JP2021054767A - Antiviral member, method for producing antiviral member, and antiviral composition - Google Patents

Abstract

To provide an antiviral member that prevents antiviral properties from degrading with time.SOLUTION: An antiviral member has a structure in which a cured product of an ultraviolet curable resin containing an antiviral agent having no photocatalytic function is formed like a film and fixed on the surface of a base material. The ultraviolet curable resin is composed of a polyfunctional (meth) acrylate with 5 or more acryloyl groups.SELECTED DRAWING: Figure 1

Description

The present invention relates to an antiviral member, a method for producing an antiviral member, and an antiviral composition.

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

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

Patent Document 1 discloses an antiviral member in which a copper compound is dispersed in a photoradical polymerization type acrylate resin (UCECOAT7200 manufactured by Daicel Ornex: substance name dipentaerythritol tetraacrylate) and fixed on a substrate. However, when such an antiviral member is used for a floor, a wall, or the like, there is a problem that the antiviral performance deteriorates with the passage of time.

Patent Document 2 describes a thermosetting urethane resin obtained by reacting an acrylic resin or an acrylic resin for curing isocyanate with diisocyanate (in the example, it is described as "Duranate (registered trademark)" in the trade name of Asahi Kasei Chemicals Co., Ltd.). Although an anti-virus coating member coated with an anti-virus composition in which a cuprous oxide is dispersed is disclosed, there is a problem that the anti-virus performance deteriorates with the passage of time.

Patent Document 3 discloses an anti-virus composition containing an inorganic solid acid such as an inorganic phosphoric acid compound in a binder such as an acrylic resin or a urethane resin emulsion, but it is said that the anti-virus performance also deteriorates with the passage of time. There was a problem.

International Publication No. 2019/74121 International Publication No. 2014/132606 International Publication No. 2017/150063

As described above, the antiviral member using the conventional antiviral composition has a problem that the antiviral performance deteriorates with the passage of time.
An object of the present invention is to provide an antiviral member whose antiviral property does not deteriorate over time.

As a result of diligent research by the present inventors, the deterioration of the antiviral performance of the antiviral member over time is caused by the ultraviolet rays constituting the antiviral member due to severe wear conditions such as trampling with shoes and cleaning with a rotating brush. It was found that this is because the cured resin wears and the antiviral agent falls off, and it has been found that the deterioration of the antiviral performance over time can be prevented by improving the wear resistance of the ultraviolet curable resin.
In the present invention, a cured product of an ultraviolet curable resin containing an antiviral agent having no photocatalytic function is fixedly formed on the surface of a substrate, and the ultraviolet curable resin has five or more acryloyl groups. It is an antiviral composition used in an antiviral member characterized by being composed of a functional (meth) acrylate, a method for producing the antiviral member, and a method for producing the antiviral member.

In the antiviral member of the present invention, since the ultraviolet curable resin is made of a polyfunctional (meth) acrylate having 5 or more acryloyl groups, the polymer chains form a strong network, and the hardness is high and the abrasion resistance is excellent. It is an antiviral member. Therefore, the antiviral agent does not fall off even under severe wear conditions such as trampling and rubbing with shoes or a rotating brush when cleaning the machine.

The antiviral composition of the present invention used for the antiviral member of the present invention is an antiviral composition made of an uncured ultraviolet curable resin containing an antiviral agent having no photocatalytic function, and is the above-mentioned ultraviolet light. The cured resin consists of a polyfunctional (meth) acrylate having 5 or more acryloyl groups.
The antiviral composition of the present invention becomes the antiviral member of the present invention by curing the uncured ultraviolet curable resin with ultraviolet rays.

In the antiviral member of the present invention and the antiviral composition of the present invention, since the antiviral agent does not have a photocatalytic function, the ultraviolet rays constituting the antiviral member are compared with the case where the antiviral agent has a photocatalytic function. The cured resin does not easily deteriorate.

