Active energy ray curable hard coating agent, hard coating layer, optical component, and electronic device.

Abstract

The objective is to provide an active energy ray-curable hard coat agent with excellent water vapor barrier properties, scratch resistance, and adhesion to a support. Furthermore, the objective is to provide a hard coat layer formed from the active energy ray-curable hard coat agent, and optical components and electronic devices having the same. [Solution] An active energy ray-curable hard coat agent comprising a compound (A) having a polycyclic moiety in which three or more rings are fused and two or more (meth)acryloyl groups, and a urethane (meth)acrylate (B) having six or more (meth)acryloyl groups, characterized in that the nonvolatile content of the active energy ray-curable hard coat agent contains 50 to 75% by mass of the compound (A) and 10 to 35% by mass of the urethane (meth)acrylate (B).

Description

Technical Field

[0001] The present invention relates to an active energy ray-curable hard coat agent, a hard coat layer formed from the hard coat agent, an optical member, and an electronic device.

Background Art

[0002] Active energy ray-curable hard coat agents are mainly used as hard coat agents for optical films for displays, taking advantage of their excellent transparency and high surface hardness. In recent years, with the thinning of displays, various optical films have been thinned. Among these, triacetyl cellulose (TAC) films used in polarizing plates for optical compensation of liquid crystal displays (LCDs) and organic light emitting diode (OLED) displays are originally materials with high moisture permeability, so there is concern about deterioration of the members due to moisture.

[0003] The display elements of OLED displays are easily deteriorated by moisture in the atmosphere and the element fabrication involves high-temperature treatment, so glass having barrier properties and heat resistance has been used as a member. However, in recent years, there has been a demand for flexible OLED displays in the market. In the case of flexibility, a flexible film that substitutes for glass is an essential member, and the film used for it is required to have water vapor barrier properties and various performances that can withstand the display fabrication process. In such a background, development of hard coat agents used for films having excellent water vapor barrier properties has been carried out. For example, Patent Document 1 discloses a curable composition containing a compound having a specific alicyclic structure. Further, Patent Document 2 discloses an active energy ray-curable resin composition containing a hydroxyl group-containing hydrogenated petroleum resin and a compound having at least one polymerizable functional group. Further, Patent Document 3 discloses an active energy ray-curable resin composition containing a petroleum resin, an acrylic resin, and a polyfunctional (meth)acrylate monomer.

[0004] However, the curable compositions described in these documents had problems such as insufficient scratch resistance required for displays as hard coat agents, and insufficient adhesion between the hard coat layer and the support. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2006-083225 [Patent Document 2] Japanese Patent Publication No. 2004-323751 [Patent Document 3] Japanese Patent Publication No. 2017-105916 [Overview of the project] [Problems that the invention aims to solve]

[0006] The problem that this invention aims to solve is to provide an active energy ray-curable hard coat agent with excellent water vapor barrier properties, scratch resistance, and adhesion to a support. Furthermore, the invention aims to provide a hard coat layer formed from the active energy ray-curable hard coat agent, and optical components and electronic devices having the same. [Means for solving the problem]

[0007] The inventors of this invention arrived at this present invention as a result of diligent research to solve the above problems. In other words, the present invention relates to a polycyclic moiety in which three or more rings are fused and two or more (meth)acrylo The present invention relates to an active energy ray-curable hard coat agent comprising a compound (A) having an yl group and a urethane (meth)acrylate (B) having six or more (meth)acryloyl groups, characterized in that the nonvolatile content of the active energy ray-curable hard coat agent contains 50 to 75% by mass of compound (A) and 10 to 35% by mass of the urethane (meth)acrylate (B).

[0008] Furthermore, the present invention relates to the active energy ray curable hard coat agent in which compound (A) is tricyclodecane dimethanol di(meth)acrylate.

[0009] Furthermore, the present invention relates to the active energy ray curable hard coating agent in which the weight-average molecular weight of the urethane (meth)acrylate (B) is 1600 to 10000.

[0010] Furthermore, the present invention relates to the active energy ray curable hard coat agent in which the above-mentioned urethane (meth)acrylate (B) comprises urethane (meth)acrylate (B-1) having nine or more (meth)acryloyl groups or urethane (meth)acrylate (B-2) having a silicone skeleton.

