JP2022057868A - Antiviral substrate - Google Patents

Abstract

To provide an antiviral substrate having high antiviral activity.SOLUTION: An antiviral substrate is provided with an antiviral layer composed of an organic binder-cured product containing an antiviral agent, and no photocatalyst in a region requiring antiviral properties of a substrate surface, where the antiviral layer is constituted so that a first region and a second region are mixed, the first region contains the antiviral agent more than the second region, and concerning a surface roughness of a surface of the antiviral layer, the arithmetic average roughness (Ra) measured in accordance with JIS B 0601-1982 is 0.1 μm or less.SELECTED DRAWING: None

Description

The present invention relates to an antiviral substrate.

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 influenza. Deaths from viral infections have also been reported.

Therefore, antiviral agents that exert antiviral effects against various viruses are being actively developed. Actually, it is possible to apply a metal such as Pd having an antiviral effect, a resin containing an antiviral agent composed of an organic compound, or the like to various members, or to manufacture a member containing a material carrying an antiviral agent. It is done.

Patent Document 1 describes an antibacterial transparent film containing a plastic base material and a curable resin layer laminated on at least one surface of the plastic base material, wherein the curable resin layer provides an antibacterial agent. The antibacterial agent has an average particle size of 0.5 to 100 nm, and the arithmetic average roughness (Ra) measured according to JIS B0601-1982 on the surface of the curable resin layer is less than 0.1 μm. , Antibacterial transparent film is disclosed.

Japanese Patent No. 5804206

However, the antibacterial transparent film described in Patent Document 1 has a problem of insufficient antiviral activity.

The present invention has been made in view of such problems, and an object of the present invention is to provide an antiviral substrate having high antiviral activity.

The antiviral substrate according to the present invention for solving the above problems is as follows.
(1) An antiviral substrate provided with an antiviral layer made of an organic binder cured product containing an antiviral agent and not a photocatalyst in a region of the surface of the substrate where antiviral properties are required.
The antiviral layer is a mixture of a first region and a second region.
The first region contains more antiviral agent than the second region.
The surface roughness of the surface of the anti-virus layer is an anti-virus substrate having an arithmetic mean roughness (Ra) of 0.1 μm or less measured in accordance with JIS B 0601-1982.

According to the present invention, it is possible to provide an antiviral substrate having high antiviral activity.

Further, the antiviral substrate according to the present invention preferably has the following aspects (2) to (10).

(2) The antiviral agent is a copper compound.

This makes it possible to provide an antiviral substrate having higher antiviral performance.

(3) The antiviral agent is an organic compound that is incompatible with an organic binder.

Thereby, the antiviral component can be exposed on the surface of the substrate, and an antiviral substrate having higher antiviral activity can be provided.

(4) The antiviral agent is at least one of a polymer biguanide and a bis-type quaternary ammonium salt.

Since both the polymer biguanide and the bis-type quaternary ammonium salt have high antiviral performance, it is possible to provide an antiviral substrate having higher antiviral activity.

(5) The first region is composed of a complex of an organic binder and a copper compound.

This makes it possible to provide an antiviral substrate having higher antiviral performance.

(6) The antiviral layer is formed on the base material in the form of a film.

The present invention can provide an antiviral substrate having high antiviral activity even if the antiviral layer is membranous and the surface roughness is small.

(7) A hard coat layer is provided on the surface of the base material, and an antiviral layer is provided on the hard coat layer.

This makes it possible to provide a highly durable antiviral substrate.

(8) Copper is present in the first region in an amount of 0.6 atomic% or more.

This makes it possible to provide an antiviral substrate having higher antiviral performance.

(9) An adhesive layer is provided on the opposite side surface of the surface of the base material on which the antiviral layer is provided.

This makes it possible to attach the antiviral substrate to members such as smartphones, electronic device displays, walls and doorknobs.

(10) The base material is translucent.

As a result, when the base material is a film or a sheet, it can be used as a protective film for a smartphone or an electronic device display, or when the base material is in a plate state such as an acrylic plate, it can be used as a tsuitate to prevent splashes.

According to the present invention, it is possible to provide an antiviral substrate having high antiviral activity.

FIG. 1 is a cross-sectional view schematically showing an embodiment of an antiviral substrate in the present invention. FIG. 2 is an electron micrograph (reflected electron image) of the antiviral substrate obtained in Example 1. FIG. 3A shows the anti-virus substrate obtained in Example 1 with respect to the first region (the region appearing white indicated by the white arrow in FIG. 3B) in which the content of the copper compound is relatively high. The results of elemental analysis using an energy dispersive X-ray fluorescence analyzer are shown. FIG. 3B is an electron micrograph (reflected electron image) of the anti-virus substrate obtained in Example 1, and the white arrow indicates the place where the elemental analysis was performed. FIG. 3C is a chart showing the results of elemental analysis of the anti-virus substrate obtained in Example 1 with respect to the first region by an energy dispersive fluorescent X-ray analyzer. FIG. 4A shows the anti-virus substrate obtained in Example 1 with respect to the second region (the region appearing black indicated by the white arrow in FIG. 4A) in which the content of the copper compound is relatively low. The results of elemental analysis using an energy dispersive fluorescent X-ray analyzer are shown. FIG. 4B is an electron micrograph (reflected electron image) of the anti-virus substrate obtained in Example 1, and the white arrow indicates the place where the elemental analysis was performed. FIG. 4 (c) is a chart showing the results of elemental analysis of the anti-virus substrate obtained in Example 1 with respect to the second region by an energy dispersive fluorescent X-ray analyzer. FIG. 5 is a schematic diagram of the antiviral substrate of Example 4.

Hereinafter, embodiments for carrying out the present invention will be described.
As shown in FIG. 1, the antiviral substrate 10 is provided with an antiviral layer 12 on the surface of the substrate 11.

The anti-virus substrate of the embodiment of the present invention is provided with an anti-virus layer made of an organic binder cured product containing an anti-virus agent and not a photocatalyst in a region of the surface of the substrate where anti-virus property is required. In the virus substrate, the antiviral layer is a mixture of a first region and a second region, and the first region contains more antiviral agent than the second region and is a surface of the antiviral layer. The surface roughness is characterized in that the arithmetic average roughness (Ra) measured according to JIS B 0601-1982 is 0.1 μm or less.
The region on the surface of the base material that is required to have antiviral properties may be the entire surface of the base material or may be a part of the surface of the base material.

In the present embodiment, the antiviral layer is made of an organic binder cured product containing an antiviral agent and not containing a photocatalyst. The cured organic binder is obtained by curing an antiviral composition (organic binder composition) containing an antiviral agent and an uncured organic binder. The antiviral layer is formed on the surface of the substrate where antiviral properties are required.

The antiviral layer is a mixture of a first region and a second region. Here, "mixed" or "mixed" means that the first region and the second region are not partially localized or unevenly distributed in the antiviral layer, but are scattered or dispersed substantially uniformly. By doing so, it means that the first region and the second region are mixed and exist.

The first region and the second region in the antiviral layer are distinguished by the content of the antiviral agent, and the first region has a higher content of the antiviral agent than the second region. That is, it can be said that the first region is a "region in which the content of the antiviral agent is relatively high" and the second region is a "region in which the content of the antiviral agent is relatively low". Further, the second region may adopt a form containing no antiviral agent at all. Of course, the second region is provided in the antiviral layer, and the region in which the antiviral layer itself does not exist is not the second region.

The antiviral layer in the present embodiment does not contain a uniformly dispersed particulate antiviral agent, but a first region composed of a complex of an organic binder and an antiviral agent, and a content of the antiviral agent. The antiviral activity can be enhanced by the state in which the second region, which is relatively less than the first region, is mixed.

In the antiviral layer of the present embodiment, the antiviral agent is mixed with an organic binder. As the antiviral agent to be mixed with the organic binder, an aqueous solution or a liquid can be used in the state before the organic binder is cured. As a result, the antiviral agent can be complexed with the organic binder at the ionic or molecular level, and as a result, the antiviral performance for inactivating the virus can be enhanced. This is because the first region having a relatively high content of the antiviral agent is exposed from the organic binder layer without being covered with the skin layer on the surface of the organic binder layer, so that the exposed first region is This is because it becomes possible to come into contact with a virus.

