JP2022008038A - Coating material and coating method - Google Patents

Abstract

To provide a coating material and coating method that can maintain a high antiviral effect on the surface layer of an object to be coated for a long period of time.SOLUTION: The coating material is obtained by using a coating agent in which polysilazane and an alkyl silicate condensate are dissolved in an inert solvent at a total concentration of 50 to 80 mass% as a base agent 110A, and adding antiviral agents 121, 122 to the base agent at a ratio of 0.1 to 20 mass%.SELECTED DRAWING: Figure 2

Description

The present invention relates to a coating material and a coating method used for surface modification of an article to be coated.

Conventionally, various articles made of materials such as resin material, metal material, wood, rubber material, etc. are used as covering objects, and the coating material is applied or sprayed on the surface of the various articles to be coated. Some are designed to enhance the antiviral property of the surface layer of an object (see Patent Document 1).

Japanese Unexamined Patent Publication No. 2018-172306 (page 3)

However, in Patent Document 1, since the coating material sprayed on the surface of the article enters the minute irregularities on the surface of the article and is in contact with the surface in a hypothesized state, it is coated over time. There is a problem that the coating film is missing or peeled off, and its antiviral effect cannot be maintained for a long period of time.

In particular, in recent years, due to the epidemic of the new coronavirus (COVID -19), it is desired to modify various articles that people come into contact with so that a high antiviral effect can be sustained for a long period of time on the surface layer.

The present invention has been made focusing on such problems, and an object of the present invention is to provide a coating material and a coating method capable of sustaining a high antiviral effect on the surface layer of a coated object for a long period of time.

In order to solve the above problems, the coating material of the present invention is used.
The total concentration of polysilazane and alkyl silicate condensate is 50 to 80% by mass, the coating agent dissolved in the inert solvent is used as the base agent, and the antiviral agent is added to the base agent by 0.1 to 20% by mass. It is characterized by being added in the ratio of.
According to this feature, the glass coating film produced by polysilazane and alkyl silicate condensate is used as a base material, and the antiviral agent is fixed in a stable state on the surface layer of the film with a large exposed portion. The high antiviral effect of the coated object covered with the material can be maintained for a long period of time.

The polysilazane is characterized by being an inorganic polysilazane.
According to this feature, since the glass coating film is easily formed into a thin film, the antiviral agent is easily exposed on the surface layer of the film.

The antiviral agent is characterized by being an organic antiviral agent.
According to this feature, by using an organic polysilazane as a base agent and using an organic antiviral agent having a relatively low affinity with the base agent, the base agent is less likely to adhere to the surface of the antiviral agent due to surface tension. Therefore, a larger exposed portion of the antiviral agent can be secured on the surface layer of the glass coating film.

Further, it is characterized in that an antibacterial agent is added at a ratio of 0.1 to 10% by mass.
According to this feature, both the antibacterial effect and the antiviral effect of the object to be coated can be enhanced.

The coating method of the present invention
The total concentration of polysilazane and alkyl silicate condensate is 50 to 80% by mass, the coating agent dissolved in the inert solvent is used as the base agent, and the antiviral agent is added to the base agent by 0.1 to 20% by mass. It is characterized by having a coating step of coating the surface of the object to be coated with the coating material added at the ratio of.
According to this feature, an antiviral agent is formed on the surface of the object to be coated with a glass coating film made of polysilazane and an alkyl silicate condensate, and the glass coating film is used as a base material and a large exposed portion is secured on the surface layer thereof. Since it is fixed in a stable state, a high antiviral effect of this coated object can be obtained for a long period of time.

The coating step is a step of forming a thin layer of a coating film as a base material containing SiO2 as a main component on the surface of the object to be coated, and expressing the antiviral agent on the surface layer surface of the coating film. It is characterized by being.
According to this feature, by expressing an antiviral agent on the surface layer of the coating film, the antiviral agent acts directly on various viruses, and a high antiviral effect can be maintained for a long period of time. .. Further, by forming the coating film into a thin layer, it is possible to secure the followability to the behavior of the surface of the object to be coated.

In the coating step, the coating material is coated on the surface of the object to be coated to which moisture is attached, and the components contained in the coating material are chemically reacted with the moisture adhering to the surface of the object to be coated. In the step of forming a coating film as a base material containing SiO2 as a main component on the surface of the object to be coated and expressing the antiviral agent in the recesses on the surface layer surface of the coating film formed by the chemical reaction. It is characterized by being.
According to this feature, the antiviral agent is exposed in the recesses on the surface layer surface of the coating film generated by the discharge of gas generated by the chemical reaction between the components contained in the coating material and the moisture on the surface of the object to be coated. , This antiviral agent acts directly on various viruses, and can maintain a high antiviral effect for a long period of time.

The coating step is characterized in that the coating material to which the antiviral agent composed of particles having a maximum diameter of 1 μm is added is coated on the surface of the object to be coated with a film thickness of 500 nm or less.
According to this feature, the antiviral agent can be reliably exposed on the surface layer surface of the coating film.

It is characterized by having a sterilization step of sterilizing the surface of the object to be coated before the coating step.
According to this feature, it is possible to form a high-quality and long-lasting coating film on the surface of the object to be coated cleaned by the sterilization step.

It is characterized by having a pretreatment step of adhering moisture to the surface of the object to be coated before the coating step.
According to this feature, by adhering moisture to the surface of the object to be coated, the chemical reaction between the moisture and the components contained in the coating material is promoted, and a coating film is quickly and firmly formed on the surface of the object to be coated. can do.

(A) to (c) are cross-sectional views showing the mechanism of forming a coating film on the article of Example 1 in chronological order. It is an enlarged view of the dotted line enclosure part of FIG. 1C. It is an enlarged view of the dotted line enclosure part of FIG. It is an enlarged view of the dotted line enclosure part of FIG. 1C in another embodiment of Example 1. FIG. It is an enlarged view of the dotted line enclosure part of FIG. 1C in still another embodiment of Example 1. FIG. It is a graph which shows the result (24 hours later) of the antiviral property test (1) of the coating film against the new type coronavirus (COVID -19). It is a graph which shows the result (24 hours later) of the antiviral property test (2) of the coating film against the new type coronavirus (COVID -19). It is a graph which shows the result (after 24 hours) of the antiviral property test of the coating film against influenza virus. It is a graph which shows the result (time) of the antiviral property test of the coating film against influenza virus. It is a graph which shows the result (after 24 hours) of the antibacterial property test of the coating film against Staphylococcus aureus. It is a graph which shows the result (after 24 hours) of the antibacterial property test of the coating film against Escherichia coli. (A) to (c) are cross-sectional views showing the mechanism of forming a coating film on an article in Example 2 in chronological order. It is an enlarged view of the dotted line enclosure part of FIG. 12C. It is an enlarged view of the dotted line enclosure part of FIG. 12C in another embodiment of Example 2. FIG. It is a figure which image | imaged the surface of the metal material coated with a coating film by AFM measurement, (a) is a figure which coated one layer of a coating film, (b) is a figure which coated three layers of a coating film. It is a table which shows the result of the ATP wiping test.

A mode for carrying out the coating material and the coating method according to the present invention will be described below based on examples.

The coating material and the embodiment for carrying out the coating method according to the first embodiment of the present invention will be described below with reference to FIGS. 1 to 11.

(Coating liquid)
The coating liquid 110 as the coating material of the present invention is mainly composed of the base agent 110A and the additive 110B added to the base agent 110A. First, the base agent 110A contains at least an inorganic or organic polysilazane and an alkyl silicate condensate as raw materials, and in the first embodiment, these inorganic or organic polysilazane and the alkyl silicate condensate are diluted with an inert solvent. ing.

When inorganic polysilazane is used as a raw material for the base agent 110A, the total concentration of the inorganic polysilazane and the alkyl silicate condensate is in the range of 10 to 80% by mass, more preferably in the range of 50 to 80% by mass. In this Example 1, it is dissolved by dibutyl ether as an inert solvent. More specifically, the inorganic polysilazane is contained in an amount of 0.1 to 5% by mass, and the rest is contained in the proportion of the alkyl silicate condensate.

More specifically, the inorganic polysilazane has perhydropolysilazane, that is, a Si—H bond, a Si—N bond and an NH bond, and is represented by, for example, the following general formula (1)-(SiH2-NH) -unit. It is an inorganic polymer having a chain structure composed of silicon.

The inorganic polysilazane is not limited to a chain structure, and may be a polymer having a cyclic structure or a polymer having a complex of these structures.

When organic polysilazane is used as a raw material for the base agent 110A, the total concentration of the organic polysilazane and the alkyl silicate condensate is in the range of 1 to 80% by mass, and in the first embodiment, dibutyl ether is used as the inert solvent. It has been dissolved. More specifically, the organic polysilazane is contained in an amount of 0.1 to 80% by mass, and the rest is contained in the proportion of the alkyl silicate condensate.

More specifically, the organic polysilazane is a polymer having a Si—N bond and functional groups (R1 to R3) and represented by the following general formula (2)-(SiR1R2-NR3) -unit, particularly. , At least one of the functional groups R1 and R2 directly linked to Si is an organic polymer composed of an organic functional group such as an alkyl group having a carbon (C).

The organic polysilazane in Example 1 is composed of a methyl group (CH3) as a functional group (R1 to R3) having a content of 50% or more. Further, the organic polysilazane is not limited to a polymer composed of one type of-(SiR1R2-NR3) -unit, but is composed of a plurality of types of-(SiR1R2-NR3) -unit having different functional groups (R1 to R3). It may be a polymer to be used. Further, the organic polysilazane may be a polymer having a chain-like, cyclic or crosslinked structure, or may be a polymer having a composite of these structures.

