WO2020166056A1

WO2020166056A1 - Coating agent, thin film, substrate with thin film, and method for producing thin film

Info

Publication number: WO2020166056A1
Application number: PCT/JP2019/005518
Authority: WO
Inventors: 誠之島田
Original assignee: 誠之島田
Priority date: 2019-02-15
Filing date: 2019-02-15
Publication date: 2020-08-20
Also published as: JP7121149B2; JPWO2020166056A1

Abstract

The objective of the present invention is to provide a coating agent which imparts flame retardancy to a substrate which is a base material, without changing the texture of the substrate and without damaging the substrate.　This coating agent is characterized by comprising: powder having an average particle size of at most 5 nm and composed of tungsten oxide, silica, tin oxide, molybdenum, selenium, and platinum; graphene powder having an average thickness of at most 5 nm; and a solvent. Furthermore, a coating agent comprising a phosphorus compound is preferable. Furthermore, more preferable is a coating agent comprising at least one kind of powder which has an average particle size of at most 5 nm and is selected from the group consisting of ruthenium, rhodium, palladium, iridium, manganese, iron, copper, silver, gold, niobium, antimony, tantalum, bismuth, gallium, and sulfur.

Description

Coating agent, thin film, substrate with thin film, and method for manufacturing thin film

The present invention relates to a coating agent, a thin film, a substrate with a thin film, and a method for manufacturing a thin film.

Currently, in the flame retardant market, there are regulations on halogen-based flame retardants that have a high environmental impact, and new materials with a low environmental impact are required. Currently, the mainstream polyphosphoric acid-based flame retardant (Patent Document 1) is usually an aqueous solution in which the polyphosphoric acid-based component elutes in water and the flame-retardant effect cannot be exhibited. However, the crystal size of the polyphosphoric acid-based component increases to about 30 μm, but if the crystal size of the polyphosphoric acid-based component is 10 μm or less, the flame-retardant effect is lost. It cannot be used and cannot be used for thin fibers that easily burn (for example, paragraph 0002 of Patent Document 2). Further, when the crystal of the polyphosphoric acid component is used as the fiber, the effect is not obtained unless about 25 to 30% of the polyphosphoric acid component is used with respect to 100% of the total of the polyphosphoric acid component and the fiber (for example, Also, the unit price burden is large due to, for example, Patent Document 3, paragraph 0013). In addition, since the flame retardant used in the kneading of polyphosphoric acid affects the physical properties of the base material, even if a flame retardant is added, it does not change the physical properties of the base material and does not change the texture. Is required. In particular, there is a great demand for wooden structures and world heritage sites that do not want to change the texture, but want to be flame retardant while preventing deterioration. Especially in World Heritage sites, there are many tourists, and it is very important to secure time for tourists to escape as a measure against accidents such as a fire.

On the other hand, in recent years, with globalization, viral infections of foreign origin such as Severe Acute Respiratory Syndrome (SARS), Middle East Respiratory Syndrome (MERS), and Ebola hemorrhagic fever have a history of increasing damage across countries.

In order to prevent these viral infectious diseases, the need for antibacterial and deodorant at airports (there are many people and secondary infections are likely to occur), which is the gateway to each country, is increasing in both advanced and underdeveloped countries. .. As a substance having an antibacterial action as a single substance, there is silver, etc., but it is not effective against airborne transmission from person to person. Therefore, there is great interest in photocatalyst technology that has antibacterial and deodorant effects in space, but photocatalysts basically react to ultraviolet light, and even if they are compatible with visible light, In the actual environment illuminance, the deodorizing effect and the antibacterial effect cannot be sufficiently exerted (for example, paragraphs 0002 and 0003 of Patent Literature 4). As the photocatalyst has higher capacity, the organic substance of the base material as the base is decomposed, and a countermeasure is required. Further, the photocatalyst changes its catalytic ability depending on the ambient temperature, and the performance deteriorates especially at 10° C. or lower. In addition, since a photocatalyst compatible with visible light has an absorption wavelength range in the visible light wavelength range, the larger the particle size and the higher the degree of coloring, the higher the performance tends to be, and the texture of the base material should not be changed. As for things, it is difficult to use. In addition, if the decomposition function is increased too much, there is a problem that organic substances of the base material that is the base are decomposed.

JP-A-56-20058 JP, 2006-63464, A JP, 7-187626, A JP, 2005-169216, A

The problem to be solved by the present invention is to provide a coating agent that imparts flame retardancy without changing the texture of the base material that is the base and without damaging the base material.

