JP2012022047A - Hard coat film including diamond fine particle containing silicon and/or fluorine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hard coat film which has excellent scratch resistance and wear resistance, on which fingerprints are hard to be adhered, from which adhered fingerprints are easily wiped away, and which is suitable for protection of various types of displays and the like.SOLUTION: There are provided the hard coat film, in which a hard coat layer including diamond fine particles containing silicon and/or diamond fine particles containing fluorine is formed on a substrate; and the hard coat film, in which a hard coat layer including diamond fine particles containing silicon and fluorine is formed on the substrate.

Description

  The present invention relates to a hard coat film, and more specifically, it has excellent scratch resistance and abrasion resistance, is difficult to adhere fingerprints, and can easily wipe off attached fingerprints, particularly for touch panels, various displays, etc. It is related with the hard coat film suitable for use.

  2. Description of the Related Art In recent years, a touch panel for inputting data by directly touching a display screen with a finger, a pen, or the like is used as an input device for a portable information terminal whose market is increasing. In order to improve the scratch resistance, a transparent protective layer and a hard coat layer are usually formed on the touch panel. Since this hard coat layer is excellent in hardness and slipperiness, it is used for preventing scratches on the surface of the transparent protective layer. Such a hard coat layer is formed by applying a curing material liquid made of an ultraviolet curable material or a thermosetting resin to the surface of the transparent protective layer, and irradiating with light or heating to cure.

  Japanese Patent Application Laid-Open No. 2004-42653 (Patent Document 1) discloses that a hard coat layer includes mica, synthetic mica, silica, alumina, calcium oxide, titania, zirconium oxide, zinc oxide, magnesium fluoride, smectite, synthetic smectite, vermiculite, ITO. A technique of adding inorganic fine particles such as (indium oxide / tin oxide), ATO (antimony oxide / tin oxide), tin oxide, indium oxide, cadmium oxide and antimony oxide is disclosed. Patent Document 1 describes that blocking of the hard coat film can be prevented by adding these inorganic fine particles.

  However, the inorganic fine particles described in Patent Document 1 have a certain effect on the scratch resistance and abrasion resistance, but the effect is reduced when used repeatedly, prevention of fingerprint adhesion, and improvement of fingerprint wiping property. Has little effect. Therefore, it is desired to develop a filler that improves the scratch resistance and wear resistance, as well as prevents the adhesion of fingerprints and improves the wiping property of fingerprints.

  In order to impart antifouling properties and stain removability, it has been practiced to include a silicone compound or a fluorine compound in the hard coat layer to impart water repellency to the hard coat layer surface. However, these silicone compounds and fluorine compounds have the disadvantage that the effects do not last for a long time, and when they are rubbed with a finger or tissue to remove the attached fingerprint, they are mixed with the additive silicone compound or fluorine compound. Accordingly, a wiping mark may remain.

  Japanese Patent Application Laid-Open No. 2004-230562 (Patent Document 2) discloses that at least one surface of a transparent base film is made of a cured product of an ionizing radiation sensitive resin composition, and the contact angle of water on the surface is 70 ° or less. Discloses a hard coat film characterized by having a hard coat layer surface-treated with an alkaline aqueous solution, which is excellent in scratch resistance and wear resistance, and is difficult to attach a fingerprint, and also has an attached fingerprint. It can be easily wiped off. In Patent Document 2, an ionizing radiation-sensitive resin composition is a resin composition that crosslinks and cures when irradiated with ultraviolet rays or an electron beam, and includes a photopolymerizable prepolymer and / or a photopolymerizable monomer. It is described that an aqueous solution containing at least one selected from alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide is generally used as the alkaline aqueous solution.

  However, even the hard coat film described in Patent Document 2 is not sufficiently satisfactory in sustaining the effect, for example, when the effect of preventing adhesion of fingerprints is lost when rubbed strongly.

JP 2004-42653 A JP 2004-230562 A

  Accordingly, an object of the present invention is a hard coat suitable for protecting touch panels, various displays, etc., which has excellent scratch resistance and abrasion resistance, is difficult to adhere fingerprints, and can easily wipe off attached fingerprints. Is to provide a film.

  As a result of diligent research in view of the above object, the present inventors have included in the hard coat film diamond fine particles containing silicon and / or fluorine obtained by siliconizing and / or fluorinating diamond fine particles in the hard coat film. As a result, the inventors have found that the scratch resistance and the wear resistance are drastically improved, and fingerprints are hardly attached, and the present invention has been conceived.

  That is, the hard coat film of the present invention is characterized in that a hard coat layer containing diamond fine particles having silicon and / or diamond fine particles having fluorine is formed on a substrate.

  The hard coat film of the present invention is characterized in that a hard coat layer containing diamond fine particles having silicon and fluorine is formed on a substrate.

  Preferably, the silicon-containing diamond fine particles are siliconized diamond fine particles, and the fluorine-containing diamond fine particles are fluorinated diamond fine particles.

  The diamond fine particles having silicon and fluorine are preferably diamond fine particles that have been siliconized and fluorinated.

  The siliconization treatment is preferably silylation treatment, and the fluorination treatment is preferably treatment with a fluoroalkyl group-containing oligomer.

  The diamond fine particles are preferably nanodiamonds obtained by an explosion method.

  The hard coat layer is preferably formed of a curable material. The curable material is preferably at least one selected from the group consisting of a thermosetting resin, an ultraviolet curable material, an electron beam curable material, and a two-component mixed curable resin.

  The hard coat layer preferably further contains inorganic fine particles. The inorganic fine particles include mica, synthetic mica, silica, alumina, calcium oxide, titania, zirconium oxide, zinc oxide, magnesium fluoride, smectite, synthetic smectite, vermiculite, ITO (indium oxide / tin oxide), ATO (antimony oxide / It is preferably at least one selected from the group consisting of (tin oxide), tin oxide, indium oxide, cadmium oxide and antimony oxide.

  The thickness of the hard coat layer is preferably 0.1 to 50 μm.

  The substrate is preferably made of polyester, acrylic resin, or polyolefin.

  It is preferable that a transparent conductive layer is formed on the surface of the substrate opposite to the surface on which the hard coat layer is formed.

  The hard coat film of the present invention is preferably used for a touch panel.

  The hard coat film of the present invention is suitable for protecting touch panels, various displays, and the like because it has excellent scratch resistance and abrasion resistance, is difficult to adhere fingerprints, and can easily wipe off the attached fingerprints.

