WO2011018939A1 - 球状コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の集積体及びその製造方法 - Google Patents
球状コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の集積体及びその製造方法 Download PDFInfo
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- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
- C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
Definitions
- the present invention relates to an aggregate of spherical core-shell cerium oxide / polymer hybrid nanoparticles (hereinafter sometimes referred to as spherical CSCP nanoparticles) synthesized by a polyol method, and more specifically, spherical CSCP.
- the volume ratio of nanoparticles is a high concentration of 32% or more, including a fixing agent composed of resin, spherical CSCP nanoparticles are uniformly distributed, excellent in mechanical strength, and easy to form a large area film
- the present invention relates to an aggregate of spherical CSCP nanoparticles, a method for producing the same, and an antireflection film which is an application product thereof, which can be manufactured and which is excellent in light transmission and ultraviolet shielding properties.
- the present invention provides a new technology and a new product relating to an aggregate of spherical CSCP nanoparticles useful for, for example, an antireflection material using a photonic crystal, an ultraviolet shielding fiber, a high refractive index film, and a high refractive index layer. Is.
- Non-patent Document 1 photonic crystals using fine particles have attracted attention. This is because emission and light propagation can be artificially controlled by the fine particles. Performance required as fine particles for photonic crystals are spherical, particle size is about 50 to 200 nm, particle size distribution (standard deviation of particle size) is small, high refractive index (n> 2), good in liquid Dispersibility. However, until now, no fine particles satisfying these conditions have been developed.
- cerium oxide has a high refractive index of 2.1 (Non-Patent Documents 2 and 3), and is a suitable material as a photonic crystal. Moreover, cerium oxide is a material that is famous for its ultraviolet shielding effect. For example, a prior art document discloses an ultraviolet shielding agent using cerium oxide (Patent Document 1). Since ultraviolet rays adversely affect the human body, fibers having an ultraviolet shielding effect are desired, but cerium oxide is promising for such fibers.
- Non-Patent Document 2 spherical CSCP nanoparticles
- the spherical CSCP nanoparticles obtained in this report have the following characteristics, unlike others (Non-Patent Documents 5-8). That is, (1) the shape of the nanoparticles is spherical, (2) the particle size distribution is narrow, (3) a structure in which primary cerium oxide particles of 2 to 3 nm are gathered into a spherical shape, and the periphery is covered with an organic polymer (4) The nanoparticles can be re-dispersed in aqueous and non-aqueous solvents very easily even when dried. (5) A highly concentrated dispersion of particles can be prepared.
- the average particle diameter of the nanoparticles can be controlled in the range of 50 to 120 nm, for example, while the particle size distribution is narrow by changing the molecular weight of the polymer added at the time of preparation.
- Simple It can be synthesized by the polyol method, which is a synthesis process.
- spherical CSCP nanoparticles are spherical and have a narrow particle size distribution (monodisperse), they are promising as colloidal crystals.
- spherical CSCP nanoparticles are very easily redispersed in aqueous and non-aqueous solvents, and are expected to be dispersed in various resins.
- the prior art document discloses an aggregate of spherical CSCP nanoparticles (Patent Document 2).
- Patent Document 2 the integrated body disclosed in the above prior art document (Patent Document 2) has a problem that it has no mechanical strength and is brittle when it is pinched with tweezers.
- a fixing agent is not used.
- the nanoparticle aggregated non-uniformly by self-organization was called an aggregate. Therefore, the technique described in this document cannot make a large-area film containing spherical CSCP nanoparticles uniformly.
- Patent Document 3 discloses a composite in which a polymer is covalently bonded to the surface of primary particles of inorganic oxide fine particles and a coating composition (resin) containing the same.
- Spherical CSCP nanoparticles and their aggregates are essentially different. It can be read from the text that the inorganic oxide fine particles disclosed in Patent Document 3 are primary particles in the first place.
- spherical CSCP nanoparticles are spherical secondary particles in which primary particles are aggregated, and they are completely different particles.
- patent document 3 describes that the shape of the inorganic oxide fine particles is arbitrary, the shape is also different.
- the primary particles of inorganic oxide fine particles are rarely spherical. This is because the primary particles are crystals, and the crystal plane often appears on the surface. Primary particles having an arbitrary shape are often agglomerated, and the shape of the secondary particles is like a bunch of grapes. For this reason, in patent document 3, since the polymer is covalently bonded to the surface of something like a bunch of grapes, the shape of each secondary particle is different. For this reason, it was impossible to arrange such secondary particles in the resin at a high density.
- the present inventors are composed of an aggregate in which spherical CSCP nanoparticles synthesized by the polyol method are uniformly distributed and accumulated, and have excellent mechanical strength.
- the goal of producing new aggregates of spherical CSCP nanoparticles that can be manufactured at low cost it is possible to increase the area of the film and have excellent transparency.
- the volume ratio of the spherical CSCP nanoparticles is a high concentration of 32% or more, the spherical CSCP nanoparticles are uniformly distributed, and excellent in mechanical strength.
- the present invention has been completed by successfully producing spherical CSCP nanoparticle aggregates.
- INDUSTRIAL APPLICABILITY The present invention provides a novel spherical CSCP nanoparticle aggregate having excellent mechanical strength, capable of increasing the area, and capable of producing a transparent film at low cost, and a method for producing the same. Is intended to provide.
- Another object of the present invention is to provide an antireflection material including a high refractive index layer using such an aggregate of spherical CSCP nanoparticles.
- the present invention for solving the above-described problems comprises the following technical means.
