JP2021098197A - Bonding method for antimicrobial hardened material and manufacturing method for antimicrobial member - Google Patents

Abstract

To provide a bonding method and a manufacturing method for an antimicrobial hardened material with excellent coating performance which has excellent antimicrobial performance and can maintain a pattern of a surface of a base material and characteristics such as hue without change.SOLUTION: A bonding method for an antimicrobial hardened material includes: a coating step of coating a surface of a base material by spraying an antimicrobial composition including antimicrobial components, an uncured binder, a dispersion medium and a polymerization starter to bond the composition to the surface of the base material; and a boding step of curing the uncured binder in the antimicrobial composition bonded thereto by the coating step and bonding the cured binder onto the surface of the base material. When a rate of coating of the surface of the base material with the antimicrobial composition at the time when t (seconds) elapses after the spraying is started is defined as S(t)%, the rate of coating of the surface of the base material is adjusted to satisfy the following inequality (1); 0.01 t<S(t)%<(33 t)1/2 (1).SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for fixing an antimicrobial cured product and a method for producing an antimicrobial member.

In recent years, so-called "pandemics", in which infectious diseases mediated by various microorganisms that are pathogens spread rapidly in a short time, have become a problem, such as SARS (Severe Acute Respiratory Syndrome), norovirus, and bird flu. Deaths from viral infections have also been reported.

Therefore, antiviral agents that exert antiviral activity against various viruses are being actively developed, and antiviral agents made of metals such as Pd and organic compounds that actually have antiviral activity on various members. It is practiced to apply a resin or the like containing the above-mentioned material, or to manufacture a member containing a material on which an anti-virus agent is carried.

Patent Document 1 is characterized in that it is a molded product having a layer made of a curable resin containing an inorganic antibacterial agent and a metal oxide on its surface, and the inorganic antibacterial agent is a fatty acid-modified metal ultrafine particle. The molded product to be used is disclosed.

Patent Document 2 discloses an anti-virus coating agent containing cuprous oxide and a sugar having a reducing property.

Japanese Unexamined Patent Publication No. 2015-105252 Japanese Patent No. 581248

However, in the molded product described in Patent Document 1, since the layer made of the curable resin is a continuous layer formed on the surface of the molded product, sufficient transparency such as a protective film or a film for a display is required. It was difficult to use as a layer to be used.
Further, regarding the coating method, it is only described that a conventionally known coating method can be appropriately selected according to the shape of the molded product, and no specific coating method has been proposed.

Further, it is disclosed that the anti-virus coating agent described in Patent Document 2 contains a binder component that cures in an environment of 10 to 120 ° C. in addition to cuprous oxide and a reducing sugar, but electromagnetic waves. A specific binder component such as a curable resin is not disclosed, and there is a problem that the coatability is inferior. Further, the sugar in the coating agent is easily eluted in water, which causes deterioration of the cured resin product and desorption of cuprous oxide, resulting in poor water resistance.

That is, both the techniques of Patent Documents 1 and 2 disclose specific methods for coating a base material of an antimicrobial composition such as a fatty acid-modified metal ultrafine particle-containing dispersion or an antivirus coating agent. It was not shown, and the effect obtained by a specific coating method was not shown.

The present invention has been made in view of such a problem, and has excellent antimicrobial properties, can maintain the characteristics such as the pattern and color of the surface of the base material as it is, and has excellent antimicrobial properties. It is an object of the present invention to provide a method for fixing a cured microbial product and a method for producing an antimicrobial member.

In the present invention, an antimicrobial composition containing an antimicrobial component, an uncured binder, a dispersion medium and a polymerization initiator is spray-sprayed on the surface of the base material and adhered to the surface of the base material to adhere to the surface of the base material. With the coating step of coating with the above antimicrobial composition,
A method for fixing an antimicrobial cured product, which comprises a fixing step of curing the uncured binder in the antimicrobial composition attached by the coating step to fix the cured binder to the surface of the substrate. ,
When the coverage of the surface of the base material with the antimicrobial composition when t (seconds) has passed from the start of spraying is S (t)%, the base material is satisfied so as to satisfy the following inequality (1). It is characterized by adjusting the coating speed of the surface.
0.01t <S (t)% <(33t) ^1/2 ... (1)

In the method for fixing an anti-microbial cured product of the present invention, the anti-microorganism is a concept including anti-virus, antibacterial, anti-mold, and anti-mold. Therefore, the antimicrobial component is a concept including an antiviral component, an antibacterial component, an antifungal component, and an antifungal component, and the antimicrobial agent includes an antiviral agent, an antibacterial agent, an antifungal agent, and an antifungal agent. It is a concept, and the antimicrobial composition is a concept including an antiviral composition, an antibacterial composition, an antifungal composition, and an antifungal composition.

The anti-microbial cured product formed by the method for fixing the anti-microbial cured product according to the present specification may be a cured product exhibiting the activity of any one of antivirus, antibacterial, antifungal and antifungal. Of antivirus, antibacterial, antifungal and antifungal, it may be a cured product showing any two kinds of activities, or it may be a cured product showing any three kinds of activities, and all four kinds of activities may be active. It may be a cured product showing.
The antimicrobial cured product formed by the method for fixing the antimicrobial cured product of the present invention is particularly effective for antivirus and antifungal among the antimicrobial properties of the antimicrobial cured product, and the antivirus has the highest activity. have.

In the method for fixing the antimicrobial cured product of the present invention, when the coverage of the substrate surface with the antimicrobial composition after t (seconds) has elapsed from the start of spray spraying is S (t)%, the above inequality (1) Adjust the coating rate to meet the requirements.

In the method for fixing the antimicrobial cured product of the present invention, the coverage S (t)% of the surface of the substrate with the antimicrobial composition when t (seconds) has passed from the start of spray spraying satisfies the above inequality (1). In addition, when the coating rate on the surface of the base material is adjusted, the antimicrobial composition containing the antimicrobial component adheres evenly to the surface of the base material, and the binder cured product formed through the above fixing step is formed in an uneven shape. .. That is, a cured binder containing an antimicrobial component is fixedly formed on the surface of the base material, and the cured binder is dispersed in an island shape and fixed to the surface of the base material, or the hardened binder is fixed on the surface of the base material. The region in which the cured product is formed and the region in which the binder cured product is not formed are mixed and provided.

For this reason, the total surface area of the cured binder containing the antimicrobial component is larger than that when the cured binder is formed on the entire surface of the base material, so that the probability of contact with microorganisms such as viruses is high. In addition, since microorganisms such as viruses can be trapped between the cured binders, high antimicrobial activity can be obtained. In addition, since the antimicrobial component is contained in the cured binder, it has excellent adhesion to the base material and can be prevented from falling off by wiping and cleaning.

If the coverage S (t)% does not satisfy the inequality 0.01t <S (t)%, that is, if S (t) ≤ 0.01t, the coating rate is too low and the antimicrobial agent The bonding step of adhering the composition to the substrate takes too much time and is not practical. On the contrary, when S (t)% <(33t) ^1/2 is not satisfied, that is, when (33t) ^1/2 ≤ S (t), the coating speed is too high and the antimicrobial agent against the surface of the substrate is used. Excessive spraying of the composition causes liquid dripping and uneven coating, resulting in deterioration of design. Further, since the antimicrobial composition is excessively sprayed on the surface of the base material, the cured binder formed through the fixing step may become a film, and an appropriate uneven shape may not be formed.

The above inequality (1) is displayed when converted to one spray nozzle. If the antimicrobial composition is sprayed with a plurality of nozzles, it is desirable to adjust the coating rate so as to satisfy the above inequality (1) in terms of one nozzle.
In the present invention, the coating speed is adjusted so as to satisfy the above inequality, 0.1t <S (t)% <(33t) ^{1/2, not only in terms of coatability but also in consideration of productivity.} Is the best.

Further, in the method for fixing the antimicrobial cured product in the present invention, the coating rate is a value obtained by dividing the amount of the substrate surface coating per unit time by the spray spray area, and the coating treatment is performed using one spray nozzle. Is defined as the antimicrobial composition coating rate in doing so. The coating speed can be adjusted by the discharge flow rate of each spray, the pressure of the spray, the number of times the spray is swept, the sweep speed, and the like.

Further, in another aspect, in the present invention, an antimicrobial composition containing an antimicrobial component, an uncured binder, a dispersion medium and a polymerization initiator is spray-sprayed on the surface of the substrate and adhered to the surface of the substrate. At the very least, the coating step of coating the surface of the base material with the antimicrobial composition and the uncured binder in the antimicrobial composition adhered by the coating step are cured, and the binder is cured on the surface of the base material. A method for producing an antimicrobial member, which comprises a fixing step of fixing an object, wherein the coverage of the surface of the base material with the antimicrobial composition when t (seconds) has passed from the start of spray spraying is S (t). )%, It is also characterized in that the coating speed of the surface of the base material is adjusted so as to satisfy the following inequality (2).
0.01t <S (t)% <(33t) ^1/2 ... (2)

In the method for producing an anti-microbial member of the present invention, the anti-microorganism is a concept including anti-virus, antibacterial, anti-fungal and anti-fungal. Therefore, the antimicrobial component is a concept including an antiviral component, an antibacterial component, an antifungal component, and an antifungal component, and the antimicrobial agent includes an antiviral agent, an antibacterial agent, an antifungal agent, and an antifungal agent. It is a concept, and the antimicrobial composition is a concept including an antiviral composition, an antibacterial composition, an antifungal composition, and an antifungal composition.

The antimicrobial member obtained by the method for producing an antimicrobial member according to the present specification may be a member exhibiting the activity of any one of antivirus, antibacterial, antifungal and antifungal, and may be an antiviral member. Of the antibacterial, antifungal and antifungal members, the members may exhibit any two types of activity, or may be members exhibiting any three types of activity, and are members exhibiting all four types of activity. You may.
The antimicrobial member obtained by the method for producing an antimicrobial member of the present invention is particularly effective for antivirus and antifungal among the antimicrobial properties of the antimicrobial member, and the antiviral member has the highest activity.

In the method for producing an antimicrobial member of the present invention, the above inequality (2) is expressed when the coverage of the substrate surface with the antimicrobial composition after t (seconds) has elapsed from the start of spray spraying is S (t)%. Adjust the coating rate to meet.

In the method for producing an antimicrobial member of the present invention, the coverage S (t)% of the surface of the substrate with the antimicrobial composition when t (seconds) has elapsed from the start of spray spraying satisfies the above inequality (2). When the coating rate on the surface of the base material is adjusted, the antimicrobial composition containing the antimicrobial component adheres evenly to the surface of the base material, and the binder cured product formed through the fixing step is formed in an uneven shape. That is, a cured binder containing an antimicrobial component is fixedly formed on the surface of the base material, and the cured binder is dispersed in an island shape and fixed to the surface of the base material, or the hardened binder is fixed on the surface of the base material. It can be an antimicrobial member in which a region in which a cured product is formed and a region in which the binder cured product is not formed are provided in a mixed manner.

For this reason, the total surface area of the cured binder containing the antimicrobial component is larger than that when the cured binder is formed on the entire surface of the base material, so that the probability of contact with microorganisms such as viruses is high. In addition, since microorganisms such as viruses can be trapped between the cured binders, high antimicrobial activity can be obtained. In addition, since the antimicrobial component is contained in the cured binder, it has excellent adhesion to the base material and can be prevented from falling off by wiping and cleaning.

When the coverage S (t)% does not satisfy the inequality 0.01t <S (t)%, that is, when S (t) ≤ 0.01t, the antimicrobial composition is attached to the substrate. It is not practical because the squeezing process takes too long. On the contrary, when S (t)% <(33t) ^1/2 is not satisfied, that is, when (33t) ^1/2 ≤ S (t), the antimicrobial composition is excessively sprayed on the surface of the substrate. , Liquid dripping and uneven coating occur, and the design is deteriorated. Further, since the antimicrobial composition is excessively sprayed on the surface of the base material, the cured binder formed through the fixing step may become a film, and an appropriate uneven shape may not be formed.