The present invention relates to a coating agent, a thin film, a substrate with a thin film, and a method for producing a thin film, which have the following configurations to solve the above problems.
[1] A coating agent comprising a powder of tungsten oxide, silica, tin oxide, molybdenum, selenium, and platinum having an average particle size of 5 nm or less, a powder of graphene having an average thickness of 5 nm or less, and a solvent. ..
[2] The coating agent according to the above [1], further containing a phosphorus compound.
[3] Further, at least one selected from the group consisting of ruthenium, rhodium, palladium, iridium, manganese oxide, iron oxide, copper oxide, silver, gold, niobium oxide, antimony oxide, tantalum oxide, gallium oxide, and sulfur. The coating agent according to [1] or [2] above, which comprises a powder having an average particle diameter of 5 nm or less.
[4] A thin film having powder and graphene contained in the coating agent according to any one of [1] to [3] above.
[5] A thin film-containing substrate containing the thin film according to [4] or [5] above, which has a thickness of 5 to 200 nm.
[6] A method for producing a thin film, which comprises a step of applying the coating agent according to any one of the above [1] to [3] and then drying it.

According to the present invention [1], it is possible to provide a coating agent which imparts flame retardancy to a base material without changing the texture of the base material and without damaging the base material.

According to the present invention [4], it is possible to provide a thin film having flame retardancy on a base material without changing the texture of the base material which is a base and without damaging the base material. According to the present invention [5], it is possible to provide a base material having flame retardancy without changing the texture of the base material which is the base and without damaging the base material. According to the present invention [6], a flame-retardant base material can be easily produced without changing the texture of the base material and without damaging the base material.

It is a result when the average particle diameter of the silica nanopowder dispersion is measured. It is a transmission electron micrograph of the cross section of the thin film formed by the standard coating agent.

〔Coating agent〕
The coating agent of the present invention (hereinafter, also referred to as a coating agent) includes a powder of tungsten oxide, silica, tin oxide, molybdenum, selenium, and platinum having an average particle diameter of 5 nm or less, and a graphene having an average thickness of 5 nm or less. And a solvent. By including the nanoparticles in the coating agent, it is possible to provide a coating agent that imparts flame retardancy to the substrate without changing the texture of the substrate that is the base and without damaging the substrate. .. If the particles contained in the coating agent are larger than 5 nm, the pores in the thin film formed from the coating agent will be large and the flame retardancy will decrease. The powder having an average particle diameter of 5 nm or less preferably has a small particle diameter, and preferably has an average particle diameter of less than 5 nm.

By forming the binder with silica nanoparticles of 5 nanometers or less, the surface area is increased, and all the materials other than silica are also 5 nanometers or less (only graphene has a thickness of 5 nm or less), which is not preferable such as aggregation and sedimentation. It becomes possible to exert a synergistic effect of preferable functions such as conductivity, antibacterial property and deodorant property in addition to flame retardancy while reducing the effect of canceling the function. Tests have shown that all of the above materials contained in the coating agent have a catalytic effect of converting carbon monoxide at high temperature to carbon dioxide, and in order to exert the catalytic effect at a lower temperature, It is important to reduce the particle size of the material itself and increase the surface area. The particle size is less than 5 nm, and the smaller, the higher the catalytic efficiency of the catalyst. Further, as an additional catalyst function, by incorporating a tungsten oxide powder having a visible light photocatalytic effect of 5 nm or less, it becomes possible to generate a photocatalytic function by visible light even at a low illuminance of 500 lx (500 lux) or less. By incorporating inorganic nanoparticles such as tin oxide and graphene that also function as a conductive material for continuous decomposability, a synergistic combined effect with the catalytic function is also possible.

A powder of tungsten oxide (WO ₃ ) having an average particle diameter of 5 nm or less (hereinafter, also referred to as tungsten oxide nanopowder) imparts flame retardancy and visible light photocatalytic property to a thin film formed from a coating agent. The average particle diameter of tungsten oxide is preferably 1 to 3 nm from the viewpoint of flame retardancy and film formation with a uniform thickness. Here, the average particle diameter is a value based on the number standard measured by the dynamic light scattering method using Zetasizer-nano manufactured by Malvern Panalytical.

A powder of silica (SiO ₂ ) having an average particle size of 5 nm or less (hereinafter, also referred to as silica nanopowder) imparts flame retardancy to a thin film formed from a coating agent. The average particle size of silica is preferably 1 to 3 nm, more preferably 1 to 2 nm, from the viewpoint of flame retardancy, flame retardancy, and film formation with a uniform thickness.

A powder of tin oxide (SnO ₂ ) having an average particle diameter of 5 nm or less (hereinafter, also referred to as tin oxide nanopowder) imparts flame retardancy and antistatic property to a thin film formed from a coating agent. The average particle diameter of tin oxide is preferably 1 to 3 nm from the viewpoint of flame retardancy and film formation with a uniform thickness.

A powder of molybdenum having an average particle size of 5 nm or less (hereinafter, also referred to as molybdenum nano powder) imparts flame retardancy, visible light photocatalytic property, antibacterial property, and abrasion resistance to a thin film formed from a coating agent. The average particle size of molybdenum is preferably 1 to 3 nm from the viewpoint of flame retardancy and film formation with a uniform thickness.

A powder of selenium having an average particle size of 5 nm or less (hereinafter, also referred to as selenium nanopowder) imparts flame retardancy and antibacterial property to a thin film formed from a coating agent. The average particle size of selenium is preferably 1 to 3 nm from the viewpoint of flame retardancy and film formation with a uniform thickness.