- the volume ratio of the core-shell type cerium oxide / polymer hybrid nanoparticles is a high concentration of at least 32%, 2) contains a fixing agent composed of resin, and 3) the core-shell type cerium oxide / It has a structure in which the fixing agent is filled between the polymer hybrid nanoparticles, 4) the core-shell cerium oxide / polymer hybrid nanoparticles are uniformly distributed, and 5) have mechanical strength.
- An aggregate of spherical core-shell cerium oxide / polymer hybrid nanoparticles characterized in that (2) The spherical core-shell cerium oxide / in the above (1), wherein the fixing agent is a resin after being cured by irradiating light or applying heat to a photocurable resin or a thermosetting resin. A collection of polymer hybrid nanoparticles. (3) The spherical core-shell type cerium oxide / polymer hybrid according to (1), wherein no silane coupling agent or surfactant is present on the surface of the core part of the spherical core-shell type oxide / polymer hybrid nanoparticle. A collection of nanoparticles.
- the spherical core-shell cerium oxide / polymer hybrid nanoparticle aggregate according to (1) which has a film-like structure formed on a substrate or a base material.
- the spherical core-shell type cerium oxide / polymer hybrid nanoparticle aggregate according to (1) which has a refractive index of 1.65 at the lowest.
- An antireflection film comprising the spherical core-shell type cerium oxide / polymer hybrid nanoparticle aggregate described in (1) above.
- a method for producing an aggregate of spherical core-shell cerium oxide / polymer hybrid nanoparticles characterized by the following. (10) The method for producing an aggregate of spherical core-shell cerium oxide / polymer hybrid nanoparticles according to (9), wherein the solvent is methyl ethyl ketone, methyl isobutyl ketone, methyl lactate, ethyl lactate, or butyl lactate.
- the present invention relates to an aggregate in which spherical core-shell type cerium oxide / polymer hybrid nanoparticles having a core part of cerium oxide and a shell part of a polymer are uniformly distributed and accumulated, the core-shell type cerium oxide / high
- the volume ratio of the molecular hybrid nanoparticles is a high concentration of at least 32%, and includes a fixing agent composed of a resin, and the fixing agent is filled between the particles of the core-shell type cerium oxide / polymer hybrid nanoparticles.
- the core-shell type cerium oxide / polymer hybrid nanoparticles have a structure, are uniformly distributed, and have mechanical strength.
- the present invention also provides an ink for producing the above spherical core-shell cerium oxide / polymer hybrid nanoparticle aggregate, comprising core-shell cerium oxide / polymer hybrid nanoparticles, a photocurable resin, and a solvent. It is characterized by being configured.
- the present invention is a method for producing an aggregate of spherical core-shell type cerium oxide / polymer hybrid nanoparticles, wherein the core-shell type cerium oxide / polymer hybrid nanoparticles, photo-curing resin or thermosetting resin, And a step of preparing an ink composed of a solvent, a step of forming the ink to form a molded body, and a step of irradiating the obtained molded body with light or applying heat to cure. It is what.
- the spherical CSCP nanoparticle is a particle in which a secondary particle in which primary particles of cerium oxide are assembled in a spherical shape is a core portion, and a polymer layer serving as a shell portion is present on the secondary particle surface. That is.
- the polymer in the shell portion is a polymer in which the polymers are cross-linked. Thereby, even if it wash
- the CSCP nanoparticle is a hybrid of cerium oxide and a polymer, and the hybrid refers to a complex of cerium oxide and a polymer.
- hybrid may be omitted. Instead of nanoparticles, they are sometimes called fine particles.
- the polymer of the shell portion is omitted, that is, it is described as core-shell type cerium oxide fine particles.
- the polymer may be described as a polymer.
- the spherical CSCP nanoparticles used in the present invention have the following characteristics: (1) the shape of the nanoparticles is spherical, (2) the particle size distribution is narrow, (3) the primary oxide of 2 to 3 nm (4) Nanoparticles are extremely easy to re-disperse in aqueous and non-aqueous solvents even when dried. (5) A high-concentration dispersion of particles can be prepared. (6) The average particle size of the nanoparticles can be changed from 10 to 1000 nm while the particle size distribution is narrow by changing the molecular weight of the polymer added during production. (7) It can be synthesized by a simple polyol method.
- the aggregate of spherical CSCP nanoparticles is an aggregate of the spherical CSCP nanoparticles in a uniformly distributed state, and the shape is arbitrary, for example, a thin film, thick film, bulk, fiber, etc. Is mentioned.
- the fixing agent means a resin component filled between the spherical CSCP nanoparticle particles in order to enhance the mechanical strength of the spherical CSCP nanoparticle aggregate.
- thermosetting resin a photo-curing resin, or the like, which is cured by light irradiation or heat
- the mechanical strength of the aggregate of spherical CSCP nanoparticles is the adhesion between the substrate and the aggregate when there is a substrate, and the difficulty of breaking when the aggregate surface is rubbed with a metal rod or the like. That is.
- excellent mechanical strength means that when there is a base material, the aggregate does not peel from the base material, and even if the surface of the aggregate is rubbed with a metal rod, it is not broken. It means having strength. Moreover, when there is no base material, it means that it has a strength that does not break even if the assembly is pinched with tweezers or the like.
- a photocurable resin means a resin that cures when irradiated with light (such as ultraviolet rays or visible light), and a thermosetting resin refers to a resin that cures when heat is applied to the resin. means.
- the polyol method which is a method for producing spherical CSCP nanoparticles.
- the cerium salt, polymer, and high-boiling organic solvent as raw materials are mixed.
- the cerium salt is a metal salt whose cation is a cerium ion. Examples thereof include cerium nitrate, cerium sulfate, and cerium acetate, and cerium nitrate is preferred.
