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

Abstract

To provide an active energy ray curable hard coat agent excellent in transparency, steam barrier property, excoriation resistance, and adhesion to a support, a hard coat layer formed by the active energy ray curable hard coat agent, an optical member having the hard coat layer, and an electronic device.SOLUTION: The active energy ray curable hard coat agent contains: (A) a compound having a polycyclic structure formed by condensating three or more rings and two or more (meth) acryloyl groups; (B) a compound having six or more (meth) acryloyl groups and a weight-average molecular weight of 5000 or lower; (C) an inorganic oxide; and (D) a polymerization initiator. A nonvolatile content of the active energy ray curable hard coat agent contains the compound (A) of 50-75% by mass, the compound (B) of 10-35% by mass, the inorganic oxide (C) of 1-20% by mass, and the polymerization initiator (D) of 0.5-15% by mass.SELECTED DRAWING: None

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, as displays have become thinner, various optical films have been made thinner. 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 susceptible to deterioration due to moisture in the atmosphere, etc., and since the device fabrication involves high-temperature treatment, glass having barrier properties and heat resistance has been used as a member. However, in recent years, there has been a demand in the market for flexible OLED displays. In the case of flexibility, a flexible film that replaces 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 view of such a background, the 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. Also, 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: they lacked sufficient scratch resistance as a hard coat agent required for displays, and the adhesion between the hard coat layer and the support was insufficient. [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 Initiative] [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 coating agent capable of forming a hard coating layer with excellent water vapor barrier properties, scratch resistance, and adhesion to a support. Furthermore, the invention aims to provide a hard coating layer formed from the active energy ray-curable hard coating 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. [1] An active energy ray curable hard coat agent comprising a compound (A) having a polycyclic structure in which three or more rings are fused and two or more (meth)acryloyl groups, a compound (B) having six or more (meth)acryloyl groups and a weight-average molecular weight of 5000 or less, an inorganic oxide (C), and a polymerization initiator (D), An active energy ray-curable hard coat agent characterized in that, in the nonvolatile content of the active energy ray-curable hard coat agent, it contains 50 to 75% by mass of compound (A), 10 to 35% by mass of compound (B), 1 to 20% by mass of inorganic oxide (C), and 0.5 to 15% by mass of polymerization initiator (D). [2] The present invention also relates to the active energy ray curable hard coat agent according to [1], wherein compound (A) is tricyclodecanedimethyl di(meth)acrylate. [3] The present invention also relates to an active energy ray curable hard coat agent as described in [1] or [2], wherein the inorganic oxide (C) is aluminum oxide fine particles having a particle size (D50) of 10 to 90 nm and a particle size (D99) of 150 to 300 nm. [4] The present invention also relates to a hard coat layer formed from an active energy ray curable hard coat agent described in any of [1] to [3]. [5] The present invention also relates to an optical member having a support and a hard coat layer as described in [4]. [6] The present invention also relates to an electronic device comprising the optical member described in [5]. [Effects of the Invention]

[0008] The active energy ray curable hard coating agent of the present invention makes it possible to form a hard coating layer with excellent transparency, water vapor barrier properties, scratch resistance, and adhesion to a support, which are necessary for optical components. Therefore, optical components and electronic devices requiring the above properties can be provided. [Modes for carrying out the invention]

[0009] 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 structure in which three or more rings are fused and two or more (meth)acryloyl groups" and "compound (B) having six or more (meth)acryloyl groups and a weight-average molecular weight of 500 to 5000" may be abbreviated as "compound (A)" and "compound (B)", respectively.