In this embodiment, the antiviral layer or the cured organic binder does not contain a photocatalyst. This is because it is possible to prevent the organic binder and the like from deteriorating due to oxidation and reduction by the photocatalyst. Here, the photocatalyst means a substance that absorbs light and exhibits a catalytic action.

In the present embodiment, the surface roughness of the surface of the antiviral layer is such that the arithmetic mean roughness (Ra) measured according to JIS B 0601-1982 is 0.1 μm or less. Generally, in the case of a smooth surface such that the surface roughness Ra of the surface of the antiviral layer is 0.1 μm or less, the contact area with the virus becomes small and the antiviral performance becomes low. In the antiviral substrate, high antiviral activity can be realized even on such a smooth surface.
Further, the surface roughness (Ra) of the surface of the antiviral layer is preferably 0.01 μm or more.

In this embodiment, the antiviral agent is preferably a copper compound. Copper compounds have high antiviral performance, and divalent copper compounds are water-soluble and can be homogenized at the organic binder and copper ion levels. Therefore, it is easy to form a state in which the "first region having a relatively high copper compound content" and the "second region having a relatively low copper compound content" are mixed in the antiviral layer. Is. In other words, the "first region having a relatively high copper compound content" forms a state of being scattered or dispersed in the matrix consisting of the "second region having a relatively low copper compound content". Because it is easy to do.

In this embodiment, the antiviral agent is also preferably an organic compound that is incompatible with the organic binder. This is because when the antiviral agent is completely uniformly compatible with the organic binder, the antiviral component is covered with the skin layer on the surface of the organic binder and is not exposed, so that the antiviral activity is lowered.

In this embodiment, the antiviral agent is also preferably at least one of a polymer biguanide and a bis-type quaternary ammonium salt. Both the polymer biguanide and the bis-type quaternary ammonium salt have high antiviral performance and are difficult to be compatible with the organic binder. Therefore, "the first region in which the content of at least one of the polymer biguanide and the bis-type quaternary ammonium salt is relatively high" and "at least one of the polymer biguanide and the bis-type quaternary ammonium salt" This is because it is easy to form a state in which the "second region having a relatively low content" is mixed in the anti-virus layer. In other words, the "first region in which the content of at least one of the polymer biguanide and the bis-type quaternary ammonium salt is relatively high" is "at least one of the polymer biguanide and the bis-type quaternary ammonium salt". This is because it is easy to form a state of being scattered or dispersed in a matrix composed of "a second region having a relatively low content on either side".

The first region, that is, a region having a relatively high content of the antiviral agent, is composed of a complex of an organic binder and an antiviral agent. By combining an antiviral agent with an ionic or molecular level and an organic binder, the antiviral performance of inactivating the virus can be enhanced. Regions with a relatively high content of antiviral agent are exposed from the organic binder layer and come into contact with the virus without being covered with the skin layer on the surface of the organic binder layer.

When the antiviral agent is a copper compound, the copper compound mixed with the organic binder before the organic binder is cured is preferably a divalent water-soluble copper compound. This is because by mixing a divalent copper compound, water as a dispersion medium, and an organic binder, the organic binder and the organic binder are mixed at the ionic level to obtain a composite of the organic binder and the copper compound.

In the present embodiment, the cured organic binder is preferably formed in the form of a film on the substrate. Since the cured organic binder, which is film-like and has a small surface roughness (Ra ≤ 0.1 μm), has a small specific surface area, it generally has a low contact probability with a virus and a low antiviral activity. In the case of the embodiment, it is advantageous because high antiviral activity can be obtained.

In the present embodiment, it is preferable that a hard coat layer is provided on the surface of the base material, and an antiviral layer is provided on the hard coat layer. This is because the durability is improved by providing the hard coat layer on the surface of the base material. The hard coat layer may be formed via a primer layer provided on the surface of the substrate.

In the present embodiment, a primer layer may be further provided on the surface of the substrate.

In the present embodiment, it is preferable that copper is present in an amount of 0.6 atomic% or more in the first region where the content of the copper compound as an antiviral agent is relatively high. This is because the antiviral activity can be enhanced by the presence of 0.6 atomic% or more of copper in the first region. It is more preferable that copper is present in the first region in an amount of 1.5 atomic% or more. Further, copper is present in the first region in an amount of less than 100 atomic%. This is because the first region is not composed only of the antiviral agent.

In the present embodiment, it is preferable that the pressure-sensitive adhesive layer is provided on the opposite side surface of the surface on which the antiviral layer of the base material is provided. This makes it easy to attach the antiviral substrate to members such as smartphones, electronic device displays, walls and doorknobs. A release sheet may be laminated on the surface of the pressure-sensitive adhesive layer to protect the pressure-sensitive adhesive layer.

As the pressure-sensitive adhesive layer, conventionally known ones can be used, and for example, an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, and the like can be used.

The acrylic pressure-sensitive adhesive is a pressure-sensitive adhesive made of an acrylic polymer, and by selecting and copolymerizing an acrylic monomer, an acrylic polymer having a necessary function is synthesized and can be used as a pressure-sensitive adhesive. Examples of the type of acrylic pressure-sensitive adhesive include solvent-based adhesives, emulsion-based adhesives, and UV-curable adhesives. As the acrylic pressure-sensitive adhesive, for example, each monomer of 2-ethylhexyl acrylate, methyl methacrylate and acrylic acid is blended in a weight ratio of 2-ethylhexyl acrylate / methyl methacrylate / acrylic acid = 85/15/3. Polymerization degree Mw = 700,000-800,000, solid obtained by polymerizing in ethyl acetate under a nitrogen stream using 2,2'-azobisisobutyronitrile (2,2'-azobis (isobutyronity)) as a catalyst. A removable acrylic pressure-sensitive adhesive or the like can be used at a rate of 30% per minute.

As the rubber-based pressure-sensitive adhesive, for example, polyisobutylene, SBR, butyl rubber, chloroprene rubber and the like can be used.

As the silicone-based pressure-sensitive adhesive, as the silicone-based pressure-sensitive adhesive, one containing what is generally called a gum component and a resin component can be used. Further, as the silicone-based pressure-sensitive adhesive, one containing a cross-linking agent, a metal catalyst, or the like can be used in addition to the above-mentioned components.

As the gum component, one that mainly serves as a binder component of a pressure-sensitive adhesive can be used, and for example, polyorganosilicone or the like can be used. As the polyorganosilicone, a peroxide curing type and an addition curing type are known, and both can be used.

As the resin component, conventionally known ones can be appropriately selected and used, but it is preferable to use a polyorganosilicone having a relatively low molecular weight, and it is more preferable to use an addition-curable polyorganosilicone.

In this embodiment, the substrate is preferably translucent. This is because when the base material is a film or a sheet, it can be used as a protective film for a smartphone or an electronic device display, or when the base material is in a plate state such as an acrylic plate, it can be used as a tsuitate to prevent splashes. Further, the base material may have flexibility. The total light transmittance and the haze value measured based on JIS K7361 are preferably 90% or more for the total light transmittance and 2% or less for the haze value, respectively.

In the present embodiment, the material of the base material is not particularly limited, but for example, polyethylene terephthalate (PET), vinyl chloride polymer, polyethylene and the like can be used.

Generally, the compound refers to a covalent compound or an ionic compound, and the complex is not included in the compound. Therefore, the copper complex (copper complex salt) is not included in the copper compound referred to in the anti-virus substrate of the present embodiment, and the amino acid salt of copper is not included in the copper compound of the present embodiment. The copper compound in the present embodiment refers to a covalent compound containing copper and an ionic compound containing copper.

In the present embodiment, the copper compound is preferably at least one selected from the group consisting of a copper carboxylate and a water-soluble inorganic salt of copper, and a copper carboxylate is further preferable. This is because when the cured organic binder is formed on the surface of the substrate, the copper compound exposed from the surface of the cured organic binder in a state where it can come into contact with a virus can exhibit excellent antiviral activity.

