Functional member

The present invention relates to a functional member.

Conventionally, functional members having antifouling properties, antibacterial properties, antiviral properties, etc. have been provided by adding or applying a functional substance such as a photocatalyst to a decorative board such as a melamine functional member. ing.

Patent Document 1 discloses an antibacterial functional member in which an inorganic binder containing Al and / or Ga-doped zinc oxide particles is baked onto the surface of a substrate.

<p><patcit num="1"><text>Japanese Unexamined Patent Publication No. 2011-190155</text></patcit></p>

<p>In the example of Patent Document 1, zinc oxide particles doped with Ga or Al are dispersed in water, and this is added to an aqueous solution of water glass and mixed to prepare a spray liquid, and the spray liquid is applied to the surface of ceramic tiles. Antibacterial tiles are made by spraying and then baking. The antibacterial activity of the obtained antibacterial tile has been measured using Escherichia coli and Staphylococcus aureus. Furthermore, the antibacterial activity after immersion in warm water has been measured, and the correlation between the antibacterial activity at the initial stage and after durability and the doped metal species has been evaluated. However, the antibacterial functional members described in Patent Document 1 do not describe antiviral activity, and their performance is unknown.</p><p>The present invention has been made in view of such a problem, and provides a functional member having high antibacterial and antiviral activities and excellent long-term durability in which the antibacterial and antiviral activities do not decrease with time. The purpose is to do.</p>

<p>The functional member of the present invention is composed of a resin base material and an inorganic binder cured layer formed on the resin base material and containing a functional component, and cracks are formed in the inorganic binder cured layer. It is characterized by that.</p><p>In the functional member of the present invention, since cracks are formed in the inorganic binder cured layer containing the functional component, the apparent surface area of the inorganic binder cured layer becomes large, and bacteria, viruses and the inorganic binder cured layer become The contact area with the contained functional components is large, and the functional components inside the cracks do not easily come off even when contacted with cleaning tools or hands, so they have excellent antibacterial and antiviral activities, and their performance. It is possible to provide a functional member capable of maintaining the above for a long period of time. The term "containing the functional component" means that the functional component is retained on the surface or inside of the inorganic binder cured layer.</p><p>Furthermore, since cracks are formed in the hardened layer of the inorganic binder, the virus or a fluid containing the virus flows into the cracks, so that the virus can be trapped and contacted with the antiviral component more frequently, which is antibacterial. It is a functional member with high antiviral activity as well as activity.</p><p>In the functional member of the present invention, the width of the crack is preferably 0.1 to 1.5 μm. In the functional member of the present invention, when the width of the crack is 0.1 to 1.5 μm, the virus is easily trapped inside the crack, and the functional member has higher antiviral activity.</p><p>In the functional member of the present invention, it is desirable that the functional component contains at least one selected from the group consisting of an antibacterial component and a deodorant component in addition to the antiviral component or the antiviral component. In the functional member of the present invention, when the functional component is at least one selected from the group consisting of an antiviral component and a deodorant component in addition to an antiviral component or an antiviral component, the functionality of the present invention The member is an excellent functional member because it has excellent antiviral performance and can be imparted with antibacterial activity and deodorant performance.</p><p>In the functional member of the present invention, it is desirable that the antiviral component comprises at least one selected from the group consisting of an inorganic antiviral agent and an organic antiviral agent. In the functional member of the present invention, if the antiviral component comprises at least one selected from the group consisting of inorganic antiviral agents and organic antiviral agents, not only high antibacterial activity but also high antiviral activity is surely achieved. It is a functional member with antiviral activity.</p><p>In the functional member of the present invention, the inorganic antiviral agent is silver, copper, zinc, platinum, zinc compound, silver compound, copper compound, metal oxide particles carrying metal or metal oxide, or metal ions. It is desirable that it be at least one selected from the group consisting of ion-exchanged zeolite and a copper complex.</p><p>In the functional member of the present invention, the inorganic antiviral agent is a silver, copper, zinc, platinum, zinc compound, a silver compound, a copper compound, a metal or a metal oxide particle carrying a metal oxide, or a metal ion. When at least one selected from the group consisting of ion-exchanged zeolite and a copper complex, the antiviral agent can be in the form of particles, and the inorganic antiviral agent is the surface of the inorganic binder cured layer. It is a functional member that is easily exposed from the surface of cracks and cracks and has higher antibacterial activity and antiviral activity.</p><p>In the functional member of the present invention, the organic antiviral agent is at least one selected from the group consisting of an antiviral resin, a sulfonic acid-based surfactant, a copper alkoxide, and a bis-type quaternary ammonium salt. Is desirable.</p><p>In the functional member of the present invention, the organic antiviral agent is at least one selected from the group consisting of an antiviral resin, a sulfonic acid-based surfactant, a copper alkoxide, and a bis-type quaternary ammonium salt. Then, the organic antiviral agent easily spreads over the entire inorganic binder cured layer, and becomes an antiviral member having high antibacterial activity and antiviral activity.</p><p>In the functional member of the present invention, an inorganic antibacterial agent or an organic antibacterial agent can be used as the antibacterial component. As the inorganic antibacterial agent, Ag-based, Ag-Zn-based, Zn-based, Ag-Cu-based, and Mo-based antibacterial agents are desirable. These metals may be supported on porous inorganic particles such as zeolite. Further, as the organic antibacterial agent, a cationic surfactant such as a quaternary ammonium salt or an amphoteric surfactant such as alkyldiaminoethylglycine hydrochloride is desirable. In the functional member of the present invention, the deodorant component is preferably composed of a platinum-supported titania catalyst, a copper-supported titania catalyst, an iron-supported titania catalyst, or an adsorptive substance and a photocatalyst supported on the adsorptive substance. .. In the functional member of the present invention, the deodorant component comprises a platinum-supported titania catalyst, a copper-supported titania catalyst, an iron-supported titania catalyst, or an adsorptive substance and a photocatalyst supported on the adsorptive substance. Then, the deodorant component is easily dispersed in the inorganic binder cured layer, and the malodorous component is decomposed by the photocatalyst to obtain a functional member having excellent deodorizing performance.</p><p>In the functional member of the present invention, the adsorptive substance is at least one selected from the group consisting of aluminum oxide, silicon oxide, magnesium oxide, zinc oxide, zirconium oxide, activated carbon, zeolite, mordenite, hydrotalcite and metallic phthalocyanine. The photocatalyst is preferably a titania, a nitrogen-doped titania catalyst, a sulfur-doped titania catalyst, a carbon-doped titania catalyst, tungsten oxide, or a lanthanoid-based perovskite composite oxide. </p><p>In the functional member of the present invention, the adsorptive substance is at least one selected from the group consisting of aluminum oxide, silicon oxide, magnesium oxide, zinc oxide, zirconium oxide, activated carbon, zeolite, mordenite, hydrotalcite and metallic phthalocyanine. If the photocatalyst is a titania, nitrogen-doped titania catalyst, sulfur-doped titania catalyst, carbon-doped titania catalyst, tungsten oxide, or lanthanoid-based perovskite composite oxide, the functionality is surely excellent in deodorizing performance. The member can be realized.</p><p>In the functional member of the present invention, the inorganic binder used for forming the cured inorganic binder layer is preferably at least one selected from the group consisting of silica sol, alumina sol, titania sol, zirconia sol and sodium silicate.</p><p>In the functional member of the present invention, when the inorganic binder used for forming the inorganic binder cured layer is at least one selected from the group consisting of silica sol, alumina sol, titania sol, zirconia sol and sodium silicate, the resin group. It is possible to form an inorganic binder cured layer that has excellent adhesion to the material, is difficult to peel off even when a cleaning tool or a hand comes into contact with the material, and the functional component is hard to fall off.</p><p>In the functional member of the present invention, it is desirable that the resin base material comprises a base material and a surface resin layer laminated on one surface or both sides of the base material.</p><p>In the functional member of the present invention, when the resin base material is composed of a base material and a surface resin layer laminated on one surface or both sides of the base material, in addition to antiviral activity and antiviral activity. It can be used as a decorative board having excellent antibacterial and deodorant performance.</p>

