JP6472703B2 - Nanodiamond dispersion composition and optical member - Google Patents

Description

  The present invention relates to a composition in which fine particles of high refractive index are dispersed, and an optical member having a portion formed from such a composition.

  In recent years, plastic materials or resin materials having excellent transparency and high refractive index have been demanded in various applications. For example, substrates for flat panel displays, various camera lenses, LED sealing materials, coatings on spectacle lens surfaces, and refractive index adjusting films (so-called index matching films and refractive index adjusting adhesive layers) and antireflection for various optical members In membrane applications. As such resin materials, composite materials in which zirconia fine particles or titanium oxide fine particles, which are high refractive index fine particles, are dispersed have been developed (for example, Patent Documents 1 to 3).

JP 2005-185924 A JP 2009-162848 A JP 2009-275115 A

  For example, it is known that fine diamond particles called nanodiamonds are produced by the detonation method. Nanodiamonds exhibit a high refractive index, etc., as do bulk diamonds. Nanoparticles, which are fine particles, generally have a large proportion of surface atoms (coordinately unsaturated), so that the sum of van der Waals forces that can act between surface atoms of adjacent particles is large and aggregates. Cheap. In addition to this, in the case of detonation nanodiamond (nanodiamond produced by detonation method), a phenomenon called agglutination, which is caused by coulomb interaction between crystal planes of adjacent crystallites, contributes to a very strong aggregation. Can occur. The detonation nanodiamond has such a unique property that the crystallites or primary particles can interact in a superimposed manner. For this reason, it is necessary to create a state in which the nanodiamond is dispersed in, for example, a resin material. With technical difficulties. Nanodiamond is a product obtained by the detonation method. First, it takes the form of an aggregate (secondary particle) in which primary particles interact with each other very strongly. There are technical difficulties associated with crushing the particles and dispersing the primary particles in the desired resin material.

  The present invention has been conceived under such circumstances, and provides a nanodiamond dispersion composition suitable for forming a resin part or a resin film having high transparency and high refractive index. The purpose is to do. Another object of the present invention is to provide an optical member having such a light-transmitting resin part or resin film.

  According to a first aspect of the present invention, a nanodiamond dispersion composition is provided. The nanodiamond dispersion composition includes a dispersion medium, fine particles of nanodiamond having a particle diameter D50 (median diameter) of 1 to 50 nm and dispersed in the dispersion medium, and emulsion particles of a transparent resin. It shows a haze of 2.0% or less and a refractive index of 1.6 to 2.2 after film formation. In the present invention, haze is measured for a film body having a thickness of 100 nm in accordance with JIS K 7136, and the refractive index is for example a film body having a thickness of 100 nm in accordance with JIS K 7142. It is measured.

  The nanodiamond dispersion composition having such a configuration is, for example, a material for forming a light-transmitting resin film or resin portion by being applied on a predetermined substrate and then dried. The emulsion particle | grains of the transparent resin contained in this composition will make a transparent resin matrix in the resin part formed from this composition. The nanodiamond fine particles contained in the composition should be dispersed and contained in the transparent resin matrix reflecting the stable dispersion state in the dispersion medium of the composition in the resin part formed from the composition. It becomes. The resin part comprising the transparent resin matrix and the nanodiamond fine particles dispersed therein has optical transparency. In the present composition, for example, by adjusting the particle diameter and content rate of the nanodiamond fine particles, the haze when formed into a film having a thickness of 100 nm is set to 2.0% or less. The content rate regarding the nano diamond fine particles is, for example, the ratio of the content of the nano diamond fine particles to the total content of the nano diamond fine particles and the transparent resin emulsion particles in the present composition.

  In addition, nanodiamond fine particles, which are high refractive index fine particles, are dispersed in the dispersion medium of the present composition. The nanodiamond fine particles are dispersed and contained in the transparent resin matrix in the resin portion formed from the composition, reflecting the stable dispersion state of the composition in the dispersion medium. The resin part including the transparent resin matrix and the high-refractive-index nanodiamond fine particles dispersed therein can have a higher refractive index than a resin body made of only the transparent resin. In this composition, the refractive index of the said resin part is set so that it may become 1.6-2.2 by adjustment of the content rate regarding nanodiamond microparticles, for example.

  As described above, in the nanodiamond dispersion composition, nanodiamond fine particles having a median diameter of 1 to 50 nm can be appropriately dispersed in a transparent resin matrix in a film-formed state, and a haze of 2.0% or less and 1. It has a configuration of showing a refractive index of 6 to 2.2. The nanodiamond dispersion composition having such a configuration is suitable for forming a resin part or a resin film having high transparency and high refractive index.