The above inequality (2) is displayed when converted to one spray nozzle. If the antimicrobial composition is sprayed with a plurality of nozzles, it is desirable to adjust the coating rate so as to satisfy the above inequality (2) in terms of one nozzle.
In the present invention, the coating speed is adjusted so as to satisfy the above inequality, 0.1t <S (t)% <(33t) ^{1/2, not only in terms of coatability but also in consideration of productivity.} Is the best.

Further, in the method for producing an antimicrobial member in the present invention, the coating rate is a value obtained by dividing the amount of the substrate surface coating per unit time by the spray spray area, and the coating treatment is performed using one spray nozzle. It is defined as the antimicrobial composition coating rate in doing so. The coating speed can be adjusted by the discharge flow rate of each spray, the pressure of the spray, the number of times the spray is swept, the sweep speed, and the like.

In the method for fixing an antimicrobial cured product and the method for producing an antimicrobial member of the present invention, it is desirable that the flow rate of the antimicrobial composition sprayed is 0.02 g / sec to 0.1 g / sec. From experience, if the above flow rate exceeds 0.1 g / sec, droplets of the antimicrobial composition adhere to the surface of the substrate in an overlapping manner before drying, resulting in uneven coating, which is not practical. Because. Further, if the flow rate of the antimicrobial composition to be sprayed is less than 0.02 g / sec, the adhesion step of adhering the antimicrobial composition to the substrate takes time, or the liquid of the antimicrobial composition in spray spraying is liquid. It is not practical because the diameter of the enemy becomes large and uneven coating occurs.

Since the antimicrobial composition in the present invention contains an antimicrobial component, an uncured binder, a dispersion medium and a polymerization initiator, the antimicrobial composition is based on the antimicrobial composition by adhering it to the surface of the substrate. It is possible to have a state in which a region in which the cured binder is fixedly formed and a region in which the cured binder is not fixedly formed on the surface of the material are mixed, or a state in which the cured binder is scattered in an island shape. That is, the antimicrobial cured product has excellent transparency to the base material and adhesion to the base material through a fixing step of adhering the antimicrobial composition to the surface of the base material and fixing the cured binder to the surface of the base material. Can be formed in an island shape or in a state where a region in which the hardened binder is fixedly formed and a region in which the hardened binder is not fixedly formed are mixed.

It should be noted that the cured product of the binder is scattered and fixed in an island shape, or the region where the cured product of the binder is fixed and formed on the surface of the base material and the region where the cured product of the binder is not fixed and formed coexist. In this case, the surface area of the cured binder is increased, and microorganisms such as viruses are easily trapped between the cured binders. Therefore, the probability of contact between the cured binder having antimicrobial properties and the microorganisms is increased. Can exhibit high antimicrobial performance.

In the present specification, it is desirable that the binder cured product covers 10% or more and 95% or less of the surface of the base material, and the binder cured product forming region on which the binder cured product is formed and the binder cured product are formed. It is desirable that the non-cured binder region is in a mixed state. That is, the cured binder is fixedly formed on the surface of the base material so as to expose a part of the surface of the base material. The binder cured product may be formed in an island shape, or the binder cured product is formed in a film shape, and a region in which the cured product is not formed is mixed in the region where the film of the binder cured product is formed. It may be in the state of being provided.

In the present specification, the island shape means that the cured binder on the surface of the base material exists in an isolated state in which it does not come into contact with other cured binders. The shape of the hardened binder scattered in an island shape is not particularly limited, and when the contour is viewed in a plan view, it may be a shape composed of curves such as a circle and an ellipse, and a shape such as a polygon. It may be a shape in which a circle, an ellipse, or the like is connected to each other through a thin portion.

Further, since the antimicrobial composition in the present invention contains an antimicrobial component, an uncured binder, a dispersion medium and a polymerization initiator, the antimicrobial composition is formed by adhering the antimicrobial composition to the surface of the substrate. Can be formed into a film on the surface of the base material, has excellent wear resistance, and does not deteriorate its antimicrobial performance even when wiped off during cleaning.
However, when the antimicrobial composition is formed into a film on the surface of the substrate, the visibility of the design on the surface of the substrate, the antimicrobial performance, and the antimicrobial binder cured product after the thermal cycle are applied to the substrate. The adhesiveness is lower than that in the case where the binder is dispersed and fixed in an island shape or in a state where the region where the cured binder is fixedly formed and the region where the cured binder is not fixed and fixed are mixed on the surface of the base material.

In the method for fixing an antimicrobial cured product and the method for producing an antimicrobial member of the present invention, the microbial composition is selected from the group consisting of an inorganic antimicrobial agent and an organic antimicrobial agent as the antimicrobial component. It is desirable to include at least one.

In the method for fixing an antimicrobial cured product and the method for producing an antimicrobial member of the present invention, the microbial composition is selected from the group consisting of an inorganic antimicrobial agent and an organic antimicrobial agent as the antimicrobial component. When at least one is contained, an antimicrobial cured product having a high antimicrobial activity can be surely fixed, and an antimicrobial member having a high antimicrobial activity can be surely produced.

In the method for fixing an anti-microbial cured product and the method for producing an anti-microbial member of the present invention, the inorganic anti-microbial agent is silver, copper, zinc, platinum, zinc compound, silver compound, copper compound, metal or metal oxide. It is desirable that it is at least one selected from the group consisting of a metal oxide catalyst carrying a metal oxide catalyst, a zeolite ion-exchanged with a metal ion, and a copper complex.

In the method for fixing an antimicrobial cured product and the method for producing an antimicrobial member of the present invention, the inorganic antimicrobial agent is silver, copper, zinc, platinum, zinc compound, silver compound, copper compound, metal or metal oxide. The antimicrobial agent can be in the form of particles if it is at least one selected from the group consisting of a metal oxide catalyst carrying a metal oxide catalyst, a zeolite ion-exchanged with a metal ion, and a copper complex. An inorganic antimicrobial agent can be easily exposed from the cured binder, an antimicrobial cured product having higher antimicrobial activity can be fixed, and an antimicrobial member having higher antimicrobial activity can be produced. it can.

In the method for fixing an antimicrobial cured product and the method for producing an antimicrobial member of the present invention, it is desirable to contain a copper compound as an antimicrobial component. The copper compound is calculated by measuring the binding energies corresponding to Cu (I) and Cu (II) in the range of 925 to 955 eV for 5 minutes by X-ray photoelectron spectroscopic analysis. The ratio of the number of ions of Cu (I) and Cu (II) contained therein (Cu (I) / Cu (II)) is preferably 0.4 to 50.

Further, since copper of Cu (I) is superior in antimicrobial performance to copper of Cu (II), the binder cured product of the present invention is in the range of 925 to 955 eV by X-ray photoelectron spectroscopic analysis. The ratio of the number of ions of Cu (I) and Cu (II) contained in the copper compound, which is calculated by measuring the binding energy corresponding to Cu (I) and Cu (II) in the above copper compound for 5 minutes. When (Cu (I) / Cu (II)) is 1.0 to 4.0, it becomes an anti-microbial cured product or an anti-microbial member having more excellent anti-microbial performance.

Note that Cu (I) means that the ionic valence of copper is 1, and may be expressed as ^{Cu +.} On the other hand, Cu (II) means that the ionic valence of copper is 2, and may be expressed as ^{Cu 2+.} Generally, the binding energy of Cu (I) is 932.5 eV ± 0.3 (932.2 to 932.8 eV), and the binding energy of Cu (II) is 933.8 eV ± 0.3 (933). It is .5 to 934.1 eV).

In the method for fixing an antimicrobial cured product and the method for producing an antimicrobial member of the present invention, the organic antimicrobial agent is an antimicrobial resin, a sulfonic acid-based surfactant, a copper alkoxide, and a bis-type quaternary agent. It is desirable that it be at least one selected from the group consisting of ammonium salts.

In the method for fixing an antimicrobial cured product and the method for producing an antimicrobial member of the present invention, the organic antimicrobial agent is an antimicrobial resin, a sulfonic acid-based surfactant, a copper alkoxide, and a bis-type quaternary agent. When it is at least one selected from the group consisting of ammonium salts, the organic antimicrobial agent easily spreads over the entire island-shaped binder cured product, and can fix the antimicrobial cured product having high antimicrobial activity. , And an antimicrobial member having high antimicrobial activity can be produced.

In the method for fixing an antimicrobial cured product and the method for producing an antimicrobial member according to the present invention, the uncured binder is selected from an organic binder, an inorganic binder, a mixture of an organic binder and an inorganic binder, and an organic / inorganic hybrid binder. It is desirable that there is at least one species selected from the group. This is because a binder cured product having excellent coatability and excellent adhesion can be fixedly formed on the surface of the base material.

It is desirable that the organic binder is at least one selected from the group consisting of thermosetting resins and electromagnetic wave curable resins.
This is because in these organic binders, the resin is cured by irradiation with electromagnetic waves or heating, and the antimicrobial component can be fixed to the surface of the base material. In addition, these resins are advantageous because they do not reduce the reducing power of the polymerization initiator. As the thermosetting resin, at least one selected from epoxy resin, melamine resin and phenol resin can be used.
As the electromagnetic wave curable resin, at least one selected from the group consisting of acrylic resin, urethane acrylate resin, polyether resin, polyester resin, epoxy resin, epoxy acrylate resin, and alkyd resin can be used. When the organic binder is these electromagnetic wave curable resins, the antimicrobial cured product fixed by the method for fixing the antimicrobial cured product and the method for producing an antimicrobial member of the present invention has transparency and is based on. It also has excellent adhesion to materials.

The inorganic binder is preferably at least one selected from the group consisting of silica sol, alumina sol, titania sol, zirconia sol, and sodium silicate. Depending on the type of the antimicrobial component, a binder using water as a dispersion medium or a binder using a solvent as a dispersion medium can be used properly, and an island-shaped cured binder in which the antimicrobial component is well dispersed can be formed. it can.

In the anti-microbial composition of the present invention, the uncured binder is an acrylic resin, a urethane acrylate resin, a polyether resin, a polyester resin, an epoxy resin, an alkyd resin, a silica sol, an alumina sol, a zirconia sol, a titania sol, a metal alkoxide, and the like. It is desirable that it be at least one selected from the group consisting of water glass.

The dispersion medium contained in the antimicrobial composition in the present invention is preferably alcohol or water. This is because the antimicrobial component is well dispersed in the dispersion medium, and as a result, a binder cured product in which the antimicrobial component is well dispersed can be formed.

The above-mentioned polymerization initiator contained in the antimicrobial composition in the present invention is preferably a water-insoluble polymerization initiator. This is because it does not elute even when it comes into contact with water, so it becomes a binder cured product with excellent water resistance.

The polymerization initiator contained in the anti-microbial composition in the present invention is at least one selected from the group consisting of alkylphenone type, benzophenone type, acylphosphine oxide type, intramolecular hydrogen abstraction type, and oxime ester type. It is more desirable that it is at least one selected from an alkylphenone-based polymerization initiator, benzophenone or a derivative thereof.
This is because these polymerization initiators have a particularly high reducing power to copper and are excellent in the effect of maintaining the state of copper ions (I) for a long period of time.

Further, the antimicrobial composition in the present invention contains a polymerization initiator, and since this polymerization initiator can generate radicals and ions and reduce the copper compound at that time, the antimicrobial activity of copper can be enhanced. It can be raised. In general, copper (I) has a higher antimicrobial activity than copper (II), and the reduction of copper improves the antimicrobial activity.

The polymerization initiator contained in the antimicrobial composition in the present invention is preferably a photopolymerization initiator. When the photopolymerization initiator is contained, the copper compound is reduced to copper ions (I) having an antimicrobial effect, and the copper ions (I) are oxidized to copper ions (II) having inferior antimicrobial properties. This is because it can suppress.

A copper compound is desirable as the antimicrobial component contained in the antimicrobial composition in the present invention. The copper compound is preferably a copper carboxylate, a copper hydroxide, or a water-soluble inorganic salt of copper, and more preferably a copper carboxylate. This is because when a binder cured product is formed on the surface of the substrate, the copper compound exposed from the surface of the binder cured product in a state where it can come into contact with microorganisms such as viruses can exhibit excellent antimicrobial properties. In addition, carboxylic acid has a COOH group, has excellent affinity with resin, is easily retained by a cured binder, and is more resistant to water than other inorganic salts of copper, copper oxides, and copper hydroxides. Excellent water resistance because it is difficult to elute.