More specifically, as the organic polysilazane in Example 1, for example, the organic polysilazane is represented by the following general formula (3)-(SiH (CH3) -NH) -unit,-(Si (CH3) 2-. A polymer containing NH) -units,-(SiR1 (CH3) -NR3) -units, in particular the functional group R1 in the-(SiR1 (CH3) -NR3) -units is H or CH3, directly with N. The bound functional group R3 is an organic functional group that promotes the reaction.

Further, the organic polysilazane contained in the base agent 110A may be a mixture of a plurality of types of organic polysilazane having different polymer structures, and for example, a plurality of types represented by the above general formula (3). Organic polysilazane of the above and organic polysilazane having other structures may be mixed. For example, in the first embodiment, at least one selected from hexamethyldisilazane, octamethylcyclotetrasilazane or tetramethyldisilazane can be mentioned.

Alkyl silicate condensates include, for example, tetramethyl orthosilicate, tetraethyl orthosilicate, tetra-n-propyl orthosilicate, tetra-i-propyl orthosilicate, tetra-n-butyl orthosilicate, tetra-sec-butyl orthosilicate, methylpoly. One or more condensates selected from silicates and ethylpolysilicates.

The inert solvent is a solvent inert to inorganic or organic polysilazane and alkyl silicate condensates, and is preferably selected from dibutyl ether, dimethyl ether, diethyl ether, dipropyl ether, terepine oil, benzene, toluene and the like. Will be done.

The additive 110B is added to the above-mentioned base agent 110A, and as will be described later, the organic antiviral agent X containing particles 121 having a particle size of about 100 nm (hereinafter, simply referred to as organic antiviral agent X). ) Is 0.1 to 20% by mass, and 0.1 to 20% by mass of an organic antiviral agent Y (hereinafter, simply referred to as an organic antiviral agent Y) containing particles 122 having a particle size of about 1 μm is added. The organic antiviral agents X and Y are more preferably added in an amount of 0.1 to 10% by mass. Furthermore, in the first embodiment, an embodiment in which only the organic antiviral agent X and the organic antiviral agent Y are added will be described, but in addition to these, for example, an inorganic antiviral agent and an inorganic or organic antibacterial agent may be added. Further may be added.

More specifically, the organic antiviral agent X and the organic antiviral agent Y contain at least diiodomethyltolyl sulfone as an active ingredient. The composition of the active ingredients of the organic antiviral agent X and the organic antiviral agent Y is partially different. The organic antiviral agent X is a deep yellow transparent particle 121 containing the active ingredient dissolved in an inert solvent, and the particles 121 containing the active ingredient dispersed in the inert solvent have a particle size of approximately 100 nm. Is. Further, the particles 122 of the organic antiviral agent Y have an off-white color and a particle size of about 1 μm.

Further, the particles 121 and 122 of the organic antiviral agents X and Y have the above-mentioned nano-level or micro-level particle size (from 100 nm) in the inert solvent depending on the type of the inert solvent constituting the coating liquid 110 and the mixing method. It may be dispersed in 1 μm) or in the inert solvent of the coating liquid 110 with a nano-level particle size (5 to 15 nm) smaller than the above-mentioned particle size. Needless to say, the inert solvent constituting the coating liquid 110 is an inert solvent not only for the organic antiviral agent but also for the inorganic antiviral agent and the inorganic or organic antibacterial agent.

(Aspect of coating material)
Further, the coating liquid 110 of the first embodiment is operated as a predetermined amount of liquid enclosed in a container made of, for example, glass or resin, and the liquid is moistened with a cloth material (not shown) and coated. A coating film is formed by applying it to the surface of various target articles. The operation of the coating material is not limited to this, and for example, a non-woven fabric or the like impregnated in the coating liquid in advance may be sealed in the bag and the bag may be opened before use, or the coating liquid may be coated. The surface of the object may be sprayed in the form of a mist to cover it.

(Coating film coating method)
When the coating liquid 110 is applied or sprayed on the surface 102 of the article 101 to be coated, it chemically reacts with moisture to form a single-layer or a plurality of thin film coating films 115, 135, 145. The film thicknesses of the coating films 115, 135, and 145 are preferably 10 μm or less, and more preferably 5 nm to 5 μm.

First, a sterilization step of sterilizing the surface 102 of the article 101 is performed prior to the coating step of the coating films 115, 135, 145. In this sterilization step, a sterilizing solution diluted with hypochlorous acid or sodium hypochlorite, which has antibacterial and antiviral effects in addition to the sterilizing effect, is sprayed or a non-woven fabric impregnated with the sterilizing solution is used. , Adhere to the surface 102 of the article 101. By sterilizing in this way, the coating films 115, 135, 145 can be easily coated on the surface 102 of the article 101 in a clean state, and the coating films 115, 135, 145, which are of good quality and are not easily peeled off, are formed. Can be generated.

After the above-mentioned sterilization step and before the coating step, water (H2O) such as purified water may be attached to the surface 102 of the article 101 with a non-woven fabric or a sprayer as a pre-step. By doing so, the chemical reaction between the moisture adhering to the surface 102 of the article 101 and the components contained in the coating liquid 110 is promoted, and the coating films 115, 135, 145 are quickly and firmly applied to the surface 102 of the article 101. Can be generated.

(Covered object)
As the object to be covered, various articles made of materials such as resin material, metal material, wood, rubber material, and leather can be applied, or fixed installation objects such as furniture may be used, for example, a portable terminal. Goods that are often in contact with multiple people, such as the surface of the operation part of the remote control, desk / table tops and drawers, tableware, carry-on items such as bags and wallets, and construction / temporary materials, are suitable as covering objects. be. Especially in recent years, considering the effects of the new coronavirus (COVID-19) to the maximum extent, items that are frequently contacted by an unspecified number of people, such as public institutions such as government offices, offices, commercial facilities, hospitals, schools, etc. Fixtures, door knobs, handrails, etc. arranged in nursing homes, etc., or articles such as straps, handrails, etc. of trains / buses, which are public transportation, are more suitable as covering objects.

(Mechanism of coating film formation)
Next, the mechanism by which the coating films 115, 135, 145 according to the present invention are formed will be described. Here, a case where inorganic polysilazane is used as a raw material of the base agent 110A constituting the coating liquid 110 will be described as an example. Further, although FIG. 1 shows the mechanism by which the coating film 115 is formed, the mechanism by which the coating films 135 and 145 (see FIGS. 4 and 5), which is another embodiment of the first embodiment, is also formed. Since it is substantially the same as FIG. 1, the description of the mechanism by illustration is omitted for another embodiment.

As shown in FIG. 1 (a), in many cases, the surface 102 of an article 101 made of, for example, a metal material as a covering target has a plurality of moistures 106, 106, ... (Water droplets) due to dew condensation or moisture in the air. ) Is attached. When the coating liquid 110 is applied or sprayed in a thin film on the surface 102 of the article 101 to cover it, perhydropolysilazane, which is an inorganic polysilazane constituting the base agent 110A contained in the coating liquid 110, becomes moisture (H2O) in the air. By chemically reacting with, a coating layer having an inorganic structure containing SiO2 as a main component is generated on the surface 102 of the article 101. Although a small amount of gas (NH3, H2) is secondarily generated by the above-mentioned chemical reaction, all of these gases naturally volatilize in the atmosphere on the surface 102 of the article 101.

That is, as shown in FIG. 1 (b), the coating liquid 110 chemically reacts with the moisture contained in the air on the surface layer surface 110a in contact with the air, thereby causing hydrogen as a by-product of the coating film 115. Gas such as hydrogen and ammonia volatilizes from the surface layer, and the coating layer 111 on the surface side of the coating film 115 is generated.

Further, the coating liquid 110 coated on the surface 102 of the article 101 exists as a terminal at the moisture 106, 106, ... (Water droplets) or the surface 102 adhering to the surface 102 on the back layer surface 110b in contact with the surface 102 of the article 101. By chemically reacting with the hydroxyl group −OH, a gas such as hydrogen or ammonia rises in the coating layer and volatilizes from the surface layer, and a coating layer 112 on the back surface side of the coating film 115 is generated.

In this way, first, the coating layers 111 and 112 are first generated on the surface layer surface 110a and the back layer surface 110b of the coating liquid 110, respectively. Next, by expanding the coating layer 111 from the surface layer side to the back layer side and expanding the coating layer 112 from the back layer side to the surface layer side, an intermediate coating layer is sequentially generated, and finally. A coating film 115 containing SiO2 as a main component is formed over the surface layer surface 114a that is in contact with the outside air and the back layer surface 114b that is in contact with the surface 102 of the article 101. As described above, the coating films 115, 135, 145 of the present invention contain SiO2 produced by reacting inorganic or organic polysilazane as a main component, so that a film layer that easily spreads in a plane and has a high density can be formed. , Nano-level thin film structures can be achieved.

As shown in FIGS. 1 (c) and 2, 4 and 5, the surface 102 of the article 101 before coating the coating films 115, 135 and 145 is not subjected to a special surface layer treatment such as mirror surface processing. , A large number of micro-level fine uneven portions 103 are formed due to small scratches or the like generated in the manufacturing process or the like. The coating liquid 110 covers the surface 102 of the article 101 and is cured as described above in a state where it has entered the uneven portion 103, so that the coating liquid 110 has entered the uneven portion 103 and is a part of the cured coating film. Functions as an anchor portion 117 (see FIGS. 2, 4, and 5), so that the coating films 115, 135, and 145 adhere more firmly to the surface 102 of the article 101.