The copper compound is more preferably a divalent copper compound (copper compound (II)). The divalent copper compound (copper compound (II)) is sufficiently dispersed in the organic binder as compared with the monovalent compound (copper compound (I)) that is insoluble in water as a dispersion medium and localized in the form of particles. This is because it can exert excellent antiviral activity. Further, by mixing the divalent copper compound with water and an organic binder and reducing the divalent copper compound, a state in which the monovalent and divalent copper compounds coexist in the cured organic binder can be easily formed. It also has the advantage of being able to. From this point as well, it is optimal to use a water-soluble divalent copper compound as the copper compound.

In this embodiment, the type of organic binder is not particularly limited. The organic binder is preferably at least one selected from the group consisting of electromagnetic wave curable resin and thermosetting resin. This is because these organic binders can be cured by irradiation with electromagnetic waves or heating to adhere the copper compound to the surface of the substrate. Further, these organic binders are advantageous because the reducing power of copper is not lowered by the photopolymerization initiator.

As the electromagnetic wave curable resin, at least one selected from the group consisting of acrylic resin, urethane acrylate resin, and epoxy acrylate resin can be preferably used. Further, as the thermosetting resin, at least one selected from the group consisting of an epoxy resin, a melamine resin, and a phenol resin can be preferably used.

The organic binder is selected from the group consisting of acrylic resin, urethane acrylate resin, polyether resin, polyester resin, epoxy resin, alkyd resin, silica sol, alumina sol, zirconia sol, titania sol, metal alkoxide, and water glass. It is preferably at least one kind.

In the present embodiment, the antiviral composition forming the antiviral layer may contain a dispersion medium. The dispersion medium is preferably alcohol and / or water. This is because an antiviral agent such as a copper compound is well dispersed in the dispersion medium, and as a result, an organic binder cured product in which the antiviral agent such as a copper compound is well dispersed can be formed.

In this embodiment, the antiviral layer may contain a photopolymerization initiator. The photopolymerization initiator is preferably a water-insoluble photopolymerization initiator. This is because such a photopolymerization initiator does not elute even when it comes into contact with water, so that it is possible to form an organic binder cured product having excellent water resistance.

The photopolymerization initiator is preferably at least one selected from the group consisting of an alkylphenone type, a benzophenone type, an acylphosphine oxide type, an intramolecular hydrogen extraction type, and an oxime ester type. This is because these photopolymerization 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.

The photopolymerization initiator is preferably at least one selected from the group consisting of an alkylphenone-based photopolymerization initiator and a benzophenone-based photopolymerization initiator. This is because these photopolymerization 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. In the present specification, the alkylphenone-based photopolymerization initiator includes alkylphenone and its derivative, and the benzophenone-based photopolymerization initiator includes benzophenone and its derivative.

The photopolymerization initiator preferably contains an alkylphenone-based photopolymerization initiator and the benzophenone-based photopolymerization initiator. The concentration of the alkylphenone-based photopolymerization initiator is preferably 0.5 to 3.0% by weight with respect to the uncured organic binder. Further, the concentration of the benzophenone-based photopolymerization initiator is preferably 0.5 to 2.0% by weight with respect to the uncured organic binder. This is because a high crosslink density can be realized even if the irradiation time of electromagnetic waves is short.

The ratio of the alkylphenone-based photopolymerization initiator to the benzophenone-based photopolymerization initiator is 1/1 to 4/1 by weight ratio of the alkylphenone-based photopolymerization initiator / benzophenone-based photopolymerization initiator. It is preferable to have. 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. The crosslink density is preferably 85% or more, particularly preferably 95% or more.

Further, as the photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator can be used, and specifically, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (2,4,6-trimethyl). Benzoylbiphenylphosphine oxide (also referred to as benzoylbiphenylphosphine oxide), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinate ethyl and the like can be mentioned. These photopolymerization initiators are used as photopolymerization initiators when UV-LED is used as a light source for generating ultraviolet rays.

In this embodiment, when a copper compound is used as an antiviral agent, the first region in which the content of the copper compound is relatively high and the second region in which the content of the copper compound is relatively low are It can be distinguished as follows. For example, as shown in FIG. 2, when the surface of the cured organic binder in the present embodiment is confirmed by an electron micrograph (reflected electron image: magnification 5000 times), the region that looks relatively white is the content of the copper compound. The region that looks black corresponds to the second region where the content of the copper compound is relatively low. The copper compound may not be contained in the second region where the content of the copper compound in the region that looks black is relatively low.

Further, the area of the first region in which the content of the copper compound is relatively high is larger than the area of the copper compound itself. That is, the form in which the copper compound particles alone or the copper compound particles are aggregated and scattered or dispersed in the matrix (resin) is excluded. That is, the form composed of the copper compound particles alone or the copper compound particles agglomerated and substantially free of the organic binder is excluded from the "first region having a relatively high content of the copper compound". It will be done.
Therefore, the copper compound becomes a composite of an antiviral agent and a resin by being scattered or dispersed in a matrix (resin) in the state of ions, molecules, etc. It is preferable to form a "region". As a result, the antiviral layer of the present embodiment is in a state in which "the first region having a relatively high content of the copper compound" and "the second region having a relatively low content of the copper compound" are mixed.

The area in the plan view of the first region in which the content of the antiviral agent such as the copper compound is relatively high is the area in the plan view of the entire region (that is, the first region in which the content of the copper compound is relatively high). It is preferably 0.5% to 50% with respect to the area in plan view and the area in plan view of the second region where the content of the copper compound is relatively small), and 1% to 30% is preferable. More preferred. This is because if the area of the first region in which the content of the copper compound is relatively high is too large or too small, sufficient antiviral activity and resistance to wiping cannot be obtained.

When the anti-virus substrate of the present embodiment contains a photopolymerization initiator, the photopolymerization initiator generates radicals and ions, and at that time, the copper compound can be reduced, thus increasing the antiviral activity of copper. be able to. In general, copper (I) has a higher antiviral activity than copper (II), and the reduction of copper improves the antiviral activity. Further, since the photopolymerization initiator is hydrophobic and insoluble in water, it becomes an antiviral substrate having an organic binder cured product having excellent water resistance.

It was first discovered by the present inventors that such a photopolymerization initiator has a reducing power with respect to copper, and the presence ratio of copper (I) is obtained by reducing the copper compound by the photopolymerization initiator. Can be increased.

In the antiviral substrate of the present embodiment, it is preferable that at least a part of the copper compound is exposed from the surface of the cured organic binder in a state of being in contact with the virus. This is because the function of the virus can be deactivated if it is exposed in a state where it can come into contact with the virus.

The thickness of the film made of the cured organic binder is preferably 0.1 to 20 μm. This is because if the film is too thick, stress is generated and the film is peeled off to reduce the antiviral activity, and if the film is too thin, the antiviral activity cannot be sufficiently exhibited.

In the present embodiment, when the base material is not designed, or when the antiviral activity is prioritized over the design, a film made of a cured organic binder is formed on the base material as described above. It may be formed.

In the antiviral substrate of the present embodiment, it is preferable that copper is present in an amount of 0.6 atomic% or more in the first region where the content of the copper compound is relatively high. This is because high antiviral activity can be exhibited by the presence of copper in an amount of 0.6 atomic% or more. The copper means copper atoms and copper ions, and is an energy-dispersed fluorescent X-ray analyzer described later. Fluorescent X-rays generated when X-rays are irradiated (X when the sample is irradiated with primary X-rays). The energy of the rays repels the electrons in the inner shell to create vacancies, and when the outer shell electrons fall into the vacancies, X-rays corresponding to the energy difference are emitted. This is called fluorescent X-rays.) It means the one that can count.

In the first region where the content of the copper compound is relatively high, it is more preferable that copper is present in an amount of 1.5 atomic% or more. Further, in the first region where the content of the copper compound is relatively high, the amount of copper is less than 100 atomic%. This is because the copper compound particles alone or the aggregates of the copper compound particles themselves are not the first region in which the content of the copper compound is relatively high. The content of the copper compound in the first region where the content of the copper compound is relatively high is determined by analyzing the antivirus substrate with an energy dispersive X-ray fluorescence analyzer and performing elemental analysis in the first region. Can be measured.

