JP2022093249A - Active energy ray-curable antiviral composition - Google Patents

Abstract

To provide an antiviral composition that allows an antiviral agent to be very easily dispersed in a composition, can be also easily applied and cured, and gives a cured film having a great antiviral ability.SOLUTION: An active energy ray-curable antiviral composition contains the following component (A) and component (B). Component (A) is a compound having an ethylenically unsaturated group. Component (B) is a (B1) component: an antiviral agent containing an inorganic solid acid with an acid-point level higher than 0.005 mmol/g.SELECTED DRAWING: None

Description

The present invention relates to an active energy ray-curable antiviral composition, and the composition of the present invention can be used for various applications such as inks and coating agents, and has fast curing property especially in a thin film. Since it can simultaneously satisfy the adjustment of the physical properties of the cured film such as surface hardness, scratch resistance, flexibility and curl property and the antiviral property, it can be preferably used as a coating agent composition and belongs to these technical fields.
In the present specification, acryloyl group and / or methacrylic acid group is referred to as (meth) acryloyl group, acrylate and / or methacrylate is referred to as (meth) acrylate, and acrylic acid and / or methacrylic acid is referred to as (meth) acrylic acid.

In recent years, due to the epidemic of MERS (Middle East Respiratory Syndrome), influenza, new coronavirus, etc., the demand for a hygienic and safe living environment is increasing, and the development of various antiviral agents and antiviral products is being considered. Has been done.

Known antiviral products include molded products in which an antiviral agent is kneaded into a resin, fibers in which an antiviral agent is kneaded into fibers, and products in which a paint containing an antiviral agent is applied to various base materials. ing.
Among these, paints containing antiviral agents have been studied in various ways because they can impart antiviral properties to various products by a simple operation of applying them to various substrates.

On the other hand, the active energy ray-curable composition can be cured by irradiating it with active energy rays such as ultraviolet rays, visible rays and electron beams for a very short time, and has high productivity. Therefore, inks and coating agents for various substrates are used. It is widely used as.
Also in the active energy ray-curable composition, studies have been made to impart an antiviral effect to the cured product.

For example, Patent Document 1 discloses an active energy ray-curable composition containing a p-styrene sulfonate sodium or p-styrene sulfonate sodium polymer and (meth) acrylate as an antiviral agent.
Further, Patent Document 2 includes photocatalyst particles, cuprous oxide particles, and metal oxide particles having no photocatalyst activity as antiviral agents, and a binder resin which is an active energy ray-curable resin and an organic solvent. A composition of an active energy ray-curable coating agent containing an active energy ray-curable coating agent composition is disclosed.
Further, Patent Document 3 discloses an aqueous active energy ray-curable composition containing a copper compound as an antiviral agent and containing an electromagnetic wave curable resin.

Japanese Unexamined Patent Publication No. 2013-193966 Japanese Patent No. 6041169 Japanese Unexamined Patent Publication No. 2010-168578

However, the above-mentioned active energy ray-curable antiviral composition has the following problems.
First, the composition of Patent Document 1 contains a sodium p-styrene sulfonate or a sodium p-styrene sulfonate polymer as an antiviral agent, but since aromatic sulfonates are generally difficult to dissolve in an organic solvent, it is difficult to dissolve them in an organic solvent. It is necessary to disperse it in a resin dissolved in an organic solvent before use. Although antiviral properties can be obtained by orienting the dispersed particles on the surface, the organic components dispersed in the resin solution settle over time during storage and harden into a cake at the bottom of the container, making redispersion difficult. There was a problem that it was easy to become.
Next, the composition of Patent Document 2 contains photocatalytic particles, cuprous oxide particles, and metal oxide particles having no photocatalytic activity as an antiviral agent, but is a molecule in a cured film in a glass state. Since the movement of the metal oxide is restricted, local deterioration of the resin due to the photocatalyst cannot be completely prevented even if a metal oxide is used in combination, and when titanium oxide is used, light in the visible light region is also absorbed. Therefore, there is a problem that curing failure may occur when the active energy ray-curable resin is cured.
Finally, the composition of Patent Document 3 contains a copper compound as an antiviral agent, and since the copper compound is sparingly soluble in an organic solvent, it is an aqueous composition in which the copper compound is dissolved in water.
The water-based composition requires drying of water after coating on the base material, and has the problem that it requires a high temperature and a long time to dry and remove water as compared with a general organic solvent-based composition. there were. Further, as a problem of the water-based composition, there is a tendency that the adhesion to various base materials to be coated with the antiviral composition tends to be poor, and there is a problem that the appearance is likely to be poor due to the influence of water.

An object of the present invention is to provide an antiviral composition in which the antiviral agent is extremely easy to disperse in the composition, easy to apply and cure, and the obtained cured film has excellent antiviral performance. be.

In order to solve the above problems, the present inventors have an active energy ray-curable composition containing an antiviral agent containing a compound having an ethylenically unsaturated group and an inorganic solid acid having a specific acid point concentration. The antiviral agent is easy to disperse in the composition, and the obtained composition has good handleability, can be applied and cured by a simple method, and the formed cured film has antiviral properties. We found it to be excellent and completed the present invention.
Hereinafter, the present invention will be described in detail.

According to the composition of the present invention, it is extremely easy to disperse the antiviral agent in the composition, and the obtained cured film has excellent antiviral properties.

The present invention relates to an active energy ray-curable antiviral composition containing the following components (A) and (B).
Component (A): Compound having an ethylenically unsaturated group (B) Component: (B1) Antiviral agent containing an inorganic solid acid having an acid point concentration of more than 0.005 mmol / g The following components (A) and (B) , Other ingredients and usage will be described.

1. 1. Component (A ) Component (A) is a compound having an ethylenically unsaturated group.
Examples of the ethylenically unsaturated group in the component (A) include (meth) acryloyl group, (meth) acrylamide group, vinyl group and (meth) allyl group, and (meth) acryloyl group is preferable.
As the component (A), a compound having one ethylenically unsaturated group (hereinafter referred to as "monofunctional unsaturated compound") and a compound having two or more ethylenically unsaturated groups (hereinafter referred to as "polyfunctional unsaturated compound"). "Compound") and the like.
Hereinafter, the monofunctional unsaturated compound and the polyfunctional unsaturated compound will be described.

1-1. In the monofunctional unsaturated compound (A) component, specific examples of the monofunctional unsaturated compound include (meth) acrylate having one (meth) acryloyl group (hereinafter referred to as “monofunctional (meth) acrylate”). And (meth) acrylamide having one (meth) acryloyl group (hereinafter referred to as “monofunctional (meth) acrylamide”) can be mentioned.

Specific examples of monofunctional (meth) acrylates include
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate nonyl Alkyl (meth) acrylates such as (meth) acrylates, lauryl (meth) acrylates, and stearyl (meth) acrylates;
Polyols such as trimethylolpropane mono (meth) acrylates, glycerin mono (meth) acrylates, pentaerythritol mono (meth) acrylates, trimethylolpropane mono (meth) acrylates, and dipentaerythritol mono (meth) acrylates. ) Acrylate:
Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, tri Monofunctional (meth) acrylates with alicyclic groups such as cyclodecanemethylol (meth) acrylates and dicyclopentenyloxyethyl (meth) acrylates;
Monofunctional (meth) acrylate having an alicyclic group such as;
Phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, o-phenylphenol (meth) acrylate, phenol alkylene oxide adduct (meth) acrylate, alkylphenol alkylene oxide adduct (meth) Aromatic monofunctional (meth) acrylates such as acrylates, (meth) acrylates of alkylene oxide adducts of p-cumylphenol, and (meth) acrylates of alkylene oxide adducts of o-phenylphenol;
Examples thereof include alkyl carbitol (meth) acrylates such as ethyl carbitol (meth) acrylate, butyl carbitol (meth) acrylate, and 2-ethylhexyl carbitol (meth) acrylate.

The monofunctional (meth) acrylate may be a compound having various functional groups.
Examples of monofunctional (meth) acrylates having a hydroxyl group include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. In addition, 2-hydroxy-3-phenoxypropyl (meth) acrylate and the like can be mentioned.
Examples of monofunctional (meth) acrylates having a carboxyl group include (meth) acrylic acid, Michael-added dimer of acrylic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, and monohydroxyethyl phthalate (meth). Examples include acrylate.
Examples of monofunctional (meth) acrylates having a cyclic ether group include glycidyl (meth) acrylates, tetrahydrofurfuryl (meth) acrylates, and (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl. Examples thereof include (meth) acrylate, cyclohexanespiro-2- (1,3-dioxolan-4-yl) methyl (meth) acrylate, 3-ethyl-3-oxetanylmethyl (meth) acrylate and the like.
Examples of the monofunctional (meth) acrylate having a heterocycle include (meth) acryloylmorpholine and a compound having a maleimide group, N- (2- (meth) acryloxyethyl) hexahydrophthalimide, and N- (2). -A monofunctional (meth) acrylate having an imide group such as (meth) acryloxyethyl) tetrahydrophthalimide and the like can be mentioned.

Specifically, as monofunctional (meth) acrylamide,
N-methyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (meth) acrylamide, N-sec-butyl (meth) acrylamide, Nt- N-alkyl (meth) acrylamide such as butyl (meth) acrylamide, Nn-hexyl (meth) acrylamide; N-hydroxyalkyl (meth) acrylamide such as N-hydroxyethyl (meth) acrylamide; and N, N-dimethyl Aminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-di-n-propyl (meth) ) Acrylamide, N, N-diisopropyl (meth) acrylamide, N, N-di-n-butyl (meth) acrylamide and N, N-dialkyl (meth) acrylamide of N, N-dihexyl (meth) acrylamide. ..

Examples of the monofunctional unsaturated compound include N-vinylpyrrolidone, N-vinylcaprolactam and the like, in addition to the above.

1-2. Polyfunctional unsaturated compound As the polyfunctional unsaturated compound, a compound having two (meth) acryloyl groups [hereinafter referred to as "bifunctional (meth) acrylate"] and a compound having three or more (meth) acryloyl groups. [Hereinafter referred to as "trifunctional or higher (meth) acrylate"].