Further, in the antimicrobial composition of the present invention, it is desirable that the copper compound is a divalent copper compound (copper compound (II)). This is because the monovalent compound is insoluble in water, which is a dispersion medium, is localized in the form of particles, is sufficiently dispersed in the binder, and is inferior in antimicrobial activity.
In addition, by adding a divalent copper compound to the antimicrobial composition, the divalent copper compound is reduced, so that the state in which the monovalent and divalent copper compounds coexist in the binder cured product can be easily achieved. It also has the advantage of being able to form.

In the anti-microbial composition of the present invention, the polymerization initiator contains an alkylphenone-based polymerization initiator and a benzophenone-based polymerization initiator, and the concentration of the alkylphenone-based polymerization initiator is 0. It is desirable that the concentration of the benzophenone-based polymerization initiator is 5 to 3.0 wt% and 0.5 to 2.0 wt% with respect to the binder. This is because a high crosslink density can be achieved even if the irradiation time of electromagnetic waves is short.
The ratio of the alkylphenone-based polymerization initiator to the benzophenone-based polymerization initiator is 1/1 to 4/1 by weight ratio of the alkylphenone-based polymerization initiator / benzophenone-based polymerization initiator. Is desirable. This is because a high crosslink density can be realized, the hardness of the cured product can be increased, the wear resistance can be improved, and the reducing power to copper can be increased.

Method of fixing the anti-microbial cured product of the present invention, and method for producing the antimicrobial member, the discharge amount of liquid antimicrobial composition is the spray Spraying is desirably 1g / m ² ~20g / m ² ..

Further, it is desirable that the method for fixing the antimicrobial curable product and the method for producing the antimicrobial member of the present invention include a drying step of drying the electromagnetic wave curable resin in the antimicrobial composition adhered by the coating step. As for the drying conditions, it is desirable to use a lamp of 50 W to 500 W, separate the lamp from the surface of the substrate by 5 cm to 50 cm ^{, convert it per 1 m 2} , and irradiate it with light for 100 to 500 seconds.

Further, in the method for fixing the antimicrobial cured product and the method for producing the antimicrobial member of the present invention, it is desirable that the fixing step includes a curing step for curing the electromagnetic wave curable resin in the antimicrobial composition, and the curing is described above. conditions, as cumulative energy of the electromagnetic ^wave, it is desirable that ^{0.1J / cm 2 ~3.0J / cm 2} .

Further, the method for fixing the cured antimicrobial product of the present invention may include a drying step of drying the antimicrobial composition adhered by the coating step to remove the dispersion medium in the antimicrobial agent.
In this case, the method for fixing the antimicrobial cured product of the present invention is to cure the uncured binder in the antimicrobial composition from which the dispersion medium has been removed at the same time as the drying step or after the drying step. , Including a curing step of fixing the binder cured product to the surface of the base material.

Further, the method for producing an antimicrobial member of the present invention may include a drying step of drying the antimicrobial composition adhered by the coating step to remove the dispersion medium in the antimicrobial member.
In this case, the method for producing an antimicrobial member of the present invention cures the uncured binder in the antimicrobial composition from which the dispersion medium has been removed at the same time as the drying step or after the drying step. It includes a curing step of fixing the cured binder to the surface of the base material.

By including the above-mentioned drying step, the curing reaction of the antimicrobial composition can be allowed to proceed at the same time as the drying step or after the drying step, and a binder cured product containing an antimicrobial component can be formed relatively easily. By exposing a part of the antimicrobial component from the surface of the binder cured product in a state where it can come into contact with the microorganism and bringing it into contact with the microorganism, the antimicrobial cured product having excellent antimicrobial components due to the antimicrobial component is fixed. be able to.
Further, since shrinkage occurs when the binder is cured, the antimicrobial component can be exposed from the binder surface during curing shrinkage.

In the method for fixing an antimicrobial cured product and the method for producing an antimicrobial member in the present invention, drying and heating can be performed with an infrared lamp, a heater, or the like, and electromagnetic waves are irradiated to perform drying and curing at the same time. You may.

In the method for fixing the antimicrobial cured product and the method for producing the antimicrobial member in the present invention, it is desirable to include a step of irradiating an electromagnetic wave having a predetermined wavelength in order to exhibit the reducing power of the polymerization initiator. Ultraviolet rays having high energy are preferably used as electromagnetic waves. When the drying step is included, the electromagnetic wave irradiation step is preferably performed before and after the drying step or before and after the curing step.

Further, it is desirable that the method for fixing the antimicrobial cured product of the present invention is a method for fixing the antiviral cured product.
Further, it is desirable that the method for producing an antimicrobial member of the present invention is a method for producing an antiviral member.

FIG. 1A is a cross-sectional view schematically showing an embodiment of the first antiviral member of the present invention, and FIG. 1B is the antiviral member shown in FIG. 1A. It is a plan view of. FIG. 2 is a graph showing the relationship between the spraying time (time from the start of spraying) of Examples and Comparative Examples and the coverage S (t)% of the substrate surface of the antiviral composition.

(Detailed description of the invention)
Hereinafter, the method for fixing the antimicrobial cured product of the present invention and the method for producing the antimicrobial member will be described in detail for each step.

In the present invention, an antimicrobial composition containing an antimicrobial component, an uncured binder, a dispersion medium and a polymerization initiator is spray-sprayed on the surface of the base material and adhered to the surface of the base material to adhere to the surface of the base material. A coating step of coating the surface with the antimicrobial composition and a fixing of the uncured binder in the antimicrobial composition adhered by the coating step to fix the cured binder to the surface of the base material. In the method for fixing the antimicrobial cured product, which comprises the step, the coverage of the surface of the base material with the antimicrobial composition when t (seconds) elapsed from the start of spray spraying was defined as S (t)%. In this case, the coating speed of the surface of the base material is adjusted so as to satisfy the following inequality (1).
0.01t <S (t)% <(33t) ^1/2 ... (1)

Further, in another aspect, in the present invention, an antimicrobial composition containing an antimicrobial component, an uncured binder, a dispersion medium and a polymerization initiator is spray-sprayed on the surface of the substrate and adhered to the surface of the substrate. At the very least, the coating step of coating the surface of the base material with the antimicrobial composition and the uncured binder in the antimicrobial composition adhered by the coating step are cured, and the binder is applied to the surface of the base material. A method for producing an antimicrobial member, which comprises a fixing step of fixing the cured product, wherein the coverage of the substrate surface with the antimicrobial composition when t (seconds) has elapsed from the start of spray spraying is S ( When t)%, the coating speed of the surface of the base material is adjusted so as to satisfy the following inequality (2).
0.01t <S (t)% <(33t) ^1/2 ... (2)

The method for fixing an antimicrobial cured product of the present invention and the method for producing an antimicrobial member according to another aspect of the present invention include the same coating step and the fixing step. Further, when the coverage of the base material surface with the antimicrobial composition when t (seconds) has passed from the start of spray spraying is S (t)%, the same inequality (the above inequalities (1) and (2)) The same applies to adjusting the coating speed of the surface of the base material so as to satisfy). Therefore, in the following, each step common to the method for fixing the antimicrobial cured product of the present invention and the method for producing the antimicrobial member, which is another aspect of the present invention, will be described.

(1) Coating Step When fixing the antimicrobial cured product of the present invention and when producing the antimicrobial member of the present invention, first, in the coating step, the antimicrobial component and the uncured antimicrobial component are applied to the surface of the substrate. It comprises a coating step of spray-spraying an antimicrobial composition containing a binder, a dispersion medium and a polymerization initiator to adhere to the surface of the substrate and coating the surface of the substrate with the antimicrobial.

The material of the base material used in the method for fixing the antimicrobial cured product of the present invention and the method for producing the antimicrobial member is not particularly limited, and for example, ceramics such as metal and glass, resins, and fiber woven fabrics. Examples include wood.
Further, the base material used in the method for fixing the antimicrobial cured product of the present invention and the method for producing the antimicrobial member is not particularly limited, and is a protective film for a touch panel or a film for a display. It may be an interior material, a wall material, a window glass, a handrail, etc. inside the building. It may also be a doorknob, a toilet slide key, or the like. Further, it may be office equipment, furniture, etc., and may be a decorative board or the like used for various purposes in addition to the above-mentioned interior material.

The decorative board has a substrate and a surface resin layer laminated on the surface of the substrate.
The substrate used for the decorative board is not particularly limited, and a noncombustible board such as core paper or magnesia cement generally used for the decorative board can be used. The core paper may be used alone or as a laminated body in which a plurality of core papers are laminated. The number of core papers is not particularly limited, but may be 1 to 20. As the core paper, for example, aluminum hydroxide paper can be used. The core paper can be impregnated with phenol resin. Further, the core paper and the magnesia cement non-combustible plate can be laminated to form a substrate.

The magnesia cement non-combustible plate can be used alone, or can be laminated on the center of the core paper to form a substrate. The magnesia cement non-combustible plate is manufactured by mixing magnesium oxide (MgO) and magnesium chloride (MgCl ₂ ), further adding aggregate and water, kneading, and forming into a plate shape. As the aggregate, inorganic fibers such as rock wool and glass wool and organic fibers such as wood chips and pulp can be used. Further, in order to increase the strength of the magnesia cement non-combustible plate, a glass fiber layer formed in a mesh shape or the like can be provided as an intermediate layer.

The resins that can be used for the surface resin layer constituting the decorative board include melamine resin, diallyl phthalate (DAP) resin, polyester resin, olefin resin, vinyl chloride resin, acrylic resin, epoxy resin, urethane resin, and phenol. Examples thereof include resins, silicone resins, fluororesins, and guanamine resins. Among these, it is desirable to use a melamine resin.

The melamine resin is a resin having improved dimensional stability and toughness without impairing optical and visual characteristics such as translucency. As the melamine resin, any known resin can be adopted as long as it is a resin using melamine and its derivative as a monomer. Further, the melamine resin may be a resin composed of a single monomer or a copolymer composed of a plurality of monomers. Examples of the melamine derivative include derivatives having a functional group such as an alkoxymethyl group such as an imino group, a methylol group, a methoxymethyl group and a butoxymethyl group. Further, a compound obtained by reacting a melamine derivative having a methylol group with a lower alcohol to partially or completely etherify it can be used as a monomer. Derivatives having a methylol group such as monomethylol melamine, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, and hexamethylol melamine (hereinafter referred to as "methylol melamine") are copolymerized with melamine as a cross-linking agent. A melamine resin can be used.

The surface resin layer may be a decorative layer in which a printing paper on which a pattern or a color is printed is impregnated with a resin, and an overlay that becomes translucent when the amount of the filler is 15% or less and the resin is impregnated. An overlay layer in which paper is impregnated with resin may be used. When the surface resin layer is an overlay layer, the decorative layer is provided below the overlay layer.
The filler is an inorganic particle (filler) for adjusting whiteness and smoothness by adding it to paper, and at least one selected from calcium carbonate, talc, clay and kaolin is desirable. Since the filler is inorganic particles, the content of the filler can be calculated from the weight of the paper and the weight of the ash remaining after the paper is heated strongly.

In the method for fixing an antimicrobial cured product and the method for producing an antimicrobial member of the present invention, the antimicrobial component contains at least one selected from the group consisting of an inorganic antimicrobial agent and an organic antimicrobial agent. It is desirable to be.
The binder cured product may contain only one type of the above-mentioned inorganic antimicrobial agent, or may contain two or more types of the above-mentioned inorganic antimicrobial agent, and the above-mentioned organic antimicrobial agent. May be contained in only one kind, or two or more kinds of organic antimicrobial agents may be contained. Further, the binder cured product may contain two or more kinds of the inorganic antimicrobial agent and the organic antimicrobial agent.

Further, in the present invention, the above-mentioned inorganic antimicrobial agent is ion-exchanged with silver, copper, zinc, platinum, zinc compound, silver compound, copper compound, metal oxide catalyst carrying metal or metal oxide, and metal ion. It is desirable that it is at least one selected from the group consisting of the obtained zeolite and the copper complex.