  Preferably, the zeta potential of the nanodiamond fine particles and the zeta potential of the transparent resin emulsion particles have the same sign. That is, the zeta potential of the nanodiamond fine particles and the zeta potential of the transparent resin emulsion particles are negative, respectively, or the zeta potential of the nanodiamond fine particles and the zeta potential of the transparent resin emulsion particles are each positive. According to such a configuration, each nanodiamond fine particle repels other nanodiamond fine particles and also repels transparent resin emulsion particles, and each transparent resin emulsion particle repels other emulsion particles and nanoscopically. Repels with diamond particles. Therefore, this configuration is suitable for stably dispersing both particle groups in the dispersion medium by suppressing the nanodiamond fine particles and the transparent resin emulsion particles from attracting and aggregating with each other. When the nanodiamond dispersion composition contains nanodiamond fine particles and transparent resin emulsion particles at a relatively high concentration, for example, in order to stably disperse nanodiamond fine particles and transparent resin emulsion particles in a dispersion medium. Is preferred.

  Preferably, the average particle diameter of the emulsion particles of the transparent resin is 1 to 300 nm. The average particle diameter is preferably 1 nm or more from the viewpoint of appropriately realizing the form of emulsion particles for the transparent resin contained in the nanodiamond dispersion composition. In addition, the average particle diameter is 300 nm or less from the viewpoint of suppressing the generation of a continuous nanodiamond layer (region where nanodiamonds are continuously present) in the resin portion formed from the nanodiamond dispersion composition. preferable. Suppression of the generation of the nanodiamond continuous layer is preferable for realizing low haze, that is, high transparency for the resin portion formed from the nanodiamond dispersion composition.

  Preferably, the nanodiamond is detonation nanodiamond (nanodiamond produced by detonation). The particle size of detonation nanodiamond primary particles is single-digit nanometers. Such a configuration is effective in realizing low haze, that is, high transparency for the resin part formed from the nanodiamond dispersion composition. Is preferred.

  Preferably, the dispersion medium is water. Such a configuration is suitable for stably dispersing the nanodiamond fine particles in the dispersion medium.

  Preferably, the nanodiamond fine particles are primary particles. The configuration in which the nanodiamond fine particles are primary particles smaller than the secondary particles is suitable for realizing low haze, that is, high transparency for the resin portion formed from the nanodiamond dispersion composition.

  Preferably, the transparent resin is a urethane resin. According to such a configuration, it becomes possible to form a urethane resin film or a urethane resin portion in which nanodiamond fine particles are appropriately dispersed from the nanodiamond dispersion composition. Moreover, such a structure is suitable when forming the resin film thru | or resin part which has water resistance from this nano diamond dispersion composition.

  Preferably, the transparent resin is a curable resin. According to such a configuration, it becomes possible to form a curable resin film or a curable resin portion in which nanodiamond fine particles are appropriately dispersed from the nanodiamond dispersion composition. The curable resin is preferably an acrylic resin or an epoxy resin. Such a configuration is suitable for forming a resin film or a resin portion excellent in mechanical properties such as abrasion resistance from the nanodiamond dispersion composition.

  According to a second aspect of the present invention, an optical member is provided. This optical member has a portion formed from the nanodiamond dispersion composition according to the first aspect of the present invention in at least a part of the light transmission region. This optical member is suitable for realizing an optical member having a resin part or a resin film having high transparency and high refractive index.

It is an expansion schematic diagram of the nano diamond dispersion composition which concerns on one Embodiment of this invention. It is an expansion partial sectional view of the optical member concerning other embodiments of the present invention.

  FIG. 1 is an enlarged schematic view of an ND dispersion composition X1, which is a nanodiamond dispersion composition according to an embodiment of the present invention. The ND dispersion composition X1 is a material for forming a light-transmitting resin film or resin portion, for example, by being applied on a predetermined substrate and then dried. The ND dispersion composition X1 of this embodiment includes ND fine particles 11, a dispersion medium 12, and emulsion particles 13 of a transparent resin, and has a haze of 2.0% or less and 1.6 to 2.2 after film formation. It is designed to show a refractive index of. In the present embodiment, the haze is measured for a film body having a thickness of 100 nm in accordance with JIS K 7136, and the refractive index is, for example, a film body having a thickness of 100 nm in accordance with JIS K 7142. Is measured.

