prepared using 10 ppm of the silicon standard solution. The silicon amount of silica-coated copper oxide particles was calculated from the calibration curve. The mass of the silica was calculated from the amount of silicon and defined as the mass of the silica coating layer.

Color value

The color value (L * a * b * value) was determined by Konica Minolta Optics, Inc. And measured with a colorimeter "CM-3700d"

Environmental test

Environmental testing was conducted by ESPEC Corp. It was done with a small environmental tester "SH-241". Antibacterial and antiviral compositions were maintained for one week at a temperature of 50 ° C and a humidity of 98%.

Evaluation of virus inactivation ability: Measurement of LOG (N / N ₀ )

The virus inactivation ability was evaluated by the following procedure in a model experiment using bacteriophage. Methods for using the inactivating ability against bacteriophage as a model of virus inactivation ability are described, for example, in Appl. Microbiol Biotechnol., 79, pp. 127-133, 2008, and it is known that reliable results can be obtained.

A filter paper is placed on the bottom of a heart-shaped Petri dish, and a small amount of sterilized water is added to the petri dish Hour. A glass platform with a thickness of about 5 mm was placed on the filter paper. A glass plate (50 mm x 50 mm x 1 mm) was placed on the glass platform. The antibacterial and antiviral materials of Examples 1 to 4 and the samples of Comparative Examples 1 to 4 were coated on these glass plates so as to have a solid content of 0.06 mg / 25 cm < 2 > The dispersion of the composition and the samples of Comparative Examples 5 to 11 were applied so as to have a solid content of 1.5 mg / 25 cm < 2 >. 100 占 퐇 of a suspension of the predetermined concentration of the preliminarily QB phage (NBRC20012) was added dropwise to each glass plate, and then an OHP film made of PET (polyethylene terephthalate) was placed on each of the glass plates to contact the sample surface with the phage . The heart culture plate was covered with a cap to prepare a measurement unit. We have prepared multiple measurement units per sample.

15 W white fluorescent lamp (full white fluorescent lamp, FL15N, manufactured by Panasonic Corporation) equipped with a UV-cutting filter (N-113, manufactured by Nitto Jushi Kogyo Co., Ltd.) was used as a light source. The measurement unit was installed under light source at a position where the illuminance (measured by an illuminometer, IM-5, manufactured by TOPCON Corporation) was 800 Lux. After elapse of a predetermined time, the holding concentration of each sample present on the glass plate was measured.

The phage concentration was measured by the following procedure. Samples present on the glass plate were collected in 10 mL of phage recovery (SM buffer) and shaken in a shaker for 10 minutes. This phage recovery solution was appropriately diluted and mixed with the cultured E. coli (NBRC13965) culture medium (OD ₆₀₀ > 1.0, 1 × 10 ⁸ CFU / mL), and the mixture was placed in a 37 ° C. thermostatic chamber. Coli infected phage. The obtained solution was added to an agar medium and cultured at 37 DEG C for 15 hours. Thereafter, the phage plaque count was visually counted. The retention concentration (N) was obtained by multiplying the dilution rate of the retention solution by the number of plaques counted.

The relative grip density LOG (N / N ₀ ) was obtained from the initial grip concentration N ₀ and the grip concentration N after a predetermined time has elapsed.

The virus inactivation performance evaluated under various conditions is shown in Tables 1-3.

Example 1

After 3,000 mL of distilled water was heated to 50 캜, 149.8 g of copper (II) sulfate pentahydrate was added with stirring to dissolve completely. Subsequently, 200 g of 1.5 mol / L glucose aqueous solution was added, and then 720 g of a 2 mol / L aqueous sodium hydroxide solution and 120 mL of an aqueous solution of 2 mol / L hydrazine hydrate were simultaneously added. After the mixture was vigorously stirred for one minute, the stirred mixture was filtered through a membrane filter of 0.3 mu m, and the filtered material was washed with 3000 mL of distilled water to recover the solid matter. After drying at 60 DEG C for 3 hours, the solid content was pulverized with agate induction to obtain copper oxide particles. The BET specific surface area of the obtained copper oxide particles was measured by a nitrogen adsorption method and found to be 29.20 m2 / g. 5 g of the obtained copper oxide particles was dispersed in 60 mL of an ethanol solvent to obtain a suspension 1. 1.827 g of TEOS having a purity of 95% was added to 20 mL of ethanol to obtain solution 2 (corresponding to 10 parts by mass of silica from the viewpoint of the total amount added to 100 parts by mass of the copper oxide particles). Solution 2 was mixed with Suspension 1, and 10 mL of pure water was added to the mixture and stirred for 2 hours. 10 mL of 5% aqueous ammonia solution was added to the mixture and stirred for 12 hours. The mixture was filtered with a 0.3 mu m membrane filter. The filtered material was washed with 100 mL of distilled water and then with 100 mL of ethanol. The collected material was dried at 60 DEG C for 3 hours and pulverized with agate to obtain an antibacterial and antiviral material (silica-coated copper oxide particles) A. Table 1 shows the mass and BET specific surface area of the silica coating layer of the obtained silica-coated copper oxide particles.