Specifically, as the bifunctional (meth) acrylate,
An aliphatic diol di (meth) acrylate such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butane diol di (meth) acrylate, hexane diol di (meth) acrylate and nonane diol di (meth) acrylate;
Di (meth) glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, and other divalent polyols. Meta) Acrylate;
Di (meth) acrylates of these polyol alkylene oxide adducts;
Di (meth) acrylate having an isocyanuric acid skeleton such as di (meth) acrylate of isocyanuric acid ethylene oxide adduct; and di (meth) acrylate of alkylene oxide adduct of bisphenol A, and di (meth) acrylate of alkylene oxide adduct of bisphenol F. Examples thereof include di (meth) acrylate of a bisphenol alkylene oxide adduct such as (meth) acrylate.
In this case, examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide, propylene oxide, tetramethylene oxide, and ethylene oxide and propylene oxide.

Specifically, as the trifunctional or higher (meth) acrylate,
Glycerintri (meth) acrylate, trimethylolpropane tri (meth) acrylate, diglycerintri or tetra (meth) acrylate, pentaerythritol tri or tetra (meth) acrylate, trimethylolpropane tri or tetra (meth) acrylate, and Poly (meth) acrylates of polyols such as tri, tetra, penta or hexa (meth) acrylates of dipentaerythritol; and tri, tetra, penta or hexa (meth) acrylates of alkylene oxide adducts of these polyols; and ethylene isocyanurate. Examples thereof include tri (meth) acrylate having an isocyanuric acid skeleton such as tri (meth) acrylate of an oxide adduct.
In this case, examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide, propylene oxide, tetramethylene oxide, and ethylene oxide and propylene oxide.

Examples of the polyfunctional unsaturated compound include urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, and polyether (meth) acrylate.
Hereinafter, these compounds will be described.

1-2-1. Urethane (meth) acrylate As the urethane (meth) acrylate, a reaction product of a polyol, an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate (hereinafter referred to as “UA1”), and a reaction of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate. Things (hereinafter referred to as "UA2") and the like can be mentioned.
Hereinafter, UA1 and UA2 will be described.

1) UA1
UA1 is a reaction product of a polyol, an organic polyisocyanate, and a hydroxyl group-containing (meth) acrylate.

As the polyol in UA1, diol is preferable.
As the diol, a low molecular weight diol, a diol having a polyester skeleton, a diol having a polyether skeleton, and a diol having a polycarbonate skeleton are preferable.
Examples of the low molecular weight diol include ethylene glycol, propylene glycol, cyclohexanedimethanol, neopentyl glycol, 3-methyl-1,5-pentanediol, and the like.
Examples thereof include 1,6-hexanediol.
Examples of the diol having a polyester skeleton include an esterification reaction product of a diol component such as the low molecular weight diol or polycaprolactone diol and an acid component such as a dicarboxylic acid or an anhydride thereof.
Examples of the dicarboxylic acid or its anhydride include adipic acid, succinic acid, phthalic acid, tetrahydraphthalic acid, hexahydrophthalic acid, terephthalic acid and the like, and their anhydrides and the like.
Examples of the polyether diol include polyethylene glycol, polypropylene glycol, polyetramethylene glycol and the like.
Examples of the polycarbonate diol include a reaction product of the low molecular weight diol and / or bisphenol such as bisphenol A and a carbonic acid dialkyl ester such as ethylene carbonate and carbonic acid dibutyl ester.

Examples of the organic polyisocyanate include an aliphatic polyisocyanate having no alicyclic group (hereinafter, simply referred to as "aliphatic polyisocyanate") and an aliphatic polyisocyanate having an alicyclic group (hereinafter, "aliphatic polyisocyanate"). ), Polyisocyanate having a heterocycle, aromatic polyisocyanate and the like.
Examples of the aliphatic polyisocyanate include 1,6-hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylhexamethylene diisocyanate and lysine diisocyanate.
Examples of the alicyclic polyisocyanate include hydrogenated tolylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, and isophorone diisocyanate trimeric. Will be.
Examples of the polyisocyanate having a heterocycle include a 1,6-hexane diisocyanate trimer.
Examples of the aromatic diisocyanate include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,5-naphthalenedi isocyanate and the like.
In the present invention, the organopolyisocyanate is preferably an aliphatic polyisocyanate in that it has good compatibility with a poor solvent, can increase the degree of freedom in blending design of the composition, and has less yellowing of the cured product.

As the hydroxyl group-containing (meth) acrylate, a hydroxyl group-containing mono (meth) acrylate is preferable.
Examples of the hydroxyl group-containing mono (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate and hydroxy. Examples thereof include hydroxyalkyl (meth) acrylates such as octyl (meth) acrylates.

1) UA2
UA2 is a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate, and is a compound called urethane adduct.
By using UA2 as the component (A), the crosslink density becomes high, and good heat resistance and hardness are maintained even if the number of compounding parts is increased for the purpose of imparting flexibility to the member on which the cured coating film is formed. It is preferable because it can be done.

In UA2, examples of the organic polyisocyanate and the hydroxyl group-containing (meth) acrylate include the above-mentioned compounds.

In UA2, as the hydroxyl group-containing (meth) acrylate, a compound having a hydroxyl group and two or more (meth) acryloyl groups (hereinafter referred to as “hydroxyl-containing polyfunctional (meth) acrylate”) can also be used.
By using the organic polyisocyanate and the hydroxyl group-containing polyfunctional (meth) acrylate (hereinafter referred to as "UA2-1") as the UA2 component, the crosslink density is increased, the heat resistance is improved, and the hardness is improved. It is preferable because it has excellent wear resistance and scratch resistance.
As the hydroxyl group-containing polyfunctional (meth) acrylate, various compounds can be used, specifically, trimethylolpropane di (meth) acrylate, pentaerythritol di or tri (meth) acrylate, and trimethylolpropane di or tri. Examples thereof include (meth) acrylate and di, tri, tetra or penta (meth) acrylate of dipentaerythritol.
Among these, a compound having three or more (meth) acryloyl groups and one hydroxyl group is preferable because the cured film is excellent in hardness, abrasion resistance and scratch resistance, and specifically, penta. Examples thereof include erythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate and dipentaerythritol penta (meth) acrylate.
Among these compounds, pentaerythritol tri (meth) acrylate is more preferable because it can prevent the obtained cured product from warping.

In the production of UA2-1, the hydroxyl group-containing polyfunctional (meth) acrylate as a raw material is usually a mixture containing a hydroxyl group-containing polyfunctional (meth) acrylate and a hydroxyl group-free polyfunctional (meth) acrylate. Can also be used as a product produced by using the mixture.
Specifically, a mixture of trimethylolpropane di (meth) acrylate and trimethylolpropane tri (meth) acrylate, a mixture of trimethylolpropane tri (meth) acrylate and trimethylolpropane tetra (meth) acrylate, and dipentaerythritol penta. Examples thereof include a mixture of (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

Another preferred compound of UA2 is a reaction product of an organic polyisocyanate having three or more isocyanate groups and a hydroxyl group-containing mono (meth) acrylate (hereinafter referred to as "UA2-2").
Examples of the hydroxyl group-containing mono (meth) acrylate in UA2-2 include compounds similar to those described above.
Examples of the organic polyisocyanate having three or more isocyanate groups include the hexamethylene diisocyanate trimer and the isophorone diisocyanate trimer described above.
Preferred examples of UA2-2 include an addition reaction product of hexamethylene diisocyanate trimer and hydroxybutyl acrylate.

Further, as UA2, a compound which is a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate and has three or more (meth) acryloyl groups is more preferable. The compound maintains rigidity due to the crosslink density of the cured product and at the same time has high toughness.
Examples of the compound include the above-mentioned UA2-1 and UA2-2.

3) Method for producing urethane (meth) acrylate Urethane (meth) acrylate is an addition reaction of polyol, organic polyisocyanate and hydroxyl group-containing (meth) acrylate in UA-1, and organic polyisocyanate and hydroxyl group in UA-2. It is produced by the addition reaction of the contained (meth) acrylate.
This addition reaction can be carried out without a catalyst, but in order to proceed the reaction efficiently, a tin-based catalyst such as dibutyltin dilaurate or an amine-based catalyst such as triethylamine may be added.

1-2-2. Polyester (meth) acrylate Examples of the polyester (meth) acrylate include a dehydration condensate of a polyester diol and (meth) acrylic acid.
Here, examples of the polyester diol include a reaction product of the diol and a dicarboxylic acid or an anhydride thereof.
Examples of the diol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, tetramethylene glycol, hexamethylene glycol, and neo. Examples thereof include low molecular weight diols such as pentyl glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol and 1,6-hexanediol, and alkylene oxide adducts thereof.
Examples of the dicarboxylic acid or its anhydride include dicarboxylic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid and trimellitic acid, and these. Anhydrous and the like can be mentioned.

1-2-3. Epoxy (meth) acrylate Epoxy (meth) acrylate is a compound obtained by addition-reacting (meth) acrylic acid to an epoxy resin. Examples of the epoxy resin include aromatic epoxy resins and aliphatic epoxy resins.

Specific examples of the aromatic epoxy resin include resorcinol diglycidyl ether and hydroquinone diglycidyl ether; bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene or a diglycidyl ether of an alkylene oxide adduct thereof; phenol novolac type epoxy resin and Novolak type epoxy resin such as cresol novolak type epoxy resin; glycidyl phthalimide; o-phthalic acid diglycidyl ester and the like can be mentioned.

Specific examples of the aliphatic epoxy resin include diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol; diglycidyl ethers of polyethylene glycol and polypropylene glycol. Diglycidyl ether of polyalkylene glycol; diglycidyl ether of neopentyl glycol, dibromoneopentyl glycol and its alkylene oxide adduct; diglycidyl ether of hydrogenated bisphenol A and its alkylene oxide adduct; tetrahydrophthalic acid diglycidyl ester and the like. Can be mentioned.
In the above, as the alkylene oxide of the alkylene oxide adduct, ethylene oxide, propylene oxide and the like are preferable.