Further, as shown in FIGS. 2 to 5, in the layers of the coating films 115, 135, 145, the additive 110B contained in the coating liquid 110, that is, the particles 121, 122 of the organic antiviral agent are as described above. It is mixed in the form of a large number of nano-level or micro-level fine particles, and a part of the surface thereof is exposed on the surface layer surface 114a as described later.

Further, the coating films 115, 135, 145 of the present invention are formed into a nano-level thin film by using inorganic polysilazane as a raw material of the base agent 110A, and in detail, the film thickness is about 5 to 500 nm. Is. Therefore, although it is a coating film containing SiO2 as a main component, it is highly flexible, and in combination with the anchor effect of the anchor portion 117 described above, the surface 102 of the article 101 is deformed even if the cloth material or the like is formed. Even if it is present, the coating properties of the coating films 115, 135, and 145 can be maintained by following the deformation of the surface 102 without peeling or the like.

In the first embodiment shown in FIGS. 2 and 3, the film thickness of the coating film and the organic antiviral agent contained in the coating film are higher than those of another embodiment shown in FIG. 4 and still another embodiment shown in FIG. The particle size of the virus is different. More specifically, the coating film 115 shown in FIGS. 2 and 3 has a film thickness of about 100 nm, and particles 121 and 122 of the organic antiviral agent are mixed in the form of fine particles having a particle size of 5 to 15 nm. ing. Further, the coating film 135 of another embodiment shown in FIG. 4 is formed to have a film thickness of approximately 100 nm, and particles 121 and 122 of the organic antiviral agent are mixed in the form of fine particles having a particle size of 100 nm to 1 μm. It is something to do. Further, the coating film 145 of still another embodiment shown in FIG. 5 is formed to have a film thickness of about 500 nm, and the particles 121 and 122 of the organic antiviral agent are formed into fine particles having a particle size of 100 nm to 1 μm. It is a mixture.

When the surface 102 of the article 101 is a smooth surface having almost no uneven portion 103 described above, the surface 102 of the article 101 is roughened by a file or the like as a pretreatment for coating the coating films 115, 135, 145. By performing the treatment, the uneven portion 103 or the relatively rough uneven portion 104 may be positively generated on the surface 102 of the article 101, and by doing so, the anchor effect of the coating films 115, 135, 145 can be obtained. Obtainable.

By performing this roughening treatment, it is preferable to form uneven portions 103, 104 having an arithmetic average roughness in the range of about 0.1 to 1 μm on the surface 102 of the article 101. By doing so, the coating film 115, The anchor effect of 135 and 145 can be enhanced. In particular, as shown in FIGS. By performing the coarsening treatment for forming 104, the large-diameter particles 121 and 122 can be held by the uneven portion 104. That is, the holding power of the antiviral agent can be enhanced by performing the arithmetic roughening treatment according to the particle size of the antiviral agent.

After the roughening treatment, a cleaning treatment is performed in which the metal powder generated by sanding or the like is blown off from the surface 102 of the article 101 by using an air injection means such as an air gun. Further, after this cleaning treatment, a predetermined time is allowed to cause dew condensation or the like on the surface 102 of the article 101, and naturally-derived moisture is attached.

Further, in this case, after the roughening treatment and the cleaning treatment of the surface 102 of the article 101, the surface 102 of the article 101 on which the uneven portions 103 and 104 are formed by the roughening is subjected to the pretreatment step prior to the coating step. For example, the water may be positively adhered by a water-imparting means such as spraying, and then the coating films 115, 135, 145 may be coated. By doing so, the water adhered to the surface 102 of the article 101. And the chemical reaction with the coating liquid 110 in contact with the surface 102 of the article 101 can be promoted. Moisture may be attached to the surface 102 of the article 101 by a moisture-imparting means without particularly roughening the surface 102.

(Shape of coating layer of coating film)
As shown in FIG. 1, the surfaces of the coating films 115, 135, 145 coated on the surface 102 of the article 101 have the coating films 115, 135, An uneven portion 116 having an uneven shape at the nano level is formed on the surface layer surface 114a of the 145. More specifically, a large number of bubbles such as hydrogen and ammonia are generated by the above-mentioned chemical reaction, and when these bubbles are released from the smooth surface surface 114a of the coating films 115, 135, 145 toward the air, they become bubbles. Due to the influence of the surface tension generated on the surface layer surface 114a of the coating films 115, 135, 145 in contact with each other and the influence of the timing of the initial curing of the surface layer surface 114a due to the chemical reaction, the nano-level recess 116b is formed on the smooth surface. It is assumed that the uneven portion 116 including the convex portion 116a is generated. In addition, in FIGS. 1 to 3, the uneven size of the uneven portion 116 is shown by being deformed from the actual size, and in FIGS. 4 and 5, the uneven portion 116 is omitted.

Further, the uneven portion 116 formed on the surface of the coating films 115, 135, 145 has a smaller uneven depth / height dimension than the uneven portion 103 initially formed on the surface 102 of the article 101 before coating. Therefore, by coating the surface 102 of the article 101 with the coating films 115, 135, 145, the surface is produced to be smoother after the coating than before the coating.

Needless to say, since the gas, which is the by-product described above, is uniformly generated on the surface of the coating films 115, 135, 145, the uneven portion 116 is formed on the coating films 115, 135, 145. It is formed uniformly without any variation in the number of pieces per unit area, the depth of the concave portion, and the height of the convex portion.

Further, as shown in FIGS. 2 to 5, on the surface layer surface 114a, a part of the additive 110B, that is, the particles 121 and 122 of the organic antiviral agent, which are mixed in the coating films 115, 135 and 145 in the form of fine particles. It is fixed with the surface exposed to the outside.

More specifically, as described above, perhydropolysilazane constituting the base agent 110A of the coating liquid 110 chemically reacts with water (H2O) to form a gas (NH3, H2) as a by-product, and these gases are generated. It rises with particles 121 and 122 of the surrounding organic antiviral agent in the coating liquid 110. Therefore, as shown in FIG. 2, some of the organic antiviral agent particles 121 and 122 in the coating liquid 110 gather in the vicinity of the surface layer surface 114a of the coating film 115, and particularly on the surface layer surface 114a due to the volatilization of the gas. It will be gathered in the uneven portion 16 formed in.

As shown in FIGS. 2 and 3, a part of the particles 121 and 122 of the organic antiviral agent is arranged on the surface layer surface 114a so as to complement the concave shape of the concave portion 116b. By doing so, the particles 121 and 122 of the organic antiviral agent act directly on various viruses, and a high antiviral effect can be maintained for a long period of time. Further, the recess 116b is partially embedded by the particles 121 and 122 of the organic antiviral agent, and the smoothness of the surface layer surface 114a can be improved.

Further, another part of the particles 121 and 122 of the organic antiviral agent (only the particles 121 are shown in FIG. 3) is arranged on the surface layer surface 114a so as to be embedded inside the coating film 115. A part of the particles 121 and 122 of the organic antiviral agent is formed by forming a groove 116e extending from the surface of the particles 121 and 122 to the surface layer surface 114a by volatilization of the gas, so that the particles 121 and 122 are formed through the grooves 116e. Part of the surface is exposed to the outside. By doing so, the particles 121 and 122 of the organic antiviral agent embedded in the surface layer surface 114a can also act directly on various viruses, and a high antiviral effect can be maintained for a long period of time. Further, as shown in FIG. 3, the groove portion 116e is formed deeper in the vertical direction than the particle size of the particles 121, and a part of the surface of the particles 121 is exposed to the outside in a stable state in which the entire particles 121 are immersed in the groove portion 116e. Therefore, its antiviral effect can be maintained for a long period of time.

Further, as shown in FIG. 2, another part of the particles 121 and 122 of the organic antiviral agent is arranged on the surface layer surface 114a so as to be embedded inside the convex portion 116a. By doing so, when the convex portion 116a having a protruding shape is partially scraped on the surface layer surface 114a of the coating film 115 due to the use of the article 101 after coating, it is embedded in the convex portion 116a. Since the particles 121 and 122 of the organic antiviral agent are exposed on the surface, a high antiviral effect can be maintained for a long period of time.

Further, the coating liquid 110 uses inorganic polysilazane as a raw material of the base agent 110A, and by using an organic antiviral agent having a relatively low affinity with the base agent 110A, the surface layer surface of the coating films 115, 135, 145 is used. Due to the influence of the surface tension generated on 114a, the base agent 110A is less likely to adhere to the surfaces of the organic antiviral agent particles 121 and 122. As a result, as shown in FIG. 3, there is a gap S between the surface of the particles 121 and 122 of the organic antiviral agent and the separation portion 116c formed in the surface layer surface 114a, the recess 116b and the groove portion 116e of the coating film 115. Is formed larger, and the exposed portion of the organic antiviral agent particles 121 and 122 can be secured larger on the surface layer surface 114a of the coating film 115. In addition, a part of the coating film cured while entering the unevenness of the surface of the organic antiviral agent particles 121 and 122 functions as the anchor portion 116d on the back layer surface 114b side and becomes the surface layer surface 114a of the coating film 115. Particles 121 and 122 of the organic antiviral agent can be fixed in a stable state.

Further, as another embodiment, the coating film 135 shown in FIG. 4 is formed to have a film thickness of about 100 nm like the coating film 115 described above, whereas the particles 121 and 122 of the organic antiviral agent are formed. The particle size of the organic antiviral agent is 100 nm to 1 μm, the particles 121 of the organic antiviral agent have substantially the same size as the film thickness of the coating film 135, and the particles 122 of the organic antiviral agent have a larger size than the film thickness of the coating film 135. Therefore, these particles 121 and 122 are exposed so that the upper portion thereof is exposed to the outside of the surface layer surface 114a of the coating film 135. By doing so, the particles 121 and 122 of these organic antiviral agents act directly on various viruses, and a high antiviral effect can be maintained for a long period of time. In particular, the particles 122 of some organic antiviral agents have a particle size of about 1 μm, which corresponds to several times the film thickness of the coating film 135, which is about several times, and up to about 10 times, so that most of the particles 122 are coated. It will be exposed to the outside of the surface layer surface 114a of the film 135, and a higher antiviral effect can be exhibited.

