Active energy ray-curable low bacterial adhesion agent, coating agent composition and 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 agent for reducing bacterial adhesion, a coating composition, and an article. [Background technology]

[0002] Conventionally, urethane (meth)acrylates have been known as active energy ray-curable resins and have been used in wood paints, plastic coating agents, and the like. Since urethane (meth)acrylate contains a urethane structure in its molecular structure, the cured coating film has internal hydrogen bond cohesive strength, which makes the coating film less likely to crack and more flexible.

[0003] Meanwhile, in recent years, cleanliness has been required for various industrial products. The demand for cleanliness is particularly strong for industrial products that are touched or approached by an unspecified number of people. These industrial products are prone to become contaminated with sweat, dirt, food debris, and other sources of nutrients for microorganisms, which can lead to explosive bacterial proliferation. For example, there is a demand for items with excellent cleanliness, from industrial products to everyday items, in medical facilities, food factories, clothing factories, schools, stations, banks, convenience stores, and various public facilities. In view of this, it has been proposed to provide a cured coating film having 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] JP 2011-57855 A Summary of the Invention [Problem to be solved by the invention]

[0005] In general, in the case of antibacterial and antifungal articles, bacteria attached to the surface are killed, but the remains of the microorganisms generated by the antibacterial action remain on the surface of the article. As a result, new microorganisms attach to the remains as if piling up over time, forming a mass of microorganisms and bacteria called a biofilm. The biofilm formed in this way is difficult to remove from the surface of the article, etc., and impairs cleanliness. Therefore, in the case of a cured coating film using a conventional antibacterial agent or antifungal agent, there is room for improvement in making it easier to remove clumps of microorganisms, etc. from the surface of the article and making it difficult for microorganisms, etc. to remain (low bacterial adhesion).

[0006] The present invention provides an active energy ray-curable anti-bacterial adhesion agent and coating composition which can give a cured coating film with excellent anti-bacterial adhesion properties; and an article with excellent anti-bacterial adhesion properties. [Means for solving the problem]

[0007] The present invention has the following aspects. [1] An active energy ray-curable bacterial low-adhesion agent comprising a urethane (meth)acrylate (A) in which an isocyanate group of a polyisocyanate (a1) forms a urethane bond with both a hydroxyl group of a hydroxyl group-containing (meth)acrylate (a2) and a hydroxyl group of an oxyalkylene group-containing compound (a3). [2] The active energy ray-curable bacterial low adhesion agent according to [1], wherein the oxyalkylene group-containing compound (a3) ​​is a compound represented by the following formula (2): H-(OX) n -OH...Formula (2) In formula (2), X is an alkylene group and n is 1 or more. [3] The active energy ray-curable bacterial low-adhesion agent according to [1], wherein the oxyalkylene group-containing compound (a3) ​​is a compound represented by the following formula (3): 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] An active energy ray-curable bacterial low-adhesion agent according to any one of [1] to [3], further comprising a (meth)acrylate (B) other than the urethane (meth)acrylate (A). [5] The active energy ray-curable bacterial low-adhesion agent according to [4], wherein the (meth)acrylate (B) is at least one selected from the group consisting of urethane (meth)acrylates (B1) having a urethane bond and (meth)acrylate monomers (B2). [6] The active energy ray-curable bacterial low-adhesion agent according to [4] or [5], wherein the content of the (meth)acrylate (B) is 25 to 1,500 parts by mass per 100 parts by mass of the urethane (meth)acrylate (A). [7] An active energy ray-curable bacterial low-adhesion agent according to any one of [1] to [6], further comprising a photopolymerization initiator (C). [8] A coating composition comprising the active energy ray-curable bacterial low-adhesion agent according to any one of [1] to [7]. [9] An article having a cured coating film of the coating composition of [8]. Effect of the Invention

[0008] According to the active energy ray-curable bacterial anti-adhesion agent and coating composition of the present invention, a cured coating film having excellent bacterial anti-adhesion properties can be obtained. The article of the present invention is excellent in low bacterial adhesion. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] As used herein, the following terms have the following meanings: (Meth)acrylate is a general term for methacrylate and acrylate. The (meth)acryloyl group is a general term for a methacryloyl group and an acryloyl group. The symbol "~" indicating a range of values ​​means that the values ​​before and after it are included as the lower and upper limits.

