WO2017200169A1 - Hollow aluminosilicate particles and method of manufacturing the same - Google Patents

Hollow aluminosilicate particles and method of manufacturing the same Download PDF

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Publication number
WO2017200169A1
WO2017200169A1 PCT/KR2016/014721 KR2016014721W WO2017200169A1 WO 2017200169 A1 WO2017200169 A1 WO 2017200169A1 KR 2016014721 W KR2016014721 W KR 2016014721W WO 2017200169 A1 WO2017200169 A1 WO 2017200169A1
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shell
particles
hollow
core
aluminosilicate particles
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PCT/KR2016/014721
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French (fr)
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Moo-Hyun CHOI
Jun-Chan LEE
Eon-Sik KIM
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Advanced Nano Products Co., Ltd.
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Publication of WO2017200169A1 publication Critical patent/WO2017200169A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C01P2004/34—Spheres hollow
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the present invention relates to hollow aluminosilicate particles and a method of manufacturing the same and, more particularly, to hollow aluminosilicate particles and a method of manufacturing the same, wherein an organic polymer in the shell may be removed without high-temperature sintering, as a consequence of which the hollow aluminosilicate particles may exhibit a low degree of aggregation and high dispersibility, and high density thereof may be obtained through a hydrothermal reaction.
  • hollow particles are used for displays and lenses requiring low reflectiveness, as indicated by a low refractive index, and may also be utilized in thermal insulation materials, drug delivery systems, and low dielectrics, which are required to have a hollow shape and a low refractive index.
  • Particles having a hollow shape with a particle diameter of 0.03 to 380 mm are manufactured in a manner in which active silica is reacted on a core (made of a material other than silica) in an acidic or alkaline metal aqueous solution to form a silica shell, and the core is removed without breaking the silica shell.
  • the aforementioned manufacturing method is performed by forming a silica shell using water glass or a silane polycondensation material on template core particles composed of acid- or base-soluble zinc, iron oxide or aluminum silicate oxide, and then dissolving the internal material (i.e. the core) with a strong acid or a strong base to discharge it.
  • this method makes it difficult to control the size of the hollow structure, and is disadvantageous in that processing uses ion exchange resin or ultrafiltration, which is complicated, undesirably increasing manufacturing costs.
  • hollow silicate particles by forming a core using a polymer such as an epoxy polymer, growing a silicate shell on the core, and removing the core (the polymer).
  • the particles thus manufactured are configured such that the silica shell is dense, and thus, it is not easy to remove the polymer from the inside of the shell using water or other solvents.
  • hollow silica particles may aggregate during the high-temperature burning, it is difficult to redisperse the manufactured particles in the solution. Furthermore, when such particles are applied to an optical coating, the resulting coating film may be very hazy or have low transmittance.
  • the process of manufacturing hollow particles using the template polymer as the core may include the formation of strong cations by adding a polymer electrolyte, such as polyvinyl pyrrolidone (PVP), polycyclic aromatic hydrocarbon (PAH), AIBN (PS core) and a metal salt, in order to uniformly form the shell material on the surface of the core.
  • a polymer electrolyte such as polyvinyl pyrrolidone (PVP), polycyclic aromatic hydrocarbon (PAH), AIBN (PS core) and a metal salt.
  • PVP polyvinyl pyrrolidone
  • PAH polycyclic aromatic hydrocarbon
  • PS core AIBN
  • metal salt a metal salt
  • Korean Patent No. 1461203 discloses a method of manufacturing hollow particles, in which a metal oxide is added to silicate particles and dissolved using a basic or acidic solution to prepare a shell having fine pores, whereby the dissolved core materials are discharged through the fine pores.
  • this method is problematic because shell particles may be non-uniformly produced due to the fine pores formed in the shell, and the shell may break down during the process of increasing the density of the shell, making it difficult to form uniform hollow particles having high density.
  • Patent Document 1 Japanese Patent Application Publication No. 2011-042527
  • Patent Document 2 Japanese Patent Application Publication No. 2010-131593
  • Patent Document 3 Korean Patent No. 1461203
  • the present invention has been made keeping in mind the problems encountered in the related art, and the present invention is intended to provide hollow aluminosilicate particles, in which an aluminosilicate shell is formed on a core composed of an organic polymer, after which the organic polymer is removed from the inside of the shell without high-temperature sintering, so the particles may exhibit a low degree of aggregation and high dispersibility, and high density thereof may be obtained through a hydrothermal reaction.
