Composition for active energy ray-curable coating agent, antibacterial composition, and antibacterial cured product

Abstract

To provide a composition for an active energy ray-curable coating agent which uses a biomass material as an antibacterial component and which exhibits excellent UV curability and excellent properties of the cured film.SOLUTION: The composition comprises a compound (A) having an unsaturated ethylene structure and a photopolymerization initiator (B), where the compound (A) having an unsaturated ethylene structure contains a compound (A1) represented by a specific formula, and the content of the compound (A1) is 0.1 to 5 pts.mass with respect to 100 pts.mass of the compound (A) having an unsaturated ethylene structure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an active energy ray-curable coating composition, an antibacterial composition containing the same, and an antibacterial cured product obtained by curing the same. More specifically, the present invention relates to an active energy ray-curable coating composition based on a compound derived from non-edible biomass, which has excellent UV curing properties and exhibits both strength and water resistance in the cured product, an antibacterial composition containing the same, and an antibacterial cured product obtained by curing the same. [Background technology]

[0002] In recent years, increased awareness of hygiene management has led to an increased demand for products with antibacterial, antiviral, and deodorizing properties, and antibacterial products are being developed for a variety of uses, including automotive interiors, electronic devices, building materials, and textiles. Some of these products have antibacterial substances kneaded into the molded article, while others have antibacterial properties simply applied to the surface of the molded article. In particular, antibacterial coating agents have attracted attention because they can easily impart antibacterial properties. The antibacterial coating agent can be used in a wide range of fields, such as electronic devices, automobile interiors, and building materials, and is expected to be used in an even wider range of fields as hygiene awareness increases in the future, so demand is expected to continue to increase.

[0003] Such antibacterial coating agents typically incorporate antibacterial metallic materials to achieve their antibacterial effect. However, coating agents incorporating antibacterial metallic materials have the problem that the active ingredient, metal ions, dissolve in water, resulting in the antibacterial effect not lasting for a long period of time depending on the conditions of use. Furthermore, antibacterial metallic materials typically have poor dispersibility in coating agents, leading to problems such as the formation of lumps during stirring when preparing the coating agent, and aggregation and sedimentation of the compounded materials when the finished coating agent is stored for a long period of time.

[0004] For example, Patent Document 1 discloses a paste containing an inorganic antibacterial powder whose main component is a surfactant, and adding this paste to paint imparts antibacterial properties. However, it shows that the inorganic antibacterial powder settles after about 10 days of storage, requiring redispersion.

[0005] On the other hand, Patent Document 2 discloses a method of using antibacterial modified polyvinyl alcohol instead of a metal-based material to solve the problem of compatibility with antibacterial materials. However, although this method may solve the problem of compatibility with antibacterial materials, when the resulting coating layer comes into contact with an aqueous liquid, the coating layer may whiten or peel due to the low water resistance of polyvinyl alcohol.

[0006] As described above, conventional antibacterial coating agents have problems with dispersibility and the fragility of the coating film.

[0007] In recent years, ultraviolet-curable coating agents have been widely used to reduce the burden on the environment, and there is also a demand for the use of biomass materials to achieve carbon neutrality. For example, in Non-Patent Document 1, no metal materials are used, and instead, cardanol extracted from cashew nut shell oil, a biomass material, is used to synthesize methacrylate and glycidyl cross-linked methacrylate monomers to produce an antibacterial UV-cured film (coating). However, this method has problems in that the reactivity of the monomer derived from biomass materials is poor, requiring long periods of UV irradiation to produce a cured film, and because a large amount of monomer must be blended in order to exhibit antibacterial properties, the properties of the resulting UV-cured film tend to be inferior. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Patent No. 3895016 [Patent Document 2] International Publication No. 2017 / 171066 [Non-patent literature]

[0009] [Non-Patent Document 1] RSC Advances (UK), The Royal Society of Chemistry, August 26, 2014, No. 4, pp. 41195-41203 Summary of the Invention [Problem to be solved by the invention]

[0010] Under these circumstances, the present invention aims to provide an active energy ray-curable coating composition, an antibacterial composition, and an antibacterial cured product that contain a biomass material as an antibacterial component and have excellent UV curability and various properties of the cured film. [Means for solving the problem]

[0011] However, in view of the above circumstances, the present inventors have conducted extensive research and have found that an active energy ray-curable coating composition having a compound (A) having a specific unsaturated ethylene structure and a photopolymerization initiator (B), wherein the compound (A) having an unsaturated ethylene structure is a compound (A1) represented by the following formula (1), and the content of the compound (A1) is 0.1 to 5 parts by mass per 100 parts by mass of the compound (A) having an unsaturated ethylene structure, results in a composition for an active energy ray-curable coating agent that is excellent in UV curability and various properties of the cured film, and have completed the present invention.