  The ND microparticles 11 are nanodiamond microparticles that are separated from each other and dispersed as colloidal particles in the dispersion medium 12. The ND fine particles 11 may be primary particles generated through a predetermined generation process, or may be secondary particles formed by aggregating primary particles. The configuration in which the ND fine particles 11 are primary particles smaller than the secondary particles is preferable for realizing low haze, that is, high transparency, for the resin film or resin portion formed from the ND dispersion composition X1. Further, the absolute value of the so-called zeta potential of the ND fine particles 11 as the colloidal particles is preferably larger from the viewpoint of the dispersion stability of the ND fine particles 11 in the dispersion medium 12. The ND fine particles 11 that are colloidal particles may be nanodiamond fine particles having a negative zeta potential or nanodiamond fine particles having a positive zeta potential.

  The particle size D50 (median diameter) of the ND fine particles 11 is 1 to 50 nm. The upper limit of the particle size D50 is preferably 20 nm, more preferably 10 nm, still more preferably 8 nm, and particularly preferably 6 nm. The smaller the particle diameter D50 of the ND fine particles 11, the more preferable it is to realize low haze, that is, high transparency, in the resin film or resin portion formed from the ND dispersion composition X1. In this specification, the particle diameter D50 of the primary particles is a value measured by TEM observation. Specifically, in this TEM observation, first, an image is photographed so that the number of primary particles contained in one field of view is 200 to 300 for the target sample. Then, a particle size is obtained for each primary particle in the image using image analysis software, and a median diameter related to the primary particle group is calculated based on the result. In this specification, the particle size D50 of the secondary particles is a value measured by a so-called dynamic light scattering method.

  The content of the ND fine particles 11 is, for example, 15 to 90% by mass. The content of the ND fine particles 11 refers to the ratio of the content of the ND fine particles 11 to the total content of components other than the dispersion medium 12 in the ND dispersion composition X1. When the ND dispersion composition X1 includes the ND fine particles 11, the dispersion medium 12, and the emulsion particles 13 of the transparent resin, the content of the ND fine particles 11 is such that the ND fine particles 11 and the emulsion particles 13 in the ND dispersion composition X1. The ratio of the content of the ND fine particles 11 to the total content. From the viewpoint of the balance of transparency and refractive index of the resin part to be formed from the ND dispersion composition X1, the lower limit of the content of the ND fine particles 11 is preferably 25% by mass, more preferably 35% by mass. More preferably, it is 45 mass%. From the viewpoint of the balance between the transparency and refractive index of the resin part to be formed from the ND dispersion composition X1, the upper limit of the content of the ND fine particles 11 is preferably 90% by mass.

  Nanodiamonds whose primary particle size D50 is single-digit nanometers can be produced by, for example, detonation. In the detonation method, for example, explosives are exploded in a sealed container. At that time, nano-diamonds are generated by the action of the pressure and energy of the shock wave generated by the explosion, using carbon that is liberated due to partial incomplete combustion of the explosive used. As the explosive, a mixture of trinitrotoluene (TNT) and cyclotrimethylenetrinitroamine, ie hexogen (RDX), can be used.

  The nanodiamond crude product obtained by the detonation method is likely to contain a metal oxide. This metal oxide is an oxide such as Fe, Co, or Ni derived from a container or the like used in the detonation method. For example, by applying a predetermined strong acid in an aqueous solvent, the metal oxide can be dissolved and removed from the nanodiamond crude product (acid treatment). The strong acid used for this acid treatment is preferably a mineral acid, and examples thereof include hydrochloric acid, hydrofluoric acid, sulfuric acid, nitric acid, and aqua regia.

  The nano-diamond crude product obtained by the detonation method contains graphite. This graphite is derived from carbon that did not form nanodiamond crystals among the carbon released by partial incomplete combustion of the explosive used. For example, after the above acid treatment, graphite can be removed from the nanodiamond crude product (oxidation treatment) by applying a predetermined oxidizing agent in an aqueous solvent, for example. Examples of the oxidizing agent used in the oxidation treatment include chromic acid, chromic anhydride, dichromic acid, permanganic acid, perchloric acid, and salts thereof, and hydrogen peroxide.