  • the amount of aluminum for forming fine pores is adjusted, whereby high-density hollow particles may result upon hydrothermal reaction without breaking the shell particles.
  • the present invention is intended to provide a method of manufacturing hollow aluminosilicate particles, which enables the formation of a uniform shell even without additional core surface treatment by forming negative charges during the preparation of a complex oxide through the reaction of an aluminum precursor and a silica precursor upon forming a shell, resulting in hollow particles wherein the shell is not broken during the high-density reaction but is uniform.
  • the roughness of the shell and degree of agglomeration is severely affected by the amount of aluminum used for the formation of complex oxide shell.
  • the present invention provides a method of manufacturing hollow aluminosilicate particles, comprising: reacting a template core composed of an organic polymer in micelle or reverse micelle form with a silane compound and an aluminum precursor, thus synthesizing core-shell particles having an aluminosilicate shell; reacting the core-shell particles with a basic aqueous solution or an acidic aqueous solution, thus simultaneously forming fine pores in the shell and removing the core, thereby producing hollow aluminosilicate particles; and performing a hydrothermal reaction so as to increase the density of the hollow aluminosilicate particles.
  • the aluminosilicate shell may include X mol of Si and Y mol of Al, and the X/Y molar ratio may range from 7 to 15.
  • the hydrothermal reaction may be carried out at a temperature ranging from 160 to 230°C.
  • the hollow aluminosilicate particles may have an average particle size ranging from 10 to 300 nm, and the shell may have a thickness of 5 to 15 nm.
  • the organic polymer may be a copolymer or a block copolymer including a polymer selected from the group consisting of polyoxyethylene, polyoxyethylene glycol, polyoxypropylene alkyl ether, polyoxypropylene monoalkylether, polyoxypropylene alkyl, polyoxyethylene tallow amine, polyoxyethylene oleyl amine, polyoxyethylene stearyl amine, polyoxyethylene lauryl amine, polyoxyethylene sorbitan ester, polyoxyethylene octyl ether, polyoxyethylene glycerin ether, polyacrylic acid, polysulfonic acid, polyacryl amine, and triethylene amine.
  • the silane compound may be represented by Chemical Formula 1 below.
  • R 1 , R 2 , R 3 and R 4 are each independently an alkyl group, an alkoxy group, a phenyl group, a vinyl group, a halogen group, an epoxy group, a glycidoxy group, an amino group or a mercapto group.
  • the aluminum precursor may be an organic salt of aluminum or aluminum alkoxide.
  • the basic aqueous solution may be sodium hydroxide, ammonium hydroxide, potassium hydroxide, hydroxyphosphate or a mixed solution thereof
  • the acidic aqueous solution may be hydrochloric acid, nitric acid, sulfuric acid, acetic acid or a mixed solution thereof.
  • the present invention provides a composition for forming a film, comprising the aforementioned hollow aluminosilicate particles.
  • the hollow aluminosilicate particles may have an average particle size ranging from 10 to 300 nm, and the shell may have a thickness of 5 to 15 nm.
  • the present invention provides an anti-reflective film, comprising a transparent film formed through a coating process using the aforementioned composition.
  • the anti-reflective film may have a transmittance increase of at least 3%, a refractive index of 1.31 or less, a reflectance of 1.5 or less, and a haze of 1 or less.
  • hollow aluminosilicate particles can result from forming an aluminosilicate shell on a core composed of an organic polymer and then removing the organic polymer from the inside of the shell without high-temperature sintering, thus exhibiting a low degree of aggregation and high dispersibility, and also high density thereof can be obtained through a hydrothermal reaction.
  • a method of manufacturing hollow aluminosilicate particles enables the formation of a uniform shell even without additional core surface treatment by forming charges during the preparation of a complex oxide through the reaction of an aluminum precursor and a silica precursor upon forming a shell, resulting in hollow particles with smooth surface wherein the shell is not broken and less aggregated during the high-density reaction but is uniform.
  • FIG. 1 schematically shows a process of manufacturing hollow aluminosilicate particles according to the present invention
  • FIGS. 2A to 2F show transmission electron microscope (TEM) images of hollow aluminosilicate particles, manufactured in Example of the present invention and Comparative Examples;
  • FIGS. 3A to 3F show TEM images of hollow aluminosilicate particles, manufactured in Example of the present invention and Comparative Examples and subjected to a high-density reaction.
  • FIG. 1 schematically shows the process of manufacturing hollow aluminosilicate particles according to the present invention.