Further, the base agent 110A is cured in a state where a part of the particles 121 and 122 of the organic antiviral agent is fitted in the uneven portion 103 formed on the surface 102 when the coating liquid 110 is applied. Therefore, the antiviral effect can be maintained for a long period of time without peeling.

Further, as another embodiment, the coating film 145 shown in FIG. 5 is formed to have a film thickness of about 500 nm as compared with the coating film 115 described above, whereas the particles 121 and 122 of the organic antiviral agent are formed. The particle size of the organic antiviral agent is 100 nm to 1 μm, the particles 121 of the organic antiviral agent are smaller than the film thickness of the coating film 135, and the particles 122 of the organic antiviral agent are larger than the film thickness of the coating film 135. Therefore, some of the organic antiviral agent particles 121 in the coating liquid 110 gather in the vicinity of the surface layer surface 114a of the coating film 145, and together with the organic antiviral agent particles 122, the upper portion thereof is the surface layer surface 114a of the coating film 145. It is exposed so that it is exposed to the outside. By doing so, the particles 121 and 122 of these organic antiviral agents act directly on various viruses, and a high antiviral effect can be maintained for a long period of time. In particular, since the particles 122 of some organic antiviral agents have a particle size of about 1 μm, which corresponds to about twice the film thickness of the coating film 145 of about 500 nm, about half of the particles 122 are the surface layer surface of the coating film 145. It will be exposed to the outside of 114a, and a higher antiviral effect can be exhibited.

Similar to the coating films 115 shown in FIGS. 2 and 3, the coating films 135 and 145 shown in FIGS. 4 and 5 are also organic antivirus due to the influence of the surface tension generated on the surface layer surface 114a of the coating films 135 and 145. It is possible to secure a larger exposed portion of the agent particles 121 and 122, and a part of the coating film cured while entering the unevenness of the surface of the organic antiviral agent particles 121 and 122 is on the back layer surface 114b side. It functions as an anchor portion 116d, and particles 121 and 122 of the organic antiviral agent can be fixed to the coating films 135 and 145 in a stable state.

Hereinafter, various evaluation tests of the coating film according to the present invention were carried out on the one coated with the coating film 115 described above.

(Evaluation method of antiviral effect (new coronavirus (1)))
As a method for evaluating the antiviral effect of the coating film against the new coronavirus (COVID -19), on the surface of a 5 cm square polyvinyl chloride (PVC) test piece (without coating film, with coating film) based on ISO21702: 2019. On the other hand, 0.4 ml of the virus solution of the new coronavirus was dropped, the surface of the test piece was covered with a 4 cm square film, and the test piece was allowed to stand at 25 ° C. for 24 hours to wash out the virus on the test piece and collect it. The virus infectivity (residual virus rate) was measured by the plaque measurement method. In addition, measurements were performed on each of the three samples, and the antiviral activity value was calculated by the following formula.
R = Ut-At
R: Anti-virus activity value Ut: Average of common logarithms of virus infection titer (PFU / cm2) after standing for 24 hours of unprocessed product (without coating film) At: 24 hours of anti-virus processed product (with coating film) Average of regular logarithms of viral load (PFU / cm2) after standing

(Evaluation of antiviral effect)
The results of the antiviral test (1) against the new coronavirus are shown in FIG. As shown in FIG. 6, for the new coronavirus, the virus reduction rate of the test piece (without the coating film) without the coating film is 81.5% as compared with that before the test, whereas the virus reduction rate according to the present invention is The virus reduction rate of the test piece coated with the coating film (with the coating film) showed a high value of 94.45%, that is, it was confirmed that the coating film of the present invention significantly reduced the residual virus rate of the new coronavirus. Was done. Further, it was confirmed that the antiviral activity value R of the coating film according to the present invention was 0.52, that is, the virus reduction rate was 69.8% as compared with the case without the coating film. As shown in FIGS. 2 and 3, the particles 121 and 122 containing the active ingredient of the organic antiviral agent fixed on the surface layer surface 114a of the coating film 115 in an exposed state come into direct contact with the new coronavirus. It is presumed that the surface layer surface 114a is kept clean because it acts and kills the virus by destroying the envelope (outer shell).

In ISO21702, it is said that an antiviral effect is evaluated when the antiviral activity value R is 2.0 or more, but the test piece with a coating film used in the above antiviral test (1). However, it is presumed that it may not have been able to fully exert its antiviral effect due to the influence of handling during transportation to overseas testing institutions.

(Evaluation method of antiviral effect (new coronavirus (2)))
Therefore, in order to eliminate the influence of handling during transportation, a method for evaluating the antiviral effect of the coating film against the new coronavirus (COVID -19) was carried out at a testing institute in Japan. As a method for evaluating the antiviral effect, based on ISO21702: 2019, the virus infectivity titer of the new coronavirus (1) is substantially the same as that of the antiviral test (1) for the new coronavirus at the overseas testing institutes. The residual virus rate) was measured, and the antivirus activity value was calculated.

(Evaluation of antiviral effect)
The results of the antiviral test (2) against the new coronavirus are shown in FIG. As shown in FIG. 7, for the new coronavirus, the virus reduction rate of the test piece (without the coating film) without the coating film is 74.3% as compared with that before the test, whereas the virus reduction rate according to the present invention is The virus reduction rate of the test piece coated with the coating film (with the coating film) showed a high value of 99.98%, that is, it was confirmed that the residual virus rate of the new coronavirus was significantly reduced by the coating film of the present invention. Was done. Further, the anti-virus activity value R of the coating film according to the present invention is 3.0, that is, the virus reduction rate is 99.9% as compared with the case without the coating film, and it exhibits an excellent anti-virus effect against the new coronavirus. It was confirmed that. As shown in FIGS. 2 and 3, the particles 121 and 122 containing the active ingredient of the organic antiviral agent fixed on the surface layer surface 114a of the coating film 115 in an exposed state come into direct contact with the new coronavirus. It is presumed that the surface layer surface 114a is kept clean because it acts and kills the virus by destroying the envelope (outer shell).

As described above, ISO21702 is evaluated to have an antiviral effect when the antiviral activity value R is 2.0 or more, but the coating film used in the antiviral test (2) is said to have an antiviral effect. As a result of an accurate test conducted at a testing institution in Japan without being affected by transportation, the existing test piece showed an antiviral activity value R of 3.0, that is, a sufficiently high antiviral effect. It is presumed that it was able to be demonstrated.

(Evaluation method of antiviral effect (influenza A virus))
As a method for evaluating the antiviral effect of the coating film against influenza A virus (H3N2), the virus infectivity of influenza A virus (residual virus) is based on ISO21702: 2019 by the same method as the above test for the new corona virus. Rate) was measured and the anti-virus activity value was calculated. In this test, the virus infectivity titer (residual viral rate) over time was also measured.

(Evaluation of antiviral effect)
The results of the antiviral test against influenza A virus are shown in FIGS. 8 and 9. As shown in FIG. 8, for influenza A virus, the virus reduction rate of the test piece without the coating film (without the coating film) was 97.6% as compared with that before the test, whereas in the present invention. The virus reduction rate of the test piece coated with the coating film (with the coating film) is as high as 99.998%, that is, the coating film of the present invention significantly reduces the residual virus rate of influenza A virus. Was confirmed. Further, the antiviral activity value R of the coating film according to the present invention is 2.5, that is, the virus reduction rate is 99.93% as compared with the case without the coating film, and it has been confirmed that an excellent antiviral effect is exhibited. rice field. This is because, as shown in FIGS. 2 and 3, the particles 121 and 122 containing the active ingredient of the organic antiviral agent fixed on the surface layer surface 114a of the coating film 115 in an exposed state are directly attached to the influenza A virus. It is presumed that the surface surface 114a is kept clean because it acts in contact and is killed by destroying the envelope (outer shell) of the virus.

In addition, based on the antibacterial product technology council sustainability standard, the antiviral activity value was calculated by the same evaluation method as above for the light-resistant treatment (Category 1) in which a xenon arc lamp was irradiated for 10 hours as a pretreatment. As a result, the antiviral activity value R of the coating film according to the present invention against influenza A virus was 3.1, that is, a virus reduction rate of 99.99% or more as compared with no coating film, and an excellent antiviral effect. It was confirmed that it exerts.

Further, as shown in FIG. 9, for influenza A virus, the virus reduction rate of the test piece (with the coating film) coated with the coating film according to the present invention is 30 minutes from the start of standing. It was 41.1% after 1 hour, 78.1% after 1 hour, 91.1% after 3 hours, 95.2% after 5 hours, and 99.998% after 24 hours, and the residual virus rate decreased significantly over time. It was confirmed that we would do it. In addition, the virus reduction rate is about 80 to 90% within 1 to 3 hours from the start of standing, indicating the immediate effect of the antiviral effect of the antiviral agent contained in the coating film according to the present invention. .. As described above, according to the coating method of the present invention, a rapid virus reduction rate of about 80% after 1 hour from the coating film, more than 90% after 3 hours, and more than 95% after 5 hours is achieved. be able to.