[0010] <A compound having a polycyclic structure in which three or more rings are fused and two or more (meth)acryloyl groups> Compound (A) used in the present invention, which has a polycyclic structure in which three or more rings are fused and two or more (meth)acryloyl groups, is not particularly limited as long as it is a compound having a polycyclic structure in which three or more rings are fused and two or more (meth)acryloyl groups. Examples of polycyclic structures in which three or more rings are fused include aromatic fused rings such as anthracene skeletons and fluorene skeletons, alicyclic fused rings such as tricyclodecane skeletons and adamantane skeletons, and heterofused rings such as xanthene skeletons and carbazole skeletons. Among these, alicyclic fused rings are preferred from the viewpoint of transparency after curing and water vapor barrier properties, and tricyclodecane skeletons are more preferred. Examples of compounds having a tricyclodecane skeleton and two or more (meth)acryloyl groups include tricyclodecane dimethanol (meth)acrylate and (meth)acrylate modified with ethylene glycol or propylene glycol of tricyclodecane dimethanol, but tricyclodecane dimethanol di(meth)acrylate is particularly preferred from the viewpoint of water vapor barrier properties. Commercially available products include, but are not limited to, NK Ester A-DCP, A-BPEF, DCP, etc. from Shin-Nakamura Chemical Co., Ltd., and AMB-10, AMB-9, etc. from SR Trading Co., Ltd. These can be used alone or in combination.

[0011] Compound (A) contains a polycyclic structure in which three or more rings are fused together, thereby restricting the movement of water vapor in the hard coat layer and enhancing its water vapor barrier properties. Furthermore, the hydrophobicity of the alicyclic fused ring reduces the solubility of water vapor in the hard coat layer, further enhancing its water vapor barrier properties.

[0012] The content of compound (A) is 50 to 75% by mass of the nonvolatile content of the active energy ray curable hard coat agent, with 55 to 70% by mass being preferred. Below 50% by mass, the water vapor barrier properties are poor, and above 75% by mass, the scratch resistance and adhesion are poor. Within the above range, the scratch resistance and adhesion are good. In particular, even when the hard coat layer is thick, it shows excellent adhesion to the support.

[0013] <A compound (B) having six or more (meth)acryloyl groups and a weight-average molecular weight of 5000 or less> Compound (B), which has six or more (meth)acryloyl groups and a weight-average molecular weight (hereinafter sometimes referred to as Mw) of 5000 or less, exhibits excellent scratch resistance, water vapor barrier properties, and adhesion due to having six or more (meth)acryloyl groups and an Mw of 5000 or less. Furthermore, an Mw of 4000 or less is more preferable, and an even more preferable of 3000 or less. In this specification, Mw is the converted value of standard polystyrene measured by gel permeation chromatography (GPC) at 40°C using tetrahydrofuran as the eluent.

[0014] Compound (B) can be any compound having six or more (meth)acryloyl groups and a weight-average molecular weight of 5000 or less. Examples include dipentaerythritol hexa(meth)acrylate, and their ethylene-oxy or propyl-oxy modified forms, caprolactone modified forms, etc., as well as polyurethane acrylate, polyester acrylate, polyacrylic acrylate, etc.

[0015] Examples of commercially available products of compound (B) (weight-average molecular weight / (meth)acryloyl group number; catalog value) include Miramer M600 (578 / 6) manufactured by MIWON, EBECRYL 220 (1000 / 6), 1290 (1000 / 6), KRM 8200 (1000 / 6), 8200AE (1000 / 6), and 8904 (1800 / 6) etc. manufactured by Daicel Ornesco as urethane acrylates,紫光UV-7605B (1100 / 6), UV-1700B (1800 / 10), UV-7630B (2200 / 6), UV-7640B (1500 / 6.5), and UV-6300B (3700 / 7) etc. manufactured by Mitsubishi Chemical, KAYARAD UX-5000 (1500 / 6), UX-5102D-M20 (3,500 / 6) etc. manufactured by Nippon Kayaku, Art Resin, UN-3320HA (1500 / 6), UN-906S (1000 / 6 containing silicone skeleton) etc. manufactured by Negami Industry, Miramer PU610 (1800 / 6), MU9800 (3500 / 9) manufactured by MIWON, and EBECRYL 450 (1600 / 6), 846 (110 / 6), 1830 (1500 / 6) etc. manufactured by Daicel Ornesco as polyester acrylates. However, the examples are not limited thereto. Compound (B) can be used alone or in combination.