In the antiviral member and antiviral composition of the present invention, as the antiviral agent, an organic antiviral agent having no photocatalytic function and / or an inorganic antiviral agent having no photocatalytic function can be used.
The inorganic antiviral agent having no photocatalytic function is preferably at least one selected from the group consisting of a metal compound having no photocatalytic function and zeolite ion-exchanged with metal ions.
Examples of the metal compound include metal oxides, inorganic phosphoric acid compounds, and inorganic silicic acid compounds.
As the metal oxide, zinc oxide, silver oxide, lead oxide and the like can be used.
Examples of the inorganic phosphoric acid compound include zinc phosphate, phosphoric acid compounds of titanium group elements such as zirconium phosphate, hafnium phosphate, and titanium phosphate, and inorganic compounds such as aluminum phosphate and hydroxyapatite (phosphate mineral). Phosphoric acid compounds: Inorganic silicate compounds such as magnesium silicate, silica gel, aluminosilicate, sepiolite (hydrous magnesium silicate), montmorillonite (silicate mineral), and zeolite (aluminosilicate) can be used.
As the zeolite substituted with metal ions, silver ion-substituted zeolite or the like can be used. As an inorganic antiviral agent, silver supported on silica has an antiviral effect, but since the surface area is small and silica itself does not have antiviral performance, silver-supported silica does not function as an antiviral agent. On the other hand, since zeolite has a large surface area and the zeolite itself has an antiviral function, zeolite substituted with silver ions is preferable to silver-supported silica. Therefore, it is preferable that the silver-supported silica is removed from the antiviral agent used in the present invention.
Further, the inorganic antiviral agent may not contain copper ions and copper compounds. This is because many copper ions and copper compounds are colored, and when the antiviral composition is formed into a film and cured, the color of the surface of the substrate is impaired.
If the color of the surface of the base material is not affected even if the copper ion or the copper compound is contained, the copper compound may be contained as an antiviral agent. Specifically, copper oxide, cuprous oxide, copper hydroxide and the like can be used.
The organic antiviral agent is preferably at least one selected from the group consisting of triazine, azole, a sulfonic acid-based surfactant, and a bis-type quaternary ammonium salt.
Examples of the organic antiviral agent include azoles such as imidazole, triazole, thiazole and benzoimidazole, triazine, halocarban, chlorophenesine, lysozyme chloride, alkyldiaminoethylglycine hydrochloride, isopropylmethylphenol, timol, hexachlorophene and berberine. , Thioxolone, salicylic acid and their derivatives, benzoic acid, sodium benzoate, paraoxybenzoic acid ester, parachlormethacresol, benzalkonium chloride, phenoxyethanol, isopropylmethylphenol, coalic acid, sorbic acid, potassium sorbate, hexachlorophene, chloride Chlorhexidine, trichlorocarbanilide, thiantol, hinokithiol, triclosan, trichlorohydroxydiphenyl ether, chlorhexidine gluconate, phenoxyethanol, resorcin, azulene, salicylic acid, zincpyridion, mononitroguaycole sodium, uikyo extract, sansho extract, cetylpyridinium chloride, benzethinium chloride And undecylene acid derivatives, alkylbenzene sulfonic acid and salts thereof, bis-type pyridinium salt, bis-type quinolinium salt, bis-type thiazolium salt and the like.

In the antiviral member and antiviral composition of the present invention, at least one (meth) acrylate selected from the group consisting of methyl methacrylate, dimethylol-tricyclodecane diacrylate and cyclohexyl methacrylate in an ultraviolet curable resin. And preferably contains a photopolymerization initiator. This is because these resins can reduce the viscosity of the ultraviolet curable resin before curing.
In the antiviral member and antiviral composition of the present invention, the weight ratios of the methyl methacrylate, the dimethylol-tricyclodecane diacrylate, and the cyclohexyl methacrylate are 50 to 70% by weight of the total (meth) acrylate, respectively. It is preferably 5 to 20% by weight and preferably 1 to 5% by weight.

In the antiviral member and antiviral composition of the present invention, a leveling agent may be contained in the ultraviolet curable resin. As the leveling agent, a silicone-based leveling agent, particularly a non-volatile silicone, can be preferably used. Since it is non-volatile, it has a high leveling effect and excellent finger slipperiness. Examples of non-volatile silicones include polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, polysiloxanes with aminofunctional substituents, polyethersiloxane copolymers and mixtures thereof. The amount of the non-volatile silicone added is preferably 0.002 to 0.007 parts by weight based on 100 parts by weight of the solid content of the total (meth) acrylate.

The antiviral composition of the present invention is preferably solvent-free (does not contain an organic solvent). This is because it can be cured by ultraviolet rays without being dried, and a solvent harmful to the human body does not volatilize.
Moreover, it is preferable that the antiviral composition of the present invention does not contain water. Further, it is preferable that the uncured ultraviolet curable resin, methyl methacrylate, dimethylol-tricyclodecane diacrylate, and cyclohexyl methacrylate are not emulsions. This is because when an uncured ultraviolet curable resin or (meth) acrylate is an emulsion, a uniform film cannot be formed.

In the antiviral member and antiviral composition of the present invention, the polyfunctional (meth) acrylate having 5 or more acryloyl groups in the molecule has a role of improving hardness. Specifically, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and two or more of these. A mixture can be mentioned.
The same applies to preferred types of polyfunctional (meth) acrylates having 5 or more acryloyl groups in the molecule contained in the antiviral composition of the present invention.

The antiviral composition of the present invention preferably contains methyl methacrylate (MMA) as a viscosity modifier, and the viscosity of the antiviral composition is preferably adjusted to less than 10 mPa · s / 25 ° C. MMA is preferably blended in an amount of 50 to 70% by weight based on the total weight of the composition.
Further, the antiviral composition of the present invention and its curing may contain dimethylol-tricyclodecanediacrylate as a bifunctional (meth) acrylate and cyclohexyl methacrylate as a monofunctional (meth) acrylate. These can reduce the viscosity of the antiviral composition and also reduce the curing shrinkage after curing.

In the antiviral member of the present invention, the thickness of the ultraviolet curable resin layer containing the antiviral agent is preferably 0.1 μm to 20 μm.

The anti-virus composition and anti-virus member of the present invention may contain (meth) acrylate having a phosphoric acid ester group in the ultraviolet curable resin, and specifically, 2- (meth) acryloyloxyethyl-. Examples thereof include dihydrophosphate, di- (2- (meth) acryloyloxy) hydrogen phosphate, ethylene oxide-modified dimethacrylate phosphate and the like. It is presumed that the presence of the phosphoric acid ester group improves the adhesion to metals and ceramics (including glass).