<figref num="1">FIG. 1 is a cross-sectional view schematically showing an embodiment of the functional member of the present invention.</figref><figref num="2">FIG. 2 is a cross-sectional view schematically showing another embodiment of the functional member of the present invention.</figref><figref num="3">3 (a) to 3 (f) are cross-sectional views schematically showing an embodiment of the method for manufacturing a functional member of the present invention.</figref><figref num="4">FIG. 4 is a cross-sectional SEM photograph of the functional member (decorative board) produced in Example 1.</figref><figref num="5">FIG. 5 is a cross-sectional SEM photograph of the functional member (decorative board) produced in Comparative Example 1.</figref>

(Detailed Description of the Invention) Hereinafter, the functional member of the present invention will be described in detail. The functional member of the present invention comprises a resin base material and an inorganic binder cured layer formed on the resin base material and containing a functional component, and cracks are formed in the inorganic binder cured layer. It is characterized by that.

In the functional member of the present invention, since cracks are formed in the inorganic binder cured layer containing the functional component, the apparent surface area of the inorganic binder cured layer becomes large and is contained in the virus and the inorganic binder cured layer. The contact area with the functional component becomes large, and the functional component inside the crack does not easily come off even when contacted by a cleaning tool or hand, so it has excellent antibacterial and antiviral activities, and its performance is maintained over the long term. It is possible to provide a functional member that can be maintained.

Further, since cracks are formed in the hardened layer of the inorganic binder, the fluid containing the virus flows into the cracks, so that the virus can be trapped and the functional member has high antiviral activity.

FIG. 1 is a cross-sectional view schematically showing an embodiment of the functional member of the present invention. As shown in FIG. 1, in the functional member 10 of the present invention, an inorganic binder curing layer 12 containing particles 13 of functional components is formed on the surface of the resin base material 11, and the inorganic binder curing layer 12 is formed. In, a plurality of cracks 14 are formed. In FIG. 1, the particles 13 of the functional component are in the form of particles, but the functional component may be uniformly dissolved in the inorganic binder cured layer 12.

The resin base material constituting the functional member of the present invention is not particularly limited, and may be a resin sheet made of various resins, or a decorative plate or the like used for various purposes. ..

Examples of the material of the resin sheet include polyester resin, acrylic resin, polycarbonate resin, silicone resin, polyamide resin, polyphenylene ether resin, melamine resin, diallyl phthalate (DAP) resin, polyethylene, polypropylene, cycloolefin polymer and the like. Examples thereof include olefin resin, vinyl chloride resin, epoxy resin, urethane resin, phenol resin, fluororesin, and guanamine resin.

The above-mentioned decorative board is composed of a base material and a surface resin layer laminated on one surface or both sides of the above-mentioned base material. The base material used for the decorative board is not particularly limited, and a non-combustible 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 sheets. As the core paper, for example, aluminum hydroxide papermaking 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 base material.

The magnesia cement non-combustible plate can be used alone, or can be laminated and arranged in the center of the core paper to form a base material. Magnesia cement non-combustible plate is magnesium oxide (MgO) and magnesium chloride (MgCl)₂) Are mixed, and aggregate and water are added and kneaded, and the mixture is formed 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.

Melamine resin is a resin with 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, hexamethylol melamine (hereinafter referred to as "methylolated 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 is at least one selected from calcium carbonate, titanium oxide, aluminum hydroxide, talc, clay and kaolin. The above 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.