- Cerium salts are usually hydrated.
- the concentration of the cerium salt is preferably 0.4 kmol / m 3 or more, because this improves the yield.
- the polymer is an organic polymer, and examples thereof include polyvinyl pyrrolidone, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and the like, and preferably polyvinyl pyrrolidone.
- the concentration of the polymer is preferably 80 kg / m 3 to 120 kg / m 3 .
- the polymer concentration is defined as the weight of the polymer added per unit solvent volume.
- the concentration of the polymer is in the range of 80 kg / m 3 to 120 kg / m 3 is that if it is less than this, the cerium oxide fine particles are likely to aggregate and do not become a core-shell type. Moreover, it is because the nucleation reaction of cerium oxide does not advance when the concentration of the polymer is more than the above range.
- the high boiling point organic solvent is a solvent having a boiling point higher than 100 ° C.
- polyols such as ethylene glycol, diethylene glycol, glycerin and propylene glycol can be listed, and preferably ethylene glycol.
- the raw material mixing step it is necessary to mix the raw materials so that they are sufficiently uniform.
- the temperature cannot be increased. This is because, when the temperature is high, cerium oxide is generated, and nanoparticles having a uniform particle size cannot be obtained.
- heating and refluxing are performed at a predetermined temperature of 110 ° C. or higher. This is the heating / refluxing step. At this time, it is preferable to raise the temperature to a predetermined temperature as quickly as possible from the temperature in the mixing step.
- cerium oxide is generated.
- the primary particles of cerium oxide are about a few nm, and these aggregate in a spherical shape to form secondary particles. This is the core part.
- the polymer aggregates on the surface of the secondary particles to form a shell portion.
- Some polymers forming the shell portion have the structure of the starting polymer, but the polymers may be crosslinked. In this way, a core part and an inseparable shell part are completed.
- a method of separation / washing for example, there is a method of precipitating nanoparticles with a centrifuge, discarding the supernatant, redispersing with an arbitrary solvent, and further repeating separation and removal of the supernatant.
- spherical CSCP nanoparticles can be dispersed in an arbitrary solvent to obtain a nanoparticle dispersion, or dried to obtain nanoparticle powder.
- the spherical CSCP nanoparticles in which the shell portion is reduced by separating and washing after dispersing the spherical CSCP nanoparticles in a solution in which the shell portion is dissolved and dissolving the shell portion. Nanoparticles can be obtained.
- the spherical CSCP nanoparticles are heated in air at a temperature of 150 ° C. or higher, more preferably at a temperature of 200 ° C. or higher, by partial combustion of the shell part, It is also possible to reduce the weight. In this case, separation and washing are performed as necessary. In this way, spherical CSCP nanoparticles having a reduced shell portion can be obtained.
- the polyol method is a very simple process, and is extremely low in cost as compared with a method for imparting dispersibility to inorganic oxide fine particles disclosed so far (for example, Patent Document 3).
- the spherical CSCP nanoparticles are mixed with, for example, a photocurable resin and a solvent to prepare an ink for manufacturing an aggregate of spherical CSCP nanoparticles.
- a photocurable resin examples include an acrylate resin and an epoxy resin.
- Monomers and oligomers having an acryloyl group include monofunctional monomers such as isooctyl acrylate, 2-hydroxyethyl methacrylate, n-acryloyloxyethyl hexahydrophthalimide, N, N-dimethylacrylamide, triethylene glycol diacrylate, 1, Examples include bifunctional monomers such as 6-hexanediol diacrylate, trifunctional or higher monomers such as pentaerythritol triacrylate, dipentaerythritol hexaacrylate, and oligomers such as urethane acrylate, epoxy acrylate, polyester acrylate, and polyether acrylate.
- monofunctional monomers such as isooctyl acrylate, 2-hydroxyethyl methacrylate, n-acryloyloxyethyl hexahydrophthalimide, N, N-dimethylacrylamide, triethylene glycol diacrylate, 1, Examples include bifunctional monomers such as
- polymerization initiator examples include diethoxyacetone phenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, isobutyl benzoin ether, isopropyl benzoin ether, benzyl dimethyl ketal, 1-hydroxy-cyclohexyl-phenyl-ketone, Examples include benzophenone, 2-chlorothioxanthone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
- solvents suitable for spherical CSCP nanoparticles there are solvents suitable for spherical CSCP nanoparticles and unsuitable solvents as solvents.
- the solvent suitable for the spherical CSCP nanoparticles include methyl ethyl ketone, methyl isobutyl ketone, methyl lactate, ethyl lactate, and butyl lactate.
- solvents that are inappropriate for spherical CSCP nanoparticles include ethanol, propylene glycol monomethyl ether, and ethylene glycol monobutyl ether.
- the influence of the solvent is not limited to the dispersibility of the spherical CSCP nanoparticles in the solvent, but the influence extends to the aggregate after immobilization, that is, after the solvent is volatilized.
- thermosetting resin can also be used instead of the photocurable resin.
- the spherical CSCP nanoparticles are mixed with a thermosetting resin and a solvent to prepare an ink for producing an aggregate of spherical CSCP nanoparticles.
- the method for forming the aggregate of spherical CSCP nanoparticles is arbitrary.
- the aggregate is formed on a substrate, screen printing, bar coating, spin coating, dip coating, etc. are exemplified.
- the surface of the base material forming the aggregate is washed, if ethanol is used as a cleaning solvent, the strength of the aggregate is reduced.