Powder of platinum with an average particle size of 5 nm or less (hereinafter also referred to as platinum nanopowder) imparts flame retardancy to a thin film formed from a coating agent. The average particle size of platinum is preferably 1 to 3 nm from the viewpoint of flame retardancy and film formation with a uniform thickness.

Powder having an average thickness of graphene of 5 nm or less (hereinafter, also referred to as graphene nanopowder) imparts flame retardancy, visible light photocatalytic property, antistatic property, and abrasion resistance to a thin film formed from a coating agent. An example of the length of graphene is 5 nm to 3 μm. The average thickness of graphene is preferably 1 to 5 nm from the viewpoint of flame retardancy and film formation with a uniform thickness. Here, the average thickness and length of graphene are mass average particle diameters obtained by observing a transmission electron micrograph (magnification: 100,000 times) (n=50).

The amount of the tungsten oxide nanopowder is preferably 1 to 3 parts by mass, more preferably 1.5 to 2.5 parts by mass with respect to 100 parts by mass of the coating agent.

The silica nanopowder is preferably 1.0 to 1.5 parts by mass with respect to 100 parts by mass of the coating agent.

The tin oxide nanopowder is preferably 0.5 to 1.2 parts by mass, more preferably 0.8 to 1.0 part by mass with respect to 100 parts by mass of the coating agent.

The molybdenum nanopowder is preferably 0.02 to 0.05 parts by mass (200 to 500 ppm) with respect to 100 parts by mass of the coating agent.

The selenium nanopowder is preferably 0.02 to 0.05 parts by mass (200 to 500 ppm) with respect to 100 parts by mass of the coating agent.

The platinum nanopowder is preferably 0.005 to 0.01 parts by mass (50 to 100 ppm) with respect to 100 parts by mass of the coating agent.

Graphene nanopowder is preferably 0.005 to 0.01 parts by mass (50 to 100 ppm) per 100 parts by mass of the coating agent.

It is preferable that the coating agent further contains a phosphorus compound from the viewpoint of flame retardancy of a thin film formed from the coating agent. Examples of the phosphorus compound include orthophosphoric acid, calcium phosphate, sodium phosphate, ammonium polyphosphate and the like.

In the case of an 85% by volume aqueous solution of orthophosphoric acid, the phosphorus compound is preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the coating agent, from the viewpoint of flame retardancy of a thin film formed from the coating agent. The phosphorus compounds may be used alone or in combination of two or more.

The coating agent further comprises at least one selected from the group consisting of ruthenium, rhodium, palladium, iridium, manganese oxide, iron oxide, copper oxide, silver, gold, niobium oxide, antimony oxide, tantalum oxide, gallium oxide, and sulfur. It is preferable to include a powder of seeds having an average particle diameter of 5 nm or less.

From the viewpoint of visible light photocatalytic property of the thin film formed from the coating agent, ruthenium is preferably 0.001 to 0.01 parts by weight with respect to 100 parts by weight of the coating agent.

From the viewpoint of the visible light photocatalytic property of the thin film formed from the coating agent, rhodium is preferably 0.001 to 0.01 parts by weight with respect to 100 parts by weight of the coating agent.

From the viewpoint of visible light photocatalytic property of the thin film formed from the coating agent, palladium is preferably 0.001 to 0.01 parts by mass with respect to 100 parts by mass of the coating agent.

From the viewpoint of the visible light photocatalytic property of the thin film formed from the coating agent, iridium is preferably 0.001 to 0.01 parts by weight with respect to 100 parts by weight of the coating agent.

From the viewpoint of the visible light photocatalytic property of the thin film formed from the coating agent, manganese oxide (MnO) is preferably 0.001 to 0.01 parts by weight with respect to 100 parts by weight of the coating agent.

Iron oxide (Fe ₂ O ₃ ) is preferably 0.01 to 0.1 parts by mass with respect to 100 parts by mass of the coating agent, from the viewpoint of visible light photocatalytic property of a thin film formed from the coating agent.

Copper oxide (CuO) is preferably 0.01 to 0.1 parts by mass based on 100 parts by mass of the coating agent from the viewpoint of visible light photocatalytic property and antibacterial property of the thin film formed from the coating agent.

From the viewpoint of antibacterial property of the thin film formed from the coating agent, silver is preferably 0.005 to 0.01 parts by weight with respect to 100 parts by weight of the coating agent.

Gold is preferably 0.001 to 0.01 parts by mass with respect to 100 parts by mass of the coating agent from the viewpoint of antibacterial property and visible light photocatalytic property of a thin film formed from the coating agent.

Niobium oxide (Nb ₂ O ₅ ) is 0.01 to 0.1 parts by mass with respect to 100 parts by mass of the coating agent from the viewpoint of abrasion resistance and visible light photocatalytic property of a thin film formed from the coating agent. Is preferable.

Antimony oxide (Sb ₂ O ₅ ) is 0.01 to 0.1 parts by mass with respect to 100 parts by mass of the coating agent from the viewpoint of flame retardancy and antistatic property of a thin film formed from the coating agent. ,preferable.