[0016] From the viewpoint of scratch resistance, dipentaerythritol hexaacrylate or urethane acrylate is preferable for compound (B), and it is more preferable to contain urethane acrylate.

[0017] The content of compound (B) is 10 to 35% by mass in the non-volatile matter of the active energy ray-curable hard coat agent. If it is less than 10% by mass, the scratch resistance and the adhesion to the support are inferior, and if it exceeds 35% by mass, the water vapor barrier property is inferior. Moreover, 15 to 30% by mass is more preferable.

[0018] <Inorganic oxide (C)> The inorganic oxide (C) used in the present invention is not particularly limited as long as it is an inorganic oxide. For example, those containing at least one element selected from the group consisting of titanium, zinc, zirconium, silicon, and aluminum are preferred. Specifically, titanium oxide, zinc oxide, zirconium oxide, silicon oxide (silica), aluminum oxide, barium titanate, etc. can be mentioned. These inorganic oxides (C) may have their surfaces treated with organic substances and / or inorganic substances. Also, two or more kinds of inorganic oxides (C) may be used in combination.

[0019] The content of the inorganic oxide (C) is 1 to 20% by mass, preferably 3 to 15% by mass, and more preferably 5 to 10% by mass in the non-volatile content of the active energy ray curable hard coat agent. When within the above range, a hard coat layer excellent in water vapor barrier property and adhesion to the support can be obtained.

[0020] Also, from the viewpoints of transparency and scratch resistance, the inorganic oxide (C) is preferably aluminum oxide fine particles having a particle diameter (D50) of 10 to 90 nm and a particle diameter (D99) of 150 to 300 nm. Thereby, a hard coat layer excellent in transparency and scratch resistance can be obtained. Also, in order to obtain excellent transparency regardless of the film thickness of the hard coat layer, the particle diameter (D99) is preferably 180 to 290 nm. Further, in order to improve the scratch resistance, the crystal structure of the aluminum oxide fine particles is preferably of the θ type and / or the α type. The particle diameter (D50) and the particle diameter (D99) represent the particle diameters at which the cumulative values are 50% and 99% respectively in the volume-based particle size distribution determined from the particle size distribution measurement values. The dispersed particle size of inorganic oxide fine particles can be determined using a microtrac particle size distribution analyzer that utilizes dynamic light scattering. Examples of microtrac particle size distribution analyzers include the "Nanotrac UPA" manufactured by Nikkiso Co., Ltd. Specifically, an inorganic oxide fine particle dispersion, obtained by dispersing inorganic oxide fine particles in a solvent, can be added to a diluent so that the loading index value is 1.0 and measured. It is preferable to use the same dispersion solvent as the main component of the dispersion solvent for the inorganic oxide fine particles as the diluent, and examples include methyl isobutyl ketone, methyl ethyl ketone, and propylene glycol monomethyl ether. Within the above range, a hard coat layer with excellent transparency can be obtained.

[0021] <Polymerization initiator (D)> The polymerization initiator (D) used in the present invention is preferably one that can induce polymerization of (meth)acryloyl groups, etc., by irradiation with active energy rays, and 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.

[0022] Specifically, examples of monocarbonyl photopolymerization initiators include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2- / 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0023] 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.

[0024] 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.

[0025] Examples of acylphosphine oxide-based photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 4-n-propylphenyl-di(2,6-dichlorobenzoyl)phosphine oxide.

[0026] 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.

[0027] Commercially available polymerization initiators (D) include Omnirad 184, 651, 500, 907, 127, 369, 784, and 2959 from IGM-Resins BV, as well as Esacure One and Lucilin TPO from BASF Ltd. In particular, Omnirad 184 and Esacure One are preferred in terms of resistance to yellowing after active energy ray curing.