[0011] Furthermore, the present invention relates to the above-mentioned active energy ray curable hard coat agent, which further contains 1 to 20% by mass of an inorganic oxide (C) in the non-volatile content of the active energy ray curable hard coat agent.

[0012] Furthermore, the present invention relates to the active energy ray curable hard coat agent, wherein the polymerization initiator (D) is present in an amount of 1 to 15% by mass of the nonvolatile content of the active energy ray curable hard coat agent.

[0013] Furthermore, the present invention relates to a hard coat layer formed from the above-mentioned active energy ray curable hard coat agent.

[0014] The present invention also relates to an optical member having a support and the hard coat layer described above.

[0015] Furthermore, the present invention relates to an electronic device comprising the above-mentioned optical component. [Effects of the Invention]

[0016] The active energy ray curable hard coat agent of the present invention makes it possible to form a hard coat layer with excellent water vapor barrier properties, scratch resistance, and adhesion to a support. Therefore, optical components and electronic devices requiring the above properties can be provided. [Modes for carrying out the invention]

[0017] Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of embodiments of the present invention, and the present invention is not limited to these contents unless it exceeds the gist of the invention. In this specification, when "(meth)acrylic", "(meth)acrylo", "(meth)acrylic acid", "(meth)acrylate", and "(meth)acryloyloxy" are written, unless otherwise specified, they represent "acrylic or methacrylic", "acrylo or methacrylo", "acrylic acid or methacrylic acid", "acrylate or methacrylate", and "acryloyloxy or methacryloyloxy", respectively. In addition, "compound (A) having a polycyclic moiety in which three or more rings are condensed and two or more (meth)acryloyl groups" and "urethane (meth)acrylate (B) having six or more (meth)acryloyl groups" may be abbreviated as "compound (A)" and "urethane (meth)acrylate (B)", respectively.

[0018] <A compound having a polycyclic moiety formed by the fusion of three or more rings and two or more (meth)acryloyl groups> The compound (A) having a polycyclic moiety in which three or more rings are condensed and two or more (meth)acryloyl groups is not particularly limited as long as it is a compound having a polycyclic moiety in which three or more rings are condensed and two or more (meth)acryloyl groups. Examples of the polycyclic moiety in which three or more rings are condensed include aromatic condensed rings such as anthracene skeleton and fluorene skeleton, alicyclic condensed rings such as tricyclodecane skeleton and adamantane skeleton, and heterocyclic condensed rings such as xanthene skeleton and carbazole skeleton. Among them, an alicyclic condensed ring is preferred from the viewpoints of transparency and water vapor barrier property after curing, and a tricyclodecane skeleton is more preferred. Examples of the compound having a tricyclodecane skeleton and two or more (meth)acryloyl groups include tricyclodecanedimethanol (meth)acrylate and (meth)acrylate modified with ethylene glycol or propylene glycol of tricyclodecanedimethanol. Among them, tricyclodecanedimethanol di(meth)acrylate is particularly preferred from the viewpoint of water vapor barrier property. Commercially available products include NK Ester A-DCP, A-BPEF, DCP, etc. manufactured by Shin-Nakamura Chemical Co., Ltd., and AMB-10, AMB-9, etc. manufactured by Essar Trading Co., Ltd., but are not limited thereto. It can be used alone or in combination.

[0019] By containing a polycyclic moiety in which three or more rings are condensed, the movement of water vapor in the hard coat layer is restricted, thereby enhancing the water vapor barrier property. Further, due to the hydrophobicity of the alicyclic condensed ring, the solubility of water vapor in the hard coat layer is reduced, thereby enhancing the water vapor barrier property.

[0020] The content of the compound (A) is 50 to 75% by mass, preferably 55 to 70% by mass, from the viewpoints of water vapor barrier property and adhesion in the nonvolatile content of the active energy ray curable hard coat agent. If it is less than 50% by mass, the water vapor barrier property is poor, and if it exceeds 75% by mass, the abrasion resistance and adhesion are poor. Within the above range, the abrasion resistance and adhesion are good. In particular, even when the film thickness of the hard coat layer is thick, excellent adhesion to the support is exhibited.