[0012] That is, the present invention has the following aspects. [1] A composition for an active energy ray-curable coating agent, comprising a compound (A) having an unsaturated ethylene structure and a photopolymerization initiator (B), The compound (A) having an unsaturated ethylene structure has a compound (A1) represented by the following formula (1), The active energy ray-curable composition for coating agents, wherein the content of the compound (A1) is 0.1 to 5 parts by mass per 100 parts by mass of the compound (A) having an unsaturated ethylene structure. [ka] [2] The active energy ray-curable coating composition according to [1], wherein Y in "aOYb" represented by X in the formula (1) is a divalent bonding group having two carbon atoms. [3] The active energy ray-curable coating composition according to [1] or [2], wherein the compound (A1) represented by the formula (1) is a compound represented by the following formula (2): [ka] [4] An antibacterial composition containing the active energy ray-curable coating agent composition according to any one of [1] to [3]. [5] An antibacterial cured product obtained by curing the antibacterial composition described in [4]. [Effects of the Invention]

[0013] The active energy ray-curable coating composition of the present invention, although containing a biomass material as an antibacterial component, is excellent in UV curability and in various properties of the cured product (cured film), and can also exhibit high antibacterial properties. Furthermore, since the active energy ray-curable coating composition of the present invention uses a biomass material as an antibacterial component, it is possible to reduce the burden on the environment and achieve carbon neutrality, thereby contributing to a sustainable recycling-based society. DETAILED DESCRIPTION OF THE INVENTION

[0014] The present invention will be described below based on examples of embodiments for carrying out the present invention, but the present invention is not limited to the embodiments described below.

[0015] In this specification, the term "major component" refers to the component that is most abundant in the target substance, and typically accounts for preferably 50% by mass or more of the target substance, more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, especially preferably 90% by mass or more, and most preferably 100% by mass.

[0016] Furthermore, in this specification, when the expression "X to Y" (X and Y are any numbers) is used, unless otherwise specified, it means "X or more and Y or less," as well as "preferably greater than X" or "preferably smaller than Y." Furthermore, when it is expressed as "X or more" (X is any number) or "Y or less" (Y is any number), it also means that "it is preferably greater than X" or "it is preferably less than Y."

[0017] <<Active energy ray curable coating composition>> A composition for an active energy ray-curable coating agent (hereinafter may be referred to as "the composition") according to one embodiment of the present invention (hereinafter may be referred to as "the present embodiment") is a composition containing a compound (A) having an unsaturated ethylene structure as a main component and a photopolymerization initiator (B), wherein the compound (A) having an unsaturated ethylene structure comprises a compound (A1) represented by the following formula (1), and the content of the compound (A1) is 0.1 to 5 parts by mass per 100 parts by mass of the compound (A) having an unsaturated ethylene structure. [ka]

[0018] Various materials that can be used in this embodiment will be described below, but this does not mean that materials not described in this specification can be used.

[0019] <Compound (A) Having an Unsaturated Ethylene Structure> The compound (A) having an unsaturated ethylene structure used in the present embodiment is a compound (A1) represented by the following formula (1), and the content of the compound (A1) is set to 0.1 to 5 parts by mass per 100 parts by mass of the compound (A) having an unsaturated ethylene structure.

[0020] [Compound (A1) represented by formula (1)] [ka]

[0021] Examples of the compound (A1) include the following: where n is an integer of 0 to 3. However, the compound (A1) is not limited to the following examples.

[0022] [ka]

[0023] In the formula (1), R represents a hydrogen atom or a methyl group, and when R is a hydrogen atom, active energy ray curing tends to be easily performed at low intensity, whereas when R is a methyl group in the formula (1), a harder cured product tends to be easily formed.

[0024] In addition, in the formula (1), R' represents a linear alkyl group or linear alkenyl group having 12 or more carbon atoms, and in particular, when R' represents a linear alkyl group or linear alkenyl group having 15 or more carbon atoms, antibacterial properties tend to be further improved.