From the viewpoint of wear resistance of the thin film formed from the coating agent, tantalum oxide (Ta ₂ O ₅ ) is preferably 0.01 to 0.1 parts by weight with respect to 100 parts by weight of the coating agent.

From the viewpoint of visible light photocatalytic property of the thin film formed from the coating agent, gallium oxide (Ga ₂ O ₃ ) is preferably 0.01 to 0.1 parts by weight with respect to 100 parts by weight of the coating agent.

From the viewpoint of visible light photocatalytic property of the thin film formed from the coating agent, sulfur is preferably 0.001 to 0.01 parts by mass with respect to 100 parts by mass of the coating agent.

The coating agent can be obtained, for example, by stirring, melting, mixing, or dispersing various kinds of nanopowder, solvent, other additives, etc. simultaneously or separately while applying heat treatment if necessary. The devices for mixing, stirring, dispersing and the like are not particularly limited, but a lei kai machine, a ball mill, a planetary mixer, a bead mill and the like can be used. Further, these devices may be appropriately combined and used.

The coating agent may further contain additives and the like within a range that does not impair the object of the present invention.

[Thin film and substrate with thin film]
The thin film of the present invention is a thin film containing powder and graphene contained in the above coating agent, and is obtained by removing the solvent from the above coating agent. The thin film of the present invention preferably has a thickness of 5 to 200 nm. When the thickness of the thin film is thicker than 200 nm, the thin film is likely to be broken, so that the flame retardancy is likely to be lowered, the tint is apt to be deteriorated, and the texture is apt to change. When the thickness is less than 5 nm, the flame retardancy is likely to decrease, but other effects such as visible light can be maintained. When the thickness of the thin film is 100 nm or more, the conductivity becomes good.

This thin film is usually formed on the base material.

-This thin film can impart flame retardancy to the base material without changing the texture of the base material and without damaging the base material.

In addition, this thin film also has visible light photocatalytic performance at room temperature, antistatic performance, and antibacterial performance.

The visible light photocatalytic performance at room temperature can bring deodorant, superhydrophilic, antibacterial, antifungal, algaeproof, mossproof, etc. to the thin film in addition to flame retardancy.

It has been confirmed that the thin film of the present invention acts as a photocatalyst at a visible light illuminance of 500 lx (500 lux) or less and decomposes dyes such as 10 ppm methylene blue and rhodamine B. The photocatalytic effect has been confirmed even with visible light of 50 lx (50 lux), but the higher the illuminance, the higher the decomposition ability. In addition, since it does not act as a photocatalyst with ultraviolet rays, it is possible to form a visible light photocatalyst coat that does not decompose the base of an organic material such as a base material. This is because the photocatalytic reaction occurs on the surface of the thin film formed of nanopowder, so that the photocatalytic decomposition reaction does not occur on the base. Although it is not possible to decompose the dye by applying the coating agent after the base material (cloth etc.) has been soaked with the dye, it is necessary to apply the coating agent to the base material in advance to form a film. When is dropped, the dye is decomposed. From this, it has been confirmed that the decomposition reaction occurs only on the surface of the coating film.

Further, the thin film of the present invention can decompose carbon monoxide into carbon dioxide from a low temperature of around 100° C. due to its visible light photocatalytic property. In the unlikely event of a fire, the catalytic catalyst decomposes toxic gases at high temperatures, instantly decomposing carbon monoxide into carbon dioxide, and interrupting the oxygen on the surface of the combustion products. It is also expected to have the effect of exhibiting flammability and making it easier to secure a safe time to escape.

The thin film of the present invention also has a deodorizing effect due to the visible light photocatalytic property. Here, the instantaneous deodorizing effect is exerted by the catalytic contact effect, and the continuous decomposition effect is exerted by the visible light photocatalytic effect. Further, since the thin film of the present invention has a high surface area and is extremely dense, it has excellent flame retardancy and also has very high antibacterial properties against antibacterial and antifungal. From this, it is possible to easily deodorize and antibacterial not only in airports but also in general places where people are likely to be infected, such as hospitals, railways, buses, stations, city halls, etc. In addition, even in a place where there is no light, visible light photocatalytic property is not exhibited, but the component having an antibacterial agent in the inorganic nanopowder has an antibacterial effect.

The thin film of the present invention can be applied with a film thickness of around 10 nm, and can also exhibit the antistatic function of the surface resistivity of 10 9 (unit: Ω/sq). The thin film of the present invention can have a contact angle with water of less than 5° due to the visible light photocatalytic property.

[Method of manufacturing thin film]
The method for producing a thin film of the present invention includes a step of applying the above-mentioned coating agent and then drying. More specifically, a substrate with a thin film can be manufactured by a step of applying the above-mentioned coating agent on the substrate and then drying.

The method of application includes brush application, dipping, spray coating, etc., but is not particularly limited.