  Detonation nanodiamonds (nanodiamonds produced by detonation method) are aggregated by a very strong interaction between primary particles even after purification through acid treatment and oxidation treatment as described above. It takes the form of adhering bodies (secondary particles). By subjecting the suspension obtained by dispersing this agglomerated material in a predetermined dispersion medium to a pulverization treatment, nanodiamonds having a particle size of single-digit nanometers can be obtained. As the dispersion medium, a solvent in which nanodiamond can exhibit solubility is preferable, and examples thereof include water, methanol, ethanol, ethylene glycol, and N-methylpyrrolidone. The crushing treatment can be performed using, for example, a high shear mixer, a high shear mixer, a homomixer, a ball mill, a bead mill, a high-pressure homogenizer, an ultrasonic homogenizer, or a colloid mill. In addition, after the crushing treatment as described above, a nanodiamond dispersion liquid having a predetermined concentration can be obtained by reducing the water content of the suspension in which nanodiamonds are dispersed, as necessary. Alternatively, after the crushing treatment as described above, a nanodiamond powder can be obtained by removing water from the suspension in which the nanodiamond is dispersed, if necessary. These water content reduction and water removal can be performed, for example, using an evaporator.

  The dispersion medium 12 is a medium for appropriately dispersing the ND fine particles 11 and the transparent resin emulsion particles 13 in the ND dispersion composition X1. The dispersion medium 12 is preferably a solvent in which nanodiamonds can exhibit solubility, and examples thereof include water, methanol, ethanol, ethylene glycol, dimethyl sulfoxide, and N-methylpyrrolidone. From the viewpoint of dispersibility of the ND fine particles 11, water is preferable. As the dispersion medium 12, one type of dispersion medium may be used, or two or more types of dispersion media may be used.

  The emulsion particles 13 of the transparent resin are separated from each other and dispersed in the dispersion medium 12, and are components that form a transparent resin matrix in the resin film or resin portion formed from the ND dispersion composition X1. . Examples of the transparent resin for forming the emulsion particles 13 include urethane resin, acrylic resin, epoxy resin, phenol resin (phenol-formaldehyde resin), AS resin (acrylonitrile-styrene copolymer), MS resin. (Methyl methacrylate-styrene copolymer), polycarbonate (PC), polystyrene (PS), polyether, polyester, polyarylate, polyacrylate, and polyamide. Among these, urethane resin is preferable from the viewpoint of water resistance, and acrylic resin and epoxy resin are preferable from the viewpoint of mechanical properties such as wear resistance. As the transparent resin forming the emulsion particles 13, one type of resin may be used, or two or more types of resins may be used.

  The urethane resin is a polymer having a urethane bond, and is obtained by reacting a polyisocyanate and a polyol. Examples of the polyisocyanate for obtaining the urethane resin include aliphatic polyisocyanate, alicyclic polyisocyanate, and aromatic polyisocyanate. Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, and methylcyclohexylene diisocyanate. Examples of the aromatic polyisocyanate include tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, and polymethylene polyphenyl polyisocyanate. On the other hand, examples of the polyol for obtaining the urethane resin include a hydroxyl group-containing conjugated diene polymer, a polyether polyol, a polyester polyol, and a polycarbonate polyol. Examples of the hydroxyl group-containing conjugated diene polymer include polybutadiene polyol and polyisoprene polyol. Examples of the polyether polyol include those obtained by addition polymerization of an alkylene oxide to a polyhydric alcohol. Examples of the polyester polyol include an esterification reaction product of a polyhydric alcohol and a polycarboxylic acid. Examples of the polycarbonate polyol include a reaction product of a carbonic acid derivative such as diphenyl carbonate, dimethyl carbonate, phosgene and a polyhydric alcohol.

  The acrylic resin is a resin including a monomer unit derived from a monomer having a (meth) acryloyl group (for example, a monomer having a (meth) acrylic ester structure) as a main monomer unit. For example, “(meth) acryl” represents “acryl”, “methacryl”, or both “acryl” and “methacryl”. Examples of the monomer for obtaining the acrylic resin include monofunctional (meth) acrylate and polyfunctional (meth) acrylate. Examples of the monofunctional (meth) acrylate include isostearyl acrylate, stearyl methacrylate, isobornyl acrylate, phenol EO modified acrylate, o-phenylphenol EO modified acrylate, paracumylphenol EO modified acrylate, nonylphenol EO modified acrylate, 2- Examples include ethylhexyl EO modified acrylate, N-acryloyloxyethylhexyl hexahydrophthalimide, and methoxypolyethylene glycol acrylate. Examples of the polyfunctional (meth) acrylate include 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, neopentyl glycol. Dimethacrylate, 1,10-decanediol diacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene Glycol diacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, poly Tetramethylene glycol diacrylate, glycerin dimethacrylate, tricyclodecane dimethalyl diacrylate, tricyclodecane dimethalyl dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, PO-modified neopentyl glycol diacrylate, bisphenol F EO-modified di Acrylate, bisphenol A EO modified diacrylate, bisphenol A EO modified dimethacrylate, bisphenol A PO modified diacrylate, isocyanuric acid EO modified diacrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, penta Erythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, trimethy Propane triacrylate, trimethylolpropane trimethacrylate, ditrimethylolpropane tetraacrylate, trimethylolpropane EO modified triacrylate, trimethylolpropane PO modified triacrylate, glycerin PO modified triacrylate, diglycerin EO modified acrylate, isocyanuric acid EO modified Di and triacrylates, and pentaerythritol EO modified tetraacrylates.