1-2-4. Polyether (meth) acrylate Polyether (meth) acrylate oligomers include polyalkylene glycol (meth) diacrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polytetramethylene glycol di (meth). ) Examples include acrylate.

As the component (A) of the present invention, only one of the above-mentioned compounds or two or more of them can be used in combination depending on the purpose and use.

1-3. Among these compounds, the preferable component (A) and component (A) have good thin film curability in air, and the surface of the component (B) can be efficiently arranged on the outermost surface of the coating film. , Polyfunctional unsaturated compounds are preferred, and polyfunctional (meth) acrylates are more preferred. As the polyfunctional unsaturated compound, a trifunctional or higher unsaturated compound [hereinafter, also referred to as “(A1) component”] is preferable, and a trifunctional or higher (meth) acrylate is more preferable, and specific examples thereof are the above-mentioned compounds. Of these, compounds having three or more (meth) acryloyl groups can be mentioned.
More preferable specific examples of the component (A1) are pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri, tetra, penta or hexa (meth). ) Acrylate, tri or tetra (meth) acrylate of alkylene oxide adduct of diglycerin, tri (meth) acrylate of alkylene oxide adduct of trimethylolpropane, and compounds having three or more (meth) acryloyl groups in UA2, etc. Can be mentioned.
Further, as the component (A1), among these compounds, a compound having a hydrophilic group is more preferable because the obtained cured film has excellent antiviral properties. Examples of hydrophilic groups include hydroxyl groups, alkylene oxide groups, and urethane groups.
Specific examples of these compounds include pentaerythritol tri (meth) acrylate and dipentaerythritol tri, tetra, or penta (meth) acrylate as examples of the compound having a hydroxyl group, and have an alkylene oxide group. Examples of the compound include tri or tetra (meth) acrylate of an alkylene oxide adduct of diglycerin, tri (meth) acrylate of an alkylene oxide adduct of trimethylolpropane, and the like, and compounds having a urethane group. Examples include compounds having three or more (meth) acryloyl groups in UA2.

Further, the component (A1) of the present invention is a tri or tetra (meth) acrylate of an alkylene oxide adduct of diglycerin [hereinafter, also referred to as “component (A1-1)” because the cured product is excellent in flexibility. ] Is preferable.
Examples of the alkylene oxide adduct in the component (A1-1) include ethylene oxide adducts, propylene oxide adducts, ethylene oxide and propylene oxide adducts, and ethylene oxide adducts are preferable.
The number of moles of the alkylene oxide adduct added in the component (A1-1) is preferably 2 to 10 mol, more preferably 4 to 8 mol.
The component (A1-1) is tri (meth) acrylate or tetra (meth) acrylate, and tetra (meth) acrylate is preferable.

As the component (A1-1), one manufactured according to a conventional method can be used, and specifically, a polyol (hereinafter, simply referred to as “polyol”) which is an alkylene oxide adduct of diglycerin and (meth). Examples thereof include a production method in which acrylic acid is esterified, a production method in which a polyol is transesterified, and the like.
As a production method by the esterification reaction and the transesterification reaction of the component (A1-1), for example, the method described in JP-A-2016-023203 may be followed.
The component (A1-1) may contain mono, di and tri (meth) acrylates.

As the component (A1-1), tetra (meth) acrylate obtained from a polyol obtained by adding 4 to 8 mol of ethylene oxide to diglycerin (hereinafter, simply referred to as “polyol”) is particularly preferable.
The polyol which is the raw material compound of the component (A1-1) is a compound having four hydroxyl groups in one molecule, and is a compound in which 4 to 8 mol of ethylene oxide is added to diglycerin.
When the number of moles of ethylene oxide added is 4 mol or more, the flexibility of the cured film can be improved, and when it is 8 mol or less, the hardness of the cured film is high and the performance as a coating agent is high. Can be excellent.

The component (A1) of the present invention includes a compound having three or more ethylenically unsaturated groups other than the component (A1-1) in addition to the component (A1-1) [hereinafter, "component (A1-2)". ]: Is preferable.
Preferred examples of the component (A1-2) are the compounds mentioned as preferable specific examples of the component (A1), such as pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and trimethylolpropane tri (meth). Acrylate, tri, tetra, penta or hexa (meth) acrylate of dipentaerythritol, tri or tetra (meth) acrylate of alkylene oxide adduct of diglycerin, tri (meth) acrylate of alkylene oxide adduct of trimethylolpropane, and Examples of UA2 include compounds having three or more (meth) acryloyl groups.
Among these compounds, a compound having three or more (meth) acryloyl groups in UA2 is preferable, and urethane (meth) acrylate, which is a reaction product of pentaerythritol tri (meth) acrylate and an organic polyisocyanate, is more preferable.

As the content ratio of the component (A1-1) and the component (A1-2), the components (A1-1) 45 to 95 are based on 100% by weight of the total amount of the component (A1-1) and the component (A1-2). By weight% and (B) component 5 to 55% by weight are preferable, and more preferably (A1-1) component 50 to 95% by weight and (A1-2) component 5 to 50% by weight, and the component (A1-1). By setting the content ratio to 45% by weight or more, or setting the content ratio of the component (A1-2) to 55% by weight or less, the obtained cured product can be made excellent in flexibility and curl. Scratch resistance (steel wool resistance) of the cured product by setting the content ratio of the (A1-1) component to 95% by weight or less, or setting the content ratio of the (A1-2) component to 5% by weight or more. Can be excellent.

2. 2. Component (B ) Component (B) is a substance having an acid point on the surface of an inorganic solid. Component (B1); an antiviral agent containing an inorganic solid acid having an acid point concentration of more than 0.005 mmol / g. ..
By including the component (B), the obtained cured film exhibits the effect of inactivating the virus (hereinafter referred to as "antiviral effect").
Here, the acid point means a place showing a property of giving a proton to a base or a property of receiving an electron pair from a base. The number of acid points can be expressed by the acid point concentration, and is usually expressed as the number of acid points or acidic centers on the surface of a solid, usually as the number per unit weight or unit surface area of a solid, or the number of moles.
Further, the component (B) is excellent in dispersibility in the composition and is stable so as not to cause precipitation or coagulation during storage of the composition.

1-1. Component (B1) In the component (B1), the concentration of acid points (acid point concentration) on the surface of the inorganic solid shall exceed 0.005 mmol / g in order to suitably exhibit the antiviral effect.
Since the higher the acid point concentration, the higher the antiviral effect, there is no upper limit to the acid point concentration of the inorganic solid acid. However, since it is not generally known that the acid point concentration exceeds 10 mmol / g, the upper limit is usually 10 mmol / g.
The acid point concentration of the component (B1) is preferably 0.008 mmol / g or more, more preferably 0.01 mmol / g or more. In particular, the antiviral effect of the (B1) component having an acid point concentration of 0.01 mmol / g or more is excellent.
As described above, the antiviral agent of the present invention exerts an antiviral effect at the acid point on the surface of the component (B1) having an acid point concentration of more than 0.005 mmol / g.
Viruses are usually found in (1) cell surface adsorption, (2) intracellular invasion, (3) unshelling, (4) component synthesis, (5) component assembly, and (6) infected cells. It proliferates through the stage of release. It is presumed that the component (B1) exerts an antiviral effect by inactivating the adsorption of the virus on the cell surface in contact with the acid point on the surface of the inorganic solid.

The acid point concentration can be determined by measuring the amount of the base that reacts with the powder (inorganic solid acid).
The acid point concentration can be measured in the liquid phase or the gas phase. A titration method is known as a method for measuring in a liquid phase. Further, as a method for measuring in the gas phase, a gas chemical adsorption method for measuring the difference between the amount of desorption of He gas or hydrogen gas and the amount of desorption of basic gas is known.
Since the reaction between the antiviral agent and the virus in the present invention is a liquid-mediated reaction, the titration method in the liquid phase is suitable for measuring the acid point concentration.

The specific method for measuring the acid point concentration of the inorganic solid acid by the titration method in the liquid phase is as follows.
The inorganic solid acid dispersed in the non-polar solvent is titrated with n-butylamine, and the end point of the titration is confirmed by the discoloration of the acid-base conversion indicator. The indicator before the reaction has a basic color, but when adsorbed on an inorganic solid acid, it has a conjugate acid color. The acid point concentration is determined from the titration amount of n-butylamine required to return from the conjugate acid type color to the base type color. One solid acid point corresponds to one n-butylamine molecule. Since the titration base must replace the indicator that has reacted with the acid point of the solid, its basicity is stronger than that of the indicator.
In the usual titration method, when an indicator is added to an inorganic solid acid / benzene dispersion, the indicator shows an acidic color due to solid acidity, but it is preferable to allow a sufficient time for the reaction to be completed. Next, n-butylamine is added dropwise, and the acid point concentration is calculated from the amount of n-butylamine when the color of the indicator returns to the basic color which is the original color.

The specific procedure for measuring the acid point concentration of the inorganic solid acid is as follows.
(1) 10 mL of benzene and 0.5 g of an inorganic solid acid are placed in a 20 mL sample bottle and stirred to disperse the inorganic solid acid. For example, 20 of these mixed dispersions are prepared.
(2) Add n-butylamine having a normal concentration of 0.1 N to each sample bottle in different amounts, and stir with a shaker to prepare 20 kinds of mixed solutions.
(3) After 24 hours, 0.5 mL of 0.1% indicator methyl red solution is added to each mixed solution, and the discoloration of the indicator is observed.
(4) The amount of n-butylamine added in the system in which the discoloration of the indicator is not confirmed is the largest amount, and the amount of base reacted with the acid point is defined as the acid point concentration (mmol / g).

The component (B1) is preferably an inorganic compound having a structure in which a substituent having proton donating property or proton accepting property is arranged on the surface with which the virus comes into contact.
Specific examples of the inorganic solid acid include phosphoric acid compounds of titanium group elements such as zirconium phosphate, hafnium phosphate and titanium phosphate, and inorganic phosphoric acid compounds such as aluminum phosphate and hydroxyapatite (phosphate mineral); Inorganic silicate compounds such as magnesium silicate, silica gel, aluminosilicate, sepiolite (hydrous magnesium silicate), montmorillonite (silicate mineral), zeolite (aluminosilicate); alumina, titania, titanium hydroxide-containing and the like. .. Among these, α-type or γ-type zirconium phosphate, α-type or γ-type titanium phosphate, amorphous magnesium silicate, active titanium oxide and the like are preferable because the acid point concentration exceeds 0.005 mmol / g.