- a decrease in strength occurs only when spherical CSCP nanoparticles are included, and it is known that the strength decrease does not occur only with a fixative that does not include spherical CSCP nanoparticles. This is a unique phenomenon caused by CSCP nanoparticles. Therefore, in the case of spherical CSCP nanoparticles, ethanol cannot be used for cleaning purposes.
- examples of a method for forming an integrated body when a substrate is not used include stereolithography and dispensing.
- a solvent is a key point for immobilizing spherical CSCP nanoparticles with a fixing agent.
- alcohol or alcohol derivative solvents such as ethanol, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, etc.
- the characteristics mentioned above that is, the volume ratio of the spherical CSCP nanoparticles is a high concentration of 32% or more, and the fixing agent is used.
- the fixing agent is, for example, a photocurable resin
- the fixing agent is, for example, a thermocurable resin
- the fixing agent is, for example, a thermosetting resin
- it is cured by applying heat.
- the spherical CSCP nanoparticles are fixed in the resin obtained by curing the thermosetting resin as a fixing agent, and have mechanical strength.
- the volume ratio of spherical CSCP nanoparticles is the volume ratio of spherical CSCP nanoparticles occupying an aggregate of spherical CSCP nanoparticles.
- V (%) 100-V (%) is a volume ratio other than the spherical CSCP nanoparticles.
- a photocurable resin or the like is cured. Resin and voids are included.
- the volume ratio of spherical CSCP nanoparticles in the aggregate of spherical CSCP nanoparticles of the present invention is 32% or more.
- the volume ratio of the spherical CSCP nanoparticles is increased, the ratio of the fixing agent composed of the resin after the photocurable resin is cured is decreased, so that the mechanical strength is considered to be decreased.
- the spherical CSCP nanoparticle aggregate of the present invention is excellent in mechanical strength even when the volume ratio of the spherical CSCP nanoparticles is as high as 32% or more.
- the uniformity of the aggregate of spherical CSCP nanoparticles can be evaluated by SEM observation. Uniformity as used herein means that there is no change in the concentration of spherical CSCP nanoparticles present in the aggregate of spherical CSCP nanoparticles.
- a typical example of the case where there is no uniformity is a case where spherical CSCP nanoparticles having a diameter of 10 ⁇ m are divided into a region where almost no spherical CSCP nanoparticles are present and a region where spherical CSCP nanoparticles are present at a high density.
- being uniform means that a uniform distribution of spherical CSCP nanoparticles is observed even when magnified 10,000 times in SEM observation.
- the uniformity is poor, the mechanical strength is deteriorated and the transparency is lowered.
- the measuring method is not limited.
- a method for obtaining the refractive index of the aggregate formed on the substrate for example, there is a method using a spectroscopic ellipsometer (spectral ellipsometry). In this method, a method is used in which light is incident on the sample surface and the optical constants (refractive index and extinction coefficient) of the sample are determined from changes in the polarization state before and after reflection.
- the refractive index of the aggregate of spherical CSCP nanoparticles formed on the substrate is preferably 1.65 or more, more preferably 1.70 or more.
- Turbidity is an index representing transparency, and a method for obtaining this is, for example, the method of JIS 7361.
- turbidity was investigated using the haze meter (Nippon Denshoku Industries Co., Ltd. make, NDH5000).
- the turbidity of the aggregate of spherical CSCP nanoparticles formed on the substrate was 2% or less (the turbidity of the aggregate was determined by subtracting and correcting the turbidity of the substrate alone).
- the aggregate of spherical CSCP nanoparticles having excellent mechanical strength means that if there is a base material, the aggregate does not peel off from the base material, and the surface of the aggregate may be rubbed with a metal rod.
- a general spatula was rubbed against a thin film-like aggregate having a base material, and it was tested and evaluated whether the aggregate did not peel or break.
- the aggregate of spherical CSCP nanoparticles of the present invention has characteristics suitable for such a test.
- the aggregate of spherical CSCP nanoparticles obtained in the present invention has optical characteristics such as unprecedented mechanical strength, uniformity and transparency, and a large refractive index.
- spherical CSCP nanoparticles and their production methods are known, and it is also known to form an antireflection film with a polymer layer containing a high refractive index metal oxide.
- an aggregate of spherical CSCP nanoparticles is a self-organized aggregation of nanoparticles, no uniformity, no mechanical strength, fragile, large area There was a problem that the film could not be made and there was no light transmission.
- the present invention has a uniform distribution of spherical CSCP nanoparticles, contains a fixing agent composed of a resin, has excellent mechanical strength, and can easily produce a large-area film.
- Excellent in light transmission and ultraviolet shielding properties in particular, has excellent performance as an antireflection material used in displays, and is essentially different from conventional aggregates of spherical CSCP nanoparticles It has characteristics.
- An aggregate of spherical core-shell cerium oxide / polymer hybrid nanoparticles (spherical CSCP nanoparticles) can be produced and provided.
- the volume ratio of the spherical CSCP nanoparticles is a high concentration of 32% or more, contains the immobilizing agent, the spherical CSCP nanoparticles are uniformly distributed, has excellent mechanical strength, and facilitates large area membranes.
- the cerium oxide constituting the spherical CSCP nanoparticle aggregate has a high refractive index, and the spherical CSCP nanoparticle aggregate is dispersed in a photocurable resin (photosensitive resin) or a thermosetting resin. By fixing, a high refractive index layer suitably used for an antireflection agent can be produced. (4) A large-area film or film-shaped antireflection material having the high refractive index layer can be provided. (5) The high refractive index layer is useful as an antireflection material used in a display because it has transparency, uniformity, and ultraviolet absorption. (6) The spherical CSCP nanoparticle aggregate can be applied to a photonic crystal and can provide a high-performance optical device. (7) Since cerium oxide is excellent in ultraviolet shielding property, an ultraviolet shielding film can be produced and provided.
