Active energy ray curing type antibacterial low-adhesion agent, coating agent composition, article

Abstract

To provide: an active energy ray-curable low bacterial adhesion agent capable of obtaining a cured coating film excellent in low bacterial adhesion property; an article excellent in low bacterial adhesion property.SOLUTION: There are provided: an active energy ray-curable low bacterial adhesion agent which comprises a urethane (meth)acrylate (A) in which an isocyanate group in a polyvalent isocyanate (a1) forms a urethane bond with both of a hydroxyl group in a hydroxyl group-containing (meth)acrylate (a2) and a hydroxyl group in an oxyalkylene group-containing compound (a3); and an article having a cured coating film of the active energy ray-curable low bacterial adhesion agent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an active energy ray-curable antibacterial agent, a coating composition, and articles. [Background technology]

[0002] Traditionally, urethane (meth)acrylate has been known as an active energy ray curing resin and has been used in wood paints, plastic coatings, and the like. Because urethane (meth)acrylate contains a urethane structure in its molecular structure, hydrogen bonding cohesive force is obtained within the cured coating film. Therefore, urethane (meth)acrylate can impart crack resistance and elasticity to the coating film.

[0003] On the other hand, in recent years, cleanliness has become increasingly important in various industrial products. This demand for cleanliness is particularly strong for industrial products that are touched or approached by a large number of people. These industrial products are prone to accumulating nutrients for microorganisms, such as sweat, dirt, and food residue, which can lead to explosive bacterial growth. For example, there is a demand for highly clean items in a wide range of settings, from industrial products to everyday goods, in medical facilities, food factories, clothing factories, schools, train stations, banks, convenience stores, and various public facilities. Therefore, it has been proposed to provide a cured coating with antibacterial and antifungal properties on the surface of an article using a composition containing an active energy ray curable resin, an antibacterial agent, and an antifungal agent (Patent Document 1). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2011-57855 [Overview of the project] [Problems that the invention aims to solve]

[0005] In general, with antibacterial and antifungal materials, bacteria and other microorganisms attached to the surface are killed, but the remains and remnants of these microorganisms, which are produced by the antibacterial action, remain on the surface of the material. As a result, over time, new microorganisms attach to these remains and other remnants, forming a mass of microorganisms and bacteria called a biofilm. Biofilms formed in this way are difficult to remove from the surface of objects, compromising cleanliness. Therefore, in conventional cured coatings using antibacterial and antifungal agents, there is room for improvement in making it easier to remove clumps of microorganisms from the surface of objects and making it difficult for microorganisms to remain (low bacterial adhesion).

[0006] The present invention provides an active energy ray curable antibacterial agent and coating agent composition that yields a cured coating film with excellent antibacterial properties; and an article with excellent antibacterial properties. [Means for solving the problem]

[0007] The present invention has the following aspects. [1] An active energy ray curable antibacterial agent containing a urethane (meth)acrylate (A) in which the isocyanate group of a polyvalent isocyanate (a1) forms a urethane bond with both the hydroxyl group of a hydroxyl group-containing (meth)acrylate (a2) and the hydroxyl group of an oxyalkylene group-containing compound (a3). [2] The active energy ray curing type anti-bacterial agent of [1], wherein the oxyalkylene group-containing compound (a3) ​​is the compound shown in formula (2) below. H-(OX) n -OH...Formula (2) In equation (2), X is an alkylene group and n is 1 or greater. [3] The active energy ray curing type anti-bacterial agent of [1], wherein the oxyalkylene group-containing compound (a3) ​​is the compound shown in formula (3) below. H-(OX) n -OC(=O)-CHR=CH2...Equation (3) In formula (3), X is an alkylene group, n is 1 or more, and R is a hydrogen atom or a methyl group. [4] Any of the active energy ray curable antibacterial agents of [1] to [3], further containing (meth)acrylate (B) other than urethane (meth)acrylate (A). [5] The active energy ray curable antibacterial agent of [4], wherein (meth)acrylate (B) is at least one selected from the group consisting of urethane (meth)acrylate (B1) and (meth)acrylate monomer (B2) having a urethane bond. [6] An active energy ray curable antibacterial low-adhesion agent according to [4] or [5], wherein the content of (meth)acrylate (B) is 25 to 1,500 parts by mass per 100 parts by mass of urethane (meth)acrylate (A). [7] Any of the active energy ray curable antibacterial agents [1] to [6] further containing a photopolymerization initiator (C). A coating composition containing one of the active energy ray curing antibacterial low-adhesion agents described in [8] [1] to [7]. An article having a cured coating film of the coating agent composition of [9] [8]. [Effects of the Invention]

[0008] According to the active energy ray curable antibacterial agent and coating agent composition of the present invention, a cured coating film with excellent antibacterial properties can be obtained. The articles of the present invention exhibit excellent low bacterial adhesion. [Modes for carrying out the invention]

[0009] The following terms used in this specification have the meanings set forth below. (Meth)acrylate refers to the general term for methacrylate and acrylate. The term (meth)acryloyl group refers to both methacryloyl and acryloyl groups. The "~" symbol indicating a numerical range means that the numbers before and after it are included as the lower and upper limits, respectively.

[0010] The active energy ray-curable bacterial low-adhesion agent of the present invention (hereinafter referred to as "this active energy ray-curable bacterial low-adhesion agent") contains a specific urethane (meth) acrylate (A). This active energy ray-curable bacterial low-adhesion agent may further contain a (meth) acrylate (B) other than the specific urethane (meth) acrylate (A) and a photopolymerization initiator (C). In addition, this active energy ray-curable bacterial low-adhesion agent may further contain other components other than the urethane (meth) acrylate (A), the (meth) acrylate (B), and the photopolymerization initiator (C) as long as the effects of the present invention can be obtained.

[0011] <Urethane (meth) acrylate (A)> In urethane (meth) acrylate (A), the isocyanate group of the polyisocyanate (a1) forms urethane bonds with both the hydroxyl group of the hydroxyl group-containing (meth) acrylate (a2) and the hydroxyl group of the oxyalkylene group-containing compound (a3). That is, urethane (meth) acrylate (A) has a urethane bond formed from the isocyanate group of polyisocyanate (a1) and the hydroxyl group of hydroxyl group-containing (meth) acrylate (a2); and a urethane bond formed from the isocyanate group of polyisocyanate (a1) and the hydroxyl group of oxyalkylene group-containing compound (a3). Urethane (meth) acrylate (A) can also be said to be a polyisocyanate-based derivative obtained from polyisocyanate (a1), hydroxyl group-containing (meth) acrylate (a2), and oxyalkylene group-containing compound (a3).