In the inorganic solid acid, the acid point on the surface of the inorganic solid has strength. That is, if the acid point concentration of the inorganic solid acid itself is high and the intensity of each acid point is high, a higher antiviral effect can be obtained. Therefore, the inorganic solid acid contained in the antiviral agent of the present invention preferably has a high acid point strength. The strength of this acid point can be expressed as pKa as the acid strength.

As the acid strength of the component (B1), pKa is preferably 3.3 or less, more preferably pKa 1.5 or less, and further preferably 0.8 or less.
When the acid strength of the acid point is small, that is, when the pKa is high, the ability to inactivate the virus tends to decrease, and when the pKa is 0.8 or less, particularly excellent antiviral performance is obtained.
The lower the pKa, the stronger the property of giving a proton to the base or the property of receiving an electron pair from the base, that is, the stronger the acid strength, and the stronger the acid strength, the higher the ability to inactivate the virus.

The acid strength of the component (B1) is the ability of the acid point on the surface of an inorganic solid acid to give a proton to a base or the ability to receive an electron pair from a base. The acid strength (pKa) of the inorganic solid acid can be measured as the ability to change the base type to its conjugate acid type using various acid-base conversion indicators for which pKa is known. When the base type changes to the conjugated acid type, the acid-base conversion indicator changes color to enable discrimination.
Acid-base conversion indicators (pKa values) that can be used to measure acid strength include methyl red (+4.8), 4-phenylazo-1-naphthylamine (+4.0), dimethyl yellow (+3.3), and 2 -Amino-5-azotoluene (+2.0), 4-phenylazo-diphenylamine (+1.5), 4-dimethylaminoazo-1-naphthalene (+1.2), crystal violet (+0.8), p-nitrobenzeneazo Examples thereof include -p'-nitro-diphenylamine (+0.43), dicinnamylacetone (-3.0), benzalacetophenone (-5.6), anthraquinone (-8.2) and the like.

An example of a method for measuring the acid strength (pKa) of an inorganic solid acid using the above acid-base conversion indicator is shown below.
(1) 2 mL of benzene and 0.1 g of an inorganic solid acid are placed in a test tube and stirred to disperse the inorganic solid acid. Prepare as many dispersions as the type of acid-base conversion indicator to be tested.
(2) Add about 2 drops of 0.1% benzene solution of various acid-base conversion indicators (Crystal Violet is not a benzene solution but a 0.1% ethanol solution) to the dispersion and shake gently to color. Observe the changes.
(3) The acid strength (pKa) of the inorganic solid acid is equal to or lower than the strongest acid strength (that is, the lowest pKa value) in which discoloration of the indicator is confirmed, and the weakest acid strength (ie, the lowest pKa value) in which discoloration of the indicator is not confirmed. It will be larger than the highest pKa value). Therefore, the pKa value of the inorganic solid acid is expressed as (the highest pKa value in which discoloration is not confirmed) to (the lowest pKa value in which discoloration is confirmed). If there is no appropriate indicator indicating the lower limit, it is "below the lowest pKa value in which discoloration is confirmed", and if there is no appropriate indicator indicating the upper limit, it is "greater than the highest pKa value in which discoloration is not confirmed". ..

The component (B1) can contain silver, copper, or both. The antiviral agent of the present invention may contain an inorganic solid acid having a silver ion (silver atom) or a copper ion (copper atom) in its structure, and may contain silver or copper or a compound thereof and silver. And may be a mixture with an inorganic solid acid containing no copper. An antiviral agent containing silver or copper has an excellent antiviral effect. The total content of silver or copper or a compound thereof in such an antiviral agent is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 1% by mass or more. be. Examples of the inorganic solid acid having a silver ion (silver atom) or a copper ion (copper atom) in the structure include zirconium silver phosphate and zirconium copper phosphate.

The component (B1) is preferably in the form of powder in order to be applied to processing into various materials and forms.
The powdery (B1) component contains the (B1) component and a binder to prepare a coating composition having excellent dispersibility, and contains the (B1) component and a molding resin, and is a resin molded product having excellent dispersibility. It is suitable for the preparation of a resin composition and the like.
The average particle size of the powdery component (B1) is preferably 0.01 to 50 μm, more preferably 0.1 to 20 μm. Powders with an average particle size of 0.01 μm or more are difficult to aggregate and have the advantage of being easy to handle. Further, the coating composition containing a powder having an average particle size of 50 μm or less has an advantage that the texture of the coated fiber is not impaired when applied to the surface of the fiber because of its good dispersibility. The particle size can be measured with a laser diffraction type particle size distribution measuring device or the like, and is a median diameter analyzed on a volume basis.

The color tone of the component (B1) is not limited, but white or a light color with high lightness is preferable in order to apply it to processing into various materials and forms. The brightness is preferably 80 or more, more preferably 85 or more, and further preferably 95 or more in terms of L value measured by a color difference meter.

The component (B1) has a certain amount of water, so that the antiviral effect is easily exhibited.
The water content in the component (B1) is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 3% by mass or more. In addition, the moisture-absorbing inorganic solid acid can retain moisture in the inorganic solid acid even when mixed with other materials or when the humidity of the atmosphere changes, so that it can inactivate the virus. It is excellent in that the antiviral agent itself has the necessary water content.

1-2. Components other than the component (B1) The component (B) contains the component (B1) as an essential component, but may contain other components other than the component (B1), if necessary.

As an example of the component other than the component (B1), an inorganic solid acid other than the component (B1), that is, an inorganic solid acid having an acid point concentration of 0.005 mmol / g or less [hereinafter referred to as “(B2) component”] is used. Can be mentioned.
Specific examples of the inorganic solid acid in (B2) formation include the above-mentioned phosphoric acid compounds of titanium group elements, inorganic phosphoric acid compounds, inorganic silicic acid compounds, alumina, titania, and hydroxide-containing titanium.

As the inorganic solid acid in the component (B2), a compound containing silver, copper, or both can be used. The inorganic solid acid in the component (B2) may contain an inorganic solid acid having a silver ion (silver atom) or a copper ion (copper atom) in the structure.
As the inorganic solid acid in the component (B2), an acid containing the above metal is preferable because it can impart antibacterial properties to the component (B) in addition to antiviral properties.

The content ratio of the component (B2) in the component (B) is arbitrary as long as the acid point concentration in the finally obtained component (B) exceeds 0.005 mmol / g, but it is preferable. It is preferable that the total amount of the component (B1) and the component (B2) is 100% by weight, and the component (B2) is contained in an amount of 0 to 50% by weight, more preferably 1 to 30% by weight.

1-3. Preferred Embodiment of (B) Component The preferred embodiment of the component (B) is the same as the preferred embodiment described in the component (B1).
The component (B) preferably has an acid point concentration of more than 0.005 mmol / g, more preferably 0.008 mmol / g or more, and particularly preferably 0.01 mmol / g or more.
As the component (B), the upper limit of the acid point concentration is preferably 10 mmol / g or less.

As the acid strength of the component (B), pKa is preferably 3.3 or less, more preferably pKa 1.5 or less, and further preferably 0.8 or less.

The component (B) is preferably in the form of powder in order to be applied to processing into various materials and forms.
The powdery component (B) contains the component (B) and a binder to prepare a coating composition having excellent dispersibility, and contains the component (B) and a molding resin, and is a resin molded product having excellent dispersibility. It is suitable for the preparation of a resin composition and the like.
The average particle size of the powdery component (B) is preferably 0.01 to 50 μm, more preferably 0.1 to 20 μm. Powders with an average particle size of 0.01 μm or more are difficult to aggregate and have the advantage of being easy to handle. Further, the coating composition containing a powder having an average particle size of 50 μm or less has an advantage that the texture of the coated fiber is not impaired when applied to the surface of the fiber because of its good dispersibility.

The color tone of the component (B) is not limited, but white or a light color with high lightness is preferable in order to apply it to processing into various materials and forms. The brightness is preferably 80 or more, more preferably 85 or more, and further preferably 95 or more in terms of L value measured by a color difference meter.

When the component (B) has a certain amount of water, the antiviral effect is likely to be exhibited.
The water content in the component (B) is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 3% by mass or more. In addition, the moisture-absorbing inorganic solid acid can retain moisture in the inorganic solid acid even when mixed with other materials or when the humidity of the atmosphere changes, so that it can inactivate the virus. It is excellent in that the antiviral agent itself has the necessary water content.

Generally, for measuring the antiviral effect, a method of measuring the amount of virus (infection titer) by utilizing the phenomenon of cell degeneration in which the shape of a cell infected with a virus changes is used.
Examples of the method for measuring the infectious titer include a method for measuring the number of plaques, a method for measuring 50% tissue culture infection (TCID50), and a method for measuring 50% chicken egg infection (EID50: egg infective dose 50).
The antiviral effect can be evaluated as an antiviral activity value obtained by the following formula (1). In the formula (1), the initial virus infectious titer means the amount of virus in the virus solution immediately after inoculation used for the evaluation, and the residual virus infectious titer means the amount of virus after a certain period of time has passed in contact with the anti-virus sample. means. The higher the value of the antiviral activity value, the higher the antiviral effect, preferably 2 or more, and more preferably 3 or more.
Antiviral activity value = Log (initial viral load) -Log (residual viral load) (1)

3. 3. Composition for active energy ray-curable anti-virus The present invention relates to a composition for active energy ray-curable anti-virus containing the components (A) and (B).
As a method for producing the composition, a conventional method may be followed, and for example, the components (A) and (B) and, if necessary, other components may be stirred and mixed to produce the composition.

As for the ratio of the components (A) and (B), it is said that the composition can be easily prepared, the liquid property with good handleability can be maintained, and the white turbidity of the cured film caused by the component (B) is less noticeable. For this reason, when the component (A) is 100 parts by weight, the mixing ratio of the component (B) is preferably 1 to 60 parts by weight, more preferably 3 to 50 parts by weight.