(Evaluation method of antibacterial effect)
As a method for evaluating the antibacterial effect of the coating film, JIS Z 2801 antibacterial processed product-antibacterial test method-based on the antibacterial effect, Staphylococcus aureus (without coating film, with coating film) on the surface of a 5 cm square test piece (without coating film, with coating film) 0.4 ml of the bacterial solution of Staphylococcus aureus NBRC 12732) and Escherichia coli NBRC 3972 was dropped respectively, and the surface of the test piece was covered with a 4 cm square film at 35 ° C ± 1 ° C and a relative humidity of 90% or more. After allowing to stand for 24 hours, the bacteria on the test piece were washed out and collected, and then the viable cell count was measured. In addition, measurements were performed on each of the three samples, and the antibacterial activity value was calculated by the same calculation method as the above-mentioned antiviral activity value.

(Evaluation of antibacterial effect)
The results of the antibacterial test against Staphylococcus aureus are shown in FIG. As shown in FIG. 10, for Staphylococcus aureus, the viable cell reduction rate of the test piece (without coating film) without the coating film is 45.0% as compared with that before the test, whereas in the present invention. It was confirmed that the viable cell reduction rate of the test piece coated with the coating film (with the coating film) was 99.99% or more, that is, the viable cell count rate of Staphylococcus aureus was significantly reduced. Further, the antibacterial activity value R of the coating film according to the present invention is 4.4, that is, the viable cell reduction rate of 99.99% as compared with the case without the coating film, that is, the viable cell count rate after 24 hours is approximately 0 (zero). ), And it was confirmed that it exhibits excellent antibacterial properties. As shown in FIGS. 2 and 3, the particles 121 and 122 containing the active ingredient of the organic antiviral agent fixed on the surface surface 114a of the coating film 115 in an exposed state come into direct contact with Staphylococcus aureus. It is presumed that the surface layer surface 114a is kept clean because it acts and kills by destroying the cell membrane of the bacterium.

In addition, the antibacterial activity value was calculated by the same evaluation method as above for the light-resistant treatment (Category 1) in which a xenon arc lamp was irradiated for 10 hours as a pretreatment based on the sustainability standard of the Antibacterial Product Technology Council. As a result, the antibacterial activity value R of the coating film according to the present invention against xenon is 4.0, that is, the viable cell reduction rate is 99.99% or more as compared with the case without the coating film, and an excellent antibacterial effect is exhibited. It was confirmed that.

The results of the antibacterial test against Escherichia coli are shown in FIG. As shown in FIG. 11, for Escherichia coli, the viable cell count rate of the test piece without the coating film (without the coating film) increased about 55 times as compared with that before the test, whereas the coating according to the present invention. It was confirmed that the viable cell reduction rate of the test piece coated with the membrane (with the coating film) was 99.999% or more, that is, the viable cell count rate of Escherichia coli was significantly reduced. Further, the antibacterial activity value R of the coating film according to the present invention is 6.1, that is, the viable cell reduction rate of 99.999% as compared with the case without the coating film, that is, the viable cell count rate after 24 hours is approximately 0 (zero). ), And it was confirmed that it exhibits excellent antibacterial properties. As shown in FIGS. 2 and 3, the particles 121 and 122 containing the active ingredient of the organic antiviral agent fixed in an exposed state on the surface layer surface 114a of the coating film 115 are in direct contact with Escherichia coli. It is presumed that the surface layer surface 114a is kept clean because it acts and kills the bacteria by destroying the cell membrane.

In addition, the antibacterial activity value was calculated by the same evaluation method as above for the light-resistant treatment (Category 1) in which a xenon arc lamp was irradiated for 10 hours as a pretreatment based on the sustainability standard of the Antibacterial Product Technology Council. As a result, the antibacterial activity value R of the coating film according to the present invention against Escherichia coli is 6.1, that is, the viable cell reduction rate is 99.99% or more as compared with the case without the coating film, and an excellent antibacterial effect can be exhibited. confirmed. As described above, it was confirmed that the particles 121 and 122 containing the active ingredient of the organic antiviral agent have a certain antibacterial effect in addition to the above-mentioned antiviral effect.

(Evaluation method of antifungal effect A)
As a method A for evaluating the antifungal effect of the coating film, test pieces (without coating film and with coating film) were attached on an inorganic salt agar medium based on JIS Z 2911: 2018, and 5 strains (Aspergillus niger NBRC 105649, A mixed spore suspension of Penicillium pinophilum NBRC 100533, Paecilomyces variotii NBRC 107725, Trichoderma virens NBRC 6355, Chaetomium globosum NBRC 6347) was sprayed, cultured at 29 ± 1 ° C and 95% or more relative humidity for 28 days, and mold on the sample piece. Table 1 shows the results of visually observing the growth of Aspergillus niger and evaluating the growth of mold and the display of mold resistance. The growth of mold was evaluated as no growth of mold (-), growth of mold under a microscope (±), and remarkable growth of mold (+). Regarding the indication of mold resistance, mold growth is not observed with the naked eye and under a microscope (0), mold growth is not observed with the naked eye, but is observed under a microscope (1), and mold growth is a sample. Within 25% of the area (2), mold growth is within 25-50% of the sample area (3), mold growth is within 50-100% of the sample area (4), hyphal growth is intense and covers the entire sample. It was evaluated as (5).

In addition, based on the antibacterial product technology council sustainability standard, mold growth and mold resistance were performed by the same evaluation method as above for water-resistant treatment (Category 1) in which the product was immersed in water at room temperature for 16 hours as a pretreatment. Table 2 shows the results of evaluation of sex indication.

In addition, based on the antibacterial product technology council sustainability standard, mold growth and mold resistance were performed by the same evaluation method as above for those subjected to light-resistant treatment (Category 1) in which a xenon arc lamp was irradiated for 10 hours as a pretreatment. Table 3 shows the results of evaluation of the sex display.

(Evaluation of antifungal effect (Method A))
As shown in Tables 1 to 3, as a result of the antifungal test, the test piece coated with the coating film according to the present invention (with the coating film) was compared with the test piece without the coating film (without the coating film). Was confirmed to have excellent mold resistance as well as suppress the growth of mold. It was also confirmed that the coating film according to the present invention is also excellent in light resistance. As shown in FIGS. 2 and 3, the particles 121 and 122 containing the active ingredient of the organic antiviral agent fixed on the surface layer surface 114a of the coating film 115 in an exposed state suppress the growth of mold. It is presumed that it is.

(Evaluation method B of antifungal effect)
Further, as a method B for evaluating the antifungal effect of the coating film, test pieces (without coating film and with coating film) were attached on a glucose / inorganic salt agar medium based on JIS Z 2911: 2018, respectively, and the above method A and A mixed spore suspension of 5 strains of the same species was sprayed, cultured at 29 ± 1 ° C. and a relative humidity of 95% or more for 28 days, and the growth of mold on the sample piece was visually observed to evaluate the mold resistance indication. The results of the above are shown in Table 4. In addition, each of the five samples was evaluated, and the mold resistance display was evaluated using the same index as in the above method A.

In addition, based on the antibacterial product technology council's sustainability standard, the mold resistance display was evaluated by the same evaluation method as above for those that had been subjected to water resistance treatment (Category 1) by immersing them in water at room temperature for 16 hours as a pretreatment. The results of the above are shown in Table 5.

In addition, based on the antibacterial product technology council's sustainability standard, the mold resistance display was evaluated by the same evaluation method as above for those that had undergone light-resistant treatment (Category 1) in which a xenon arc lamp was irradiated for 10 hours as a pretreatment. The results of the above are shown in Table 6.

(Evaluation of antifungal effect (Method B))
As shown in Tables 4 to 6, as a result of the antifungal test, the test piece coated with the coating film according to the present invention (with the coating film) was compared with the test piece without the coating film (without the coating film). Was confirmed to have excellent mold resistance. As shown in FIGS. 2 and 3, the particles 121 and 122 containing the active ingredient of the organic antiviral agent fixed on the surface layer surface 114a of the coating film 115 in an exposed state suppress the growth of mold. It is presumed that it is.

As described above, the particles 121 and 122 containing the active ingredient of the organic antiviral agent fixed on the surface layer surface 114a of the coating film 115 according to the present invention in an exposed state have not only an antiviral effect but also an antibacterial effect. It was confirmed that it has an excellent antifungal effect, and also has excellent water resistance and light resistance.

(Action and effect of the present invention)
As described above, the coating liquid 10 (coating material) of the present invention is based on a coating agent in which polysilazane and an alkyl silicate condensate are dissolved in an inert solvent at a total concentration of 50 to 80% by mass. As an agent, a glass coating film produced by polysilazane and an alkyl silicate condensate is used as a base material by adding an antiviral agent to the base agent at a ratio of 0.1 to 20% by mass, and the surface layer of the film is used. Since the antiviral agent is fixed in a stable state with a large exposed portion secured, the high antiviral effect of the object to be coated coated with this coating material can be maintained for a long period of time. For example, when an antiviral agent is kneaded into a resin product, most of the antiviral agent is embedded inside, making it difficult to expose the antiviral agent to the surface, and there is a lot of loss in the added antiviral agent. Since the antiviral agent is stably fixed on the surface layer of the glass coating film formed by the coating material according to the present invention in a state where a large exposed portion is secured, a high antiviral agent can be suppressed while suppressing the addition amount of the antiviral agent. It can be effective.

Further, since the coating film is formed on a thin film having a thickness of 10 μm or less, the antiviral agent is added to the base agent in a small amount in a small amount of 0.1 to 20% by mass in the coating liquid. In addition to being effective, the amount of antiviral agent added is small and the manufacturing cost can be reduced.

Further, since polysilazane as a raw material of the base agent is inorganic polysilazane, it is easy to form a glass coating film on a thin film, so that the antiviral agent is easily exposed on the surface layer of the film.