[0025] When Y in "aOYb" represented by X in the formula (1) is a divalent linking group having two carbon atoms, antibacterial properties tend to be further improved.

[0026] The compound (A1) is preferably a compound represented by formula (2), and in particular, the compounds represented by formula (1-1) and (1-2) are preferred in that they have properties such as water resistance and also make it easier to improve the biomass content of the cured product.

[0027] [ka]

[0028] The compound (A1) may be used alone or in combination of two or more kinds.

[0029] The compound (A1) can be easily produced by known organic synthesis techniques. However, from the viewpoint of utilizing non-edible biomass, it is preferable to use unsaturated cardanol, which is abundant in cashew nut shell liquid (CNSL), a non-edible biomass, as a starting material, which is derived and purified.

[0030] In the composition of the present embodiment, the content of the compound (A1) is 0.1 to 5 parts by mass, preferably 0.5 to 4 parts by mass, and more preferably 0.7 to 2 parts by mass, relative to 100 parts by mass of the compound (A) having an unsaturated ethylene structure. If the content of the compound (A1) is below the lower limit, it becomes difficult for the resulting cured film to exhibit various properties such as hardness, whereas if the content of the compound (A1) is above the upper limit, it becomes difficult for the compound (A2) to exhibit various properties, resulting in an imbalance in the properties of the resulting cured film.

[0031] The compound (A) having an unsaturated ethylene structure may include, in addition to the compound (A1), a compound having an unsaturated ethylene structure such as a monofunctional monomer (A2) or a polyfunctional monomer (A3).

[0032] [Monofunctional Monomer (A2)] Examples of the monofunctional monomer (A2) include styrene-based monomers such as urethane (meth)acrylate, styrene, vinyltoluene, chlorostyrene, and α-methylstyrene, methyl (meth)acrylate, ethyl (meth)acrylate, acrylonitrile, 2-methoxyethyl (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, and disilane. Clopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)-methyl (meth)acrylate, cyclohexanespiro-2-(1,3-dioxolan-4-yl)-methyl (meth)acrylate, 3-ethyl-3-oxetanylmethyl (meth)acrylate, γ-butyrolactone (meth)acrylate, n-butyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (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 monomers such as half (meth)acrylates of phthalic acid derivatives, such as 2-(meth)acryloyloxyethyl acid phosphate and 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, carbitol (meth)acrylate, benzyl (meth)acrylate, butoxyethyl (meth)acrylate, allyl (meth)acrylate, (meth)acryloylmorpholine, and polyoxyethylene secondary alkyl ether acrylate, 2-hydroxyethyl acrylamide, N-methylol (meth)acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, and vinyl acetate. These compounds (A2) may be used alone or in combination. When the compound (A2) is used, the content thereof is preferably 0 to 99.9, more preferably 50 to 99, and further preferably 70 to 98.

[0033] [Polyfunctional Monomer (A3)] The polyfunctional monomer (A3) can be used as a crosslinking agent, and 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 di(meth)acrylate, propylene oxide-modified bisphenol A di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, and the like. (meth)acrylate, ethoxylated cyclohexanedimethanol di(meth)acrylate, dimethyloldicyclopentane di(meth)acrylate, tricyclodecane dimethanol 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, isocyanuric acid ethylene oxide-modified diacrylate, and bifunctional urethane (meth)acrylate.

[0034] Further, examples of trifunctional or higher functional 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, caprolactone modified dipentaerythritol penta(meth)acrylate, Examples of the dipentaerythritol hexa(meth)acrylate include 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, ethoxylated glycerin triacrylate, and tri- or higher functional urethane(meth)acrylates. These compounds (A3) may be used alone or in combination. When the compound (A3) is used, the content thereof is preferably 0 to 99.9, more preferably 1 to 50, and even more preferably 2 to 40.

[0035] <Photopolymerization initiator (B)> The photopolymerization initiator (B) used together with the compound (A) having an unsaturated ethylene structure is not particularly limited as long as it generates radicals by the action of light. Examples of such photopolymerization initiators (B) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, and 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one. Acetophenones such as benzoin, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer; benzoins such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenylsulfonate benzophenones such as benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethanaminium bromide, and (4-benzoylbenzyl)trimethylammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1 thioxanthones such as 2-chloro-4-propoxythioxanthone and 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthone-9-one mesochloride; and acylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. These photopolymerization initiators (B) may be used alone or in combination of two or more.