The composition of the present invention can exert an antiviral effect against various viruses.
For example, influenza virus, enveloped virus such as coronavirus, and non-embelope virus such as norovirus can be mentioned.
The composition of the present invention is preferably applicable to enveloped viruses.

The composition of the present invention contains the above-mentioned components (A) and (B) as essential components, but various components can be blended depending on the purpose.
Specific examples of the other components include a photopolymerization initiator [hereinafter referred to as “(C) component”], an organic solvent [hereinafter referred to as “(D) component”], an antioxidant, an ultraviolet absorber, and a pigment. Examples include dyes, leveling agents, silane coupling agents and the like.
Hereinafter, these components will be described.

3-1. Component (C) Component (C) is a photopolymerization initiator.
The component (C) is a component to be blended when ultraviolet rays and visible light are used as active energy rays. When an electron beam is used as the active energy ray, it is not always necessary to blend it, but a small amount may be blended if necessary in order to improve the curability.

Specific examples of the component (C) include benzyldimethylketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropane-. 1-on, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, oligo [2-hydroxy-2-methyl-1- [4-1] -(Methylvinyl) phenyl] propanone, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) benzyl] phenyl] -2-methylpropane-1-one, 2-methyl- 1- [4- (Methylthio)] Phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2-dimethylamino -2- (4-Methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butane-1-one, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n- Aromatic ketone compounds such as octylcarbazole, methyl phenylglioxyate, ethylanthraquinone and phenanthrenquinone;
Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4- (methylphenylthio) phenylphenylmethane, methyl-2-benzophenone, 1- [4- (4-Benzoylphenyl sulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis Benzophenone compounds such as (diethylamino) benzophenone and 4-methoxy-4'-dimethylaminobenzophenone;
Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate and bis (2,6-- Acylphosphine oxide compounds such as dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide;
Thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl-9-oxo-9H-thioxanthone-2-yl-oxy]- Examples thereof include thioxanthone compounds such as 2-hydroxypropyl-N, N, N-trimethylammonium chloride and fluorothioxanthone.

Among these compounds, α-hydroxyphenyl ketones are preferable because they have good surface curability even when coated with a thin film in the atmosphere, and specifically, 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2. -Methyl-1-phenyl-propane-1-one is more preferable.
Further, when it is necessary to increase the thickness of the cured film, for example, when it is necessary to make it 50 μm or more, for the purpose of improving the curability inside the cured film, or when using an ultraviolet absorber or a pigment together, a screw is used. (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl- (2,4,6-trimethylbenzoyl) phenylphosphinate and bis (2,6) -Acylphosphine oxide compounds such as dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2-methyl-1- [4- (methylthio)] phenyl] -2-morpholinopropane-1-one, 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) ) -Butan-1-on and the like are preferably used in combination.

The content ratio of the component (C) is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the total amount of the component (A). By setting the ratio of the component (C) to 0.1 parts by weight or more, the photocurability of the composition can be improved and the adhesion can be improved, and by setting the ratio to 10 parts by weight or less, the cured film can be obtained. The internal curability of the material can be improved, and the adhesion to the substrate can be improved.

3-2. Component (D) The composition of the present invention can be used as a solvent-free composition, but the component (D) component (organic solvent) may be blended and used as a solvent-type composition. You can also.
By including the component (D), the coatability can be improved by adjusting the viscosity of the composition, and the film thickness can be adjusted according to the purpose. Further, by containing the component (D), the component (B) can be effectively exposed on the outermost surface of the coating film by drying after coating on the substrate, whereby the component (B) can be finally exposed. The component (B) can be effectively exposed on the outermost surface of the obtained cured film, and the antiviral property can be effectively exhibited.

Specific examples of the component (D) include alcohols such as methanol, ethanol and isopropanol; alkylene glycol monoethers such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone alcohols such as diacetone alcohol; aromatics such as toluene and xylene. Compounds; esters such as propylene glycol monomethyl ether acetate, ethyl acetate, and butyl acetate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethers such as dibutyl ether; and N-methylpyrrolidone and the like.
As the component (D), among the above compounds, alkylene glycol monoethers, aromatic compounds, esters, and ketones are preferable because they have good compatibility with the component (A) and dryness.

The content ratio of the component (D) is preferably 0.01 to 200 parts by weight, more preferably 10 to 150 parts by weight, and 20 parts by weight, based on 100 parts by weight of the total solid content of the composition. It is more preferably to 100 parts by weight.

3-3. Antioxidants Antioxidants are added for the purpose of improving the durability such as heat resistance and weather resistance of the cured film.
Examples of the antioxidant include a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like.
Examples of the phenolic antioxidant include hindered phenols such as dit-butylhydroxytoluene. Examples of commercially available products include AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80 manufactured by Adeca Co., Ltd.
Examples of the phosphorus-based antioxidant include phosphines such as trialkylphosphine and triarylphosphine, and trialkyl phosphite and triaryl phosphite. Commercially available products of these derivatives include, for example, Adecaster PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010. And so on.
Examples of the sulfur-based antioxidant include thioether-based compounds, and examples of commercially available products include AO-23, AO-412S, and AO-503A manufactured by Adeca Co., Ltd.
These may be used alone or in combination of two or more. Preferred combinations of these antioxidants include a combination of a phenol-based antioxidant and a phosphorus-based antioxidant, and a combination of a phenol-based antioxidant and a sulfur-based antioxidant.
The blending ratio of the antioxidant may be appropriately set according to the purpose, and is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total amount of (A) components. It is a department.
The durability of the composition can be improved by setting the blending ratio to 0.01 parts by weight or more, while the curability and adhesion can be improved by setting the blending ratio to 5 parts by weight or less.

3-4. Ultraviolet absorber The ultraviolet absorber is added for the purpose of improving the light resistance of the cured film.
Examples of the ultraviolet absorber include triazine-based ultraviolet absorbers such as TINUVIN400, TINUVIN405, TINUVIN460, and TINUVIN479 manufactured by BASF, and benzotriazole-based ultraviolet absorbers such as TINUVIN900, TINUVIN928, and TINUVIN1130.
The blending ratio of the ultraviolet absorber may be appropriately set according to the purpose, and is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total amount of (A) components. It is a department. When the blending ratio is 0.01 parts by weight or more, the light resistance of the cured film can be improved, while when it is 5 parts by weight or less, the curability of the composition is excellent. be able to.

3-5. Pigments / Dyes Pigments include organic pigments and inorganic pigments.
Specific examples of organic pigments include insoluble azo pigments such as toluidin red, toluidin maroon, hanza ero, benzidine ero and pyrazolone red; soluble azo pigments such as litol red, heliobordeaux, pigment scarlet and permanent red 2B; alizarin and indantron. And derivatives from building dyes such as thioindigomaroon; phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green; quinacridone organic pigments such as quinacridone red and quinacridone magenta, perylene organic pigments such as perylene red and perylene carlet; iso Isoindolinone-based organic pigments such as indolinone-ero and isoindolinone orange; pyranthron-based organic pigments such as pyranthron red and pyranthron orange; thioindigo-based organic pigments; condensed azo-based organic pigments; benzimidazolone-based organic pigments; quinophthalone Kinophthalone-based organic pigments such as ero, isoindrin-based organic pigments such as isoindrin ero; and other pigments include flavanthron ero, acylamide ero, nickel azo ero, copper azomethin ero, perinone orange, anthron orange, and dianthra. Examples thereof include quinonyl red and dioxazine violet.
Specific examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc flower, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, dark blue, and oxidation. Examples include chrome green, cobalt green, amber, titanium black and synthetic iron black. The carbon black exemplified by the filler can also be used as an inorganic pigment.
As the dye, various conventionally known compounds can be used.

3-6. Leveling agents Silicone-based leveling agents, fluorine-based leveling agents, and the like can be mentioned, and various commercially available leveling agents can be used.

3-7. Silane coupling agent The silane coupling agent is blended for the purpose of improving the interfacial adhesive strength between the cured film and the substrate.
The silane coupling agent is particularly limited as long as it can contribute to improving the adhesiveness with the base material.

Specific examples of the silane coupling agent include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-. Glycydoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-Aminopropyltriethoxysilane, 3-Aminopropyltrimethoxysilane, 3-Aminopropyltriethoxysilane, 3-Triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3 -Aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like can be mentioned.

The blending ratio of the silane coupling agent may be appropriately set according to the purpose, and is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the total amount of (A) components. be.
By setting the blending ratio to 0.1 parts by weight or more, the adhesive strength of the composition can be improved, while by setting the blending ratio to 10 parts by weight or less, it is possible to prevent the adhesive strength from changing with time.

3-8. Hydrophilic polymer When the composition of the present invention is applied to a base material, the coating film after the composition is applied to the base material and dried depending on the type of the base material to be applied and the coating method. In some cases, repelling or the like may occur, and the finally obtained cured film may have a poor appearance.
In this case, it is preferable to add a hydrophilic polymer to the curable composition for the purpose of preventing repelling of the coating film.

Examples of the hydrophilic polymer include polymers having a hydrophilic group.
Examples of the hydrophilic group include an acidic group, a hydroxyl group, a quaternary base and the like, and an acidic group is preferable.
Examples of the acidic group include a carboxyl group, a sulfonic acid group, a phosphoric acid group and the like, and a carboxyl group or a sulfonic acid group is preferable, and a carboxyl group is more preferable.
Examples of the quaternary base include a trialkylammonium halide group such as a trimethylammonium chloride group (methyl chloride addition to a dimethylamino group) and a triethylammonium chloride group (ethyl chloride addition to a diethylamino group), and a dimethylammonium sulfoxide. Examples thereof include a sulfoxide group of dialkylammonium such as a group (sulfate addition to a dimethylamino group) and a diethylammonium sulfoxide group (sulfate addition to a diethylamino group).
As the polymer in which the hydrophilic polymer has an acidic group (hereinafter, referred to as “acid group-containing polymer”), a neutralized salt in which a part or all of the acidic groups are neutralized is preferable. As a method for producing a neutralized salt of the acidic group-containing polymer, a method for producing a neutralized salt as a raw material vinyl-based monomer and a method for producing the acidic group-containing polymer and then neutralizing the polymer are performed. Examples include a manufacturing method.