It is a schematic cross section which shows an example of the hard coat film of this invention. It is a schematic cross section which shows another example of the hard coat film of this invention.

1. Hard Coat Film As shown in FIG. 1, the hard coat film 1 of the present invention has a hard coat layer 3 containing diamond fine particles 10 formed on a substrate 2, and the diamond fine particles 10 are: Diamond fine particles having silicon, (b) diamond fine particles having fluorine, (c) a mixture of diamond fine particles having silicon and diamond fine particles having fluorine, or (d) diamond fine particles having silicon and fluorine.

(1) Hard coat layer The hard coat layer is a high-hardness layer showing a hardness of 4H or higher in the pencil hardness test shown in JIS K5600-5-4, and is formed of a hardened material (hard coat agent). Alternatively, those formed by laminating a base material and a hard coat layer by coextrusion are preferable.

  The content of the silicon-containing diamond fine particles, fluorine-containing diamond fine particles, and silicon and fluorine-containing diamond fine particles in the hard coat layer is not particularly limited, but is 0.001 to a total for the material forming the hard coat layer. The content is preferably 10% by mass, more preferably 0.01 to 2% by mass. The thickness of the hard coat layer is preferably about 0.1 to 50 μm, more preferably 1 to 30 μm. When diamond fine particles having silicon and diamond fine particles having fluorine are mixed and used, their ratio may be any ratio, but is preferably in the range of 2: 8 to 9: 1, and 3: 7 More preferably, it is in the range of ~ 8: 2.

(a) Method using hardened material (hard coat agent) Hard diamond agent-containing fine particles and / or fluorine-containing diamond fine particles or silicon and fluorine-containing diamond fine particles are dispersed in a hard coat agent or a solution containing a hard coat agent. A coat layer is formed.

  Examples of the hard coating agent include a silicone resin hard coating agent and an organic resin hard coating agent.

  The silicone resin hard coat agent forms a cured resin layer having a siloxane bond, and is a partially hydrolyzed condensate of a compound mainly composed of a compound corresponding to a trifunctional siloxane unit (trialkoxysilane compound or the like). Further, a partial hydrolysis condensate preferably containing a compound corresponding to a tetrafunctional siloxane unit (tetraalkoxysilane compound or the like), a partial hydrolysis condensate filled with metal oxide fine particles such as colloidal silica, and the like. . The silicone resin hard coat agent may further contain a bifunctional siloxane unit and a monofunctional siloxane unit. These include alcohol generated during the condensation reaction (in the case of a partially hydrolyzed condensate of alkoxysilane) and the like, but if necessary, may be dissolved or dispersed in any organic solvent, water, or a mixture thereof. Good. Examples of the organic solvent include lower fatty acid alcohols, polyhydric alcohols and ethers and esters thereof. Note that various surfactants such as siloxane-based and alkyl fluoride-based surfactants may be added to the hard coat layer in order to obtain a smooth surface state.

  Examples of the organic resin hard coat agent include thermosetting resins, ultraviolet curable materials, electron beam curable materials, and two-component mixed curable resins.

  A thermosetting resin is a resin that undergoes a curing reaction due to intermolecular crosslinking under the action of heat and takes an insoluble and infusible three-dimensional network structure. It is an acrylic resin, phenol resin, urea resin, melamine resin, Saturated polyester resin, epoxy resin, silicon resin, polyurethane resin, diallyl phthalate resin and the like can be mentioned.

  Examples of the ultraviolet curable material and the electron beam curable material include monomers or oligomers having two or more, particularly 3 to 6, photopolymerizable functional groups. Examples of the monomer or oligomer include urethane acrylate, epoxy acrylate, polyester acrylate, polyether acrylate, acrylate monomer, and silicon acrylate. The ultraviolet curable material is one that causes polymerization or cross-linking by ultraviolet irradiation among the monomers or oligomers, and the electron beam curable material causes polymerization or cross-linking by electron beam irradiation among the monomers or oligomers. Is. The monomer or oligomer may be one kind, or two or more kinds may be used in combination.

  Examples of the two-component mixed curable resin include epoxy resins and urethane resins.

  Among these hard coat agents, a silicone resin hard coat agent that has excellent long-term durability and a relatively high surface hardness, or an ultraviolet curable acrylic that forms a hard coat layer that is relatively simple and easy to process. Resins are preferred.

  As the silicone resin hard coat agent, either a so-called two-coat type composed of a primer layer and a top layer or a so-called one-coat type composed of only one layer can be selected. As the resin for forming the primer layer (first layer), urethane resin, acrylic resin, polyester resin, epoxy resin, melamine resin, amino resin, polyester acrylate, urethane acrylate, epoxy acrylate, various block isocyanate components and polyol components are used. Various polyfunctional acrylic resins such as phosphazene acrylate, melamine acrylate, and amino acrylate can be used, and these can be used alone or in combination of two or more. Among these, an acrylic resin or a polyfunctional acrylic resin is preferably contained in an amount of 50% by weight, more preferably 50% by weight or more, and an acrylic resin and a urethane acrylate are particularly preferred. These can be applied either by applying a predetermined reaction after application of an unreacted material to obtain a cured resin, or by directly applying the reacted resin to form a cured resin layer. In the latter case, the resin is usually dissolved in a solvent to form a solution, which is then applied and then the solvent is removed. In the former case, a solvent is generally used.

  As a coating method, a method such as a bar coating method, a dip coating method, a flow coating method, a spray coating method, a spin coating method, or a roller coating method is appropriately selected depending on the shape of a molded product to be coated. be able to. Among these, the dip coating method, the flow coating method, and the spray coating method that can easily cope with complicated shapes of molded products are preferable.

  For the hard coat layer, an anion, cationic or nonionic surfactant, light stabilizer or ultraviolet absorber, catalyst, thermal / photopolymerization initiator, polymerization inhibitor, silicone antifoaming agent, leveling as necessary Agents, thickeners, suspending agents, anti-sagging agents, flame retardants, various additives of organic / inorganic pigments / dyes, additive aids, and the like.