  The epoxy resin can be obtained by curing a polymer compound having an oxirane ring by acting a curing agent such as amine or acid anhydride. Examples of the epoxy resin include a bifunctional glycidyl ether type epoxy resin, a polyfunctional type glycidyl ether type epoxy resin, and a glycidyl amine type epoxy resin. Examples of the bifunctional glycidyl ether type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and biphenyl type epoxy resin. Examples of multifunctional glycidyl ether type epoxy resins include phenol novolac type epoxy resins, orthocresol novolak type epoxy resins, alkyl-modified triphenolmethane type epoxy resins, trishydroxyphenylmethane type epoxy resins, and tetraphenylolethane type epoxy resins. Resin. Examples of the glycidylamine type epoxy resin include tetraglycidyldiaminidiphenylmethane type epoxy resin, triglycidyl isocyanurate type epoxy resin, aminophenol type epoxy resin, aniline type epoxy resin, and toluidine type epoxy resin.

  The content of the emulsion particles 13 in the ND dispersion composition X1 is a balance between the coating properties of the ND dispersion composition X1 and the ease of drying after coating, and the strength of the film formed from the ND dispersion composition X1. From this viewpoint, it is, for example, 5 to 90% by mass.

  The average particle diameter of the emulsion particles 13 of the transparent resin is preferably 1 to 300 nm. The average particle diameter is preferably 1 nm or more from the viewpoint of appropriately realizing the form of emulsion particles for the transparent resin contained in the ND dispersion composition X1. The average particle diameter is preferably 300 nm or less from the viewpoint of suppressing the occurrence of a nanodiamond continuous layer (region where nanodiamonds are continuously present) in the resin portion formed from the ND dispersion composition X1. Suppression of the generation of the nanodiamond continuous layer is preferable for realizing low haze, that is, high transparency, for the resin portion formed from the ND dispersion composition X1. In this specification, the average particle diameter of the emulsion particles 13 is a value measured by a dynamic light scattering method.

  The absolute value of the zeta potential of the emulsion particles 13 of the transparent resin is preferably larger from the viewpoint of dispersion stability of the emulsion particles 13 in the dispersion medium 12. Moreover, it is preferable that the zeta potential of the emulsion particles 13 of the transparent resin and the zeta potential of the ND fine particles 11 described above have the same sign. That is, the zeta potential of the transparent resin emulsion particles 13 and the zeta potential of the ND fine particles 11 are negative, respectively, or the zeta potential of the transparent resin emulsion particles 13 and the zeta potential of the ND fine particles 11 are positive, respectively. is there. Such a configuration is suitable for stably dispersing the emulsion particles 13 and the ND fine particles 11 of the transparent resin in the dispersion medium 12 together. When the ND dispersion composition X1 contains the ND fine particles 11 and the transparent resin emulsion particles 13 at a relatively high concentration, for example, when the ND fine particles 11 and the emulsion particles 13 are stably dispersed in the dispersion medium 12. Is preferred.

  The ND dispersion composition X1 can be produced, for example, as follows. A dispersion of ND fine particles 11 (water dispersion or the like) and an emulsion of the above-described transparent resin (dispersion of emulsion particles 13 of the transparent resin) are mixed (first method). The ND fine particles 11 are added to and mixed with the emulsion of the transparent resin (second method). The ND fine particles 11 and the transparent resin are mixed in the dispersion medium 12 to emulsify the transparent resin (third method). From the viewpoint of dispersibility of the ND fine particles 11, the first method is preferable.

  The ND dispersion composition X1 may contain other components in addition to the ND fine particles 11 and the emulsion particles 13 of the transparent resin. Examples of the other components include a curing agent, an antifoaming agent, and a leveling agent for curing the compound when a curable compound is employed as the constituent material of the emulsion particles 13 of the transparent resin.