As the hydrophilic polymer, a polymer having a vinyl-based monomer having a hydrophilic group as an essential constituent monomer unit is preferable. Examples of the vinyl-based monomer having a hydrophilic group include a vinyl-based monomer having an acidic group and a vinyl-based monomer having a hydroxyl group.

Examples of the vinyl-based monomer having an acidic group include an ethylenically unsaturated compound having a carboxyl group, an ethylenically unsaturated compound having a sulfonic acid group, and an ethylenically unsaturated compound having a phosphoric acid group.
Examples of the ethylenically unsaturated compound having a carboxyl group include (meth) acrylic acid, maleic acid, itaconic acid, crotonic acid, and salts of these compounds. Examples of the ethylenically unsaturated compound having a sulfonic acid group include acrylamide 2-methylpropanesulfonic acid, styrenesulfonic acid, and (meth) allylsulfonic acid. Examples of the ethylenically unsaturated compound having a phosphoric acid group include a phosphoric acid group-containing (meth) acrylate such as an esterified product of phosphoric acid and (meth) acrylic acid.
When the acidic group-containing polymer is a neutralized salt in which a part or all of the acidic groups are neutralized, it is preferable to use the neutralized salt as the vinyl-based monomer having an acidic group.
The alkaline compounds for forming the neutralizing salt of the vinyl-based monomer having an acidic group include hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide and lithium hydroxide; ammonia; and triethylamine and triethanol. Examples thereof include amine compounds such as amines.

Examples of the vinyl-based monomer having a hydroxyl group include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate.

Examples of the vinyl-based monomer having a quaternary base include (meth) acryloyloxyethyltrimethylammonium halides such as (meth) acryloyloxyethyltrimethylammonium chloride and (meth) acryloyloxyethyltriethylammonium chloride, and (meth) acryloyloxyalkyltrialkylammonium halides. Examples thereof include (meth) acryloyloxyethyl dialkylammonium sulfoxide such as acryloyloxyethyl dimethylammonium sulfoxide and (meth) acryloyloxyethyl diethylammonium sulfoxide.

The hydrophilic polymer may be a copolymer of a vinyl-based monomer (hereinafter referred to as “other monomer”) other than the vinyl-based monomer having a hydrophilic group.
Other monomers include alkyl (meth) acrylate, alkylaminoalkyl (meth) acrylate, styrene, alkyl vinyl ether, vinylidene chloride, (meth) acrylamide, N-vinylformamide, N-vinylacetamide, vinyl acetate, vinylpyrrolidone, etc. Examples thereof include (meth) acrylonitrile and (meth) acryloylmorpholine.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, and nonyl (meth) acrylate. ) Acrylate, decyl (meth) acrylate and the like can be mentioned.
Examples of the dialkylaminoalkyl (meth) acrylate include dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate.

When a polymer having a quaternary base is used as the hydrophilic polymer, a polymer having an unsaturated group such as a vinyl group or a (meth) acryloyl group can be further used in the polymer. ..
Examples of the polymer include a polymer in which a vinyl-based monomer having at least a quaternary base and a glycidyl (meth) acrylate are used as constituent monomer units, to which (meth) acrylic acid is added, at least 4. Examples thereof include a vinyl-based monomer having a class base and a polymer having (meth) acrylic acid as a constituent monomer unit to which glycidyl (meth) acrylate is added.

As the hydrophilic polymer, in the case of a hydrophilic polymer having an acidic group and / or a hydroxyl group, the weight average molecular weight (hereinafter referred to as “Mw”) is preferably 1,000 to 100,000, preferably 1,000 to 100,000. 30,000 is more preferable.
In the present invention, Mw of the hydrophilic polymer means a value obtained by GPC using standard polystyrene as a calibration curve.
In the case of a polymer having an acidic group such as a carboxylic acid as a hydrophilic group, it means a value measured before neutralization. In addition, since GPC measurement cannot be performed when an amine-based monomer is contained as another monomer, ordinary alkyl (meth) acrylate is used instead of these components, and the same polymerization temperature, initiator concentration, and monomer are used. It means a value obtained by using the GPC measurement result of the polymer polymerized under the conditions such as concentration and solvent concentration as an estimated value.

As the hydrophilic polymer, a polymer produced by using the above-mentioned monomer according to a conventional polymerization method can be used.
For example, a radical polymerization method, a living anion polymerization method, a living radical polymerization method and the like can be mentioned.
Moreover, as a form of polymerization, for example, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method and the like can be mentioned.
In order to produce the above-mentioned low molecular weight polymer by a usual polymerization method, it is usually necessary to increase the amount of chain transfer agent and polymerization initiator. When a polymer using a large amount of chain transfer agent is used, the cured film is easily colored by irradiation with active energy rays, and when a polymer using a large amount of a polymerization initiator is used, the storage stability of the composition is stable. Is likely to decrease.
Therefore, a polymer produced by high-temperature polymerization that does not require a large amount of chain transfer agent or polymerization initiator is preferable.
The temperature of the high temperature polymerization is preferably 160 to 350 ° C, more preferably 180 to 300 ° C.

The form of the hydrophilic polymer may be selected according to the intended purpose, and examples thereof include a hydrophilic polymer, a solution of the hydrophilic polymer, a dispersion liquid of the hydrophilic polymer, and powder. In particular, the hydrophilic polymer obtained by the above-mentioned high-temperature continuous polymerization method is a low-viscosity polymer, and is preferable in that it can be used as it is without being used as a solution or a dispersion.
Specific examples of the solution or dispersion of the hydrophilic polymer include an organic solvent solution of the hydrophilic polymer, an aqueous solution or aqueous dispersion of the hydrophilic polymer, a mixed solution or water dispersion of the organic solvent and water of the hydrophilic polymer. Examples include liquids.
The solid content of the hydrophilic polymer solution and the dispersion is preferably 3 to 70% by weight.
The viscosity of the hydrophilic polymer solution and the dispersion is preferably 5 to 20,000 mPa · s.

The Mw of the polymer obtained by high-temperature continuous polymerization in the hydrophilic polymer is preferably 1,000 to 30,000, more preferably 2,000 to 20,000, and the glass of the polymer obtained by high-temperature continuous polymerization. The transition point (hereinafter referred to as “Tg”) is preferably in the range of −85 ° C. to 120 ° C., and more preferably in the range of −80 ° C. to 100 ° C.
In the present invention, Tg means a value measured at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC), and is a value at the glass transition temperature midpoint (Tmg) in the ΔT-temperature curve. Means.
The polymer obtained by high-temperature continuous polymerization in the hydrophilic polymer is commercially available, and a commercially available product can also be used.
Specifically, as a copolymer having a hydroxyl group, ARUFON UH-2041 (Mw: 2,500, Tg: -50 ° C), ARUFON UH-2190 (Mw: 6,000, Tg: -47 ° C), ARUFON. Examples thereof include UHE-2012 (Mw: 5,800, Tg: 20 ° C.) and ARUFON UH-2170 (Mw: 14,000, polydispersity: 3.5, Tg: 60 ° C.).

As for the content ratio of the hydrophilic polymer, whether the hydrophilic polymer is used as it is or when an aqueous solution or an aqueous dispersion is used, the total amount of the composition is 100 parts by weight based on the solid content. It is preferably 0.5 to 50 parts by weight, more preferably 2 to 40 parts by weight.
By setting the content ratio of the hydrophilic polymer to 0.5 parts by weight or more, it is possible to prevent repelling of the cured film, improve the adhesion to various substrates, and make it a thin substrate such as a film. It is possible to prevent deformation and warpage of the base material when the composition of the present invention is applied and cured, and when the composition is 50 parts by weight or less, the appearance of the cured film is poor, such as cloudiness, uneven streaks, and citron skin. Can be prevented.

4. Method of use As a method of using the composition of the present invention, a conventional method may be followed.
For example, a method of irradiating an active energy ray after applying a composition to a base material can be mentioned.
When the composition contains the component (D) (organic solvent), a method in which the composition is coated on a substrate, heated and dried to evaporate the component (D), and then irradiated with active energy rays. And so on.

Examples of the base material to which the composition of the present invention can be applied include plastics, wood, metals, inorganic materials, paper and the like, which can be applied to various materials.
Specific examples of the plastic include cellulose acetate resins such as polyvinyl alcohol, triacetyl cellulose and diacetyl cellulose, and cyclic polyolefin resins using cyclic olefins such as acrylic resin, polyethylene terephthalate, polycarbonate, polyarylate, polyether sulfone and norbornene as monomers. , Polyvinyl chloride, epoxy resin, polyurethane resin and the like.
Examples of wood include natural wood and synthetic wood.
Examples of the metal include steel plates, metals such as aluminum and chromium, and metal oxides such as zinc oxide (ZnO) and indium tin oxide (ITO).
Examples of the inorganic material include glass, mortar, concrete and stone.

The method for applying the composition of the present invention to the substrate may be appropriately set according to the intended purpose, and is a bar coater, an applicator, a doctor blade, a dip coater, a roll coater, a spin coater, a flow coater, a knife coater, and a comma. Examples thereof include a method of coating with a coater, a reverse roll coater, a die coater, a lip coater, a gravure coater, a microgravure coater and the like.

The film thickness of the composition cured film with respect to the substrate may be appropriately set according to the purpose. The thickness of the cured film may be selected depending on the use of the substrate to be used and the application of the manufactured substrate having the cured film, but is preferably 1 to 100 μm, more preferably 2 to 40 μm. ..

Examples of the active energy ray for curing the composition of the present invention include ultraviolet light, visible light, electron beam and the like, but ultraviolet light is preferable.
Examples of the ultraviolet irradiation device include a high-pressure mercury lamp, a metal halide lamp, a UV electrodeless lamp, and an LED.
The irradiation energy should be appropriately set according to the type and composition of the active energy rays. For example, when a high-pressure mercury lamp is used, the irradiation energy in the UV-A region is 100 to 5,000 mJ /. cm ² is preferable, and 200 to 1,000 mJ / cm ² is more preferable.