The above coating agent can be dried at room temperature to form a film. The method for drying is also not particularly limited. An example of drying conditions is 0 to 40° C. and 5 to 60 minutes.

The present invention will be described with reference to examples, but the present invention is not limited to these. In the following examples, parts and% mean parts by mass and% by mass, unless otherwise specified.

As the tungsten oxide nanopowder dispersion, a mixture of 4 parts by mass of tungsten oxide nanopowder having an average particle diameter of 3 nm and 96 parts by mass of water was used.
For the silica nanopowder dispersion, a silica binder manufactured by Japan Nanocoat (average particle size: 1.3 nm, silica particles: 3%, water: 97%) was used.
As the tin oxide nanopowder dispersion, a mixture of 1 part by mass of tin oxide nanopowder having an average particle diameter of 2 nm and 99 parts by mass of water was used.
As the molybdenum nanopowder dispersion, a mixture of 0.3 parts by mass of molybdenum nanopowder having an average particle size of 2 nm and 99.7 parts by mass of water was used.
As the selenium nanopowder dispersion, a mixture of 0.9 part by mass of water and 0.9 part by mass of selenium nanopowder having an average particle diameter of 2 nm was used.
As the platinum nanopowder dispersion, a mixture of 0.05 parts by mass of platinum nanopowder having an average particle diameter of 2 nm and 99.95 parts by mass of water was used.
As the graphene dispersion nano-powder, a mixture of 0.1 parts by mass of graphene having an average thickness of 2 nm and an average length of 5 μm and 99.9 parts by mass of water was used.
As the ruthenium nanopowder dispersion, a mixture of 0.05 parts by mass of ruthenium nanopowder having an average particle diameter of 2 nm and 99.95 parts by mass of water was used.
As the palladium nanopowder dispersion, a mixture of 0.05 parts by mass of palladium nanopowder having an average particle diameter of 2 nm and 99.95 parts by mass of water was used.
As the iron oxide (Fe ₂ O ₃ ) nanopowder dispersion, a mixture of 3 parts by mass of iron oxide nanopowder having an average particle diameter of 3 nm and 97 parts by mass of water was used.
As the copper oxide (CuO) nanopowder dispersion, a mixture of 3 parts by mass of copper oxide nanopowder having an average particle diameter of 3 nm and 97 parts by mass of water was used.
As the silver nanopowder dispersion, a mixture of 0.5 parts by mass of silver nanopowder having an average particle diameter of 2 nm and 99.5 parts by mass of water was used.
As the niobium oxide (Nb ₂ O ₅ ) nanopowder dispersion, a mixture of 3 parts by mass of niobium oxide nanopowder having an average particle diameter of 4 nm and 97 parts by mass of water was used.
As the calcium phosphate (Ca ₃ (PO ₄ ) ₂ ) powder dispersion liquid, a mixture of 0.3 parts by mass of calcium phosphate powder having an average particle size of 3 nm and 99.7 parts by mass of water was used.

FIG. 1 shows the results of measuring the average particle size of the silica nanopowder dispersion by the dynamic light scattering method using Zetasizer-nano manufactured by Malvern Panalytical. Other nanopowder particles (excluding graphene nanopowder) were similarly measured for average particle diameter.

[Example 1]
Tungsten oxide nanoparticle aqueous solution: 2 parts by mass, silica nanoparticle aqueous solution: 1 part by mass, tin oxide nanoparticle aqueous solution: 0.8 parts by mass, molybdenum nanoparticle aqueous solution: 0.075 parts by mass, selenium nanoparticle aqueous solution: 0.025 parts by mass. A platinum nanoparticle aqueous solution: 0.0025 parts by mass, a graphene aqueous solution: 0.0025 parts by mass, and the balance: water were mixed to prepare a coating agent having a standard composition (hereinafter referred to as a standard coating agent).

The standard coating agent was applied on a glass plate, dried, and then observed with a transmission electron microscope. It was found from the transmission electron micrograph that the particles were uniformly dispersed.

A standard coating agent was applied on a glass substrate and naturally dried to form a thin film.
FIG. 2 shows a transmission electron micrograph of the cross section of the formed thin film. As can be seen from FIG. 2, the film had a uniform thickness of about 9 nm.

<Flame resistance test>
Kanaquin No. 3 (according to JIS L 0803) of 100% cotton was prepared by dipping a standard coating agent (10 parts by mass) and pure water (90 parts by mass). The coating material thus prepared was dehydrated until the mass thereof was twice the mass of Kanakin No. 3, and a test sample was prepared.

The limiting oxygen index (LOI) of the test sample was measured at the General Incorporated Foundation Kaken Test Center in accordance with JIS L 1901 (E-2). The measurement was performed twice, and the limiting oxygen index was a high value of 26.6. Generally, if the limiting oxygen index is 26 or more, it is considered to have flameproofness (self-extinguishing property).

<Photocatalytic performance test>
<Ammonia and formaldehyde decomposition test>
Width: 10 cm x length: 10 cm x thickness: 3 mm A glass plate having a standard coating agent of 10 parts by mass of pure water of 90 parts by mass is applied and dried to form an evaluation film having a thickness of about 0.1 μm. did.