In the second region where the content of the copper compound is relatively low, the copper content is preferably less than 0.6 atomic%, and the copper compound may not be present. Regarding the content of the copper compound in the second region where the content of the copper compound is relatively low, the anti-virus substrate is analyzed by an energy-dispersed fluorescent X-ray analyzer, and the content of the copper compound is relatively low in the second region. The abundance of the copper compound can be confirmed by performing elemental analysis of the region.

(Detailed description of the invention)
<Antiviral composition>
The antiviral layer made of an organic binder cured product provided on the surface of the substrate can be obtained by curing the following antiviral composition (organic binder composition) in a region on the substrate where antiviral properties are required.
The antiviral composition in the present embodiment is composed of a liquid A containing an antiviral agent and a dispersion medium, and a liquid B containing an uncured organic binder. The antiviral agent contained in the liquid A is preferably at least one selected from a divalent copper compound, a polymer biguanide and a bis-type quaternary ammonium salt. Further, the liquid B may contain a photopolymerization initiator.

Moreover, the antiviral composition in this embodiment does not contain a photocatalyst. This is because it is possible to prevent the organic binder and the like from deteriorating due to oxidation and reduction by the photocatalyst. Here, the photocatalyst means a substance that absorbs light and exhibits a catalytic action.

The content ratio of the antiviral agent in the liquid A is preferably 0.1 to 30.0% by weight, and the content ratio of the dispersion medium is preferably 70.0 to 99.9% by weight. The content ratio of the organic binder in the liquid B is preferably 85.0 to 99.5% by weight, and the content ratio of the photopolymerization initiator is preferably 0.5 to 15.0% by weight. Further, the mixing ratio of the liquid A and the liquid B is preferably liquid A / liquid B = 1/1 to 5/1 in terms of weight ratio.

The copper compound is preferably at least one selected from the group consisting of a copper carboxylate and a water-soluble inorganic salt of copper.

As the carboxylic acid salt of copper, for example, an ionic compound of copper can be used, and examples thereof include copper acetate, copper benzoate, and copper phthalate. As the water-soluble inorganic salt of copper, an ionic compound of copper can be used, and examples thereof include copper nitrate and copper sulfate.

The copper compound is preferably a divalent copper compound (copper compound (II)). Since the monovalent compound (copper compound (I)) is insoluble in water as a dispersion medium, it is localized in the form of particles, the dispersion in the organic binder is insufficient, and the antiviral activity is inferior. This is because the copper compound of the above does not cause such a problem. Further, by adding a divalent copper compound to the antiviral composition and reducing the divalent copper compound, a state in which the monovalent and divalent copper compounds coexist in the cured organic binder can be easily formed. It also has the advantage of being able to. From this point as well, it is optimal to use a water-soluble divalent copper compound.

As the copper product, a divalent copper carboxylate is particularly preferable. Examples of the divalent copper carboxylate include copper acetate (II), copper benzoate (II), and copper phthalate (II). Further, as the water-soluble inorganic salt of the divalent copper, an ionic compound of copper can be used, and examples thereof include copper (II) nitrate and copper (II) sulfate.

Examples of other divalent copper compounds include copper (II) methoxydo, copper (II) ethoxydo, copper (II) propoxide, copper (II) butoxide, and examples of the copper covalently binding compound include copper. Oxide, copper hydroxide and the like.

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 preferable.

(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. )

(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 are the same or different. Represents a good alkyl group.)

First, the bis-type pyridinium salt represented by the above 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 an alkyl group having 1 to 20 carbon atoms, and the alkyl group 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 preferably represented by ₂ -O- (CH ₂ ) ₄ -O-CH _2- (where Ph represents a phenylene group).

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} . n is 8-18, preferably 8, 10, 12, 14, 16 or 18. Further, m is 3 to 10, preferably 3, 4, 6, 8, and 10.
The substituent R ¹¹ of the compound shown below is also the same as the above general formula (3).

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 preferable.

Next, the bis-type thiazolium salt will be described. 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 kinorium salt, for example, a pyridinium group represented by the following general formula (13) constituting the bis-type pyridinium salt represented by the general formulas (3) to (10) can be used as a general formula (1). Examples thereof include a bis-type quinolinium salt having a chemical structure substituted with the kinorium group shown in 14).
In the bis-type quinolinium salt, other substituents and the like are the same as the bis-type pyridinium salt represented by the general formulas (3) to (10).

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.

The polymer biguanide used in the present embodiment is preferably a polyalkylene biguanide compound, and is preferably represented by the following formula (I).

[In the formula, Ra represents an alkylene group having 2 to 8 carbon atoms, and n represents an integer of 2 to 18. ]

In the above formula (I), the alkylene group having 2 to 8 carbon atoms represented by ^Ra includes ethylene, propylene, butylene, pentylene, hexylene (hexamethylene), heptylene (heptamethylene), octylene (octamethylene) and the like. In addition to linear ones, branched ones such as isopropylene, isobutylene, isopentylene, dimethylpropylene, and dimethylbutylene are also included, but linear alkylene groups are preferable. Further, from the viewpoint of virus inactivating effect, an alkylene group having 4 to 8 carbon atoms is preferable, and a hexamethylene group is particularly preferable. In addition, n in the formula (I) is 2 to 18, preferably 10 to 14, more preferably 11 to 13, considering the virus inactivating effect, handleability and the like.

The polyalkylene biguanide compound represented by the formula (I) can also be used in the form of a salt with an inorganic acid such as hydrochloric acid, nitric acid or sulfuric acid, or a salt with an organic acid such as acetic acid, lactic acid or gluconic acid. Among such salts, hydrochlorides, acetates and gluconates are preferable, and hydrochlorides are most preferably used. For the virus inactivating composition of the present embodiment, one or more selected from the group consisting of the polyalkylene biguanide compound represented by the formula (I) and a salt thereof is used.
In particular, in the present invention, a hydrochloride of polyhexamethylene biguanide can be preferably used as the polyalkylene biguanide compound.

In the present embodiment, as the polyalkylene biguanide compound or a salt thereof, a compound produced according to a known method, for example, the method described in British Patent No. 702,268 or the like may be used, or a commercially available product may be used. good. Examples of commercially available products include "Eccrine Side BG" (manufactured by Riko Kyosan Co., Ltd.), "Proxel IB" (manufactured by Arch Chemicals Co., Ltd.), "Lonza Back BG" (manufactured by Lonza Japan Co., Ltd.) and the like.

The liquid A contains a dispersion medium. The dispersion medium is preferably alcohol and / or water in consideration of stability. This is because the copper compound is well dispersed in the dispersion medium, and as a result, an organic binder cured product in which the copper compound is well dispersed can be formed.

Examples of the alcohol include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol and the like in consideration of lowering the viscosity. Among these alcohols, methyl alcohol and ethyl alcohol, which do not easily increase in viscosity, are preferable. Further, as the dispersion medium, a mixed solution of alcohol and water can be used.

The liquid B contains an uncured organic binder. As the organic binder, at least one selected from the group consisting of electromagnetic wave curable resin and thermosetting resin can be used. This is because these organic binders can be cured by irradiation with electromagnetic waves or heating to adhere the copper compound to the surface of the substrate. Further, these organic binders are advantageous because they do not reduce the reducing power of the photopolymerization initiator with respect to copper.

As the electromagnetic wave curable resin, at least one selected from the group consisting of acrylic resin, urethane acrylate resin, and epoxy acrylate 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.

As a specific example of the uncured organic binder, at least one selected from the group consisting of acrylic resin, urethane acrylate resin, polyether resin, polyester resin, epoxy resin and alkyd resin is preferable.

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 combination of a glycidyl ether type epoxy resin and an oxetane resin.

Examples of the alkyd resin include polyester alkyd resin and the like. These resins have transparency and are also excellent in adhesion to a substrate.

The electromagnetic wave curable resin means a resin produced by the progress of polymerization reaction, cross-linking reaction, etc. of a monomer or an oligomer as a raw material by electromagnetic wave irradiation. Therefore, the anti-virus composition contains a monomer and an oligomer (uncured electromagnetic wave curable resin) which are raw materials for the electromagnetic wave curable resin.

