JP7031785B1 - Composition for active energy ray-curable antiviral - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curable antiviral composition in which an antiviral agent does not need to be dispersed in a composition, coating and curing are easy, and the obtained cured film has excellent antiviral performance. An active energy ray-curable antiviral composition containing the following components (A) and (B). As the component (B), a compound having a phosphoric acid group and an ethylenically unsaturated group is preferable. (A) Component: Compound having an ethylenically unsaturated group (B) Component: Compound other than the (A) component having an acidic group and an ethylenically unsaturated group [Selection diagram] 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 sodium p-styrene sulfonate or a sodium p-styrene sulfonate polymer and (meth) acrylate as an antiviral agent.
Further, Patent Document 2 includes photocatalytic particles, cuprous oxide particles, and metal oxide particles having no photocatalytic activity as antiviral agents, and a binder resin which is an active energy ray-curable resin and an organic solvent are used. The active energy ray-curable coating agent composition containing the present invention is disclosed.
Further, Patent Document 3 discloses an aqueous curable composition containing a copper compound as an antiviral agent and containing polyvinyl alcohol.

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, they are difficult to dissolve. 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 solidify 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 substrate, 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 liable to be poor due to the influence of water.

An object of the present invention is to obtain an active energy ray-curable antiviral composition in which the antiviral agent does not need to be dispersed in the composition, coating and curing are easy, and the obtained cured film has excellent antiviral performance. To provide.

In order to solve the above problems, the present inventors use an active energy ray-curable composition containing a compound having an ethylenically unsaturated group and a compound having an acidic group and an ethylenically unsaturated group as an antiviral agent. However, it was found that the obtained composition does not need to be dispersed in the composition, has good handleability, can be coated and cured by a simple method, and the formed cured film has excellent antiviral properties. , The present invention has been completed.
Hereinafter, the present invention will be described in detail.

According to the composition of the present invention, it is not necessary to disperse the antiviral agent in the composition, and the obtained cured film has excellent antiviral properties.

The present invention contains the following components (A) and (B), does not contain an antibacterial lipid component , and does not contain an antiviral agent having no photocatalytic function (however, excluding the following component (B)) . The present invention relates to a linear curable antiviral coating agent composition.
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): Compound having 3 or more ethylenically unsaturated groups, including a compound having a hydrophilic group and 3 or more ethylenically unsaturated groups (B) Component: Phosphoric acid group and ethylenically unsaturated group Compounds other than the component (A) having the above, the components (A) and (B), other components, and the method of use will be described below.

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 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 nonan 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 "alicyclic polyisocyanate") and an aliphatic polyisocyanate having an alicyclic group (hereinafter, "alicyclic 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, as the organic polyisocyanate, an aliphatic polyisocyanate is preferable 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 above-mentioned hexamethylene diisocyanate trimer and isophorone diisocyanate trimer.
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 polyol and (meth) acrylic acid.
Here, examples of the polyester diol include a reaction product of a polyol and a dicarboxylic acid or an anhydride thereof.
Examples of the polyol include diol, triol and tetraol.
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 triol include glycerin and trimethylolpropane.
Examples of tetraol include pentaerythritol and ditrimethylolpropane.
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), which are 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 (A1-1) component. 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 compound other than the component (A) having an acidic group and an ethylenically unsaturated group.
Since the component (B) is a compound having an ethylenically unsaturated group in addition to an acidic group, not only the cured composition film has excellent antiviral properties, but also the cured composition film is exposed to wind and rain. Antiviral properties can be maintained both in the environment and specifically after the water resistance test.
Examples of the ethylenically unsaturated group of the component (B) include a (meth) acryloyl group, a (meth) allyl group, a vinyl group, a styryl group and the like, and a (meth) acryloyl group is preferable.
As the component (B), a compound having one or two ethylenically unsaturated groups is preferable, and a compound having one or two (meth) acryloyl groups is more preferable.

As the acidic group of the component (B), an acidic group having a high acidity is preferable, and examples thereof include a phosphoric acid group, a sulfonic acid group, an alkyl sulfate group and a carboxyl group.
As the component (B), a compound having one or two acidic groups is preferable.

Examples of the compound having a phosphoric acid group in the component (B) include an esterification reaction product of hydroxyalkyl (meth) acrylate and phosphoric acid.
Specific examples of hydroxyalkyl (meth) acrylates include 2-hydroxyethyl (meth) acrylates, 2-hydroxypropyl (meth) acrylates, and 4-hydroxybutyl (meth) acrylates.
Examples of the compound include a compound having one unit derived from hydroxyalkyl (meth) acrylate, a compound having two units derived from hydroxyalkyl (meth) acrylate, and the like, and a mixture of these compounds may be used. , It may contain unreacted phosphoric acid.
As the compound, a commercially available product can be used, and as the esterification reaction product of one 2-hydroxyethyl methacrylate and phosphoric acid (2-methacryloyloxyethyl acid phosphate), the light ester P-1M [Kyoeisha Chemical Co., Ltd.] Manufactured by Co., Ltd., product name] and the like, and examples thereof include an esterification reaction product of 2-hydroxyethyl acrylate and phosphoric acid (2-acryloyloxyethyl acid phosphate) as light acrylate P-1A (N) [ Kyoeisha Chemical Co., Ltd., product name], etc. are mentioned, and as the esterification reaction product of two 2-hydroxyethyl methacrylate and phosphoric acid [bis (2-methacryloyloxyethyl) acid phosphate], light ester P- 2M [manufactured by Kyoeisha Chemical Co., Ltd., product name] and the like can be mentioned.