FIG. 1 shows TEM photographs of the antibacterial and antiviral material A (copper oxide particles coated with silica). In FIG. 1, it was confirmed that a silica layer having a thickness of about 5.6 nm was formed. Fig. 2 shows an X-ray diffraction pattern of the antibacterial and antiviral material A (silica-coated copper oxide particles). In Fig. 2, only the peak of copper oxide was observed. Thus, an amorphous silica coating layer was clearly formed.

Example 2

Copper disulfide particles were prepared in the same manner as in Example 1. 5 g of the obtained copper oxide particles was dispersed in 60 mL of an ethanol solvent to obtain a suspension 1. 2.742 g of TEOS having a purity of 95% was added to 20 mL of ethanol to obtain a solution 2 (corresponding to 15 parts by mass of silica in terms of the total added amount with respect to 100 parts by mass of the copper oxide particles). Solution 2 was mixed with Suspension 1, and 10 mL of pure water was added to the mixture. Thereafter, antibacterial and antiviral materials (copper oxide particles coated with silica) B were obtained in the same manner as in Example 1. Table 1 shows the mass and BET specific surface area of the silica coating layer of the obtained silica-coated copper oxide particles.

Example 3

Copper disulfide particles were prepared in the same manner as in Example 1. 5 g of the obtained copper oxide particles was dispersed in 60 mL of an ethanol solvent to obtain a suspension 1. To 20 mL of ethanol was added 3.654 g of TEOS having a purity of 95% to obtain a solution 2 (corresponding to 20 parts by mass of silica from the viewpoint of the total amount added to 100 parts by mass of the copper oxide particles). Solution 2 was mixed with Suspension 1, and 10 mL of pure water was added to the mixture. Thereafter, an antimicrobial and antiviral material (silica-coated copper oxide particles) C was obtained in the same manner as in Example 1. Table 1 shows the mass and BET specific surface area of the silica coating layer of the obtained silica-coated copper oxide particles.

Example 4

Copper disulfide particles were prepared in the same manner as in Example 1. 5 g of the obtained copper oxide particles was dispersed in 60 mL of an ethanol solvent to obtain a suspension 1. To 20 mL of ethanol was added 4.59 g of TEOS having a purity of 95% to obtain Solution 2 (corresponding to 25 parts by mass of silica from the viewpoint of the total amount added to 100 parts by mass of the copper oxide particles). Solution 2 was mixed with Suspension 1, and 10 mL of pure water was added to the mixture. Thereafter, antibacterial and antiviral materials (silica-coated copper oxide particles) D were obtained in the same manner as in Example 1. Table 1 shows the mass and BET specific surface area of the silica coating layer of the obtained silica-coated copper oxide particles.

Comparative Example 1

Copper disulfide particles were prepared in the same manner as in Example 1. Table 1 shows the BET specific surface area of the obtained copper oxide particles.

Comparative Example 2

Copper disulfide particles were prepared in the same manner as in Example 1. 5 g of the obtained copper oxide particles was dispersed in 60 mL of an ethanol solvent to obtain a suspension 1. To 20 mL of ethanol was added 0.918 g of TEOS having a purity of 95% to obtain a solution 2 (equivalent to 5 parts by mass of silica with respect to 100 parts by mass of the copper oxide particles in terms of the total added amount). Solution 2 was mixed with Suspension 1, and 10 mL of pure water was added to the mixture. Thereafter, an antibacterial and antiviral material (silica-coated copper oxide particles) E was obtained in the same manner as in Example 1. Table 1 shows the mass and BET specific surface area of the silica coating layer of the obtained silica-coated copper oxide particles.

