Coating film and article

Abstract

The present invention is a coating film having a base layer and a coating layer, the coating film being characterized in that the transmission definition is 50 or more, and the coating layer is formed from a coating layer-forming composition containing component (A): a urethane acrylate-based material and component (B): a surface conditioning agent, and the amount of residual organic solvent in the coating layer is 50 ppm or less. According to the present invention, it is possible to provide: a coating film which is environmentally friendly, has excellent coatability, and also has excellent optical and mechanical properties; and an article having the coating film.

Description

TECHNICAL FIELD

[0001] The present application relates to a coated film having a substrate layer and a coating layer, and an article having the coated film. BACKGROUND

[0002] In recent years, touch panels and the like, which have both a display device and an input means, are used in various electronic devices. A coated film having a coating layer is provided on the surface of the touch panel in order to prevent scratches and the like. In addition, in addition to the touch panel, a coated film is provided on the surface of, for example, a vehicle (an automobile, a train, or the like), a transport machine (an airplane, a cargo plane, or the like), a ship, an interior member or an exterior member of a building, or the like in order to prevent scratches and the like. Furthermore, a coated film is also provided in a surface protective film that is used in order to protect the surface of an adherend until the film is peeled off at the time of use.

[0003] Conventionally, the coating layer of such a coated film is formed by using a coating layer-forming composition (coating agent) containing a large amount of an organic solvent. However, in recent years, from the viewpoint of the promotion of SDGs, consideration of the environment, and the promotion of the health of workers, there is a demand in society to reduce the amount of use of organic solvents. As a coating agent in which the amount of use of an organic solvent is reduced, a coating agent (water-based coating agent) in which water or a mixed solvent (water-based solvent) formed of water and an organic solvent compatible with water is used as a solvent is known.

[0004] However, when a conventional water-based coating agent is used, it is sometimes difficult to form a coating layer having durability required in optical applications such as display devices and the like, transport machine applications such as vehicles, transport machines, ships, and the like, building applications, surface protective applications for various articles, and the like. In addition, since the types of polymerization initiators and leveling agents that can be used in water-based coating agents are small, water-based coating agents that are thermosetting are mainstream, and it is difficult to form a coating layer having excellent optical properties and mechanical strength.

[0005] Therefore, a coated film having equivalent optical properties and mechanical properties to a coating layer obtained by using a coating agent containing an organic solvent, and obtained by using a water-based coating agent that is friendly to the environment is desired.

[0006] In relation to the present application, laminates having a hydrophilic coating layer formed using a coating agent containing a water-based solvent as a solvent are described in Patent Documents 1 to 3. However, in these documents, there is no description that the obtained laminate is excellent in interlayer adhesion even after being left in a severe environment, or the like, or is excellent in transmission clarity (C / L), or the like. In addition, it is difficult to say that the laminate is a laminate having excellent optical properties and mechanical properties to such an extent that it is suitable for optical displays such as touch panels and the like. )and the like. In addition, it is difficult to say that the laminate is a laminate having excellent optical properties and mechanical properties to such an extent that it is suitable for optical displays such as touch panels and the like.

[0007] On the other hand, the pandemic of the novel coronavirus (SARS-CoV-2) and other infectious diseases, including COVID-19, have made the threat of viral infection a major global problem. In such situations, for example, if a virus adheres to the surface of a touch panel, there is a concern that touching the surface with a finger could allow the virus to enter the body and cause infection. Therefore, it is desirable to impart not only antibacterial properties but also high antiviral properties (the ability to inactivate viruses attached to the surface and inhibit viral replication) to the surface of touch panels that are touched by fingers.

[0008] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2018-180099 (WO2018 / 185590A1) Patent Document 2: Japanese Patent Application Publication No. 2020-104499 Patent document 3: Japanese Patent Application Publication No. 2020-168764 (US2022 / 0145029A1). Summary of the Invention

[0009] The problem that the invention aims to solve The present invention was made in view of the following facts, and its object is to provide an environmentally friendly coating film with low residual organic solvent content, excellent optical properties and mechanical properties, and further excellent antibacterial / antiviral properties, as well as articles having the aforementioned coating film.

[0010] Solution for solving the problem To solve the aforementioned problems, the inventors have repeatedly conducted intensive research on coatings having a substrate layer and a coating layer. As a result, it was discovered that (α) the aforementioned coating is formed by a coating-forming composition containing a polyurethane acrylate-based material and a surface conditioner, (β) the residual organic solvent in the aforementioned coating is 50 ppm or less, and (γ) the transmittance is 50 or more, resulting in a coating with excellent coatability of the coating-forming composition and optical and mechanical properties equivalent to those of coatings obtained using conventional organic solvents. Furthermore, it was discovered that by adding a water-soluble antibacterial / antiviral agent, a coating with excellent antibacterial / antiviral properties can be obtained, thus completing the present invention.

[0011] Therefore, according to the present invention, coatings of [1] to [9] and articles of

[10] and

[11] can be provided.

[0012] [1] A coating having a substrate layer and a coating layer, characterized in that the transmittance resolution is 50 or higher, the coating layer is formed by a coating forming composition containing component (A) and component (B) below, and the amount of residual organic solvent in the coating layer is 50 ppm or less. (A) Composition: Polyurethane acrylate material, (B) Ingredients: surface conditioner.

[0013] [2] According to the coating of [1], wherein the (A) component is an emulsion containing emulsified particles of polyurethane acrylate with an average particle size of less than 300 nm and having more than 5 active energy ray polymerizable functional groups.

[0014] [3] The coating according to [1], wherein the (B) component is a water-soluble leveling agent and / or surfactant.

[0015] [4] According to the coating of [1], wherein the content of component (B) in the coating forming composition is 0.1 parts by mass or more and 20 parts by mass or less relative to 100 parts by mass of component (A).

[0016] [5] According to the coating of [1], the water contact angle of the surface of the coating on the side opposite to the substrate layer is 70° or more.

[0017] [6] The coating according to [1], wherein the coating forming composition further contains filler as component (C).

[0018] [7] The coating according to [1], wherein the coating forming composition further contains particulate antibacterial / antiviral agent as component (D).

[0019] [8] According to the coating of [7], wherein the average particle size of the particulate antibacterial / antiviral agent is 0.5 μm or more and 5 μm or less, and the film thickness of the coating is 5 μm or less.

[0020] [9] The coating according to [7] has an antibacterial activity value of 2.0 or higher in the antibacterial test according to JIS Z2801:2010 and an antiviral activity value of 2.0 or higher in the antiviral test according to ISO 21702.

[0021]

[10] An article having any one of [1] to [9] of the following.

[0022]

[11] The article according to

[10] , wherein the article is any one of an optical display, a vehicle, a transport aircraft, a ship, a building, and a surface protective film.

[0023] The effects of the invention According to the present invention, an environmentally friendly coating film with low residual organic solvent content and excellent optical and mechanical properties can be provided. Furthermore, according to the present invention, a coating film having a coating obtained using an environmentally friendly aqueous coating agent can be provided, which has the same coatability as that obtained using organic solvents, and has the same optical and mechanical properties as coating films with coatings formed using conventional organic solvents. Moreover, according to the present invention, by adding particulate antibacterial / antiviral agents as needed, a coating film with excellent antibacterial / antiviral properties in addition to excellent optical and mechanical properties can be provided.