[0036] Furthermore, as an auxiliary agent for the photopolymerization initiator (B), it is possible to use in combination triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, etc. These auxiliary agents may be used alone or in combination of two or more.

[0037] The photopolymerization initiator (B) is usually contained in an amount of 0.1 to 20 parts by mass, preferably 0.5 to 15 parts by mass, more preferably 0.5 to 12 parts by mass, and particularly preferably 1 to 10 parts by mass, relative to 100 parts by mass of the compound (A) having an unsaturated ethylene structure. If the content of the photopolymerization initiator (B) is less than the lower limit, it tends to be difficult to produce a cured film, whereas if the content exceeds the upper limit, the physical properties of the cured film due to the photopolymerization initiator (B) tend to be more likely to deteriorate.

[0038] The composition of the present embodiment uses the compound (A1) represented by the formula (1) as an antibacterial component, which is a biomass material, and therefore reduces the burden on the environment and is carbon neutral. Moreover, since it has excellent UV curability and various properties of the cured film, and can exhibit high antibacterial properties, it can be suitably used as a material for antibacterial compositions in combination with other materials.

[0039] <<Antibacterial composition>> The composition of the present embodiment can be made into an antibacterial composition by adding, in addition to the compound (A) having an unsaturated ethylene structure and the photopolymerization initiator (B), a solvent, a colorant, and other general components used in the field of active energy ray-curable coating agents, within a range that does not impair the effects of the present embodiment.

[0040] [solvent] That is, the antibacterial composition of the present embodiment may contain a known or commercially available solvent in order to lower the viscosity and improve the wetting and spreading properties on the substrate. Examples of such solvents include water, aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, esters such as ethyl acetate and butyl acetate, aliphatic alcohols such as n-propyl alcohol and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. These organic solvents can be used alone or in combination of two or more.

[0041] When the antibacterial composition of the present embodiment contains a solvent, the content thereof can be determined appropriately depending on the component composition and application of the composition, and can be, for example, 0.1 to 50 parts by mass per 100 parts by mass of the antibacterial composition.

[0042] [Coloring agent] The antibacterial composition of the present embodiment may also contain a colorant. When the antibacterial composition of the present embodiment contains a colorant, for example, a pigment, a dye, or the like can be used as the colorant. These may be used alone or in combination of two or more. Among these, pigments are preferably used from the viewpoint of light resistance. As the pigment, for example, known pigments can be used, and both inorganic pigments and organic pigments can be used.

[0043] Examples of the inorganic pigment include carbon blacks such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide.

[0044] Examples of the organic pigments include soluble azo pigments such as β-naphthol, β-oxynaphthoic acid, β-oxynaphthoic acid anilide, acetoacetate anilide, and pyrazolone; insoluble azo pigments such as β-naphthol, β-oxynaphthoic acid anilide, acetoacetate anilide monoazo, acetoacetate anilide disazo, and pyrazolone; copper phthalocyanine blue, halogenated (e.g., chlorinated, brominated) copper phthalocyanine blue, and sulfuric acid pigments such as phthalocyanine blue. Phthalocyanine pigments such as sulfonated copper phthalocyanine blue and metal-free phthalocyanine; polycyclic pigments and heterocyclic pigments such as quinacridones, dioxazines, threnes (pyranthrones, anthanthrones, indanthrones, anthrapyrimidines, flavanthrones, thioindigo, anthraquinones, perinones, perylenes, etc.), isoindolinones, metal complexes, quinophthalones, and diketopyrrolopyrroles; and the like. When the antibacterial composition of the present embodiment uses a colorant, a known dispersant may be used to improve the dispersibility of the colorant.

[0045] [Other common ingredients] The antibacterial composition of the present embodiment may contain, in addition to the solvent and colorant, general components used in active energy ray-curable compositions. Specifically, known or commercially available components that can impart desired functions, properties, etc. to the active energy ray-curable composition can be used without limitation, and examples of such components include polymerization initiators, polymerization inhibitors, surfactants, fillers, sensitizers, pH adjusters, humectants, antioxidants, oxygen scavengers, reducing agents, anti-fading agents, antihalation agents, fluorescent brighteners, plasticizers, flame retardants, foaming agents, antistatic agents, magnetic materials, storage stabilizers, surface tension adjusters, slipping agents, anti-blocking agents, light stabilizers, leveling agents, antifoaming agents, ultraviolet absorbers, infrared absorbers, thickeners (thixotropic agents), antibacterial and antifungal agents, etc. These may be used alone or in combination of two or more.