Comparative Example 3

Copper disulfide particles were prepared in the same manner as in Example 1. 5 g of the obtained copper oxide particles was dispersed in 60 mL of an ethanol solvent to obtain a suspension 1. 6.40 g of TEOS having a purity of 95% was added to 20 mL of ethanol to obtain a solution 2 (corresponding to 35 parts by mass of silica in terms of the total added amount relative to 100 parts by mass of the copper oxide particles). Solution 2 was mixed with Suspension 1, and 10 mL of pure water was added to the mixture. Thereafter, an antibacterial and antiviral material (silica-coated copper oxide particles) F was obtained in the same manner as in Example 1. Table 1 shows the mass and BET specific surface area of the silica coating layer of the obtained silica-coated copper oxide particles.

The results before the environmental test showed that the virus inactivation ability decreased with increasing amount of silica coating.

The results before and after the environmental test showed that in Examples 1 to 4, the virus inactivating ability and the color value did not change before and after being kept in the environmental test chamber. It is believed that it contained antioxidant because it contained a silica coating layer. Particularly, any one of Examples 1 to 3 had a high level of virus-inactivating performance before and after the environmental test.

On the other hand, in Comparative Examples 1 and 2, the virus had significantly reduced inactivating ability, reduced color strength and black after the environmental test. This is considered to be because the content of the silica coating layer is small and thus it is not antioxidant. In Comparative Example 3, since the silica coating layer was contained too much, it had poor virus-inactivating performance before the environmental test.

Example 5

An anatase type titanium oxide (manufactured by Showa Titanium Co., Ltd., average particle diameter: 15 nm) was suspended in 2-propyl alcohol (hereinafter referred to as "IPA") to prepare a dispersion having a solid content concentration of 5 mass%. 2 parts by mass of Triton 占 X-100 (octylphenoxy polyethoxy ethanol produced by Kanto Chemical Co., Ltd.) was added to 100 parts by mass of titanium oxide, and then 2 parts by mass of tetrabutyl per 100 parts by mass of titanium oxide Ammonium hydroxide (40 mass% aqueous solution of tetrabutylammonium hydroxide (manufactured by Kanto Chemical Co., Ltd.)) was added.

Thereafter, the suspension was dispersed with a beads mill using a 0.1 mm-size medium to obtain a dispersion (hereinafter referred to as "dispersion G"). Dispersion G and the antibacterial and antiviral material A obtained in Example 1 were added to a total amount of 100 parts by mass of the antibacterial and antiviral material and titanium oxide in an amount of 4.8 parts by mass of the antibacterial and antiviral material A 95.2 parts by mass). Thereafter, a dispersion of the antibacterial and antiviral composition was obtained.

The dispersion of the obtained antimicrobial and antiviral composition was applied to a glass plate (50 mm x 50 mm x 1 mm) to have a solid content of 1.5 mg / 25 cm < 2 >. The solvent on the glass plate was evaporated, and the virus inactivation ability was evaluated (evaluation method will be described later). The results are shown in Fig.

In Fig. 3, "blank" represents the evaluation result of the virus inactivation ability only on the glass plate. "Cow" represents the evaluation result of the glass plate coated with the dispersion under the dark condition. "Visible light irradiation" shows the evaluation result of the glass plate coated with the dispersion under visible light irradiation.

The visible light irradiation was performed under the condition of light guided from a white fluorescent lamp through an optical filter (N-113 manufactured by Nitto Jushi Co., Ltd.) cutting light of 400 nm or less. The light intensity was 800 Lux.

As shown in Fig. 3, only the glass plate did not exhibit virus inactivation ability. In the glass plate coated with the dispersion, the virus showed inactivation ability even in the cow. The glass plate coated with the dispersion showed a high virus inactivation ability under visible light irradiation. Therefore, it has been found that the antibacterial and antiviral composition of the present invention exhibits excellent virus inactivation ability. In addition, it was confirmed that the antimicrobial and antiviral composition of the present invention, which is used as a photocatalyst material, has an effect of improving the virus inactivating ability under light irradiation of a cow.

Example 6

50 g of brookite type titanium oxide (average particle size: 10 nm, manufactured by Showa Titanium Co., Ltd.) was suspended in 1000 mL of distilled water, and 0.133 g of CuCl 2 ₂ .2H ₂ O (manufactured by Kanto Chemical Co., Ltd.) was added and the mixture was heated at 90 ° C with stirring for 1 hour. The heated mixture was washed and dried to obtain copper (II) ion-modified titanium oxide H. A dispersion of the antibacterial and antiviral composition was obtained in the same manner as in Example 5 except that the copper (II) ion-modified titanium oxide H was used in place of the anatase-type titanium oxide.