[0012] (Polyisocyanate (a1)) Polyisocyanate (a1) is a compound having two or more isocyanate groups. Examples of polyisocyanate (a1) include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. Specifically, for example, polyisocyanates such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H-MDI), polyphenylmethane polyisocyanate (crude MDI), modified diphenylmethane diisocyanate (modified MDI), hydrogenated xylylene diisocyanate (H-XDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), trimethylhexamethylene diisocyanate (TMXDI), tetramethylxylylene diisocyanate (m-TMXDI), isophorone diisocyanate (IPDI), norbornene diisocyanate (NBDI), phenylene diisocyanate, lysine diisocyanate, lysine triisocyanate, naphthalene diisocyanate (NDI); trimer compounds of these polyisocyanates, burette-type polyisocyanates, water-dispersed polyisocyanates (such as "Aquate 100", "Aquate 110", "Aquate 200", "Aquate 210" manufactured by Nippon Polyurethane Industry Co., Ltd.) can be mentioned. Among these, in terms of low bacterial adhesion, modified forms of the trimers of isophorone diisocyanate and hexamethylene diisocyanate are preferred. The polyisocyanate may be used alone or in combination of two or more.

[0013] The polyvalent isocyanate (a1) may also be a reaction product of these polyisocyanates (however, limited to those having 3 or more isocyanate groups) and polyols. Examples of polyols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, 1,4-butanediol, polybutylene glycol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, hydrogenated bisphenol A, polycaprolactone, trimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, glycerin, polyglycerin, poly Examples include polyhydric alcohols such as tetramethylene glycol; polyether polyols having at least one structure of block copolymerization and random copolymerization of polyethylene oxide, polypropylene oxide, and ethylene oxide / propylene oxide; polyester polyols which are condensates of polyhydric alcohols or polyether polyols with polybasic acids such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, and isophthalic acid; caprolactone-modified polyols such as caprolactone-modified polytetramethylene polyol; polyolefin-based polyols; and polybutadiene-based polyols such as hydrogenated polybutadiene polyol.

[0014] Other examples of polyols include carboxyl group-containing polyols such as 2,2-bis(hydroxymethyl)butyric acid, tartaric acid, 2,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,2-bis(hydroxymethyl)propionic acid, 2,2-bis(hydroxyethyl)propionic acid, 2,2-bis(hydroxypropyl)propionic acid, dihydroxymethylacetic acid, bis(4-hydroxyphenyl)acetic acid, 4,4-bis(4-hydroxyphenyl)pentanoic acid, and homogentisic acid; and sulfonic acid group-containing polyols such as sodium 1,4-butanediol sulfonate. The reaction product of polyisocyanate and polyol may be used individually or in combination of two or more types.

[0015] In such reactions between polyisocyanates and polyols, catalysts can be used to accelerate the reaction. Examples of catalysts include organometallic compounds such as dibutyltin dilaurate, trimethyltin hydroxide, and tetra-n-butyltin; metal salts such as zinc octate, tin octate, cobalt naphthenate, stannous chloride, and stannous chloride; amine catalysts such as triethylamine, benzyldiethylamine, 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[5,4,0]undecene, N,N,N',N'-tetramethyl-1,3-butanediamine, and N-ethylmorpholine; and bismuth nitrate, bismuth bromide, and bismuth iodide. Examples of bismuth-based catalysts include organic bismuth compounds such as dibutylbismuth dilaurate and dioctylbismuth dilaurate, as well as organic acid bismuth salts such as bismuth 2-ethylhexanoate, bismuth naphthenate, bismuth isodecanate, bismuth neodecanoate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth lybisneodecanoate, bismuth disalicylate, and bismuth digallate. Among these, dibutyltin dilaurate and 1,8-diazabicyclo[5,4,0]undecene are preferred.

[0016] (Hydroxyl group-containing (meth)acrylate (a2)) A hydroxyl group-containing (meth)acrylate (a2) is a (meth)acrylate having one or more hydroxyl groups. A hydroxyl group-containing (meth)acrylate (a2) is not particularly limited as long as it contains at least one hydroxyl group. Examples of hydroxyl group-containing (meth)acrylates (a2) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl acryloyl phosphate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, caprolactone-modified 2-hydroxyethyl (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, ethylene oxide-modified dipentaerythritol penta(meth)acrylate, and ethylene oxide-modified pentaerythritol tri(meth)acrylate. Among these, dipentaerythritol pentaacrylate is preferred in terms of its low bacterial adhesion. Hydroxyl group-containing (meth)acrylate (a2) may be used alone or in combination of two or more types.

[0017] (Oxyalkylene group-containing compound (a3)) The oxyalkylene group-containing compound (a3) ​​has an oxyalkylene group and also has a hydroxyl group capable of forming a urethane bond with the isocyanate group of the polyvalent isocyanate (a1). Examples of oxyalkylene group-containing compounds (a3) ​​include compounds represented by the following formula (1). Furthermore, oxyalkylene group-containing compounds (a3) ​​may be used individually or in combination of two or more.

[0018] H-(OX) n -OY...Formula (1)

[0019] In formula (1), X is an alkylene group, and these may be the same alkylene group or multiple different alkylene groups. The number of carbon atoms in the alkylene group of X is preferably 2 to 5, and more preferably 2 to 4. From the viewpoint of low bacterial adhesion, the number of carbon atoms in the alkylene group of X is particularly preferably 2. In formula (1), n ​​is 1 or greater, preferably 5 to 500, more preferably 5 to 100, and even more preferably 6 to 50. When the oxyalkylene group in formula (1) has two or more different alkylene groups, the total number of moles added (n) of each oxyalkylene group is preferably 5 to 500, more preferably 5 to 100, and even more preferably 6 to 50.