(b) A method of laminating and forming a base material and a hard coat layer When a base material and a hard coat layer are laminated and formed, a material for forming the base material described later, diamond fine particles having silicon, and / or A diamond fine particle having fluorine or a material for forming a hard coat layer containing diamond fine particles having silicon and fluorine may be laminated by coextrusion, or each may be extruded to form a single layer sheet, They may be bonded together by dry lamination, thermal lamination or the like. However, the thing laminated | stacked by coextrusion from the point of productivity is preferable. In the case of coextrusion molding, it is not necessary to go through a complicated process (drying process or coating process), so that there is little mixing of external foreign matters such as dust, and excellent optical performance can be exhibited. As a material for forming the hard coat layer, it is preferable to use a material for forming a base material described later.

(c) Properties of Hard Coat Film The hard coat film of the present invention comprises a hard coat layer containing diamond fine particles having silicon and / or diamond fine particles having fluorine or diamond fine particles having silicon and fluorine on a substrate. It is a laminated film having a high surface hardness. By providing a hard coat layer containing diamond fine particles having silicon and / or diamond fine particles having fluorine, or diamond fine particles having silicon and fluorine, the film can have excellent scratch resistance and high hardness, The pencil hardness of the film can be increased, high surface hardness can be realized, fingerprints are difficult to adhere, and attached fingerprints can be easily wiped off. The pencil hardness is a value obtained by a pencil hardness evaluation method specified by JIS K5600-5-4, and is an index for measuring the surface hardness of the film. If the pencil hardness is 4H or more, the film has a sufficient surface hardness, preferably 5H or more.

  The thickness of the hard coat film of the present invention is preferably 50 to 300 μm, more preferably 80 to 260 μm.

(2) Diamond fine particles having silicon, diamond fine particles having fluorine, and diamond fine particles having silicon and fluorine The diamond fine particles having silicon of the present invention, diamond fine particles having fluorine, and diamond fine particles having silicon and fluorine are 10 to Diamond fine particles of about 500 nm are modified with a group containing a silicon atom and / or a group containing a fluorine atom. That is, diamond fine particles having only silicon, diamond fine particles having only fluorine, or diamond fine particles having silicon and fluorine may be used.

  As diamond fine particles for modifying a group containing a silicon atom and / or a group containing a fluorine atom, it is preferable to use nanodiamond obtained by an explosion method. The unpurified nanodiamond obtained by the blasting method has a core / shell structure in which the surface of the nanodiamond is covered with graphite-based carbon, and is colored black. Although unpurified nanodiamonds may be used as they are, in order to obtain a hard-coated film with less coloration, unpurified nanodiamonds are oxidized and used by removing some or almost all of the graphite phase. Is preferred.

  Nanodiamonds obtained by oxidation treatment are secondary particles having a median diameter of 30 to 250 nm (dynamic light scattering method) composed of diamond primary particles of about 2 to 10 nm. By removing the graphite phase, there is almost no coloring component, but because there are hydrophilic functional groups such as -COOH and -OH on the surface of the remaining graphite carbon, a hydrophilic solvent such as water and alcohol. Excellent dispersion.

  Diamond fine particles having silicon, diamond fine particles having fluorine, and diamond fine particles having silicon and fluorine are obtained by converting unpurified nanodiamonds obtained by the above-described explosion method or nanodiamonds obtained by the above oxidation treatment into silicon. A group having a silicon atom and / or a group having a fluorine atom is bonded to a hydrophilic functional group such as —COOH or —OH obtained on the surface of the nanodiamond, which is obtained by fluorination treatment and / or fluorination treatment. Is.

  The amount of silicon atoms in the diamond fine particles having silicon or the diamond fine particles having silicon and fluorine is not particularly limited, but is preferably 0.1 to 25% by mass, and preferably 0.2 to 20% by mass with respect to the diamond fine particles. More preferably. The amount of fluorine atoms in the diamond fine particles having fluorine or the diamond fine particles having silicon and fluorine is not particularly limited, but is preferably 0.1 to 20% by mass, and preferably 0.2 to 15% by mass with respect to the diamond fine particles. Is more preferable.

(3) Substrate The substrate is not particularly limited, and can be appropriately selected from known plastic films as a substrate for optical hard coat films. Examples of such plastic films include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyester films such as polycarbonate, acrylic films such as polymethyl methacrylate, polyethylene, polypropylene, polymethylpentene, and alicyclic structure-containing polymers. Polyolefin films such as cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polysulfone Film, polyetheretherketone film, polyethersulfone film, polyether An imide film, a polyimide film, a fluororesin film, a polyamide film, or the like can be used.

  Among these transparent substrate films, polyester films, acrylic films, and polyolefin films are used as optical film substrates such as touch panel and various display surface protection films from the viewpoint of performance and economy. An alicyclic structure-containing polyolefin film or the like is preferably used for applications that are suitable and particularly require heat resistance.

  These base films may be either transparent or translucent, may be colored, or may be uncolored, and may be appropriately selected depending on the application. When used for protecting a liquid crystal display, a colorless and transparent film is suitable.

  The thickness of these transparent substrate films is not particularly limited and is appropriately selected depending on the situation, but is usually in the range of 15 to 300 μm, preferably 30 to 250 μm. Moreover, this transparent base film can be surface-treated by an oxidation method, an uneven | corrugated method, etc. on one side or both sides as needed for the purpose of improving the adhesiveness with the layer provided in the surface. Examples of the oxidation method include corona discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment and the like, and examples of the unevenness method include a sand blast method and a solvent treatment method. It is done. These surface treatment methods are appropriately selected according to the type of the transparent substrate film, but generally, the corona discharge treatment method is preferably used from the viewpoints of effects and operability.

(4) Inorganic fine particles In addition to diamond fine particles containing silicon, diamond fine particles containing fluorine, or diamond fine particles containing silicon and fluorine, the hard coat layer contains inorganic fine particles for the purpose of increasing hardness and improving scratch resistance. May be included. Examples of the inorganic fine particles include mica, synthetic mica, silica, alumina, calcium oxide, titania, zirconium oxide, zinc oxide, magnesium fluoride, smectite, synthetic smectite, vermiculite, ITO (indium oxide / tin oxide), ATO (antimony oxide). / Tin oxide), tin oxide, indium oxide, cadmium oxide, antimony oxide and the like.

  Among these, mica, synthetic mica, silica, titania, zirconium oxide, magnesium fluoride, smectite, synthetic smectite, ITO (indium oxide / tin oxide), ATO (antimony oxide / tin oxide), tin oxide, vermiculite are preferable, mica, Synthetic mica, smectite, synthetic smectite, and vermiculite are more preferable. One kind of inorganic fine particles may be used, or two or more kinds may be used in combination.