[0024] The coating of this invention is suitable for use on various articles such as optical displays, vehicles, transport aircraft, ships, buildings, and surface protective films. In optical displays, it is particularly suitable for touch panels. In vehicles, transport aircraft, and ships, it is particularly suitable for windows, license plates, and exterior components. In buildings, it is suitable for the surfaces of interior or exterior components. Furthermore, as a surface protective film, it is suitable for protecting the surfaces of various objects until use. Detailed Implementation

[0025] The present invention will now be described in detail in sections 1) coatings and 2) articles having coatings.

[0026] 1) Coating The coating of the present invention is preferably a coating having a substrate layer and a coating layer, having a transmittance resolution of 50 or higher. The coating layer is formed from a coating-forming composition containing (A) a polyurethane acrylate material and (B) a surface conditioner, and the amount of residual organic solvent in the coating layer is 50 ppm or less. The coating of the present invention has excellent optical and mechanical properties, extremely low residual organic solvent content, and is environmentally friendly.

[0027] 1. Substrate layer The coating of the present invention has a substrate layer. As this substrate layer, a material appropriately selected from known resin films conventionally used as optical films can be used.

[0028] Examples of resin materials constituting the resin film include polyethylene terephthalate (PET), polybutylene terephthalate (PET), polyethylene naphthalate (PET), polyethylene, polypropylene, viscose, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinyl alcohol (PVA), ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone (PEEK), polyethersulfone, polyetherimide, polyimide, fluoropolymers, polyamides, acrylic resins, norbornene resins, and cyclic olefin resins. Among these, from the viewpoints of excellent transparency, adhesion, heat resistance, and mechanical strength, and from the viewpoint of easily satisfying the optical properties described later, polyethylene terephthalate (PET), polycarbonate, cellulose triacetate, and cyclic olefin resins are preferred, and polyethylene terephthalate and cellulose triacetate are more preferred. Furthermore, from the perspective of SDGs, materials that constitute the aforementioned resin membrane can be materials with high biomass content, or materials that are recyclable or reusable, or materials that have been recycled or reused.

[0029] The substrate layer can be composed of a single layer or two or more resin films. In addition, regarding the surface of the substrate layer, when forming coatings or the like, physical treatments such as corona discharge treatment or oxidation treatment may be applied to improve adhesion.

[0030] The thickness of the substrate layer can be selected according to the desired purpose and is not particularly limited. Preferably, it is 25–500 μm; more preferably, 40–400 μm; particularly preferably, 60–300 μm; further preferably, 80–250 μm; more preferably, 120–220 μm; and most preferably, 130–200 μm. This tends to improve the scratch resistance and hardness of the coating. In addition, the resulting coating has improved workability and a superior user experience during application.

[0031] 2. Coating In addition to the aforementioned substrate layer, the coating of the present invention also has a coating layer. This coating layer (sometimes referred to in this specification as "the coating of the present invention") is preferably formed from a coating forming composition (sometimes referred to in this specification as "the coating forming composition of the present invention") containing component (A): polyurethane acrylate material and component (B): surface conditioner.

[0032] (1) (A) Ingredient The coating-forming composition of the present invention preferably contains a polyurethane acrylate-based material as component (A). Examples of polyurethane acrylates include substances obtained by reacting a hydroxyl-containing (meth)acrylate compound with a polyisocyanate compound, and substances obtained by reacting an isocyanate-containing (meth)acrylate compound with a polyol compound. Among these, oligomers having urethane bonds obtained by reacting isocyanate groups with hydroxyl groups and acryloyl groups are preferred. For example, a polyurethane oligomer can be obtained by esterifying a polyurethane oligomer with (meth)acrylic acid, wherein the polyurethane oligomer is obtained by reacting a polyether polyol or a polyester polyol with a polyisocyanate.

[0033] It should be noted that in this specification, (meth)acrylic acid refers to both acrylic acid and methacrylic acid. The same applies to other similar terms.

[0034] The polyurethane acrylate used in this invention has a reactive energy radiation polymerizable functional group. A reactive energy radiation polymerizable functional group is a group that has the property of being crosslinked and cured by irradiation with reactive energy radiation such as ultraviolet light or electron beams. Examples of reactive energy radiation polymerizable functional groups include, for example, functional groups containing vinyl, (meth)acryloyl, epoxy, oxetanyl, isocyanate, etc.

[0035] The polyurethane acrylate preferably has 5 or more active energy-emitting polymerizable functional groups, more preferably 6 to 20, even more preferably 8 to 16, and particularly preferably 9 to 12. Therefore, the resulting coating (and film) readily meets the physical properties described later.

[0036] (A) The polyurethane acrylate material contains polyurethane acrylate, preferably polyurethane acrylate containing 5 or more of active energy ray polymerizable functional groups. As long as the coating forming composition containing (A) can form a coating with a residual organic solvent amount of 50 ppm or less, there are no particular restrictions on its form, etc.

[0037] In this invention, the polyurethane acrylate-based material of component (A) is preferably an emulsion containing polyurethane acrylate emulsion particles, more preferably an emulsion containing polyurethane acrylate emulsion particles with 5 or more active energy-emitting polymerizable functional groups. The emulsion containing polyurethane acrylate emulsion particles is preferably a so-called oil-in-water droplet emulsion formed by emulsifying an acrylic component without hydrophilic groups within a polyurethane component with hydrophilic groups. Regarding the emulsion containing polyurethane acrylate emulsion particles, it exhibits good stability over time, does not use organic solvents that have adverse effects on human health and the environment, can be diluted with water, and has good coatability to resin substrates, etc. By using such a material as component (A), as described later, an environmentally friendly aqueous solvent can be used instead of an organic solvent to form a coating. Furthermore, the resulting coating readily possesses optical and mechanical properties equivalent to those of coatings obtained using conventional organic solvents.

[0038] The average particle size of the emulsified particles contained in the aforementioned emulsion is preferably 300 nm or less. Therefore, even with a reduction in the amount of organic solvent used, it is easy to obtain a coating with optical and mechanical properties equivalent to those obtained using a coating-forming composition containing a large amount of organic solvent. Furthermore, the resulting coating (and film) readily meets the physical properties described later. From this viewpoint, the average particle size is preferably 5–260 nm, more preferably 10–220 nm, even more preferably 20–200 nm, and particularly preferably 30–180 nm. The average particle size of the emulsified particles can be determined using dynamic light scattering.

[0039] Emulsions containing polyurethane acrylate emulsion particles can be manufactured by methods known in the past. For example, they can be obtained by emulsifying and dispersing a mixture obtained by mixing an oil-soluble polyurethane acrylate and a water-soluble substance containing an aqueous solvent and an emulsifier in a specified ratio using a high-speed mixer such as a homogenizer or a sand mill, or a high-pressure microfluidizer, or by permeating the aforementioned mixture through a porous membrane (Japanese Patent Application Publication No. 5-320283, Japanese Patent Application Publication No. 2005-247884, Japanese Patent No. 7033232, etc.).

[0040] Furthermore, in this invention, commercially available products can be used as the polyurethane acrylate emulsion. Examples of commercially available products include ART RESIN WEH-1 (manufactured by Negami Kogyo Co., Ltd.), Beamset EM-94 (manufactured by Arakawa Chemical Co., Ltd.), and Beamset EM-90 (manufactured by Arakawa Chemical Co., Ltd.). The aforementioned polyurethane acrylate materials can be used alone or in combination of two or more.

[0041] (2) (B) Component The coating-forming composition of the present invention preferably contains a surface conditioner as component (B). This makes it easier to form a coating with excellent appearance. In the present invention, as will be described later, based on the objectives of the invention, an aqueous solvent is preferred; therefore, the surface conditioner used is preferably water-soluble.