[0020] In formula (1), Y is one of a hydrogen atom, an alkyl group, a (meth)acryloyl group, an allyl group, or an acyl group. From the viewpoint of low bacterial adhesion, a hydrogen atom is preferred as Y, and from the viewpoint of low bacterial adhesion, an allyl group or a (meth)acryloyl group is preferred. From the viewpoint of the appearance of the coating film, a (meth)acryloyl group is particularly preferred as Y.

[0021] When Y is a hydrogen atom, the oxyalkylene group-containing compound (a3) ​​is represented by the following formula (2).

[0022] H-(OX) n -OH...Formula (2)

[0023] In equation (2), X is an alkylene group and n is 1 or greater. In equation (2), the details of X and n and preferred embodiments are the same as those described for equation (1).

[0024] Examples of oxyalkylene group-containing compounds (a3) ​​represented by formula (2) include glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, and polytetramethylene glycol; and polyether polyols having at least one structure of polyethylene oxide, polypropylene oxide, or block copolymerization and random copolymerization of ethylene oxide / propylene oxide.

[0025] When Y is an alkyl group, the number of carbon atoms in the alkyl group of Y is preferably 1 to 5, and more preferably 1 to 3. When Y is an alkyl group, examples of oxyalkylene group-containing compounds (a3) ​​include polyethylene glycol monomethyl ether, polyethylene glycol lauryl ether, polyethylene glycol cetyl ether, polyethylene glycol stearyl ether, polyethylene glycol nonylphenyl ether, polyethylene glycol tridecyl ether, polyethylene glycol oleyl ether, polyethylene glycol octylphenyl ether, polyoxyethylene oleyl cetyl ether, and polypropylene glycol monomethyl ether.

[0026] When Y is a (meth)acryloyl group, the oxyalkylene group-containing compound (a3) ​​is represented by the following formula (3).

[0027] H-(OX) n -OC(=O)-CHR=CH2...Equation (3)

[0028] In formula (3), X is an alkylene group, n is 1 or greater, and R is a hydrogen atom or a methyl group. Also, in formula (3), "-C(=O)-" is a carbonyl group and is sometimes abbreviated as "-C(O)-". In equation (3), the details of X and n and preferred embodiments are the same as those described for equation (1).

[0029] Examples of oxyalkylene group-containing compounds (a3) ​​represented by formula (3) include polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, poly(ethylene glycol-propylene glycol) mono(meth)acrylate, poly(ethylene glycol-tetramethylene glycol) mono(meth)acrylate, and poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate.

[0030] When Y is an allyl group, examples of oxyalkylene group-containing compounds (a3) ​​include polyethylene glycol monoallyl ether, polypropylene glycol monoallyl ether, and poly(ethylene glycol-propylene glycol) monoallyl ether.

[0031] When Y is an acyl group, the number of carbon atoms in the acyl group is preferably 10 to 30, and more preferably 12 to 18. Examples include polyethylene glycol monolaurate, polypropylene glycol monolaurate, poly(ethylene glycol-propylene glycol) monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, and the like.

[0032] The weight-average molecular weight of the oxyalkylene group-containing compound (a3) ​​is preferably 100 to 20,000, more preferably 200 to 10,000, and even more preferably 400 to 4,000. If the weight-average molecular weight of the oxyalkylene group-containing compound (a3) ​​is below the lower limit, the low bacterial adhesion performance of the cured coating film tends to be difficult to achieve. If the weight-average molecular weight of the oxyalkylene group-containing compound (a3) ​​exceeds the upper limit, the durability of the cured coating film, such as water resistance, tends to decrease, and the hardness as a coating material for the outermost layer tends to be inferior, which is not practically desirable.

[0033] The ratio of the oxyalkylene group-containing compound (a3) ​​to 100% by mass of the total amount of urethane (meth)acrylate (A) and (meth)acrylate (B) is preferably 3 to 50% by mass, more preferably 8 to 40% by mass, and even more preferably 10 to 35% by mass. If the ratio of the oxyalkylene group-containing compound (a3) ​​is below the lower limit, it tends to be difficult to achieve low bacterial adhesion. If the ratio of the oxyalkylene group-containing compound (a3) ​​exceeds the upper limit, the durability of the cured coating film, such as water resistance, deteriorates, and the hardness as a coating material for the outermost layer tends to be inferior, which is not practically desirable.

[0034] The weight-average molecular weight of urethane (meth)acrylate (A) is preferably 1,000 to 100,000, and more preferably 2,000 to 50,000. If the weight-average molecular weight is below the lower limit, the antibacterial adhesion performance tends to decrease. If the weight-average molecular weight is above the upper limit, the hardness of the cured coating film tends to decrease, which is not practically desirable.

[0035] The number-average molecular weight and weight-average molecular weight are calculated based on the molecular weight of standard polystyrene and are measured using a high-performance liquid chromatograph (Waters, "ACQUITY APC system") with four columns in series: one ACQUITY APC XT 450, one ACQUITY APC XT 200, and two ACQUITY APC XT 45.

[0036] (Preparation of urethane (meth)acrylate (A)) Urethane (meth)acrylate (A) is obtained by reacting a polyvalent isocyanate (a1), a hydroxyl group-containing (meth)acrylate (a2), and an oxyalkylene group-containing compound (a3), in which the isocyanate group in the polyvalent isocyanate (a1) forms urethane bonds with the hydroxyl group of the hydroxyl group-containing (meth)acrylate (a2) and the hydroxyl group of the oxyalkylene group-containing compound (a3), respectively.

[0037] For example, if a polyvalent isocyanate (a1) has two isocyanate groups, one isocyanate group forms a urethane bond with the hydroxyl group of a hydroxyl group-containing (meth)acrylate (a2), and the remaining isocyanate group forms a urethane bond with the hydroxyl group of an oxyalkylene group-containing compound (a3), resulting in a urethane (meth)acrylate (A). Furthermore, if the polyvalent isocyanate (a1) has three isocyanate groups, one isocyanate group forms a urethane bond with the hydroxyl group-containing (meth)acrylate (a2) (or oxyalkylene group-containing compound (a3)), and the remaining two isocyanate groups form a urethane bond with the hydroxyl groups of the oxyalkylene group-containing compound (a3) ​​(or hydroxyl group-containing (meth)acrylate (a2)), resulting in a urethane (meth)acrylate (A).