  The average particle size of the inorganic fine particles is preferably 10 to 300 nm, more preferably 10 to 200 nm, and most preferably 30 to 150 nm. When the average particle size is 10 nm or more, a hard coat layer having a smaller surface roughness can be formed. On the other hand, when the average particle size is 300 nm or less, it has better optical properties. A hard coat layer can be formed.

  By using scale-like and / or irregular flake-like inorganic fine particles, a hard coat layer having a better anti-blocking effect can be formed. Examples of the inorganic fine particles having such a shape include those obtained by molding silica, titania, zirconium oxide, ITO and the like into a scale, mica, synthetic mica, smectite, synthetic smectite, vermiculite and the like.

  The content of the inorganic fine particles in the hard coat layer is preferably 0.01 to 6% by weight, and more preferably 0.01 to 5.5% by weight. When the content is 0.01% by weight or more, a bird coat layer having a more excellent anti-blocking effect can be formed. When the content is 6% by weight or less, a hard coat layer having more excellent optical properties can be formed. Can be formed.

(5) Transparent conductive layer As shown in FIG. 2, the transparent conductive layer 4 can be provided on the surface opposite to the surface on which the hard coat layer 3 is formed on the hard coat film. As the transparent conductive layer 5, metal oxides such as tin oxide (SnO ₂ etc.), indium oxide, antimony oxide, zinc oxide (ZnO), cadmium oxide, indium tin oxide (ITO), gold, silver, copper, aluminum , Metal films of tin, nickel and the like. Among them, the metal oxide film is preferable because it grows quickly, and oxides made of a single metal such as ZnO and SnO ₂ are particularly easy to control by the stoichiometric ratio and provide a high-performance thin film. The method for forming the transparent conductive layer is not particularly limited, and examples thereof include a sputtering method, a vacuum deposition method, an ion plating method, a low pressure plasma, a coating method, and an atmospheric pressure plasma CVD method. The thickness of the transparent conductive layer is preferably a thickness where surface resistance is expressed and transparency is maintained. In order to exhibit infrared and electromagnetic wave reduction performance and a visible light transmittance of 60% or more, The film thickness is preferably 30 to 200 nm.

(6) Antireflection layer The hard coat film can be provided with an antireflection layer on the hard coat layer 3 as long as the object of the present invention is not impaired. As the antireflection layer 4, TiO ₂ , ZrO ₂ , SiO ₂ , MgF or the like is used. In order to provide a high-performance antireflection function, it is preferable to use a laminate of a TiO ₂ layer and a SiO ₂ layer. Such laminates, high TiO ₂ layers having a refractive index on the hard coat layer (refractive index: about 1.8-2.1) is formed and a lower SiO ₂ layer having a refractive index in the TiO ₂ layer on the (refractive index: A two-layer laminate formed by forming about 1.4 to 1.5) and a four-layer laminate formed by forming a TiO ₂ layer and an SiO ₂ layer in this order on the _two- layer laminate are preferable. By providing such an antireflection layer of a two-layer laminate or a four-layer laminate, the reflectance of light having a specific wavelength can be lowered.

  When the thickness of the antireflection layer is d, the refractive index is n, and the wavelength of incident light is λ, the relational expression nd = λ / 4 holds between the thickness of the antireflection layer and its refractive index. Is provided with an antireflection layer. When the refractive index of the antireflection layer is smaller than the refractive index of the base material, the reflectance is minimized under the condition that the above relational expression is satisfied. Therefore, if the refractive index n of the obtained antireflection layer is known, the film thickness d can be determined by the film formation speed and the processing time in the production of the antireflection layer, and the wavelength λ (monochromatic light) of the specific incident light. On the other hand, the reflectance can be minimized.

  When forming the antireflection layer with two or more thin films, the uppermost layer (surface layer) should be near the λ / 4 film of the low refractive index material, and the high refractive index material and low refractive index should be It is preferable to arrange them alternately. Here, the film thickness of the second and subsequent layers from the surface is set so that the reflectance at a wavelength of 450 to 650 nm is small, and it is in balance with the refractive index, but generally has a thickness of λ / 2 film or less. Thereby, the wavelength range of low reflection can be expanded compared with a single-layer antireflection layer.

  The method for laminating the antireflection layer is not particularly limited, and examples thereof include sputtering, vapor deposition, low pressure plasma CVD, and coating. The atmospheric pressure plasma CVD method is preferable.

2. Diamond fine particles containing silicon, diamond fine particles containing fluorine, and diamond fine particles containing silicon and fluorine. Diamond fine particles containing silicon, diamond fine particles containing fluorine, and diamond fine particles containing silicon and fluorine are siliconized diamond fine particles. It can be obtained by treatment and / or fluorination treatment. The siliconization treatment is preferably performed prior to the fluorination treatment.

[1] Method for producing diamond fine particles As diamond fine particles, unpurified nanodiamond (sometimes referred to as BD) obtained by an explosion method, or a part or all of graphite-based carbon by oxidizing it. The removed nanodiamond is preferred. The nanodiamond obtained by the oxidation treatment is preferably nanodiamond from which a part of the graphite phase described later is removed (referred to as graphite-diamond particles) and purified nanodiamond particles from which the graphite phase is almost removed.

The specific gravity of the oxidized nanodiamond approaches the specific gravity of diamond (3.50 g / cm ³ ) as the residual amount of graphite-based carbon (graphite specific gravity: 2.25 g / cm ³ ) decreases. Therefore, the specific gravity increases as the degree of purification increases and the remaining amount of graphite carbon decreases. The specific gravity of the nano diamond used in the present invention is preferably 2.55 g / cm ³ (24% by volume of diamond) or more and 3.48 g / cm ³ (98% by volume of diamond) or less, 3.0 g / cm ³ (84% by volume of diamond). It is more preferably 3.46 g / cm ³ (diamond 97% by volume) or less, and most preferably 3.38 g / cm ³ (diamond 90% by volume) or more and 3.45 g / cm ³ (diamond 96% by volume). . The volume percentage of diamond in the nanodiamond was calculated from the specific gravity of the nanodiamond using the specific gravity of the diamond of 3.50 g / cm ³ and the specific gravity of graphite of 2.25 g / cm ³ .