The method for producing an antiviral member of the present invention comprises an uncured ultraviolet curable resin containing an antiviral agent having no photocatalytic function, and the ultraviolet curable resin is polyfunctional (meth) having 5 or more acryloyl groups. ) An antiviral composition composed of an acrylate is coated on the surface of a base material in a film form, and then the ultraviolet curable resin is cured by irradiating with ultraviolet rays.
The method for producing an antiviral member of the present invention can be said to be a method for producing an antiviral member of the present invention using the antiviral composition of the present invention.

In the method for producing an antiviral member of the present invention, it is preferable that the antiviral composition does not contain an organic solvent.
In this case, the antiviral composition can be cured with ultraviolet rays without drying, and the solvent harmful to the human body does not volatilize.
Further, in the method for producing an antiviral member of the present invention, it is preferable that the antiviral composition does not contain water.

FIG. 1 is a cross-sectional view schematically showing an example of a viral member of the present invention.

(Detailed description of the invention)
The antiviral member of the present invention is formed by forming a film of an ultraviolet curable resin containing an antiviral agent on the surface of a base material.
The material of 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 antiviral member of the present invention may be used as an interior material, a wall material, a window glass, a door, office equipment, furniture, etc. inside a building.
Moreover, you may use the antiviral member of this invention as a decorative board.

Hereinafter, the antiviral member of the present invention will be described with reference to the drawings.
FIG. 1 is a cross-sectional view schematically showing an example of the antiviral member of the present invention.

As shown in FIG. 1, the antiviral member 1 has a decorative plate as the base material 10 and a cured product 20 of an ultraviolet curable resin fixedly formed on the surface of the base material 10.
The cured product 20 of the ultraviolet curable resin contains an antiviral agent 30.

In the antiviral member 1, the cured product 20 of the ultraviolet curable resin is composed of a polyfunctional (meth) acrylate having 5 or more acryloyl groups, but the polyfunctional (meth) having 5 or more acryloyl groups in the molecule. Acrylate has a role of improving hardness. Specifically, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and two or more of these. A mixture can be mentioned.

Further, in the antiviral member of the present invention, the antiviral agent is preferably an inorganic antiviral agent having no photocatalytic function and / or an organic antiviral agent having no photocatalytic function.
Further, the inorganic antiviral agent is preferably at least one selected from the group consisting of a metal compound having no photocatalytic function and a zeolite substituted with a metal ion.
Examples of the metal compound include metal oxides, inorganic phosphoric acid compounds, and inorganic silicic acid compounds.
As the metal oxide, zinc oxide, silver oxide, lead oxide and the like can be used.
Examples of the inorganic phosphoric acid compound include zinc phosphate, phosphoric acid compounds of titanium group elements such as zirconium phosphate, hafnium phosphate, and titanium phosphate, and inorganic compounds such as aluminum phosphate and hydroxyapatite (phosphate mineral). Phosphoric acid compounds: Inorganic silicate compounds such as magnesium silicate, silica gel, aluminosilicate, sepiolite (hydrous magnesium silicate), montmorillonite (silicate mineral), and zeolite (aluminosilicate) can be used.
As the zeolite substituted with metal ions, silver ion-substituted zeolite can be used. As an inorganic antiviral agent, silver supported on silica has an antiviral effect, but since the surface area is small and silica itself does not have antiviral performance, silver-supported silica does not function as an antiviral agent. On the other hand, since zeolite has a large surface area and the zeolite itself has an antiviral function, zeolite substituted with silver ions is preferable to silver-supported silica. Therefore, it is preferable that the silver-supported silica is removed from the antiviral agent used in the present invention.
Further, the inorganic antiviral agent may not contain copper ions and copper compounds. This is because many copper ions and copper compounds are colored, and when the antiviral composition is formed into a film and cured, the color of the surface of the substrate is impaired.
If the color of the surface of the base material is not affected even if the copper ion or the copper compound is contained, the copper compound may be contained as an antiviral agent. Specifically, copper oxide, cuprous oxide, copper hydroxide and the like can be used.

Further, in the antiviral member of the present invention, the organic antiviral agent is at least one selected from the group consisting of triazine, azole, a sulfonic acid-based surfactant, and a bis-type quaternary ammonium salt. Is preferable.
Examples of the organic antiviral agent include azoles such as imidazole, triazole, thiazole and benzoimidazole, triazine, halocarban, chlorophenesine, lysozyme chloride, alkyldiaminoethylglycine hydrochloride, isopropylmethylphenol, timol, hexachlorophene and berberine. , Thioxolone, salicylic acid and their derivatives, benzoic acid, sodium benzoate, paraoxybenzoic acid ester, parachlormethacresol, benzalkonium chloride, phenoxyethanol, isopropylmethylphenol, coalic acid, sorbic acid, potassium sorbate, hexachlorophene, chloride Chlorhexidine, trichlorocarbanilide, thiantol, hinokithiol, triclosan, trichlorohydroxydiphenyl ether, chlorhexidine gluconate, phenoxyethanol, resorcin, azulene, salicylic acid, zincpyridion, mononitroguaycole sodium, uikyo extract, sansho extract, cetylpyridinium chloride, benzethinium chloride And undecylene acid derivatives, alkylbenzene sulfonic acid and salts thereof, bis-type pyridinium salt, bis-type quinolinium salt, bis-type thiazolium salt and the like.