[0042] The content of component (B) in the coating (composition for coating formation) is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of component (A), more preferably 0.3 to 10 parts by mass, even more preferably 0.6 to 7 parts by mass, particularly preferably 0.8 to 4 parts by mass, and most preferably 1 to 3 parts by mass. This readily yields a coating with excellent mechanical properties while easily satisfying the physical properties described later.

[0043] Examples of surface conditioners include leveling agents and surfactants. A single surface conditioner can be used alone, or in combination of two or more.

[0044] (Leveling agent) As a surface conditioner, a leveling agent is preferably included in the coating-forming composition. This effectively suppresses the occurrence of craters, streaks, etc., when the coating-forming composition is applied to a substrate, resulting in a coating with uniform thickness and a good appearance. Furthermore, by using a leveling agent, the resulting coating (and film) readily meets the physical properties described later.

[0045] The leveling agent is preferably a water-soluble leveling agent. Here, a water-soluble leveling agent refers to a leveling agent that, when mixed with water at a 1:1 mass ratio at 25°C, cannot be visually confirmed to be cloudy or separated.

[0046] Preferred leveling agents include water-soluble polyether-modified silicone leveling agents, acrylic leveling agents, and fluorinated leveling agents. Polyether-modified silicone leveling agents are substances in which a portion of the substituents bonded to the silicon atoms in a siloxane structure are replaced by organic groups having alkylene oxide. Acrylic leveling agents are substances obtained, for example, by copolymerizing monomers having (meth)acryloyl groups. Fluorinated leveling agents are compounds with perfluoroalkyl or fluoroalkenyl groups in their main chain or side chains.

[0047] Commercially available leveling agents are suitable. Examples of commercially available polyether-modified silicone leveling agents include BYK-348 and BYK-3530 (manufactured by BYK-Chemie Japan). Examples of commercially available acrylic leveling agents include BYK-381 and BYK-3441 (manufactured by BYK-Chemie Japan). Examples of commercially available fluorinated leveling agents include Megaface F-477, Megaface F-553, Megaface F555-A, Megaface F-557, Megaface F-559, and Megaface F-569 (manufactured by IDC). Leveling agents can be used alone or in combination of two or more.

[0048] When using a leveling agent as a surface conditioner, its mixing ratio is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of component (A), more preferably 0.2 to 8 parts by mass, even more preferably 0.3 to 5 parts by mass, and particularly preferably 0.4 to 3 parts by mass. This ensures a sufficient leveling effect. In particular, the resulting coating (and film) readily meets the physical properties described later.

[0049] <surfactants> As a surface conditioner, a surfactant is also preferably included in the coating-forming composition. This surfactant is suitable, for example, for use with fillers described later. Specifically, when using fillers with low water affinity in aqueous solvents described later, the use of a surfactant increases the dispersibility of the filler, thereby improving the transmittance clarity and anti-glare properties of the resulting coating.

[0050] Examples of surfactants include, for instance, well-known surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, silicone surfactants, and fluorinated surfactants. From the viewpoint of maximizing the effects of the present invention, nonionic surfactants are preferred.

[0051] Examples of nonionic surfactants include ether-based surfactants such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether, and polyoxyethylene alkyl ether; ester-based surfactants such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan lauryl ester, sorbitan monostearate, sorbitan monooleate, and polyoxyethylene stearate; alkynyl diol-based or alkynyl alcohol-based surfactants such as 2,4,7,9-tetramethyl-5-decyn-4,7-diol, 3,6-dimethyl-4-octyyn-3,6-diol, and 3,5-dimethyl-1-hexyn-3-ol; and polyethylene glycol ether-based surfactants. Among these, alkynyl diol-based or alkynyl alcohol-based surfactants are preferred. Commercially available examples include OLFINE PD-201, OLFINE PD-003, OLFINE PD-301, and OLFINE AF103 (all manufactured by Nissin Chemical Industries, Ltd.). Surfactants can be used alone or in combination of two or more.

[0052] When using a surfactant, the mixing ratio is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of component (A), more preferably 0.2 to 4 parts by mass, even more preferably 0.3 to 3 parts by mass, and particularly preferably 0.4 to 2 parts by mass. This allows for the full utilization of the surfactant's effects. In particular, the resulting coating (and film) readily meets the physical properties described later.

[0053] (3) (C) Component The coating-forming composition of the present invention preferably contains filler as component (C) in addition to the aforementioned components (A) and (B). By including filler, the optical properties of the coating, such as haze value, can be easily adjusted to the desired values. Furthermore, the resulting coating (and film) readily meets the properties described later, and is particularly capable of imparting anti-glare properties to the resulting film.

[0054] Examples of fillers include inorganic fillers such as silica, calcium carbonate, aluminum hydroxide, magnesium hydroxide, clay, talc, and titanium dioxide; organic fillers formed from resins such as acrylic resins, polystyrene resins, polyethylene resins, and epoxy resins; and organic-inorganic fillers formed from silicon-containing compounds with intermediate inorganic and organic structures.

[0055] The shape of the filler can be a fixed shape such as a sphere, or an irregular shape without a specific shape. From the viewpoint of easily obtaining the desired optical properties, the average particle size of the filler is preferably 0.1 to 10 μm, more preferably 0.5 to 7 μm, particularly preferably 0.8 to 5 μm, even more preferably 1.0 to 4 μm, and most preferably 1.2 to 3 μm.

[0056] Commercially available fillers such as SEAHOSTAR KE-P250, SEAHOSTAR KE-S150 (manufactured by Nippon Shokubai Co., Ltd.), and SYLYSIA 530 (manufactured by Fuji Silysia Co., Ltd.) can also be used as fillers. These fillers can be used alone or in combination of two or more.

[0057] When using filler, its content relative to 100 parts by mass of component (A) is preferably 0.1 to 60 parts by mass, more preferably 0.5 to 45 parts by mass, even more preferably 1 to 30 parts by mass, particularly preferably 3 to 20 parts by mass, and most preferably 4 to 15 parts by mass. As a result, the resulting coating (and film) readily meets the physical properties described later, and at the same time, it is particularly easier to achieve optical properties such as anti-glare.

[0058] (4) (D) Component The coating-forming composition of the present invention preferably contains, in addition to components (A) and (B), an antibacterial / antiviral agent as component (D). Thus, the resulting coating film exhibits antibacterial / antiviral properties. Here, an antibacterial / antiviral agent refers to an agent that exhibits antibacterial and / or antiviral properties. Antibacterial properties refer to the property of killing or eliminating bacteria and fungi, or inhibiting the production, reproduction, and proliferation of these bacteria. Antiviral properties refer to the property of inactivating viruses and inhibiting viral proliferation. In the present invention, the antibacterial / antiviral agent preferably possesses both antibacterial and antiviral properties.

[0059] (D) The shape of the component is not particularly limited and can be either fixed or amorphous. However, from the viewpoint of easily and effectively exerting antibacterial / antiviral properties, a fixed shape is preferred, and particularly preferred is a particulate form. Particulate forms include any shape such as spherical, polyhedral, konpeito-like, eyebrow-shaped, or flat. When the antibacterial / antiviral agent is in particulate form, its average particle size is preferably 0.1–5 μm, more preferably 0.4–3 μm, and even more preferably 0.8–2 μm. The average particle size can be determined by laser diffraction. By producing an average particle size within this range and, as described later, making the coating thickness less than 5 μm, the antibacterial / antiviral properties can be further enhanced.