The evaluation film was placed in an evaluation box having an internal volume of 10 dm ³ . A test gas was introduced into an evaluation box with a humidity of 21%, and in a static test without air convection, a visible gas of 200 lx (200 lux) was irradiated to detect a change in gas concentration, and a gastec detector tube was used. Was measured. Ammonia: 60 ppm or formaldehyde: 50 ppm was used as the evaluation gas.

When ammonia was used as the evaluation gas, the initial ammonia concentration, which was 60 ppm, dropped to 35 ppm after 25 minutes and to 22 ppm after 140 minutes. The test was conducted in the same manner except that only the graphene nanopowder dispersion was removed from the standard coating agent diluted 10 times with water and ammonia: 50 ppm was used as the evaluation gas. At this time, the ammonia concentration, which was initially 50 ppm, decreased to 30 ppm after 80 minutes and to 25 ppm after 120 minutes, showing sufficient photocatalytic performance with visible light. When only the graphene nanopowder dispersion was removed, the ammonia concentration decreased more slowly than the standard coating agent, but it showed photocatalytic performance under visible light.

When formaldehyde was used as the evaluation gas, the formaldehyde concentration, which was initially 50 ppm, decreased to 45 ppm after 60 minutes and to 30 ppm after 120 minutes, showing sufficient photocatalytic performance with visible light.

<Carbon monoxide decomposition test>
A standard coating agent: 3 g was applied to a glass slide having a width of 26 mm, a length of 76 mm, and a thickness of 3 mm, and dried to prepare a film for evaluation.

Inner volume: 93 cm ^{3 An} evaluation membrane was placed in a glass test tube container for evaluation, and a test gas was enclosed. This evaluation glass container is connected to a gas chromatograph/thermal conductivity detector (GC/TCD) via a nozzle in order to measure the carbon monoxide (CO) gas concentration in the evaluation glass container.

This glass container for evaluation was placed on a hot plate and covered with aluminum foil for uniform heating. Next, the change in carbon monoxide (CO) gas concentration was measured. The initial concentration of carbon monoxide was 400 ppm (80 vol% He gas containing 500 ppm CO gas+20 vol% atmospheric air). First, visible light was irradiated at room temperature (25° C.). After 1 minute, CO gas was reduced to 398 ppm, and the visible light photocatalytic property at room temperature was confirmed. Next, the initial concentration of carbon monoxide was returned to, and the hot plate was heated. The hot plate was heated to 400° C. after 5 minutes. After reaching 400° C., the CO gas concentration after 1 minute had decreased to 0 ppm, indicating a very good catalytic catalytic performance.

<Photocatalytic performance evaluation by wet decomposition with ultraviolet rays>
Methylene blue aqueous solution 35 cm ³ of 10 .mu.mol / dm ³ based on JIS1703-2, and 0.2g coating liquid of standard coated on a glass of 100 mm × 100 mm × thickness 3 mm, dried, inner diameter 40 mm × height 3cm the methylene blue aqueous solution (UV irradiance 1.00 mW/cm ² , wavelength 351 nm). The methylene blue concentration at this time was measured with a spectrophotometer UV-3100PC manufactured by Shimadzu Corporation. The methylene blue concentration (unit: μmol/dm ³ ) is plotted on the vertical axis and the ultraviolet irradiation time (unit: minutes) is plotted on the horizontal axis, and the decomposition activity index, which is the slope when plotted, is 0.3 or less [(nmol /Dm ³ )/min], and it was found that photocatalytic performance was not exhibited with ultraviolet rays.

<Antibacterial test>
Kanaquin No. 3 (according to JIS L 0803) of 100% cotton was prepared by dipping a standard coating agent (10 parts by mass) and pure water (90 parts by mass). Repeated dehydration was carried out until the mass of the prepared coating agent became twice the mass of Kanakin No. 3 to prepare a test sample.

The Kaken Test Center, a general incorporated foundation, measured the test samples using Staphylococcus aureus NBRC 12732 in accordance with the “bacteria solution absorption method” specified in JIS L 1902. The common logarithm of the viable cell count (maximum and minimum difference in parentheses) was 4.61 (0.1) immediately after inoculation and 7.09 (0.1) after 18 hours of culture, and the growth value F Was 2.6, which was a good antibacterial property.

Similarly, an antibacterial test was performed on a doormat: chenille using a spray gun to which 10 parts by mass of a standard coating agent and 90 parts by mass of 90 parts of pure water were applied at 10 cm ³ /m ² . The common logarithm of the viable cell count of the original chenille (maximum difference between parentheses) is 3.86 (0.1) immediately after inoculation and 1.90 (0.0) after 18 hours of culture. And the antibacterial activity value was 5.8. The common logarithm of the viable cell count of chenille after washing 5 times (maximum difference between parentheses) was 4.38 (0.1) immediately after inoculation, and 1.30 (0. 0), and the antibacterial activity value was 5.8. In general, it is considered that the antibacterial activity is good when the antibacterial activity value is 2.0 or more. Here, the washing method was the washing method (for standard washing) of the SKE mark textile product of the Fiber Evaluation Technology Council.