In the antiviral member of the present invention, as the antiviral component, at least one selected from the group consisting of an inorganic antiviral agent and an organic antiviral agent, an organic binder, an inorganic binder, and an organic / inorganic hybrid binder are used. A cured product can be obtained by curing a mixture of the virus and the ultraviolet curable resin.

The antiviral member of the present invention may contain a (meth) acrylate having a phosphoric acid ester group in the ultraviolet curable resin, and specifically, 2- (meth) acryloyloxyethyl-dihydrophosphate, di-. Examples thereof include (2- (meth) acryloyloxy) hydrogen phosphate and ethylene oxide-modified dimethacrylate phosphate. It is presumed that the presence of the phosphoric acid ester group improves the adhesion to metals and ceramics (including glass).

Next, a cured product of the ultraviolet curable resin in the antiviral member of the present invention will be described.
After forming a film on the surface of the substrate using an antiviral composition containing an uncured ultraviolet curable resin, a polymerization initiator, various additives, and an antiviral agent, the polymerization initiator can be obtained by irradiating with ultraviolet rays. Reactions such as cleavage reaction, hydrogen abstraction reaction, electron transfer, etc. occur, and the photoradical molecules, photocation molecules, photoanion molecules, etc. generated by these reactions attack the monomers and oligomers constituting the uncured ultraviolet curable resin, and the monomers and The polymerization reaction and cross-linking reaction of the oligomer proceed to form a cured product of an ultraviolet curable resin containing an antiviral agent.

According to the antiviral member of the present invention, for example, for interior materials, wall materials, windowpanes, doors, kitchen utensils, etc. inside buildings, office equipment, furniture, etc., decorative boards used for various purposes, etc. , The antiviral function can be added without changing the pattern, color, design, color tone, etc. formed on the surface.

Next, a method for manufacturing the above-mentioned antiviral member will be described.
When producing the antiviral member, first, an antiviral agent and an uncured ultraviolet curable resin, that is, a polyfunctional (meth) acrylate having 5 or more acryloyl groups and photopolymerization are started on the surface of the base material. A coating step of applying the antiviral composition containing the agent in a film form is performed, and if necessary, the antiviral composition applied by the coating step is dried, and finally the uncured ultraviolet curing is performed. By performing a curing step of curing the resin, it is possible to obtain an antiviral member in which a cured product of an ultraviolet curable resin containing an antiviral agent is fixedly formed in a film shape on the surface of a base material.

(1) Coating Step When producing the antiviral member of the present invention, first, as a coating step, an antiviral agent, an uncured ultraviolet curable resin, and if necessary, a dispersion medium and a photopolymerization initiator are included. An antiviral composition is prepared and applied to the surface of the substrate. When a metal or ceramic is used as the base material, the uncured ultraviolet curable resin may further contain a (meth) acrylate compound having a phosphoric acid ester group.
The antiviral agent is preferably an organic antiviral agent having no photocatalytic function and / or an inorganic antiviral agent having no photocatalytic function.
Further, the inorganic antiviral agent is preferably at least one selected from the group consisting of metal compounds and zeolites substituted with metal ions.
Examples of the metal compound include metal oxides, inorganic phosphoric acid compounds, and inorganic silicic acid compounds. As the metal oxide, zinc oxide, silver oxide, lead oxide and the like can be used. Examples of the inorganic phosphoric acid compound include zinc phosphate, phosphoric acid compounds of titanium group elements such as zirconium phosphate, hafnium phosphate, and titanium phosphate, and inorganic compounds such as aluminum phosphate and hydroxyapatite (phosphate mineral). Phosphoric acid compounds: Inorganic silicate compounds such as magnesium silicate, silica gel, aluminosilicate, sepiolite (hydrous magnesium silicate), montmorillonite (silicate mineral), and zeolite (aluminosilicate) can be used. As an inorganic antiviral agent, silver supported on silica has an antiviral effect, but since the surface area is small and silica itself does not have antiviral performance, silver-supported silica does not function as an antiviral agent. On the other hand, since zeolite has a large surface area and the zeolite itself has an antiviral function, zeolite substituted with silver ions is preferable to silver-supported silica. Therefore, it is preferable to remove silver-supported silica from the antiviral agent of the present invention.
Further, the inorganic antiviral agent may not contain copper ions and copper compounds. This is because many copper ions and copper compounds are colored, and when the antiviral composition is formed into a film and cured, the color of the surface of the substrate is impaired.
If the color of the surface of the base material is not affected even if the copper ion or the copper compound is contained, the copper compound may be contained as an antiviral agent. Specifically, copper oxide, cuprous oxide, copper hydroxide and the like can be used.
As the zeolite substituted with metal ions, silver ion-substituted zeolite or the like can be used. As an inorganic antiviral agent, silver supported on silica has an antiviral effect, but since the surface area is small and silica itself does not have antiviral performance, silver-supported silica does not function as an antiviral agent. On the other hand, since zeolite has a large surface area and the zeolite itself has an antiviral function, zeolite substituted with silver ions is preferable as an antiviral agent rather than silver-supported silica.
Further, the organic antiviral agent is preferably at least one selected from the group consisting of triazine, azole, a sulfonic acid-based surfactant, and a bis-type quaternary ammonium salt.
Examples of the organic antiviral agent include azoles such as imidazole, triazole, thiazole and benzoimidazole, triazine, halocarban, chlorophenesin, lysozyme chloride, alkyldiaminoethylglycine hydrochloride, isopropylmethylphenol, timol, hexachlorophene, and the like. Velberin, thioxolone, salicylic acid and their derivatives, benzoic acid, sodium benzoate, paraoxybenzoic acid ester, parachlormethacresol, benzalkonium chloride, phenoxyethanol, isopropylmethylphenol, coalic acid, sorbic acid, potassium sorbate, hexachlorophene, Chlorhexidine chloride, trichlorocarbanilide, thiantol, hinokithiol, triclosan, trichlorohydroxydiphenyl ether, chlorhexidine gluconate, phenoxyethanol, resorcin, azulene, salicylic acid, dincupyrithione, mononitroguanacol sodium, uikyo extract, sansho extract, cetylpyridinium chloride, chloride. Examples thereof include benzethonium and undecylene acid derivatives, alkylbenzene sulfonic acid or a salt thereof, bis-type pyridinium salt, bis-type quinolinium salt, and bis-type thiazolium salt.