- the microstructure of sample 1-3 (Example 1) by SEM observation is shown.
- the microstructure (low magnification) of SEM observation of Sample 1-3 (Example 1) is shown.
- the portion that appears slightly white at the center is a color change at the time of observation at high magnification.
- the result of having evaluated the relationship between the wavelength and refractive index of the high refractive index layer of Sample 1-3 (Example 1) and the relationship between the wavelength and the extinction coefficient by spectroscopic ellipsometry is shown.
- the microstructure of Comparative Sample 1-1 is shown.
- spherical CSCP nanoparticles were synthesized. Ethylene glycol (EG), polyvinyl pyrrolidone (PVP), and cerium nitrate hexahydrate were used as raw materials, and these were mixed to prepare a raw material mixture. The concentrations of PVP and cerium nitrate hexahydrate on EG were 120 kg / m 3 and 0.6 kmol / m 3 , respectively.
- EG Ethylene glycol
- PVP polyvinyl pyrrolidone
- cerium nitrate hexahydrate were 120 kg / m 3 and 0.6 kmol / m 3 , respectively.
- the average molecular weight of PVP is 10,000 as a catalog value.
- the organic synthesizer CC200 manufactured by SIBATA
- the raw material mixture was heated to reflux at a predetermined temperature and time.
- the set temperature at this time was 165 ° C.
- the heating reflux time was 120 min after reaching the set temperature.
- the raw material mixture became cloudy.
- the cloudy liquid was quenched.
- the white turbid liquid was centrifuged at 18000 rpm, and washed with water and ethanol. After washing, it was dried at 80 ° C. to obtain a powder.
- This powder is spherical CSCP nanoparticles.
- As the solvent a mixed solvent of methyl ethyl ketone (MEK) and isophorone was used.
- the volume ratio of MEK to isophorone was 90:10.
- the weight of the spherical CSCP nanoparticle powder, the photocurable resin, and the spherical CSCP nanoparticle powder and the photocurable resin contained in the ink after mixing the solvent with respect to 1 mL of the ink. It was 0.1 g.
- the weight ratio of the spherical CSCP nanoparticle powder, PETA, and Irgacure 184 was 40: 20: 1.
- Samples 1-1 (Lot. 1020-2) and 1-2 (Lot. 1020-4) were obtained when slide glass and Si / SiO 2 were used as the base materials, respectively.
- a final sample was obtained by irradiating the integrated body with ultraviolet rays using a high-pressure mercury lamp.
- the ink for making Sample 1-3 is exactly the same as the above method except that the solvent is a mixed solvent of methyl isobutyl ketone (MIBK) and isophorone.
- MIBK methyl isobutyl ketone
- the volume ratio of MIBK to isophorone was 95: 5.
- Sample 1-3 (Lot. 1114-6) was prepared under the same conditions as described above.
- the TAC film was used without washing the surface with ethanol before coating.
- Table 1 Various characteristics of the obtained samples are summarized in Table 1. In this table, comparative examples described later are also described.
- FIG. 1 shows the microstructure of sample 1-3 (Example 1) by SEM observation.
- FIG. 2 shows the microstructure (low magnification) of Sample 1-3 (Example 1) by SEM observation. From these figures, the particle distribution was uniform and uniform (FIGS. 1 and 2). In FIG. 2, the portion that appears slightly white at the center is a color change during SEM observation at high magnification. This is presumably because the resin changed due to the electron beam.
- FIG. 3 shows the relationship between the wavelength and refractive index of the high refractive index layer of Sample 1-3 (Example 1), and the relationship between the wavelength and the extinction coefficient.
- a 54 nm layer having a refractive index of 1.548 (wavelength 550 nm) on the substrate was found to exist.
- a high refractive index layer and a low refractive index layer could be easily formed on a substrate.
- the average refractive index of the aggregate was 1.702.
- the haze value was evaluated with a haze meter. As a result, the haze value was 1.65% (corrected by removing the haze value of the base material).
- the volume ratio of the spherical CSCP nanoparticles in the sample 1-3 aggregate was 40% or more.
- the densities of the core (cerium oxide), the shell (polymer), and the cured resin after irradiating the photocurable resin with light are 7.28, 1.26, and 1.41 g, respectively.
- the volume fraction was calculated as / cm 3 .
- the volume ratio of the spherical CSCP nanoparticles in the layer having a refractive index of 1.720 is 73.8% as predicted from the refractive index.
- the refractive indexes of the core (cerium oxide), the shell (polymer), and the cured resin after irradiating light to the photocurable resin are 2.1, 1.52, and 1.
- the volume fraction was calculated as 53.
- Comparative Example 1 For comparison with the present invention, Comparative Samples 1-1 to 6 will be described.
- the method for producing the comparative sample is basically the same as in Example 1, but the differences from Example 1 are shown below.
- Comparative Sample 1-1 (Lot. 902-5) ...
- Solvent Ethanol, Aggregate Forming Method: Ink Dropping Only, Base Material: Slide Glass Comparative Sample 1-2 (Lot. 902-6) ...
- Solvent Ethanol, aggregate formation method: Ink dripping only, substrate: Si / SiO 2
- Comparative Sample 1-3 (Lot. 116-1)
- Solvent Propylene glycol monomethyl ether
- Base material Polyethylene terephthalate (PET) film
- Comparative sample 1-4 (Lot. 116-4) ...