[0038] Examples of reaction methods for forming urethane bonds include the following methods (a), (b), and (c). (i): A method of simultaneously charging and reacting polyvalent isocyanate (a1), hydroxyl group-containing (meth)acrylate (a2), and oxyalkylene group-containing compound (a3). (b): A method in which a polyvalent isocyanate (a1) is reacted with a hydroxyl group-containing (meth)acrylate (a2), followed by a reaction with an oxyalkylene group-containing compound (a3). (h): A method of reacting a polyvalent isocyanate (a1) with an oxyalkylene group-containing compound (a3), followed by a hydroxyl group-containing (meth)acrylate (a2). Among these, method (b) is preferred in terms of the stability of reaction control and the reduction of manufacturing time.

[0039] When preparing urethane (meth)acrylate (A), it is also preferable to use metal catalysts such as dibutyltin dilaurate or amine catalysts such as 1,8-diazabicyclo[5.4.0]undecene-7 to accelerate the reaction. The reaction temperature is preferably 30 to 90°C, and more preferably 40 to 70°C.

[0040] <(meth)acrylate(B)> (Meth)acrylate (B) is a (meth)acrylate other than the urethane (meth)acrylate (A) described above. Examples of (meth)acrylate (B) include urethane (meth)acrylate (B1) and (meth)acrylate monomer (B2) having a urethane bond. (Meth)acrylate (B) may be used alone or in combination of two or more types.

[0041] The urethane (meth)acrylate (B1) is not particularly limited to any urethane (meth)acrylate other than urethane (meth)acrylate (A). For example, an example is a urethane (meth)acrylate in which all two or more isocyanate groups of the above-mentioned polyvalent isocyanate (a1) form a urethane bond with the hydroxyl group of the hydroxyl group-containing (meth)acrylate (a2). Another example is a urethane (meth)acrylate in which the isocyanate group of a monoisocyanate having one isocyanate group forms a urethane bond with the hydroxyl group of the above-mentioned hydroxyl group-containing (meth)acrylate (a2). Urethane (meth)acrylate (B1) may be used alone or in combination of two or more types.

[0042] Examples of (meth)acrylate monomers (B2) include monofunctional monomers, difunctional monomers, and monomers with three or more functionalities, depending on the number of (meth)acryloyl groups. (Meth)acrylate monomer (B2) may be used alone or in combination of two or more types.

[0043] Examples of monofunctional monomers include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycerin mono (meth)acrylate, glycidyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, n-butyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, and Examples include syl(meth)acrylate, isodecyl(meth)acrylate, dodecyl(meth)acrylate, n-stearyl(meth)acrylate, benzyl(meth)acrylate, phenolethylene oxide-modified (n=2)(meth)acrylate, nonylphenolpropylene oxide-modified (n=2.5)(meth)acrylate, 2-(meth)acryloyloxyethyl acid phosphate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, and other phthalic acid derivatives such as half(meth)acrylate, furfuryl(meth)acrylate, carbitol(meth)acrylate, benzyl(meth)acrylate, butoxyethyl(meth)acrylate, allyl(meth)acrylate, acryloylmorpholine, 2-hydroxyethylacrylamide, N-methylol(meth)acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, and polyoxyethylene secondary alkyl ether acrylate. Monofunctional monomers may be used individually or in combination of two or more.

[0044] Examples of difunctional monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide modified bisphenol A type di(meth)acrylate, and Examples include propyl sulfate-modified bisphenol A type di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate diglycidyl ester di(meth)acrylate, hydroxypivalic acid-modified neopentyl glycol di(meth)acrylate, and isocyanurate ethylene oxide-modified diacrylate. A single difunctional monomer may be used alone, or two or more may be used in combination.

[0045] Examples of monomers with three or more functionalities include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly(meth)acrylate, isocyanurate ethylene oxide modified triacrylate, caprolactone modified dipentaerythritol penta(meth)acrylate, and cap. Examples include loractone-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, ethylene oxide-modified dipentaerythritol penta(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, and ethoxylated glycerin triacrylate. A monomer with three or more functionalities may be used alone or in combination of two or more.

[0046] Other examples of (meth)acrylate monomers (B2) include Michael adducts of acrylic acid and 2-acryloyloxyethyl dicarboxylic acid monoesters. Examples of Michael adducts of acrylic acid include acrylate dimers, methacrylate dimers, acrylate trimers, methacrylate trimers, acrylate tetramers, and methacrylate tetramers. Examples of 2-acryloyloxyethyl dicarboxylic acid monoesters include 2-acryloyloxyethyl succinate monoester, 2-methacryloyloxyethyl succinate monoester, 2-acryloyloxyethyl phthalate monoester, 2-methacryloyloxyethyl phthalate monoester, 2-acryloyloxyethyl hexahydrophthalate monoester, and 2-methacryloyloxyethyl hexahydrophthalate monoester. In addition, other oligoester acrylates can also be mentioned.

[0047] In these (meth)acrylate monomers (B2), using monomers that further have an oxyalkylene structure can be expected to further improve the low bacterial adhesion performance.

[0048] When using urethane (meth)acrylate (A) as an aqueous dispersion, it is preferable to use a water-soluble or water-dispersible (meth)acrylate monomer (B2). In particular, it is preferable to use a water-soluble or water-dispersible ethylenically unsaturated monomer such as acryloyl morpholine, 2-hydroxyethyl acrylamide, ethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, isocyanurate ethylene oxide-modified diacrylate, isocyanurate ethylene oxide-modified triacrylate, ethylene oxide-modified epoxy acrylate, polyoxyethylene secondary alkyl ether acrylate, ethoxylated glycerin triacrylate, or polyester acrylate mainly composed of polyethylene glycol. Among these, acryloyl morpholine, ethylene glycol di(meth)acrylate, ethylene oxide-modified diacrylate isocyanurate, ethylene oxide-modified triacrylate isocyanurate, and tri(meth)acryloyloxyethoxytrimethylolpropane are particularly suitable.

[0049] The content of (meth)acrylate (B) is preferably 25 to 1,500 parts by mass, more preferably 35 to 600 parts by mass, and even more preferably 40 to 300 parts by mass, per 100 parts by mass of urethane (meth)acrylate (A). If the content of (meth)acrylate (B) is outside the above numerical range, it tends to be difficult to exhibit low bacterial adhesion.