[0021] <Urethane (meth)acrylate (B) having 6 or more (meth)acryloyl groups> Urethane (meth)acrylate (B) can be manufactured, for example, by methods 1 to 4 below, but the manufacturing method is not particularly limited. Method 1: A method obtained by reacting polyisocyanate with (meth)acrylates having hydroxyl groups. Method 2: A method obtained by reacting an isocyanate group-containing urethane prepolymer, which is produced by reacting a polyol and a polyisocyanate under conditions of excess isocyanate groups, with a (meth)acrylate having a hydroxyl group. Method 3: A method in which a hydroxyl group-containing urethane prepolymer, obtained by reacting a polyol and a polyisocyanate under conditions of excess hydroxyl groups, is reacted with (meth)acrylates having isocyanate groups. Method 4: A method in which a carboxyl group-containing urethane prepolymer, obtained by reacting a polyol having a carboxyl group with a polyisocyanate under conditions of excess hydroxyl groups, is reacted with an epoxy group-containing (meth)acrylate.

[0022] Commercially available urethane (meth)acrylate (B) products (weight-average molecular weight / (meth)acryloyl group count; catalog value) include EBECRYL 220 (1000 / 6), 1290 (1000 / 6), KRM 8200 (1000 / 6), 8200AE (1000 / 6), and 8904 (1800 / 6) from Daicel-Ornescu, etc., Shiko UV-7605B (1100 / 6), UV-1700B (1800 / 10), UV-7610B (11000 / 9), UV-7630B (2200 / 6), UV-7640B (1500 / 6.5), and UV-6300B (3700 / 7) from Mitsubishi Chemical Corporation, etc., and KAYAR from Nippon Kayaku Co., Ltd. Examples include, but are not limited to, Art Resin manufactured by Negami Kogyo Co., Ltd., such as AD UX-5000 (1500 / 6), UX-5102D-M20 (3,500 / 6), UN-3320HA (1500 / 6), UN-906S (1000 / 6 containing silicone skeleton), and Miramer PU610 (1800 / 6), MU9800 (3500 / 9), SIU2400 (8000 / 10 containing silicone skeleton) manufactured by MIWON Co., Ltd. Acrylate (B) can be used alone or in combination with other ingredients.

[0023] The weight-average molecular weight (sometimes abbreviated as "Mw") of urethane (meth)acrylate (B) is preferably 1600 to 10000 from the viewpoint of scratch resistance, water vapor barrier properties, and adhesion. More preferably, Mw is 1600 to 9000, and even more preferably 1700 to 5000. In this specification, Mw is the converted value to standard polystyrene measured by gel permeation chromatography (GPC) at 40°C using tetrahydrofuran as the eluent.

[0024] Furthermore, from the viewpoint of scratch resistance, it is preferable that the urethane (meth)acrylate (B) includes urethane (meth)acrylate (B-1) having nine or more (meth)acryloyl groups or urethane (meth)acrylate (B-2) having a silicone skeleton.

[0025] The content of urethane (meth)acrylate (B) in the non-volatile components of the active energy ray curable hard coat agent is 10 to 35% by mass, from the viewpoint of water vapor barrier properties and adhesion. Below 10% by mass, scratch resistance and adhesion are poor, and above 35% by mass, water vapor barrier properties are poor. Furthermore, 15 to 30% by mass is more preferable.

[0026] <Inorganic oxide (C)> The active energy ray-curable hard coat agent of the present invention may contain an inorganic oxide (C). The inorganic oxide (C) is not particularly limited as long as it is an inorganic oxide, but it is preferable that it contains at least one element selected from the group consisting of titanium, zinc, zirconium, silicon, and aluminum. In particular, it is preferable that it contains silicon and / or aluminum. Inorganic oxides are more preferable from the viewpoint of scratch resistance. Specifically, examples include titanium oxide, zinc oxide, zirconium oxide, silicon oxide (silica), aluminum oxide, and barium titanate. The surfaces of these inorganic oxides (C) may be treated with organic and / or inorganic materials. Furthermore, two or more types of inorganic oxides (C) may be used in combination.