  The ND dispersion composition X1 is a material for forming a light-transmitting resin film or resin part by, for example, being applied on a predetermined substrate and then dried. As described above, the emulsion particles 13 of the transparent resin form a transparent resin matrix in the resin portion formed from the ND dispersion composition X1. As described above, the ND fine particles 11 are dispersed and contained in the transparent resin matrix in the resin portion formed from the ND dispersion composition X1, reflecting the stable dispersion state of the composition in the dispersion medium 12. Will be. The resin part including the transparent resin matrix and the ND fine particles 11 dispersed therein has light transmittance. In the ND dispersion composition X1, for example, by adjusting the particle size and the content rate of the ND fine particles 11, the haze when the film is formed to a thickness of 100 nm is set to 2.0% or less.

  Further, ND fine particles 11 which are high refractive index fine particles are dispersed in the dispersion medium 12 of the ND dispersion composition X1. As described above, the high refractive index ND fine particles 11 are contained in the transparent resin matrix reflecting the stable dispersion state of the composition in the dispersion medium 12 in the resin portion formed from the ND dispersion composition X1. It will be included in a distributed manner. The resin part including the transparent resin matrix and the high refractive index ND fine particles 11 dispersed therein may have a higher refractive index than a resin body made of only the transparent resin. In the ND dispersion composition X1, for example, the refractive index of the resin part is set to 1.6 to 2.2 by adjusting the content of the ND fine particles 11. The refractive index is preferably set to 1.7 to 2.1.

  As described above, in the ND dispersion composition X1, the ND fine particles 11 having a median diameter of 1 to 50 nm can be appropriately dispersed in the transparent resin matrix in the film formation state, and the haze of 2.0% or less and 1.6% It has a configuration of exhibiting a refractive index of .about.2.2. The ND dispersion composition X1 having such a configuration is suitable for forming a resin part or a resin film having high transparency and high refractive index.

  FIG. 2 is an enlarged partial sectional view of an optical member Y according to another embodiment of the present invention. The optical member Y includes a transparent substrate 20 and an ND dispersion resin film X2 that is a nanodiamond dispersion resin film. The optical member Y is an optical member that transmits light, such as a transparent substrate for a flat panel display such as a liquid crystal display, an organic electroluminescence display, and a plasma display, a lens, and a transparent panel for a touch panel. The transparent substrate 20 is a transparent member that is a main structural element of such an optical member Y, and includes a region through which light is transmitted. Such a transparent substrate 20 is made of, for example, a plastic material, a resin material, or a glass material. The ND-dispersed resin film X2 is formed from the above-described ND-dispersed composition X1 (not shown for the internal structure), and is provided so as to cover at least a part of the light transmission region of the transparent substrate 20. . That is, the optical member Y has a portion formed from the above-described ND dispersion composition X1 in at least a part of the light transmission region. The thickness of the ND dispersion resin film X2 is, for example, 0.01 to 10 μm. For example, the refractive index and / or thickness of the ND dispersed resin film X2 is set according to the refractive index of the transparent substrate 20, so that the ND dispersed resin film X2 is a refractive index adjusting film (index matching film) or antireflection. It can function as a membrane.

  Such an optical member Y can be manufactured by applying the above-mentioned ND dispersion composition X1 on the transparent substrate 20 to form a thin film, and then drying and solidifying (hardening if necessary). Examples of the coating means include a bar coater, spray coating, spin coater, dip coater, die coater, comma coater, and gravure coater.

  The optical member Y has an ND-dispersed resin film X2 formed from an ND-dispersed composition X1 suitable for forming a resin part or resin film having high transparency and a high refractive index. Therefore, the optical member Y is suitable for realizing an optical member having a resin portion or a resin film having high transparency and a high refractive index.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

[Example 1]
Urethane emulsion (trade name “Superflex (SF) 170”, urethane component concentration 33 mass%, average particle size 10 nm, zeta potential at pH 8; −50 mV, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and nanodiamond aqueous dispersion (product) Name “Vox D”, nanodiamond concentration 5 mass%, particle size D50; 5 nm, zeta potential at pH 9; −55 mV, manufactured by Carbodeon) The mixture was mixed while being dispersed in ultrasonic waves at a certain ratio. In this way, the nanodiamond dispersion composition of Example 1 was prepared. This nano-diamond dispersion composition is a polyethylene terephthalate (PET) film (trade name “Cosmo Shine A4300” having a hard coat layer (thickness 3 μm) on the surface and subjected to corona treatment on the surface, thickness 188 μm, It was dripped on the product (made by TOYOBO), and it applied so that the thickness after drying might be set to 100 nm using the bar coater. Then, it dried for 2 minutes at 80 degreeC with the dryer. As described above, the nanodiamond-dispersed resin film of Example 1 was formed.