[0050] <Photopolymerization initiator (C)> When obtaining a coating film by ultraviolet irradiation, it is preferable that this active energy ray-curable antibacterial agent contains a photopolymerization initiator (C). However, when electron beam irradiation is performed, this active energy ray-curable antibacterial agent can cure even without the photopolymerization initiator (C). The photopolymerization initiator (C) is not particularly limited as long as it generates radicals upon the action of light. For example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylenephenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal, benzophenone, benzoyl benzoate Examples include acids, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, camphorquinone, dibenzosverone, 2-ethylanthraquinone, 4',4''-diethylisophthalophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, α-acyloxime esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthylenequinone, and 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone. Among these, benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, benzoin isopropyl ether, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl) ketone, and 2-hydroxy-2-methyl-1-phenylpropan-1-one are preferably used. The photopolymerization initiator (C) may be used alone or in combination of two or more types.

[0051] When urethane (meth)acrylate (A) is used as an aqueous coating agent in an active energy ray curable antibacterial low-adhesion agent, a water-soluble or water-dispersible photopolymerization initiator (C) is preferred. For example, 2-(3-dimethylamino-2-hydroxypropoxy)-3,4-dimethyl-9H-thioxanthon-9-one metochloride (Octel Chemicals, "Quantacure QTX") and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (Ciba Specialty Chemicals, "Irgacure 2959") are preferred. Among these, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (Ciba Specialty Chemicals, "Irgacure 2959") is particularly preferred.

[0052] Furthermore, auxiliary agents for the photopolymerization initiator (C) may be used in combination. Examples of auxiliary agents for the photopolymerization initiator (C) include triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoate ethyl, 4-dimethylaminobenzoate (n-butoxy)ethyl, 4-dimethylaminobenzoate isoamyl, 4-dimethylaminobenzoate 2-ethylhexyl, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone. The photopolymerization initiator (C) may be used alone or in combination of two or more auxiliary agents.

[0053] <Other ingredients> Other components include antibacterial agents, antifungal agents, antiviral agents, antiallergen agents, thermoplastic resins, polymerization inhibitors, UV absorbers, thermal polymerization initiators, chain transfer agents, crosslinking agents, bluing agents, thickeners, dyes and pigments, oils, plasticizers, waxes, drying agents, dispersants, wetting agents, emulsifiers, gelling agents, stabilizers, defoaming agents, leveling agents, thixotropy-imparting agents, antioxidants, flame retardants, antistatic agents, fillers, reinforcing agents, matting agents, and various other fillers. Other ingredients may be used individually or in combination of two or more.

[0054] Examples of antibacterial agents include metals such as silver, copper, and zinc (including their metal ions); metal oxides such as zinc oxide, magnesium oxide, and titanium oxide; metal salts such as sodium percarbonate, sodium hypochlorite, and silver phosphate; boric acid compounds such as orthoboric acid, metaboric acid, and borax; complex compounds such as thiosulfate silver salt, 2-(4-thiazolyl)benzimidazole silver salt, 2-pyridinethiol-1-oxide sodium salt, and bis(2-pyridinethiol-1-oxide)zinc salt; inorganic compounds such as zeolite-supported, ceramic-supported, silica gel-supported, and montmorillonite-supported materials; quaternary ammonium salt compounds, monocyclic hydrocarbon compounds, phenolic compounds, pyridine compounds, alcoholic compounds, phosphonium salt compounds, allyl compounds, haloallyl sulfone compounds, iodopropagyl compounds, N-haloalkylthio compounds, nitrile compounds, and 8-oxyquinone compounds. Organic compounds such as phosphorus compounds, benzoithiazole compounds, isothiazolin compounds, organotin compounds, triazine compounds, thiadiazine compounds, anilide compounds, adamantane compounds, dithiocarbamate compounds, brominated indanone compounds, phenol ether compounds, sulfone compounds, pyrrole compounds, imidazole compounds, benzimidazole compounds, benzoic acid compounds, phenol ether compounds, sulfone compounds, pyrrole compounds, halodiallylurea compounds, guanidine compounds, fatty acid ester compounds, cyano compounds, aldehyde compounds, amide compounds, iodine compounds, carboxyimide compounds, benzoquinone compounds, paraben compounds, and tyrosol compounds; natural compounds such as chitosan, bamboo extract, Japanese mustard extract, wasabi extract, cypress extract, oyster shell, protamine, and polylysine.

[0055] Examples of organic compound antibacterial agents include 3-(trimethoxysilyl)propyldimethyloctadecylammonium chloride, tetradecyldimethylbenzylammonium chloride, 1-hexadecylpyridinium chloride, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, N-polyoxyethylene-N,N,N-trimethylammonium chloride, cetyltrimethylammonium chloride, octadecyltrimethylammonium chloride, didecyldimethylammonium chloride, benzalkonium chloride, behenyltrimethylammonium chloride, benzethonium chloride, 4,4'-(tetramethylenedicarbonyldiamino)bis(1-decylpyridinium bromide), and N,N'-hexamethylenebis Examples include quaternary ammonium salt compounds such as (4-carbamoyl-1-decylpyridinium salt), 4,4'-(p-phthalamide)bis(1-octylpyridinium bromide), and 3,3'-(m-phthalamide)bis(1-octylpyridinium iodide); monovalent phenolic compounds such as 5-chloro-2-(2,4-dichlorophenoxy)phenol; pyridine compounds such as 2-(3,5-dimethylpyrazolyl)-4-hydroxy-6-phenylpyridine; alcoholic compounds such as 2-(hydroxymethylamino)ethanol and 2-(hydroxymethylamino)-2-methylpropanol; phosphonium salt compounds such as tetradecyltrimethylphosphonium chloride and didecyldimethylphosphonium chloride; and chlorohexidine gluconate compounds.