Example 7

50 g of tungsten oxide (manufactured by Wako Pure Chemical Industries, Ltd.) was suspended in 1000 ml of distilled water and 0.133 g of CuCl ₂ .2H ₂ O (manufactured by Kanto Chemical Co Co., Ltd.) was added thereto so that 0.1 mass part of copper (II) Ltd.) was added, and the mixture was heated at 90 DEG C with stirring for 1 hour. The heated mixture was washed and dried to produce copper (II) ion-modified tungsten oxide I. A dispersion of the antibacterial and antiviral composition was obtained in the same manner as in Example 5 except that copper (II) ion-modified tungsten oxide I was used in place of the anatase-type titanium oxide.

Example 8

10 g of titanium oxide (rutile type crystal structure, manufactured by TAYCA Corporation, average particle size: 15 nm) was suspended in 20 mL of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a titanium oxide suspension. 1 g of tungsten hexachloride (manufactured by Sigma-Aldrich Co., Ltd.) was dissolved in 10 mL of ethanol to prepare a tungsten solution. 1 g of gallium (III) nitrate hydrate (manufactured by Sigma-Aldrich Co., Ltd.) was dissolved in 10 mL of ethanol to prepare a gallium solution. A tungsten solution and a gallium solution were mixed in a titanium oxide suspension so that the molar ratio of tungsten: gallium: titanium was 0.03: 0.06: 0.91. While stirring the mixture, the ethanol solvent was evaporated. The obtained powder was heated at 950 占 폚 for 3 hours. As a result, titanium oxide balls doped with tungsten and gallium were obtained. 5 g of titanium oxide co-doped with tungsten and gallium was suspended in 100 g of distilled water, and 0.013 g of CuCl ₂ .2H ₂ O (0.015 g) was added to 100 parts of titanium oxide co-doped with tungsten and gallium so that 0.1 part of copper (Manufactured by Kanto Chemical Co., Ltd.) was added, and the mixture was heated at 90 DEG C with stirring for 1 hour. The heated mixture was washed and dried to prepare titanium oxide J in which copper (II) ion-modified tungsten and gallium were co-doped. A dispersion of the antibacterial and antiviral composition was obtained in the same manner as in Example 5 except that copper (II) ion-modified tungsten and titanium oxide co-doped with gallium were used in place of the anatase-type titanium oxide.

Example 9

In Example 5, the dispersion G and the antibacterial and antiviral material A obtained in Example 1 were added to 100 parts by mass of the total amount of the antibacterial and antiviral material and the titanium oxide in an amount of 15.0 mass parts of the antibacterial and antiviral material A (The content of the photocatalyst material was 85.0 parts by mass). Thereafter, a dispersion of the antibacterial and antiviral composition was obtained.

Example 10

In Example 5, the dispersion G and the antibacterial and antiviral material A obtained in Example 1 were mixed in an amount of 25.0 parts by mass per 100 parts by mass of the total amount of the antibacterial and antiviral material and titanium oxide (The content of the photocatalyst material was 75.0 parts by mass). Thereafter, a dispersion of the antibacterial and antiviral composition was obtained.

Comparative Example 4

Copper oxide particles coated with silica were obtained in the same manner as in Example 1 except that commercially available copper oxide (trade name: "Regular", manufactured by Furukawa Chemicals Co., Ltd., BET specific surface area: 1 m 2 / g) . Table 2 shows the mass and BET specific surface area of the silica coating layer of the obtained silica-coated copper oxide particles. 1 g of the obtained copper oxide coated with silica was dispersed in 100 ml of ethanol to obtain a dispersion. The dispersion was coated on a glass plate so that the coating amount was 24 mg / m < 2 > to form a coating film of copper oxide.

Comparative Example 5

The copper oxide particles obtained in Comparative Example 1 were left in an environmental test chamber (50 DEG C, 98% RH) for 7 days and oxidized with copper (II) oxide. The copper oxide (II) and the dispersion G were mixed so that copper (II) oxide: titanium oxide was 4.8: 95.2. Thereafter, copper (II) oxide / titanium oxide dispersion was obtained.

Comparative Example 6

The copper oxide particles obtained in Comparative Example 1 and the dispersion G were mixed so that the amount of copper oxide (I): titanium oxide was 4.8: 95.2. Thereafter, copper (I) oxide / titanium oxide dispersion was obtained.