  Oxidation treatment of unpurified crude diamond includes (a) high-temperature and high-pressure treatment in the presence of nitric acid (oxidation treatment A), and (b) treatment in a supercritical fluid composed of water and / or alcohol. (Oxidation treatment B), (c) A method in which oxygen is present in a solvent consisting of water and / or alcohol, and the treatment is performed at a temperature not lower than the normal boiling point of the solvent and at a pressure not lower than 0.1 MPa (gauge pressure) (oxidation treatment C). ) Or (d) a method (oxidation treatment D) in which treatment is performed with a gas containing oxygen at 380 to 450 ° C. These oxidation treatments may be performed alone or in combination. When combining the oxidation treatment, it is preferable to first subject the unpurified crude diamond obtained by the explosion method to oxidation treatment A, and then to any one of oxidation treatments B to C.

  By applying oxidation treatment A to the unpurified crude diamond obtained by the explosion method, nanodiamonds (graphite-diamond particles) from which a part of the graphite phase has been removed are obtained. The graphite phase can be further removed by performing any one of the processes of ~ C.

(1) Synthesis of BD by explosion method BD synthesis by explosion method is, for example, explosives in which an electric detonator is mounted on a pressure vessel made of pure titanium filled with water and a large amount of ice [for example, TNT (trinitrotoluene ) / HMX (Cyclotetramethylenetetranitramine) = 50/50] is stored in the body, a steel pipe with a single-sided plug is submerged horizontally, and this steel pipe is covered with a steel helmet-like cover. This can be done by exploding the explosive. BD as a reaction product is recovered from water and ice in the container.

  The above-mentioned explosion method is described in Science, Vol. 133, No. 3467 (1961), pp 1821-1822, JP-A No. 1-234311, JP-A No. 21-14414, Bull. Soc. Chem. Fr. Vol. 134 (1997). ), pp. 875-890, Diamond and Related materials Vol. 9 (2000), pp861-865, Chemical Physics Letters, 222 (1994), pp. 343-346, Carbon, Vol. 33, No. 12 (1995) , pp. 1663-1671, Physics of the Solid State, Vol. 42, No. 8 (2000), pp. 1575-1578, K. Xu. Z. Jin, F. Wei and T. Jiang, Energetic Materials, 1 , 19 (1993), JP-A-63-303806, JP-A-56-26711, British Patent No. 1154633, JP-A-3-271109, JP-A-6-505694 (WO93 / 13016), Carbon , Vol. 22, No. 2, 189-191 (1984), Van Thiei. M. & Rec., FH, J. Appl. Phys. 62, pp. 1761-1767 (1987), 7-1-1 No. 505831 (WO94 / 18123), US Pat. No. 5,861,349, JP-A-2006-239511, and the like can be used.

(2) Oxidation process
(i) Oxidation treatment A
The unpurified crude diamond (BD) obtained by the explosion method is preferably first subjected to oxidation treatment A. By performing the oxidation treatment A, graphite-diamond particles from which a part of the graphite phase has been removed can be obtained. Oxidation treatment A consists of (a) a process in which BD obtained by the explosion method is subjected to an oxidative decomposition process in an acid, and (b) an oxidative etching process in which the BD that has been subjected to an oxidative decomposition process is processed under more severe conditions , (C) a step of neutralizing the solution after the oxidative etching treatment, (d) a desolvation step, and (e) a washing step, and (f) pH and concentration of the graphite-diamond particle dispersion as necessary. Or (g) a step of drying into a fine powder.

(a) Oxidative decomposition treatment process Collected BD together with 55-56 mass% concentrated nitric acid or a mixture of concentrated nitric acid and concentrated sulfuric acid at a pressure of about 1.4 MPa and a temperature of about 150-180 ° C for 10-30 minutes Process and decompose impurities such as mixed metal such as electric detonator, carbon and other impurities.

(b) Oxidative Etching Process Step The BD subjected to the oxidative decomposition treatment is performed under concentrated conditions (for example, 1.4 MPa, 200 to 240 ° C.) in concentrated nitric acid. When treated for 10 to 30 minutes under such conditions, most of the hard carbon, ie, graphite, covering the BD surface can be removed.

(c) Neutralization process Neutralization reaction by adding a volatile basic substance itself or its decomposition product to an aqueous nitric acid solution (pH 2 to 6.95) containing graphite-diamond particles after oxidative etching. Let The pH rises to 7.05-12 by the addition of basic substances. By using the basic substance, the base that has penetrated into the agglomerated graphite-diamond particles reacts with nitric acid in the particles and gasifies to break up the agglomerates into individual graphite-diamond particles. Is obtained. This process seems to form a large specific surface area and pore adsorption space of graphite-diamond particles.

  Basic materials include ammonia, hydrazine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethanolamine, propylamine, isopropylamine, dipropylamine, allylamine, aniline, N, N-dimethylaniline, diisopropylamine. And polyalkylene polyamines such as diethylenetriamine and tetraethylenepentamine, 2-ethylhexylamine, cyclohexylamine, piperidine, formamide, N, N-methylformamide, urea and the like.

(d) Desolvation step The obtained liquid containing graphite-diamond particles is preferably desolvated by centrifugation, decantation or the like.

(e) Water washing step The desolvated graphite-diamond particles are preferably washed by decantation. The washing operation is preferably performed three times or more. The graphite-diamond particles washed with water are preferably centrifuged again and dehydrated.

(f) Step of adjusting pH and concentration The graphite-diamond particle dispersion is adjusted to pH 4 to 10, preferably pH 5 to 8, more preferably pH 6 to 7.5. The graphite-diamond particle concentration is preferably adjusted to 0.05 to 16%, preferably 0.1 to 12%, more preferably 1 to 5%.

  It is preferable that the nanodiamond having graphite phase (graphite-diamond particles) is further subjected to oxidation treatments B to D to further remove the graphite layer. Of course, BD may be directly subjected to oxidation treatments B to D.

(ii) Oxidation treatment B
Oxidation treatment B prepares a mixture A (sometimes referred to simply as “mixture A”) comprising (a) a nanodiamond having a graphite phase, an oxidizing compound, and a solvent comprising water and / or alcohol; (b) Treating this mixture A with nanodiamond having a graphite phase in a state where the temperature and pressure are higher than the critical point of the solvent, and (c) centrifuging the resulting liquid containing purified diamond particles to remove the solvent. Removing. Furthermore, it is preferable to provide a step (d) of dewatering the purified diamond particles that have been desolvated by water washing and centrifugation. Between steps (c) and (d), if necessary, a step of neutralizing the desolvated purified diamond particles with (e) a basic solution and a step of (f) treating with a weak acid may be provided . The refined diamond particles obtained in step (c) or (d) are dried to a fine powder.