By irradiating a composition containing the uncured electromagnetically curable resin monomer or oligomer, the photopolymerization initiator and various additives with electromagnetic waves, the photopolymerization initiator can be subjected to a cleavage reaction hydrogen abstraction reaction. Reactions such as electron transfer occur, and the photoradical molecules, photocation molecules, photoanionic molecules, etc. generated by this attack the monomer and the oligomer, and the polymerization reaction and the crosslinking reaction of the monomer and the oligomer proceed, and the organic binder is cured. Can produce things. In the present specification, the resin produced by such a reaction is referred to as an electromagnetic wave curable resin.

The liquid B may contain a photopolymerization initiator. As the photopolymerization initiator, it is preferable to use a photopolymerization initiator having a reducing power. According to the photopolymerization initiator, when the solution A and the solution B are mixed, the copper compound is reduced to copper ions (I) having high antiviral activity, and the copper ions (I) are oxidized. This is because it can suppress the conversion to copper ion (II), which has inferior antiviral activity.

Therefore, the antiviral substrate of this embodiment acts most effectively on viruses and / or molds. By the reducing power of copper (I), copper ion (I) reduces water and oxygen in the air to generate active oxygen, hydrogen peroxide solution, superoxide anion, hydroxyl radical, etc., resulting in virus or mold. This is because it effectively destroys the proteins that make up the radical.

The photopolymerization initiator is preferably a water-insoluble photopolymerization initiator. This is because it does not elute even when it comes into contact with water, so that the cured organic binder does not deteriorate and the copper compound is not desorbed. Even if the copper compound is water-soluble, if it is retained by the cured organic binder, desorption can be suppressed, but if the cured organic binder contains a water-soluble substance, the cured organic binder is described above. It is presumed that the holding power for the copper compound is reduced and the copper compound is desorbed.

Further, the water-insoluble photopolymerization initiator can easily proceed with the polymerization reaction by light such as visible light and ultraviolet rays when an electromagnetic wave curable resin is used as an uncured organic binder. ..

The photopolymerization initiator is preferably at least one selected from the group consisting of an alkylphenone type, a benzophenone type, an acylphosphine oxide type, an intramolecular hydrogen extraction type, and an oxime ester type. This is because these photopolymerization 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.

Examples of the alkylphenone-based photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy-2-methyl-1. -Phenyl-Propane-1-one, 1- [4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-Hirodoxy-1- {4- [ 4- (2-Hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- On, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- ( 4-morphonyl) phenyl] -1-butanone and the like can be mentioned.

Examples of the benzophenone-based photopolymerization initiator include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, or 3, Examples thereof include 3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and the like.

Examples of the acylphosphine oxide-based photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (also referred to as 2,4,6-trimethylbenzoylbiphenylphosphine oxide) and bis (also referred to as 2,4,6-trimethylbenzoylbiphenylphosphine oxide). 2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinate ethyl and the like can be mentioned. This is because it can be used even when the UV-LED is used as a light source of ultraviolet rays.

Examples of the above-mentioned intramolecular hydrogen abstraction type photopolymerization initiator include phenylglycylic acid methyl ester, oxyphenylsuccin, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester tooxyphenylacetic acid and 2-. Examples thereof include a mixture with (2-hydroxyethoxy) ethyl ester.

Examples of the oxime ester-based photopolymerization 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.

The photopolymerization initiator is preferably at least one selected from the group consisting of an alkylphenone-based photopolymerization initiator and a benzophenone-based photopolymerization initiator, and particularly contains a benzophenone-based photopolymerization initiator. Is preferable. This is because these photopolymerization 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.

The photopolymerization initiator contains an alkylphenone-based photopolymerization initiator and a benzophenone-based photopolymerization initiator, and the concentration of the alkylphenone-based photopolymerization initiator in the above solution B is 0.5 to 10. It is preferable that the concentration of the benzophenone-based photopolymerization initiator is 0% by weight and the concentration of the benzophenone-based photopolymerization initiator is 0.5 to 5.0% by weight in the liquid B. This is because a high crosslink density can be realized even if the irradiation time of electromagnetic waves is short.

The ratio of the alkylphenone-based photopolymerization initiator to the benzophenone-based photopolymerization initiator is 1/1 to 4/1 by weight ratio of the alkylphenone-based photopolymerization initiator / benzophenone-based photopolymerization initiator. It is preferable to have. 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. The crosslink density is preferably 85% or more, particularly preferably 95% or more.

When an electromagnetic wave curable resin (monomer or oligomer) is used as the uncured organic binder, the content ratio of the copper compound in the liquid A is preferably 0.1 to 30.0% by weight, and the dispersion medium. The content ratio of is preferably 70.0 to 99.9% by weight.
The content ratio of the electromagnetic wave curable resin (monomer or oligomer) in the liquid B is preferably 85.0 to 99.5% by weight, and the content ratio of the photopolymerization initiator is 0.5 to 15. 0% by weight is preferable. When the alkylphenone-based photopolymerization initiator and the benzophenone-based photopolymerization initiator are contained, the concentration of the alkylphenone-based photopolymerization initiator is 0.5 to 10.0% by weight, and the above. It is more preferable that the concentration of the benzophenone-based photopolymerization initiator is 0.5 to 5.0% by weight.
Further, the mixing ratio of the liquid A and the liquid B is preferably liquid A / liquid B = 1/1 to 5/1 in terms of weight ratio.

The liquid A and / or the liquid B may contain 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, if necessary. It may be blended. Since it is reduced to copper ion (I) again, the reducing power is always maintained. Therefore, a reducing agent such as a reducing sugar is not required, and the photopolymerization initiator is suitable because it can prevent oxidation of an antiviral agent such as a copper compound without deteriorating the organic binder.

The base material is not particularly limited, and examples thereof include ceramics such as metal and glass, resins, fiber woven fabrics, and wood. Further, the member used as a base material is not particularly limited, and may be a protective film for a touch panel, a film for a display, an interior material inside a building, a wall material, a window glass, a handrail, or the like. May be good. It may also be a doorknob, a slide key for a toilet, 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.

It is preferable that a hard coat layer is provided on the surface of the base material, and an antiviral layer is formed on the hard coat layer. This is because the durability is increased.

It is preferable that the pressure-sensitive adhesive layer is provided on the opposite side surface of the base material on which the antiviral layer is provided. This makes it easy to attach the antiviral substrate to members such as smartphones, electronic device displays, walls and doorknobs. A release sheet may be laminated on the surface of the pressure-sensitive adhesive layer to protect the pressure-sensitive adhesive layer.

The substrate is preferably translucent. This is because when the base material is a film or a sheet, it can be used as a protective film for a smartphone or an electronic device display, or when the base material is in a plate state such as an acrylic plate, it can be used as a tsuitate to prevent splashes. The substrate may be flexible.

In the anti-virus substrate of the present embodiment, it is calculated by measuring the bond energy corresponding to Cu (I) and Cu (II) in the range of 925 to 955 eV for 5 minutes by X-ray photoelectron spectroscopy. The ratio of the number of ions of Cu (I) and Cu (II) contained in the copper compound (Cu (I) / Cu (II)) is preferably 0.4 to 50. The coexistence with Cu (II) has higher antiviral activity than the case of Cu (I) alone. The reason for this is not clear, but it is not because it is possible to prevent the Cu (I) from being oxidized by coexisting with the stable Cu (II) as compared with the case of only the unstable Cu (I). I presume that. The ratio of the number of ions of Cu (I) and Cu (II) contained in the copper compound (Cu (I) / Cu (II)) is more preferably 0.5 to 50, more preferably 1.0. It is more preferably to 4.0, particularly preferably 1.4 to 2.9, and particularly preferably 1.4 to 1.9.

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⁺ . In general, 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).

The thickness of the film made of the cured organic binder in the present embodiment is preferably 0.1 to 20 μm. This is because if the film is too thick, stress is generated and the film is peeled off to reduce the antiviral activity, and if the film is too thin, the antiviral activity cannot be sufficiently exhibited. If the base material is not designed, or if the antiviral activity is prioritized over the design, even if a film made of an organic binder cured product is formed on the base material as described above. good.