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

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

[0012] (Polyisocyanate (a1)) The polyisocyanate (a1) is a compound having two or more isocyanate groups. Examples of the polyisocyanate (a1) include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. Specific examples include 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), and tetramethylxylylene diisocyanate. Examples of polyisocyanates include polyisocyanates such as m-TMXDI, isophorone diisocyanate (IPDI), norbornene diisocyanate (NBDI), phenylene diisocyanate, lysine diisocyanate, lysine triisocyanate, and naphthalene diisocyanate (NDI); trimer compounds of these polyisocyanates, biuret-type polyisocyanates, and water-dispersible polyisocyanates (such as "Aquanate 100," "Aquanate 110," "Aquanate 200," and "Aquanate 210," manufactured by Nippon Polyurethane Industry Co., Ltd.). Among these, from the viewpoint of low bacterial adhesion, modified products of isophorone diisocyanate and hexamethylene diisocyanate trimers are preferred. The polyisocyanates may be used alone or in combination of two or more kinds.

[0013] The polyisocyanate (a1) may be a reaction product of these polyisocyanates (limited to those having 3 or more isocyanate groups) with a polyol. Examples of the polyol 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 of the polyol include polyhydric alcohols such as tetramethylene glycol; polyether polyols having at least one structure of polyethylene oxide, polypropylene oxide, block copolymerization and random copolymerization of 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, isophthalic acid, etc.; caprolactone-modified polyols such as caprolactone-modified polytetramethylene polyol; polyolefin-based polyols; and polybutadiene-based polyols such as hydrogenated polybutadiene polyols.

[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- or sulfonate salt group-containing polyols such as 1,4-butanediol sodium sulfonate. The reaction products of polyisocyanate and polyol may be used alone or in combination of two or more kinds.

[0015] In the reaction between polyisocyanate and polyol, a catalyst can be used to promote the reaction. Examples of the catalyst include organometallic compounds such as dibutyltin dilaurate, trimethyltin hydroxide, and tetra-n-butyltin, metal salts such as zinc octylate, tin octylate, cobalt naphthenate, stannous chloride, and stannic 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 catalysts include bismuth sulfide, as well as organic bismuth compounds such as dibutyl bismuth dilaurate and dioctyl bismuth dilaurate; and organic acid bismuth salts such as bismuth 2-ethylhexanoate, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth tribisneodecanoate, bismuth disalicylate, and bismuth digallate. Among these, dibutyltin dilaurate and 1,8-diazabicyclo[5,4,0]undecene are preferable.

[0016] (Hydroxyl group-containing (meth)acrylate (a2)) The hydroxyl group-containing (meth)acrylate (a2) is a (meth)acrylate having one or more hydroxyl groups. The hydroxyl group-containing (meth)acrylate (a2) is not particularly limited as long as it is a (meth)acrylate containing at least one hydroxyl group. Examples of the hydroxyl group-containing (meth)acrylate (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 from the viewpoint of low bacterial adhesion. The hydroxyl group-containing (meth)acrylate (a2) may be used alone or in combination of two or more kinds.

[0017] (Oxyalkylene Group-Containing Compound (a3)) The oxyalkylene group-containing compound (a3) ​​has an oxyalkylene group and further has a hydroxyl group capable of forming a urethane bond with the isocyanate group of the polyisocyanate (a1). The oxyalkylene group-containing compound (a3) ​​may be a compound represented by the following formula (1): The oxyalkylene group-containing compound (a3) ​​may be used alone or in combination of two or more kinds.

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

[0019] In formula (1), X is an alkylene group, which may be the same alkylene group or different alkylene groups. The number of carbon atoms in the alkylene group of X is preferably 2 to 5, 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 the formula (1), n ​​is 1 or more, and is preferably 5-500, more preferably 5-100, and even more preferably 6-50. When the oxyalkylene group in formula (1) has two or more different alkylene groups, the total added mole number (n) of the oxyalkylene groups is preferably 5-500, more preferably 5-100, and even more preferably 6-50.

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

[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 formula (2), X is an alkylene group and n is 1 or more. In formula (2), details and preferred embodiments of X and n are the same as those explained for formula (1).