The type of the dispersion medium is not particularly limited, but alcohols and water can be used in consideration of stability. Examples of alcohols include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and sec-butyl alcohol in consideration of lowering the viscosity. Among these alcohols, methyl alcohol and ethyl alcohol, which do not easily increase in viscosity, are preferable, and a mixed solution of alcohol and water is preferable.
Further, an organic solvent such as methyl ethyl ketone or ethyl acetate may be used.
When water is used as the dispersion medium, the ultraviolet curable resin, the (meth) acrylate, and the photopolymerization initiator become emulsions, which causes a problem that a uniform film cannot be formed when applied. It is not preferable to emulsify the ultraviolet curable resin, the (meth) acrylate, the photopolymerization initiator, etc. using water.

In addition, the most preferable form for preparing the antiviral composition is a form in which the antiviral composition is prepared without using a dispersion medium and without a solvent.
When the antiviral composition is prepared without solvent, the ultraviolet curable resin can be cured in a short time by irradiating ultraviolet rays after application without performing a drying step of drying the dispersion medium later. In addition, when an organic solvent is used as the dispersion medium, the organic solvent volatilizes even when the antiviral composition is applied and cured, which adversely affects the health of workers and humans living in the space where the antiviral member is arranged. there is a possibility. Therefore, it is preferable that it is solvent-free from the viewpoint of health.
In order to reduce the viscosity of the antiviral composition, it is preferable to add at least one (meth) acrylate selected from the group consisting of methyl methacrylate, dimethylol-tricyclodecane diacrylate, and cyclohexyl methacrylate.

Specifically, the polymerization initiator is preferably at least one selected from the group consisting of an alkylphenone type, an acylphosphine oxide type, an intramolecular hydrogen abstraction type, and an oxime ester type.

Examples of the alkylphenone-based polymerization 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-one , 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4) -Morhonyl) phenyl] -1-butanone and the like.

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

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

Examples of the oxime ester-based polymerization initiator include 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6-. (2-Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime) and the like can be mentioned.

The content ratio of the antiviral agent in the antiviral composition is preferably 2 to 30% by weight, and the content ratio of the uncured ultraviolet curable resin (polyfunctional (meth) acrylate having 5 or more acryloyl groups) is 15 to 60% by weight is preferable, and if a dispersion medium is required, the content ratio of the dispersion medium is preferably 1 to 80% by weight.

If necessary, the antiviral composition may contain an ultraviolet absorber, an antioxidant, a light stabilizer, an adhesion accelerator, a rheology adjuster, a leveling agent, an antifoaming agent and the like. As the leveling agent, a silicone-based leveling agent, particularly a non-volatile silicone, can be preferably used. Since it is non-volatile, it has a high leveling effect and excellent finger slipperiness. Examples of non-volatile silicones include polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, polysiloxanes with aminofunctional substituents, polyethersiloxane copolymers and mixtures thereof. The amount of the non-volatile silicone added is preferably 0.002 to 0.007 parts by weight based on 100 parts by weight of the solid content of the total (meth) acrylate.

As the above-mentioned coating method, for example, the antiviral composition can be coated on the surface of the base material by using a sponge roller, a brush, a mop, a squeegee or the like.

(2) Curing Step When producing the above-mentioned antiviral member, as a curing step, the monomer or oligomer constituting the above-mentioned uncured ultraviolet curable resin in the antiviral composition is irradiated with ultraviolet rays to form a cured product. To do.
The conditions for irradiating with ultraviolet rays are not particularly limited, but the conditions ^{are preferably 1 to 300 mW / cm 2} and 1 to 800 seconds.

(Other processes)
When the antiviral composition contains a dispersion medium, after the above (1) coating step, the antiviral composition is dried, the dispersion medium is evaporated and removed, and the antiviral composition is temporarily applied to the surface of the substrate. The antiviral agent can be exposed from the surface of the antiviral composition by fixing and drying and shrinking the antiviral composition.
The drying conditions are preferably 60 to 100 ° C. and 0.5 to 5.0 minutes.
When the antiviral composition contains an inorganic binder, the curing of the inorganic binder proceeds by removing the dispersion medium in this drying step.