Examples of the inorganic antimicrobial agent contained in the cured binder include a metal composed of at least one of silver, copper, zinc and platinum.
The cured binder may contain silver, copper, zinc and platinum particles alone, and may contain two or more kinds of metal particles among silver, copper, zinc and platinum. For example, metal particles of an alloy containing at least two of silver, copper, zinc and platinum may be fixed.

Examples of the inorganic antimicrobial agent contained in the cured binder include copper compounds such as copper oxide, copper hydroxide, copper carboxylate, copper complex, and water-soluble inorganic salt of copper. And so on. In particular, a divalent copper compound (copper compound (II)) is desirable. This is because the divalent copper compound dissolves in water, which is a dispersion medium, so that copper ions can be easily uniformly dispersed in the binder. On the other hand, the monovalent copper compound does not dissolve in water and is suspended in the form of particles, resulting in poor uniformity.
In addition, by adding a divalent copper compound to the antimicrobial composition, the divalent copper compound is reduced, so that the state in which the monovalent and divalent copper compounds coexist in the binder cured product can be easily achieved. It also has the advantage of being able to form.
Examples of the copper carboxylate include copper (II) acetate, copper (I) acetate, copper (I) oxalate, copper (II) benzoate, copper (II) phthalate, and the like. Valuable copper carboxylates are preferred.
Examples of the copper complex include a complex of acetylacetone and copper, a complex of β-diketone such as 5-methyl-2,4-hexanedione and copper, copper (I) (1-butanethiolate), and copper ( I) (Hexafluoropentandionate cyclooctadiene) and the like can be mentioned.
Examples of the water-soluble inorganic salt of copper include copper (II) nitrate and copper (II) sulfate. As the other copper compound, a divalent copper compound is desirable, and examples thereof include copper (II) (methoxide), copper (II) ethoxydo, copper (II) propoxide, copper (II) butoxide and the like. It is desirable to add the copper compound (II) to the uncured binder and reduce the copper compound to monovalent with a polymerization initiator. Other examples of the covalent bond compound of copper include the same oxide and a hydroxide of copper.

In the method for fixing an antimicrobial cured product and the method for producing an antimicrobial member of the present invention, it is desirable to use a copper compound as the antimicrobial component, and it is more desirable to use a copper carboxylic acid salt. This is because when the binder cured product is formed on the surface of the base material, the copper compound exposed from the surface of the binder cured product in a state where it can come into contact with microorganisms can exhibit excellent antimicrobial properties. In addition, carboxylic acid has a COOH group, has excellent affinity with resin, is easily retained by a cured binder, and elutes with water compared to other inorganic salts of copper, copper oxides, and copper hydroxides. Excellent water resistance because it is difficult to do.

As a metal oxide catalyst in which the metal or metal oxide contained in the antimicrobial composition is supported, for example, platinum, palladium, rhodium, ruthenium or other platinum group, silver, copper or the like is supported on titanium oxide or the like. Examples include those that have been made to do so. Specific examples of the metal oxide catalyst carrying a metal or metal oxide include a platinum-supported titania catalyst, a copper-supported titania catalyst, a silver-supported titania catalyst, a platinum-supported nitrogen-doped titania catalyst, and a platinum-supported sulfur-doped titania catalyst. , Carbon-doped titanium dioxide catalyst, copper-supported titanium oxide catalyst, silver-supported titanium oxide catalyst, and other visible light-responsive photocatalysts. Examples of the copper-supported titania catalyst include CuO described in JP-A-2006-232729. Anatase-type titanium oxide containing copper in the range of / TiO ₂ (% by weight) = 1.0 to 3.5, and cuprous oxide (copper (I) oxide (I): Cu) described in JP2012-210557A. _A photocatalyst composition in which 2O) and titanium oxide are composited, titanium oxide having a surface containing a mixture containing a monovalent copper compound and a divalent copper compound described in JP2013-166705, and international publication. Examples thereof include copper and titanium-containing compositions containing titanium oxide containing crystalline rutyl-type titanium oxide and a divalent copper compound described in No. 2013/094573.

Further, as the inorganic antimicrobial agent, particles of a metal oxide or a metal hydrate containing at least one metal selected from silver, copper, zinc, titanium, tungsten and the like can also be used. Specific examples of the inorganic antimicrobial agent include copper (I) oxide (copper oxide), copper (II) oxide, copper (II) carbonate, copper (II) hydroxide, copper (II) chloride, and silver. At least one of the exchanged zeolite, nanosilver and copper of at least one of the ions and copper ions, alumina in which at least one of the nanosilver and copper was supported, silica in which at least one of the nanosilver and copper was supported, nanosilver and copper were supported. Examples thereof include inorganic particles such as titanium oxide in which at least one of zinc oxide, nanosilver and copper is supported, or calcium phosphate in which at least one of tungsten oxide, nanosilver and copper is supported. The zeolite exchanged at least one of the silver ion and the copper ion may be further exchanged with another metal ion such as zinc ion. Further, the inorganic antimicrobial agent used in the present invention is preferably a copper complex.

The organic antimicrobial agent used in the method for fixing an antimicrobial cured product and the method for producing an antimicrobial member according to the present invention is an antimicrobial resin, a sulfonic acid-based surfactant, a copper alkoxide, and a screw type. It is desirable that it be at least one selected from the group consisting of quaternary ammonium salts.

Examples of the organic antimicrobial agent include halocarban, chlorophenesine, lysozyme chloride, alkyldiaminoethylglycine hydrochloride, isopropylmethylphenol, timol, hexachlorophen, velverin, thioxolone, salicylic acid and derivatives thereof, benzoic acid and benzoic acid. Sodium acid, paraoxybenzoic acid ester, parachlormethacresol, benzalkonium chloride, phenoxyethanol, isopropylmethylphenol, coalic acid, sorbic acid, potassium sorbate, hexachlorophene, chlorhexidine chloride, trichlorocarbanilide, thiantolu, hinokithiol, triclosan, Trichlorohydroxydiphenyl ether, chlorhexidine phenolate, phenoxyethanol, resorcin, azulene, salicylic acid, zincpyrythion, mononitroguayacol sodium, uikyo extract, sansho extract, cetylpyridinium chloride, benzethonium chloride and undecylenic acid derivatives, alkylbenzene sulfonic acid or salts thereof, etc. Can be mentioned. Of these, alkylbenzene sulfonic acid or a salt thereof is preferable.

The antimicrobial resin comprises an acidic functional group and a resin. Examples of the acidic functional group include a sulfonic acid group, a phosphoric acid group, a carboxyl group, a hydroxyl group, a nitro group and the like. Of these, a sulfonic acid group, a phosphoric acid group, and a carboxyl group are preferable.

The resin is preferably a polymer of a monomer having a vinyl group.
Since the polymer of the monomer having a vinyl group is synthesized by addition polymerization, there is no by-product such as water, and a highly transparent antimicrobial resin can be obtained. Therefore, the influence on the design of the base material can be reduced.

The monomer having a vinyl group is preferably one or more monomers selected from styrene, methacrylic acid, methacrylic acid ester, divinylbenzene, and trivinylbenzene.
Styrene, methacrylic acid, methacrylic acid ester, divinylbenzene, and trivinylbenzene can provide an antimicrobial resin having particularly high transparency. Further, divinylbenzene and trivinylbenzene can be crosslinked by adding them to a monomer to form a three-dimensional network structure. By forming a three-dimensional network structure, it becomes difficult to disassemble and durability can be increased.

In the method for fixing the antimicrobial cured product and the method for producing the antimicrobial member of the present invention, the antimicrobial resin composed of an acidic functional group and a resin is not particularly limited, but for example, a cation exchange resin can be used. It can be used as it is or after being pulverized to make it finer. The cation exchange resin also has an acidic functional group in the resin, and can be used as the antimicrobial resin of the present invention.

Examples of the bis-type quaternary ammonium salt include a bis-type pyridinium salt represented by the following general formula (1), a bis-type quinolinium salt, a bis-type thiazolium salt, and a compound represented by the following general formula (2). Is desirable.

（上記一般式（１）中、Ｒ^１及びＲ^２は、同一または異なっていてもよいアルキル基、Ｒ^３はエーテル結合を含んでもよい有機基であり、Ｘ−は、ハロゲン陰イオンを示す。）

(In the above general formula (1), R ¹ and R ² are alkyl groups which may be the same or different, R ³ is an organic group which may contain an ether bond, and X- represents a halogen anion. )

（上記一般式（２）中、Ｒ^４は、官能基を有してもよいアルキル基を表し、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は、アルキル基を表す。）

(In the above general formula (2), R ⁴ represents an alkyl group which may have a functional group, and R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represent an alkyl group. )

First, the bis-type pyridinium salt represented by the general formula (1) will be described.
In the bis-type pyridinium salt represented by the general formula (1), examples of X- include Cl-, Br-, I- and the like.
R ¹ and R ² are preferably alkyl groups having 1 to 20 carbon atoms, and the alkyl groups may have a side chain.
In the above general formula (1), the ^{organic group represented by R 3} is -CO-O- (CH ₂ ) _6- O-CO-, -CONH- (CH ₂ ) _6- CO-, -NH-CO. -(CH ₂ ) _4- CO-NH-, -S-Ph-S-, -CONH-Ph-NHCO-, -NHCO-Ph-CONH-, _{-O- (CH 2} ) _6- O- or -CH _{It is desirable that it is represented by 2-} O- (CH ₂ ) _4- O-CH _2- (where Ph represents a phenylene group).

上記一般式（３）中、Ｒ^１１は、Ｃ_ｎＨ_２ｎ＋１で表されるアルキル基であり、ｎは、８、１０、１２、１４、１６または１８が望ましい。また、ｍは、３、４、６、８、１０が望ましい。以下に示す化合物の置換基Ｒ^１１についても、同様である。 Specifically, examples of the bis-type pyridinium salt include those represented by the following general formulas (3) to (10).

In the above general formula (3), R ¹¹ is _{an alkyl group represented by C n} H _{2n + 1} , and n is preferably 8, 10, 12, 14, 16 or 18. Further, m is preferably 3, 4, 6, 8 and 10. Substituents R ¹¹ of the compound shown below is also the same.

Further, as the bis-type pyridinium salt, 1,1'-didecyl-3,3'-[butane-1,4-diylbis (oxymethylene)] dipyridinium = dibromid represented by the following general formula (11). Is particularly desirable.

Next, the bis-type thiazolium salt will be described.
Further, examples of the bis-type thiazolium salt include bis-type thiazolium salts represented by the following general formula (12).

Next, the bis-type quinolinium salt will be described.
As the bis-type quinolinium salt, a pyridinium group represented by the following general formula (13) constituting the bis-type pyridinium salt represented by the general formulas (3) to (10) is used in the general formula (14). Examples thereof include a bis-type quinolinium salt having a chemical structure substituted with the quinolium group shown in. In the above bis-type quinolinium salt, other substituents and the like are the same as those of the bis-type pyridinium salt represented by the general formulas (3) to (10).

上記一般式（２）中、Ｒ^４は、官能基を有してもよいアルキル基を示す。アルキル基は、側鎖を有してもよく、その炭素数は、１〜２０が望ましい。上記官能基としては、ヒドロキシル基、アルデヒド基、カルボキシル基、シアノ基、ニトロ基、アミノ基、エーテル基等が挙げられる。また、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は、アルキル基を表し、上記アルキル基は、側鎖を有してもよく、その炭素数は、１〜２０が望ましい。 Further, the compound represented by the general formula (2) used in the present invention will be described.

In the above general formula (2), R ⁴ represents an alkyl group which may have a functional group. The alkyl group may have a side chain, and the number of carbon atoms thereof is preferably 1 to 20. Examples of the functional group include a hydroxyl group, an aldehyde group, a carboxyl group, a cyano group, a nitro group, an amino group and an ether group. Further, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represent an alkyl group, and the above alkyl group may have a side chain, and the number of carbon atoms thereof is preferably 1 to 20. ..

Examples of the compound represented by the general formula (2) include 2,3-bis (hexadecyldimethylammonium bromide) -1-propanol and the like.

In the method for fixing an anti-microbial cured product and the method for producing an anti-microbial member of the present invention, the uncured binder is selected from at least an organic binder, an inorganic binder, an organic / inorganic hybrid binder, and an electromagnetically curable resin binder. It is desirable that it is one kind. This is because the cured binder, which has excellent adhesion, can be relatively easily fixed to the surface of the base material. An organometallic compound can be used as the binder of the organic / inorganic hybrid.