[0027] Furthermore, the inorganic oxide (C) preferably has a D50 particle size (volume-based median diameter) of 0.005 to 0.500 μm. The D50 particle size of the inorganic oxide (C) is, for example, dynamic Measurements can be taken using the "NanoTrack UPA" manufactured by Nikkiso Co., Ltd., which utilizes light scattering. Within the above range, a highly transparent hard coat layer is more likely to be obtained.

[0028] Furthermore, in terms of the transparency of the hard coat layer, the inorganic oxide (C) is preferably similar in refractive index (nD = approximately 1.46 to 1.52) to that of compound (A) or urethane (meth)acrylate (B). Examples of such inorganic oxides (C) include silica (nD = 1.47). Silica may be used alone, or two or more types, including other inorganic oxides (C), may be used in combination.

[0029] Examples of commercially available silica products include the AEROSIL series manufactured by Nippon Aerosil Co., Ltd. Z (50, 90G, 130, OX50, TT600), manufactured by Nissan Chemical Industries, Ltd.: Organo Silica sol series (MA-ST-M, MA-ST-L, IPA-ST-L, IPA-ST-ZL, MEK-ST-L, MEK-ST-ZL, MIBK-ST-L, MIBK-ST-M, MEK-AC-4130Y, MEK-AC-5140Z, PGM-AC-4130Y, MIBK-SD-L, MEK-ST-2040), Manufactured by CI Kasei Co., Ltd.: Nano Examples include TechSiO2.

[0030] The content of inorganic oxides (C) is not particularly limited, but in terms of the non-volatile content of the active energy ray curable hard coat agent, it is preferably 1 to 20% by mass, more preferably 3 to 18% by mass, and even more preferably 5 to 15% by mass. Within the above range, a hard coat layer with excellent water vapor barrier properties and adhesion is easily obtained.

[0031] <Polymerization initiator (D)> The active energy ray-curable hard coat agent of the present invention may contain a polymerization initiator (D). The polymerization initiator (D) is preferably one that can induce polymerization of (meth)acryloyl groups, etc., by irradiation with active energy rays, and is more preferably a photopolymerization initiator. Examples of polymerization initiators (D) that can be used include monocarbonyl photopolymerization initiators, dicarbonyl photopolymerization initiators, acetophenone photopolymerization initiators, benzoin ether photopolymerization initiators, acylphosphine oxide photopolymerization initiators, and aminocarbonyl photopolymerization initiators.

[0032] Specifically, monocarbonyl photopolymerization initiators include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, and 3,3',4,4'-tetra(t-butylperoxide). Examples include xycarbonyl)benzophenone, 2- / 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0033] Examples of dicarbonyl photopolymerization initiators include 2-ethylanthraquinone, 9,10-phenanthrenequinone, and methyl-α-oxobenzene acetate. Examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, and 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime.

[0034] Examples of benzoin ether-based photopolymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin n-butyl ether.

[0035] Examples of acylphosphine oxide-based photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 4-n-propylphenyl-di(2,6-dichlorobenzoyl)phosphine oxide.

[0036] Examples of aminocarbonyl-based photopolymerization initiators include ethyl-4-(dimethylamino)benzoate, 2-n-butoxyethyl-4-(dimethylamino)benzoate, isoamyl-4-(dimethylamino)benzoate, 2-(dimethylamino)ethylbenzoate, 4,4'-bis-4-dimethylaminobenzophenone, 4,4'-bis-4-diethylaminobenzophenone, and 2,5'-bis(4-diethylaminobenzal)cyclopentanone.

[0037] A commercially available polymerization initiator (D) is Omni from IGM-Resins BV. Examples include rad184, 651, 500, 907, 127, 369, 784, 2959, Esacure One, and Lucilin TPO manufactured by BASF Corporation. In particular, active energy rays From the standpoint of resistance to yellowing after curing, Omnirad184 and EsaCureOne are preferred.

[0038] Polymerization initiators (D) may be used in combination by mixing two or more types. They may also be used in combination with sensitizers.

[0039] The content of polymerization initiator (D) is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass, of the nonvolatile content in the active energy ray curable hard coat agent. Within this range, a hard coat layer with excellent curability and scratch resistance is easily obtained.

[0040] The active energy ray curable hard coat agent of the present invention may also contain compound (E) having a (meth)acryloyl group other than compound (A) and urethane (meth)acrylate (B) (hereinafter sometimes abbreviated as compound (E)).