(Example 1)
As a polyfunctional (meth) acrylate having (a) 250 parts by weight of MMA (methyl methacrylate) and (b) 5 or more acryloyl groups in the molecule, a mixture of dipentaerythritol pentaacrylate and hexaacrylate (trade name: KAYARAD DPHA). , Made by Nippon Kayaku Co., Ltd., solid content 100%, penta ratio about 40%) 100 parts by weight, and (c) dimethylol-tricyclodecanediacrylate as bifunctional (meth) acrylate (trade name: light acrylate DCP-A) , Kyoeisha Chemical Co., Ltd., viscosity 130-170 mPa · s / 25 ° C.) with 80 parts by weight, and (d) cyclohexyl methacrylate (trade name: light ester CH, manufactured by Kyoeisha Chemical Co., Ltd.) as monofunctional (meth) acrylate. 20 parts by weight, 13.5 parts by weight of 1-hydroxy-cyclohexyl-phenylketone (trade name: Irgacure184, manufactured by BASF, 100% solid content) as a photopolymerization initiator, and polyester modification having an acrylic group as a leveling agent. A solution of polydimethylsiloxane (trade name: BYK-UV3570, manufactured by Big Chemie Japan Co., Ltd.) is blended with 1.35 parts by weight to obtain a solvent-free ultraviolet curable resin composition.

Next, 15 parts by weight of zinc phosphate (high-purity chemistry) is added to 100 parts by weight of the solvent-free ultraviolet curable resin composition and kneaded with a three-roller to obtain an antiviral composition.

The obtained antiviral composition is coated on a white melamine plate having a size of 500 mm × 500 mm using a rubber squeegee. The film thickness is 3 μm.

After that, by using an ultraviolet irradiation device (MP02 manufactured by COATTEC) to ^{irradiate ultraviolet rays at an irradiation intensity of 30 mW / cm 2} for 80 seconds, the surface of the white melamine plate as the base material is coated with an ultraviolet curable resin containing zinc phosphate. An anti-virus member in which the cured product is formed into a film is obtained.

(Example 2)
Zinc phosphate is changed to silver ion-substituted zeolite (trade name: Zeomic, manufactured by Sinanen Zeomic Co., Ltd.), and 30 parts by weight of silver ion-substituted zeolite is added to 100 parts by weight of the solvent-free ultraviolet curable resin composition. Others obtain an anti-virus member in which a cured product made of an ultraviolet curable resin exhibiting anti-virus property is formed in a film shape as in Example 1.

(Example 3)
Zinc phosphate was changed to an imidazole-based antimicrobial agent (Nippon Sotatsu Co., Ltd. trade name Biocut BM-100F), and an imidazole-based antimicrobial agent was added to 100 parts by weight of the solvent-free ultraviolet curable resin composition. Other than adding 20 parts by weight, an antiviral member is obtained in which a cured product made of an ultraviolet curable resin exhibiting antiviral properties is formed in a film shape as in Example 1.
(Comparative Example 1)
After dissolving 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 0.7 wt%, use a magnetic stirrer at 600 rpm. A copper acetate aqueous solution was prepared by stirring with. The cupric acetate aqueous solution becomes an antiviral agent through a subsequent step.
A photoradical polymerization type acrylate resin (trade name: UCECOAT7200 dipentaerythritol tetraacrylate, manufactured by Daicel Ornex) and a photopolymerization initiator (Omnirad500 manufactured by IGM) are mixed at a weight ratio of 98: 2, and a homogenizer is used at 8000 rpm. A binder solution, which is an ultraviolet curable resin, was prepared by stirring for 30 minutes. The 0.7 wt% cupric acetate aqueous solution, the binder solution which is an ultraviolet curable resin, and colloidal silica (trade name: methanol silica sol, manufactured by Nissan Chemical Industries, Ltd., solid content 30%) are mixed in a weight ratio of 4.5: 2.4: 1.0. To prepare an antiviral composition, the mixture was mixed with a magnetic stirrer and stirred at 600 rpm for 2 minutes. 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.

Then, the antiviral composition was applied in a film form on a white melamine plate having a size of 500 mm × 500 mm with a brush, and then the white melamine plate was dried at 80 ° C. for 3 minutes, and further, an ultraviolet irradiation device (COATTEC). By irradiating ultraviolet rays for 80 seconds at an irradiation intensity of 30 mW / cm ² using MP02), a cured film made of a cured product of an ultraviolet curable resin containing a copper compound was formed on the surface of a white melamine plate as a base material. An anti-virus member was obtained.

(Comparative Example 2)
Zinc phosphate and a urethane emulsion binder having a non-volatile content of 30% are mixed so as to have a solid content weight ratio of 1: 1 to produce an antiviral composition.
Next, this antiviral composition is applied to a white melamine plate having a size of 500 mm × 500 mm in a film form with a brush and dried at 105 ° C. to produce an antiviral member.