(a) Preparation Step of Mixture A Mixture A is prepared by mixing nanodiamond powder having a graphite phase with an oxidizing compound and a solvent composed of water and / or alcohol. Alternatively, the oxidizing compound or a solution thereof may be added to a liquid in which nanodiamond having a graphite phase is dispersed in advance in the solvent. In order to promote the oxidation reaction by the oxidizing compound, a basic compound or an oxidizing compound may be added to the mixture A.

  Examples of oxidizing compounds include nitric acid, hydrogen peroxide, sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, sodium hypochlorite, potassium hypochlorite, sodium chlorite, chlorite Potassium, lithium chlorate, sodium chlorate, potassium chlorate, lithium perchlorate, sodium perchlorate, potassium perchlorate, sodium permanganate, potassium permanganate, sodium manganate, potassium manganate, sodium persulfate Potassium persulfate, potassium dichromate, potassium chromate and the like, and nitric acid and hydrogen peroxide are preferred. In particular, when an oxidizing compound is used alone, it is most preferable to use hydrogen peroxide.

  Acidic compounds include inorganic acids such as nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, boric acid, hydrofluoric acid, hydrobromic acid, and organic acids such as formic acid, acetic acid, methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid. An acid is mentioned, An inorganic acid is preferable and nitric acid is more preferable.

  Basic compounds include lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, lithium tetraborate, sodium tetraborate, potassium tetraborate , Ammonia and the like.

  A combination of hydrogen peroxide and nitric acid is preferable when using a combination of an oxidizing compound and an acidic compound, and a combination of hydrogen peroxide and ammonia is used when a combination of an oxidizing compound and a basic compound is used. Is preferred.

  As the solvent, water, alcohol or a mixture thereof is used. The alcohol is preferably a lower alcohol having 1 to 3 carbon atoms. Specific examples of the lower alcohol include methanol, ethanol, n-propanol, isopropanol, and a mixture thereof.

(b) Supercritical processing step Mixture A is processed at a temperature and pressure above the critical point of the solvent. The treatment temperature is preferably not lower than the critical temperature of the solvent and not higher than 600 ° C., more preferably not higher than 550 ° C. The treatment pressure is preferably not less than the critical pressure of the solvent and not more than 100 MPa, more preferably not more than 70 MPa, and most preferably not more than 50 MPa. The treatment time may be appropriately set depending on the temperature and pressure, but is preferably 1 to 24 hours.

(c) Desolvation step Performed in the same manner as oxidation treatment A.

(d) Washing step Performed in the same manner as oxidation treatment A.

(e) Neutralization step The purified diamond particles removed in the step (c) may be neutralized with a base such as sodium hydroxide or potassium hydroxide. The concentration of the basic solution is preferably 0.01 to 0.5 mol / L. It is preferable to add a basic solution to the purified diamond particles from which the solvent has been removed, followed by ultrasonic treatment.

(f) Weak acid treatment step The purified diamond particles neutralized in step (e) are preferably washed with a weak acid solution. An example of a weak acid solution is 0.01 to 0.5 mol / L hydrochloric acid. It is preferable to add a weak acid solution to the neutralized purified diamond particles and sonicate.

(iii) Oxidation treatment C
The oxidation treatment C comprises (a) preparing a mixture B composed of nanodiamond having a graphite phase and a solvent composed of water and / or alcohol, and (b) treating the solvent in a state where oxygen is present in the mixture B. (C) a step of removing the solvent by centrifuging the liquid containing the purified diamond particles and treating the nanodiamond having a graphite phase at a temperature higher than the normal boiling point and a pressure of 0.1 MPa (gauge pressure) or higher. Have. Further, it is preferable to provide (d) a step of dewatering the purified diamond particles that have been subjected to the detreatment solvent by water washing and centrifugation. The refined diamond particles obtained in step (c) or (d) are dried to a fine powder.

(a) Preparation Step of Mixture B The mixture B is prepared by mixing nanodiamond having a graphite phase and a solvent composed of water and / or alcohol. The concentration of the nanodiamond having a graphite phase in the mixture B is preferably 0.05 to 16% by mass, more preferably 0.1 to 12% by mass, and most preferably 1 to 10% by mass. If this concentration exceeds 16% by mass, purification may be insufficient. On the other hand, if it is less than 0.05% by mass, the ratio of loss at the time of recovery increases and productivity deteriorates.

  As the solvent, the same solvents that can be used in the preparation of the mixture A can be used.

(b) Purification treatment step Mixture B is placed in an autoclave and oxygen is introduced. The amount of oxygen introduced is preferably 0.1 mol or more, more preferably 0.15 mol or more, and most preferably 0.2 mol or more with respect to 1 g of graphite in the nanodiamond having a graphite phase. The upper limit of the introduction amount is not particularly limited.

  The temperature and pressure in the autoclave are adjusted so that the standard boiling point Tb and 0.1 MPa (gauge pressure) of the processing solvent will be exceeded. As long as the processing solvent is Tb or higher and 0.1 MPa (gauge pressure) or higher, the processing solvent is in a subcritical state [temperature of Tb or higher and pressure of 0.1 MPa (gauge pressure) or lower, and / or lower than the critical temperature Tc. It may be in a state less than Pc] or in a supercritical state. The graphite phase can be efficiently selectively oxidized by subcritical or supercritical oxygen and the processing solvent.

  The lower limit of the treatment temperature is preferably (critical temperature of treatment solvent Tc-150 ° C), more preferably (Tc-100 ° C). The upper limit of the treatment temperature is preferably 800 ° C, more preferably 600 ° C. The lower limit of the processing pressure is preferably 30% of the critical pressure Pc of the processing solvent, more preferably 50% of Pc, and most preferably 70% of Pc. The upper limit of the treatment pressure is preferably 70 MPa, more preferably 50 MPa. The treatment time may be appropriately set depending on the temperature and pressure, but is preferably 0.1 to 24 hours.

(c) Desolvation step Performed in the same manner as oxidation treatment A.

(d) Washing step Performed in the same manner as oxidation treatment A.