FIG. 2 is a cross-sectional view schematically showing another embodiment of the functional member of the present invention. In the functional member 20 of the present invention shown in FIG. 2, the resin base material 21 is composed of the base material 21a and the surface layer resin layer 21b formed on one surface of the base material 21a, and the resin base material 21 is composed of the surface layer resin layer 21b. An inorganic binder cured layer 22 in which functional components are uniformly dissolved is formed on the surface of the inorganic binder cured layer 22, and a plurality of cracks 24 are formed on the inorganic binder cured layer 22. In FIG. 2, as described above, the functional components are uniformly dissolved and dispersed in the inorganic binder cured layer 22.

In the functional member of the present invention, the width of the crack is not particularly limited, but is preferably 0.1 to 1.5 μm. In the functional member of the present invention, when the crack width is 0.1 to 1.5 μm, it is sufficiently wider than the size of pathogenic viruses such as influenza virus and norovirus, so that the virus inactivity is equal to or equal to -3.00. It becomes a value excellent in antiviral activity, and becomes a functional member having sufficient antiviral activity.

If the width of the crack is less than 0.1 μm, the width of the crack is too narrow and it is difficult for the virus to be trapped inside the crack. On the other hand, if the width of the crack exceeds 1.5 μm, not only the design is deteriorated but also the design is deteriorated. Fine foreign matter is likely to get inside the crack, making it difficult for viruses to be trapped.

The mode of the crack is not particularly limited, but as shown in FIG. 1, the crack is connected from the surface of the inorganic binder cured layer to the surface of the resin substrate, or from the surface of the resin substrate to the inorganic binder cured layer. It exists connected to the surface. Further, it is desirable that the surface of the inorganic binder cured layer is connected to the vicinity of the antiviral component or the antiviral component, or the vicinity of the antiviral component or the antiviral component is connected to the surface of the inorganic binder cured layer. ..

The virus inactivity is a numerical value indicated by the common logarithm log (1-X) when the amount of the original virus is 1 and the relative amount of the virus deactivated after the virus deactivation process is X. (Indicated by a negative value), and the larger the absolute value, the higher the ability to inactivate the virus. For example, if 99.9% of the original virus is inactivated, the virus inactivity is expressed as log (1-0.999) =-3.00. The ratio of the amount of virus deactivated after virus deactivation processing to the total amount of virus before virus deactivation processing is expressed in% (99.9% in the above case) is called virus inactivation degree.

The width of the cracks in the inorganic binder cured layer can be obtained by dividing the functional member in the thickness direction and then calculating the average value of each from a cross-sectional photograph taken by a scanning electron microscope (SEM). The crack width of the inorganic binder cured layer is obtained by calculating the average value of the crack widths of the cracks generated in the inorganic binder cured layer at any 10 positions. Specifically, the maximum width and the minimum width are measured by focusing on one vertical crack, the average is taken as the width of the crack, and the same measurement is performed for the other nine vertical cracks. The average crack width is measured by calculating the average for a total of 10 cracks.

In the functional member of the present invention, it is desirable that the functional component contains at least one selected from the group consisting of an antibacterial component and a deodorant component in addition to the antiviral component or the antiviral component.

It is desirable that the functional member of the present invention contains at least one selected from the group consisting of an inorganic antiviral agent and an organic antiviral agent as the antiviral component. The inorganic binder cured layer may contain only one type of the above-mentioned inorganic antiviral agent, may contain two or more types of the above-mentioned inorganic antiviral agent, and may contain the above-mentioned organic antiviral agent. Only one type of agent may be contained, or two or more types of organic antiviral agents may be contained. Further, the inorganic binder cured layer may contain two or more kinds of the inorganic antiviral agent and the inorganic antiviral agent in total.

In the functional member of the present invention, the inorganic antiviral agent is silver, copper, zinc, platinum, zinc compound, silver compound, copper compound, metal oxide particles carrying metal or metal oxide, or metal ions. It is desirable that it be at least one selected from the group consisting of ion-exchanged zeolite and a copper complex.

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

As the metal oxide fine particles carrying the metal or metal oxide contained in the inorganic binder cured layer, for example, titanium oxide, tungsten oxide and the like, platinum group such as platinum, palladium, rhodium and ruthenium, iron and copper. , Silver and the like, and specific examples thereof include platinum-supported titania catalyst, copper-supported titania catalyst, iron-supported titania catalyst, nitrogen-doped titania catalyst, sulfur-doped titania catalyst, carbon-doped titania catalyst, and tungsten oxide. Examples of the copper-supported titania catalyst include CuO / TiO described in JP-A-2006-232729.₂Anatase-type titanium oxide containing copper in the range of (% by weight) = 1.0 to 3.5, cuprous oxide (copper (I) oxide: Cu) described in JP2012-210557₂A photocatalyst composition in which O) and titanium oxide are compounded, titanium oxide having a mixture containing a monovalent copper compound and a divalent copper compound described in JP-A-2013-166705 on its surface, and Titanium Oxide, which is published internationally. Examples thereof include copper and titanium-containing compositions containing titanium oxide containing crystalline rutile-type titanium oxide and a divalent copper compound described in 2013/094573.

Further, as the inorganic antiviral agent, particles of a metal oxide or a metal hydrate containing at least one metal selected from silver, copper, zinc, titanium and the like can also be used. Specific examples of the inorganic antiviral 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, alumina with at least one of the ions and copper ions, silica with at least one of nanosilver and copper, 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, and calcium phosphate in which at least one of nanosilver and copper is supported. Zeolites exchanged for at least one of silver and copper ions may be further exchanged for other metal ions such as zinc ions.

The shape of the inorganic antiviral agent is not particularly limited, but it is preferably in the form of particles, and at least a part of the particulate antiviral agent is exposed from the surface of the inorganic binder cured layer. Is desirable. This is because it is easy to come into contact with bacteria and viruses, and the antibacterial activity and antiviral activity are likely to be high.