[0024] Examples of the oxyalkylene group-containing compound (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, and ethylene oxide / propylene oxide block copolymer and random copolymer.

[0025] When Y is an alkyl group, the alkyl group of Y preferably has 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms. When Y is an alkyl group, examples of the oxyalkylene group-containing compound (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, polypropylene glycol monomethyl ether, and the like.

[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 more, and R is a hydrogen atom or a methyl group. In formula (3), "-C(=O)-" is a carbonyl group and may be abbreviated as "-C(O)-". In formula (3), details and preferred embodiments of X and n are the same as those explained for formula (1).

[0029] Examples of the oxyalkylene group-containing compound (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 the oxyalkylene group-containing compound (a3) ​​include polyethylene glycol monoallyl ether, polypropylene glycol monoallyl ether, poly(ethylene glycol-propylene glycol) monoallyl ether, and the like.

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

[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 less than the lower limit, the cured coating film tends to have difficulty in exhibiting the low bacterial adhesion performance. If the weight average molecular weight of the oxyalkylene group-containing compound (a3) ​​is more than 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 preferable.

[0033] The proportion of the oxyalkylene group-containing compound (a3) ​​relative to the total amount of the urethane (meth)acrylate (A) and the (meth)acrylate (B) (100% by mass) 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 proportion of the oxyalkylene group-containing compound (a3) ​​is less than the lower limit, it tends to be difficult to achieve low bacterial adhesion. If the proportion of the oxyalkylene group-containing compound (a3) ​​is more than the upper limit, the durability of the cured coating film, such as water resistance, tends to deteriorate, and the hardness of the outermost coating material tends to be inferior, which is not practically preferable.

[0034] The weight-average molecular weight of the urethane (meth)acrylate (A) is preferably 1000 to 100000, more preferably 2000 to 50000. If the weight-average molecular weight is less than the lower limit, the anti-bacterial adhesion performance tends to decrease. If the weight-average molecular weight is more than the upper limit, the hardness of the cured coating film tends to decrease, which is not practically preferable.

[0035] The number average molecular weight and weight average molecular weight are number average molecular weight and weight average molecular weight converted into standard polystyrene molecular weight, and are measured using a high performance liquid chromatograph (Waters, "ACQUITY APC System") equipped 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)) The urethane (meth)acrylate (A) can be obtained by reacting a polyisocyanate (a1), a hydroxyl group-containing (meth)acrylate (a2), and an oxyalkylene group-containing compound (a3) ​​so that the isocyanate groups in the polyisocyanate (a1) form urethane bonds with the hydroxyl groups of the hydroxyl group-containing (meth)acrylate (a2) and the hydroxyl groups of the oxyalkylene group-containing compound (a3), respectively.

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

[0038] Examples of the reaction method for forming a urethane bond include the following methods (a), (b) and (c). (A): A method in which a polyisocyanate (a1), a hydroxyl group-containing (meth)acrylate (a2), and an oxyalkylene group-containing compound (a3) ​​are charged together and reacted; (ii) A method of reacting a polyisocyanate (a1) with a hydroxyl group-containing (meth)acrylate (a2) and then reacting the reacted product with an oxyalkylene group-containing compound (a3); (c): A method in which a polyisocyanate (a1) is reacted with an oxyalkylene group-containing compound (a3), and then a hydroxyl group-containing (meth)acrylate (a2) is reacted therewith. Among these, method (b) is preferred from the viewpoints of stability of reaction control and shortening of production time.

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

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

[0041] The urethane (meth)acrylate (B1) is not particularly limited as long as it is a urethane (meth)acrylate other than the urethane (meth)acrylate (A). For example, there is a urethane (meth)acrylate in which all of the 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). In addition, there is a urethane (meth)acrylate in which an 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). The urethane (meth)acrylate (B1) may be used alone or in combination of two or more kinds.

[0042] Examples of the (meth)acrylate monomer (B2) include monofunctional monomers, difunctional monomers, and trifunctional or higher functional monomers depending on the number of (meth)acryloyl groups. The (meth)acrylate monomer (B2) may be used alone or in combination of two or more kinds.