As described above, when the composition contains the component (D), it is preferable to apply the composition to the substrate and then heat and dry it to evaporate the component (D).
The drying temperature is not particularly limited as long as the applied base material is at a temperature or lower that does not cause problems such as deformation. The preferred heating temperature is 40 to 100 ° C. The drying time may be appropriately set depending on the substrate to be applied and the heating temperature, and is preferably 0.5 to 20 minutes.

5. Uses The composition of the present invention can be used for various uses requiring antiviral properties.
Specific examples include ink applications such as offset and inkjet printing, hard coats such as plastic films, plastic molded products, and woodwork products, and coatings for keeping parts such as doorknobs and touch panels that are often touched by humans clean. It can be used for various purposes.
The composition of the present invention has a fast-curing property, especially in a thin film, and can simultaneously satisfy the adjustment of the physical properties of the cured film such as surface hardness, scratch resistance, flexibility and curl property, and the antiviral property. It can be preferably used as an agent.
Specific examples of the coating agent include a face shield, the outside of goggles, and a coating agent for various molded members. Specific examples of various molded members include straps, handrails, interiors, etc.; office supplies such as office desks; and antiviral coating agents such as furniture in public vehicles such as trains and buses.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
In the following, "part" means a part by weight, and "%" means% by weight.
Further, in the following, ethylene oxide is abbreviated as "EO".

0. Evaluation Method of Inorganic Solid Powder The inorganic solid powder used as the raw material for the component (B) used in the examples was evaluated by the following method.

1) Color toning Evaluated by the L value when measured with a color difference meter.

2) Average particle size This is a volume-based median diameter (μm) obtained by measuring with a laser diffraction type particle size distribution measuring device.

3) Moisture content Weigh about 5 g of the sample in an aluminum cup constant weighted at 250 ° C for 1 hour in a dryer, dry at 250 ° C for 2 hours, weigh again, and divide the drying loss by the mass before drying. As a display, the water content of the inorganic solid acid powder was used.

4) Acid point concentration Add 0.5 g of inorganic solid powder to each of 20 20 mL sample bottles, add 10 mL of benzene to them, and shake gently. Next, 0.1 N of n-butylamine is added to each sample bottle in different amounts to prepare a mixed solution of 20 kinds, and the mixture is stirred with a shaker. After 24 hours, 0.5 mL of a 0.1% methyl red solution diluted with benzene is added to each mixture, and the discoloration of methyl red is visually observed. The amount of n-butylamine added in which the discoloration of methyl red is not confirmed is the largest, and the amount of base reacted with the acid point is defined as the acid point concentration (mmol / g).

5) 0.1 g of a sample was collected in an acid strength test tube, 2 mL of benzene and 2 drops of a 0.1% benzene solution of the following indicator were added, shaken lightly, and the color change was observed. In the case of crystal violet, a 0.1% ethanol solution was used.
The acid strength is less than or equal to the strongest acid strength (lowest pKa value) in which discoloration of the indicator was confirmed, and is considered to be higher than the weakest acid strength (highest pKa) in which the indicator did not discolor, so the range is pKa. Recorded as a value.
Indicators are methyl red (pKa = 4.8), 4-phenylazo-1-naphthylamine (pKa = 4.0), dimethyl yellow (pKa = 3.3), 4-phenylazo-diphenylamine (pKa = 1.5). , Crystal Violet (pKa = 0.8), dissocinamylacetone (pKa = -3.0), benzalacetophenone (pKa = -5.6) and anthraquinone (pKa = -8.2).

6) Anti-virus effect Purified water was added to the inorganic solid acid powder to adjust the concentration to 1 mg / mL, and the virus infectivity titer was 5.95 × 10 ⁷ PFU / mL for 900 μL of this liquid. Add 100 μL of virus solution and let stand at 25 ° C. for 2 hours. In addition, PBS (phosphate buffered saline) is prepared as a control sample, 100 μL of the virus solution is added in the same manner as the test sample, and the mixture is allowed to stand at 25 ° C. for 2 hours. Then, the mixed solution is recovered, and the recovered solution is subjected to a plaque measurement method to measure the virus infectivity titer. Measure the viral load.
The antiviral effect was evaluated by the antiviral activity value obtained by the following formula.
Anti-virus activity value = Log (virus infectious titer of control sample after 2 hours) -Log (virus infectious titer after 2 hours)

1. 1. Manufacturing example
1) Production Example 1 [Production of (A1-1) component: Production of tetraacrylate of diglycerin EO4 mol adduct]
In a 2 L 4-port flask with a side tube equipped with a reflux tube, 500 g of EO4 mol adduct of diglycerin, 518 g of acrylic acid, 550 g of toluene, 41 g of paratoluenesulfonic acid monohydrate (hereinafter referred to as "PTS"), polymerization. As a inhibitor, 1.59 g of cupric chloride [1000 wtppm with respect to the total amount of the reaction solution (hereinafter simply referred to as ppm)] and 1.59 g of hydroquinone monomethyl ether (hereinafter referred to as "MQ") (with respect to the total amount of the reaction solution). The reaction solution temperature was adjusted to 80 to 100 ° C. and the reaction system pressure was adjusted to 400 to 760 mmHg while blowing nitrogen gas containing oxygen. A dehydration esterification reaction was carried out for 7 hours while removing the generated water out of the system with a Dean-Stark tube.

The obtained reaction solution is added to a separating funnel, washed and separated with pure water, then the organic layer is further washed and separated with an aqueous sodium hydroxide solution, and the organic layer is further washed and separated with pure water. Liquid.
Then, 0.4 g of MQ was added to the obtained organic layer, and toluene was removed under a reduced pressure of 80 ° C. while blowing nitrogen gas containing oxygen to obtain tetraacrylate of the target diglycerin EO 4 mol adduct. Obtained (hereinafter referred to as "acrylate 4EO").

2) Production Example 2 (Production of antiviral agent)
(Manufacturing of α-type zirconium phosphate)
A 15% aqueous solution of zirconium oxychloride was added to a 75% aqueous solution of phosphoric acid, and the mixture was aged at 100 ° C. for 12 hours.
Then, the obtained precipitate was filtered, washed with water, dried and crushed to obtain a white α-type zirconium phosphate powder.
The color L value, average particle size, water content, acid point concentration and acid strength of the obtained α-type zirconium phosphate powder (hereinafter referred to as “b-1”) were measured. The results are shown below.
Color L value: 96, average particle size: 0.9 μm, water content: 2.2%, acid point concentration: 0.02 mmol / g, acid strength (pKa): -8.2 to -5.6
The antiviral effect of b-1 was as follows.
Antiviral activity value: 4.5 <

(Manufacturing of NASICON type zirconium silver phosphate)
While stirring an aqueous solution of zirconium oxychloride (0.2 mol), oxalic acid (0.1 mol) is added thereto, and phosphoric acid (0.3 mol) is further added. Adjust the pH of the reaction solution to 3.0 with an aqueous solution of caustic soda, heat at 98 ° C. for 10 hours, and then filter, wash, and dry the precipitate. NASION-type sodium zirconium phosphate [NaZr ₂ (PO ₄ ) ₃ . 1.1H ₂ O] was obtained.
0.09 mol of zirconium phosphate prepared earlier was added to 450 ml of a 1N nitric acid aqueous solution in which 0.015 mol of silver nitrate was dissolved, and the mixture was stirred at 60 ° C. for 4 hours to retain silver ions. After that, it was washed well, dried at 120 ° C., and calcined at 750 ° C. for 4 hours. The powder after firing was lightly pulverized to obtain NASICON type zirconium silver phosphate.
The acid point concentration, color L value, average particle size, and water content of the obtained NASION-type zirconium silver phosphate powder (hereinafter referred to as "b'-1") were measured. The results are shown below.
Acid point concentration: <0.001 mmol / g, color L value: 97, average particle size: 1 μm, water content: 0.4%

90 parts of b-1 and 10 parts of b'-1 obtained above were stirred and mixed to produce the component (B) (antiviral agent). Hereinafter, this is referred to as B1.
The acid point concentration of B1 was measured. The results are shown below.
Acid point concentration: 0.01 mmol / g
The antiviral effect of B1 was as follows.
Antiviral activity value: 4.5

2. 2. Examples and Comparative Examples
1) Production of active energy ray-curable composition The compounds shown in Table 1 below were stirred and mixed at the ratios shown in Table 1 to produce an active energy ray-curable composition.
The obtained composition was used and evaluated later. The results are shown in Table 2.

The numbers in Table 1 mean the number of copies.
The abbreviations in Table 1 mean the following.
(A) Ingredient
UAd: Urethane acrylate, which is a reaction product of pentaerythritol triacrylate and hexanediol diisocyanate [manufactured by Kyoeisha Chemical Co., Ltd., product name: UA-306H]
-M-402: Mixture of dipentaerythritol penta and hexaacrylate [manufactured by Toagosei Co., Ltd., product name: Aronix M-402]
OT-2501: Bisphenol A type epoxy acrylate [Aronix OT-2501 manufactured by Toagosei Co., Ltd.]
M-5700: 2-Hydroxy-3-phenoxypropyl acrylate [Aronix M-5700 manufactured by Toagosei Co., Ltd.]
UH-2041: An acrylate polymer having a hydroxyl group of Mw2,400, Alfon UH-2041 manufactured by Toagosei Co., Ltd.
(C) Ingredient
HCPK: 1-Hydroxycyclohexylphenyl ketone, IGM RESINS B.I. V. Omnirad 184 manufactured by the company
(D) component
-PGM: Propylene glycol monoethyl ether

2) Evaluation method
(1) Production of Specimen A bar coater was applied to the obtained composition on a polyethylene terephthalate (PET) film [Cosmo Shine (registered trademark) A4360 (thickness 100 μm) manufactured by Toyobo Co., Ltd.] so that the film thickness was 1 μm and 3 μm. And heated with a dryer at 60 ° C. for 3 minutes to evaporate the component (D).
After that, using a high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd., the irradiation energy was adjusted to 200 mJ / cm ² per pass at an ultraviolet region (UV-A) intensity of 250 mW / cm ² centered on 365 nm. It was transported in an air atmosphere on the conveyor, and was irradiated with ultraviolet rays for 5 passes.
The following evaluation was carried out using the obtained test piece.