- Solvent ethylene glycol monobutyl ether
- substrate TAC film
- Comparative sample 1-5 (Lot. 1104-1)
- Solvent ethanol
- Base material TAC film comparison sample 1-6 (Lot. 1114-3)
- Base material TAC film, the surface was washed with ethanol before coating.
- Comparative Samples 1-1 to 4 used ethanol, propylene glycol monomethyl ether, and ethylene glycol monobutyl ether as the solvent.
- FIG. 4 shows the microstructure of comparative sample 1-1. As can be seen from the figure, there was a problem in the non-uniformity of the microstructure (FIG. 4), and there was a problem in the mechanical strength. The upper right portion of FIG. 4 is where only the resin is present, and the lower left portion is where the spherical CSCP nanoparticles are densely present. Thus, in Comparative Sample 1-1, spherical CSCP nanoparticles are present non-uniformly.
- Comparative Sample 1-5 is a case where ethanol is used as a solvent and ink containing no spherical CSCP nanoparticles is used. In this case, a film is formed. Therefore, when the spherical CSCP nanoparticles are not contained, ethanol is suitable as the solvent. However, when the spherical CSCP nanoparticles are contained, there arises a problem that the spherical CSCP nanoparticles have an uneven distribution.
- spherical CSCP nanoparticles were synthesized in the same manner as in Example 1 above.
- the spherical CSCP nanoparticle powder was mixed with a photocurable resin and a solvent to prepare an ink.
- the monomer of the photocurable resin and the polymerization initiator are the same as in Example 1.
- the weight ratio of PETA, which is a monomer of the photocurable resin, and Irgacure 184, which is a polymerization initiator was also the same as in Example 1, and was 100: 5.
- As the solvent a mixed solvent of MIBK and isophorone was used.
- the volume ratio of MIBK to isophorone was 95: 5.
- the weight of the spherical CSCP nanoparticle powder and the photocurable resin (PETA and Irgacure 184) contained in the ink after mixing the spherical CSCP nanoparticle powder, the photocurable resin, and the solvent is 0 with respect to 1 mL of the ink. 0.1 g.
- the weight ratio of the spherical CSCP nanoparticle powder, PETA, and Irgacure 184 was 40: 20: 1.
- Sample 2-1 was not damaged and was found to have excellent mechanical strength in a scratch test with a spatula. Further, when the microstructure was examined by SEM observation, it was confirmed that the resin was present between the spherical CSCP nanoparticles without any gap. Further, the particle distribution was uniform with no roughness.
- Refractive index was evaluated by spectroscopic ellipsometry. As a result, there is a 158.6 nm layer with a refractive index of 1.686 (wavelength 550 nm) on the substrate, and a 35.6 nm layer with a refractive index of 1.576 (wavelength 550 nm) on the substrate. It was found that there was a 122.6 nm layer having a refractive index of 1.698 (wavelength 550 nm) and a 42.5 nm layer having a refractive index of 1.529 (wavelength 550 nm).
- the average refractive index of the entire layer was 1.661.
- the haze value was evaluated with a haze meter. As a result, the haze value was 0.77% (corrected by removing the haze value of the base material). Similar to Sample 1-3 of Example 1, the volume fraction of spherical CSCP nanoparticles in the aggregate was calculated to be 40% or more.
- spherical CSCP nanoparticles were synthesized in the same manner as in Example 1.
- the spherical CSCP nanoparticle powder was heat-treated at 200 ° C. in the air for 4 hours to reduce the shell weight.
- the spherical CSCP nanoparticle powder after firing was mixed with a photocurable resin and a solvent to prepare an ink.
- the monomer of the photocurable resin and the polymerization initiator are the same as in Example 1.
- As the solvent a mixed solvent of MIBK and 3-methoxy-3-methyl-1-butanol was used.
- the volume ratio of MIBK to 3-methoxy-3-methyl-1-butanol was 80:20.
- the weight of the sintered spherical CSCP nanoparticle powder and the photocurable resin (PETA and Irgacure 184) contained in the ink after mixing the spherical CSCP nanoparticle powder, the photocurable resin, and the solvent is 1 mL of ink. 0.05 g.
- the weight ratio of the spherical CSCP nanoparticle powder, PETA, and Irgacure 184 was 40: 20: 1.
- Sample 3-1 was found not to be scratched and excellent in mechanical strength by a scratch test using a spatula. Further, when the microstructure was examined by SEM observation, it was confirmed that the resin was present between the spherical CSCP nanoparticles without any gap. Further, the particle distribution was uniform with no roughness.
- an aggregate was produced under the same conditions as in Example 3 except for the weight ratio of spherical CSCP nanoparticle powder, PETA, and Irgacure 184.
- the weight ratio of spherical CSCP nanoparticle powder, PETA, and Irgacure 184 was 60: 20: 1.
- the aggregate thus obtained is Sample 4-1 (Lot. 615-2).
- Sample 4-1 was also scratched with a spatula and was found not to be scratched and excellent in mechanical strength. Further, when the microstructure was examined by SEM observation, it was confirmed that the resin was present between the spherical CSCP nanoparticles without any gap. Further, the particle distribution was uniform with no roughness.
- Refractive index was evaluated by spectroscopic ellipsometry. As a result, there is a 75 nm layer with a refractive index of 1.834 (wavelength 550 nm) on the substrate, and there is a 61 nm layer with a refractive index of 1.565 (wavelength 550 nm) on it. As a result.
- the volume ratio of the spherical CSCP nanoparticles having a refractive index exceeding 1.8 is 72% or more when predicted from the refractive index when it is fired.
- the refractive indexes of the core (cerium oxide), the shell (polymer), and the cured resin after irradiating light to the photocurable resin are 2.1, 1.52, and 1.