[0056] The bacteria targeted by antibacterial agents include, for example, the genera Staphylococcus (including methicillin-resistant Staphylococcus aureus), Streptococcus (including Streptococcus pyogenes), Enterococcus, Peptostreptococcus, Bacillus (including Bacillus subtilis), Clostridium (including Clostridium tetani), Mycobacterium (including Mycobacterium tuberculosis), Actinomyces, Nocardia, Streptomyces, Pseudomonas (including Pseudomonas aeruginosa), Escherichia (including pathogenic Escherichia coli), Salmonella (including Salmonella typhi), Vibrio (including Vibrio cholerae), Shigella (including Shigella dysenteriae), Enterobacter (including Enterobacter cloacae), and Klebsiella. Examples include bacteria belonging to the genera Klebsiella (including pneumoniae), Serratia (including Serratiamarcescens), Haemophilus (including Haemophilus influenzae), Alcaligenes (including Alcaligenes faecalis), Leionella (including Legionella pneumophila), Campylobacter (including Campylobacter jejuni), Bacteroides (including Bacteroides fragilis), Neisseria (including Neisseria gonorrhoeae), and Treponema (including Treponema pallidum).

[0057] Examples of antifungal agents include haloallyl sulfone compounds such as 1-[(diiodomethyl)sulfonyl]-4-methylbenzene; iodopropagyl compounds such as 3-iodo-2-propagylbutylcarbamate; N-haloalkylthio compounds such as N,N-dimethyl-N'-(fluorodimethylthio)-N'-phenylsulfanide and N,N-dimethyl-N'-(fluorodichloromethylthio)-N'-phenylsulfamide; and nitrile compounds such as 2,3,5,6-tetrachloroisophthalonitrile and 2,4,5,6-tetrachloroisophthalonitrile. Compounds; pyridine compounds such as 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine; benzoichiazole compounds such as 2-(thiocyanomethylthio)benzothiazole; isothiazolin compounds such as 2-n-octyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, and 5-chloro-2-methyl-4-isothiazolin-3-one; pheno compounds such as p-chloro-m-cresol, alkylene bisphenol sodium, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, and o-phenylphenol. Triazine compounds; triazine compounds such as hexahydro-1,3,5-tri(2-hydroxyethyl)-s-triazine; thiadiazine compounds such as 3,5-dimethyl-tetrahydro-1,3,5,2H-thiadiazine-2-thion; anilide compounds such as 3,4,5-tribromosaltylanilide; adamantane compounds such as 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantanchloride; tetramethylthiuram disulfide, bis(dimethylthiocarbamoyl) disulfide, bis(diethylthiocarbamoyl) disulfide Dithiocarbide compounds such as phido; brominated indanone compounds such as 2,2-dibromo-1-indanone; benzoic acid compounds such as benzyl bromoacetate and p-hydroxybenzoic acid esters; sulfone compounds such as 3,4,5-tribromosalicylanilide; phthalimide compounds such as N-(trichloromethylthio)phthalimide, N-trichloromethylthio-4-cyclohexen-1,2-dicarboximide, N-1,1,2,2-tetrachloroethylthiotetrahydrophthalimide, and N-(fluorodichloromethylthio)phthalimide;Imidazole compounds such as 2-(4-thiazolyl)benzimidazole, 2-(carbomethoxyamino)benzimidazole, benzimidazole carbamate methyl ester, and 2-benzimidazole methylcarbamate; halodiallylurea compounds such as triclocarban; guanidine compounds such as polyhexamethylene biguanidine hydrochloride and chlorohexidine hydrochloride; fatty acid ester compounds such as propylene glycol mono fatty acid ester and glycerin fatty acid ester; 2,2-dibro Examples include amide compounds such as mo-2-cyanopropionamide; iodine compounds such as diiodomethyl-p-tolylsulfone; carboxyimide compounds such as N-(1,1,2,2-tetrachloroethylthio)-4-cyclohexen-1,2-dicarboximide and N-(trichloromethylthio)-4-cyclohexen-1,2-dicarboximide; benzoquinone compounds such as 2,6-dimethoxy-p-benzoquinone; and paraben compounds such as methylparaben and ethylparaben.

[0058] Examples of fungi targeted by antifungal agents include those belonging to genera such as Aspergillus (including Aspergillus flavus), Penicillium (including Penicillium chrysogenum), Aureobasidium, Cladosporium (including Cladosporium herbabarum), Alteraria (including Alteraria alternata), Fusarium (including Fusarium solani), Nigarospora (including Nigarospora oryzae), Rhizopus (including Rizopus stolonifer), Candida (including Candida albicnas), Trichophyton, Microsporum, Epidermophyton, Curvularia, Eurotium, Cochliobolus, and Acremonium.

[0059] Some antibacterial agents also exhibit antifungal properties, and some antifungal agents also exhibit antibacterial properties. For convenience, this specification describes them separately, but strict distinction can be difficult in some cases. Furthermore, antibacterial and antifungal properties often result in deodorizing and preservative properties as well. Antibacterial and antifungal agents are sometimes also called shelf-life enhancers and preservatives.

[0060] Examples of antiviral agents include silver thiosulfate, hydroxytyrosol, glutaraldehyde, hexachlorophene, and chlorohexidine. Antiviral agents typically target membranous viruses such as HIV, measles virus, herpes simplex virus, and influenza virus; and non-membranous viruses such as poliovirus.

[0061] Examples of anti-allergen agents include polyphenol compounds such as polyphenols, polycresols, and polymethoxyphenols; polyvinylphenol compounds; polybisphenol A compounds; lignophenol compounds; tannic acid; and polytyrosine. Antiallergens target allergens that cause allergic diseases such as atopic dermatitis, bronchial asthma, and allergic rhinitis. Examples include dust mite allergens, cedar pollen allergens, and allergen substances generated from these allergens.

[0062] (Application) This active energy ray-curable antibacterial agent can be used as a coating composition containing such antibacterial agent. Furthermore, such a coating composition hardens upon irradiation with active energy rays to form a cured coating film. Examples of active energy rays include far-ultraviolet, ultraviolet, near-ultraviolet, and infrared rays, as well as electromagnetic waves such as X-rays and gamma rays, and electron beams, proton beams, and neutron beams. Ultraviolet irradiation is advantageous in terms of curing speed, availability of irradiation equipment, and cost. Examples of light sources for ultraviolet irradiation include chemical lamps, xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps. While there are no particular limitations on the irradiation energy, it is typically 100-1,000 mJ / cm². 2 A certain amount of irradiation is sufficient. After UV irradiation, heating may be performed as needed to ensure complete curing.