(iv) Oxidation treatment D
The oxidation treatment D includes a step of putting nanodiamond having the graphite phase into a reaction tube and heating to 380 to 450 ° C. while flowing a gas containing oxygen under normal pressure. The heating temperature is preferably 400 to 430 ° C. As the gas containing oxygen, oxygen gas, air, or the like can be used, but air is preferable for simplicity.

(3) Media dispersion treatment BD or graphite-diamond particles are pulverized by a known media dispersion method such as a bead mill before oxidation treatment B to D in order to efficiently carry out oxidation treatment and obtain purified diamond particles with less coloring. Is preferred. For dispersion by a bead mill, zirconia beads are preferably used. By dispersing the media of BD or graphite-diamond particles, the median diameter is preferably 100 nm or less, more preferably 50 nm or less, and most preferably 30 nm or less.

[2] Siliconation treatment By reacting unpurified nanodiamond obtained by the above-mentioned explosion method or nanodiamond obtained by the above oxidation treatment with a silylating agent, alkoxysilane, silane coupling agent, or the like. A hydrophilic group such as a hydroxyl group on the surface of the nanodiamond can be substituted with an organic group containing silicon. In the siliconization treatment, a silylating agent is preferably used.

  Preferred silylating agents include triethylchlorosilane, trimethylchlorosilane, diethyldichlorosilane, dimethyldichlorosilane, acetoxytrimethylsilane, acetoxysilane, diacetoxydimethylsilane, methyltriacetoxysilane, phenyltriacetoxysilane, diphenyldiacetoxysilane, trimethylethoxy Silane, trimethylmethoxysilane, 2-trimethylsiloxypent-2-en-4-one, n- (trimethylsilyl) acetamide, 2- (trimethylsilyl) acetic acid, n- (trimethylsilyl) imidazole, trimethylsilylpropiolate, nonamethyltrisilazane , Hexamethyldisilazane, hexamethyldisiloxane, trimethylsilanol, triethylsilanol, triphenylsilanol, t-butyldimethylsilane Examples include lanol and diphenylsilanediol. The silylating agent used in the present invention is not limited to these compounds.

  The solvent of the silylating agent solution is preferably a hydrocarbon such as hexane, cyclohexane, pentane or heptane, a ketone such as acetone or methyl isobutyl ketone, or an aromatic compound such as benzene or toluene.

  Although depending on the type and concentration of the silylating agent, the silylation reaction is preferably allowed to proceed at 10 to 40 ° C. with sufficient stirring. If it is less than 10 ° C., the reaction hardly proceeds, and if it exceeds 40 ° C., it is not uniformly silylated on the nanodiamond surface. For example, when a hexane solution of triethylchlorosilane is used as a silylating agent, the hydroxyl group on the surface of the nanodiamond is sufficiently silyl modified by reacting at 10 to 40 ° C. with stirring for about 10 to 40 hours.

[3] Fluorination treatment The unpurified nanodiamond obtained by the explosion method or the nanodiamond obtained by the oxidation treatment is a method using a fluoroalkyl group-containing oligomer, a method of directly reacting with fluorine gas, The surface can be modified with fluorine or a fluorine-containing group by a method using fluorine plasma or the like.

(1) Method using a fluoroalkyl group-containing oligomer A polymer surfactant (fluorinated oligomer) in which a fluoroalkyl group is directly introduced into both ends of a polymer main chain by a carbon-carbon bond is used in an aqueous solution or an organic solvent. It is known to form nano-level molecular assemblies that are self-assembled therein. By using this fluorine-containing oligomer having a fluoroalkyl group introduced at the terminal, nanodiamonds modified with a fluoroalkyl group can be formed.

  For nanodiamonds modified with a fluoroalkyl group, unpurified nanodiamonds obtained by the explosion method or nanodiamonds obtained by the oxidation treatment are treated with a fluorine-containing oligomer represented by the general formula (1). Can be obtained.

Here, R _F is a fluoroalkyl group, specifically, a group such as —CF (CF ₃ ) OC ₃ F ₇ , —CF (C ₃ F) OCF ₂ CF (CF ₃ ) OC ₃ F _7, etc. preferable. R is a substituent, and groups such as —N (CH ₃ ) ₂ , —OH, —NHC (CH ₃ ) ₂ CH ₂ C (═O) CH ₃ , —Si (OCH ₃ ) ₃ , —COOH, etc. are preferred. . n is preferably 5 to 2000.

The nano-diamond and the fluorine-containing oligomer represented by the general formula (1) are mixed in an alcohol solvent such as methanol and ethanol, and stirred at room temperature to 80 ° C. for 2 to 48 hours to form a fluoroalkyl group ( Composite particles modified with R _F ) can be obtained in high yield. To accelerate the reaction, a base such as ammonia may be used.

(2) Method of reacting directly with fluorine gas The method of reacting directly with fluorine gas is to mix a mixed gas of fluorine gas and inert gas such as argon in a reaction tube (made of nickel, etc.) containing nano diamond. It is carried out by flowing at a temperature of 10 to 500 hours.

  The fluorine content of the fluorinated diamond fine particles is preferably 0.1 to 20 wt%, and preferably 0.2 to 15 wt%. When the fluorine content is less than 0.1 wt%, compatibility with the resin is reduced when a fluorine-containing polymer resin is used. When the fluorine content is 20 wt% or more, the compatibility with non-fluorinated solvents and additives decreases.

  The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Example 1
(1) Fabrication of nano diamond
An atmosphere for storing BD produced by detonating 0.65 kg of explosives containing TNT (trinitrotoluene) and RDX (cyclotrimethylenetrinitroamine) in a ratio of 60/40 in a 3 m ³ explosion chamber. After formation, BD was synthesized by causing a second explosion under the same conditions. After the explosion product expanded and reached thermal equilibrium, the gas mixture was allowed to flow out of the chamber for 35 seconds through a supersonic Laval nozzle with a 15 mm cross section. Due to the heat exchange with the chamber walls and the work done by the gas (adiabatic expansion and vaporization), the product cooling rate was 280 ° C./min. The product (black powder, BD) captured by the cyclone had a specific gravity of 2.55 g / cm ³ and a median diameter (dynamic light scattering method) of 220 nm. This BD was calculated from specific gravity, and was estimated to be composed of 76% by volume of graphite-based carbon and 24% by volume of diamond.