[0060] There are no particular limitations on the bacteria targeted by antibacterial / antiviral agents; examples include Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa. Viruses targeted by antibacterial / antiviral agents can be either enveloped or non-enveloped. Examples of enveloped viruses include influenza virus, SARS-CoV-2, herpesvirus, rubella virus, hepatitis B virus, hepatitis C virus, HIV, and human immunodeficiency virus. Examples of non-enveloped viruses include norovirus, rotavirus, poliovirus, adenovirus, and feline calicivirus.

[0061] Examples of antibacterial / antiviral agents include organic and inorganic types. Among these, antibacterial / antiviral agents with high water dispersibility are preferred. Organic antibacterial / antiviral agents can be substances formed from anionic, cationic, or ether groups with antibacterial / antiviral properties and a resin matrix. Examples of anionic groups include sulfonic acid groups, phosphate groups, carboxyl groups, hydroxyl groups, and nitro groups. Examples of cationic groups include quaternary amino groups. Examples of ether groups include alkyl ether groups such as ethyl ether and propyl ether. The resin matrix is ​​preferably a polymer containing vinyl monomers. Examples of vinyl monomers include styrene, (meth)acrylates, divinylbenzene, and trivinylbenzene.

[0062] As an inorganic antiviral agent, it is preferable to contain inorganic particles selected from at least one of antibacterial / antiviral metal oxides, metal salts (including complex salts, the same below), and metal ion carriers. Examples of metal oxides include silver oxide, zinc oxide, copper oxide, iron oxide, titanium oxide, tin oxide, tungsten oxide, chromium oxide, zirconium oxide, and molybdenum oxide. Among these, silver oxide, zinc oxide, copper oxide (I), or copper oxide (II) are preferred.

[0063] As metal salts, salts of Group 11 elements such as silver and copper, Group 12 elements such as zinc, and Group 6 elements such as molybdenum are preferred, and salts of silver, copper, zinc, and molybdenum are more preferred. Examples of preferred metal salts include silver salts such as silver nitrate, silver acetate, and silver sulfate; copper salts such as copper nitrate, copper acetate, and copper sulfate; zinc salts such as zinc nitrate, zinc acetate, and zinc sulfate; alkali metal salts of molybdenum oxyacids such as sodium molybdate, potassium molybdate, lithium molybdate, polymolybdate, and isopolymolybdate; and ammonium molybdate, etc.

[0064] Examples of metal ions that can serve as carriers include silver ions, copper ions, and zinc ions. Examples of ion exchangers that can support these metal ions include zeolites, silica gel, clay minerals, zirconium phosphate, calcium phosphate, calcium apatite, calcium silicate, magnesium aluminosilicate, titanium dioxide, potassium titanate, silica-alumina, soluble glass, thiosulfites, and metals.

[0065] Antibacterial / antiviral agents can be used alone or in combination of two or more.

[0066] These antibacterial / antiviral agents are available as commercially available products. Examples of commercially available products include NOVARON AG1100 (manufactured by Toa Synthetic Co., Ltd.), IonPure (manufactured by Ishizuka Glass Co., Ltd.), and Virutaker VM (manufactured by Sekisui Material Co., Ltd.).

[0067] Relative to 100 parts by mass of component (A), the content of component (D) in the coating (composition for coating formation) is preferably 0.1 to 40 parts by mass, more preferably 0.5 to 30 parts by mass, even more preferably 1 to 25 parts by mass, particularly preferably 2 to 20 parts by mass, and most preferably 3 to 15 parts by mass. As a result, the obtained coating (and film) readily meets the physical properties described later, and at the same time, readily exhibits excellent antibacterial / antiviral properties.

[0068] (4) Other components [(E) components] In addition to the aforementioned components (A) to (D), the coating-forming composition of the present invention may also contain other components [(E)].

[0069] As a component (E), photopolymerization initiators are preferably included.

[0070] By using a photopolymerization initiator, the amount of light irradiation and the polymerization and curing time during coating formation can be reduced. In particular, when crosslinking is carried out by irradiation with active light such as ultraviolet light as an active energy ray, the presence of a photopolymerization initiator is preferred.

[0071] The preferred photopolymerization initiator is a substance that can be stably present in an emulsion of polyurethane acrylate with active energy ray polymerizable functional groups, and whose polymerization can be initiated by irradiation with active energy rays.

[0072] Examples of photopolymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketal, benzophenone, p-phenylbenzophenone, 2-methylanthraquinone, 2-methyl thioxanthone, 2-ethyl thioxanthone, benzil dimethyl ketal, p-dimethylaminobenzoate, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylprop-1-one, phenyl-2,4,6-trimethylbenzoylphosphonite lithium, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-methylpropanone, Eosin Y, N-vinylpyrrolidone, triethanolamine, and 1-hydroxycyclohexylphenyl ketal.

[0073] Among these, water-soluble photopolymerization initiators such as 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-methylacetone are preferred. Commercially available examples include OMNIRAD 2959 (manufactured by IGM RESINS) and H1361 (manufactured by Tokyo Chemical Industry Co., Ltd.). A single photopolymerization initiator can be used alone, or two or more can be used in combination.

[0074] When using a photopolymerization initiator, the mixing ratio is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of component (A), more preferably 0.2 to 10 parts by mass, and even more preferably 1.0 to 7 parts by mass. As a result, the resulting coating (and film) readily meets the physical properties described later (especially scratch resistance and hardness).

[0075] In the coating-forming composition of the present invention, other additives such as antioxidants, ultraviolet absorbers, silane coupling agents, light stabilizers, defoamers, infrared absorbers, colorants, and antistatic agents can be appropriately mixed without affecting the effect of the present invention.

[0076] (5) Formation of coating The coating can be formed by applying (coating-forming composition) to the surface of a substrate layer or other layers stacked on the substrate layer, and then irradiating the resulting coating film with active energy rays to cure the coating film.

[0077] The coating-forming composition can be prepared by adding the above-mentioned essential components (A), (B), and optional components (C), (D), and other components to a solvent, thereby dissolving or dispersing these components.

[0078] In this invention, from the viewpoints of promoting SDGs, reducing environmental burden, and managing worker health, the solvent used is preferably an aqueous solvent with reduced organic solvent content, and more preferably water.

[0079] Examples of aqueous solvents include water, water, and mixtures of water and organic solvents compatible with water. Examples of organic solvents compatible with water include alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone and methyl ethyl ketone; cellosols such as methyl cellosol; amides such as N,N-dimethylformamide; and ethers such as tetrahydrofuran.

[0080] The amount of solvent used can be appropriately determined to achieve a concentration and viscosity suitable for film formation in the coating-forming composition of the present invention. Typically, the amount used is 10 to 500 parts by weight relative to 100 parts by weight of component (A), preferably 30 to 300 parts by weight, and more preferably 50 to 200 parts by weight.

[0081] There are no particular limitations on the method of applying the coating composition to the surface of a substrate layer or other layers laminated on the substrate layer, and conventionally known methods such as bar coating, knife coating, roller coating, doctor blade coating, mold coating, and gravure printing coating can be used. The coating film is preferably dried at 40 to 120°C for about 30 seconds to 5 minutes.

[0082] The coating composition of the present invention has excellent coatability. That is, during coating, no pinholes are generated, or defects such as streaks or spots are observed, and a coating film with uniform thickness can be formed.