Examples of the compound having a sulfonic acid group include sulfoalkyl (meth) acrylates such as 2- (meth) acrylamide-2-methylpropanesulfonic acid and 2-[(meth) acloyloxy] ethanesulfonic acid, vinyl sulfonic acid, and the like. And allyl sulfonic acid and the like.

Compounds having an alkyl sulfate group include (meth) acryloyloxypropylene sulfate, polyoxyethylene-1-((meth) allyloxymethyl) alkyl ether sulfate, and polyoxyethylene nonylpropenylphenyl ether sulfate alkyl (meth) allylsulfosuccinic acid. , And ({α- [2- (meth) allyloxy) -1-({[alkyl (C = 10-14)] oxy} methyl) ethyl] -ω-hydroxypoly (n = 1-100) (oxyethylene )} Sulfate ester of {alkanol (C = 10-14, branched type) and 1-(reaction product of (meth) allyloxy) -2,3-epoxypropane} oxylan heavy adduct) containing alkanol (C = 10-14, branched) as the main component. Examples include compounds.

Examples of the compound having a carboxyl group include (meth) acrylic acid, Michael-added dimer of acrylic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, and monohydroxyethyl (meth) phthalate.

Among these compounds, a compound having one or two phosphoric acid groups and an ethylenically unsaturated group is preferable, and an esterification reaction product of hydroxyalkyl (meth) acrylate and phosphoric acid is more preferable. Esteration compounds of 2-hydroxyethyl (meth) acrylate and phosphoric acid and esterification compounds of two 2-hydroxyethyl (meth) acrylates and phosphoric acid are particularly preferred.

As the component (B), only one kind of the above-mentioned compound may be used, or two or more kinds thereof may be used in combination.

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 content ratios of the components (A) and (B), the component (A) is 50 to 95% by weight and the component (B) is 5 to 5 to 100% by weight in the total of the components (A) and (B). 50% by weight is preferable, and more preferably, the component (A) is 60 to 85% by weight, and the component (B) is 15 to 40% by weight.
By setting the ratio of the component (B) to 5% by weight or more, a coating film having a low surface acidity can be obtained, and by setting the ratio to 50% by weight or less, good curability can be obtained and curing can be obtained. The surface hardness of the coating film can be improved.

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-enveloped virus such as norovirus can be mentioned.
The composition of the present invention is preferably applicable to enveloped viruses.

Generally, for measuring the antiviral effect, a method of measuring the viral load (infection titer) by utilizing the phenomenon of cell degeneration in which the shape of a virus-infected cell changes is used.
Examples of the method for measuring the infectious titer include a plaque number measuring method, a 50% tissue culture infection amount (TCID50) measuring method, and a 50% chicken egg infection amount (EID50: egg infective dose 50) measuring method.
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 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)

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) phenylphosphinoxide, 2,4,6-trimethylbenzoyldiphenylphosphinoxide, 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-trimethylbenzoyldiphenylphosphinoxide, 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-) It is preferable to use phenyl) -butane-1-one or the like in combination.

The content ratio of the component (C) is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total amount of the component (A) and the component (B) (hereinafter referred to as "curable component"). 0.5 to 8 parts by weight. 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.

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 ADEKA CORPORATION.
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, ADEKA CORPORATION 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 ADEKA CORPORATION.
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 curable components. Is.
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 (SB-UVA6928), 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 the curable component. Is. 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 white, 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 not particularly limited as long as it can contribute to improving the adhesiveness with the substrate.

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 the curable component. ..
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 (a methyl chloride adduct to a dimethylamino group) and a triethylammonium chloride group (an ethyl chloride adduct to a diethylamino group), and a dimethylammonium sulfoxide. Examples thereof include a sulfoxide group of dialkylammonium such as a group (adduct of sulfuric acid to a dimethylamino group) and a diethylammonium sulfoxide group (adduct of sulfuric acid to a diethylamino group).
As the polymer in which the hydrophilic polymer has an acidic group (hereinafter, referred to as “acidic group-containing polymer”), a neutralized salt in which a part or all of the acidic group is 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 amine.

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 vinyl-based monomers having a quaternary base include (meth) acryloyloxyalkyltrialkylammonium halides such as (meth) acryloyloxyethyltrimethylammonium chloride and (meth) acryloyloxyethyltriethylammonium chloride, and (meth). Examples thereof include (meth) acryloyloxyalkyldialkylammonium sulfoxide such as acryloyloxyethyldimethylammonium sulfoxide and (meth) acryloyloxyethyldiethylammonium 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 obtained by adding (meth) acrylic acid to a polymer having a vinyl-based monomer having at least a quaternary base and a glycidyl (meth) acrylate as a constituent monomer unit, 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. 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 micro gravure 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 rays, visible rays, electron beams and the like, but ultraviolet rays are 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".