Comparative Example 7

Except that the copper (II) ion-modified titanium oxide H used in Example 6 was used in place of the anatase-type titanium oxide used in Example 5, Thereby obtaining a dispersion product K. The copper oxide particles and the dispersion K obtained in Comparative Example 1 were mixed so that the mass ratio of copper oxide particles: copper (II) ion-modified titanium oxide H was 4.8: 95.2. Thereafter, a copper oxide (I) / copper (II) ion modified titanium oxide dispersion was obtained.

Comparative Example 8

Except that the copper (II) ion-modified tungsten oxide I used in Example 7 was used instead of the anatase-type titanium oxide, the copper (II) ion-modified tungsten oxide I Thereby obtaining a dispersion L. The copper oxide particles and the dispersion L obtained in Comparative Example 1 were mixed so that the mass ratio of copper oxide particles: copper (II) ion-modified tungsten oxide I was 4.8: 95.2. Thereafter, a copper oxide (I) / copper (II) ion-modified tungsten oxide dispersion was obtained.

Comparative Example 9

Except that copper (II) ion-modified tungsten used in Example 8 and titanium oxide J co-doped with gallium J were used in place of the anatase-type titanium oxide, copper II) Ion Modification A dispersion M of a titanium oxide J co-doped with tungsten and gallium was obtained. The copper oxide particles and the dispersion M obtained in Comparative Example 1 were mixed so that the mass ratio of the copper oxide particles: copper (II) ion-modified tungsten and the gallium-co-doped titanium oxide was 4.8: 95.2. Thereafter, a dispersion of titanium oxide co-doped with copper (I) / copper (II) ion-modified tungsten and gallium was obtained.

Comparative Example 10

Except that aluminum oxide (produced by Kanto Chemical Co., Ltd., average particle diameter: 40 탆) was used in place of anatase-type titanium oxide, the same procedure as in the production process of dispersion G in Example 5 was carried out except that aluminum oxide dispersion N ≪ / RTI > The copper oxide particles obtained in Comparative Example 1 and the dispersion N were mixed so that the mass ratio of copper oxide particles: aluminum oxide obtained in Comparative Example 1 was 4.8: 95.2. Thereafter, a copper suboxide (I) / aluminum oxide dispersion was obtained.

Comparative Example 11

The antibacterial viral material E and the dispersion G obtained in Comparative Example 2 were added in an amount of 4.8 parts by mass based on 100 parts by mass of the total amount of the antibacterial and antiviral material and titanium oxide (the content of the photocatalyst material was 95.2 parts by mass ). Thereafter, a dispersion of the antibacterial and antiviral composition was obtained.

Table 2 is a table comparing the virus inactivation ability and color values of the antibacterial and antiviral materials of Example 1 and Comparative Example 4. The results clearly show that the antimicrobial and antiviral material of Example 1 having a large BET specific surface area has higher activity than the antimicrobial and antiviral materials of Comparative Example 4. [ Therefore, the antibacterial and antiviral composition of the present invention can be expected to have a virus inactivation ability at least at a high application amount. The results also show that the antimicrobial and antiviral materials of Example 1 having a large BET specific surface area are lighter and less reddish, providing an excellent design.

Table 3 shows the antiviral performance of the material combined with the photocatalyst material after storage in a high load environment of an environmental tester (50 DEG C, 98% RH, shading) immediately after the synthesis.

Examples 5 to 10 were antibacterial and antiviral compositions having a combination of an antibacterial and antiviral material and a photocatalyst. Comparative Example 5 was an antimicrobial and antiviral composition having no silica coating layer and having a combination of copper oxide and a photocatalyst. Comparative Examples 6 to 9 were antibacterial and antiviral compositions having no silica coating layer and having a combination of copper oxide and photocatalyst. Comparative Example 10 was an antimicrobial and antiviral composition having no silica coating layer and a combination of copper oxide and aluminum oxide having no photocatalytic performance. Comparative Example 11 was an antibacterial and antiviral composition having a silica coating layer containing a small amount of silica and having a combination of copper oxide and a photocatalyst.

From the evaluation results immediately after the synthesis, Comparative Examples 5 to 10 and Comparative Examples 6 to 9 and 11 (antibacterial and antiviral compositions having a combination of copper oxide and photocatalyst), regardless of the presence or absence of the silica coating layer, Antimicrobial and antiviral compositions having a combination of copper (II) and a photocatalyst). Therefore, it is considered that copper oxide is required to show the virus inactivation ability in the cow from the beginning.