[0046] The content of the other general components is preferably 0.1 to 5 parts by mass of the compound (A1) represented by formula (1) above, more preferably 0.5 to 4 parts by mass, and even more preferably 0.7 to 2 parts by mass, per 100 parts by mass of the entire antibacterial composition including the other general components, in order to achieve an excellent balance between antibacterial properties and other properties.

[0047] The antibacterial composition of this embodiment can be obtained by mixing the compound (A) having an unsaturated ethylene structure, the photopolymerization initiator (B), and other components as needed. The mixing method is not particularly limited, and various methods can be used. For example, the components can be mixed all at once, or any component can be mixed first and then the remaining components can be mixed. This method can be appropriately selected.

[0048] The antibacterial composition of the present embodiment can be applied to the surface of an object to a predetermined thickness, and then irradiated with active energy rays to form a cured film.

[0049] Examples of materials to which the antibacterial composition of this embodiment can be applied include plastic materials such as polyolefin resins, polyester resins, polycarbonate resins, acrylic resins, acrylonitrile butadiene styrene copolymers (ABS), polystyrene resins, etc., and molded products thereof (films, sheets, cups, etc.), composite materials thereof, composite materials of the above materials mixed with glass fiber or inorganic substances, metals (aluminum, copper, iron, SUS, zinc, magnesium, alloys thereof, etc.), and materials having a primer layer provided on a material such as glass.

[0050] Examples of methods for applying the antibacterial composition of the present embodiment include wet coating methods such as spraying, showering, dipping, rolling, spinning, and screen printing, and the composition is usually applied to the surface of the target member under room temperature conditions.

[0051] Thus, the antibacterial composition of the present embodiment can be used to coat the surfaces of, for example, automobile interiors, electronic devices, building materials, fibers, etc. In addition, the composition can be used, for example, as a sealant, printing ink, printing varnish, paint, photosensitive resin for printing plates, color proofs for printing, resists for color filters, resists for black matrices, photospacers for liquid crystal displays, rib materials for plasma displays, dry film resists, resists for printed circuit boards, solder resists, photoresists for semiconductors, resists for microelectronics, resists for manufacturing micromachine parts, etching resists, microlens arrays, insulating materials, overcoats, release coats, etc.

[0052] <<Antibacterial cured product>> The antibacterial composition of the present embodiment can be cured using active energy rays to obtain the antibacterial cured product of the present embodiment. Examples of the active energy rays that can be used 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. However, curing by ultraviolet irradiation is advantageous in terms of curing speed, ease of availability of an irradiation device, cost, and the like.

[0053] To cure the antibacterial composition of the present embodiment by ultraviolet irradiation to obtain an antibacterial cured product (cured film), for example, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, an LED, or the like that emits light in the wavelength range of 150 to 450 nm is used, and the cumulative light amount is usually 30 to 3,000 mJ / cm. 2 , preferably 100 to 1,500 mJ / cm 2 It is preferable to irradiate with ultraviolet light so that the intensity is 1,000 mJ / cm. 2 The amount is less than. After the ultraviolet irradiation, heating may be carried out as necessary to complete the curing, and the heating temperature may be, for example, 120 to 200°C.

[0054] The thickness of the cured film is usually 3 to 1,000 μm, preferably 5 to 500 μm, and particularly preferably 10 to 200 μm, in order to allow the photopolymerization initiator (B) to react uniformly.

[0055] If an organic solvent remains in the cured film, it is preferable to remove the organic solvent by drying. The drying conditions for the drying are not particularly limited, but drying at a temperature of 40 to 120°C for 1 to 20 minutes is preferable, and drying at a temperature of 50 to 100°C for 2 to 10 minutes is more preferable.

[0056] The cured film thus obtained preferably has a surface pencil hardness of 6BH or more, more preferably 5B or more, and even more preferably 4B or more, in order to provide appropriate scratch resistance. The pencil hardness is a value measured in accordance with JIS K5600-5-4. As a measuring device, for example, a pencil hardness tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) can be used.

[0057] The cured film contains the antibacterial compound (A1), and therefore has excellent antibacterial activity, and therefore, by covering the surface of a molded article with the cured film, the molded article can be imparted with antibacterial properties.