[0028] Polymerization initiator (D) may be used in combination of two or more types. It may also be used in combination with a sensitizer.

[0029] The content of polymerization initiator (D) is 0.5 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.

[0030] The active energy ray-curable hard coat agent of the present invention may also contain a compound (E) having a (meth)acryloyl group other than compound (A) and compound (B) (hereinafter sometimes abbreviated as compound (E)).

[0031] Examples of compound (E) include monomers having 1 to 5 (meth)acryloyl groups, oligomers having 2 to 5 (meth)acryloyl groups, and oligomers having 6 or more (meth)acryloyl groups and a weight-average molecular weight exceeding 5000.

[0032] For example, compounds having 3 to 5 (meth)acryloyl groups include 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, and their ethylene-oxy or propyl-oxy modified forms, caprolactone-modified forms, etc.

[0033] 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.

[0034] 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.

[0035] 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, and acrylic-based (meth)acrylates.

[0036] The active energy ray-curable hard coat agent of the present invention may contain a solvent as needed, and may further contain 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.

[0037] When a solvent is added, it is preferable to allow the solvent to evaporate before curing with active energy rays 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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 and less than 4 μm. Furthermore, if higher water vapor barrier properties are required, it is preferably 4 μm or more and 20 μm or less. Generally, as the thickness of the hard coat layer increases, cracks are more likely to occur, delamination from the support becomes more likely, and transparency decreases. However, the hard coat layer of the present invention has the characteristics of high transparency even at the above thickness, and is less prone to cracking and delamination from the support.

[0042] 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.

[0043] 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, and acrylic film. When TAC film is used among the above films, particularly excellent effects in water vapor barrier properties, scratch resistance, and adhesion can be expected. When using a film as a support, so-called easy-adhesion type films, which have a resin layer such as acrylic resin, copolymerized polyester resin, polyurethane resin, styrene-maleic acid graft polyester resin, or acrylic graft polyester resin, can also be used.

[0044] 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]

[0045] 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.

[0046] Measurement of particle size (D50) and (D99) Inorganic oxide dispersions containing dispersed inorganic oxides (C) were measured using a Microtrac particle size distribution analyzer employing dynamic light scattering, by adding them to a diluent so that the loading index value was 1.0. The measurement was performed using the "NanoTrac UPA" Microtrac particle size distribution analyzer manufactured by Nikkiso Co., Ltd., and the diluent used was the same as the main dispersion solvent of the inorganic oxide, depending on the dispersion solvent of the inorganic oxide.

[0047] <Manufacturing of polyfunctional polyester acrylate> (Preparation of polyfunctional polyester acrylate PE1) In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer, 80.0 parts of 3,3',4,4'-biphenyltetracarboxylic dianhydride, 250.0 parts of pentaerythritol triacrylate with a hydroxyl value of 122 mg KOH / g (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD PET-30, containing pentaerythritol tetraacrylate as a by-product), 0.24 parts of methylhydroquinone, and 217.8 parts of cyclohexanone were charged and the mixture was heated to 60°C. Then, 1.65 parts of 1,8-diazabicyclo[5.4.0]-7-undecene was added as a catalyst, and the mixture was stirred at 90°C for 8 hours. Subsequently, 78.3 parts of methacrylate glycidyl ether and 54.0 parts of cyclohexanone were added, followed by 2.65 parts of dimethylbenzylamine as a catalyst. The mixture was stirred at 100°C for 6 hours, and the acid value of the reactants was measured periodically while the reaction continued. When the acid value fell below 5.0 mg KOH / g, the reaction was stopped by cooling to room temperature. The resulting resin varnish was pale yellow and transparent, and was a polyfunctional polyester acrylate PE1 solution, a mixture of polyester acrylate and pentaerythritol tetraacrylate with a solid content of 60% (solid content mass ratio of polyester acrylate:pentaerythritol tetraacrylate = 76:24). Polyfunctional polyester acrylate PE1 had 8 functional groups and a weight-average molecular weight of 3500.