Further, the antiviral substrate in the present embodiment preferably has a total light transmittance of 90% or more. When the total light transmittance is 90% or more, light rays such as visible light are transmitted, so that it can be used for applications utilizing the light transmittance.

In the antiviral substrate of the present embodiment, it is preferable that copper is present in an amount of 0.6 atomic% or more in the first region where the content of the copper compound is relatively high. This is because high antiviral activity can be exhibited by the presence of copper in an amount of 0.6 atomic% or more.

The copper means copper atoms and copper ions, and is an energy-dispersed fluorescent X-ray analyzer described later. Fluorescent X-rays generated when X-rays are irradiated (X when a sample is irradiated with primary X-rays). The energy of the rays repels the electrons in the inner shell to create vacancies, and when the outer shell electrons fall into the vacancies, X-rays corresponding to the energy difference are emitted. This is called fluorescent X-rays.) It means the one that can count.

In the region where the content of the copper compound is relatively high, it is more preferable that copper is present in an amount of 1.5 atomic% or more. Further, in the first region where the content of the copper compound is relatively high, the amount of copper is less than 100 atomic%. This is because the first region is not composed only of the antiviral agent.
Regarding the content of the copper compound in the first region where the content of the copper compound is relatively high, the anti-virus substrate is analyzed by an energy-dispersed fluorescent X-ray analyzer, and the content of the copper compound is relatively high in the region. The abundance of the copper compound can be confirmed by performing elemental analysis.

In the second region where the content of the copper compound is relatively low, the copper content is preferably less than 0.6 atomic%, and the copper compound may not be present. Regarding the content of the copper compound in the second region where the content of the copper compound is relatively low, the antivirus substrate is analyzed by an energy-dispersed fluorescent X-ray analyzer, and the matrix region in which the content of the copper compound is relatively low is analyzed. The abundance of the copper compound can be confirmed by performing the elemental analysis of.

Next, a method for producing the antiviral substrate of the present embodiment will be described.

(1) Antiviral composition preparation step An antiviral composition is produced by individually preparing a solution A containing an antiviral agent and a dispersion medium and a solution B containing an uncured organic binder in the above-mentioned content ratios. be able to. The antiviral agent contained in the liquid A is preferably at least one selected from a divalent copper compound, a polymer biguanide and a bis-type quaternary ammonium salt. Further, the liquid B may contain a photopolymerization initiator.
The antiviral composition is stored and cured in a dark place at 25 ° C. or higher for 24 hours or longer. In the antiviral composition, since the copper compound in the solution A and the uncured organic binder in the solution B do not come into contact with each other, the curing reaction does not proceed during storage, so that the antiviral composition does not turn yellow and deteriorates. do not. Therefore, long-term storage is possible even at high temperatures.

The liquid A and the liquid B are mixed immediately before being attached to the surface of the substrate. It is preferable that the liquid A and the liquid B are mixed and then sufficiently stirred with a mixer or the like to obtain an antiviral composition for adhesion that is dispersed at a uniform concentration, and then adhered to the surface of the substrate. A primer layer may be provided on the surface of the base material, or the surface may be hydrophilized by a plasma treatment or a corona discharge treatment. Further, a hard coat layer may be provided. As the hard coat layer, the hard coat layer may be formed after the primer layer is provided on the surface of the base material. As the hard coat layer, an acrylic, urethane, or polyoxysilane hard coat material can be used.

(2) Adhesion Step In the method for producing an antiviral substrate of the present embodiment, the antiviral composition for attachment is attached to the substrate as an attachment step. Specifically, the antiviral composition for adhesion is formed by applying the antiviral composition for adhesion to a region on the surface of the substrate where antiviral activity is required in the form of a film. In order to bring the surface of the base material into the above-mentioned state, for example, a method of applying and adhering the above composition using a bar coater for coating, a coating jig such as gravure printing, or a printing device can be mentioned.

(3) Drying Step An anti-virus composition for adhesion, which comprises an anti-virus agent such as a copper compound adhered by the above-mentioned adhesion step, an uncured organic binder, a dispersion medium, and, if necessary, a photopolymerization initiator. After drying, the dispersion medium is evaporated and removed, the cured organic binder containing the copper compound and the like is temporarily fixed on the surface of the substrate, and the cured organic binder is shrunk to expose the copper compound from the surface of the cured organic binder. be able to. 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. Further, it may be dried under reduced pressure (vacuum).
When producing the antiviral substrate of the present embodiment, the drying step and the curing step described later may be performed at the same time.

(4) Curing Step When the antiviral substrate of the present embodiment is produced, as a curing step, it is used in the antiviral composition for adhesion from which the dispersion medium has been removed in the drying step, or for adhesion containing the dispersion medium. The above-mentioned uncured organic binder in the antiviral composition is cured to obtain an organic binder cured product.

Methods for curing the uncured organic binder include removal of the dispersion medium by drying, promotion of polymerization of monomers and oligomers by heating or irradiation with electromagnetic waves. Examples of the drying include vacuum drying, heat drying and the like. When the organic binder is a thermosetting resin, the curing proceeds by heating. Heating can be performed by a heater, an infrared lamp, an ultraviolet lamp, or the like. The electromagnetic wave emitted when the uncured organic binder is an electromagnetic wave curable resin is not particularly limited, and for example, ultraviolet rays (UV), infrared rays, visible light, microwaves, electron beams (EB) and the like are used. Of these, ultraviolet light (UV) is preferred. When ultraviolet rays are used, it is preferable to use UV-LED as a light source. This is because it is possible to prevent the temperature of the irradiated object from rising.
By these steps, the antiviral substrate of the present embodiment described above can be produced.

Since the above-mentioned photopolymerization initiator is added to the above-mentioned antiviral composition for adhesion as needed, when a monomer or an oligomer is contained as an organic binder, the polymerization reaction thereof proceeds. Further, since the photopolymerization initiator reduces copper, copper (II) can be reduced to copper (I) and the amount of copper (I) can be increased, so that an organic binder cured product having high virus activity can be obtained. It is.

Then, it is irradiated with ultraviolet rays to develop the reducing power of the photopolymerization initiator. In any step of the method for producing an anti-virus substrate, it is preferable to irradiate an electromagnetic wave having a predetermined wavelength, for example, ultraviolet rays, in order to develop the reducing power of the photopolymerization initiator. In particular, when a photopolymerization initiator is used, radicals are generated by irradiation with electromagnetic waves, and by reducing copper ions, the amount of copper (I) having high antiviral activity, particularly antiviral activity, can be increased. ,It is valid.

Further, the cured organic binder is formed by being fixedly formed in a film shape in a region of the surface of the substrate where antiviral activity is required, and an antiviral substrate having excellent durability against wiping and cleaning can be produced. Therefore, compared to the case where it is dispersed and fixed in an island shape or the area where the hardened organic binder is fixedly formed on the surface of the base material and the area where the hardened organic binder is not fixedly formed are mixed, it is necessary to wipe off and clean it. Has excellent resistance.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
(Example 1)
(1) Preparation of solution A 210 parts by weight of copper (II) acetate / monohydrate powder (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) is 12300 parts by weight of pure water so that the concentration of copper acetate is 1.68% by weight. After dissolving in, a copper acetate aqueous solution was prepared by stirring at 700 rpm for 15 minutes using a magnetic stirrer.

(2) Preparation of Solution B 160 parts by weight of the photopolymerization initiator (Omnirad 184 manufactured by IGM) and 80 parts by weight of the photopolymerization initiator benzophenone were mixed. Omnirad 184 manufactured by IGM is the same substance as Irgacure 184 manufactured by BASF, and is 1-hydroxy-cyclohexyl-phenyl-ketone (alkylphenone). As a photopolymerization initiator, alkylphenone and benzophenone are in weight ratio. It exists in a 2: 1 ratio.
After mixing 195 parts by weight of this photopolymerization initiator mixture with 6300 parts by weight of a photoradical polymerization type acrylate resin (UCECOAT7200 manufactured by Dycel Ornex), the mixture is stirred and mixed in a propeller type stirring bath at 700 rpm for 60 minutes, and is subjected to ultraviolet rays. A cured resin solution was prepared.
The weight of the ultraviolet curable resin solution is a photoradical polymerization type acrylate resin (UCECOAT7200 manufactured by Dycel Ornex), a photopolymerization initiator 1-hydroxy-cyclohexyl-phenyl-ketone (alkylphenone), and a photopolymerization initiator benzophenone. It is mixed at a ratio of 97: 2: 1.