<Mold resistance test>
1) Preparation of medium A mold resistance test was carried out by MIC Co., Ltd. by the Pacific Beam Mold Method (Pacific Beam Mold Method). An inorganic salt agar medium was used as the medium. The medium composition component names and contents are shown below.
KH ₂ PO ₄ : 0.7 g
K ₂ HPO ₄ : 0.7 g
MgSO ₄ · _7H 2 O: 0.7g
NH ₄ NO ₃ : 1.0 g
NaCl: 0.005 g
FeSO ₄ · _7H 2 O: 0.002g
ZnSO ₄ · _7H 2 O: 0.002g
MnSO ₄ · _7H 2 O: 0.001g
Agar: 15g
Pure water: 1000 cm ³
The medium prepared by mixing the above culture components was heat-treated at 121° C. for 20 minutes to sterilize it. The pH of the solution was adjusted to 6.0-6.5 by adding 0.01% NaOH.

2) Preparation of test bacterial solution (1) Preparation of mixed spore solution Equal amounts of an aqueous solution obtained by filtering agar from a medium and a solution adjusted to a spore amount of 10 ⁶ ± 200,000 cells/cm ³ are mixed. The test bacteria will be described later.
(2) Preparation of Wetting Liquid An aqueous solution of sodium lauryl sulfate 0.05 g/dm ³ was prepared.
(3) Preparation of Test Bacterial Fluid The mixed spore fluid was added to the wetting fluid and sufficiently dispersed.

3) Culture (1) Culture container and culture conditions Using a circulator with temperature/humidity thermostat, culture was performed under the conditions of temperature: 28 to 30° C. and humidity: 85% RH or higher.
(2) The culture period was 28 days.

4) Test bacterium The test bacterium (71 fungi) used was a stock culture pure culture strain stored at 6 ± 4°C for 30 days or less. The test bacteria (71 fungi) used are as follows.
1. Alternaria alternata, 2. 2. Aspergillus niger. 3. Aspergillus oryzae, 4. 4. Aspergillus flavus 5. Aspergillus versicolor, 6. 6. Aspergillus humigatus, 7. Aspergillus terreus, 8. 8. Aspergillus restrictus, 9. Aspergillus ocraceus, 10. Aspergillus candidus, 11. Alternaria tenuis, 12. Alcaligenes faecalis, 13. Alternaria brassicola, 14. Aureobasidium pullulans, 15. Candida albicans, 16. Chaetomium globosum, 17. Cladosporium cladosporioides, 18. Cladosporium sphaerospermum, 19. Cladosporium herbarum, 20. Cladosporium resinae, 21. Curvularia lunata, 22. Dressresla australiensis, 23. Epicoccum purpurascens, 24. Eurotium tonophilum, 25. Eurotium rubrum, 26. Eurotium chevalieri, 27. Eurotium amsterodami, 28. Fusarium semitectum, 29. Fusarium oxysporum, 30. Fusarium solani, 31. Fusarium roseum, 31. Fusarium moniliforme, 33. Fusarium proliferatum, 34. Geotricham candidum, 35. Geotricham lactus, 36. Gliocladium virens, 37. Monilia fructigene, 38. Monilia nigra, 39. Mucor racemosus, 40. Myrothecium vulcaria, 41. Mucor spinescens, 42. Nigrospora oryzae, 43. Nigrospora sperica, 44. Neurospora sitophila, 45. Penicillium Frequentance, 46. Penicillium islandicum, 47. Penicillium citrinum, 48. Pullularia pullulans, 49. Penicillium Expansum, 50. Penicillium cyclopium, 51. Penicillium citreo-viride, 52. Penicillium funiculosum, 53. Penicillium niglycans, 54. Penicillium lilacinum, 55. Pestalotia adusta, 56. 57. Pestalotia neglecta, 57. Forma citricarpa, 58. Forma terrestius, 59. Forma glomerata, 60. Rhizopus niglycans, 61. Rhizopus oryzae, 62. Rhizopus stolonifer, 63. Rhizopus solani, 64. Sedosporium abiospermum, 65. Trichophyton mentagrophytes, 66. Trichoderma viride, 67. Trichoderma koningii, 68. T-1 Trichoderma, 69. Trichoderma harzianum, 70. Ulocladium atrum, 71. Wallemia sevi

3) Evaluation method The growth state of the bacteria was evaluated according to the following criteria.
0: No bacterial growth 1:10% or less growth 2:10-30% or less growth 3:30-60% or less growth 4: 60% or more complete growth

4) Test Standard coating agent 10 parts by mass A solution of 90 parts by mass of pure water was prepared, and the sample was applied with a spray gun at 10 cm ³ /m ² and the mold resistance was 71 days by the Pacific Beam Mold method for 28 days. A sex test was conducted. As a result, after 28 days, mold growth was not observed in the sample to which PBM was added, and therefore it is considered that the sample has mold resistance. Here, as the test sample, a polyethylene bag coated with the above liquid agent was used. A polyethylene bag was used as a blank.