[0083] Next, the coating is cured by irradiating it with active energy rays, thus forming a coating layer. Examples of active energy rays used in curing the coating include ultraviolet light; electron beams; lasers such as semiconductor lasers, argon lasers, and He-Cd lasers; and ionizing radiation such as alpha rays, beta rays, gamma rays, neutron beams, X-rays, and accelerated electron beams. Among these, ultraviolet light and electron beams are preferred as active energy rays because they can be generated using relatively simple devices, and ultraviolet light is more preferred.

[0084] When using ultraviolet light as an active energy ray, ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, black light lamps, metal halide lamps, etc., can be used as ultraviolet light sources.

[0085] The optimal intensity of ultraviolet light is 50–1000 mJ / cm. 2 More preferably 100–700 mJ / cm 2 In addition, the preferred ultraviolet irradiance is typically 100–1000 mW / cm². 2 More preferably 200–700 mW / cm 2 The irradiation time is usually from 1 second to 1 hour, and the irradiation temperature is usually from 20 to 100°C.

[0086] Electron beam irradiation can be performed using an electron beam accelerator or similar device. The preferred irradiation dose is 10–1000 krad.

[0087] Irradiation by active energy rays can be carried out in an air atmosphere or an inert gas atmosphere. Examples of inert gases include nitrogen, argon, and helium.

[0088] The thickness of the resulting coating can be selected according to the desired purpose and application, typically ranging from 0.1 to 50 μm, preferably from 0.5 to 30 μm, more preferably from 1 to 20 μm, and even more preferably from 2 to 10 μm, with 3 to 7 μm being the most desirable. Thus, the resulting coating (and film) readily meets the physical properties described later. When the coating contains the aforementioned component (C), by achieving such a film thickness, it is easy to adjust the coating to exhibit the desired anti-glare properties. It should be noted that when the film thickness is less than 0.1 μm, it is sometimes difficult to obtain the hardness required for practical use.

[0089] From an environmental perspective, the amount of residual organic solvent in the coating involved in this invention is preferably 50 ppm or less, more preferably 30 ppm or less, more preferably 10 ppm or less, and particularly preferably 1 ppm or less. To ensure that the amount of residual organic solvent is within the above-mentioned range, when forming the coating, an aqueous solvent with a low organic solvent content is preferably used, and water is more preferably used. The amount of residual organic solvent can be calculated by cutting the coating film (coating layer) into 4 cm × 5 cm pieces, heating them at 120°C for 20 minutes, and measuring the amount of vaporized solvent using a gas chromatograph (equipment name "GC-2010", manufactured by Shimadzu Corporation).

[0090] (6) Other layers The coating of the present invention may include a primer layer, an anti-reflective layer, an adhesive layer, etc., as other layers, depending on the purpose.

[0091] In the coating of this invention, a primer layer is sometimes disposed between the substrate layer and the coating layer. This improves the adhesion between the substrate layer and the coating layer. For example, the primer layer can be applied to the surface of the substrate layer at a concentration of 0.5–2 g / m². 2 It is formed by applying a reactive coating solution composed of polyester polyol or polyether polyol and polyisocyanate.

[0092] In the coating of the present invention, the anti-reflective layer is sometimes disposed at a position on the side of the coating opposite to the substrate layer, etc., to achieve its intended performance. This improves transparency by eliminating reflections of images generated by sunlight, fluorescent lights, etc., and by suppressing surface reflectivity. Depending on the type of anti-reflective layer, improvements in antistatic properties may also be sought.

[0093] In the coating of this invention, the adhesive layer is sometimes disposed on the side of the substrate layer opposite to the side with the coating. This provides a good fit to the surface of the touch panel. The adhesive constituting this adhesive layer is not particularly limited, and known adhesives such as acrylic adhesives, rubber adhesives, silicone adhesives, polyurethane adhesives, and polyester adhesives with specified transparency can be used.

[0094] It should be noted that when the coating of the present invention has an adhesive layer, a release film may also be laminated on the surface of the adhesive layer. This release film serves to protect the surface of the adhesive layer and is peeled off during use. There are no particular limitations on the release film as long as it has the desired peelability on its peeling surface (the surface in contact with the adhesive layer), and known release films can be used.

[0095] (7) Surface protective film For purposes such as protecting the surface of the coating during use, the coating of the present invention may also have a surface protective sheet. The surface protective sheet is peeled off during use. As the surface protective sheet, a conventionally known resin film is preferably used.

[0096] (8) Layer composition Examples of the layer composition of the coating film of the present invention can be listed below, but are not limited to these. It should be noted that the following symbols are used hereinafter. BL: Substrate layer AVC: Coating PL: Primer layer SP: Surface Protector RF: Release membrane AL: Adhesive layer AR: Anti-reflective layer BL / AVC, BL / AVC / SP, BL / AVC / AR, BL / AVC / AR / SP, AVC / BL / AVC, SP / AVC / BL / AVC / SP, BL / PL / AVC, BL / PL / AVC / SP, RF / AL / BL / AVC, RF / AL / BL / AVC / SP, RF / AL / BL / AVC / AR / SP, RF / AL / BL / PL / AVC / AR / SP.

[0097] 3. Characteristics of the coating film (1) Total light transmittance From a transparency perspective, the total light transmittance of the coating film of the present invention is preferably 85% or more, more preferably 88% or more, and even more preferably 90% or more. The upper limit of the total light transmittance is typically 100%. This results in excellent visibility of the displayed image. It is also suitable for applications requiring transparency other than displays (e.g., windows in vehicles, transport aircraft, ships, or buildings). Furthermore, by applying the coating film, an excellent appearance is easily achieved. The total light transmittance can be measured using a haze meter according to JIS K 7361-1.

[0098] (2) Haze value From the viewpoint of easily maintaining visibility, the haze value of the coating of the present invention is preferably 50% or less, more preferably 25% or less, further preferably 15% or less, particularly preferably 5% or less, and most preferably 1% or less. When the coating is used in a display, the transparency of the displayed image becomes excellent, and visibility is easily maintained. It is also suitable for use in items requiring transparency other than displays, such as windows of vehicles, transport aircraft, ships, etc., or windows of buildings. The lower limit of this haze value is generally 0% or more, and from the viewpoint of balancing transparency, visibility, and scratch resistance, it is preferably 0.01% or more. From the viewpoint of imparting anti-glare properties, the haze value of the coating of the present invention is preferably 0.1% or more, more preferably 1% or more, further preferably 3% or more, particularly preferably 5% or more, and most preferably 10% or more and 50% or less. Thus, both visibility and anti-glare properties of the displayed image can be balanced. Furthermore, when used in windows of vehicles, transport aircraft, ships, etc., or windows of buildings, it can impart desired light scattering properties and crime prevention. Furthermore, when used for surface protective films, the resulting white haze (cloudiness) serves as an indicator to prevent the protective film from being forgotten during peeling. The haze value can be measured using a haze meter according to JIS K7136:2000.

[0099] (3) Transmission clarity The transmittance sharpness of the coating of the present invention is preferably 50 or higher, more preferably 100 or higher, even more preferably 140 or higher, particularly preferably 180 or higher, and most preferably 250 or higher. Furthermore, there is no particular limitation on the upper limit of transmittance sharpness, which is typically 500 or lower. Therefore, good visibility is easily obtained in displays and the like. It is particularly suitable for high-precision displays. It is also suitable for applications requiring transparency other than displays (e.g., windows in vehicles, transport aircraft, ships, etc., or windows in buildings). In addition, the appearance is easily improved by applying the coating. The transmittance sharpness can be obtained according to JIS K7374 using an image sharpness testing machine, irradiating the coating side in transmittance mode, and calculating the total image sharpness value of the five combs (comb widths: 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, 2.0 mm).