- the volume fraction was calculated as 53. In this way, by accumulating spherical CSCP nanoparticles, it was possible to produce a CSCP nanoparticle aggregate having a very high concentration.
- spherical CSCP nanoparticles were synthesized in the same manner as in Example 1. However, the average molecular weight of PVP was a catalog value of 55,000, and the heating reflux time was changed to 100 min. The spherical CSCP nanoparticles thus obtained had a particle size of about 60 nm.
- Example 3 The same baking treatment (heat treatment) as in Example 3 was added to the obtained spherical CSCP nanoparticle powder. Next, this was mixed with a photocurable resin and a solvent to prepare an ink. Dipentaerythritol hexaacrylate (DPHA) was used as a monomer for the photocurable resin.
- the polymerization initiator is Irgacure 184 as in the previous examples.
- the same solvent as in Example 3 was used.
- the weight of the fired spherical CSCP nanoparticle powder and the photocurable resin contained in the ink after mixing the spherical CSCP nanoparticle powder, the photocurable resin, and the solvent was 0.046 g with respect to 1 mL of the ink. It was.
- the weight ratio of the spherical CSCP nanoparticle powder, DPHA, and Irgacure 184 was 40: 20: 1.
- the refractive index was evaluated by spectroscopic ellipsometry and calculated with a one-layer model, which was about 1.733. Further, a scratch test using a spatula revealed that the scratch was not found and the mechanical strength was excellent. Further, when the microstructure was examined by SEM observation, it was confirmed that the resin was present between the spherical CSCP nanoparticles without any gap. Further, the particle distribution was uniform with no roughness.
- the present invention relates to an aggregate of spherical core-shell cerium oxide / polymer hybrid nanoparticles, and according to the present invention, the volume ratio of spherical CSCP nanoparticles is a high concentration of 32% or more.
- the cerium oxide constituting the spherical core-shell type cerium oxide / polymer hybrid nanoparticle aggregate of the present invention has a high refractive index and has various properties such as absorption of ultraviolet rays.
- the present invention is useful as a new spherical CSCP nanoparticle aggregate, a method for producing the same, and an antireflection material having a high refractive index layer.
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Abstract
Description
(1)コア部が酸化セリウムの一次粒子が集合した球状の二次粒子であり、シェル部が高分子である球状のコアシェル型酸化セリウム/高分子ハイブリッドナノ粒子を均一分布させて集積した集積体であって、1)当該コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の体積割合が少なくとも32%の高濃度であり、2)樹脂から構成される固定剤を含み、3)当該コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の粒子間に、当該固定剤が充填された構造を有し、4)当該コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子が均一に分布し、5)機械的強度を有している、ことを特徴とする球状コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の集積体。
(2)前記固定剤が、光硬化性樹脂又は熱硬化性樹脂に、光を照射して又は熱を与えて、硬化した後の樹脂である、前記(1)記載の球状コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の集積体。
(3)前記球状のコアシェル型酸化物/高分子ハイブリッドナノ粒子のコア部分の表面に、シランカップリング剤又は界面活性剤が存在しない、前記(1)記載の球状コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の集積体。
(4)基板又は基材上に成膜された膜状構造を有する、前記(1)記載の球状コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の集積体。
(5)屈折率が、低くても1.65である、前記(1)記載の球状コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の集積体。
(6)濁度が、高くても2%である、前記(1)記載の球状コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の集積体の集積体。
(7)前記(1)記載の球状コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の集積体で構成されることを特徴とする光反射防止膜。
(8)前記(1)記載の球状コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の集積体を作製するためのインクであって、コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子、光硬化性樹脂、及び溶剤から構成されることを特徴とするインク。
(9)前記(1)記載の球状コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の集積体を製造する方法であって、コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子、光硬化性樹脂又は熱硬化性樹脂、及び溶剤から構成されるインクを調製する工程と、そのインクを成形して成形体とする工程と、得られた成形体に光を照射して又は熱を与えて硬化する工程からなることを特徴とする球状コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の集積体の製造方法。
(10)前記溶剤が、メチルエチルケトン、メチルイソブチルケトン、乳酸メチル、乳酸エチル、又は乳酸ブチルである、前記(9)に記載の球状コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の集積体の製造方法。