(3) Storage (curing)
The prepared solutions A and B were used as antiviral compositions. The antiviral composition (solutions A and B) was allowed to stand at 35 ° C. for 120 hours in a dark place.

(4) Mixing of Liquid A and Liquid B A liquid A was mixed in an amount of 470 parts by weight and a liquid B was mixed in an amount of 250 parts by weight, and the mixture was stirred for 1 minute to obtain an antiviral composition for adhesion.

(5) Preparation of hard coat base material 64 parts by weight of a mixture of pentafunctional and hexafunctional (M-400 manufactured by Toa Synthetic) as a polyfunctional (meth) acrylic monomer, 27 parts by mass of diethylene glycol diacrylate, photopolymerization initiator (trade name). : Omnirad 184, IGM Resins B.V. 5 parts by mass, photostabilizer (trade name: TINUVIN152, BASF) 4 parts by mass, a diluted solvent in which methyl ethyl ketone (MEK) and cyclohexanone are mixed 1: 1. Was mixed so that the solid content was 40% by mass to prepare a composition for forming a hard coat layer.

(6) Formation of hard coat layer A composition for forming a hard coat layer is applied on the surface of a polyethylene terephthalate (PET) film with a bar coater, then heated and dried at 80 ° C. for 60 seconds, and then used with a high-pressure mercury lamp ultraviolet irradiator. Then, ultraviolet rays were irradiated at 30 mW / cm ² to cure and form a hard coat layer having a thickness of 3 μm on the polyethylene terephthalate substrate as a curable resin layer to form the hard coat layer 23.

(7) Application of antiviral composition for adhesion This antiviral composition for adhesion was applied to the surface of the polyethylene terephthalate film of (6) above using a bar coater to form a continuous film having a thickness of 4 μm. ..

(8) Drying / Curing The silicon substrate is dried at 80 ° C. for 3 minutes, and then irradiated with ultraviolet rays at an irradiation intensity of 30 mW / cm ² for 80 seconds using an ultraviolet irradiation device (MP02 manufactured by COATTEC). An anti-virus substrate was obtained in which a cured organic binder containing a copper compound was fixedly formed as a coating film on the surface of a certain silicon substrate in the form of a continuous film.

3 (a) and 3 (b) show that the anti-virus substrate obtained in Example 1 has a white color indicated by a white arrow in the first region (in FIG. 3 (a)) in which the content of the copper compound is relatively high. The result of elemental analysis of the visible region) by the energy dispersive X-ray fluorescence analyzer is shown. As a result, Cu was 2.89 atomic% (12.85% by weight), Si was 0.50 atomic% (0.99% by weight), and O was 17.15 atomic% (19.24% by weight) in the first region. %), C was present in 79.46 atomic% (66.92% by weight).
Further, in FIGS. 4 (a) and 4 (b), the anti-virus substrate obtained in Example 1 is indicated by a white arrow in the second region (in FIG. 4 (a)) in which the content of the copper compound is relatively low. The result of elemental analysis by the energy dispersive X-ray fluorescence analyzer for the region (the region that looks black) is shown. As a result, O was present in 18.56 atomic% (23.28% by weight) and C was present in 81.44 atomic% (76.72% by weight) in the second region. On the other hand, the presence of Cu was not confirmed.
That is, in the antiviral substrate of Example 1, the first region having a high Cu content (that is, containing a large amount of antiviral agent) and the second region in which Cu is not confirmed (that is, not containing an antiviral agent) are mixed. It was confirmed that the virus was running.

(Example 2)
(1) Preparation of Solution A An antibacterial agent consisting of a bis-type quaternary ammonium salt (1,1'-didecyl-3,3'-[butane-1,4-diylbis (oxymethylene)] dipyridinium = dibromid) After dissolving in 12300 parts by weight of pure water so as to be 2.66% by weight, the mixture was prepared by stirring at 700 rpm for 15 minutes using a magnetic stirrer.

(2) Preparation of Solution B 160 parts by weight of the photopolymerization initiator (Omnirad 184 manufactured by IGM) and 80 parts by weight of the photopolymerization initiator benzophenone were mixed. Omnirad 184 manufactured by IGM is the same substance as Irgacure 184 manufactured by BASF, and is 1-hydroxy-cyclohexyl-phenyl-ketone (alkylphenone). As a photopolymerization initiator, alkylphenone and benzophenone are in weight ratio. It exists in a 2: 1 ratio.
After mixing 195 parts by weight of this photopolymerization initiator mixture with 6300 parts by weight of a photoradical polymerization type acrylate resin (UCECOAT7200 manufactured by Dycel Ornex), the mixture is stirred and mixed in a propeller type stirring bath at 700 rpm for 60 minutes, and is subjected to ultraviolet rays. A cured resin solution was prepared.
The weight of the ultraviolet curable resin solution is a photoradical polymerization type acrylate resin (UCECOAT7200 manufactured by Dycel Ornex), a photopolymerization initiator 1-hydroxy-cyclohexyl-phenyl-ketone (alkylphenone), and a photopolymerization initiator benzophenone. It is mixed at a ratio of 97: 2: 1.

(3) Storage (curing)
The prepared solutions A and B were used as antiviral compositions. The antiviral composition (solutions A and B) was allowed to stand at 35 ° C. for 120 hours in a dark place.

(4) Mixing of Liquid A and Liquid B A liquid A was mixed in an amount of 470 parts by weight and a liquid B was mixed in an amount of 250 parts by weight, and the mixture was stirred for 1 minute to obtain an antiviral composition for adhesion.

(5) An antiviral substrate was produced in the same manner as in Example 1. Elemental analysis of this anti-virus substrate was performed with an energy dispersive X-ray fluorescence analyzer, and the distribution of nitrogen was mapped. As a result, 1,1'-didecyl-3,3'-[, which is a nitrogen-containing antivirus agent. Butane-1,4-diylbis (oxymethylene)] The first region, which is thought to have a high content of dipyridinium = dibromid, and the second region, where nitrogen is not confirmed (that is, it does not contain an antiviral agent), are mixed. The status is confirmed.

(Example 3)
(1) Preparation of solution A A 6000 ppm aqueous solution of polyhexamethylene biguanide hydrochloride was used as solution A.

(2) Preparation of Solution B 160 parts by weight of the photopolymerization initiator (Omnirad 184 manufactured by IGM) and 80 parts by weight of the photopolymerization initiator benzophenone were mixed. Omnirad 184 manufactured by IGM is the same substance as Irgacure 184 manufactured by BASF, and is 1-hydroxy-cyclohexyl-phenyl-ketone (alkylphenone). As a photopolymerization initiator, alkylphenone and benzophenone are in weight ratio. It exists in a 2: 1 ratio.
After mixing 195 parts by weight of this photopolymerization initiator mixture with 6300 parts by weight of a photoradical polymerization type acrylate resin (UCECOAT7200 manufactured by Dycel Ornex), the mixture is stirred and mixed in a propeller type stirring bath at 700 rpm for 60 minutes, and is subjected to ultraviolet rays. A cured resin solution was prepared.
The weight of the ultraviolet curable resin solution is a photoradical polymerization type acrylate resin (UCECOAT7200 manufactured by Dycel Ornex), a photopolymerization initiator 1-hydroxy-cyclohexyl-phenyl-ketone (alkylphenone), and a photopolymerization initiator benzophenone. It is mixed at a ratio of 97: 2: 1.

(3) Storage (curing)
The prepared solutions A and B were used as antiviral compositions. The antiviral composition (solutions A and B) was allowed to stand at 35 ° C. for 120 hours in a dark place.

(4) Mixing of Liquid A and Liquid B A liquid A was mixed in an amount of 470 parts by weight and a liquid B was mixed in an amount of 250 parts by weight, and the mixture was stirred for 1 minute to obtain an antiviral composition for adhesion.