[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, decamethyl (meth)acrylate, methyl (meth)acrylate, ethyl ... Examples of the acrylates include sil (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, n-stearyl (meth)acrylate, benzyl (meth)acrylate, phenol ethylene oxide modified (n=2) (meth)acrylate, nonylphenol propylene oxide modified (n=2.5) (meth)acrylate, 2-(meth)acryloyloxyethyl acid phosphate, half (meth)acrylates of phthalic acid derivatives such as 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, furfuryl (meth)acrylate, carbitol (meth)acrylate, benzyl (meth)acrylate, butoxyethyl (meth)acrylate, allyl (meth)acrylate, acryloylmorpholine, 2-hydroxyethyl acrylamide, N-methylol (meth)acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, and polyoxyethylene secondary alkyl ether acrylate. The monofunctional monomer may be used alone or in combination of two or more kinds.

[0044] Examples of bifunctional 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, Examples of suitable di(meth)acrylates include propylene oxide-modified bisphenol A 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, phthalic acid diglycidyl ester di(meth)acrylate, hydroxypivalic acid-modified neopentyl glycol di(meth)acrylate, and isocyanuric acid ethylene oxide-modified diacrylate. The bifunctional monomer may be used alone or in combination of two or more kinds.

[0045] Examples of trifunctional or higher monomers 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, isocyanuric acid ethylene oxide modified triacrylate, caprolactone modified dipentaerythritol penta(meth)acrylate, caprylic acid, ethyl ether, glycerin ... Examples of the polyether ether ester include lactone-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. The tri- or higher functional monomer may be used alone or in combination of two or more kinds.

[0046] Other examples of the (meth)acrylate monomer (B2) include Michael adducts of acrylic acid and 2-acryloyloxyethyl dicarboxylic acid monoesters. Examples of the Michael adduct of acrylic acid include acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, methacrylic acid trimer, acrylic acid tetramer, and methacrylic acid tetramer. Examples of 2-acryloyloxyethyl dicarboxylate monoesters include 2-acryloyloxyethyl succinate monoester, 2-methacryloyloxyethyl succinate monoester, 2-acryloyloxyethyl phthalate monoester, 2-methacryloyloxyethyl phthalate monoester, 2-acryloyloxyethyl hexahydrophthalate monoester, 2-methacryloyloxyethyl hexahydrophthalate monoester, etc. Furthermore, other oligoester acrylates are also included.

[0047] When a monomer further having an oxyalkylene structure is used among these (meth)acrylate monomers (B2), further improvement in the low bacterial adhesion performance can be expected.

[0048] When the urethane (meth)acrylate (A) is used as an aqueous dispersion, it is preferable to use a water-soluble or water-dispersible (meth)acrylate monomer (B2).Among them, 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, isocyanuric acid ethylene oxide modified diacrylate, isocyanuric acid ethylene oxide modified triacrylate, ethylene oxide modified epoxy acrylate, polyoxyethylene secondary alkyl ether acrylate, ethoxylated glycerin triacrylate, polyester acrylate mainly composed of polyethylene glycol, etc. Among these, acryloylmorpholine, ethylene glycol di(meth)acrylate, isocyanuric acid ethylene oxide modified diacrylate, isocyanuric acid ethylene oxide modified triacrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, and the like are preferred.

[0049] The content of the (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, relative to 100 parts by mass of the urethane (meth)acrylate (A). If the content of the (meth)acrylate (B) is outside the above-mentioned numerical range, it tends to be difficult to exhibit low bacterial adhesion.

[0050] <Photopolymerization initiator (C)> When a coating film is obtained by ultraviolet irradiation, the active energy ray curable bacterial adhesion reducing agent preferably contains a photopolymerization initiator (C). However, when electron beam irradiation is performed, the active energy ray curable bacterial adhesion reducing agent can be cured without the photopolymerization initiator (C). The photopolymerization initiator (C) is not particularly limited as long as it generates radicals by 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-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, benzophenone, benzoylbenzoin Acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 4',4''-diethylisophthalophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, α-acyloxime ester, acylphosphine oxide, methylphenyl glyoxylate, benzyl, 9,10-phenanthrenequinone, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, and the like. Among these, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl 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 kinds.