[0058] The cured film also has excellent water resistance, and is therefore unlikely to whiten or peel even when exposed to water-based liquids, making it suitable for use in a wide range of fields. [Example]

[0059] 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 as long as it does not depart from the gist of the invention. In the examples, "parts" and "%" are by mass.

[0060] First, a compound (A1) having an unsaturated ethylene structure was synthesized as follows, and then the composition of the present embodiment was prepared using the compound (A1) as described below.

[0061] <Synthesis Example: Synthesis of Compound (A1) Having an Unsaturated Ethylene Structure> A compound (A1) having an unsaturated ethylene structure was synthesized by the method shown below. That is, under a nitrogen atmosphere, unsaturated cardanol (5.0 g, 14.3 mmol, 1.0 eq.), 4-dimethylaminopyridine (88 mg, 0.72 mmol, 0.05 eq.), triethylamine (1.89 g, 18.6 mmol, 1.3 eq.), and tetrahydrofuran (7 ml) were placed in a reaction vessel, the internal temperature was lowered to 5°C, and acryloyl chloride (1.55 g, 17.2 mmol, 1.2 eq.) was added dropwise at an internal temperature of 25°C or less, and the temperature was raised to 40°C, followed by reaction for 1 hour. After the reaction was completed, sodium bicarbonate water was added to quench the reaction, and ethyl acetate (AcOEt) was added and the mixture was filtered to remove insoluble matter. After separation, the aqueous layer was extracted again with AcOEt, and the combined organic layer was washed with sodium bicarbonate water and saturated brine, dried over magnesium sulfate, and then filtered. The filtrate was concentrated under reduced pressure, and the crude product was purified by silica gel chromatography (developing solvent: Hex / AcOEt=20 / 1→10 / 1) to obtain ethylene oxide-added cardanol acrylate (CEA) (3.82 g, 66%) as compound (A1).

[0062] The materials used in the synthesis of the compound (A1) are as follows. ·Unsaturated cardanol: Cardorite Ultra LITE 2020 (manufactured by Cardorite) 4-Dimethylaminopyridine: 99% purity (Tokyo Chemical Industry Co., Ltd.) Triethylamine: 99% purity (Wako Pure Chemical Industries, Ltd.) Tetrahydrofuran: 99.5% purity (Wako Pure Chemical Industries, Ltd.) Acryloyl Chloride (stabilized with Phenothiazine): 98% purity (Tokyo Chemical Industry Co., Ltd.) Ethyl acetate (AcOEt): 99% purity (Kishida Chemical Co., Ltd.) Silica gel: particle size 63-210 μm (Kanto Chemical Co., Ltd.) · Hexane: purity 95% (manufactured by Kishida Chemical Co., Ltd.)

[0063] [Example 1] 1 part of the compound (A1) prepared in the above Synthesis Example, 97 parts of the following compound (A2), 2 parts of the compound (A3), and 2 parts of the photopolymerization initiator (B) were mixed to obtain a composition. The prepared materials are as follows respectively. · Compound (A2): Isobornyl acrylate · Compound (A3): 1,6 - Hexanediol diacrylate · Photopolymerization initiator (B): α - Hydroxyalkylphenone - based photopolymerization initiator (Omnirad 184, manufactured by IGM Resins B.V.) (1 - Hydroxycyclohexyl - phenyl ketone)

[0064] [Example 2, Comparative Examples 1 - 3] A composition was obtained in the same manner as in Example 1, except that the blending amounts of the compound (A1) and the photopolymerization initiator (B) were changed as shown in Table 1 below.

[0065] The obtained composition was evaluated for UV curability as follows. The results are shown together with Table 1 below. In addition, the cured film obtained from the composition was evaluated for pencil hardness, antibacterial activity, and water resistance as follows. Their results are shown together with Table 1 below.

[0066] [UV Curability] After applying 1 g of the obtained composition onto a polyethylene terephthalate film (T60 Lumirror, manufactured by Toray Industries, Inc.) with a film thickness of 50 μm, a release - treated polyethylene terephthalate film with a film thickness of 38 μm was placed on top, and a laminate in which the composition was sandwiched between the films was prepared. A 1 - kg hand roller was reciprocated once on the laminate to remove the air that had entered the composition, and the film thickness of the laminate was made uniform. For the obtained laminate, the integrated light quantity was 200 mJ / cm 2 or 400 mJ / cm 2 or 600 mJ / cm2 The composition sandwiched between the films was UV-cured by irradiating the film with ultraviolet light so that the film was irradiated with ultraviolet light until the film reached a temperature of 100°C. Thereafter, the release-treated polyethylene terephthalate film was peeled off, and the exposed surface of the composition was visually observed and evaluated for UV curability based on the following criteria. (Evaluation criteria) ◯: The composition was completely cured, and the surface of the cured film was not sticky. Δ: The composition was cured, but the surface of the cured film was sticky. ×: The composition did not cure and did not form a cured film.