In the functional member of the present invention, when the inorganic antiviral agent is in the form of particles, it is desirable that the average particle size of the particles of the inorganic antiviral agent is 0.1 to 10 μm. If the average particle size of the particles of the inorganic antivirus agent is small, it is difficult to expose the particles of the inorganic antivirus agent to the surface of the inorganic binder cured layer even if the film thickness of the inorganic binder cured layer is reduced, and the inorganic binder is inorganic. Since the particles of the anti-virus agent are buried inside the hardened layer of the inorganic binder, it becomes difficult for the particles of the inorganic anti-virus agent to exert their original functions. On the other hand, if the average particle size of the particles of the inorganic antiviral agent is large, not only the design of the functional member is deteriorated, but also it is difficult to fix the particles of the inorganic antiviral agent to the cured inorganic binder layer, which is inorganic. Since the particles of the antiviral agent are easily shed from the inorganic binder cured layer, it becomes difficult to exhibit antiviral property and its long-term durability as a result.

In the decorative board of the present invention, the amount of particles of the inorganic antiviral agent contained in the inorganic binder cured layer is 0.01 to 10 g / m.²Is desirable, 0.02 ~ 5g / m²Is more desirable. The amount of particles of the inorganic antiviral agent contained in the inorganic binder cured layer is 0.01 to 10 g / m.²If this is the case, the antiviral function can be exhibited without deteriorating the design of the decorative board due to discoloration or the like. The amount of particles of the inorganic antiviral agent contained in the inorganic binder cured layer is 0.01 g / m.²If it is less than, the amount of particles of the inorganic antiviral agent is too small, and it is difficult to obtain sufficient antiviral activity and antibacterial activity. On the other hand, the amount of particles of the inorganic antiviral agent contained in the inorganic binder cured layer is 10 g / m.²If it exceeds, the design of the decorative board is likely to be deteriorated by the particles of the inorganic antiviral agent.

In the functional member of the present invention, the organic antiviral agent is at least one selected from the group consisting of an antiviral resin, a sulfonic acid-based surfactant, a copper alkoxide, and a bis-type quaternary ammonium salt. Is desirable.

In the functional member of the present invention, examples of the organic antiviral agent include halocarban, chlorophenesine, lysozyme chloride, alkyldiaminoethylglycine hydrochloride, isopropylmethylphenol, timole, hexachlorophene, velverine, thioxolone, salicylic acid and Derivatives of them, benzoic acid, sodium benzoate, paraoxybenzoic acid ester, parachlormethacresol, benzalkonium chloride, phenoxyethanol, isopropylmethylphenol, phenolic acid, sorbic acid, potassium sorbate, hexachlorophene, chlorhexidine chloride, trichlorocarbani Lido, thiantol, hinokithiol, triclosan, trichlorohydroxydiphenyl ether, chlorhexidine phenolate, phenoxyethanol, resorcin, azulene, salicylic acid, zincpyrythion, mononitroguayacol sodium, uikyo extract, sansho extract, cetylpyridinium chloride, benzethonium chloride and undecylene acid derivatives, Examples thereof include alkylbenzene sulfonic acid or a salt thereof. Of these, alkylbenzene sulfonic acid or a salt thereof is preferable.

In the functional member of the present invention, the antiviral resin comprises an acidic functional group and a resin substrate. 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 substrate 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 antiviral 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 be used to obtain an antiviral 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 decorative board of the present invention, the antiviral resin composed of the acidic functional group and the resin substrate is not particularly limited, but for example, the cation exchange resin may be used as it is or after being pulverized to be finely divided. it can. The cation exchange resin also has an acidic functional group on the resin substrate, and can be used as the antiviral resin of the present invention.

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

<chemistry num="1"><img file="JP2020040267A_D0001.tif" /></chemistry>(In the above general formula (1), R¹And R²Are alkyl groups that may be the same or different, R³Is an organic group that may contain ether bonds, X^-Indicates a halogen anion. )

<chemistry num="2"><img file="JP2020040267A_D0002.tif" /></chemistry>(In the above general formula (2), R⁴Represents an alkyl group that may have a functional group, R⁵, R⁶, R⁷, R⁸, R⁹And R¹⁰Represents an 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 above general formula (1), X^-For example, Cl^-, Br^-, I^-And so on. R¹, R²Is 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), R³The organic group represented by is -CO-O- (CH).₂)₆-O-CO-, -CONH- (CH₂)₆-CO-, -NH-CO- (CH₂)₄-CO-NH-, -S-Ph-S-, -CONH-Ph-NHCO-, -NHCO-Ph-CONH-, -O- (CH₂)₆-O- or -CH²-O- (CH₂)₄-O-CH₂-(However, Ph represents a phenylene group.) It is desirable that it is represented by.

Specifically, examples of the bis-type pyridinium salt include those represented by the following general formulas (3) to (10).<chemistry num="3"><img file="JP2020040267A_D0003.tif" /></chemistry>In the above general formula (3), R¹¹Is C_nH_{2n + 1}It is an alkyl group represented by, and n is preferably 8, 10, 12, 14, 16 or 18. In addition, m is preferably 3, 4, 6, 8, and 10. Substituents R of the compounds shown below¹¹The same applies to.

<chemistry num="4"><img file="JP2020040267A_D0004.tif" /></chemistry>

<chemistry num="5"><img file="JP2020040267A_D0005.tif" /></chemistry>

<chemistry num="6"><img file="JP2020040267A_D0006.tif" /></chemistry>

<chemistry num="7"><img file="JP2020040267A_D0007.tif" /></chemistry><chemistry num="8"><img file="JP2020040267A_D0008.tif" /></chemistry>

<chemistry num="9"><img file="JP2020040267A_D0009.tif" /></chemistry>

<chemistry num="10"><img file="JP2020040267A_D0010.tif" /></chemistry>

As the bis-type pyridinium salt, 1,1'-didecyl-3,3'-[butane-1,4-diylbis (oxymethylene)] dipyridinium = dibromid represented by the following chemical formula (11) is used. Especially desirable.<chemistry num="11"><img file="JP2020040267A_D0011.tif" /></chemistry>

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).<chemistry num="12"><img file="JP2020040267A_D0012.tif" /></chemistry>

Next, the bis-type quinolinium salt will be described. As the bis-type quinolinium salt, the pyridinium group represented by the following chemical formula (13) constituting the bis-type pyridinium salt represented by the general formulas (3) to (10) is shown in the chemical formula (14). Examples thereof include a bis-type quinolinium salt having a chemical structure substituted with a quinolium group. 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).