[0051] When the urethane (meth)acrylate (A) is used as a water-based coating agent in an active energy ray curable bacterial low adhesion agent, the photopolymerization initiator (C) is preferably a water-soluble or water-dispersible photopolymerization initiator. For example, 2-(3-dimethylamino-2-hydroxypropoxy)-3,4-dimethyl-9H-thioxanthone-9-one methchloride (manufactured by Octel Chemicals, "Quantacure QTX"), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (manufactured by Ciba Specialty Chemicals, "Irgacure 2959"), etc. are preferred. Among them, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (manufactured by Ciba Specialty Chemicals, "Irgacure 2959") is preferred.

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

[0053] <Other ingredients> Examples of other components include antibacterial agents, antifungal agents, antiviral agents, antiallergen agents, thermoplastic resins, polymerization inhibitors, ultraviolet 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. The other components may be used alone or in combination of two or more.

[0054] Examples of antibacterial agents include metals (including metal ions) such as silver, copper, and zinc; 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 silver thiosulfate, 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 compounds, ceramic-supported compounds, silica gel-supported compounds, and montmorillonite-supported compounds; quaternary ammonium salt-based compounds, monocyclic hydrocarbon-based compounds, phenol-based compounds, pyridine-based compounds, alcohol-based compounds, phosphonium salt-based compounds, allyl-based compounds, haloarylsulfone-based compounds, iodopropargyl-based compounds, N-haloalkylthio-based compounds, nitrile-based compounds, and 8-oxyquinoline-based compounds. Organic compounds such as phosphorus compounds, benzoithiazole compounds, isothiazolinone compounds, organic tin 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, halodiallyl urea compounds, guanidine compounds, fatty acid ester compounds, cyano compounds, aldehyde compounds, amide compounds, iodine compounds, carboximide compounds, benzoquinone compounds, paraben compounds, and tyrosol compounds; and natural compounds such as chitosan, moso bamboo extract, Japanese mustard extract, wasabi extract, hiba extract, oyster shell, protamine, and polylysine.

[0055] Examples of organic compound antibacterial agents include 3-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride, tetradecyl dimethylbenzyl ammonium 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), N,N'-hexamethylene bis(1-decylpyridinium bromide), Examples of such compounds include quaternary ammonium salts such as 4-carbamoyl-1-decylpyridinium salts, 4,4'-(p-phthalamido)bis(1-octylpyridinium bromide), and 3,3'-(m-phthalamido)bis(1-octylpyridinium iodide); monohydric phenol compounds such as 5-chloro-2-(2,4-dichlorophenoxy)phenol; pyridine compounds such as 2-(3,5-dimethylpyrazolyl)-4-hydroxy-6-phenylpyridine; alcohol 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] Examples of bacteria that can be targeted by the antibacterial agent include the genus Staphylococcus, such as Staphylococcus aureus (including methicillin-resistant Staphylococcus aureus), the genus Streptococcus, such as Streptococcus pyogenes, the genus Enterococcus, the genus Peptostreptococcus, the genus Bacillus, such as Bacillus subtilis, the genus Clostridium, such as Clostridium tetani, the genus Mycobacterium, such as Mycobacterium tuberculosis, the genus Actinomyces, the genus Nocardia, the genus Streptomyces, the genus Pseudomonas, such as Pseudomonas aeruginosa, the genus Escherichia, such as Escherichia coli (including pathogenic E. coli), the genus Salmonella, such as Salmonella typhi, the genus Vibrio, such as Vibrio cholerae, the genus Shigella, such as Shigella dysenteriae, the genus Enterobacter, such as Enterobacter cloacae, the genus Klebsiella, Examples of bacteria that can be used include bacteria of the genus Klebsiella including S. pneumoniae, the genus Serratia including Serratia marcescens, the genus Haemophilus including Haemophilus influenzae, the genus Alcaligenes including Alcaligenes faecalis, the genus Leionella including Legionella pneumophila, the genus Campylobacter including Campylobacter jejuni, the genus Bacteroides including Bacteroides fragilis, the genus Neisseria including Neisseria gonorrhoeae, and the genus Treponema including Treponema pallidum.