[Example 2]
Example 1 The same manner as in Example 1 except that the amount ratio of the urethane component and the nanodiamond component was changed to 60 parts by weight (urethane component) and 40 parts by weight (nanodiamond component) instead of 70 parts by weight and 30 parts by weight. Two nanodiamond dispersion compositions were prepared and the nanodiamond dispersion resin film of Example 2 was formed.

Example 3
Example The same as Example 1 except that the amount ratio of the urethane component and the nanodiamond component was changed to 50 parts by weight (urethane component) and 50 parts by weight (nanodiamond component) instead of 70 parts by weight and 30 parts by weight. 3 nanodiamond dispersion compositions were prepared and the nanodiamond dispersion resin film of Example 3 was formed.

Example 4
Example The same as Example 1 except that the amount ratio of the urethane component and the nanodiamond component was changed to 40 parts by weight (urethane component) and 60 parts by weight (nanodiamond component) instead of 70 parts by weight and 30 parts by weight. Four nanodiamond dispersion compositions were prepared and the nanodiamond dispersion resin film of Example 4 was formed.

Example 5
Example 1 The same manner as in Example 1 except that the amount ratio of the urethane component and the nanodiamond component was changed to 30 parts by weight (urethane component) and 70 parts by weight (nanodiamond component) instead of 70 parts by weight and 30 parts by weight. 5 nanodiamond dispersion composition was prepared, and the nanodiamond dispersion resin film of Example 5 was formed.

Example 6
Example 1 The same manner as in Example 1 except that the amount ratio of the urethane component and the nanodiamond component was changed to 20 parts by weight (urethane component) and 80 parts by weight (nanodiamond component) instead of 70 parts by weight and 30 parts by weight. Six nanodiamond dispersion compositions were prepared and the nanodiamond dispersion resin film of Example 6 was formed.

Example 7
Example 1 The same manner as in Example 1 except that the amount ratio of the urethane component and the nanodiamond component was changed to 10 parts by weight (urethane component) and 90 parts by weight (nanodiamond component) instead of 70 parts by weight and 30 parts by weight. 7 nanodiamond dispersion composition was prepared and the nanodiamond dispersion resin film of Example 7 was formed.

Example 8
Urethane emulsion (trade name “Superflex 130”, urethane component concentration 35 mass%, average particle size 30 nm, zeta potential at pH 8; −52 mV, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and nanodiamond aqueous dispersion (trade name “Vox” D ”(manufactured by Carbodeon Co., Ltd.) was mixed while being dispersed in an ultrasonic wave in an amount ratio such that the nanodiamond component was 50 parts by weight with respect to 50 parts by weight of the urethane component. Thus, the nanodiamond dispersion composition of Example 8 was prepared. This nanodiamond dispersion composition is dropped on a polyethylene terephthalate film (trade name “Cosmo Shine A4300”, thickness 188 μm, manufactured by TOYOBO), and the thickness after drying becomes 100 nm using a bar coater. It was applied as follows. Then, it dried for 2 minutes at 80 degreeC with the dryer. As described above, the nanodiamond dispersed resin film of Example 8 was formed.

Example 9
Urethane emulsion (trade name “Superflex 620”, urethane component concentration 30% by mass, average particle size 20 nm, zeta potential at pH 7; +35 mV, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and nanodiamond aqueous dispersion (trade name “Hydrogen D”) ”, A nanodiamond concentration of 2.5% by mass, a particle size D50; a zeta potential at 5 nm, pH 6; +42 mV, manufactured by Carbodeon), and an amount ratio of the nanodiamond component to 50 parts by weight relative to 50 parts by weight of the urethane component And mixing while dispersing in ultrasonic waves. In this way, the nanodiamond dispersion composition of Example 9 was prepared. This nanodiamond dispersion composition is dropped on a polyethylene terephthalate film (trade name “Cosmo Shine A4300”, thickness 188 μm, manufactured by TOYOBO), and the thickness after drying becomes 100 nm using a bar coater. It was applied as follows. Then, it dried for 2 minutes at 80 degreeC with the dryer. As described above, the nanodiamond-dispersed resin film of Example 9 was formed.

Example 10
Example 9 As in Example 9, except that the amount ratio of the urethane component and the nanodiamond component was changed to 20 parts by weight (urethane component) and 80 parts by weight (nanodiamond component) instead of 50 parts by weight and 50 parts by weight. Ten nanodiamond dispersion compositions were prepared and the nanodiamond dispersion resin film of Example 10 was formed.