<chemistry num="13"><img file="JP2020040267A_D0013.tif" /></chemistry>

<chemistry num="14"><img file="JP2020040267A_D0014.tif" /></chemistry>

Furthermore, the compound represented by the general formula (2) used in the present invention will be described.<chemistry num="15"><img file="JP2020040267A_D0015.tif" /></chemistry>In the above general formula (2), R⁴Indicates 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. Also, R⁵, R⁶, R⁷, R⁸, R⁹And R¹⁰Represents an alkyl group, and the 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 organic antiviral agent can be uniformly dissolved in the inorganic binder cured layer by directly dissolving it in an inorganic binder or by dissolving it in a solvent or the like and then adding it to the inorganic binder, and has high antibacterial activity. , It becomes an antiviral member having antiviral activity. If the organic antiviral agent does not dissolve in the hardened inorganic binder layer, it may be uniformly dispersed.

In the functional member of the present invention, the deodorant component is a platinum-supported titania catalyst, a palladium-supported titania catalyst, a silver-supported titania catalyst, an iron-supported titania catalyst, or an adsorptive substance and a photocatalyst supported on the adsorptive substance. It is desirable to consist of. The platinum-supported titania catalyst, the palladium-supported titania catalyst, the silver-supported titania catalyst, and the iron-supported titania catalyst may be directly supported on the hardened inorganic binder layer, in which case the catalyst decomposes malodorous gas.

When the functional member is composed of an adsorptive substance and a photocatalyst supported on the adsorptive substance, the adsorptive substance is aluminum oxide, silicon oxide, magnesium oxide, zinc oxide, zirconium oxide, activated carbon, zeolite, and the like. It is at least one selected from the group consisting of mordenite, hydrotalcite and metallic phthalocyanine, and the photocatalyst is preferably titania, nitrogen-doped titania catalyst, sulfur-doped titania catalyst, carbon-doped titania catalyst, and tungsten oxide.

The adsorptive substance is preferably a porous material, and is preferably a functional member in which a photocatalyst is supported on the surface of the adsorptive substance which is such a porous material. This is because the porous material secures a function of adsorbing a large amount of malodorous gas into the pores, so that the malodorous gas is easily adsorbed, and the malodorous gas can be decomposed by a photocatalyst.

In the functional member of the present invention, the inorganic binder used for forming the cured inorganic binder layer 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 above-mentioned 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 antiviral component to be added, and the antiviral component can be selected. Can be obtained as a mixed composition in which is uniformly dissolved or dispersed.

In the functional member of the present invention, it is desirable that the inorganic binder cured layer further contains a dried or cured body of an inorganic polymer. Specifically, it is more desirable that the inorganic binder cured layer further contains a dried or cured body of an inorganic polymer containing siloxane. When the inorganic binder cured layer contains a dried or cured body of an inorganic polymer containing siloxane, the surface lubricity and feel of the inorganic binder cured layer are improved, and the functional durability against physical loads such as cleaning is improved. It can be made more sexual.

Examples of the siloxane-containing inorganic polymer include silicone oil and a silane coupling agent. These may be one kind or two or more kinds. Further, as the inorganic polymer containing siloxane, for example, a commercially available product such as "My Block Wako 101" (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) can be used. By adjusting the blending amount of this inorganic polymer, the coefficient of thermal expansion of the cured inorganic binder can be changed, and the difference in the coefficient of thermal expansion between the cured inorganic binder and the resin substrate can be adjusted to introduce cracks. ..

The functional member of the present invention may contain only an antiviral component, and may contain at least one selected from the group consisting of an antibacterial component and a deodorant component in addition to the antiviral component. Good.

Although the functional member of the present invention is in the form of a sheet, it can be used for, for example, interior materials of buildings and toilets, wall materials, doors, office equipment, furniture, etc., and has high antibacterial properties against these members. It can impart activity, antiviral activity and deodorant performance.

Next, a method for manufacturing the above-mentioned functional member will be described. The method for manufacturing the functional member is not particularly limited, but for example, it can be manufactured by the following method. In the following manufacturing method, first, an inorganic binder layer for transfer, which is an inorganic binder curing layer containing a functional component, is formed on the surface of the transfer film. Subsequently, transfer is performed on the surface of the resin base material, and an inorganic binder layer for transfer containing a functional component is transferred to the surface of the resin base material, and if necessary, heating and pressurization are performed to cure the resin base material. Form an inorganic binder cured layer containing a functional component.

When forming a transfer inorganic binder layer containing particles of a functional component (for example, particles of an inorganic antiviral agent) on the surface of a transfer film, first, particles of the functional component are formed on the surface of the transfer film. May be followed by forming an inorganic binder layer for transfer containing particles of functional components. When the functional component is an organic antiviral agent, etc., an inorganic binder containing the functional component is applied to the resin base material and cured to directly cure the inorganic binder containing the functional component. May be formed.

3 (a) to 3 (f) are cross-sectional views schematically showing an embodiment of the method for manufacturing a functional member of the present invention.