In the method for fixing an antimicrobial cured product and the method for producing an antimicrobial member of the present invention, at least one selected from the group consisting of an inorganic antimicrobial agent and an organic antimicrobial agent is used as the antimicrobial component. A mixture of an uncured binder, an organic binder, an inorganic binder, an organic / inorganic hybrid binder, and at least one of an electromagnetically curable resin can be used, and a cured binder is obtained by curing the mixture. be able to.

It is desirable that the organic binder is at least one selected from the group consisting of thermosetting resins and electromagnetic wave curable resins. This is because in these organic binders, the resin is cured by irradiation with electromagnetic waves or heating, and the copper compound can be fixed to the surface of the base material. Further, these resins are advantageous because the polymerization initiator does not reduce the reducing power for antimicrobial components such as copper compounds.
As the electromagnetic wave curable resin, at least one selected from the group consisting of acrylic resin, urethane acrylate resin, epoxy acrylate resin, polyether resin, polyester resin, epoxy resin, and alkyd resin can be used. Further, as the thermosetting resin, at least one selected from the group consisting of epoxy resin, melamine resin, and phenol resin can be used.

Examples of the acrylic resin include epoxy-modified acrylate resin, urethane acrylate resin (urethane-modified acrylate resin), and silicone-modified acrylate resin.
Examples of the polyester resin include polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).

Examples of the epoxy resin include an alicyclic epoxy resin and a glycidyl ether type epoxy resin in which an oxetane resin is combined.
Examples of the alkyd resin include polyester alkyd resin and the like.
These resins have transparency and are also excellent in adhesion to a base material.

Next, an inorganic binder that can be used in the method for fixing the antimicrobial cured product of the present invention and the method for producing the antimicrobial member will be described.
A step of spraying an antimicrobial composition, which is a mixture of an inorganic binder, an antimicrobial component, and if necessary, various additives and dispersion media, and adhering the substrate surface to the substrate surface, and then coating the substrate surface with the antimicrobial composition. After that, a binder cured product (cured product of an inorganic binder) containing an antimicrobial component is formed by undergoing a drying step.

In the above coating step, when the antimicrobial composition is isolated and adheres to the surface of the substrate, the cured binder becomes island-like, and when the antimicrobial composition is superimposed on the surface of the substrate and adheres, the cured binder becomes a film. The formed binder cured product has a form in which a region in which the cured binder is formed and a non-formed region in which the cured binder is not formed are mixed. This also applies to the electromagnetic wave curable resin described above.

The inorganic binder is preferably at least one selected from the group consisting of silica sol, alumina sol, titania sol, zirconia sol and sodium silicate. The content ratio of the inorganic oxide such as silica in the inorganic binder is preferably 2 to 80% by weight in terms of solid content.
Since there are two types of the above-mentioned inorganic binders, one using water and the other using an organic solvent as the dispersion medium, the inorganic binder can be selected in consideration of the type of the antimicrobial component to be added, and the antimicrobial component can be selected. The above-mentioned antimicrobial composition in which is uniformly dispersed can be obtained.

In the method for fixing an anti-microbial cured product and the method for producing an anti-microbial member of the present invention, the binder is an acrylic resin, a urethane acrylate resin, a polyether resin, a polyester resin, an epoxy resin, an alkyd resin, a silica sol, an alumina sol, or a zirconia. It is desirable that it be at least one selected from the group consisting of sol, titania sol, metal alkoxide, and water glass.

Next, the electromagnetic wave curable resin used as the uncured binder in the method for fixing the antimicrobial cured product of the present invention and the method for producing the antimicrobial member of the present invention will be described.
An anti-microbial composition containing a monomer or oligomer which is an uncured electromagnetically curable resin, a polymerization initiator, various additives, and an anti-microbial component is spray-sprayed and adhered to the surface of the base material to resist the surface of the base material. After coating with the microbial composition, the polymerization initiator undergoes reactions such as cleavage reaction, hydrogen abstraction reaction, and electron transfer by irradiating with electromagnetic waves, and the resulting photoradical molecule, photocation molecule, and photoanion molecule are generated. Etc. attack the above-mentioned monomer and the above-mentioned oligomer, and the polymerization reaction and the cross-linking reaction of the monomer and the oligomer proceed, and a binder cured product containing an anti-microbial component is formed. The resin constituting the binder cured product produced by such a reaction is called an electromagnetic wave curable resin.

In the method for fixing the antimicrobial cured product and the method for producing the antimicrobial member of the present invention, the type of the dispersion medium is not particularly limited, but alcohol or water is used when stability is taken into consideration. It is desirable to do. Examples of alcohols include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and sec-butyl alcohol in consideration of lowering the viscosity. Among these alcohols, methyl alcohol and ethyl alcohol, which do not easily increase in viscosity, are preferable, and a mixture of alcohol and water is preferable.
In the method for fixing the cured antimicrobial product and the method for producing the antimicrobial member of the present invention, it is desirable that the viscosity is 1 to 200 mPa · s at 25 ° C. This is because if it is too low, it will not be applied to the surface of the substrate, and if it is too high, it cannot be sprayed.
As a method for measuring the viscosity, the viscosity can be measured at 25 ° C. using a rotary viscometer. The rotation speed of the blade of the rotary viscometer is 62.5 rpm. As the device, RION VT-04F is recommended.

In the method for fixing the antimicrobial cured product and the method for producing the antimicrobial member in the present invention, it is desirable to use a water-insoluble polymerization initiator as the polymerization initiator. This is because it does not elute even when it comes into contact with water, so that the cured binder does not deteriorate and the antimicrobial component is not desorbed. Even if the antimicrobial component is water-soluble, if it is retained by the binder cured product, desorption can be suppressed, but if the binder cured product contains a water-soluble substance, the antimicrobial component of the binder cured product can be suppressed. It is presumed that the holding power is reduced and the antimicrobial component is eliminated.
The water-insoluble polymerization initiator is preferably a photopolymerization initiator. This is because when the electromagnetic wave curable resin is used, the polymerization reaction can be easily promoted by light such as visible light and ultraviolet rays.

In the method for fixing the antimicrobial cured product and the method for producing the antimicrobial member in the present invention, it is desirable to use a photopolymerization initiator having a reducing power. When the antimicrobial component contained in the antimicrobial composition in the present invention is a copper compound, it is reduced to copper ion (I) having an antimicrobial effect such as an antiviral effect, and the copper ion (I) is oxidized. This is because it is possible to suppress the conversion to copper ion (II), which is inferior to the antimicrobial agent. The antimicrobial composition used in the present invention acts most effectively against viruses and molds when a copper compound is used as an antimicrobial component. By the reducing power of copper (I), copper ions (I) reduce water and oxygen in the air to generate active oxygen, hydrogen peroxide solution, superoxide anion, hydroxyl radical, etc. to generate viruses or mold. This is because it effectively destroys the constituent proteins.

In the method for fixing an antimicrobial cured product and the method for producing an antimicrobial member in the present invention, the polymerization initiator is an alkylphenone type, a benzophenone type, an acylphosphine oxide type, an intramolecular hydrogen abstraction type, and an oxime ester type. It is desirable that it be at least one selected from the group consisting of.

Examples of the alkylphenone-based polymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one and 1-hydroxy-cyclohexyl-phenyl-ketone (as the polymerization initiator of Examples 1 to 4). Equivalent), 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1- On, 2-Hirodoxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-methyl-1- (4-) Methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-4-) Methylphenyl) Methyl] -1- [4- (4-morphonyl) phenyl] -1-butanone and the like can be mentioned.

Examples of the acylphosphine oxide-based polymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like.

Examples of the intramolecular hydrogen abstraction type polymerization initiator include phenylglycilic acid methyl ester, oxyphenyl succinate, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester tooxyphenylacetic acid and 2- (2). Examples thereof include a mixture with −hydroxyethoxy) ethyl ester.

Examples of the oxime ester-based polymerization initiator include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6-. (2-Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime) and the like can be mentioned.

In the method for fixing an antimicrobial cured product and the method for producing an antimicrobial member in the present invention, the polymerization initiator contains at least one selected from an alkylphenone-based polymerization initiator, a benzophenone or a derivative thereof. Is desirable. This is because the reducing power is exhibited by electromagnetic waves such as ultraviolet rays. Among the above photopolymerization initiators, benzophenone or a derivative thereof is particularly preferable.

In the method for fixing the antimicrobial cured product and the method for producing the antimicrobial member in the present invention, it is desirable that the polymerization initiator contains an alkylphenone-based polymerization initiator and a benzophenone-based polymerization initiator. Further, the concentration of the alkylphenone-based polymerization initiator is 0.5 to 3.0 wt% with respect to the binder, and the concentration of the benzophenone-based polymerization initiator is 0.5 to 2.0 wt% with respect to the binder. It is desirable to have. This is because a high crosslink density can be achieved even if the irradiation time of electromagnetic waves is short.
The ratio of the alkylphenone-based polymerization initiator to the benzophenone-based polymerization initiator is preferably 1/1 to 4/1 by weight ratio of the alkylphenone-based polymerization initiator / benzophenone-based polymerization initiator. This is because a high crosslink density can be realized, the hardness of the cured product can be increased to improve wear resistance, and the reducing power to antimicrobial components such as copper compounds can be increased.

In the present invention, the polymerization initiator can be used as a reducing agent for antimicrobial components. Since the polymerization initiator can generate radicals and ions and reduce the antimicrobial component at that time, the antimicrobial activity of the antimicrobial component in the obtained antimicrobial substrate can be enhanced. In particular, when the antimicrobial component is a copper compound, copper (I) generally has higher antimicrobial activity than copper (II), and the reduction of copper improves the antimicrobial activity.

The polymerization initiator is preferably a photopolymerization initiator. Copper (II) can be reduced to copper (I) with a polymerization initiator.
Since copper (I) has higher antimicrobial performance than copper (II), the antimicrobial performance of the antimicrobial composition can be enhanced by the polymerization initiator.
Further, the polymerization initiator may be added not only to the electromagnetic wave curable resin but also to the antimicrobial composition composed of an inorganic binder, a copper compound and a dispersion medium.

Further, when an electromagnetic wave curable resin (monomer or oligomer) is used as the uncured binder in the antimicrobial composition in the method for fixing the antimicrobial cured product of the present invention and the method for producing the antimicrobial member, the above antimicrobial agent is used. The content ratio of the antimicrobial component in the microbial composition is preferably 2.0 to 30.0% by weight, and the content ratio of the uncured electromagnetically curable resin (monomer or oligomer) is preferably 15 to 40% by weight. The content ratio of the dispersion medium is preferably 30 to 80% by weight. It is desirable to use a copper compound as the antimicrobial component.
When an inorganic binder is used as the uncured binder, the content ratio of the antimicrobial component in the antimicrobial composition is preferably 2 to 30% by weight, and the content ratio of the dispersion medium is 30 to 80% by weight. % Is desirable. In this case, the content ratio of the inorganic oxide such as silica in the antimicrobial composition is 5 to 20% by weight. Further, it is desirable to use a copper compound as the antimicrobial component.

The antimicrobial composition in the present invention contains, if necessary, a pH adjuster, an ultraviolet absorber, an antioxidant, a light stabilizer, an adhesion accelerator, a rheology adjuster, a leveling agent, an antifoaming agent and the like. May be.

When preparing the antimicrobial composition of the present invention, after adding the antimicrobial component, the binder component and the polymerization initiator to the dispersion medium, the composition is sufficiently stirred with a mixer or the like to disperse at a uniform concentration. After that, it is desirable to spray and spray it to adhere to the surface of the substrate.