(2) (B) Confirmation of dispersion status For the cured film obtained in (1) above, use a scanning electron microscope (SEM) [JEOL Ltd. (JSM-7900F) to measure secondary electrons under the following conditions at a low acceleration voltage. Carried out.
・ Detector: LED (observation of secondary electron image)
・ Acceleration voltage: 1.0kV, 3.0kV, 5.0kV
-Irradiation current: W. D. : 10 mm, vapor deposition: Pt (5 seconds)
With respect to the obtained image, the dispersion state of the component (B) was visually observed and evaluated at the following three levels. The results are shown in Table 2 below.
◯: Concavities and convexities due to the component (B) were confirmed on the surface of the cured film, and the component (B) was dispersed without any problem. , Δ: (B) component is unevenly distributed and not uniform, ×: A uniform composition itself could not be obtained.

(3) The test was carried out according to the antiviral ISO 21702 (2019 Measurement of antiviral activity on plastics and other non-porous surfaces).
-Test method: Plaque measurement method-Test virus: Influenza A virus: A / Hong Kong / 8/68 (H3N2) ATCC VR-1679
-Test virus solution In Examples 1 to 3 and Comparative Example 1, the following solution was used.
Infectious titer (PFU / mL): 2.55 × ¹⁰⁷ , inoculation volume (mL): 0.4
In Examples 4, 5, and Comparative Example 2, the following solutions were used.
Infectious titer (PFU / mL): 3.05 × ¹⁰⁷ , inoculation volume (mL): 0.4
The test results are shown in Table 2 below.

(4) Pencil hardness With respect to the obtained cured film, the pencil hardness was measured under a load of 750 g according to JIS K5600-5-4.
The results are shown in Table 3 below.

(5) According to the flexible mandrel test (JIS K5600-5-1), a PET film having a coating film formed on a core rod having a diameter of 2 mm to 10 mm is wrapped around the core rod, and the diameter of the core rod having the minimum diameter at which no cracking or peeling is observed is evaluated. did.
Even with a 10 mm core rod, if the cured film shows cracks or peeling, it is described as ">10". The smaller the core rod diameter, the higher the flexibility of the cured film. Since the core rod having the smallest diameter is 2 mm, the one having no crack at 2 mm is described as "<2" in the table.
The results are shown in Table 3 below.

(6) Scratch resistance For the obtained cured film, use steel wool # 0000, visually observe the surface of the cured film after 100 g load and 100 round trips, check for scratches, and check the following 3 levels. evaluated.
⊚: No scratches, ◯: 5 scratches or less, ×: 5 scratches exceeded The results are shown in Table 3 below.

As is clear from the results of Examples 1 to 5, the composition of the present invention had a cured film in which the component (B) was dispersed on the surface, and was further excellent in antiviral property. In addition, the compositions of Examples 1 to 3 and 5 are compositions in which the components (A1-1) and (A1-2) are used in combination as the component (A1), and the cured film thereof has a pencil hardness. It was excellent in flexibility and scratch resistance. The composition of Example 4 is a composition using only the component (A1-2) as the component (A1), and the cured film thereof is compared with the compositions of Examples 1 to 3 and 5. Although the flexibility was reduced, the scratch resistance was about the same and the pencil hardness was better.
On the other hand, in the compositions of Comparative Examples 1 and 2, the cured film had excellent pencil hardness, flexibility, and scratch resistance, but did not have antiviral properties.

In the composition of the present invention, the cured film exhibits antiviral properties.
Therefore, the composition of the present invention can be preferably used as a coating agent, and specifically, can be preferably used for various uses such as a face shield, the outside of goggles, and a coating agent for various molded members. ..

The present invention relates to an active energy ray-curable antiviral composition containing the following components (A) and (B).
Component (A): A compound having two or more ethylenically unsaturated groups and having two or more ethylenically unsaturated groups is a compound having an ethylenically unsaturated group containing the following component (A1) .
(A1) Component: A compound having 3 or more ethylenically unsaturated groups, including a compound having a hydrophilic group and 3 or more ethylenically unsaturated groups.
Component (B): (B1) Antiviral agent containing an inorganic solid acid having an acid point concentration of more than 0.005 mmol / g Hereinafter, components (A) and (B), other components, and a method of use will be described.

The present invention relates to an active energy ray-curable antiviral composition containing the following components (A) and (B).
Component (A): A compound having two or more ethylenically unsaturated groups, and the compound having two or more ethylenically unsaturated groups is a compound having an ethylenically unsaturated group containing the following component (A1). Component (A1): A compound having three or more ethylenically unsaturated groups, including a compound having a hydrophilic group and three or more ethylenically unsaturated groups, the following component (A1-1) and the following (A1-1). Compounds containing A1-2)
(A1-1) component: Tri or tetra (meth) acrylate of alkylene oxide adduct of diglycerin
(A1-2) component: A compound having three or more ethylenically unsaturated groups other than the (A1-1) component.
(B) component: (B1) component; an antiviral agent containing an inorganic solid acid having an acid point concentration of more than 0.005 mmol / g.

Hereinafter, the components (A) and (B), other components, and the method of use will be described.

(3) The test was carried out according to the antiviral ISO 21702 (2019 Measurement of antiviral activity on plastics and other non-porous surfaces).
-Test method: Plaque measurement method-Test virus: Influenza A virus: A / Hong Kong / 8/68 (H3N2) ATCC VR-1679
-Test virus solution In Examples 1 to 3 and Comparative Example 1, the following solution was used.
Infectious titer (PFU / mL): 2.55 × ¹⁰⁷ , inoculation volume (mL): 0.4
In Example 4, Reference Example 1 , and Comparative Example 2, the following solutions were used.
Infectious titer (PFU / mL): 3.05 × ¹⁰⁷ , inoculation volume (mL): 0.4
The test results are shown in Table 2 below.

As is clear from the results of Examples 1 to 4 , the composition of the present invention had a cured film in which the component (B) was dispersed on the surface, and was further excellent in antiviral property. In addition, the compositions of Examples 1 to 4 are compositions in which the components (A1-1) and (A1-2) are used in combination as the component (A1), and the cured film thereof has pencil hardness, flexibility, and the like. And it was excellent in scratch resistance. The composition of Reference Example 1 is a composition using only the component (A1-2) as the component (A1), and the cured film thereof is more flexible than the compositions of Examples 1 to 4 . Although it was reduced, the scratch resistance was about the same and the pencil hardness was better.
On the other hand, in the compositions of Comparative Examples 1 and 2, the cured film had excellent pencil hardness, flexibility, and scratch resistance, but did not have antiviral properties.

Claims (19)

An active energy ray-curable antiviral composition containing the following components (A) and (B).
Component (A): Compound having an ethylenically unsaturated group (B) Component: Component (B1); Antiviral agent containing an inorganic solid acid having an acid point concentration of more than 0.005 mmol / g. The active energy ray-curable antiviral composition according to claim 1, wherein the component (A) contains a compound having two or more ethylenically unsaturated groups. The active energy ray-curable anti-virus according to claim 2, wherein the compound having two or more ethylenically unsaturated groups in the component (A) contains the component (A1): a compound having three or more ethylenically unsaturated groups. Composition for viruses. The active energy ray-curable antiviral composition according to claim 3, wherein the component (A1) contains a compound having a hydrophilic group and three or more ethylenically unsaturated groups. The active energy ray-curable antiviral composition according to any one of claims 1 to 4, wherein the compound having an ethylenically unsaturated group contains (meth) acrylate. The active energy ray-curable antiviral composition according to any one of claims 3 to 5, wherein the component (A1) contains the following component (A1-1).
(A1-1) component: Tri or tetra (meth) acrylate of alkylene oxide adduct of diglycerin The active energy ray-curable antiviral composition according to claim 6, wherein the component (A1-1) contains a tetra (meth) acrylate obtained from a polyol obtained by adding 4 to 8 mol of ethylene oxide to diglycerin. The active energy ray-curable antiviral composition according to any one of claims 3 to 7, wherein the component (A) contains the component (A1-1) and the following (A1-2).
(A1-2) component: A compound having three or more ethylenically unsaturated groups other than the (A1-1) component. The active energy ray-curable antiviral composition according to claim 8, wherein the component (A1-2) contains urethane (meth) acrylate. The active energy ray-curable antiviral composition according to any one of claims 1 to 9, wherein the acid strength (pKa) of the acid point of the component (B1) is 3.3 or less. The active energy ray-curable antiviral composition according to any one of claims 1 to 10, wherein the component (B1) contains an inorganic phosphoric acid compound, an inorganic silicic acid compound or an inorganic oxide. The active energy ray-curable antiviral composition according to any one of claims 1 to 11, wherein the water content of the component (B1) is 0.5% by weight or more. The active energy ray-curable antiviral according to any one of claims 1 to 12, wherein the component (B1) contains at least one selected from the group consisting of silver, copper, and compounds thereof. Composition. One of claims 1 to 13, wherein the component (B1) is one or more selected from the group consisting of α-type zirconium phosphate, α-type zirconium-silver phosphate, and α-type copper phosphate zirconium. The active energy ray-curable antiviral composition according to the section. The active energy ray-curable antiviral according to any one of claims 1 to 14, wherein the component (B) contains an inorganic substance other than the component (B1) and the component (B2); the component (B1). Composition. The active energy ray-curable antiviral composition according to any one of claims 1 to 15, wherein the component (B2) contains zirconium silver phosphate. The active energy ray-curable antiviral composition according to any one of claims 1 to 16, further comprising a component (C): a photopolymerization initiator. The active energy ray-curable antiviral composition according to any one of claims 1 to 17, further comprising a component (D): an organic solvent. An active energy ray-curable antiviral coating agent composition comprising the composition according to any one of claims 1 to 18.