[0063] The coating composition of the present invention is suitably used as a surface protective layer for articles that may come into contact with people, ranging from industrial products to daily necessities, in medical facilities, food factories, clothing factories, schools, train stations, banks, convenience stores, and various public facilities. The surface protective layer can be applied to the surface of an article as a cured coating film, which is a cured product obtained by curing this active energy ray-curable antibacterial anti-adhesion agent. [Examples]

[0064] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. In addition, in the following description, "parts" and "%" mean "parts by mass" and "% by mass," respectively, unless otherwise specified.

[0065] <Raw materials> (Manufacturing of urethane (meth)acrylate (A-1)) First, 99.3 g (0.45 mol) of isophorone diisocyanate (a1) (isocyanate group content 37.8%), 1.5 g of 2,6-di-tert-butyl cresol, and 0.1 g of dibutyltin dilaurylate were charged into a four-necked flask equipped with a thermometer, stirrer, and water-cooled condenser. Dipentaerythritol pentaacrylate (a2) (0.54 mol) was then reacted at 60°C for 2 hours at a temperature below 60°C. Here, dipentaerythritol pentaacrylate (a2) was prepared as a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 51.0 mg KOH / g) in 590.0 g. After the reaction began, when the remaining isocyanate groups reached 2.2%, 310.7 g (0.31 mol) of polyethylene glycol (a3) ​​(number average molecular weight 993.1, ethylene oxide addition moles 22, hydroxyl value 113 mg KOH / g) was added dropwise at 55°C, and the reaction was carried out at 60°C for 4 hours. The reaction was terminated when the remaining isocyanate groups reached 0.1%, yielding a resin composition containing urethane (meth)acrylate (A-1) (weight average molecular weight 3,700). The resin composition obtained in this manner contained 66.6% urethane (meth)acrylate (A-1) and 33.4% dipentaerythritol hexaacrylate as the (meth)acrylate monomer (B2-1).

[0066] (Manufacturing of urethane (meth)acrylate (A-2)) First, 239.4 g (0.40 mol) of modified hexamethylene diisocyanate trimer (a1) (isocyanate group content 21.1%), 3.7 g of 2,6-di-tert-butyl cresol, and 0.02 g of dibutyltin dilaurylate were charged into a four-necked flask equipped with a thermometer, stirrer, and water-cooled condenser. Dipentaerythritol pentaacrylate (a2) (0.80 mol) was then reacted at 60°C for 5 hours at a temperature below 60°C. Here, dipentaerythritol pentaacrylate (a2) was charged as a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 46.0 mg KOH / g). After the reaction started, when the remaining isocyanate groups reached 1.4%, the mixture was cooled to 50°C. Then, 643.9 g (0.41 mol) of polyethylene glycol monoallyl ether (a3) ​​(number average molecular weight 1562.95, ethylene oxide addition moles 34, hydroxyl value 35.9 mg KOH / g) was added dropwise at 55°C, and the mixture was reacted at 60°C for 3 hours. The reaction was terminated when the remaining isocyanate groups reached 0.1%, yielding a resin composition containing urethane (meth)acrylate (A-2) (weight average molecular weight 15,700). The resin composition obtained in this manner contained 68.7% urethane (meth)acrylate (A-2) and 31.3% dipentaerythritol hexaacrylate as the (meth)acrylate monomer (B2-1).

[0067] (Manufacturing of urethane (meth)acrylate (B1-1)) First, 150.0 g of isophorone diisocyanate (a1) (isocyanate group content 37.8%), 0.8 g of 2,6-di-tert-butyl cresol, and 0.05 g of dibutyltin dilaurylate were charged into a four-necked flask equipped with a thermometer, stirrer, and water-cooled condenser. Pentaerythritol triacrylate (a2) was then reacted at 60°C for 4 hours at a temperature below 60°C. Here, pentaerythritol triacrylate (a2) was prepared as 850 g of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (hydroxyl value 120.0 mg KOH / g). The reaction was terminated when the remaining isocyanate group content reached 0.1% after the start of the reaction, yielding a resin composition containing urethane (meth)acrylate (B1-1) (weight-average molecular weight 1,100). The resin composition thus obtained contained 51.1% urethane (meth)acrylate (B1-1) and 48.9% a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate as (meth)acrylate monomer (B2-2).

[0068] As the photopolymerization initiator (C-1), 1-[4-(2-hydroxyethoxyl)-phenyl]-2-hydroxymethylpropanone (IGMresins, "Omnirad 2959") was prepared.

[0069] <Example 1> To 100 parts by mass of a resin composition containing urethane (meth) acrylate (A-1), 4 parts by mass of a photopolymerization initiator (C-1) was mixed, and the mixture was diluted with ethyl acetate so that the resin content became 50%, to prepare an active energy ray-curable antibacterial low-adhesion agent. The obtained active energy ray-curable antibacterial low-adhesion agent was coated onto a 125-μm-thick PET film provided with an easy-adhesion layer using a bar coater so that the film thickness after drying became 5 μm, and dried at 60°C for 3 minutes. Then, using an 80-W high-pressure mercury lamp, one lamp, ultraviolet rays were irradiated at a conveyor speed of 5.1 m / min from a height of 18 cm for 2 passes (integrated irradiation dose: 450 mJ / cm 2 ), and a cured coating film was obtained. The following evaluations were performed on the cured coating film. The results are shown in Table 2.

[0070] (Antibacterial low-adhesion property) Staphylococcus aureus (NBRC12732) and Escherichia coli (NBRC3972) were pre-cultured at 37°C overnight, and a diluted culture solution was prepared using phosphate-buffered saline (pH 7.0) so that the OD 600 was within the range of 0.4 to 0.6. A test piece cut out to 3 cm square from the cured coating film was attached to the inside of a cell culture flask made of TPP, then 100 mL of the diluted culture solution was added, and various bacteria were allowed to adhere by standing at 37°C for 1 hour. After adhesion, the diluted culture solution was aspirated and removed, and the inside of the flask was washed 3 times with 100 mL of phosphate-buffered saline (pH 7.0). After removing the droplets remaining in the flask, the inner wall surface of the flask was wiped with an ATP measurement kit (Kikkoman Lucipac A3 Surface) in which the tip cotton swab was moistened with ion-exchanged water, and the amount of adhered bacteria was measured by the luminescence amount (Relative Light Unit; RLU). A: The RLU is less than 2.0×10 3 . B: The RLU is 2.0×10 3 or more and less than 5.0×10 3 . C: The RLU is 5.0×10 3 or more.