In the method for fixing the cured antimicrobial product of the present invention, the following inequality is used when the coverage of the surface of the base material with the antimicrobial composition when t (seconds) has passed from the start of spray spraying is S (t)%. The coating speed of the substrate surface is adjusted so as to satisfy (1).
0.01t <S (t)% <(33t) ^1/2 ... (1)

Further, in the method for producing an antimicrobial member of the present invention, when t (seconds) elapses from the start of spray spraying and the coverage of the substrate surface with the antimicrobial composition is S (t)%, the following The coating speed of the substrate surface is adjusted so as to satisfy the inequality (2).
0.01t <S (t)% <(33t) ^1/2 ... (2)

In the method for fixing the antimicrobial cured product and the method for producing the antimicrobial member of the present invention, the coverage S (t)% by the antimicrobial composition on the surface of the base material when t (seconds) elapses from the start of spray spraying. When the coating speed of the base material surface is adjusted so as to satisfy the above inequality (1) or (2), the antimicrobial composition containing the antimicrobial component adheres evenly to the base material surface and is formed through the above fixing step. The binder cured product to be formed is formed in an uneven shape. That is, a cured binder containing an antimicrobial component is fixedly formed on the surface of the base material, and the cured binder is dispersed in an island shape and fixed to the surface of the base material, or the hardened binder is fixed on the surface of the base material. The region in which the cured product is formed and the region in which the binder cured product is not formed are mixed and provided.

For this reason, the total surface area of the cured binder containing the antimicrobial component is larger than that when the cured binder is formed on the entire surface of the base material, so that the probability of contact with microorganisms such as viruses is high. In addition, since microorganisms such as viruses can be trapped between the cured binders, high antimicrobial activity can be obtained. In addition, since the antimicrobial component is contained in the cured binder, it has excellent adhesion to the base material and can be prevented from falling off by wiping and cleaning.

If the coverage S (t)% does not satisfy the inequality 0.01t <S (t)%, that is, if S (t) ≤ 0.01t, the coating rate is too low and the antimicrobial agent The bonding step of adhering the composition to the substrate takes too much time and is not practical. On the contrary, when S (t)% <(33t) ^1/2 is not satisfied, that is, when (33t) ^1/2 ≤ S (t), the coating speed is too high and the antimicrobial agent against the surface of the substrate is used. Excessive spraying of the composition causes liquid dripping and uneven coating, resulting in deterioration of design. Further, since the antimicrobial composition is excessively sprayed on the surface of the base material, the cured binder formed through the fixing step may become a film, and an appropriate uneven shape may not be formed.

The above inequalities (1) and (2) are displayed when converted to one spray nozzle. If the antimicrobial composition is sprayed with a plurality of nozzles, it is desirable to adjust the coating rate so as to satisfy the above inequalities (1) and (2) in terms of one nozzle.
In the present invention, the coating speed is adjusted so as to satisfy the above inequality, 0.1t <S (t)% <(33t) ^{1/2, not only in terms of coatability but also in consideration of productivity.} Is the best.

In the present invention, "spraying the antimicrobial composition onto the surface of the base material" means that the antimicrobial composition is dispersed on the surface of the base material in an island shape in a divided state, or the base material is used. The antimicrobial composition is such that a region in which the antimicrobial composition is attached to the surface and a region in which the antimicrobial composition is not adhered are mixed, that is, a state in which a part of the surface of the base material is exposed. It may be in either a state in which an object is attached or the antimicrobial composition is attached to the surface of the base material in a film form.

As the spray spraying method used in the method for fixing the antimicrobial cured product of the present invention and the method for producing the antimicrobial member, for example, a spray method, a two-fluid spray method, an electrostatic spray method and the like can be used.

In the spray method, the antimicrobial composition is sprayed in a mist state using a gas such as high-pressure air or mechanical movement (finger, piezo element, etc.), and droplets of the antimicrobial composition are sprayed on the surface of the substrate. It means to attach.
The two-fluid spray method is a kind of spray method. After mixing a gas such as high-pressure air and an antimicrobial composition, the antimicrobial composition is sprayed from a nozzle in a mist state on the surface of the base material. It means to attach the droplets of.
The electrostatic spray method is a spraying method using a charged antimicrobial composition. The antimicrobial composition is sprayed in a mist state by the above spray method, but the antimicrobial composition is atomized. There are two methods for this purpose: a gun type in which the antimicrobial composition is sprayed with a sprayer, and an electrostatic atomization method using the repulsion of the charged antimicrobial composition. Further, the gun type has a charged antimicrobial composition. There are a method of spraying an object and a method of applying a charge to the sprayed atomized antimicrobial composition by corona discharge from an external electrode. Since the mist-like droplets are charged, they easily adhere to the surface of the base material, and the antimicrobial composition can be satisfactorily adhered to the surface of the base material in a finely divided state.

In the method for fixing the antimicrobial cured product and the method for producing the antimicrobial member of the present invention, the spray pressure is preferably 0.05 to 5 MPa and the spray width is preferably 1 cm to 15 cm as the spraying conditions. The spray pitch is preferably 1 to 10 cm, and the distance from the spray nozzle to the surface of the substrate is preferably 5 to 30 cm. The discharge flow rate of the antimicrobial composition per spray is preferably 0.02 to 0.1 g / sec.
Further, in the method for fixing the antimicrobial cured product and the method for producing the antimicrobial member of the present invention, the amount of the discharged liquid of the antimicrobial composition sprayed is 1 g / m ^{2 from the viewpoint of cost and productivity.} It is desirable that it is ~ 20 g / m ^2. The amount of discharged liquid is a value obtained by dividing the total amount of the antimicrobial composition used for the adhesion coating of the antimicrobial composition by the coating area.

In the method for fixing the antimicrobial cured product and the method for producing the antimicrobial member of the present invention, the viscosity of the antimicrobial composition can be appropriately set within a range that can be sprayed, and is, for example, 1 to 200 mPa · s. It is desirable to do. If it is too low, it will not be applied to the surface of the substrate, and if it is too high, it cannot be sprayed. The viscosity is measured at 25 ° C. with a rotary viscometer. The rotation speed of the blade of the rotary viscometer is 62.5 rpm. RION VT-04F is recommended as the measuring device.

By such a coating step, the antimicrobial composition containing the copper compound, the uncured binder, the dispersion medium, and the polymerization initiator is scattered on the surface of the base material in an island shape in a divided state, or the surface of the base material. The region to which the antimicrobial composition is attached and the region to which the antimicrobial composition is not attached are mixed. Of course, the antimicrobial composition may be formed in a film shape on the surface of the base material.

(2) Drying Step In the method for fixing the antimicrobial cured product and the method for producing the antimicrobial member of the present invention, the antimicrobial component sprayed by the coating step, the uncured binder, the dispersion medium and the polymerization initiator are used. It may include a step of drying the containing antimicrobial composition. In the drying step, the dispersion medium in the antimicrobial composition is evaporated and removed, and a binder cured product containing an antimicrobial component such as a copper compound is temporarily fixed to the surface of the substrate, and the shrinkage of the binder cured product causes the copper compound and the like The antimicrobial component can be exposed from the surface of the cured binder. The drying conditions are preferably 20 to 100 ° C. and 0.5 to 5.0 minutes. Drying can be performed with an infrared lamp, a heater, or the like. Alternatively, it may be dried under reduced pressure (vacuum).
It is desirable from the viewpoint of cost and productivity that the drying is carried out using a lamp of 50 W to 500 W, separated from the surface of the base material by 5 cm to 50 cm ^{, converted per 1 m 2 and irradiated for 100 to 500 seconds.} ..

In the method for fixing the antimicrobial cured product and the method for producing the antimicrobial member of the present invention, the drying step and the following fixing step may be performed after the drying step is completed, and the drying step and the fixing step may be performed at the same time. You may go.

(3) Fixing Step In the method for fixing an antimicrobial cured product and the method for producing an antimicrobial member according to the present invention, as a curing step, the antimicrobial composition from which the dispersion medium has been removed in the drying step or the coating thereof. This includes a fixing step of curing the uncured binder in the antimicrobial composition containing the dispersion medium after the step to fix the cured binder to the surface of the substrate.

Methods for curing the uncured binder include removal of the dispersion medium by drying, promotion of polymerization of monomers and oligomers by heating and irradiation with electromagnetic waves. Examples of the drying include vacuum drying and heat drying. When the binder is a thermosetting resin, curing proceeds by heating. Heating can be performed with a heater, an infrared lamp, an ultraviolet lamp, or the like. The electromagnetic wave emitted when the uncured binder is an electromagnetic wave curable resin is not particularly limited, and examples thereof include ultraviolet rays (UV), infrared rays, visible rays, microwaves, and electron beams (EB). However, among these, ultraviolet rays (UV) are desirable.
By these steps, the uncured binder can be fixed to the surface of the base material.
Curing conditions of the electromagnetic wave curable resin, the cumulative energy of the electromagnetic ^wave, it is desirable that ^{0.1J / cm 2 ~3.0J / cm 2} . This is because if the integrated energy is too low, it will not cure, and if it is too high, the substrate may be damaged.

Further, the electromagnetic wave has a function of exciting a photopolymerization initiator and reducing a copper compound. Therefore, copper (II) can be reduced to increase the amount of copper (I) to increase the antimicrobial activity.
In the method for fixing an antimicrobial cured product and the method for producing an antimicrobial member of the present invention, Cu (in the range of 925 to 955 eV) is used as an antimicrobial component contained in the antimicrobial composition by X-ray photoelectron spectroscopy. The ratio of the number of ions of Cu (I) and Cu (II) contained in the copper compound, which is calculated by measuring the binding energy corresponding to I) and Cu (II) for 5 minutes (Cu (I). ) / Cu (II)) is preferably contained so as to be 0.4 to 50.
Since the copper of Cu (I) is superior in antimicrobial properties to the copper of Cu (II), in the first antimicrobial member of the present invention, 925 to 955 eV by X-ray photoelectron spectroscopic analysis was performed. The number of ions of Cu (I) and Cu (II) contained in the copper compound calculated by measuring the binding energy corresponding to Cu (I) and Cu (II) in the range for 5 minutes. When the ratio (Cu (I) / Cu (II)) is 1.0 to 4.0, an anti-microbial cured product having more excellent anti-microbial properties can be fixed, and an anti-microbial member having more excellent anti-microbial properties can be adhered. Can be manufactured. This is because the coexistence of Cu (I) and Cu (II) has higher antimicrobial activity as compared with the case where Cu (I) and Cu (II) are present alone.

In the method for fixing the antimicrobial cured product and the method for producing the antimicrobial member of the present invention, the maximum width of the binder cured product obtained in the fixing step in the direction parallel to the substrate surface is 0.1 to 500 μm. The average value of the thickness is preferably 0.1 to 20 μm.

In the method for fixing the antimicrobial cured product and the method for producing the antimicrobial member of the present invention, when the average value of the thickness of the binder cured product obtained in the fixing step is 0.1 to 20 μm, the thickness of the binder cured product is Since the thickness is thin, it is difficult to form a continuous layer of the binder cured product, and the binder cured product is scattered in an island shape, or the binder cured product is formed in a film shape and cured in the region where the film of the binder cured product is formed. It becomes easy to make the region where an object is not formed mixedly provided, and it is possible to prevent the appearance and aesthetic appearance of the design and the like from being impaired, and it is possible to obtain high antimicrobial activity.

In the method for fixing an antimicrobial cured product and the method for producing an antimicrobial member of the present invention, it is a technique to form a binder cured product in which the average thickness of the binder cured product obtained in the fixing step is less than 0.1 μm. This is difficult, and the coverage of the surface of the cured binder is also low, resulting in a decrease in antimicrobial activity. On the other hand, if the average thickness of the cured binder exceeds 20 μm, the cured binder is too thick. Therefore, if a design or the like having a predetermined pattern is formed on the surface of the base material, the cured binder interferes with the design or the like. Is difficult to see, and there is a risk that the appearance and aesthetics of the design will be impaired.

Further, in the method for fixing the antimicrobial cured product and the method for producing the antimicrobial member of the present invention, the maximum width of the binder cured product obtained in the fixing step in the direction parallel to the surface of the substrate is set to 0.1 to 500 μm. By doing so, the proportion of the portion where the surface of the base material is not covered with the cured binder can be appropriately maintained, and even when a design or the like having a predetermined pattern is formed on the surface of the base material, the appearance and appearance of the design or the like can be maintained. Can be prevented from being damaged.