From the evaluation results immediately after the synthesis, Examples 5 to 10 (antibacterial and antiviral compositions having a combination of an antibacterial and antiviral material and a photocatalyst) and Comparative Examples 6 to 9 (antibacterial and antiviral composition without a silica coating layer) , And Comparative Example 11 (an antimicrobial and antiviral composition having a silica coating layer containing a small amount of silica and having a combination of copper oxide and photocatalyst) showed a virus inactivating ability in the dark and improved virus inactivation ability under light irradiation . Thus, no profound difference was found in the composition. On the other hand, in the evaluation results after storage in the environmental test chamber, Comparative Examples 6 to 9 in which the silica coating layer is not provided and Comparative Example 11 in which the silica coating layer containing a small amount of silica is contained are combined with the photocatalyst as in Examples 5 to 10, It was not found that it exhibited an activating ability.

The antimicrobial and antiviral composition of Comparative Example 10 having a combination of copper oxide and aluminum oxide that does not have photocatalytic activity exhibits virus inactivation ability in the cow immediately after the synthesis, There was no. In addition, the antibacterial and antiviral composition of Comparative Example 10 decreased in viral inactivation ability after storage in the environmental test chamber.

Therefore, as in Examples 5 to 10, it was confirmed that the antimicrobial and antiviral composition having a combination of an antibacterial and antiviral material and a photocatalyst can maintain a high virus inactivation ability from the viewpoint of resistance to temperature, moisture resistance and durability I could.

Claims (14)

An antibacterial and antiviral material comprising copper oxide particles and a silica coating layer of at least a part of the surface of the copper oxide particles,
Wherein the content of the silica coating layer is 5 to 20 parts by mass based on 100 parts by mass of the copper oxide particles, and the BET specific surface area of the silica coated copper oxide particles is 5 to 100 m < 2 > / g. material. An antimicrobial and antiviral composition comprising the antibacterial and antiviral material according to claim 1. 3. The method of claim 2,
Lt; RTI ID = 0.0 > antimicrobial < / RTI > and antiviral composition. The method of claim 3,
Wherein the content of the photocatalyst material is 70 to 99.9 mass% with respect to the total amount of the antibacterial and antiviral material and the photocatalyst material. The method according to claim 3 or 4,
Wherein the photocatalyst material comprises at least one selected from titanium oxide and tungsten oxide. The method according to claim 3 or 4,
Wherein the photocatalyst material is a visible light-responsive photocatalyst which is modified by at least one selected from copper (II) ions and iron (III) ions, wherein the substrate containing at least one kind selected from titanium oxide and tungsten oxide is an antibacterial And antiviral compositions. The method according to claim 6,
Wherein the substrate comprises at least one selected from titanium oxide doped with at least one of a transition metal and a nonmetal, and tungsten oxide doped with at least one of a transition metal and a nonmetal. 8. The method according to any one of claims 2 to 7,
Wherein the antibacterial and antiviral material has an L * value of 50 or more, an a * value of 8 or less, and a b * value of 20 or more in an L * a * b * color system according to JIS Z8701 Composition. A method for producing a non-aqueous organic solvent, which comprises 1 to 30 mass% of the antimicrobial and antiviral composition according to any one of claims 2 to 8, 40 to 98.98 mass% of a non-aqueous organic solvent, and 0.01 To 10% by mass of the composition. 10. The method of claim 9,
And 0.01 to 20% by mass of a surfactant soluble in the non-aqueous organic solvent. A coating agent comprising an antibacterial and antiviral composition according to any one of claims 9 to 10, and a binder component curable under an environment of 10 to 120 캜. An antimicrobial and antiviral membrane characterized by applying a coating containing the antimicrobial and antiviral composition according to claim 11 and curing. An antimicrobial and antiviral product characterized by comprising an antimicrobial and antiviral membrane according to claim 12 at least in part of the outermost side. A method for producing an antibacterial and antiviral material according to claim 1,
(1) a step of synthesizing copper oxide particles by adding a basic substance, a particle growth inhibitor and a reducing agent to an aqueous solution of a copper (II) compound;
(2) Copper oxide particles are mixed with silica in a solvent to hydrolyze the silica source, and the copper oxide particles are coated with silica so that the content of silica is 5 to 20 parts by mass with respect to 100 parts by mass of the copper oxide particles ; And
(3) a step of separating the solid component and then pulverizing the separated solid component.

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