[0048] 《Inorganic oxide (C)》 <Manufacturing of aluminum oxide fine particle dispersions> [Manufacturing Example 1: Aluminum Oxide Microparticle Dispersion (1)] 35 parts of aluminum oxide (1) (θ-type crystalline primary particle size 10 nm), 14 parts of polyfunctional polyester acrylate PE1 (by solid content), 25.5 parts of methyl ethyl ketone and 25.5 parts of methoxybutanol were mixed and stirred with a disperser, and then dispersed using a sand mill to obtain a homogeneous aluminum oxide nanoparticle dispersion (1) containing θ-type crystalline aluminum oxide nanoparticles (C-1). The aluminum oxide nanoparticles (C-1) had a particle size (D50) of 80 nm and a particle size (D99) of 200 nm.

[0049] [Manufacturing Example 2: Aluminum Oxide Microparticle Dispersion (2)] 14.3 parts of aluminum oxide (1), 5.7 parts of polyfunctional polyester acrylate PE1 (by solid content), 40 parts of methyl ethyl ketone as an organic solvent, and 4 parts of methoxybutanol. Except for mixing 0 parts, the dispersion treatment was carried out in the same procedure as in Production Example 1, and the θ-type crystalline aluminum oxide A homogeneous dispersion of aluminum oxide fine particles (2) containing aluminum oxide fine particles (C-2) was obtained. The aluminum nanoparticles (C-2) have a particle size (D50) of 60 nm and a particle size (D99) of 160 nm. It was in nm.

[0050] [Manufacturing Example 3: Aluminum Oxide Microparticle Dispersion (3)] Except for using aluminum oxide (2) (θ-type crystal primary particle size 30 nm), this is manufacturing example 1. Dispersion treatment is performed using the same procedure, and a homogeneous solution containing θ-type crystalline aluminum oxide nanoparticles (C-3) is obtained. A dispersion of aluminum oxide nanoparticles (3) was obtained. Aluminum oxide nanoparticles (C-3) The particle size (D50) was 90 nm, and the particle size (D99) was 280 nm.

[0051] [Manufacturing Example 4: Aluminum Oxide Microparticle Dispersion (4)] Except for using aluminum oxide (3) (α-type crystal primary particle size 30 nm), this is manufacturing example 2. Dispersion treatment is performed using the same procedure, and a homogeneous mixture containing α-type crystalline aluminum oxide nanoparticles (C-4) is formed. A dispersion of aluminum oxide nanoparticles (4) was obtained. Aluminum oxide nanoparticles (C-4) The particle size (D50) was 80 nm, and the particle size (D99) was 200 nm.

[0052] [Manufacturing Example 5: Aluminum Oxide Microparticle Dispersion (5)] Except for using aluminum oxide (4) (γ-type crystal primary particle size 10 nm), this is the same as Manufacturing Example 1. Dispersion treatment is performed using a similar procedure to obtain a homogeneous material containing γ-type crystalline aluminum oxide nanoparticles (C-5). A fine alumina dispersion (5) was obtained. The aluminum oxide fine particles (C-5) had a particle size (D5 The particle size (D99) was 80 nm, and the particle diameter (D99) was 200 nm.

[0053] [Manufacturing Example 6: Aluminum Oxide Microparticle Dispersion (6)] Except for using aluminum oxide (5) (α-type crystal primary particle size 50 nm), this is the same as in Manufacturing Example 2. Dispersion treatment was performed using a similar procedure to obtain a homogeneous mixture containing α-type crystalline aluminum oxide nanoparticles (C'-1). A dispersion of aluminum oxide nanoparticles (6) was obtained. Aluminum oxide nanoparticles (C'-1) The particle size (D50) was 110 nm, and the particle size (D99) was 280 nm.