In the method for fixing an antimicrobial cured product and the method for producing an antimicrobial member of the present invention, a binder cured product having a maximum width of less than 0.1 μm in a direction parallel to the surface of the substrate obtained in the fixing step. It is technically difficult to form the binder, and the coverage of the surface of the cured binder is also low, resulting in a decrease in antimicrobial activity. On the other hand, if the maximum width of the cured binder product in the direction parallel to the surface of the base material exceeds 500 μm, the size of one cured binder product becomes too large, and a design or the like having a predetermined pattern is formed on the surface of the base material. If this is the case, the cured binder obstructs the design and the like, making it difficult to see the design and the like, and the appearance and appearance of the design and the like are impaired.

The maximum width in the direction parallel to the surface of the substrate of the cured binder and the average value of the thickness can be measured by using a scanning microscope or a laser microscope.
Specifically, by using a scanning microscope or a laser microscope equipped with image analysis / image measurement software, or by using an image analysis / image measurement software to analyze an image obtained by the scanning microscope or a laser microscope. By performing the above, the maximum width in the direction parallel to the surface of the substrate of the cured binder and the average value of the thickness can be obtained.

In the method for fixing an antimicrobial cured product and the method for producing an antimicrobial member of the present invention, the arithmetic mean roughness (Ra) of the surface of the substrate containing the binder cured product obtained in the fixing step according to JIS B 0601 is determined. It is preferably 0.1 to 5 μm.
The arithmetic mean roughness (Ra) can be obtained by measuring with a measurement length of 8 mm using HANDYSURF, which is a contact type surface roughness measuring machine manufactured by Tokyo Seimitsu Co., Ltd.

In the method for fixing the antimicrobial cured product and the method for producing the antimicrobial member of the present invention, the arithmetic average roughness (Ra) of the surface of the base material containing the binder cured product obtained in the fixing step according to JIS B 0601 is determined. When it is 0.1 to 5 μm, the surface area of the substrate surface containing the cured binder is in an appropriate range, the probability of contact between microorganisms such as viruses and antimicrobial components is high, and the valleys of surface irregularities are formed. Microorganisms such as viruses are easily trapped, and as a result, microorganisms such as viruses are easily inactivated.

In the method for fixing the antimicrobial cured product of the present invention and the method for producing the antimicrobial member, when the binder cured product obtained in the fixing step is scattered on the surface of the base material in an island shape, the island-shaped binder curing is performed. It is desirable that there are ^{0.05 × 10 8} to 30 × 10 ⁸ objects per square meter of the substrate surface.

In the method for fixing the antimicrobial cured product and the method for producing the antimicrobial member of the present invention, when the binder cured product obtained in the fixing step is scattered on the surface of the base material in an island shape, the island-shaped binder curing is performed. ^{If there are 0.05 × 10 8} to 30 × 10 ⁸ objects per square meter of the surface of the substrate, the size of the cured binder is set appropriately, and the design formed on the surface of the substrate, etc. It is possible to prevent the appearance and aesthetics of the product from being spoiled, and it becomes an antimicrobial member having high antimicrobial activity per unit carrying amount.

According to the method for fixing the antimicrobial cured product of the present invention and the method for producing the antimicrobial member, for example, a knob, a slide key, a handle, a handle, a handrail, etc., which are frequently contacted by human hands, can be attached to the surface. The antimicrobial function can be added without changing the formed pattern, color, design, color tone and the like. In addition, patterns, colors, and designs formed on the surface of interior materials, wall materials, windowpanes, doors, kitchen utensils, office equipment, furniture, etc., and decorative boards used for various purposes inside buildings. , Anti-microbial function can be added without changing the color tone and the like.

(Examples 1 to 3)
(1) Dissolve cupric acetate (II) monohydrate powder (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in pure water so that the concentration of copper acetate is 1.75 wt%, and then use a magnetic stirrer. A copper acetate aqueous solution was prepared by stirring at 600 rpm for 15 minutes. The ultraviolet curable resin solution is a photoradical polymerization type acrylate resin (UCECOAT7200 manufactured by Daicel Ornex), a photopolymerization initiator (Omnirad 500 manufactured by IGM), and a photopolymerization initiator (Omnirad 184 manufactured by IGM) in a weight ratio of 97: 2: 1. The mixture was prepared by stirring at 8000 rpm for 30 minutes using a homogenizer.
The 1.75 wt% copper acetate aqueous solution and the ultraviolet curable resin solution were mixed at a weight ratio of 1.9: 1.0 and stirred at 600 rpm for 2 minutes using a magnetic stirrer to prepare an antimicrobial composition. The Omnirad 500 manufactured by IGM is the same as the IRGACURE 500 manufactured by BASF, and is a mixture of 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone in a weight ratio of 1: 1. This photopolymerization initiator is insoluble in water and exhibits reducing power by ultraviolet rays. The photopolymerization initiator (Omnirad 184 manufactured by IGM) is 1-hydroxy-cyclohexyl-phenyl-ketone (alkylphenone), and the photopolymerization initiator includes an alkylphenone-based polymerizer and a benzophenone-based polymerizer by weight. It is a mixture containing a ratio of 2: 1.

(2) The above anti-microbial composition was filled in a paint cup of an Anest Iwata spray gun (LPH-50), spray pressure: 0.1 MPa, coating pitch interval: 4 cm, and 1 m square (1 m square) of the base material from the spray nozzle. The coating distance to the surface of the black glossy melamine substrate of 1 m ^{2) was set to be 20 cm.} Under the above conditions, a 1 m square (1 m ² ) black glossy melamine substrate was applied, and the pattern aperture was adjusted so that the coating width was 8 cm.
The amount of liquid ejected is 0.02 g / sec, 0.05 g / sec, and 0.10 g / sec, and 1 m ² of black glossy melamine substrate is applied twice, four times, and six times. Coating was performed under various spray conditions to obtain a black glossy melamine substrate coated with the antiviral composition according to Examples 1 to 3.
In addition, since a total of two spray sprays, one spray spray in the vertical direction and one spray spray in the horizontal direction, are included in one set, the above two coats are spray sprayed once in the vertical direction and once in the horizontal direction. One set, the above four coats, two sets of spray spraying once in the vertical direction and once in the horizontal direction, and the above six coats, three sets of spray spraying once in the vertical direction and once in the horizontal direction. Means.
The spray sweep rate in Examples 1 to 3 and Comparative Example 1 can be read from FIG. 2 showing the relationship between the coating time and the coverage in Examples 1 to 3 and Comparative Example 1. The dots in each liquid discharge amount in the graph of FIG. 2 indicate the spray time (seconds) required for the spray spraying 1 set, 2 sets, and 3 sets, and the coverage rate (%) at that time. Therefore, for example, when the liquid ejection amount is 0.02 g / sec, it takes 210 seconds from the end of the first set to the end of the second set (430 seconds-210 seconds) = 220 seconds. It can be confirmed from the graph that it takes (590 seconds-430 seconds) = 160 seconds from the end of the second set to the end of the third set. As mentioned above, 1m square (1m ² ) per set is sprayed twice, once in the vertical direction and once in the horizontal direction, so if the first set takes 210 seconds, 2 x 1m ² / It means that the spray was performed at a sweep rate of 210 seconds = 0.0095 m ^{2 / sec.} Similarly, the sweep speed of the second set is 0.0091 m ² / sec, and the sweep speed of the third set is 0.0125 m ² / sec.
Under the above conditions, ^{a mist-like antiviral composition was sprayed on a 1 m 2} black glossy melamine substrate, and droplets of the antiviral composition were coated on the surface of the black glossy melamine substrate in an island shape.

(3) Next, a 1000 W halogen lamp was placed 20 cm away from the black glossy melamine decorative plate on the black melamine decorative plate to which the antimicrobial composition was attached, and irradiated for 3 to 5 seconds per ^{150 cm 2 to dry (1 m 2).} Per, 200-330 seconds irradiation).
(4) The obtained sample was further irradiated with ultraviolet rays for 80 seconds at an irradiation intensity of ^{30 mW / cm 2} using an ultraviolet irradiation device (MP02 manufactured by COATTEC) (2.4 ^{J / cm 2 as an integrated energy amount).} ), An antimicrobial member was obtained in which a cured binder containing a copper compound was fixedly formed on the surface of a black glossy melamine decorative plate as a base material so that a part of the surface was exposed. This was used as an evaluation sample for each example.
From the black glossy melamine substrate coated with the antimicrobial composition according to Examples 1 to 3, 25 5 cm square samples were cut out at equal intervals (the center distance interval between adjacent 5 cm square samples was 20 cm). , The coverage was measured.

(Comparative Example 1)
^{In the same manner as in Examples 1 to 3, 1 m 2} of black glossy melamine decorative substrate was applied twice, four times, and six times, except that the liquid ejection amount was changed to 1.30 g / sec. The coating was performed under the conditions to obtain a black glossy melamine substrate coated with the antimicrobial composition according to Comparative Example 1.
Under the above conditions, the coating speed when the liquid ejection amount was 1.30 g / sec was 0.03 g / s · m ² . The relationship between the coating time and the coverage in Comparative Example 1 in this case was as follows.
(Time (seconds) / coverage (%)) = (100/70), (200/89), (280/97).

FIG. 2 shows the relationship between the coating time and the coverage in Examples 1 to 3 and Comparative Example 1.

(Measurement of coverage of antimicrobial composition at time t (seconds))
The surface of one evaluation sample was observed with an optical microscope (Keyence microscope VHX-5000) at a magnification of 200, and the image was binarized to obtain a binder cured product on the surface of the substrate per 241291 ^{μm 2 (1552 μm □).} Measure the area of and calculate the surface coverage. The surface coverage was calculated equally for all the remaining 24 samples, and the average value of the 25 evaluation samples was taken as the average coverage. Discharge flow rate: 0.02 g / sec, 0.05 g / sec, 0.10 g / sec, average coating at the time of applying 2 times, 4 times, 6 times each with 3 types of discharge flow rate The rate was measured and the graph of FIG. 2 was created.

(Anti-virus evaluation using bacteriophage)
In order to evaluate the antiviral property of the samples obtained in Examples 1 to 3 and Comparative Example 1, JIS Z 2801 antibacterial processed product-antibacterial test method-a method in which the antibacterial effect was modified was used. The modification is that "inoculation of test bacterial solution" was changed to "inoculation of test virus". All changes due to the use of virus were changed based on the anti-virus test method for JIS L 1922 textile products. The measurement results are based on JIS L 1922 Annex B for the antimicrobial members obtained in Examples and Comparative Examples, and the concentration of phage virus that has lost the ability to infect Escherichia coli is displayed as virus inactivity. Here, the concentration of the virus inactivated against Escherichia coli (virus inactivity) was used as an index of the virus concentration, and the antiviral activity value was calculated based on this virus inactivity.
The procedure will be described in detail below.
(1) With respect to the antimicrobial members obtained in Examples and Comparative Examples, the antimicrobial members were cut into squares having a side of 50 mm square and used as test samples. This test sample was placed in a sterilized plastic petri dish and inoculated with 0.4 mL of test virus solution (> 107 PFU / mL). The test virus solution used was a stock of 108 PFU / mL diluted 10-fold with purified water.
(2) A 50 mm square polyethylene film was prepared as a control sample, and the virus solution was inoculated in the same manner as the test sample.
(3) A 40 mm square polyethylene was covered over the inoculated virus solution, the test virus solution was evenly inoculated, and then the reaction was carried out at 25 ° C. for a predetermined time.
(4) Immediately after inoculation or after the reaction, 10 mL of SCDLP medium was added to wash away the virus solution.
(5) The virus infection value was determined by JIS L 1922 Annex B.
(6) The anti-virus activity value was calculated using the following formula.
Mv = Log (Vb / Vc)
Mv: Antiviral activity value Log (Vb): Logistic value of infection value after reaction of polyethylene film for a predetermined time Log (Vc): Logistic value reference standard of infection value after reaction for a predetermined time of test sample JIS L 1922, JIS Z 2801
The measuring method was a plaque measuring method.
The anti-virus activity values of Examples 2 and 3 were all 5.0. The anti-virus activity value of Example 1 was 4.8. Further, the antiviral activity value of Comparative Example 1 was 4.4.