[0057] Examples of the fungicide include haloarylsulfone compounds such as 1-[(diiodomethyl)sulfonyl]-4-methylbenzene; iodopropargyl compounds such as 3-iodo-2-propagyl butylcarbamate; 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. pyridine compounds such as 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine; benzothiazole compounds such as 2-(thiocyanomethylthio)benzothiazole; isothiazoline 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; phenols such as p-chloro-m-cresol, sodium alkylene bisphenol, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, and o-phenylphenol. 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-thione; anilide compounds such as 3,4,5-tribromosalthylanilide; adamantane compounds such as 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride; tetramethylthiuram disulfide, bis(dimethylthiocarbamoyl) disulfide, bis(diethylthiocarbamoyl) disulfide dithiocarbide compounds such as phthalimide; 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-cyclohexene-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 carbamic acid methyl ester, and 2-benzimidazole methylcarbamate; halodiallyl urea compounds such as triclocarban; guanidine compounds such as polyhexamethylenepyrguanidine hydrochloride and chlorhexidine hydrochloride; fatty acid ester compounds such as propylene glycol mono fatty acid ester and glycerin fatty acid ester; 2,2-dibromo Amide compounds such as mo-2-cyanopropionamide; iodine compounds such as diiodomethyl-p-tolylsulfone; carboximide compounds such as N-(1,1,2,2-tetrachloroethylthio)-4-cyclohexene-1,2-dicarboximide and N-(trichloromethylthio)-4-cyclohexene-1,2-dicarboximide; benzoquinone compounds such as 2,6-dimethoxy-p-benzoquinone; and paraben compounds such as methylparaben and ethylparaben.

[0058] Examples of molds (fungi) targeted by the antifungal agent include fungi belonging to the genus Aspergillus, such as Aspergillus flavus; the genus Penicillium, such as Penicillium chrysogenum; the genus Aureobasidium; the genus Cladosporium, such as Cladosporium herbabarum; the genus Alternaria, such as Alternaria alternata; the genus Fusarium, such as Fusarium solani; the genus Nigarospora, such as Nigarospora oryzae; the genus Rhizopus, such as Rizopus stolonifer; the genus Candida, such as Candida albicnas; the genus Trichophyton; the genus Microsporum; the genus Epidermophyton; the genus Curvularia; the genus Eurotium; the genus Cochliobolus; the genus Acremonium; and the like.

[0059] Some antibacterial agents also exhibit antifungal properties, and some antifungal agents also exhibit antibacterial properties. In this specification, the two are described separately for convenience, but it may be difficult to strictly distinguish them. Furthermore, antibacterial and antifungal properties often result in deodorizing and preservative properties as well. Antibacterial and antifungal agents are sometimes called shelf life improvers or preservatives.

[0060] Examples of antiviral agents include silver thiosulfate, hydroxytyrosol, glutaral, hexachlorophene, and chlorhexidine. Viruses targeted by antiviral agents generally include membraned viruses such as AIDS virus, measles virus, herpes simplex virus, and influenza virus; and membraneless viruses such as poliovirus.

[0061] Examples of the anti-allergen agent include polyphenol compounds such as polyphenol, polycresol, and polymethoxyphenol; polyvinylphenol compounds; polybisphenol A compounds; lignophenol compounds; tannic acid; and polytyrosine. The allergens targeted by the anti-allergen agent include those that cause allergic diseases such as atopic dermatitis, bronchial asthma, allergic rhinitis, etc. Examples include mite allergens, cedar pollen allergens, and allergen substances generated from these allergens.

[0062] (Application) The active energy ray curable bacterial low adhesion agent can be used as a coating composition containing the bacterial low adhesion agent. In addition, the coating composition is cured by irradiation with active energy rays to form a cured coating film. Examples of active energy rays include light rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, and infrared rays, electromagnetic waves such as X-rays and gamma rays, as well as electron beams, proton beams, and neutron beams. In terms of curing speed, availability of irradiation equipment, price, etc., ultraviolet irradiation is advantageous. Examples of the light source for ultraviolet irradiation include chemical lamps, xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, etc. The irradiation energy is not particularly limited, but is usually 100 to 1,000 mJ / cm. 2 After the ultraviolet irradiation, heating may be carried out as necessary to complete the curing.