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-necked flask with a side tube equipped with a reflux tube, 500 g of EO4 mol addition 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 in 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 reduced pressure at 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. 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 [manufactured by Toagosei Co., Ltd., product name: Aronix OT-2501]
-M-5700: 2-Hydroxy-3-phenoxypropyl acrylate [manufactured by Toagosei Co., Ltd., product name: Aronix M-5700]
(B) Ingredient
-P-2M: 2-methacryloxyethyl acid phosphate [manufactured by Kyoeisha Chemical Co., Ltd., product name: light ester P-2M] * Esterification reaction product of two 2-hydroxyethyl methacrylates and phosphoric acid
(C) Ingredient
HCPK: 1-Hydroxycyclohexylphenyl ketone, IGM RESINS B. V. Omnirad 184 manufactured by the company
Other ingredients
-UVA6928: UV absorber [manufactured by BASF, product name: SB-UVA6928]
-UH-2041: An acrylate polymer having a hydroxyl group of Mw2,400, manufactured by Toagosei Co., Ltd., product name: Alfon UH-2041
-Phosphoric acid: An 85 wt% phosphoric acid aqueous solution was used.

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. Was applied so as to be 10 μm.
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 conveyed 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.
For Example 5, Comparative Example 3, and 4, the test piece after the water resistance test was used. The water resistance test was carried out by immersing the obtained test piece in water and immersing it at room temperature for 16 hours.

(2) The test was carried out according to the antiviral ISO 21702 (2019 Measurement of antiviral activity on plastics and other non-porous surfaces).
a) Test method: Plaque measurement method b) Test virus: Influenza A virus: A / Hong Kong / 8/68 (H3N2) ATCC VR-1679
c) Test virus solution The following solution was used as the test virus solution.
-Example 1 and Comparative Example 1
Infectious titer (PFU / mL): 2.55 × ¹⁰⁷ , inoculation volume (mL): 0.4
-Examples 2 to 4 and Comparative Example 2
Infectious titer (PFU / mL): 3.05 × ¹⁰⁷ , inoculation volume (mL): 0.4
-Example 5, Comparative Example 3, and 4
Infectious titer (PFU / mL): 3.30 × ¹⁰⁷ , inoculation volume (mL): 0.4
The test results are shown in Table 2 below.

(3) 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.

(4) 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 core rod having a diameter of 2 mm and having no crack is described as "<2" in the table.
The results are shown in Table 3 below.

(5) 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.

In Table 2, the antiviral activity value (R) means the following, respectively.
Example 1: Represents the activity value for Ut of Comparative Example 1.
-Examples 2 to 3: Represents the activity value of Comparative Example 2 with respect to Ut.
Example 5 and Comparative Example 4: Represents the activity value of Comparative Example 3 with respect to Ut.

As is clear from the results in Table 2, the cured films of Examples 1 to 5 according to the present invention had excellent antiviral properties.
In addition, from the results in Table 3, the cured films of Examples 1, 3, and 5 were excellent in pencil hardness, flexibility, and scratch resistance. From the results in Table 3, the composition of Example 3 is a composition whose cured film has insufficient flexibility, but is intended to have a higher hardness. This is because the cured film of Example 4 has insufficient pencil hardness and scratch resistance, but the cured film is intended to have excellent flexibility. be. That is, the composition of the present invention exhibits antiviral properties even when the physical properties of the cured film are hard to soft.
On the other hand, the compositions of Comparative Examples 1 to 4 have excellent pencil hardness, flexibility, and scratch resistance from the results in Table 3, but have antiviral properties from the results in Table 2. I didn't have it.

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. ..

Claims (8)

An active energy ray-curable antiviral agent containing the following components (A) and (B), not containing an antibacterial lipid component , and not containing an antiviral agent having no photocatalytic function (however, excluding the following component (B)) . Coating agent composition for viruses.
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): Compound having 3 or more ethylenically unsaturated groups, including a compound having a hydrophilic group and 3 or more ethylenically unsaturated groups (B) Component: Phosphoric acid group and ethylenically unsaturated group Compounds other than the component (A) The active energy ray-curable antiviral coating agent composition according to claim 1 , wherein the compound having an ethylenically unsaturated group in the component (A) contains (meth) acrylate. The active energy ray-curable antiviral coating agent composition according to claim 1 or 2 , 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 coating agent composition according to claim 3 , 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 coating agent composition according to any one of claims 3 or 4 , 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 coating agent composition according to claim 5 , wherein the component (A1-2) contains urethane (meth) acrylate. A claim containing the component (A) in a proportion of 50 to 95% by weight and the component (B) in a proportion of 5 to 50% by weight in 100% by weight of the total amount of the component (A) and the component (B). The active energy ray-curable antiviral coating agent composition according to any one of items 1 to 6 . The active energy ray-curable antiviral coating agent composition according to any one of claims 1 to 7 , further comprising a component (C): a photopolymerization initiator.