(Comparative Example 3)
Acrydic (registered trademark) A801 (manufactured by DIC Co., Ltd.) and hexamethylene diisocyanate (trade name: Duranate TPA100 (manufactured by Asahi Kasei Chemicals Co., Ltd.)) as a bifunctional acrylic resin for curing isocyanate are used as an isocyanate group and a hydroxyl group. The mixture was mixed so that the ratio with and was NCO: OH = 1: 1. Next, a thermosetting resin is prepared by diluting this mixture with methyl ethyl ketone so that the heating residue is 20% by mass.
The anti-virus composition according to Comparative Example 3 is produced by mixing 20 parts by weight of cuprous oxide, 30 parts by mass of a phosphoric acid ester type anionic surfactant, and 1000 parts by mass of methyl ethyl ketone with 100 parts by weight of the thermosetting resin.
The antiviral composition is applied in a film form on a white melamine plate having a size of 500 mm × 500 mm with a brush, dried and cured at 100 ° C. to produce an antiviral member according to Comparative Example 3.

(Comparative Example 4)
Methyl methacrylate (100 parts by weight), zinc phosphate (20 parts by weight), 1-hydroxy-cyclohexyl-phenylketone (trade name: Irgacure184, manufactured by BASF, 100% solid content) as a photopolymerization initiator, 3 parts by weight, and methyl ethyl ketone as a dispersion medium. To make an antiviral composition.
Next, the above anti-virus composition was applied to a white melamine plate in the form of a film with a brush, dried for 10 minutes, and then used with an ultraviolet irradiation device (MP02 manufactured by COATTEC) at an irradiation intensity of ^{30 mW / cm 2 for 80 seconds.} By irradiating with ultraviolet rays, an antiviral member having a cured film made of a cured product of an ultraviolet curable resin containing a copper compound formed on the surface of a white melamine plate as a base material is obtained.

(Comparative Example 5)
The silver-supported silica particles are adjusted as described in (1) to (3) below.
(1) Add 2% by mass sodium hydroxide aqueous solution to 10% by weight aqueous dispersion of colloidal silica to adjust the pH to 10.
(2) Prepare water glass diluted to 0.1% by weight, 0.7% by weight sodium aluminate aqueous solution, and 0.05% by mass silver nitrate aqueous solution, respectively.
(3) To 85.5 parts by weight of the aqueous dispersion of silica whose pH was adjusted to 10, 13 parts by weight of the previously prepared water glass and 1.5 parts by mass of the sodium aluminate aqueous solution were added and reacted. Dealkalization treatment was performed to obtain a silica-alumina suspension. 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, the suspension was filtered with a filter paper, dried, and an antibacterial agent powder in which silver was supported on silica. To get.
Next, in place of the zinc phosphate of Example 1, 20 parts by weight of an antibacterial agent powder in which silver is supported on silica is added to 100 parts by weight of the solvent-free ultraviolet curable resin composition. In the same manner as in 1, the antiviral composition according to Comparative Example 5 is obtained.
The antiviral composition according to Comparative Example 5 is applied to a white melamine decorative board in the same manner as in Example 1 and cured by irradiating with ultraviolet rays to obtain an antiviral member according to Comparative Example 5.

(Evaluation of antiviral members)
The color tone of the white melamine plate was visually confirmed with respect to the obtained antiviral members according to each example and each comparative example. In addition, the presence or absence of surface irregularities is confirmed with an optical microscope (Microscope VHX-5000 manufactured by KEYENCE CORPORATION).
The results are shown in Table 1.

(Antiviral evaluation using feline calicivirus)
This antiviral test is carried out as follows.
In order to evaluate the antiviral property of the antiviral member obtained in each Example and each Comparative Example, JIS Z 2801 antibacterial processed product-antibacterial test method / method modified antibacterial effect is used. The modification is to change "inoculation of test bacterial solution" to "inoculation of test virus". All changes due to the use of viruses will be made based on the antiviral test method for JIS L 1922 textile products. The measurement results are based on JIS L 1922 Annex B for the antiviral members obtained in each Example and each Comparative Example, and the concentration of feline calicivirus that has lost the ability to infect CRFK cells is displayed as the feline calicivirus inactivity. To do. Here, the concentration of the virus inactivated to the CRFK cells (virus inactivity) is used as an index of the virus concentration, and the antiviral activity value is calculated based on the virus inactivity.

The procedure will be described in detail below.
(1) the antiviral member according to each of Examples and Comparative Examples was cut out into a square one side 50mm square as a test sample, put the test sample sterilized plastic Petri dish, test virus solution (> 10 ⁷ PFU / ML) is inoculated with 0.4 mL.
Test virus solution is used after diluting 10-fold stock of ¹⁰ 8 PFU / mL 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, add 10 mL of SCDLP medium and wash away the virus solution. Obtain the virus infection value based on JIS L 1922 Annex B.

(5) Calculate the antiviral activity value using the following formula.
Mv = Log (Vb / Vc)
Mv: Antiviral activity value Log (Vb): Logistic value of the infection value after the reaction of the polyethylene film for a predetermined time Log (Vc): Logistic reference standard of the infection value after the reaction of the test sample for a predetermined time JIS L 1922, JIS Z 2801
The measuring method was a plaque measuring method.
In addition, Feline calicivirus; Strine: F-9 ATCC VR-782 is used as the test virus.

(Accelerated test)
A wear test of 150 Pa and 11000 times is performed using a microfiber cloth soaked in tap water. This accelerated test is based on the assumption that wiping is performed three times a day, which corresponds to a change over time for about three years.
Using the test samples related to each Example and each Comparative Example before and after the accelerated test, the antiviral activity value is calculated by the same method as in the above-mentioned "Antiviral evaluation using feline calicivirus". The results are shown in Table 1.