[0054] [Manufacturing Example 7: Aluminum Oxide Microparticle Dispersion (7)] Except for using aluminum oxide (3) (α-type crystal primary particle size 30 nm), this is the same as Manufacturing Example 1. Dispersion treatment was performed using a similar procedure to obtain a homogeneous mixture containing α-type crystalline aluminum oxide nanoparticles (C'-2). A dispersion of aluminum oxide nanoparticles (5) was obtained. Aluminum oxide nanoparticles (C'-2) The particle size (D50) was 90 nm, and the particle size (D99) was 320 nm.

[0055] <Silica microparticles> Inorganic oxide (C-6): MEK-AC-2140Y (manufactured by Nissan Chemical Corporation, silica nanoparticles, particle size (D50) 20 nm, particle size (D99) 150 nm)

[0056] Table 1 summarizes the types, crystal systems, and average particle sizes of inorganic oxides.

[0057] [Table 1]

[0058] [Example 1] <Manufacturing of activated energy ray polymerizable hard coat agents> In a light-shielded glass bottle, 70 parts by mass of compound (A) A-DCP (tricyclodecanedimethanol diacrylate, manufactured by Shin Nakamura Chemical Industry Co., Ltd., trade name NK Ester A-DCP), 20.8 parts by mass of compound (B) DPHA (manufactured by MIWON, trade name Miramer Mw600), and a dispersion (1) containing aluminum oxide fine particles (C-1) were added so that (C-1) amounted to 3 parts by mass. At this time, the amount of PE1 (polyfunctional polyester acrylate) contained in the dispersion (1) containing aluminum oxide fine particles (C-1) was 1.2 parts by mass and classified as compound (B). Furthermore, 5 parts by mass of Esacure One (manufactured by DKSH Japan Co., Ltd., trade name Esacure One) was added as a polymerization initiator (D), and 35 parts by mass of dimethyl carbonate and 35 parts by mass of 1-methoxy-2-propanol were added as solvents. The mixture was thoroughly stirred and defoamed 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), compound (B), inorganic oxide (C), and polymerization initiator (D), which was 100 parts by mass.

[0059] <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, the active energy ray-curable hard coat agent prepared above was applied to a triacetylcellulose film (manufactured by Fuji Photo Film Co., Ltd.) with a thickness of approximately 40 μm using a bar coater #3. After removing the solvent in a hot air oven, the coating layer was cured by irradiating it with ultraviolet light from a high-pressure mercury lamp with an output of 80 W / cm, and an optical component having a hard coat layer with a thickness of 2 μm was obtained.

[0060] The transparency, 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.

[0061] Transparency (HZ; measurement of haze value) The haze value (Hz) of the low refractive index layer surface was measured using the "Haze Meter SH7000" manufactured by Nippon Denshoku Industries Co., Ltd. △ and ○ indicate levels that are acceptable for practical use. ·〇: 1.5% or less. Good • △: Over 1.5% and under 2.0%. Usable. • ×: 2.0% over the limit. Not practical.

[0062] Adhesion Test Following the JIS K5400 grid peeling method, 100 grid-like cuts were made in the hard coat layer at 1 mm intervals using a utility knife. Cellophane tape (manufactured by Nichiban Co., Ltd.) was applied and peeled off in one swift motion. The number of hard coat layers remaining on the support without peeling (n) was counted and expressed as n / 100 to determine adhesion. This adhesion was evaluated in the following three stages. An evaluation of ○ or △ indicates a level that is acceptable for practical use. ○: 100 / 100 (No peeling). Good. △: 90~99 / 100. Usable. Practical. ×: Less than 90 / 100. Unusable. Not practical.

[0063] 《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.