This BD was mixed with a 60% by mass nitric acid aqueous solution, subjected to an oxidative decomposition treatment at 160 ° C. and 14 atm for 20 minutes, and then an oxidative etching treatment at 130 ° C. and 13 atm for 1 hour. Particles from which graphite was partially removed from BD were obtained by oxidizing etching treatment. The particles were refluxed with ammonia at 210 ° C., 20 atm for 20 minutes, neutralized, then naturally settled, washed with 35% by mass nitric acid by decantation, and further washed with water three times by decantation. The powder was dehydrated by centrifugation and dried by heating at 120 ° C. to obtain nanodiamond powder having a graphite phase. The specific gravity of the nanodiamond powder was 3.38 g / cm ³ and the median diameter was 5.5 μm (dynamic light scattering method). Calculated from the specific gravity, it was estimated to be composed of 90 vol% diamond and 10 vol% graphite carbon.

(2) Siliconation treatment The obtained nanodiamond powder was dispersed in methyl isobutyl ketone at a concentration of 3% by mass, and a methyl isobutyl ketone solution of trimethylchlorosilane (concentration 7.5% by mass) was added at a volume of 1: 1. The nanodiamond was modified with trimethylsilane by stirring for a period of time. The obtained dispersion was washed with methyl isobutyl ketone and then dried to obtain trimethylsilane-modified nanodiamond powder.

(3) Production of Hard Coat Film A sheet in which a 20 nm ITO layer was formed by sputtering on the surface of a polyethylene terephthalate film (Toyobo Co., Ltd., O-PET, 75 μm) as a base film was obtained as an upper electrode. The surface resistivity of the upper electrode was 300 Ω / cm ² .

As a hard coating agent, 100 parts by weight of a polyfunctional acrylate (manufactured by Dainichi Seika Co., Ltd., EXF37), 10 parts by weight of colloidal silica (manufactured by Toshiba Silicone, UVHC-1105), and 3 mass of the resulting trimethylsilane-modified nanodiamond powder The mixed solution was adjusted by diluting with toluene so that the mixed solution content was 40%. The hard coat agent was applied by a bar coater to the side having no upper electrode of the sheet on which the ITO layer had been formed, dried by heating, and then irradiated with an ultraviolet lamp at 300 MJ / cm ² to a thickness of 5 μm. A hard coat layer was prepared. The surface of the obtained hard coat film was subjected to corona discharge treatment four times at 0.6 kW and 3 m / min.

Example 2
(1) Fluorination treatment The nanodiamond powder prepared in Example 1 was dispersed in methanol at a concentration of 3% by mass, and the following formula:

(R _F is —CF (CF ₃ ) OC ₃ F ₇ group, R is —OH group, and n is about 800.) The fluorine-containing oligomer represented, and 28% by mass of ammonia water were added to the nanodiamond dispersion 100. 50 parts by mass and 10 parts by mass were added to each part by mass, and the mixture was stirred at 80 ° C. for 20 hours for reaction. The obtained dispersion was neutralized, washed and dried to obtain composite particles in which the nanodiamond surface was modified with a fluoroalkyl group.

(2) Production of Hard Coat Film A hard coat film was produced in the same manner as in Example 1 except that a fluoroalkyl group-modified nanodiamond powder was used instead of the trimethylsilane-modified nanodiamond powder.

Example 3
Preparation of Hard Coat Film Instead of trimethylsilane-modified nanodiamond powder, the trimethylsilane-modified nanodiamond powder prepared in Example 1 and the fluoroalkyl group-modified nanodiamond powder prepared in Example 2 were mixed at a mass ratio of 6: 4. A hard coat film was produced in the same manner as in Example 1 except that the mixed powder was used.

Example 4
(1) Siliconation and fluorination Using the trimethylsilane-modified nanodiamond dispersion prepared in Example 1, the nanodiamond surface was modified with a fluoroalkyl group in the same manner as in Example 2, and the nanodiamond surface was trimethylsilane. And composite particles modified with fluoroalkyl groups were obtained.

(2) Production of Hard Coat Film A hard coat film was produced in the same manner as in Example 1, except that trimethylsilane and fluoroalkyl group-modified nanodiamond powder were used instead of trimethylsilane-modified nanodiamond powder.

Claims (15)

  A hard coat film having a hard coat layer formed on a substrate, wherein the hard coat layer contains diamond fine particles having silicon and / or diamond fine particles having fluorine.   A hard coat film in which a hard coat layer is formed on a substrate, wherein the hard coat layer contains diamond fine particles having silicon and fluorine.   2. The hard coat film according to claim 1, wherein the silicon-containing diamond fine particles are silicon-treated diamond fine particles, and the fluorine-containing diamond fine particles are fluorinated diamond fine particles. Coat film.   The hard coat film according to claim 2, wherein the diamond fine particles having silicon and fluorine are diamond fine particles that have been subjected to siliconization treatment and fluorination treatment.   The hard coat film according to claim 3 or 4, wherein the siliconization treatment is a silylation treatment.   The hard coat film according to claim 3, wherein the fluorination treatment is treatment with a fluoroalkyl group-containing oligomer.   The hard coat film according to claim 1, wherein the diamond fine particles are nanodiamonds obtained by an explosion method.   The hard coat film according to claim 1, wherein the hard coat layer is formed of a curable material.   9. The hard coat film according to claim 8, wherein the curable material is at least one selected from the group consisting of a thermosetting resin, an ultraviolet curable material, an electron beam curable material, and a two-component mixed curable resin. A hard coat film characterized by   The hard coat film according to claim 1, wherein the hard coat layer further contains inorganic fine particles.   The hard coat film according to claim 10, wherein the inorganic fine particles are mica, synthetic mica, silica, alumina, calcium oxide, titania, zirconium oxide, zinc oxide, magnesium fluoride, smectite, synthetic smectite, vermiculite, ITO (oxidation). A hard coat film, which is at least one selected from the group consisting of indium / tin oxide), ATO (antimony oxide / tin oxide), tin oxide, indium oxide, cadmium oxide and antimony oxide.   The hard coat film according to claim 1, wherein the hard coat layer has a thickness of 0.1 to 50 μm.   The hard coat film according to claim 1, wherein the substrate is made of polyester, acrylic resin, or polyolefin.   14. The hard coat film according to claim 1, wherein a transparent conductive layer is formed on a surface of the base material opposite to the surface on which the hard coat layer is formed. Coat film.   15. The hard coat film according to claim 1, wherein the hard coat film is used for a touch panel.