(Evaluation of antibacterial properties using Staphylococcus aureus)
Antibacterial evaluation using Staphylococcus aureus was carried out as follows.
(1) The functional member (decorative plate) obtained in Example 1 and Comparative Example was cut into a square of 50 mm square, and a test sample was placed in a sterilized plastic petri dish. Inoculate 0.4 mL of ⁵ to 10 x 10 ^{5 / mL).}
For the test bacterial solution, the cultured bacteria pre-cultured in the incubator at a temperature of 35 ± 1 ° C. for 16 to 24 hours are further transplanted to the slope medium and pre-cultured in the incubator at a temperature of 35 ± 1 ° C. for 16 to 20 hours. The one that has been appropriately adjusted with 1/500 NB medium is used.
(2) Prepare a 50 mm square polyethylene film as a control material, and inoculate the test bacterial solution in the same manner as the test sample.
(3) Cover the inoculated test bacterial solution with a 40 mm square polyethylene film, inoculate the test bacterial solution evenly, and then react at a temperature of 35 ± 1 ° C. for 24 ± 1 hour.
(4) Immediately after inoculation or after the reaction, add 10 mL of SCDLP medium and wash out the test bacterial solution.
(5) The wash-out solution is appropriately diluted, mixed with a standard agar medium to prepare a petri dish for measuring the viable cell count, cultured at a temperature of 35 ± 1 ° C. for 40 to 48 hours, and then the number of colonies is measured.
(6) Calculation of viable cell count The viable cell count is calculated using the following formula.
N = C × D × V
N: Number of viable bacteria C: Number of colonies D: Dilution ratio V: Liquid volume (mL) of SCDLP medium used for washing out
(7) Calculate the antibacterial activity value using the following formula.
R = (Ut-U0)-(At-U0) = Ut-At
R: Antibacterial activity value U0: Average logarithmic number of viable cells immediately after inoculation of the unprocessed test piece Ut: Average logarithmic number of viable cells 24 hours after inoculation of the unprocessed test piece At: Antibacterial processed test piece Average value of logarithmic counts of viable bacteria after 24 hours Reference standard JIS Z 2801
Staphylococcus aureus NBRC12732 was used as the test bacterium.
The antibacterial activity values of Examples 1 to 3 and Comparative Example 1 were both> 3.7.

(Evaluation of antifungal properties using Aspergillus niger)
The antifungal property evaluation using Aspergillus niger was carried out as follows.
(1) The functional members obtained in Examples and Comparative Examples were cut into 50 mm squares, and a test sample was placed in a sterilized plastic petri dish, and a spore suspension (spore concentration> 2x10 ⁵ pieces / ml) was added to 0. Inoculate 4 mL.
(2) Prepare a 50 mm square polyethylene film as a control sample, and inoculate the spore suspension in the same manner as the test sample.
(3) Cover the inoculated spore suspension with a 40 mm square polyethylene film, inoculate the spore suspension evenly, and then react for 42 hours while irradiating with light of about 900 LUX at a temperature of 26 ° C.
(4) Immediately after inoculation or after the reaction, the amount of ATP is measured according to the measurement of JIS L 1921 13 luminescence amount.
(5) Calculate the antifungal activity value using the following formula.
A _a = (LogC _t- LogC ₀ )-(LogT _t- LogT ₀ )
A _a : Antifungal activity value LogC ₀ : Arithmetic mean of ATP amount of 3 control samples immediately after inoculation LogC _t : Arithmetic mean of ATP of 3 control samples after culture LogT ₀ : Arithmetic mean of ATP of 3 test samples immediately after inoculation LogT _t : Arithmetic mean of ATP of 3 test samples after culture

Reference standards JIS Z 2801, JIS L 1921
Aspergillus niger NBRC105649 was used as the test mold.
The antifungal activity values of Examples 2 and 3 were 3.1, and the antifungal activity value of Example 1 was 2.9. The antifungal activity value of Comparative Example 1 was 2.8.

The antiviral activity values of the samples prepared in Examples (1 to 3) are 4.8 to 5.0, the antibacterial activity values are 3.7 or more, and the antifungal activity values are 2.9 to 5.0. Good results were obtained with 3.1. In addition, no uneven coating was observed. On the other hand, the sample produced in Comparative Example 1 has an antiviral activity value of 4.4, an antibacterial activity value of 3.7 or more, and an antifungal activity value of 2.8, which are not practically problematic, but have antiviral and antifungal activity. Was slightly lower than in Examples 1 to 3, and there was uneven coating, dripping was observed, and the appearance was deteriorated.

10 Anti-virus member 11 Base material 12 Resin cured product (cured product of electromagnetic wave curable resin)

Claims (28)

An antimicrobial composition containing an antimicrobial component, an uncured binder, a dispersion medium and a polymerization initiator is spray-sprayed on the surface of the base material to adhere it to the surface of the base material, and the surface of the base material is attached to the surface of the base material. The coating process of coating with the composition and
A method for fixing an antimicrobial cured product, which comprises a fixing step of curing the uncured binder in the antimicrobial composition attached by the coating step to fix the cured binder to the surface of the substrate. ,
When the coverage of the surface of the base material with the antimicrobial composition when t (seconds) has passed from the start of spraying is S (t)%, the base material is satisfied so as to satisfy the following inequality (1). A method for fixing an antimicrobial cured product, which comprises adjusting the coating rate of the surface.
0.01t <S (t)% <(33t) ^1/2 ... (1) The method for fixing an antimicrobial cured product according to claim 1, wherein the flow rate of the antimicrobial composition sprayed is 0.02 g / sec to 0.1 g / sec. The fixation of the antimicrobial cured product according to claim 1 or 2, wherein the antimicrobial composition contains at least one selected from the group consisting of an inorganic antimicrobial agent and an organic antimicrobial agent as the antimicrobial component. Method. The inorganic antimicrobial agent includes silver, copper, zinc, platinum, zinc compounds, silver compounds, copper compounds, metal oxide catalysts carrying metals or metal oxides, zeolite ion-exchanged with metal ions, and The method for fixing an antimicrobial cured product according to claim 3, which is at least one selected from the group consisting of copper complexes. The third aspect of claim 3, wherein the organic antimicrobial agent is at least one selected from the group consisting of an antimicrobial resin, a sulfonic acid-based surfactant, a copper alkoxide, and a bis-type quaternary ammonium salt. Method of fixing antimicrobial cured product. The antimicrobial cured product according to any one of claims 1 to 5, wherein the uncured binder contains at least one selected from the group consisting of an organic binder, an inorganic binder, and an organic / inorganic hybrid binder. Fixing method. The method for fixing an antimicrobial curable product according to claim 6, wherein the organic binder is at least one selected from the group consisting of a thermosetting resin and an electromagnetic wave curable resin. The method according to claim 7, wherein the electromagnetic wave curable resin is at least one selected from the group consisting of an acrylic resin, a urethane acrylate resin, a polyether resin, a polyester resin, an epoxy resin, an epoxy acrylate resin, and an alkyd resin. A method for fixing an anti-microbial cured product. The method for fixing an antimicrobial cured product according to claim 6, wherein the inorganic binder is at least one selected from the group consisting of silica sol, alumina sol, titania sol, zirconia sol, and sodium silicate. The polymerization initiator contains an alkylphenone-based polymerization initiator and a benzophenone-based polymerization initiator, and the ratio of the alkylphenone-based polymerization initiator to the benzophenone-based polymerization initiator is a weight ratio of the alkylphenone-based polymerization initiator. / The method for fixing an anti-microbial cured product according to any one of claims 1 to 9, wherein the benzophenone-based polymerization initiator = 1/1 to 4/1. Discharge fluid amount of the antimicrobial composition is the spray spraying, fixing method of the antimicrobial cured product according to any one of claims 1 to 10 is ^{1g / m 2 ~20g / m 2} . The drying condition includes a drying step of drying the electromagnetic wave curable resin in the antimicrobial composition adhered by the coating step, and the drying conditions are 5 cm to 50 cm from the surface of the base material using a lamp of 50 W to 500 W. The method for fixing an antimicrobial cured product according to claim 7 or 8, wherein the antimicrobial cured product is separated and ^{irradiated with light for 100 to 500 seconds in terms of 1 m 2.} The fixing step may include a curing step of curing the electromagnetic wave curable resin in the antimicrobial composition, wherein the curing conditions, as cumulative energy of the electromagnetic ^wave, is 0.1J / cm ² ~3.0J / cm 2 The method for fixing an antimicrobial cured product according to claim 7, 8 or 12. The method for fixing an antimicrobial cured product according to any one of claims 1 to 13, which is a method for fixing an antiviral cured product. An antimicrobial composition containing an antimicrobial component, an uncured binder, a dispersion medium and a polymerization initiator is spray-sprayed on the surface of the base material to adhere it to the surface of the base material, and the surface of the base material is attached to the surface of the base material. The coating process of coating with the composition and
A method for producing an antimicrobial member, which comprises a fixing step of curing the uncured binder in the antimicrobial composition attached by the coating step to fix the cured binder to the surface of the base material.
When the coverage of the surface of the base material with the antimicrobial composition when t (seconds) has passed from the start of spraying is S (t)%, the base material is satisfied so as to satisfy the following inequality (2). A method for producing an antimicrobial member, which comprises adjusting the coating rate of a surface.
0.01t <S (t)% <(33t) ^1/2 ... (2) The method for producing an antimicrobial member according to claim 15, wherein the flow rate of the antimicrobial composition sprayed is 0.02 g / sec to 0.1 g / sec. The method for producing an antimicrobial member according to claim 15 or 16, wherein the antimicrobial composition contains at least one selected from the group consisting of an inorganic antimicrobial agent and an organic antimicrobial agent as the antimicrobial component. .. The inorganic antimicrobial agent includes silver, copper, zinc, platinum, zinc compounds, silver compounds, copper compounds, metal oxide catalysts carrying metals or metal oxides, zeolite ion-exchanged with metal ions, and The method for producing an antimicrobial member according to claim 17, which is at least one selected from the group consisting of copper complexes. The 17th claim, wherein the organic antimicrobial agent is at least one selected from the group consisting of an antimicrobial resin, a sulfonic acid-based surfactant, a copper alkoxide, and a bis-type quaternary ammonium salt. A method for producing an antimicrobial member. The production of the antimicrobial member according to any one of claims 15 to 19, wherein the uncured binder contains at least one selected from the group consisting of an organic binder, an inorganic binder, and an organic / inorganic hybrid binder. Method. The method for producing an antimicrobial member according to claim 20, wherein the organic binder is at least one selected from the group consisting of a thermosetting resin and an electromagnetic wave curable resin. The 21st claim, wherein the electromagnetic wave curable resin is at least one selected from the group consisting of an acrylic resin, a urethane acrylate resin, a polyether resin, a polyester resin, an epoxy resin, an epoxy acrylate resin, and an alkyd resin. A method for producing an anti-microbial member. The method for producing an antimicrobial member according to claim 20, wherein the inorganic binder is at least one selected from the group consisting of silica sol, alumina sol, titania sol, zirconia sol, and sodium silicate. The polymerization initiator contains an alkylphenone-based polymerization initiator and a benzophenone-based polymerization initiator, and the ratio of the alkylphenone-based polymerization initiator to the benzophenone-based polymerization initiator is a weight ratio of the alkylphenone-based polymerization initiator. / The method for producing an anti-microbial member according to any one of claims 15 to 23, wherein the benzophenone-based polymerization initiator = 1/1 to 4/1. Discharge fluid amount of the antimicrobial composition is the spray spraying ^method antimicrobial member according to any one of claims 15 to 24 is ^{1g / m 2 ~20g / m 2} . The drying step includes a drying step of drying the electromagnetic wave curable resin in the antimicrobial composition adhered by the coating step, and the drying conditions are such that a lamp of 50 W to 500 W is used and the lamp is placed 5 cm to 50 cm from the surface of the base material. The method for producing an antimicrobial member according to claim 21 or 22, wherein the antimicrobial members are separated from each other and ^{irradiated with light for 100 to 500 seconds in terms of 1 m 2.} The fixing step may include a curing step of curing the electromagnetic wave curable resin in the antimicrobial composition, wherein the curing conditions, as cumulative energy of the electromagnetic ^wave, is 0.1J / cm ² ~3.0J / cm 2 The method for producing an antimicrobial member according to claim 21, 22 or 26. The method for producing an antimicrobial member according to any one of claims 15 to 27, which is a method for producing an antiviral member.

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