[0041] For example, compounds having three or more (meth)acryloyl groups include dipentaerythritol (meth)hexaacrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, isocyanuric acid-modified tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and their ethylene-oxy or propyl-oxy modified forms, caprolactone-modified forms, and the like.

[0042] Examples of compounds having two (meth)acryloyl groups include polyethylene glycol diacrylate, polypropylene glycol diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, nonanediol diacrylate, bisphenol A diacrylate, bisphenol F diacrylate, and their ethylene oxy or propyl oxy modified forms.

[0043] Furthermore, examples of monofunctional compounds include alkyl (meth)acrylates such as methyl (meth)acrylate, mono(meth)acrylates having hydroxyl groups at the terminals such as ethylene glycol mono(meth)acrylate and 4-hydroxybutyl (meth)acrylate, mono(meth)acrylates having alkoxy groups at the terminals and polyoxyalkylene chains such as methoxyethylene glycol (meth)acrylate, polyoxyalkylene mono(meth)acrylates having phenoxy or aryloxy groups at the terminals such as phenoxyethylene glycol (meth)acrylate, mono(meth)acrylates having carboxyl groups such as acrylic acid, nitrogen-containing mono(meth)acrylic compounds such as N-methylol (meth)acrylamide, perfluoroalkylalkyl (meth)acrylates having perfluoroalkyl groups with 1 to 20 carbon atoms such as perfluoromethyl (meth)acrylate, alkoxysilyl group-containing vinyl compounds such as γ-(meth)acryloxypropyltrimethoxysilane and their derivatives, and glycidyl group-containing acrylates such as glycidyl acrylate.

[0044] Furthermore, examples of oligomers having a (meth)acryloyl group include (meth)acrylate oligomers, such as polyurethane-based (meth)acrylate oligomers, polyester-based (meth)acrylate oligomers, epoxy-based (meth)acrylate oligomers, Acrylic (meth)acrylates are one example.

[0045] The active energy ray-curable hard coat agent of the present invention may contain a solvent as needed, and may also contain various additives. Examples of additives include polymerization inhibitors, leveling agents, slip agents, defoaming agents, surfactants, antibacterial agents, antiblocking agents, plasticizers, ultraviolet absorbers, infrared absorbers, antioxidants, silane coupling agents, conductive agents, inorganic fillers, pigments, dyes, and the like.

[0046] When a solvent is added, it is preferable to perform curing with active energy rays after the solvent has evaporated when forming the hard coat layer. The solvent is not particularly limited, and various known solvents can be used. Specifically, examples include cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, acetone, acetylacetone, toluene, xylene, n-butanol, isobutanol, tert-butanol, n-propanol, isopropanol, ethanol, methanol, 3-methoxy-1-butanol, 3-methoxy-2-butanol, ethylene glycol monomethyl ether, ethylene glycol mono-n-butyl ether, 2-ethoxyethanol, 1-methoxy-2-propanol, diacetone alcohol, ethyl lactate, butyl lactate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, 2-ethoxyethyl acetate, butyl acetate, tetrahydrofuran, methylpyrrolidone, and the like. It is acceptable to use two or more solvents in combination.

[0047] In this invention, "non-volatile components of the active energy ray-curable hard coat agent" refers to components that remain as constituent elements of the hard coat layer (either in their original state or in a reacted state) at the stage when the hard coat layer is formed (residual components). These residual components are usually the components remaining after the solvent is removed from the active energy ray-curable hard coat agent, but in this specification, they are values ​​measured by Section 2, Residue after heating, of the paint component test method of Japanese Industrial Standard JIS K5601-1-2:2008.

[0048] The active energy ray-curable hard coat agent of the present invention can be applied to a support to obtain an optical component having a hard coat layer. Preferably, the active energy ray-curable hard coat agent of the present invention is applied to a plastic film and used as a hard coat film. If necessary, known functional layers such as a high refractive index layer, a low refractive index layer, a near-infrared absorption layer, and an electromagnetic wave shielding layer may be formed on or below the active energy ray-curable hard coat agent layer of the present invention.