[0100] (4) 60° gloss In the coating of the present invention, the 60° gloss value of the coating surface is preferably 30 or more, more preferably 60 or more, further preferably 90 or more, particularly preferably 120 or more, and even more preferably 150 or more, from the viewpoint of easily satisfying the aforementioned optical properties. From the viewpoint of easily obtaining excellent appearance, this 60° gloss value is preferably 180 or less. Furthermore, from the viewpoint of anti-glare properties, it is preferably 160 or less, further preferably 150 or less, particularly preferably 130 or less, and from the viewpoint of balancing antibacterial and antiviral properties, it is preferably 120 or less. The 60° gloss can be measured using a gloss meter according to JIS Z8741:1997.

[0101] (5) Scratch resistance In the coating of this invention, the coating surface preferably exhibits excellent abrasion resistance. Excellent abrasion resistance can be confirmed by the absence of any visible change in an abrasion resistance test using steel wool. Specifically, for the coating surface, according to JIS K5600-5-10, #0000 steel wool is used at 250 g / cm³. 2 After wiping the surface for 10cm under load and 10 times back and forth, it was confirmed that no scratches were produced. Therefore, when used on the surface of objects to which the object is to be attached, such as displays, it can provide excellent surface protection and maintain the appearance of the object well.

[0102] (6) Pencil hardness In the coating of the present invention, the pencil hardness of the coating surface is preferably H or higher, more preferably 2H or higher. Furthermore, the upper limit of this pencil hardness is not particularly limited, but it is generally preferred to be 9H or lower, more preferably 7H or lower, further preferably 5H or lower, and particularly preferably 3H or lower. This results in excellent scratch resistance, providing excellent surface protection when used on the surface of objects to which the coating is applied, such as displays. In particular, because the surface is difficult to scratch, the appearance of the objects to which the coating is applied is well maintained. In addition, it has moderate hardness, and its rigidity easily becomes a workable rigidity, thus making it suitable for application to displays; windows of vehicles, transport aircraft, ships, etc.; windows of buildings, etc. The pencil hardness can be measured according to JIS K 5600 using the method described in the examples.

[0103] (7) Water contact angle and oleic acid contact angle In the coating of the present invention, the water contact angle of the coating surface is preferably 60–110°, more preferably 65–100°, further preferably 70–95°, and particularly preferably 72–90°. Additionally, the oleic acid contact angle is preferably 10–80°, more preferably 15–60°, further preferably 20–50°, and particularly preferably 25–40°. By setting the water contact angle and oleic acid contact angle within the above ranges, fingerprints, stains, etc., are difficult to adhere to. Even if fingerprints, stains, etc., adhere, they easily blend with the coating surface and are difficult to detect, thus maintaining the aesthetic appearance of the layer surface. The contact angle can be measured using the method described in the examples.

[0104] (8) Anti-glare The coating of the present invention exhibits excellent anti-glare properties, and the coating of the present invention is formed using a coating-forming composition containing the aforementioned component (C): filler. The excellent anti-glare properties can be confirmed using the evaluation methods described in the examples.

[0105] (9) Fit The coating of this invention exhibits excellent adhesion between the substrate layer and the coating layer. This excellent adhesion can be confirmed using the checkerboard adhesion method according to JIS K 5400. Specifically, a 10×10 grid (100 grids in total) is drawn on the surface of the coating at 1mm intervals using a cutter. Then, transparent tape manufactured by NICHIBAN is applied to each of these grids after (i) immediately following, (ii) after 1000 hours of exposure at 85°C, (iii) after 1000 hours of exposure at 60°C and 90% humidity, and (iv) after 1000 hours of exposure at -40°C. Upon peeling off the tape, the coating is visually observed to see if it peels off from the substrate layer. No grids peeled off, thus demonstrating excellent adhesion.

[0106] (10) Antibacterial / antiviral activity The coating of the present invention has antibacterial / antiviral properties, and the coating of the present invention has a coating formed using a coating-forming composition containing the aforementioned component (D): an antibacterial / antiviral agent. The antibacterial activity value of the coating surface in an antibacterial test according to JIS Z 2801:2010 is preferably 2.0 or higher, more preferably 2.4 or higher, and even more preferably 2.7 or higher. Furthermore, the antiviral activity value of the coating surface in an antiviral test according to ISO 21702 is preferably 0.4 or higher, more preferably 2.0 or higher, and even more preferably 2.7 or higher. The antibacterial activity value and the antiviral activity value can be obtained using the test methods described in the examples.

[0107] 4. Application of coatings The coating of the present invention is an environmentally friendly film that can be made using aqueous solvents, has a residual organic solvent content of less than 50 ppm, and possesses optical and mechanical properties equivalent to those of coatings made using conventional organic solvents. Therefore, it is safely and reliably suitable for use in various displays such as liquid crystal displays, organic electroluminescent (EL) displays, and light-emitting diode (LED) displays. Furthermore, the presence of antibacterial / antiviral agents in the coating makes it suitable for use as a surface layer of touch panels that are touched by hand. Specifically, it is preferably used by laminating the coating onto a cover material in a display module such as a liquid crystal display module, a light-emitting diode (LED) module, or an organic EL module. The lamination of the coating onto the cover material is preferably performed by attachment via the aforementioned adhesive layer. Additionally, it is suitable for use in articles such as vehicles, transport aircraft, ships, buildings, and surface protective films.

[0108] 2) Items with a coating The articles of the present invention have the aforementioned coating of the present invention.

[0109] The type of item can be anything that has the coating of this invention, and there is no particular limitation. Examples include optical displays, vehicles, transport aircraft, ships, buildings, surface protective films, etc.

[0110] The optical display of the present invention can be obtained, for example, by bonding (laminating) the display surface side of the display body to the substrate layer (or adhesive layer) of the coating of the present invention, for example, with respect to the display body and the coating of the present invention. The coating of the present invention can be directly laminated onto the display surface of the display body, or it can be laminated onto the display surface side of the display body via other components or layers (covering materials, etc.).

[0111] For vehicles, examples include automobiles and trains. For transport aircraft, examples include passenger planes and cargo planes. The coating can be appropriately applied to the surfaces of interior or exterior components of these vehicles, transport aircraft, ships, etc., especially to the surfaces of license plates, windows, etc.

[0112] In buildings, coatings are suitable for use on the surfaces of exterior or interior components, especially windows.

[0113] A surface protective film is applied to protect the surface of an object before use, and is peeled off when the object is in use. There are no particular limitations on the object being protected; examples include various optical films, electronic devices, and electrical products.

[0114] The embodiments described above are provided for ease of understanding of the contents of this invention and are not intended to limit the scope of this invention. Therefore, the essence of the elements disclosed in the above embodiments also includes all design modifications or equivalents that fall within the technical scope of this invention.

[0115] It should be noted that in this specification, when the terms "α to β" (where α and β are arbitrary values) are used, unless otherwise specified, they include both "more than α and less than β" and "preferably greater than α" or "preferably less than β". Furthermore, when the terms "more than α" (where α is any number) are used, unless otherwise specified, they also include "preferably greater than α", and when the terms "less than β" (where β is any number) are used, unless otherwise specified, they also include "preferably less than β". Example

[0116] The present invention will be further described in detail below through examples, etc., but the scope of the present invention is not limited to these examples, etc.