(5) An antiviral substrate was produced in the same manner as in Example 1. Elemental analysis of this anti-virus substrate was performed with an energy dispersive X-ray fluorescence analyzer, and the distribution of nitrogen was mapped. As a result, it is considered that the content of polyhexamethylene biguanide, which is a nitrogen-containing anti-virus agent, is high. It is confirmed that the first region and the second region where nitrogen is not confirmed (that is, the antivirus agent is not contained) are mixed.

(Example 4)
An acrylic pressure-sensitive adhesive (trade name S-1511X manufactured by Toagosei Co., Ltd.) was applied to the opposite side surface of the anti-virus substrate of Example 1 on which the anti-virus layer was formed, dried at room temperature, and the pressure-sensitive adhesive layer 24 was applied. Formed. Further, a Teflon (registered trademark) sheet was laminated as a release sheet 25 (FIG. 5).

(Comparative Example 1)
(1) 1 part by mass of silica (trade name AEROSIL300, manufactured by EVONIK, average particle diameter 7 nm) was dispersed in 90 parts by mass of water to obtain an aqueous dispersion of silica. A 2% by mass aqueous sodium hydroxide solution was added thereto to adjust the pH to 10.
Separately, water glass diluted to 0.1% by mass, 0.7% by mass sodium aluminate aqueous solution, and 0.05% by mass silver nitrate aqueous solution were prepared.
To 85.5 parts by mass of the aqueous dispersion of silica whose pH was adjusted to 10, 13 parts by mass of the previously prepared water glass and 1.5 parts by mass of the sodium aluminate aqueous solution were added and reacted, and then dealkalized. A silica-alumina suspension was obtained. To 100 parts by mass of the obtained silica alumina suspension, 30 parts by mass of the silver nitrate aqueous solution prepared above was added to obtain silver-silica antibacterial agent particles (presumed to be aggregated) in which silver was supported on silica. ..

(2) 64 parts by weight of a mixture of pentafunctional and hexafunctional (M-400 manufactured by Toa Synthetic) as a polyfunctional (meth) acrylic monomer, 27 parts by mass of diethylene glycol diacrylate, a photopolymerization initiator (trade name: Omnirad 184, IGM Resins B.). V.) 5 parts by mass, light stabilizer (trade name TINUVIN152, manufactured by BASF) 4 parts by mass, silver-silica antibacterial agent particles 0.4 parts by mass, methyl ethyl ketone MEK) and cyclohexanone mixed 1: 1. An antibacterial composition was prepared by mixing the diluted solvent with the solid content so as to have a solid content of 40% by mass.

(3) An antibacterial substrate (antiviral substrate) was produced in the same manner as in Example 1.
The antibacterial substrate was observed with an electron microscope (reflected electron image), and the presence of antibacterial agent particles (antivirus agent particles) was confirmed. Moreover, the particle diameter was measured for any 100 antibacterial agent particles (antiviral agent particles), and the average value was obtained. The average particle size was 0.1 μm.

(Comparative Example 2)
(1) Dissolve copper (II) acetate / monohydrate powder (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) in pure water so that the concentration of copper acetate becomes 6.0 wt%, and then use a magnetic stirrer. A copper acetate aqueous solution was prepared by stirring at 600 rpm for 15 minutes. The mixed composition is prepared by mixing a photoradical polymerization type acrylate resin (UCECOAT7200 manufactured by Dycel Ornex) and a photopolymerization initiator (Omnirad500 manufactured by IGM) at a weight ratio of 98: 2, and stirring at 8000 rpm for 30 minutes using a homogenizer. Prepared an electromagnetic wave curing type binder solution. The above 6 wt% copper acetate aqueous solution and an electromagnetic wave curing type binder solution were mixed at a weight ratio of 1.0: 1.7, and the mixture was stirred at 600 rpm for 2 minutes using a magnetic stirrer to prepare a mixed 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. This photopolymerization initiator is insoluble in water and exhibits reducing power by ultraviolet rays.

(2) Using the mixed composition prepared in (1) above, an antiviral substrate was produced in the same manner as in Example 1.
The anti-virus substrate was observed with an electron microscope (reflected electron image), and the presence of aggregates of the anti-virus agent was confirmed. In addition, the diameters of any 10 aggregates were measured and the average value was obtained. The average diameter was 0.5 μm.

(Surface roughness measurement test)
The surface roughness was measured with a measurement length of 8 mm using HANDYSURF, which is a contact type surface roughness measuring machine manufactured by Tokyo Seimitsu. The measurement results are shown in Table 1.

(Antiviral evaluation using phage virus)
This antiviral test was performed as follows.
In order to evaluate the antiviral activity in the antiviral substrates obtained in Examples and Comparative Examples, JIS Z 2801 antibacterial processed product-antibacterial test method / method modified antibacterial effect 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 viruses were made based on the antiviral test method for JIS L 1922 textile products. The measurement result is based on JIS L 1922 Annex B for the anti-virus substrate obtained in Example 1, and the concentration of the phage virus that has lost the ability to infect E. coli is displayed as the virus inactivation degree. Here, the concentration of the virus inactivated against Escherichia coli (virus inactivation degree) was used as an index of the virus concentration, and the antiviral activity value was calculated based on this virus inactivation degree.

The procedure will be described in detail below.
(1) With respect to the antiviral substrates obtained in Examples and Comparative Examples, the antiviral substrate was cut into a square having a side of 50 mm square and used as a test sample. Place this test sample in a sterile plastic petri dish and inoculate 0.1 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 antiviral activity value was calculated using the following formula.
Mv = Log (Vb / Vc)
Mv: Antiviral activity value Log (Vb): Log of infection value after reaction of polyethylene film for a predetermined time Log (Vc): Logistic reference standard of infection value of test sample after reaction for a predetermined time JIS L 1922, JIS Z 2801
The measuring method was a plaque measuring method.
The obtained antiviral activity values are shown in Table 1.

The antiviral activity values of the antiviral substrates of Examples 1 to 4 were all as high as 4.6 to 5.3.
On the other hand, in the antiviral substrates of Comparative Examples 1 and 2, aggregates presumed to be aggregated by the particulate antiviral agent or the antiviral agent were confirmed in the antiviral layer. This means that the antiviral layer is not formed in the first region and the second region. Therefore, the antiviral activity values of the antiviral substrates of Comparative Examples 1 and 2 were all at low levels.

10, 20 Anti-virus substrate 11, 21 Substrate 12, 22 Anti-virus layer 23 Hard coat layer 24 Adhesive layer 25 Release sheet

Claims (10)

An antiviral substrate provided with an antiviral layer made of an organic binder cured product containing an antiviral agent and not a photocatalyst in a region of the surface of the substrate where antiviral properties are required.
The antiviral layer is a mixture of a first region and a second region.
The first region contains more of the antiviral agent than the second region.
The surface roughness of the surface of the anti-virus layer is an anti-virus substrate having an arithmetic mean roughness (Ra) of 0.1 μm or less measured in accordance with JIS B 0601-1982. The antiviral substrate according to claim 1, wherein the antiviral agent is a copper compound. The antiviral substrate according to claim 1, wherein the antiviral agent is an organic compound that is incompatible with an organic binder. The antiviral substrate according to claim 1, wherein the antiviral agent is at least one of a polymer biguanide and a bis-type quaternary ammonium salt. The antiviral substrate according to any one of claims 1 to 4, wherein the first region is composed of a complex of an organic binder and a copper compound. The antiviral substrate according to any one of claims 1 to 5, wherein the antiviral layer is formed in a film shape on the substrate. The antiviral substrate according to any one of claims 1 to 6, wherein a hardcoat layer is provided on the surface of the substrate, and the antiviral layer is provided on the hardcoat layer. The antiviral substrate according to claim 2, wherein copper is present in the first region in an amount of 0.6 atomic% or more. The antiviral substrate according to any one of claims 1 to 8, wherein an adhesive layer is provided on the opposite side surface of the surface of the substrate on which the antiviral layer is provided. The antiviral substrate according to any one of claims 1 to 9, wherein the substrate is translucent.

Images