[0049] Methods for forming a hard coat layer include, for example, applying an active energy ray-curable hard coat agent to a support using coating methods such as bar coating, blade coating, spin coating, reverse coating, dyeing, spray coating, roll coating, gravure coating, microgravure coating, lip coating, air knife coating, and dipping, then volatilizing the solvent as needed, and finally irradiating it with active energy rays such as ultraviolet light. Active energy rays include light emitted from light sources such as xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arc lamps, and tungsten lamps, as well as electron beams extracted from electron beam accelerators such as Cockcroff-Warton type, Van de Graaff type, resonant transformer type, insulated core transformer type, linear type, Dynamitron type, and high-frequency type, typically ranging from 20 to 2000 KeV, and radiation such as alpha rays, beta rays, and gamma rays.

[0050] The thickness of the hard coat layer is not particularly limited, but is usually used in the range of 0.5 to 50 μm. However, to meet the recent demand for thinner films in displays and the like, it is preferably 1 μm or more. The thickness is less than 4 μm. Furthermore, if higher water vapor barrier properties are required, the thickness is preferably between 4 μm and 20 μm. Generally, as the thickness of the hard coat layer increases, cracks and delamination from the support become more likely. However, the hard coat layer of the present invention has the characteristic of being less prone to cracking and delamination from the support, even at the above thickness.

[0051] In the present invention, there are no particular limitations on the support (also called the base material), and examples include glass, synthetic resin molded products, and films. Examples of synthetic resin molded products include polymethyl methacrylate resin, copolymer resin mainly composed of methyl methacrylate, polystyrene resin, styrene-methyl methacrylate copolymer resin, styrene-acrylonitrile copolymer resin, polycarbonate resin, cellulose acetate butyrate resin, polyallyl diglycol carbonate resin, polyvinyl chloride resin, and polyester resin.

[0052] Examples of films include polyester film, polyethylene film, polypropylene film, cellophane film, diacetylcellulose film, triacetylcellulose (TAC) film, acetylcellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, polyolefin film, polystyrene film, polycarbonate film, polymethylpentel film, polysulfone film, polyetheretherketone film, polyethersulfone film, polyetherimide film, polyimide film, fluororesin film, nylon film, acrylic film, etc. Among the above films, when TAC film is used, the water vapor barrier It is expected to have particularly excellent properties in terms of durability, scratch resistance, and adhesion. When using a film as a support, so-called easy-adhesion type films, which have a resin layer such as acrylic resin, copolymer polyester resin, polyurethane resin, styrene-maleic acid graft polyester resin, or acrylic graft polyester resin, can also be used.

[0053] The active energy ray curable hard coating agent of the present invention can be suitably used in various applications, such as optical displays like LCDs and OLEDs, and surface coatings for plastic molded products. [Examples]

[0054] The present invention will be described in more detail below with reference to examples, but these examples do not limit the technical scope of the present invention in any way.

[0055] [Example 1] <Manufacturing of activated energy ray polymerizable hard coat agents> In a light-shielded glass bottle, 70 parts by mass of A-DCP (tricyclodecanedimethanol diacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name NK Ester A-DCP) as compound (A), 25 parts by mass of PU610 (manufactured by MIWON, trade name Miramer PU610) as urethane (meth)acrylate (B), and 5 parts by mass of Esacure One (manufactured by DKSH Japan Co., Ltd., trade name Esacure One) as polymerization initiator (D) were added. Furthermore, 35 parts by mass of dimethyl carbonate and 35 parts by mass of 1-methoxy-2-propanol were added as solvents, and the mixture was thoroughly stirred and degassed to obtain an active energy ray polymerizable hard coat agent. The non-volatile content in the hard coat agent was equivalent to the total amount of compound (A), urethane (meth)acrylate (B), and polymerization initiator (D), which was 100 parts by mass.

[0056] <Manufacturing of a hard coat layer formed from an active energy ray-curable hard coat agent and an optical component having a hard coat layer> As a support, a triacetylcellulose film (manufactured by Fuji Photo Film Co., Ltd.) with a thickness of approximately 40 μm was coated with the above-prepared active energy ray-curable hard coat agent using a bar coater #3. After removing the solvent in a hot air oven, the purple light was removed using a high-pressure mercury lamp with an output of 80 W / cm. The coating layer was cured by irradiating it with an external light source, and an optical component having a hard coat layer with a thickness of 2 μm was obtained.