[0067] <Pencil hardness> The laminate obtained in the evaluation of UV curability was subjected to an accumulated light dose of 1000 mJ / cm 2 The composition sandwiched between the films was UV-cured by irradiating it with ultraviolet light using a high-pressure mercury lamp so that the release-treated polyethylene terephthalate film was removed, and the hardness of the exposed cured film surface of the composition was measured in accordance with JIS K5600-5-4 and evaluated based on the following criteria. (Evaluation criteria) ◯: Pencil hardness was 6B or higher. ×: The pencil hardness was less than 6B.

[0068] <Antibacterial activity> A cured film identical to that produced in the above pencil hardness evaluation was prepared, and the antibacterial activity of this cured film against Escherichia coli and Staphylococcus aureus was measured in accordance with JIS Z 2801 and evaluated based on the following criteria. (Evaluation criteria) ○: Antibacterial activity values ​​were 2 or higher for both Escherichia coli and Staphylococcus aureus. △: The antibacterial activity value for only one of Escherichia coli and Staphylococcus aureus was 2 or higher. ×: Antibacterial activity values ​​for both Escherichia coli and Staphylococcus aureus were less than 2.

[0069] <Water resistance> A cured film identical to that produced in the pencil hardness evaluation was prepared, and a polyethylene terephthalate film (T60 Lumirror, manufactured by Toray Industries, Inc.) was peeled off from the cured film to leave only the cured film of the composition. The haze value of this cured film was measured using a haze meter (NDH4000, manufactured by Nippon Denshoku Kogyo Co., Ltd.). Next, the film-like cured film was immersed in purified water for 24 hours so that the entire film was immersed, and then the film-like cured film was taken out, and the haze value was measured in the same manner as above. The difference in haze value (Δ haze) of the film-like cured film before and after immersion was calculated and evaluated based on the following criteria. (Evaluation criteria) ◯: Δ haze was less than 0.6. Δ: Δ haze was 0.6 or more and less than 0.7. ×: Δ haze was 0.7 or more.

[0070] [Table 1]

[0071] From the results in Table 1 above, it can be seen that Examples 1 and 2, which contain a predetermined amount of (A1), achieved satisfactory results in all evaluations. On the other hand, Comparative Examples 1 and 2, which contain more than the specified amount of (A1), are excellent in antibacterial activity, but are poor in UV curability and pencil hardness, and Comparative Example 2 in particular is also poor in water resistance. Comparative Example 3 is excellent in UV curability, pencil hardness, and water resistance, but does not contain (A1), and therefore does not exhibit antibacterial activity, and naturally is unable to reduce the burden on the environment or achieve carbon neutrality. [Industrial Applicability]

[0072] The active energy ray-curable coating composition of the present invention uses a biomass material as an antibacterial component and has excellent UV curability and cured film properties, so it can be used as an antibacterial coating agent that can contribute to a sustainable, recycling-oriented society.

Claims

1. A composition for an active energy ray-curable coating agent, comprising a compound (A) having an unsaturated ethylene structure and a photopolymerization initiator (B), The compound (A) having an unsaturated ethylene structure has a compound (A1) represented by the following formula (1), a composition for an active energy ray-curable coating agent, wherein the content of the compound (A1) is 0.1 to 5 parts by mass per 100 parts by mass of the compound (A) having an unsaturated ethylene structure. 【Chemical 1】

2. 2. The active energy ray-curable coating composition according to claim 1, wherein Y in "a-O-Y-b" represented by X in formula (1) is a divalent bonding group having two carbon atoms.

3. 3. The active energy ray-curable coating composition according to claim 1, wherein the compound (A1) represented by formula (1) is a compound represented by the following formula (2): 【Chemistry 2】

4. An antibacterial composition comprising the active energy ray-curable coating composition according to claim 1 or 2.

5. An antibacterial cured product obtained by curing the antibacterial composition according to claim 4.

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