[0071] (Pencil hardness) The pencil hardness of the cured coating film was measured in accordance with JIS K 5600-5-4.

[0072] (flexibility) The flexibility of the cured coating was evaluated using a cylindrical mandrel bending tester in accordance with JIS K 5600-5-1. The maximum diameter (integer value, mm) at which cracking or peeling occurred when the cured coating was wrapped around a test rod was measured. A smaller value for the maximum diameter at which cracking or peeling occurs indicates better flexibility.

[0073] (exterior) The cured coating film was visually inspected and evaluated according to the following criteria. A: The coating surface is free of foreign matter and imperfections (tiny holes), and the surface is smooth. B: Foreign matter and paint repellency are visible on the surface of the coating.

[0074] <Examples 2-4> An active energy ray-curable antibacterial anti-adhesion agent was prepared in the same manner as in Example 1, except that urethane (meth)acrylate (A-1) and urethane (meth)acrylate (B1-1) were mixed to obtain the composition shown in Table 1, and a cured coating film was obtained. The obtained cured coating film was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0075] <Example 5> An active energy ray-curable antibacterial agent was prepared in the same manner as in Example 1, except that a resin composition containing urethane (meth)acrylate (A-2) was used instead of a resin composition containing urethane (meth)acrylate (A-1). The resulting cured coating film was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0076] <Comparative Example 1> An active energy ray-curable antibacterial agent was prepared in the same manner as in Example 1, except that a resin composition containing urethane (meth)acrylate (B1-1) was used instead of a resin composition containing urethane (meth)acrylate (A-1). The resulting cured coating film was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0077] [Table 1]

[0078] [Table 2]

[0079] As shown in the results of Examples 1 to 5 described above, it was confirmed that a cured coating film with excellent bacterial adhesion properties can be obtained using an active energy ray-curable antibacterial agent containing urethane (meth)acrylate (A). Furthermore, the active energy ray-curable antibacterial agents of Examples 1 to 4 also yielded a cured coating film with excellent appearance.

Claims

1. A urethane (meth)acrylate (A) in which the isocyanate group of polyvalent isocyanate (a1) forms a urethane bond with both the hydroxyl group of hydroxyl group-containing (meth)acrylate (a2) and the hydroxyl group of oxyalkylene group-containing compound (a3), Urethane (meth)acrylate (B1) having a urethane bond, other than urethane (meth)acrylate (A), (Meth)acrylate monomer (B2) other than urethane (meth)acrylate (A), It contains, At least a portion of the polyvalent isocyanate (a1) is isophorone diisocyanate, The oxyalkylene group-containing compound (a3) ​​is the compound represented by the following formula (2), The ratio of the oxyalkylene group-containing compound (a3) ​​to 100% by mass of the total amount of urethane (meth)acrylate (A), urethane (meth)acrylate (B1), and (meth)acrylate monomer (B2) is 3 to 30% by mass. The following RLU is 5.0 x 10 ３ An active energy ray curing type anti-bacterial agent that is less than or equal to [amount missing]. H-(OX) ｎ -OH ・・・Form (2) In formula (2), X is an alkylene group and n is 1 or greater. The RLU is the amount of light emitted after adding 100 mL of a diluted culture solution prepared by culturing Escherichia coli (NBRC3972) overnight at 37°C and using phosphate-buffered saline (pH 7.0) so that the OD600 is in the range of 0.4 to 0.6 to the cured coating film of the coating agent composition containing the active energy ray curable bacterial low-adhesion agent, and then allowing it to stand at 37°C for 1 hour, after which the diluted culture solution is aspirated and removed, and the inside of the flask is washed three times with 100 mL of phosphate-buffered saline (pH 7.0).

2. A urethane (meth)acrylate (A) in which the isocyanate group of polyvalent isocyanate (a1) forms a urethane bond with both the hydroxyl group of hydroxyl group-containing (meth)acrylate (a2) and the hydroxyl group of oxyalkylene group-containing compound (a3), Urethane (meth)acrylate (B1) having a urethane bond, other than urethane (meth)acrylate (A), (Meth)acrylate monomer (B2) other than urethane (meth)acrylate (A), It contains, At least a portion of the polyvalent isocyanate (a1) is isophorone diisocyanate, The oxyalkylene group-containing compound (a3) ​​is the compound represented by the following formula (3), The ratio of the oxyalkylene group-containing compound (a3) ​​to 100% by mass of the total amount of urethane (meth)acrylate (A), urethane (meth)acrylate (B1), and (meth)acrylate monomer (B2) is 3 to 30% by mass. The following RLU is 5.0 x 10 ３ An active energy ray curing type anti-bacterial agent that is less than or equal to [amount missing]. H-(OX) ｎ -O-C(=O)-CHR=CH ２ ...Form (3) In formula (3), X is an alkylene group, n is 1 or more, and R is a hydrogen atom or a methyl group. The RLU is the amount of light emitted after adding 100 mL of a diluted culture solution prepared by culturing Escherichia coli (NBRC3972) overnight at 37°C and using phosphate-buffered saline (pH 7.0) so that the OD600 is in the range of 0.4 to 0.6 to the cured coating film of the coating agent composition containing the active energy ray curable bacterial low-adhesion agent, and then allowing it to stand at 37°C for 1 hour, after which the diluted culture solution is aspirated and removed, and the inside of the flask is washed three times with 100 mL of phosphate-buffered saline (pH 7.0).

3. The active energy ray curable antibacterial agent according to claim 1 or 2, wherein the total content of urethane (meth)acrylate (B1) and (meth)acrylate monomer (B2) is 25 to 1,500 parts by mass per 100 parts by mass of urethane (meth)acrylate (A).

4. The active energy ray curable antibacterial agent according to any one of claims 1 to 3, further comprising a photopolymerization initiator (C).

5. A coating agent composition containing an active energy ray curable antibacterial low-adhesion agent according to any one of claims 1 to 4.

6. An article having a cured coating film of the coating agent composition described in claim 5.

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