[0057] The adhesion, scratch resistance, and water vapor barrier properties of the optical components with the obtained hard coat layer were evaluated. The results are shown in Table 1.

[0058] Adhesion Test In accordance with JIS K5400 grid pattern peeling method, the hard coat layer was peeled using a utility knife in 1 mm increments. 100 grid-like cuts were made at intervals, cellophane tape (manufactured by Nichiban Co., Ltd.) was applied, and then peeled off in one swift motion. The number of squares (n) of the hard coat layer that remained on the support without peeling off was counted and expressed as n / 100, representing the adhesion level. This adhesion level was evaluated on the following three scales. If the evaluation criteria are ○ or △, it is at a level that does not pose any practical problems. ○: 100 / 100 (No peeling). Good. △:90~99 / 100. Usable ×: Less than 90 / 100. Unavailable.

[0059] 《Abrasion test》 A 1-square-centimeter rectangular pad fitted with #0000 steel wool was placed on the surface of the hard coat layer of the optical component and moved back and forth 10 times under a load of 4.41 N. The appearance was then visually evaluated, and the number of scratches that occurred was measured to determine the abrasion resistance. This abrasion resistance was evaluated on the following four-point scale. An evaluation of ◎, ○, or △ indicates a level that is not problematic for practical use. ◎: 0 pieces (no damage). Excellent condition. ○: 1 to 5 pieces. Good △: 6~20 pieces. Usable ×: More than 20 items. Unusable.

[0060] 《Water vapor barrier properties test 1 (hard coat layer 2 μm)》 The water vapor transmittance of the above optical component was measured using a water vapor transmittance measuring device (manufactured by PARMTRAN MOCON). The measurement was performed in an environment of 40°C and 90% relative humidity. The water vapor transmittance was evaluated in the following three stages. If the evaluation criterion is ○ or △, it is at a level that does not pose a practical problem. ○: 325g / m 2 Less than 24 hours: Good △: 325g / m 2 ·24hr or more 350g / m 2 • Usable for less than 24 hours ×: 350g / m 2 ·Cannot be used for more than 24 hours

[0061] [Example 2] Except for changing the bar coater #3 used in Example 1 to bar coater #12, the same procedure as in Example 1 was performed to obtain an optical component having a hard coat layer with a thickness of 9 μm. The adhesion and scratch resistance of the obtained optical component with the hard coat layer were evaluated in the same manner as in Example 1. For water vapor barrier properties, the water vapor transmittance was measured in the same manner as in Example 1 and evaluated in the following three stages. The results are shown in Table 2.

[0062] 《Water vapor barrier properties test 2 (hard coat layer 9 μm)》 The water vapor barrier performance was measured in the same manner as in Water Vapor Barrier Test 1, and the water vapor transmission rate was evaluated on the following three-point scale. If the evaluation criteria are ○ or △, it is at a level that does not pose a practical problem. ○: 125g / m 2 Less than 24 hours: Good △: 125g / m 2 ·24hr or more 150g / m 2 • Usable for less than 24 hours ×: 150g / m 2 ·Cannot be used for more than 24 hours

[0063] [Examples 3-36], [Comparative Examples 1-12] Optical components having an active energy ray-curable hard coat agent and a hard coat layer were manufactured and evaluated in the same manner as in Examples 1 and 2, according to the compositions shown in Tables 1 and 2. In Tables 1 and 2, unless otherwise specified, the numerical values ​​represent parts by mass (mass%), and blank spaces indicate that the ingredient was not included.