[Comparative Example 1]
A urethane emulsion (trade name “Superflex 170”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and a nanodiamond aqueous dispersion (trade name “Vox D”, manufactured by Carbodeon) were combined with 90 parts by weight of a urethane component using nanodiamonds. The components were mixed while being dispersed in ultrasonic waves at a quantitative ratio of 10 parts by weight. In this way, a nanodiamond dispersion composition of Comparative Example 1 was prepared. This nanodiamond dispersion composition is dropped on a polyethylene terephthalate film (trade name “Cosmo Shine A4300”, thickness 188 μm, manufactured by TOYOBO), and the thickness after drying becomes 100 nm using a bar coater. It was applied as follows. Then, it dried for 2 minutes at 80 degreeC with the dryer. As described above, the nanodiamond-dispersed resin film of Comparative Example 1 was formed.

[Comparative Example 2]
Urethane emulsion (trade name “Superflex 620”, zeta potential at pH 7; +35 mV, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and nanodiamond aqueous dispersion (trade name “Vox D”, zeta potential at pH 9; −55 mV, Carbodeon) Manufactured in a supersonic wave at a quantitative ratio of 30 parts by weight of the nanodiamond component to 70 parts by weight of the urethane component. However, the components aggregated and settled in the liquid. Since the zeta potential of the emulsion particles in the used urethane emulsion and the zeta potential of the nanodiamond fine particles in the aqueous nanodiamond dispersion used have opposite signs, the emulsion particles and the nanodiamond fine particles attract each other to cause aggregation. It is thought that it occurred. Thus, a nanodiamond dispersion composition could not be prepared.

[Comparative Example 3]
Urethane emulsion (trade name “Superflex 170”, zeta potential at pH 8; −50 mV, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and nanodiamond aqueous dispersion (trade name “Hydrogen D”, zeta potential at pH 6; +42 mV, Carbodeon) Manufactured in a supersonic wave at a quantitative ratio of 30 parts by weight of the nanodiamond component to 70 parts by weight of the urethane component. However, the components aggregated and settled in the liquid. Since the zeta potential of the emulsion particles in the used urethane emulsion and the zeta potential of the nanodiamond fine particles in the aqueous nanodiamond dispersion used have opposite signs, the emulsion particles and the nanodiamond fine particles attract each other to cause aggregation. It is thought that it occurred. Thus, a nanodiamond dispersion composition could not be prepared.

<Haze>
About each nano diamond dispersion resin film formed on PET film as mentioned above, haze was measured using a haze meter (brand name: "Haze meter 300A", Nippon Denshoku Industries Co., Ltd. make). The haze measurement was performed according to JIS K 7136. The results are listed in Table 1.

<Refractive index>
About each nano diamond dispersion resin film | membrane formed as mentioned above, the refractive index in wavelength 633nm was measured using the ellipsometer (Brand name "automatic ellipsometer DVA-36LA", the product made from a groove bottom optical industry). The results are listed in Table 1.

X1 ND dispersion composition X2 ND dispersion resin film Y Optical member 11 ND fine particle 12 Dispersion medium 13 Emulsion particle 20 Transparent substrate

Claims (8)

A dispersion medium;
Fine particles of nanodiamond having a particle size D50 of 1 to 50 nm and dispersed in the dispersion medium;
Transparent resin emulsion particles dispersed in the dispersion medium ,
The zeta potential of the nanodiamond fine particles and the zeta potential of the emulsion particles of the transparent resin have the same sign,
After film formation on a 100 nm-thick film body, a haze of 2.0% or less is shown as a value measured in accordance with JIS K 7136 , and a value measured in accordance with JIS K 7142 is 1.6 to A nanodiamond dispersion composition exhibiting a refractive index of 2.2. The nanodiamond dispersion composition according to claim 1 , wherein an average particle diameter of the emulsion particles is 1 to 300 nm. The nanodiamond dispersion composition according to claim 1 or 2 , wherein the nanodiamond is detonation nanodiamond. The nanodiamond dispersion composition according to any one of claims 1 to 3 , wherein the dispersion medium is water. The nanodiamond dispersion composition according to any one of claims 1 to 4 , wherein the fine particles are primary particles. The nanodiamond dispersion composition according to any one of claims 1 to 5 , wherein the transparent resin is a urethane resin. The nanodiamond dispersion composition according to any one of claims 1 to 5 , wherein the transparent resin is a curable resin. The optical member which has the site | part formed from the nano diamond dispersion composition as described in any one of Claim 1 to 7 in at least one part of a light transmissive area | region.

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