In addition, since the antiviral agent is an organic antiviral agent, the base agent is made of inorganic polysilazane as a base agent, and by using an organic antiviral agent having a relatively low affinity with the base agent, the base agent becomes antiviral due to surface tension. It becomes difficult to adhere to the surface of the virus agent, and a larger exposed portion of the antiviral agent can be secured on the surface layer of the glass coating film. In addition, the dispersibility of the antiviral agent in the coating liquid based on inorganic polysilazane is maintained well.

Further, as the antiviral agent, particularly by using the organic antiviral agent X, the particles containing the active ingredient can be made into nano-level fine particles having a particle size of about 100 nm or less, and have a size of 50 to 200 nm. It can exert a high antiviral effect against various viruses such as the new coronavirus (COVID -19) and the influenza virus having a size of 80 to 120 nm.

Further, in the coating liquid 10 (coating material) of the present invention, an antibacterial agent may be further added in a proportion of 0.1 to 10% by mass in addition to the antiviral agent, whereby the antibacterial effect of the object to be coated may be added. And antiviral effect can be enhanced.

Further, in the coating method of the present invention, a coating agent dissolved in an inert solvent at a total concentration of 50 to 80% by mass of polysilazane and an alkyl silicate condensate is used as a base agent, and an antivirus is applied to the base agent. By having a coating step of coating the surface of the object to be coated with a coating material to which the agent is added at a ratio of 0.1 to 20% by mass, the surface of the object to be coated is made of glass with polysilazane and an alkylsilicate condensate. Since the antiviral agent is stably fixed in a state where the coating film is formed and the exposed portion is largely secured on the surface layer of the glass coating film as the base material, the high antiviral effect of this coated object can be obtained for a long period of time. Can be done.

Further, the coating step is a step of forming a thin layer of a coating film as a base material containing SiO2 as a main component on the surface of the object to be coated, and expressing an antiviral agent on the surface layer surface of the coating film. By exposing the antiviral agent on the surface layer of the coating film, the antiviral agent acts directly on various viruses, and a high antiviral effect can be maintained for a long period of time. Further, by forming the coating film into a thin layer, it is possible to secure the followability to the behavior of the surface of the object to be coated. Here, in the present invention, the thin layer means a micro-level or nano-level film thickness of 10 μm or less, and more preferably a nano-level film thickness of less than 1 μm.

Further, in the coating step, the coating material is coated on the surface of the object to be coated to which moisture is attached, and the component contained in the coating material and the moisture adhering to the surface of the object to be coated are chemically reacted to cause the object to be coated. A coating film that is a base material containing SiO2 as a main component is formed on the surface of the coating material, and an antiviral agent is exposed in the recesses on the surface layer surface of the coating film formed by a chemical reaction. By expressing an antiviral agent in the recesses on the surface layer of the coating film generated by the discharge of gas generated by the chemical reaction between the components contained in the coating film and the moisture on the surface of the object to be coated, various antiviral agents can be used. It acts directly on the virus and can maintain a high antiviral effect for a long period of time.

Further, the coating step is a step of coating the surface of the object to be coated with a coating material to which an antiviral agent consisting of particles having a maximum diameter of 1 μm is added, so that the surface layer surface of the coating film is coated. The antiviral agent can be easily exposed (particularly, see FIGS. 4 and 5).

Further, by having a sterilization step of sterilizing the surface of the object to be coated before the coating step, a high-quality and highly durable coating film is generated on the surface of the object to be coated cleaned by the sterilization step. be able to.

Further, by having a pretreatment step of adhering moisture to the surface of the object to be coated prior to the coating step, the moisture is adhering to the surface of the object to be coated, and this moisture and the components contained in the coating material are combined. It is possible to accelerate the chemical reaction of the coating film and quickly and firmly form a coating film on the surface of the object to be coated.

From the viewpoint of ensuring a large exposed portion of the antiviral agent on the surface layer of the glass coating film, the coating step is preferably performed by a plurality of layers such as a two-layer coating.

A form for carrying out the coating material and the coating method according to the second embodiment of the present invention will be described below with reference to FIGS. 12 to 16.

(Coating liquid)
The coating liquid 10 as the coating material of the present invention is mainly composed of the base agent 10A and the additive 10B added to the base agent 10A. First, the base agent 10A contains at least an inorganic polysilazane and an alkyl silicate condensate as raw materials, and in Example 2, these inorganic polysilazane and the alkyl silicate condensate are diluted with an inert solvent.

The inorganic polysilazane and the alkyl silicate condensate are dissolved in dibutyl ether as an inert solvent in Example 2 at a concentration in the range of 50 to 80% by mass in total. More specifically, the inorganic polysilazane is contained in an amount of 0.1 to 5% by mass, and the rest is contained in the proportion of the alkyl silicate condensate.

More specifically, the inorganic polysilazane of Example 2 has perhydropolysilazane, that is, a Si—H bond, a Si—N bond, and an NH bond, and is represented by, for example, the following general formula (1)-(SiH2). -NH) -A chain-structured inorganic polymer composed of units.

The inorganic polysilazane is not limited to a chain structure, but may be a polymer having a cyclic structure or a polymer having a composite of these structures.

Alkyl silicate condensates include, for example, tetramethyl orthosilicate, tetraethyl orthosilicate, tetra-n-propyl orthosilicate, tetra-i-propyl orthosilicate, tetra-n-butyl orthosilicate, tetra-sec-butyl orthosilicate, methylpoly. One or more condensates selected from silicates and ethylpolysilicates.

The inert solvent is a solvent inert to inorganic polysilazane and alkyl silicate condensates, and is preferably selected from dibutyl ether, dimethyl ether, diethyl ether, dipropyl ether, terepine oil, benzene, toluene and the like. ..

The additive 10B is added to the above-mentioned base agent 10A, and the inorganic antibacterial agent 21 is 0.01 to 10% by mass and the inorganic antiviral agent 22 is 0.01 to 40% by mass. , And the organic antibacterial / antiviral agent 23 is added in an amount of 0.01 to 20% by mass, more preferably 0.1 to 10% by mass.

More specifically, the inorganic antibacterial agent 21 contains silver oxide-calcium zinc phosphate (Ag2O-CaαZnβAlγ (PO4) 6). Further, the inorganic antiviral agent 22 contains at least a molybdenum compound or a silver compound. The organic antibacterial / antiviral agent 23 contains diiodomethyltolyl sulfone.

(Aspect of coating material)
Further, the coating liquid 10 of the second embodiment is operated as a predetermined amount of liquid enclosed in a container made of, for example, glass or resin, and the liquid is moistened with a cloth material (not shown) to be coated. A coating film is formed by applying it to the surface of various articles and the like. The operation of the coating material is not limited to this, and for example, a non-woven fabric or the like impregnated in the coating liquid in advance may be sealed in the bag and the bag may be opened before use, or the coating liquid may be coated. The surface of the object may be sprayed in the form of a mist to cover it.

(Coating film coating method)
The coating liquid 10 is applied or sprayed on the surface 2 of the article 1 to be coated to chemically react with moisture to form single-layer or multi-layer coating films 15 and 35. The coating film 15 shown in FIG. 13 is stratified at the micro level. Further, the coating film 35 shown in FIG. 14 is formed into a thin layer at the nano level, and the film thickness is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm. It is stratified.

First, a sterilization step of sterilizing the surface 2 of the article 1 is performed prior to the coating steps of the coating films 15 and 35. In this sterilization step, a sterilizing solution diluted with hypochlorous acid or sodium hypochlorite, which has antibacterial and antiviral effects in addition to the sterilizing effect, is sprayed or a non-woven fabric impregnated with the sterilizing solution is used. , Adhere to the surface 2 of the article 1. By sterilizing in this way, it is possible to produce high-quality and highly durable coating films 15 and 35 that are easy to coat the coating films 15 and 35 on the surface 2 of the clean article 1 and are difficult to peel off. can.

After the above-mentioned sterilization step and before the coating step, water (H2O) such as purified water may be attached to the surface 2 of the article 1 with a non-woven fabric or a sprayer as a pre-step. By doing so, the chemical reaction between the moisture adhering to the surface 2 of the article 1 and the components contained in the coating liquid 10 is promoted, and the coating films 15 and 35 are quickly and firmly formed on the surface 2 of the article 1. can do.

(Covered object)
As the object to be covered, various articles made of materials such as resin material, metal material, wood, rubber material, and leather can be applied, or fixed installation objects such as furniture may be used, for example, a portable terminal. Multiple people come into contact with the surface of the operation part of the remote control, desk / table tops and drawers, tableware, personal belongings such as bags and wallets, door knobs and handrails, leather for trains and buses, construction / temporary materials, etc. Articles with many opportunities are suitable as covering objects.

(Mechanism of coating film formation)
Next, the mechanism by which the coating films 15 and 35 according to the present invention are formed will be described. As shown in FIG. 12 (a), in many cases, the surface 2 of an article 1 made of, for example, a metal material as a covering target has a plurality of moistures 6, 6, ... (Water droplets) due to dew condensation or moisture in the air. ) Is attached. When the coating liquid 10 is applied or sprayed in a thin film on the surface 2 of the article 1 to cover it, perhydropolysilazane, which is an inorganic polysilazane constituting the base agent 10A contained in the coating liquid 10, becomes moisture (H2O) in the air. By chemically reacting with the above, a coating layer having an inorganic structure is generated on the surface 2 of the article 1. Although a small amount of gas (NH3, H2) is secondarily generated by the above-mentioned chemical reaction, all of these gases naturally volatilize in the atmosphere on the surface 2 of the article 1.