[0064] The materials used in the examples and comparative examples, along with their abbreviations, are shown below. <Compound (A)> A-DCP: Tricyclodecanedimethanol diacrylate, Molecular weight: 304, Manufactured by Shin-Nakamura Chemical Co., Ltd., Trade name: NK Ester A-DCP A-BPEF: 9,9-Bis[4-(2-hydroxyethoxy)phenyl]ful orange acrylate, molecular weight: 546, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name NK Ester A-BPEF)

[0065] <Urethane (meth)acrylate (B)> UN-3320HA: Manufactured by Negami Kogyo Co., Ltd. Mw: 1500, (meth)acryloyl group count: 6, Product name: Art Resin UN-3320HA PU610: Manufactured by MIWON, Mw: 1800, (meth)acryloyl base number: 6, Product name: Miramer PU610) <Urethane (meth)acrylate (B-1)> UV-1700B: (Manufactured by Mitsubishi Chemical Corporation, Mw: 1800, (meth)acryloyl group count: 10, Product name: Shiko UV-1700B) MU9800: Manufactured by MIWON, Mw: 3500, (meth)acryloyl base number: 9, Product name: Miramer MU9800) UV-UV-7610B: (Manufactured by Mitsubishi Chemical Corporation, Mw: 1000, (meth)acryloyl group count: 9, Product name: Shiko UV-7610B) <Urethane (meth)acrylate (B-2)> UN-906S: Manufactured by Negami Kogyo Co., Ltd. Mw: 1000, (meth)acryloyl group count: 6 Product name: Art Resin UN-906S SIU2400: Manufactured by MIWON, Mw: 8000, (meth)acryloyl base count: 10, Product name: Miramer SIU2400)

[0066] <Inorganic oxide (C)> ST-2040: Manufactured by Nissan Chemical Industries, Ltd.: Product name: Organo Silica Sol Series MEK-ST-2040 (particle size 200nm, silica component 40%). Only the silica component amount is listed in the table as mass %.

[0067] <Polymerization initiator (D)> Esacure One: Acetophenone-based photopolymerization initiator. Manufactured by DKSH Japan Co., Ltd. Product name: Esacure One

[0068] <Compound (E)> UV-3310B: Polyurethane-based acrylate oligomer, manufactured by Mitsubishi Chemical Corporation. Mw: 5000, (meth)acryloyl group count: 2, Product name: Shiko UV-3310B M600: Dipentaerythritol hexaacrylate (a compound having 3 or more (meth)acryloyl groups), manufactured by MIWON, molecular weight: 578, number of (meth)acryloyl groups: 6, trade name: Miramer M600

[0069] As shown in Tables 1 and 2, the optical components having a hard coat layer formed using the active energy ray curable hard coat agent of the examples demonstrated excellent adhesion to the support, regardless of the thickness of the hard coat layer, and exhibited superior water vapor barrier properties and scratch resistance. .

[0070] [Table 1]

[0071] [Table 2]

Claims

1. An active energy ray curable hard coating agent for forming a hard coating layer of an optical component having a support and a hard coating layer, An active energy ray-curable hard coat agent comprising a compound (A) having a polycyclic moiety in which three or more rings are fused and two or more (meth)acryloyl groups, and a urethane (meth)acrylate (B) having six or more (meth)acryloyl groups, characterized in that the nonvolatile content of the active energy ray-curable hard coat agent contains 50 to 75% by mass of compound (A) and 10 to 35% by mass of the urethane (meth)acrylate (B).

2. The active energy ray curable hard coat agent according to claim 1, wherein the compound (A) is tricyclodecanedimethanol di(meth)acrylate.

3. The active energy ray curable hard coat agent according to claim 1 or 2, wherein the weight-average molecular weight of the urethane (meth)acrylate (B) is 1600 to 10000.

4. The active energy ray curable hard coat agent according to any one of claims 1 to 3, wherein the urethane (meth)acrylate (B) comprises a urethane (meth)acrylate (B-1) having nine or more (meth)acryloyl groups or a urethane (meth)acrylate (B-2) having a silicone skeleton.

5. Furthermore, the active energy ray curable hard coat agent according to any one of claims 1 to 4, characterized in that it contains 1 to 20% by mass of an inorganic oxide (C) in the nonvolatile content of the active energy ray curable hard coat agent.

6. Furthermore, the active energy ray-curable hard coat agent according to any one of claims 1 to 5 is characterized by containing 1 to 15% by mass of polymerization initiator (D) in the nonvolatile content of the active energy ray-curable hard coat agent.

7. A hard coat layer formed from an active energy ray curable hard coat agent according to any one of claims 1 to 6.

8. An optical member having a support and a hard coat layer according to claim 7.

9. An electronic device comprising the optical member described in claim 8.

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