[0063] The coating composition of the present invention is suitably used as a surface protective layer for articles that people may touch, ranging from industrial products to everyday items, in medical facilities, food factories, clothing factories, schools, stations, banks, convenience stores, various public facilities, etc. The surface protective layer can be provided on the surface of the article as a cured coating film that is a cured product obtained by curing the active energy ray-curable bacterial low-adhesion agent of the present invention. 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 the following description, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

[0065] <Raw materials> (Production 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-butylcresol, and 0.1 g of dibutyltin dilaurate were charged into a four-neck flask equipped with a thermometer, a stirrer, and a water-cooled condenser, and dipentaerythritol pentaacrylate (a2) (0.54 mol) was reacted at 60° C. or less for 2 hours at 60° C. Here, the dipentaerythritol pentaacrylate (a2) was charged as 590.0 g of a mixture (hydroxyl value 51.0 mgKOH / g) of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. After the start of the reaction, when the residual isocyanate groups reached 2.2%, 310.7 g (0.31 mol) of polyethylene glycol (a3) ​​(number average molecular weight 993.1, ethylene oxide addition mole number 22, hydroxyl value 113 mgKOH / g) was further added dropwise at 55°C, and the reaction was continued at 60°C for 4 hours. When the residual isocyanate groups reached 0.1%, the reaction was terminated, and a resin composition containing urethane (meth)acrylate (A-1) was obtained (weight average molecular weight 3,700). The resin composition thus obtained contained 66.6% of the urethane (meth)acrylate (A-1) and 33.4% of dipentaerythritol hexaacrylate as the (meth)acrylate monomer (B2-1).

[0066] (Production 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-butylcresol, and 0.02 g of dibutyltin dilaurate were charged into a four-neck flask equipped with a thermometer, a stirrer, and a water-cooled condenser, and dipentaerythritol pentaacrylate (a2) (0.80 mol) was reacted at 60° C. or less for 5 hours at 60° C. Here, the dipentaerythritol pentaacrylate (a2) was charged as a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 46.0 mgKOH / g) 975.8 g. After the reaction started, when the residual isocyanate groups reached 1.4%, the mixture was cooled to 50°C, and 643.9 g (0.41 mol) of polyethylene glycol monoallyl ether (a3) ​​(number average molecular weight 1562.95, ethylene oxide addition mole number 34, hydroxyl value 35.9 mgKOH / g) was added dropwise at 55°C, and the reaction was continued for 3 hours at 60°C. When the residual isocyanate groups reached 0.1%, the reaction was terminated, and a resin composition containing urethane (meth)acrylate (A-2) was obtained (weight average molecular weight 15,700). The resin composition thus obtained contained 68.7% of the urethane (meth)acrylate (A-2) and 31.3% of dipentaerythritol hexaacrylate as the (meth)acrylate monomer (B2-1).

[0067] (Production 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-butylcresol, and 0.05 g of dibutyltin dilaurate were charged into a four-neck flask equipped with a thermometer, a stirrer, and a water-cooled condenser, and pentaerythritol triacrylate (a2) was reacted at 60° C. or less for 4 hours at 60° C. Here, the pentaerythritol triacrylate (a2) was charged as 850 g of a mixture (hydroxyl value 120.0 mg KOH / g) of pentaerythritol triacrylate and pentaerythritol tetraacrylate. After the start of the reaction, the reaction was terminated when the amount of remaining isocyanate groups reached 0.1%, thereby obtaining a resin composition containing a urethane (meth)acrylate (B1-1) (weight average molecular weight 1,100). The resin composition thus obtained contained 51.1% of urethane (meth)acrylate (B1-1) and 48.9% of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate as the (meth)acrylate monomer (B2-2).

[0068] As a photopolymerization initiator (C-1), 1-[4-(2-hydroxyethoxyl)-phenyl]-2-hydroxy-methylpropanone (manufactured by IG Resins, "Omnirad 2959") was prepared.

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

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

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

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

[0073] (exterior) The surface of the cured coating film was visually observed and evaluated according to the following criteria. A: There are no foreign objects or repelling marks (tiny holes) on the coating surface, and the surface is smooth. B: Foreign matter or cissing is found on the coating surface.