That is, as shown in FIG. 12 (b), the coating liquid 10 is a by-product of the coating films 15 and 35 by chemically reacting with the moisture contained in the air on the surface layer surface 10a in contact with the air. A certain gas such as hydrogen or ammonia volatilizes from the surface layer, and the coating layer 11 on the surface side of the coating films 15 and 35 is formed.

Further, the coating liquid 10 coated on the surface 2 of the article 1 exists on the back layer surface 10b in contact with the surface 2 of the article 1 as water 6, 6, ... (Water droplets) adhering to the surface 2 or as a terminal on the surface 2. By chemically reacting with the hydroxyl group −OH, a gas such as hydrogen or ammonia rises in the coating layer and volatilizes from the surface layer, and the coating layer 12 on the back surface side of the coating films 15 and 35 is formed.

In this way, first, the coating layers 11 and 12 are first generated on the surface layer surface 10a and the back layer surface 10b of the coating liquid 10, respectively. Next, the coating layer 11 is expanded from the surface layer side to the back layer side, and the coating layer 12 is expanded from the back layer side to the surface layer side to sequentially generate an intermediate coating layer, and finally. The coating films 15 and 35 are formed over the surface layer surface 14a that is in contact with the outside air and the back layer surface 14b that is in contact with the surface 2 of the article 1.

As shown in FIG. 12 (c), the surface 2 of the article 1 before coating the coating films 15 and 35 has small scratches or the like generated in the manufacturing process or the like unless a special surface layer treatment such as mirror surface processing is performed. A large number of fine uneven portions 3 at the micro level are formed. The coating liquid 10 covers the surface 2 of the article 1 and is cured as described above in a state where it has entered the uneven portion 3, so that the coating material that has entered the uneven portion 3 and is cured is the anchor portion 17. The coating films 15 and 35 adhere more firmly to the surface 2 of the article 1.

Further, as shown in FIGS. 13 and 14, the surface layer and the inside of the coating films 15 and 35 have an additive 10B contained in the coating liquid 10, that is, an inorganic antibacterial agent 21, an inorganic antiviral agent 22, and an inorganic antiviral agent 22. The organic antibacterial / antiviral agent 23 is mixed in the form of a large number of micro-level fine particles, and some of them are exposed on the surface layer surface 14a as described later.

The coating film 15 shown in FIG. 13 is formed at the micro level. Further, as another embodiment, the coating film 35 shown in FIG. 14 is formed at a nano level thinner than the coating film 15 described above. Therefore, although it is a glass-coated film, it is highly flexible, and in combination with the anchor effect of the anchor portion 17 described above, even if the surface 2 of the object to be coated causes deformation of the cloth material or the like, it is peeled off. The coating property of the coating film 35 can be maintained by following the deformation of the surface 2 without the like.

When the surface 2 of the article 1 is a smooth surface having almost no uneven portion 3 described above, the surface 2 of the article 1 is roughened by a file or the like as a pretreatment for coating the coating film 15. Therefore, the uneven portion 3 may be positively generated on the surface 2 of the article 1, and by doing so, the anchor effect of the coating film 15 can be obtained.

It is preferable to form the uneven portion 3 having an arithmetic average roughness in the range of about 0.1 to 1 μm on the surface 2 of the article 1 by performing this roughening treatment, and by doing so, the anchor effect of the coating film 15 is achieved. Can be enhanced.

After the roughening treatment, a cleaning treatment is performed in which the metal powder generated by sanding or the like is blown off from the surface 2 of the article 1 by using an air injection means such as an air gun. Further, after this cleaning treatment, a predetermined time is allowed to cause dew condensation or the like on the surface 2 of the article 1 to allow naturally-derived moisture to adhere.

Further, in this case, after the roughening treatment and the cleaning treatment of the surface 2 of the article 1, the surface 2 of the article 1 on which the uneven portion 3 is formed by the roughening is subjected to a pretreatment step prior to the coating step. For example, the moisture may be positively adhered by a moisture-imparting means such as mist blowing, and then the coating film 15 may be coated. By doing so, the moisture adhered to the surface 2 of the article 1 and the moisture of the article 1 It is possible to promote a chemical reaction with the coating liquid 10 in contact with the surface 2. Moisture may be attached to the surface 2 of the article 1 by a moisture-imparting means without particularly roughening the surface 2.

(Shape of coating layer of coating film)
As shown in FIG. 13, the surface of the coating film 15 coated on the surface 2 of the article 1 is nanon on the surface layer surface 14a of the coating film 15 at the trace of the volatilization of gas bubbles which are by-products. An uneven portion 16 having an uneven shape is formed at the level. More specifically, a large number of bubbles such as hydrogen and ammonia are generated by the above-mentioned chemical reaction, and when these bubbles are released into the air from the smooth surface layer surface 14a of the coating film 15, the coating film 15 in contact with the bubbles. Due to the influence of the surface tension generated on the surface layer surface 14a and the influence of the timing of the initial curing of the surface layer surface 14a due to the chemical reaction, the uneven portion composed of the nano-level concave portions 16b and the convex portions 16a on the smooth surface. It is assumed to generate 16. In addition, in FIGS. 12 and 13, the uneven size of the uneven portion 16 is shown in a deformed shape from the actual size, and in FIG. 14, the uneven portion 16 is omitted.

Further, since the uneven portion 16 formed on the surfaces of the coating films 15 and 35 has a smaller uneven depth / height dimension than the uneven portion 3 initially formed on the surface 2 of the article 1 before coating. By coating the surface 2 of the article 1 with the coating films 15 and 35, the surface is produced to be smoother after the coating than before the coating.

Needless to say, since the gas, which is the by-product described above, is uniformly generated on the surface of the coating film 15, the dimples 16 have the number of dimples 16 per unit area of the coating film 15 and the depth of the recesses. In addition, the height of the convex portion is uniformly formed without any variation.

Further, the coating films 15 and 35 coated on the surface 2 of the article 1 are the dimples 16 formed on the coating films 15 and 35 when a single layer is applied as shown in FIG. 15A, and FIG. 15 ( Comparing with the dimples 26 formed on the coating films 15 and 35 when applying multiple layers as shown in b), the dimples 26 when applying multiple layers have higher unevenness depth and height dimensions. It has been confirmed to be small. It is presumed that this is because the coating film is coated a plurality of times to smooth out the unevenness of the dimples 16 at the time of single-layer coating and to form smoother dimples 26.

Further, on the surface layer surface 14a, an additive B mixed in the coating films 15 and 35 in the form of fine particles, that is, an inorganic antibacterial agent 21, an inorganic antiviral agent 22, and a part of an organic antibacterial / antiviral agent 23. It is fixed with the surface exposed to the outside.

More specifically, as described above, perhydropolysilazane constituting the base agent 10A of the coating liquid 10 chemically reacts with water (H2O) to form a gas (NH3, H2) as a by-product, and these gases are generated. It rises with fine particles of the peripheral additive B in the coating liquid 10. Therefore, as shown in FIG. 13, a part of the additive B in the coating liquid 10 gathers in the vicinity of the surface layer surface 14a of the coating film 15, and particularly, the uneven portion 16 formed on the surface layer surface 14a by the volatilization of the gas. Will gather at.

A part of the fine particles of the additive B is arranged on the surface layer surface 14a so as to complement the concave shape of the concave portion 16b. By doing so, these inorganic antibacterial agents 21, inorganic antiviral agents 22, and organic antibacterial / antiviral agents 23 act directly on various germs and viruses to prolong the antibacterial and antiviral effects. Can be enhanced to. Further, the recess 16b is partially embedded by the additive B, and the smoothness of the surface layer surface 14a can be improved.

Further, another part of the fine particles of the additive B is arranged on the surface layer surface 14a so as to be embedded inside the convex portion 16a. By doing so, when the convex portion 16a having a protruding shape is partially scraped on the surface layer surface 14a of the coating film 15 due to the use of the article 1 after coating, it is embedded in the convex portion 16a. Since the additive B is exposed on the surface, the antibacterial / antiviral effect can be maintained for a long period of time.

Further, the coating films 15 and 35 formed on the surface 2 of the article 1 by applying the coating liquid 10 according to the present invention have an inorganic component as a base thereof, and further have an antibacterial agent 21 and an antiviral agent as additives. Since 22 is also an inorganic component, it is possible to maintain the film state for a long period of time without deteriorating without elution and vaporization to the substrate or the outside.

Further, as another embodiment, the coating film 35 shown in FIG. 14 is formed at a nano level thinner than the coating film 15 described above, and more specifically, the film thickness is about 1 to 500 nm. .. On the other hand, the inorganic antibacterial agent 21 has a particle size of about 0.8 to 1 μm, the inorganic antiviral agent 22 has a particle size of about 3 μm, and the organic antibacterial / antiviral agent 23 has a particle size of about 1 μm. It is larger than the film thickness of the coating film 35. Therefore, these particles are exposed so that the upper portion thereof is exposed to the outside of the surface layer surface 34a of the coating film 35. By doing so, these inorganic antibacterial agents 21, inorganic antiviral agents 22, and organic antibacterial / antiviral agents 23 act directly on various germs and viruses to prolong the antibacterial and antiviral effects. Can be enhanced to. Further, by forming the coating film 35 in a thin layer, it is possible to secure the followability to the behavior even when the surface 2 of the article 1 has flexibility.

Further, some particles of the additive B are peeled off because the base agent A is cured while the lower portion thereof is fitted in the uneven portion 3 formed on the surface 2 when the coating liquid 10 is applied. Antibacterial and antiviral effects can be sustained for a long period of time.