[0117] (Example 1) A coating-forming composition is prepared by uniformly mixing 100 parts by weight of cationic polyurethane acrylate material as component (A) [trade name: ART RESIN WEH-1, molecular weight: 2000, average particle size: 50-100 nm, number of functional groups: 10, manufactured by Negami Kogyo Co., Ltd.] (referred to as "A1" in Table 1 below), 1.0 part by weight of acryloyl-containing polyether-modified siloxane (leveling agent) as component (B) [trade name: BYK-3530, manufactured by BYK Corporation] (referred to as "B1-1" in Table 1 below), 5.0 parts by weight of photopolymerization initiator [1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylacetone] (referred to as "E1" in Table 1 below) as component (E) and water as solvent.

[0118] The aforementioned coating composition was applied to a polyethylene terephthalate (PET) film (trade name "Lumirror U40", thickness: 188 μm, manufactured by TORAY) as the substrate layer using a wire-wound rod to form a coating film. The film was then placed in an oven maintained at 110°C for 1 minute to dry. Next, under a nitrogen atmosphere, an ultraviolet irradiation device (EYE Grandage ECS-401GX type, manufactured by EYE GRAPHICS) was used, employing a high-pressure mercury lamp as the light source, with an illuminance of 200 mW / cm². 2 Light intensity: 200 mJ / cm 2 The coating is subjected to ultraviolet irradiation under certain irradiation conditions to cure the aforementioned coating film, thereby producing a coating film (coating film 1) with a film thickness of 4 μm.

[0119] (Examples 2 and 3) In Example 1, B1-2 and B1-3 (described in Table 1 below) were used instead of B1-1 as component (B). Otherwise, coatings 2 and 3 were prepared in the same manner as in Example 1.

[0120] (Example 4) In Example 1, in addition to B1-1, 0.8 parts by weight of B2-1 was used as component (B), and 8.0 parts by weight of C1 was used as component (C). Otherwise, the coating composition was prepared in the same manner as in Example 1, and the coating film 4 was made in the same manner as in Example 1. B2-1 and C1 are as follows.

[0121] (Examples 5-9, Comparative Examples 1-3) In Example 4, for components (A) to (E), the substances of the types shown in Table 1 were used in the amounts shown in Table 1 below. Otherwise, the coating-forming composition was prepared in the same manner as in Example 4, and coatings having film thicknesses of 5 to 9 mm and 1 to 3 mm as shown in Table 1 were produced in the same manner as in Example 4. However, in Comparative Example 3, instead of drying in an oven maintained at 110°C for 1 minute, the coating was dried by immersion in an oven maintained at 70°C for 1 minute. The types of components (A) to (E) in Table 1 below are as follows.

[0122] A2: NK ester A-DPH (dipentaerythritol polyacrylate), manufactured by Shin-Nakamura Chemical Co., Ltd. B1-2: F-477 (an oligomer containing fluorinated, hydrophilic, and lipophilic groups), manufactured by DIC Corporation; B1-3: F-553 (an oligomer containing fluorinated, hydrophilic, and lipophilic groups), manufactured by DIC Corporation; B1-4: SH28 (silicone-based leveling agent), manufactured by Dow Toray; B2-1: PD-201 (alkynyl alcohol surfactant), manufactured by Nissin Chemical Co., Ltd. C1: Seahostar KE-P250 (spherical silica, particle size: 2.5μm), manufactured by Nippon Shokubai Co., Ltd. C2: KE-S150 (spherical silica, particle size: 1.5μm), manufactured by Nippon Shokubai Co., Ltd. C3: SYLYSIA 530 (amorphous silica, particle size: 2.7μm), manufactured by Fuji Silysia. D1: NOVARON AG1100 (silver-supported hexagonal zirconium phosphate, average particle size: 1μm), manufactured by Toa Synthetic Co., Ltd. D2: IonPure (water-soluble glass containing metal ions), manufactured by Ishizuka Glass Co., Ltd. D3: Virutaker VM (organic anionic antibacterial / antiviral agent), manufactured by Sekisui Material Co., Ltd. E2: 1-Hydroxycyclohexylphenyl ketone.

[0123] The following tests were conducted on the coatings 1-9 and 1r-3r obtained in Examples 1-9 and Comparative Examples 1-3.

[0124] [Determination of residual organic solvent content] For the aforementioned coatings 1–9 and 1r–3r, cut them into 4cm × 5cm pieces and heat them at 120°C for 20 minutes. The amount of vaporized solvent was determined using a gas chromatograph (GC-2010, manufactured by Shimadzu Corporation). The results are shown in Table 2. In the table, "nd" indicates that the amount of residual organic solvent was not detected.

[0125] [Topical] For the aforementioned coatings 1–9 and 1r–3r, the surface of the coating layer in the coating film was visually inspected. A case where no traces of pinholes or streaks / spots were observed on the coating surface was rated as ○; a case where traces of pinholes were observed on the coating surface was rated as NG1; and a case where streaks or spots were observed was rated as NG2. The results are shown in Table 2.

[0126] [Total light transmittance] For coatings 1–9 and 1r–3r, according to JIS K 7361-1, using a haze meter (“NDH-5000”, manufactured by Nippon Denshoku Kogyo Co., Ltd.), after blank correction, light was irradiated from the coating side to measure the total light transmittance (%). The results are shown in Table 2.

[0127] [Haze] For coatings 1–9 and 1r–3r, according to JIS K 7136:2000, a haze meter (“NDH-5000”, manufactured by Nippon Denshoku Kogyo Co., Ltd.) was used. After blank calibration, light was shone from the coating side to measure the haze value (%) of the coating surface. The results are shown in Table 2.

[0128] [Transmission clarity] For coatings 1–9 and 1r–3r, according to JIS K 7374, using an image sharpness testing machine (“ICM-1T”, manufactured by Suga Testing Machine Co., Ltd.), light was irradiated from the coating side in transmission mode, and the total image sharpness value of the five combs (comb widths: 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, 2.0 mm) was calculated. This calculated value was set as the transmission sharpness value. The results are shown in Table 2.

[0129] [60° Gloss] For the aforementioned coatings 1–9 and 1r–3r, the 60° gloss of the coating surface was measured using a gloss meter (“VG7000”, manufactured by Nippon Denshoku Co., Ltd.) according to JIS Z 8741:1997. The results are shown in Table 2.

[0130] [Abrasion resistance] For the aforementioned coatings 1–9 and 1r–3r, the scratch resistance of the coating surface was evaluated. Specifically, according to JIS K5600-5-10, #0000 steel wool was used at 250 g / cm³. 2 The coating surface was wiped back and forth 10 times with a load and a sliding distance of 10 cm. Then, the surface was visually inspected for scratches under a three-wavelength fluorescent lamp, and evaluated according to the following criteria. The results are shown in Table 2.

[0131] ○: The number of confirmed scratches is 3 or less; △: The number of confirmed scratches is 4 to 10; ×: The number of confirmed scratches is 11 or more.

[0132] [Pencil Hardness] For the aforementioned coatings 1–9 and 1r–3r, the pencil hardness of the coating surface was measured according to JIS K 5600. Specifically, pencils with different lead hardness ("Mitsubishi Pencil UNI," manufactured by Mitsubishi Pencil Corporation) were moved at a 45° angle for more than 7 mm while a load of 750g was applied, and the degree of scratching on the surface was observed. This was performed 5 times for each type, and the hardest pencil lead that showed no scratches on the surface after 4 or more tests was defined as the pencil hardness. The results are shown in Table 2.