本発明は、コア部が酸化セリウムで、シェル部が高分子である球状のコアシェル型酸化セリウム/高分子ハイブリッドナノ粒子を均一分布させて集積した集積体であって、当該コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の体積割合が少なくとも32%の高濃度であり、樹脂から構成される固定剤を含み、当該コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の粒子間に、当該固定剤が充填された構造を有し、当該コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子が均一に分布し、機械的強度を有している、ことを特徴とするものである。
(1)球状コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子(球状CSCPナノ粒子)の集積体を製造し、提供することができる。
(2)球状CSCPナノ粒子の体積割合が32%以上の高濃度であり、固定化剤を含み、球状CSCPナノ粒子が均一に分布し、機械的強度に優れていて、大面積の膜を容易に作製することができ、光の透過性と紫外線遮蔽性に優れている球状CSCPナノ粒子の集積体を提供することができる。
(3)上記球状CSCPナノ粒子の集積体を構成する酸化セリウムは、屈折率が高く、該球状CSCPナノ粒子の集積体を、光硬化性樹脂(感光性樹脂)又は熱硬化性樹脂に分散して、固定化することで、反射防止剤に好適に使われる高屈折率層を作製することができる。
(4)上記高屈折率層を有する大面積の膜ないしフィルム状の反射防止材を提供することができる。
(5)上記高屈折率層は、透明性、均一性があり、紫外線吸収性があることから、ディスプレイに使用される反射防止材として有用である。
(6)上記球状CSCPナノ粒子の集積体は、フォトニック結晶への応用が可能であり、高機能光学デバイスを提供することができる。
(7)酸化セリウムが紫外線遮蔽性に優れていることから、紫外線遮蔽フィルムを作製し、提供することができる。
本実施例では、まず初めに、球状CSCPナノ粒子の合成を行った。原料として、エチレングリコール(EG)、ポリビニルピロリドン(PVP)、硝酸セリウム六水和物を使用し、これらを混合し、原料混合液を調製した。PVP及び硝酸セリウム六水和物のEGに対する濃度は、それぞれ120kg/m3及び0.6kmol/m3であった。
次に、上記球状CSCPナノ粒子粉体を、光硬化性樹脂、及び溶剤と混合して、インクを調製した。光硬化性樹脂のモノマーとして、ペンタエリスリトールトリアクリレート(PETA、NKエステル A-TMM-3LM-N、新中村化学製、トリエステル含量57%)を使用し、光硬化性樹脂の重合開始剤として、イルガキュア184(チバスペシャリティケミカルズ製、1-ヒドロキシ-シクロヘキシル フェニルケトン)を使用した。
本発明と対比するために、比較サンプル1-1から6について説明する。比較サンプルの作製方法については、基本的には、実施例1と同条件であるが、実施例1との相違点を、以下に示す。
比較サンプル1-1(Lot.902-5)・・・溶剤:エタノール、集積体形成方法:インクの滴下のみ、基材:スライドガラス
比較サンプル1-2(Lot.902-6)・・・溶剤:エタノール、集積体形成方法:インクの滴下のみ、基材:Si/SiO2
比較サンプル1-3(Lot.116-1)・・・溶剤:プロピレングリコールモノメチルエーテル、基材:ポリエチレンテレフタラート(PET)フィルム
比較サンプル1-5(Lot.1104-1)・・・溶剤:エタノール、球状CSCPナノ粒子は含有しない、基材:TACフィルム
比較サンプル1-6(Lot.1114-3)・・・基材:TACフィルム、塗膜前にエタノールで表面を洗浄した。
Claims (10)
- コア部が酸化セリウムの一次粒子が集合した球状の二次粒子であり、シェル部が高分子である球状のコアシェル型酸化セリウム/高分子ハイブリッドナノ粒子を均一分布させて集積した集積体であって、(1)当該コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の体積割合が少なくとも32%の高濃度であり、(2)樹脂から構成される固定剤を含み、(3)当該コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の粒子間に、当該固定剤が充填された構造を有し、(4)当該コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子が均一に分布し、(5)機械的強度を有している、ことを特徴とする球状コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の集積体。
- 前記固定剤が、光硬化性樹脂又は熱硬化性樹脂に、光を照射して又は熱を与えて、硬化した後の樹脂である、請求項1記載の球状コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の集積体。
- 前記球状のコアシェル型酸化物/高分子ハイブリッドナノ粒子のコア部分の表面に、シランカップリング剤又は界面活性剤が存在しない、請求項1記載の球状コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の集積体。
- 基板又は基材上に成膜された膜状構造を有する、請求項1記載の球状コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の集積体。
- 屈折率が、低くても1.65である、請求項1記載の球状コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の集積体。
- 濁度が、高くても2%である、請求項1記載の球状コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の集積体の集積体。
- 請求項1記載の球状コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の集積体で構成されることを特徴とする光反射防止膜。
- 請求項1記載の球状コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の集積体を作製するためのインクであって、コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子、光硬化性樹脂、及び溶剤から構成されることを特徴とするインク。
- 請求項1記載の球状コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の集積体を製造する方法であって、コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子、光硬化性樹脂又は熱硬化性樹脂、及び溶剤から構成されるインクを調製する工程と、そのインクを成形して成形体とする工程と、得られた成形体に光を照射して又は熱を与えて硬化する工程からなることを特徴とする球状コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の集積体の製造方法。
- 前記溶剤が、メチルエチルケトン、メチルイソブチルケトン、乳酸メチル、乳酸エチル、又は乳酸ブチルである、請求項9に記載の球状コアシェル型酸化セリウム/高分子ハイブリッドナノ粒子の集積体の製造方法。
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US13/389,140 US9139745B2 (en) | 2009-08-11 | 2010-07-23 | Aggregate of spherical core-shell cerium oxide/polymer hybrid nanoparticles and method for producing the same |
KR1020127002385A KR101398506B1 (ko) | 2009-08-11 | 2010-07-23 | 구상 코어셸형 산화세륨/고분자 하이브리드 나노입자의 집적체 및 그 제조 방법 |
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JP2016532678A (ja) * | 2013-07-18 | 2016-10-20 | ユニバーシテ ニース ソフィア アンティポリス | 活性または生理活性ネットワークの重合化酸化セリウムナノ粒子、その保護局所処置、調製方法、およびそれらの用途 |
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KR101398506B1 (ko) | 2014-05-30 |
CN102625817B (zh) | 2014-04-23 |
KR20120064666A (ko) | 2012-06-19 |
US20120142808A1 (en) | 2012-06-07 |
TWI439419B (zh) | 2014-06-01 |
US9139745B2 (en) | 2015-09-22 |
CN102625817A (zh) | 2012-08-01 |
TW201107239A (en) | 2011-03-01 |
JP4682368B2 (ja) | 2011-05-11 |
JP2011057960A (ja) | 2011-03-24 |
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