5) Test Results The test sample was evaluated as “0” even after 28 days, and was good. On the other hand, in the blank, after 14 days, the evaluation was "1", and after 24 days, the evaluation was "2", and the reproduction of the bacteria was recognized.

[Example 2]
5 parts by mass of the ruthenium nanopowder dispersion was added to 95 parts by mass of the standard coating agent. The visible light photocatalytic function was improved. * Under 500 lux (lx), the dye decomposition rate was improved as compared with the standard coating solution.

[Example 3]
5 parts by mass of the palladium nanopowder dispersion was added to 95 parts by mass of the standard coating agent. The visible light photocatalytic function was improved. * Under 500 lux (lx), the dye decomposition rate was improved as compared with the standard coating solution.

[Example 4]
2 parts by mass of the iron oxide nanopowder dispersion was added to 98 parts by mass of the standard coating agent. The visible light photocatalytic function was improved. * Under 500 lux (lx), the dye decomposition rate was improved as compared with the standard coating solution.

[Example 5]
2 parts by mass of the copper oxide nanopowder dispersion was added to 98 parts by mass of the standard coating agent. The visible light photocatalytic function was improved. * Under 500 lux (lx), the dye decomposition rate was improved as compared with the standard coating solution.

[Example 6]
1 part by mass of the silver nanopowder dispersion was added to 99 parts by mass of the standard coating agent. The visible light photocatalytic function was improved. * Under 500 lux (lx), the dye decomposition rate was improved as compared with the standard coating solution.

[Example 7]
To 99 parts by mass of the standard coating agent, 1 part by mass of the niobium oxide nanopowder dispersion was added. The visible light photocatalytic function was improved. * Under 500 lux (lx), the dye decomposition rate was improved as compared with the standard coating solution.

[Example 8]
A standard coating agent of 20 parts by mass and pure water of 76 parts by mass was prepared, and 3.8 parts by mass of orthophosphoric acid (85% by volume) was used as phosphoric acid, and tricalcium phosphate was additionally used as tricalcium phosphate. A liquid containing 2 parts by mass was prepared. As a result of measuring the surface resistance value of the film formed on Kinnkin No. 3 in the same manner as the standard coating agent, the standard coating solution was 10 8th power, whereas 10 6th power (unit: Ω As to the flame retardant performance, the standard coating liquid has an oxygen index of 26.6, while the oxygen index of 29.8 is further improved and the texture is improved. Here, the surface resistance value was measured by a surface resistance meter (model number: WA-400, two-point resistance method) manufactured by Taiyo Denki Sangyo.

[Comparative Example 1]
A coating solution containing no tungsten oxide nanopowder dispersion was prepared as a standard coating agent. The visible light photocatalytic function was not exhibited.

[Comparative Example 2]
A coating liquid containing no silica nanopowder dispersion was prepared as a standard coating agent. Adhesiveness and flame retardancy decreased.

[Comparative Example 3]
A coating solution containing no tin oxide powder dispersion was prepared as a standard coating agent. Antistatic performance is degraded.

[Comparative Example 4]
A coating solution containing no molybdenum nano-powder dispersion was prepared as a standard coating agent. Visible light photocatalytic performance was reduced.

[Comparative Example 5]
A coating liquid containing no selenium nanopowder dispersion was prepared as a standard coating agent. Antibacterial properties are reduced.

[Comparative Example 6]
A coating liquid containing no platinum nanopowder dispersion liquid was prepared as a standard coating agent. Visible light photocatalytic property and flame retardancy were lowered.

[Comparative Example 7]
A coating solution containing no graphene nanopowder dispersion was prepared as a standard coating agent. Visible light photocatalytic property and conductivity decreased.

INDUSTRIAL APPLICABILITY The coating agent of the present invention is very useful because it can provide a coating agent that imparts flame retardancy to a base material without changing the texture of the base material and not damaging the base material. is there.

Claims

A coating agent comprising a powder of tungsten oxide, silica, tin oxide, molybdenum, selenium, and platinum having an average particle size of 5 nm or less, a graphene powder having an average thickness of 5 nm or less, and a solvent.
The coating agent according to claim 1, further comprising a phosphorus compound.
Further, at least one average particle selected from the group consisting of ruthenium, rhodium, palladium, iridium, manganese oxide, iron oxide, copper oxide, silver, gold, niobium oxide, antimony oxide, tantalum oxide, gallium oxide, and sulfur. The coating agent according to claim 1 or 2, which contains a powder having a diameter of 5 nm or less.
A thin film comprising powder and graphene contained in the coating agent according to any one of claims 1 to 3.
The thin film according to claim 4, which has a thickness of 5 to 200 nm.
A substrate with a thin film, comprising the thin film according to claim 4 or 5.
A method for producing a thin film, comprising a step of applying the coating agent according to any one of claims 1 to 3 and then drying.