In the method for producing a functional member of the present invention, a coating liquid (mixed composition) containing an inorganic binder and a functional component is sprayed on the surface of a transfer film 36 (see FIG. 3A), or is used. , Bar coater, brush, roll, etc., apply the above coating liquid to the surface of the transfer film 36 (see FIG. 3 (a)). When the functional component is in the form of particles, coating using a spray or a coat bar is desirable from the viewpoint that the particles, which are the functional component, can be coated uniformly and with little overlap. In this case, the amount of particles of the upper functional component sprayed on the surface of the transfer film 36 is 0.1 to 20 g / m.²Is desirable. It is desirable that the coating liquid further contains an inorganic polymer containing siloxane in addition to the inorganic binder.

When the functional component is in the form of particles, the liquid containing the inorganic binder, siloxane, and the like may be applied again after the above step. This is because not only the particulate functional component is less likely to fall off from the coating base material, but also the feel of the surface can be smoothed.

In the method for producing a functional member of the present invention, it is desirable that the coating liquid is applied to the surface of the transfer film and then the coating liquid is naturally dried. By the above-mentioned natural drying, a transfer inorganic binder layer 32'containing the functional component particles 33 can be formed on the transfer film 36 (see FIG. 3 (b)). As shown in FIG. 2, the transfer inorganic binder layer 32'may be a layer in which the functional components are uniformly dissolved.

In the method for producing a functional member of the present invention, for example, a biaxially stretched polypropylene (OPP) film, a polyethylene terephthalate (PET) film or the like can be used as the transfer film 36. The transfer film 36 is peeled off after transfer.

It is desirable that the surface of the transfer film on the side forming the transfer inorganic binder layer is subjected to a corona discharge treatment. Therefore, as the transfer film, it is desirable to use an OPP film or a PET film whose surface has been subjected to a corona discharge treatment.

The surface of the transfer film on the side where the inorganic binder layer for transfer is formed may be matted, but the surface roughness Rmax of the transfer film is preferably 5 μm or less. This is because if the surface roughness of the transfer film is large, fine irregularities are generated on the surface of the decorative plate, and the design and feel are likely to be deteriorated. The matte treatment is a treatment for forming irregularities on the surface.

Next, as shown in FIG. 3C, the transfer inorganic binder layer 32'is a surface resin layer on the resin base material 31 in which the resin-impregnated paper serving as the surface resin layer 31b is laminated on the surface of the base material 31a. The transfer film 36 is laminated on the surface resin layer 31b so as to be in contact with 31b.

As described in the section of the functional member of the present invention, the resin base material may be a single resin sheet, and the surface layer resin layer 31b is formed on the surface of the base material 31a as described above. It may be a resin base material (decorative board) 31 on which resin-impregnated paper is laminated.

Subsequently, as shown in FIG. 3D, a transfer inorganic binder layer 32'containing the functional component particles 33 is formed on the surface of the resin base material 31 composed of the base material 31a and the surface resin layer 31b. The transferred transfer film 36 is placed so that the transfer inorganic binder layer 32'is in contact with the surface resin layer 31b, and then pressure-bonded and hot-press molded. As a result, as shown in FIG. 3 (e), the inorganic binder cured layer 32 containing the functional component can be formed on the resin base material 31 composed of the base material 31a and the surface layer resin layer 31b, and the inorganic binder can be formed. The cured layer 32 can be adhered to the surface resin layer 31b of the resin base material 31.

When the resin base material used in the present invention is a decorative board, the method for forming the surface resin layer on the surface of the base material is not particularly limited, and can be performed by a general method. As a specific method for forming the surface resin layer, for example, a resin-impregnated paper such as melamine resin is laminated on one side or both sides of a base material made of a laminated body of core paper, and a resin-impregnated paper such as melamine resin is laminated. Examples thereof include a method of hot-press molding a base material. When the above method is used, the melamine resin of the melamine resin-impregnated paper permeates the core paper, and the curing reaction proceeds there to develop the adhesive force of the melamine resin-impregnated paper to the core paper.

The temperature of the veneer can be 125 to 150 ° C as the heating condition for hot pressure molding, and 1.96 to 9.80 MPa (20 to 100 kg / cm) as the pressurizing condition.²) Can be. When the temperature is less than 125 ° C or the pressure is less than 1.96 MPa, the adhesion of the resin-impregnated paper to the base material is insufficient, and peeling is likely to occur. On the other hand, if the temperature exceeds 150 ° C or the pressure exceeds 9.80 MPa, discoloration and visible large cracks may occur. In the present invention, the surface resin layer 31b is formed and the inorganic binder cured layer 32 in which a plurality of cracks 34 are formed is formed by the thermal pressure molding.

The resin base material used in the method for producing a functional member of the present invention, the functional component contained in the coating liquid, the inorganic binder, and the inorganic polymer containing siloxane have been described in detail in the functional member of the present invention. The detailed description thereof will be omitted here.

Then, by removing the transfer film 36 by peeling or the like, as shown in FIG. 3 (f), it is formed on the resin base material 31 (base material 31a and surface layer resin layer 31b) and the resin base material 31. The functional member 30 of the present invention is composed of an inorganic binder cured layer 32 containing a functional component (particles 33 of the functional component), and a plurality of cracks 34 are formed in the inorganic binder cured layer 32. can get.

Hereinafter, examples in which the present invention is disclosed more specifically will be shown. The present invention is not limited to these examples.

(Example 1) (Primary melamine impregnation step) A paper roll having a thickness of 0.2 to 0.3 mm was immersed in a solution containing a melamine resin. The roll paper was impregnated with the melamine resin by passing the roll paper while immersing it in the solution so that the temperature of the solution was 20 ° C. and the immersion time was 2 minutes. The moving speed of the roll paper was 10 to 20 cm / sec.

(Drying step) The roll paper passed through the melamine solution was dried from a dryer at a temperature of 100 ° C. and a drying time of 30 seconds.

(Secondary melamine impregnation step) The paper roll that had undergone the drying step was immersed in a solution made of melamine resin. The paper roll was impregnated with the melamine resin by passing the roll paper while immersing it in the solution so that the temperature of the solution was 20 ° C. and the immersion time was 30 minutes. The moving speed of the roll paper was 10 to 20 cm / sec.