[0064] 《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 • Less than 24 hours. Usable. ×: 350g / m 2 ·24hr or more. Not available

[0065] [Examples 2-27], [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 Example 1, according to the compositions shown in Tables 2 and 4. In Tables 2 and 4, unless otherwise specified, the values ​​represent parts by mass (mass%), and blank spaces indicate that the agent was not included.

[0066] [Example 29] An active energy ray-curable hard coat agent was prepared in the same manner as in Example 1, according to the composition shown in Table 3. The procedure was the same as in Example 1, except that bar coater #3 used in Example 1 was replaced with bar coater #12, 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.

[0067] 《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 / m2 • Less than 24 hours. Usable. ×: 150g / m 2 ·24hr or more. Not available

[0068] [Examples 30-55], [Comparative Examples 13-24] 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 Example 29, according to the compositions shown in Tables 3 and 4. In Tables 3 and 4, unless otherwise specified, the values ​​represent parts by mass (mass%), and blank spaces indicate that the ingredient was not included.

[0069] [Table 2]

[0070] [Table 3]

[0071] [Table 4]

[0072] 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., Product 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., product name "NK Ester A-BPEF)"

[0073] <Compound (B)> DPHA: Dipentaerythritol hexaacrylate, manufactured by MIWON, molecular weight: 578, number of (meth)acryloyl groups: 6, trade name "Miramer M600" 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" 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" UN-904: Polyurethane-based acrylate oligomer, manufactured by Negami Kogyo Co., Ltd., Mw: 4900, (meth)acryloyl group count: 10, product name "Art Resin UN904" PE1: Polyfunctional polyester acrylate synthesized by the method described above. Mw: 3500, (meth)acryloyl group count: 8

[0074] <Inorganic oxide (C)> (C-1~C-5 and C'-1~2): Aluminum oxide fine particles prepared by the method described above. (C-6): Silica microparticles, 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 %.

[0075] <Polymerization initiator (D)> Esacure One: Acetophenone-based photopolymerization initiator, manufactured by DKSH Japan Co., Ltd., product name "Esacure One"

[0076] <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" UV-7610B: Polyurethane-based acrylate oligomer, manufactured by Mitsubishi Chemical Corporation. Mw: 11000, (meth)acryloyl group count: 9, Product name: "Shiko UV-7610B" UV-7550B: Polyurethane-based acrylate oligomer, manufactured by Mitsubishi Chemical Corporation. Mw: 2400, (meth)acryloyl group count: 3, Product name: "Shiko UV-7550B" TMPTA: Trimethylolpropane triacrylate (a compound with 3 (meth)acryloyl groups), manufactured by MIWON, molecular weight: 296, number of (meth)acryloyl groups: 3, trade name "Miramer M300"

[0077] As shown in Tables 2 and 3, the optical components having a hard coat layer formed using the active energy ray curable hard coat agent of the examples exhibited adhesion to the support regardless of the thickness of the hard coat layer, and demonstrated excellent transparency, water vapor barrier properties, and scratch resistance.

Claims

1. An active energy ray-curable hard coat agent comprising a compound (A) having a polycyclic structure in which three or more rings are fused and two or more (meth)acryloyl groups, a compound (B) having six or more (meth)acryloyl groups and a weight-average molecular weight of 5000 or less, an inorganic oxide (C), and a polymerization initiator (D), wherein the nonvolatile content of the active energy ray-curable hard coat agent comprises 50 to 75% by mass of compound (A), 10 to 35% by mass of compound (B), 1 to 20% by mass of inorganic oxide (C), and 0.5 to 15% by mass of polymerization initiator (D), wherein the inorganic oxide (C) comprises aluminum oxide fine particles with a particle size (D50) of 10 to 90 nm and a particle size (D99) of 150 to 300 nm.

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

3. A hard coat layer formed from the active energy ray curable hard coat agent described in claim 1 or 2.

4. An optical member having a support and a hard coat layer according to claim 3.

5. An electronic device comprising the optical member described in claim 4.

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