[0133] [Water contact angle and oleic acid contact angle] For the aforementioned coatings 1–9 and 1r–3r, the water contact angle and oleic acid contact angle of the coating surface were measured. Specifically, a glass plate was attached to the substrate-side surface of the coating, and then the coating with the glass plate facing down was placed on the test bench of a contact angle meter (“DH350 test bench”, manufactured by KYOWA). Next, 2 μL of water (or oleic acid) was dropped onto the coating surface of the aforementioned coating with the glass plate, and the contact angle (°) immediately after the drop was added was measured using the contact angle meter. This measured value was set as the water contact angle (or oleic acid contact angle) (°). The results are shown in Table 2.

[0134] [Anti-glare] The aforementioned coatings 1-9 and 1r-3r were placed on a black plate with the coated surface facing upwards. Under three wavelength fluorescent lamps, the reflected light from the coating surface was observed visually at an angle of 70-80°. The anti-glare performance was evaluated based on the shape of the reflected fluorescent light. A non-linear appearance of the fluorescent light was rated as ○, and a linear appearance was rated as ×. The results are shown in Table 2.

[0135] [Checkerboard Test (Fitness)] For the aforementioned coatings 1–9 and 1r–3r, the adhesion was evaluated using the checkerboard method according to JIS K5400. Specifically, a 10×10 grid (100 pieces in total) was drawn on the surface of the coating at 1mm intervals using a cutter. After initial exposure, 1000 hours at 85°C, 1000 hours at 60°C and 90% relative humidity, and 1000 hours at -40°C, transparent tape manufactured by NICHIBAN was applied. Upon peeling off the tape, it was confirmed whether the coating had peeled off from the substrate layer, and the number of pieces that did not peel off was evaluated. The results are shown in Table 2.

[0136] [Antibacterial test] For the coatings 7-9 obtained in Examples 7-9 that used antibacterial / antiviral agents, antibacterial tests were performed according to JIS Z 2801:2010 "Antibacterial processed articles - Antibacterial article tests / antibacterial effects". The results are shown in Table 2.

[0137] <Experimental Methods> Prepare test bacterial suspensions A (for Staphylococcus aureus, a Gram-positive bacterium) and B (for Escherichia coli, a Gram-negative bacterium) at specified concentrations using 1 / 500 nutrient medium.

[0138] 0.4 ml of test bacterial solutions A and B were respectively added to the surface of coating films cut into 5 cm × 5 cm pieces. The films were then covered with polyethylene films cut into 4 cm × 4 cm pieces and placed at 35°C and relative humidity above 90% for 24 hours. Afterward, the bacteria adhering to the coating surface were thoroughly washed out in a petri dish, and the number of viable bacteria in 1 ml of the solution was determined.

[0139] Furthermore, instead of coating, the substrate monomer (PET film: standard sample) was covered with an uncoated substrate monomer and the viable count was determined in the same manner as above.

[0140] The antibacterial activity value is obtained by measuring the viable count of the standard sample and the viable count of the test sample.

[0141] [Antiviral test] For the coatings 7-9 obtained in Examples 7-9 using antibacterial / antiviral agents, antiviral tests were conducted according to ISO 21702 using seasonal influenza A virus (enveloped) and feline calicivirus (non-enveloped), using the following method. The results are shown in Table 2.

[0142] <Experimental Methods> A viral suspension of a specified concentration was prepared by infecting and culturing host cells with the virus. A coating (5 cm × 5 cm; for the sample to be measured) was placed in a petri dish with the coated surface facing up. 0.4 mL of the aforementioned viral suspension was placed on the surface of the coating and covered with a polyethylene film (4 cm × 4 cm) to ensure that the viral suspension was distributed across the entire surface of the coating.

[0143] After storing the aforementioned culture dishes in a constant temperature and humidity environment for a specified period, the eluent was washed out using SCDLP (Soybean-Casein Digest Broth with Lecithin & Polysorbate 80) medium and then subjected to staged dilutions using EMEM (Eagle's minimalessential medium). The viral infection titer of these dilutions was then determined using a plaque assay.

[0144] Using a polyethylene film (5cm×5cm; standard sample) instead of the aforementioned coating, the viral infection titer was determined in the same manner as described above.

[0145] The difference between the viral infection titer of the measured standard sample and the viral infection titer of the measured sample is calculated as a log value and set as the antiviral activity value.

[0146] As shown in Table 2, the coatings 1 to 9 of the present invention exhibit high total light transmittance and transmission clarity, excellent hardness, and excellent scratch resistance and adhesion. Furthermore, coatings 4 to 9, which use fillers in the coating, also demonstrate excellent anti-glare properties, and coatings 7 to 9, which utilize antibacterial / antiviral agents, exhibit excellent antibacterial and antiviral properties.

[0147] On the other hand, in Comparative Example 1, which used a coating-forming composition that did not contain component (B), pinholes occurred during coating formation, resulting in poor coatability. The coating 2r of Comparative Example 2 exhibited low transmittance clarity. Furthermore, spot-like defects frequently occurred during coating, leading to poor coatability. Additionally, in Comparative Example 3, which did not use polyurethane acrylate-based materials as component (A), residual organic solvents exceeded 50 ppm, which is environmentally unfriendly.

[0148] Industrial availability As detailed above, the coating of the present invention is environmentally friendly, has excellent coatability, and exhibits superior optical and mechanical properties. Furthermore, it can impart antibacterial / antiviral properties, making it suitable for use in items such as touch panels during infectious disease outbreaks.

Claims

1. A coating film having a substrate layer and a coating layer, characterized in that, Transmission resolution is 50 or higher. The coating is a layer formed by a coating-forming composition containing components (A) and (B) below, and The amount of residual organic solvent in the coating is less than 50 ppm. (A) Composition: Polyurethane acrylate material, (B) Ingredients: surface conditioner.

2. The coating according to claim 1, wherein, The component (A) is an emulsion containing emulsified particles of polyurethane acrylate with an average particle size of less than 300 nm and having more than 5 active energy ray polymerizable functional groups.

3. The coating according to claim 1, wherein, The component (B) is a water-soluble leveling agent and / or surfactant.

4. The coating according to claim 1, wherein, The content of component (B) in the coating forming composition is 0.1 parts by mass or more and 20 parts by mass or less relative to 100 parts by mass of component (A).

5. The coating according to claim 1, wherein, The water contact angle of the coating on the side opposite to the substrate layer is greater than 70°.

6. The coating according to claim 1, wherein, The coating-forming composition further contains filler as component (C).

7. The coating according to claim 1, wherein, The coating-forming composition further contains particulate antibacterial / antiviral agents as component (D).

8. The coating according to claim 7, wherein, The average particle size of the particulate antibacterial / antiviral agent is greater than 0.5 μm and less than 5 μm, and the film thickness of the coating is less than 5 μm.

9. The coating according to claim 7, wherein the antibacterial activity value is 2.0 or higher in the antibacterial test according to JIS Z2801:2010, and the antiviral activity value is 2.0 or higher in the antiviral test according to ISO 21702.

10. An article having the coating as described in any one of claims 1 to 9.

11. The article according to claim 10, wherein, The article is any one of optical displays, vehicles, transport aircraft, ships, buildings, and surface protective films.

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