As shown in Table 1, the antiviral compositions according to Examples 1 to 3 contain polyfunctional acrylates having 5 and 6 acryloyl groups, and are therefore excellent in abrasion resistance. Therefore, practical antiviral performance can be maintained even after the accelerated test. Further, since it is solvent-free, there are no voids due to the volatilization of the dispersion medium, the film surface is smooth, and a uniform film can be formed.
Furthermore, since it does not contain copper ions or copper compounds as an antiviral agent, the color of the substrate surface does not change even if it is coated in a film form.

As shown in Table 1, since the antiviral composition according to Comparative Example 1 contains a polyfunctional acrylate having four acryloyl groups, the formation of a network of polymer chains at the time of cross-linking becomes insufficient. Therefore, the wear resistance is low, and the antiviral performance deteriorates after the accelerated test. Further, since copper is contained as an antiviral agent, the cured film of the antiviral composition is bluish, and the color of the surface of the base material is impaired.
The antiviral composition according to Comparative Example 2 is obtained by drying and thermosetting a urethane emulsion binder, and has irregularities on the surface of the cured film and is a linear polymer, so that it is three-dimensional. No network structure is formed and the wear resistance is poor. Therefore, the antiviral performance deteriorates after the accelerated test.
The antiviral composition according to Comparative Example 3 uses a thermosetting urethane resin, and since the ratio of the isocyanate group to the hydroxyl group is NCO: OH = 1: 1, an acrylic resin molecule that functions as a curing agent. Since it is a linear polymer in which one hexamethylenediamine molecule is bonded to one, the formation of a network of polymer chains at the time of cross-linking becomes insufficient. Therefore, the wear resistance is low, and the antiviral performance deteriorates after the accelerated test.
The antiviral composition according to Comparative Example 4 is a polymer of methyl methacrylate, and the polymer chain is linear, so that the formation of a network is insufficient. Therefore, the wear resistance is low, and the antiviral performance deteriorates after the accelerated test.
It can be seen that the resin composition containing silver-supported silica according to Comparative Example 5 cannot be confirmed to have antiviral properties.

From the above results, it was found that by using a polyfunctional (meth) acrylate having 5 or more acryloyl groups, it is possible to obtain an antiviral member having excellent wear resistance and antiviral performance not deteriorating with time. ..

1 Antiviral member 10 Base material 20 Cured product of UV curable resin 30 Antiviral agent

Claims (16)

A cured product of an ultraviolet curable resin containing an antiviral agent having no photocatalytic function is fixedly formed on the surface of a base material in a film shape, and the ultraviolet curable resin is polyfunctional (meth) having 5 or more acryloyl groups. An antiviral member characterized by being composed of acrylate. The antiviral member according to claim 1, wherein the antiviral agent is an organic antiviral agent having no photocatalytic function and / or an inorganic antiviral agent having no photocatalytic function. The antiviral member according to claim 1 or 2, wherein the antiviral agent does not contain copper ions and copper compounds. Claims 1 to 1, wherein the ultraviolet curable resin contains at least one (meth) acrylate selected from the group consisting of methyl methacrylate, dimethylol-tricyclodecane diacrylate and cyclohexyl methacrylate, and a photopolymerization initiator. The antiviral member according to any one of 3. The antiviral member according to any one of claims 1 to 4, which contains a leveling agent in the ultraviolet curable resin. The antiviral member according to any one of claims 1 to 5, wherein the ultraviolet curable resin contains a (meth) acrylate having a phosphoric acid ester group. An antiviral composition composed of an uncured ultraviolet curable resin containing an antiviral agent having no photocatalytic function and the ultraviolet curable resin having a polyfunctional (meth) acrylate having 5 or more acryloyl groups is used as a base material. A method for producing an antiviral member, which comprises curing the ultraviolet curable resin by irradiating the surface with an ultraviolet ray after coating the surface in a film form. The method for producing an antiviral member according to claim 7, wherein the antiviral composition does not contain an organic solvent. The method for producing an antiviral member according to claim 7 or 8, wherein the antiviral composition does not contain water. An antiviral composition composed of an uncured ultraviolet curable resin containing an antiviral agent having no photocatalytic function, wherein the ultraviolet curable resin is composed of a polyfunctional (meth) acrylate having 5 or more acryloyl groups. Stuff. The antiviral composition according to claim 10, wherein the antiviral composition does not contain an organic solvent. The antiviral composition according to claim 10 or 11, wherein the antiviral composition does not contain water. Claims 10 to 10 include, in the ultraviolet curable resin, at least one (meth) acrylate selected from the group consisting of methyl methacrylate, dimethylol-tricyclodecane diacrylate, and cyclohexyl methacrylate, and a photopolymerization initiator. The antiviral composition according to any one of 12. The antiviral composition according to any one of claims 10 to 13, which contains a (meth) acrylate having a phosphoric acid ester group in the ultraviolet curable resin. The antiviral composition according to any one of claims 10 to 14, wherein the antiviral agent is an organic antiviral agent having no photocatalytic function and / or an inorganic antiviral agent. The antiviral composition according to any one of claims 10 to 15, wherein the antiviral agent does not contain copper ions and copper compounds.

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