(Evaluation method of antibacterial and antiviral effects)
As a method for evaluating the antibacterial and antiviral effects of the coating film, the surface 2 coated with the coating films 15 and 35 is subjected to an ATP (adenosine triphosphate) wiping test over time, and the evaluation is performed based on the numerical value of ATP. rice field. Here, ATP is a chemical substance that exists as an energy source for all living things on the earth, and the existence of ATP confirms that there is evidence of bacteria / viruses themselves or traces of bacteria / viruses. can do. That is, the larger the value in the ATP wiping test, the higher the degree of contamination of the surface (higher risk of infection), and the smaller the value in the ATP wiping test, the smaller the degree of contamination of the surface (risk of infection). Low).

The ATP wiping inspection will be described. In this ATP wiping inspection, a glass test material (A) whose surface is coated with the coating material according to the present invention and a test material (B) whose surface is coated with another type of coating material described later for comparison. )-(E) and the test material (unmarked) not coated with any coating material are exposed to the normal temperature environment in the same laboratory, and the surface of each test material is exposed every day (every 24 hours). The above ATP wiping was performed, and the number of detected ATPs was compared. The laboratory is in an environment where multiple people come and go and bacteria and viruses can invade along with it. When wiping the ATP on the surface, the tip of the cotton swab-shaped detection wire is rubbed on the surface of the test material under certain conditions, and the tip is inserted into a dedicated ATP detector (not shown). It detects the value of ATP attached to.

The test material (B) is coated with a coating material composed only of the base agent 10A without the additive 10B contained in the coating liquid 10 according to the present invention being added. Next, the test material (C) is coated with an inorganic glass coating material for sports equipment and the like. The test material (D) is coated with an inorganic glass coating material for mobile terminals and the like. The test material (E) is coated with an inorganic ceramic coating material.

(Evaluation of antibacterial and antiviral effects)
The ATP wiping inspection result is shown in FIG. In the test material (A) coated with the coating material according to the present invention, an increase in ATP was hardly confirmed over time, and the highest antibacterial / antiviral effect was maintained as compared with other test materials. It was confirmed that there was. As shown in FIGS. 13 and 14, this is an inorganic antibacterial agent 21, an inorganic antiviral agent 22, and an organic antibacterial / antiviral agent fixed in an exposed state on the surface layer surface 14a of the coating films 15 and 35. 23 keeps the surface surface 14a clean because it comes into direct contact with bacteria and viruses that fly in the outside air together with droplets and dust and try to adhere to the surface surface 14a and act to prevent their colonization. It is inferred that.

Further, in the test material (B), although ATP increased with time, the rate of increase remained slight. This is due to the absence of the above-mentioned inorganic antibacterial agent 21, the inorganic antiviral agent 22, and the organic antibacterial / antiviral agent 23, and the base agent 10A containing inorganic polysilazane, and the surface layer surface of the coating film is mainly composed of SiO2. It is presumed that it is formed on the smooth surface, that is, the smoothness is higher than that of the surface of the test material before coating, so that the colonization of bacteria and viruses can be prevented to some extent.

In addition, ATP of the test material (C) increased significantly with time, and the rate of increase was also higher than that of the test material (B). This is presumed to be poor in resistance to bacteria and viruses because the inorganic antibacterial agent or antiviral agent is not exposed on the surface layer surface of the coating film, unlike the test material (A) described above.

Similarly, in the test material (D) and the test material (E), ATP increased significantly with time, and the rate of increase was also higher than that of the test material (B). It is presumed that this is because, like the test material (C), the inorganic antibacterial agent or antiviral agent was not exposed on the surface layer surface of the coating film and could not cause a resistance action against bacteria and viruses.

(Action and effect of the present invention)
As described above, the coating liquid 10 (coating material) of the present invention is a coating agent in which the inorganic polysilazane and the alkyl silicate condensate are dissolved in an inert solvent at a total concentration of 50 to 80% by mass. As the base agent 10A, the inorganic antibacterial agent 21 is added at a ratio of 0.1 to 5% by mass and the inorganic antiviral agent 22 is added at a ratio of 0.1 to 20% by mass to the base agent 10A to form inorganic polysilazane and alkyl. Using the glass coating film produced by the silicate condensate as a base material, the inorganic antibacterial agent 21 and the inorganic antiviral agent 22 are stably fixed on the surface layer surface 14a of the coating films 15 and 35, and thus coated with this coating liquid 10. The antibacterial effect and the antiviral effect of the article 1 (covered object) can be compatible with each other for a long period of time.

Further, the coating liquid 10 is further added with the organic antibacterial / antiviral agent 23 at a ratio of 0.1 to 10% by mass, so that both the antibacterial effect and the antiviral effect of the article 1 can be enhanced.

Further, in the coating step of the coating liquid 10, the coating liquid 10 is coated on the surface 2 of the article 1 to which water has adhered, and the components contained in the coating liquid 10 and the water adhering to the surface 2 of the article 1 are chemically reacted. As a result, coating films 15 and 35 serving as a base material containing SiO2 as a main component are formed on the surface 2 of the article 1, and the recesses 16b of the surface layer surface 14a of the coating films 15 and 35 formed by the chemical reaction are formed. By expressing the antibacterial agent 21 and the antiviral agent 22, these antibacterial agent 21 and the antiviral agent 22 can act directly on various germs and viruses, and the antibacterial and antiviral effects can be enhanced for a long period of time. .. Further, by disposing the particles of the antibacterial agent 21 and the antiviral agent 22 in the recess 16b of the surface layer surface 14a of the coating films 15 and 35, the recess 16b can be embedded, and thus the base agent containing no additive. The smoothness of the surface layer surface 14a can be improved as compared with the coating liquid consisting of only a single layer.

Although examples of the present invention have been described above with reference to the drawings, the specific configuration is not limited to these examples, and any changes or additions that do not deviate from the gist of the present invention are included in the present invention. Will be.

For example, in Example 1, at least the organic antiviral agent X may be added as the antiviral agent, and the organic antiviral agent Y may not be added. The organic antiviral agent X may be in the form of a liquid or may be in the form of a powder. Similarly, the organic antiviral agent Y may be in the form of a liquid or may be in the form of a powder.

Further, in the second embodiment, the inorganic antibacterial agent 21 and the inorganic antiviral agent 22 are added to the coating liquid 10, but the coating liquid 10 is not limited to this, and one material has both antibacterial and antiviral effects. If so, only the material may be added.

Further, in Examples 1 and 2, the case where the inorganic polysilazane is used as the base agent has been described, but the organic polysilazane may be used as the base agent. In this case, by controlling the film thickness to a nano level, preferably a thin film of about 500 nm, it is possible to easily expose the antiviral agent to the surface layer of the coating film. Further, by using organic polysilazane, it is easy to form a micro-level coating film thicker than the nano-level.

Further, in Examples 1 and 2, the embodiment in which the coating film is formed into a nano-level thin layer having a film thickness of about 100 to 500 nm has been described, but if the film thickness is 10 μm or less, the micro-level thin layer is described. It may be formed into a film.

1 Article (covered object)
2 Surface 3 Concavo-convex part 6 Moisture 10 Coating liquid (coating material)
10A Base agent 10B Additive 11,12 Coating layer 14a Surface layer surface 14b Back layer surface 15,35 Coating film 16 Concavo-convex part 16a Convex part 16b Concave part 17 Anchor part 21 Inorganic antibacterial agent 22 Inorganic antiviral agent 23 Organic antibacterial / antibacterial Viral agent 101 Article (covered object)
102 Surface 103 Concavo-convex part 106 Moisture 110 Coating liquid (coating material)
110A Base agent 110B Additive 111, 112 Coating layer 114a Surface surface 114b Back layer surface 115, 135, 145 Coating film 116 Concavo-convex part 116a Convex part 116b Concave part 116c Separation part 116d Anchor part 116e Groove part 117 Anchor part 121,122 Particles (antiviral) Agent)
S gap

Claims (10)

The total concentration of polysilazane and alkyl silicate condensate is 50 to 80% by mass, the coating agent dissolved in the inert solvent is used as the base agent, and the antiviral agent is added to the base agent by 0.1 to 20% by mass. A coating material characterized by being added in the proportion of. The coating material according to claim 1, wherein the polysilazane is an inorganic polysilazane. The coating material according to claim 2, wherein the antiviral agent is an organic antiviral agent. The coating material according to any one of claims 1 to 3, further comprising adding an antibacterial agent at a ratio of 0.1 to 10% by mass. The total concentration of polysilazane and alkyl silicate condensate is 50 to 80% by mass, the coating agent dissolved in the inert solvent is used as the base agent, and the antiviral agent is added to the base agent by 0.1 to 20% by mass. A coating method comprising a coating step of coating the surface of an object to be coated with a coating material added at the ratio of. In the coating step, a coating film as a base material containing SiO ₂ as a main component is formed on the surface of the object to be coated in a thin layer, and the antiviral agent is exposed on the surface layer surface of the coating film. The coating method according to claim 5, wherein the coating method is characterized by the above. In the coating step, the coating material is coated on the surface of the object to be coated to which moisture is attached, and the component contained in the coating material is chemically reacted with the moisture adhering to the surface of the object to be coated. A step of forming a coating film as a base material containing SiO ₂ as a main component on the surface of the object to be coated, and expressing the antiviral agent in the recesses on the surface layer surface of the coating film formed by the chemical reaction. The coating method according to claim 5, wherein the coating method is characterized by the above. 6. The coating step is a step of coating the surface of the object to be coated with the coating material having the antiviral agent added, which is composed of particles having a maximum diameter of 1 μm, with a film thickness of 500 nm or less. Alternatively, the coating method according to 7. The coating method according to any one of claims 5 to 8, further comprising a sterilization step of sterilizing the surface of the object to be coated prior to the coating step. The coating method according to any one of claims 5 to 9, further comprising a pretreatment step of adhering moisture to the surface of the object to be coated prior to the coating step.

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