(Drying / cutting step) The roll paper passed through the melamine solution was dried from a dryer at a temperature of 100 ° C. and a drying time of 2 hours. After drying, it was cut into 300 mm × 300 mm to obtain a melamine resin-impregnated paper.

[Formation process of inorganic binder layer for transfer 1 (process of adhering particles of functional components to the surface of transfer film)]

As the particles of the functional component, silver ion and zinc ion exchange zeolite powder (Zeomic AK-10N manufactured by Sinanen Zeomic) with an average particle diameter of 2.5 μm and silica sol (SiO)₂A spray solution consisting of a methanol mixed composition containing My Block Wako 101 (solid content concentration: 25 wt%) and My Block Wako 101 (solid content concentration: 25 wt%) in a weight ratio of 420: 20: 1 was prepared. 566.1 g / m with methanol dispersion medium on the surface of an OPP film with a size of 300 x 300 mm that has been subjected to corona discharge treatment by filling the spray with the spray liquid at room temperature.²The mixed composition corresponding to the above was sprayed in a mist form at an air pressure of 0.3 MPa, and zeolite particles carrying silver ions and zinc ions, which are particles of functional components, were adhered to the surface of the OPP film.

[Formation process of inorganic binder layer for transfer part 2 (Formation of layer containing only inorganic binder)]

Silica sol (SiO) on the surface of OPP film (transfer film) to which particles of functional components are attached.₂A coating solution prepared by mixing My Block Wako 101 (solid content concentration 25 wt%) and methanol at a weight ratio of 20: 1:10 was applied using a coat bar with a count of 4 and then at room temperature. A transfer film in which an inorganic binder layer for transfer containing particles of functional components was fixed on the surface of the OPP film was produced by air-drying with.

(Combination step) Four sheets of phenol resin-impregnated core paper having a thickness of 0.3 to 0.4 mm were laminated, and melamine resin-impregnated paper was laminated on the four sheets. Further, the transfer film is laminated on the melamine resin impregnated paper so that the transfer inorganic binder layer is in contact with the melamine resin impregnated paper, and the temperature is 143 ° C and the press pressure is 80 kg / cm.², Thermocompression bonding was performed with a pressing time (including heating time) of 50 minutes. Further, a functional member (decorative board) in which an inorganic binder curing layer containing particles of functional components is formed on the surface of a resin base material in which an OPP film is peeled off and a surface resin layer is laminated on the base material is formed. Made.

FIG. 4 is a cross-sectional SEM photograph of the functional member produced in Example 1. From FIG. 4, it can be confirmed that the inorganic binder curing layer 32 containing the particles 33 of the functional component is arranged on the melamine resin layer which is the surface resin layer 31b. Further, as shown in FIG. 4, cracks are formed in the hardened layer of the inorganic binder, and when the fluid containing the virus flows into the cracks, the virus exists in the vicinity of the antiviral component or the antiviral component (functional component). It is trapped in the cracks connected to the particles 33), and its antiviral activity is enhanced.

(Comparative Example 1) A melamine resin-impregnated paper was obtained by performing a primary melamine impregnation step, a drying step, a secondary melamine impregnation step, and a drying / cutting step in the same manner as in Example 1.

[Formation process of inorganic binder layer for transfer 1 (process of adhering particles of functional components to the surface of transfer film)]

As the particles of the functional component, silver ion and zinc ion exchange zeolite powder (Zeomic AK-10N manufactured by Sinanen Zeomic) with an average particle diameter of 2.5 μm and silica sol (SiO)₂A spray solution consisting of a methanol mixed composition containing My Block Wako 101 (solid content concentration: 25 wt%) and My Block Wako 101 (solid content concentration: 25 wt%) in a weight ratio of 110: 10: 1 was prepared. 566.6 g / m with methanol dispersion medium on the surface of an OPP film with a size of 300 x 300 mm that has been subjected to corona discharge treatment by filling the spray with the spray liquid at room temperature.²The mixed composition corresponding to the above was sprayed in a mist form at an air pressure of 0.3 MPa, and zeolite particles carrying silver ions and zinc ions, which are particles of functional components, were adhered to the surface of the OPP film.

[Formation process of inorganic binder layer for transfer part 2 (Formation of layer containing only inorganic binder)]

A coating liquid in which My Block Wako 101 (solid content concentration 25 wt%) and methanol are mixed at a weight ratio of 1: 1 is applied to the surface of the OPP film (transfer film) to which the particles of the functional component are attached. A transfer film in which an inorganic binder layer for transfer containing particles of functional components was fixed on the surface of the OPP film was prepared by applying the film using the No. No. coat bar and then naturally drying it at room temperature.

After that, a combination step is performed in the same manner as in Example 1, and a functional member in which an inorganic binder cured layer containing particles of functional components is formed on the surface of a resin base material in which a surface resin layer is laminated on the base material ( Decorative board) was produced.

FIG. 5 is a cross-sectional SEM photograph of the functional member produced in Comparative Example 1. As shown in FIG. 5, no cracks are formed in the hardened inorganic binder layer.

(Evaluation of design) When the appearance of the functional members (decorative board) produced in each Example and Comparative Example was visually observed, it was confirmed that there was no problem in any of them.