[0074] <Examples 2 to 4> An active energy ray-curable antibacterial agent was prepared and a cured coating film was obtained in the same manner as in Example 1, except that the urethane (meth)acrylate (A-1) and the urethane (meth)acrylate (B1-1) were mixed to obtain the composition shown in Table 1. 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 obtained 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 (A-1) was not used, and a resin composition containing urethane (meth)acrylate (B1-1) was used. The obtained 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 the active energy ray-curable anti-adhesion agent containing the urethane (meth)acrylate (A) can provide a cured coating film with excellent anti-adhesion properties. In addition, the active energy ray-curable anti-adhesion agents of Examples 1 to 4 provided cured coating films with excellent appearance.

Claims

1. a urethane (meth)acrylate (A) in which an isocyanate group of the polyisocyanate (a1) forms a urethane bond with both a hydroxyl group of the hydroxyl group-containing (meth)acrylate (a2) and a hydroxyl group of an oxyalkylene group-containing compound (a3); a urethane(meth)acrylate (B1) having a urethane bond other than the urethane(meth)acrylate (A); a (meth)acrylate monomer (B2) other than the urethane (meth)acrylate (A); Contains At least a part of the polyisocyanate (a1) is isophorone diisocyanate, The oxyalkylene group-containing compound (a3) ​​is a compound represented by the following formula (2): the proportion of the oxyalkylene group-containing compound (a3) ​​relative to 100% by mass of the total amount of the urethane (meth)acrylate (A), the urethane (meth)acrylate (B1), and the (meth)acrylate monomer (B2) is 3 to 30% by mass; The RLU below is 5.0 x 10 ３ An active energy ray curable bacterial low adhesion agent having a bacterial adhesion of less than or equal to 100%. H-(OX) ｎ -OH ・・・Formula (2) In formula (2), X is an alkylene group and n is 1 or more. The RLU is the amount of luminescence measured after culturing Escherichia coli (NBRC3972) overnight at 37°C on a cured coating film of a coating composition containing the active energy ray-curable bacterial low-adhesion agent, adding 100 mL of a diluted culture solution prepared using phosphate buffered saline (pH 7.0) so that the OD600 falls within the range of 0.4 to 0.6, allowing the mixture to stand at 37°C for 1 hour, removing the diluted culture solution by suction, and washing the inside of the flask three times with 100 mL of phosphate buffered saline (pH 7.0).

2. a urethane (meth)acrylate (A) in which an isocyanate group of the polyisocyanate (a1) forms a urethane bond with both a hydroxyl group of the hydroxyl group-containing (meth)acrylate (a2) and a hydroxyl group of an oxyalkylene group-containing compound (a3); a urethane(meth)acrylate (B1) having a urethane bond other than the urethane(meth)acrylate (A); a (meth)acrylate monomer (B2) other than the urethane (meth)acrylate (A); Contains At least a part of the polyisocyanate (a1) is isophorone diisocyanate, The oxyalkylene group-containing compound (a3) ​​is a compound represented by the following formula (3): the proportion of the oxyalkylene group-containing compound (a3) ​​relative to 100% by mass of the total amount of the urethane (meth)acrylate (A), the urethane (meth)acrylate (B1), and the (meth)acrylate monomer (B2) is 3 to 30% by mass; The RLU below is 5.0 x 10 ３ An active energy ray curable bacterial low adhesion agent having a bacterial adhesion of less than or equal to 100%. H-(OX) ｎ -O-C(=O)-CHR=CH ２ ・・・Formula (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 luminescence measured after culturing Escherichia coli (NBRC3972) overnight at 37°C on a cured coating film of a coating composition containing the active energy ray-curable bacterial low-adhesion agent, adding 100 mL of a diluted culture solution prepared using phosphate buffered saline (pH 7.0) so that the OD600 falls within the range of 0.4 to 0.6, allowing the mixture to stand at 37°C for 1 hour, removing the diluted culture solution by suction, and washing the inside of the flask three times with 100 mL of phosphate buffered saline (pH 7.0).

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

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

5. A coating composition comprising the active energy ray-curable bacterial low adhesion agent according to any one of claims 1 to 4.

6. An article having a cured coating film of the coating composition according to claim 5.

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