(Evaluation of antiviral property) In order to evaluate the antiviral property of the functional member (decorative board) produced in each Example and Comparative Example, JIS R 1756 The antiviral property was measured by a modified method of the antiviral property test method of the visible light responsive photocatalytic material. The modification is that "1000 lux light irradiation for 4 hours" is changed to "leaving under indoor fluorescent light (about 300 lux)". The measurement result is expressed by the virus concentration inactivated against Escherichia coli. Here, the concentration of the virus inactivated against Escherichia coli (virus inactivation degree) was used as an index of the virus concentration. Virus inactivity is an antiviral test using bacteriophage. Phagevirus Qβ concentration: 8.3 million cells / milliliter is used to measure the concentration of a virus that can infect Escherichia coli. On the other hand, it is the result of calculating the concentration of the inactivated virus. That is, the virus inactivity is the degree of concentration that cannot infect Escherichia coli with respect to the concentration of phage virus Qβ, and (phage virus Qβ concentration-concentration of virus that can infect Escherichia coli) / (phage virus). It can be calculated by (Qβ concentration) x 100. It can be said that the higher the virus inactivity value (the higher the absolute value of the virus inactivity), the higher the antiviral activity.

Further, as described above, the virus inactivity can be calculated from the virus inactivity. The virus inactivity is a numerical value (negative) indicated by the common logarithm log (1-X) when the amount of the original virus is 1 and the relative amount of the virus deactivated after the virus deactivation process is X. (Indicated by the value), and the larger the absolute value, the higher the ability to inactivate the virus. For example, if 99.9% of the original virus is inactivated, the virus inactivity is expressed as log (1-0.999) =-3.00. The ratio of the amount of virus deactivated after virus deactivation processing to the total amount of virus before virus deactivation processing is expressed in% (99.9% in the above case) is called virus inactivation degree. As described above, the virus inactivity was determined from the virus inactivity. The results are shown in Table 1.

(Evaluation of antiviral property using feline calicivirus) This antiviral property test was conducted as follows. In order to evaluate the antiviral property of the functional member (decorative board) obtained in Example 1, 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 have been 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 functional member (decorative board) obtained in Example 1, and the concentration of feline calicivirus that has lost the ability to infect CRFK cells is displayed as the degree of feline calicivirus inactivity. .. Here, the concentration of the virus inactivated to CRFK cells (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) The functional member (decorative board) obtained in Example 1 was cut into a square with a side of 50 mm square, and the test sample was placed in a sterilized plastic petri dish, and the test virus solution (&gt; 10) was placed.⁷Inoculate 0.4 mL of PFU / mL). Test virus solution is 10⁸Use a PFU / mL stock diluted 10-fold with purified water. (2) Prepare a 50 mm square polyethylene film as a control material and inoculate the virus solution in the same manner as the test sample.

(3) Cover the inoculated virus solution with 40 mm square polyethylene, inoculate the test virus solution evenly, and then react at 25 ° C for 24 hours. (4) Immediately after inoculation or after the reaction, add 10 mL of SCDLP medium and wash away the virus solution. (5) Obtain the virus infection value according to JIS L 1922 Annex B.

(6) Calculate the antiviral activity value using the following formula. Mv = Log (Vb / Vc) = Log (Vb) -Log (Vc) Mv: Antiviral activity value Log (Vb): Log of infection value after 24-hour reaction of polyethylene film Log (Vc): Of test sample Logarithmic reference standard for infection value after 24-hour reaction JIS L 1922, JIS Z 2801 The measurement method was based on the plaque measurement method. In addition, Feline calcivirus; Strain: F-9 ATCC VR-782 was used as the test virus. The obtained antiviral activity values are shown in Table 1.

(Evaluation of antibacterial properties using Staphylococcus aureus) Evaluation of antibacterial properties using Staphylococcus aureus was carried out as follows. (1) The functional member (decorative board) obtained in Example 1 was cut into a square of 50 mm square, and a test sample was placed in a sterilized plastic petri dish, and a test bacterial solution (number of bacteria 2.5 × 10) was placed.⁵~10×10⁵/ mL) is inoculated with 0.4 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 the cultured bacteria are further transplanted into the incubator at a temperature of 35 ± 1 ° C for 16 to 20 hours. Use the pre-cultured product prepared appropriately with 1/500 NB medium. (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 hours. (4) Immediately after inoculation or after the reaction, add 10 mL of SCDLP medium and wash out the test bacterial solution. (5) Dilute the washout solution appropriately, mix it with standard agar medium to prepare a petri dish for measuring viable cell count, incubate at a temperature of 35 ± 1 ° C for 40 to 48 hours, and then measure the number of colonies. (6) Calculation of viable cell count Calculate the viable cell count using the following formula. N = C × D × VN: Number of viable bacteria C: Number of colonies D: Dilution factor V: Volume of SCDLP medium used for washing (mL) (7) Calculate the antibacterial activity value using the following formula. R = (U_t-U₀) (A_t-U₀) = U_t-A_tR: Antibacterial activity value U₀: Average logarithmic number of viable bacteria immediately after inoculation of unprocessed test piece U_t: Average logarithmic count of viable cells 24 hours after unprocessed test piece A_t: Average value of logarithmic number of viable cells after 24 hours of antibacterial processing test piece Reference standard JIS Z 2801 Staphylococcus aureus NBRC12732 was used as the test bacteria. The obtained antibacterial activity values are shown in Table 1.

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As is clear from Table 1, FIG. 4 and FIG. 5, in Example 1, the inactivation of phage virus Qβ was 99.9% or more (the virus inactivation was equal to or higher than -3.00, or more antiviral. The result was that the activity was excellent), and it was confirmed that the feline calicivirus, which does not have an envelope, also has an inactivating effect. On the other hand, in Comparative Example 1, the inactivity of phage virus Qβ was 96.84% (virus inactivity was about -1.50), and it was confirmed that the antiviral activity was lower than that of Example 1. In addition, for micron-sized Staphylococcus aureus, which is less likely to be trapped in cracks, there was no difference between Example 1 and Comparative Example 1.

10, 20, 30 Functional members 11, 21, 31 Resin base material 21a, 31a Base material 21b, 31b Surface layer Resin layer 12, 22, 32 Inorganic binder curing layer 32'Inorganic binder layer for transfer 13, 33 Functional components Particles 14, 24, 34 Crack 36 Transfer film