  • the method of manufacturing hollow aluminosilicate particles according to the present invention includes the steps of synthesizing core-shell particles, forming hollow aluminosilicate particles, and performing a hydrothermal reaction.
  • the step of synthesizing core-shell particles is performed in a manner in which a template core comprising an organic polymer in micelle or reverse micelle form is reacted with a silane compound and an aluminum precursor, thus synthesizing core-shell particles having an aluminosilicate shell.
  • the template core may be provided in the form of a micelle or reverse micelle in the solvent.
  • the micelle or reverse micelle is prepared from the organic polymer.
  • the organic polymer exhibits amphoteric functional characteristics, that is, hydrophobic and hydrophilic properties, and such amphoteric functional characteristics are manifested as functional groups having the same properties becoming attached to each other.
  • amphoteric functional characteristics that is, hydrophobic and hydrophilic properties, and such amphoteric functional characteristics are manifested as functional groups having the same properties becoming attached to each other.
  • the counterpart functional group namely a hydrophilic functional group
  • a hydrophobic functional group is formed in an outward direction.
  • a hydrophobic functional group is formed in an outward direction, thus forming a micelle.
  • Such functional characteristics may vary depending on the polarity of the solvent that is added upon preparation of the micelle and on the molecular weight of the functional group.
  • the organic polymer forms micelle- or reverse micelle-type particles which are uniform in a specific solvent, is easily dispersed in the solvent, and is bondable to the silane compound so as to form a shell.
  • the organic polymer may include a copolymer or block copolymer of the polymer.
  • the copolymer or block copolymer of the polymer may typically function as a surfactant.
  • Specific examples of the polymer may include polyoxyethylene, polyoxyethylene glycol, polyoxypropylene alkyl ether, polyoxypropylene monoalkylether, polyoxypropylene alkyl, polyoxyethylene tallow amine, polyoxyethylene oleyl amine, polyoxyethylene stearyl amine, polyoxyethylene lauryl amine, polyoxyethylene sorbitan ester, polyoxyethylene octyl ether, polyoxyethylene glycerin ether, polyacrylic acid, polysulfonic acid, polyacryl amine, and triethylene amine.
  • the copolymer or block copolymer of the polymer may include a polyoxyethylene-polyoxyethylene block copolymer, or may include at least one selected from the group consisting of polyoxyethylene glycol, polyoxyethylene-polyoxypropylene alkyl ether, polyoxyethylene-polyoxypropylene monoalkylether, polyoxyethylene-polyoxypropylene alkyl copolymer, polyoxyethylene tallow amine, polyoxyethylene oleyl amine, polyoxyethylene stearyl amine, polyoxyethylene lauryl amine, polyoxyethylene sorbitan ester, polyoxyethylene octyl ether, and polyoxyethylene glycerin ether.
  • useful as the organic polymer is a mixture of polyacrylic acid and polystyrene sulfonic acid.
  • the organic polymer is able to form a micelle or a reverse micelle in the solvent.
  • the kind of solvent is not particularly limited, and may be selected depending on the properties of the organic polymer.
  • the solvent may include an alcohol, glycol ester, ketone or a mixture thereof.
  • the alcohol may include methyl alcohol, ethyl alcohol and isopropyl alcohol
  • examples of the glycol ester may include methyl cellosolve and ethyl cellosolve
  • examples of the ketone may include methyl ethyl ketone and methyl isobutyl ketone.
  • the amount of the organic polymer is not particularly limited, and may be set within the range of 1 to 50 parts by weight based on 100 parts by weight of the solvent. Given the above amount range, it is easy to form the micelle or reverse micelle, and high dispersibility may result.
  • the shell is formed from the silane compound and the aluminum precursor, and is specifically formed in a manner in which the silane compound and the aluminum precursor are added to the solvent containing the core comprising the organic polymer in micelle or reverse micelle form.
  • the silane compound may be easily coupled with the organic polymer that forms a template core. This coupling may be performed through a St?ber method (Werner, 1968) known in the art. In the preparation of the shell using a sol-gel process through the St?ber method, a stable shell may be manufactured through hydrolysis and polycondensation synthesis using an acidic solution or a basic solution contained in the solvent.
  • the silane compound may be represented by Chemical Formula 1 below.
  • R 1 , R 2 , R 3 and R 4 are each independently an alkyl group, an alkoxy group, a phenyl group, a vinyl group, a halogen group, an epoxy group, a glycidoxy group, an amino group or a mercapto group.
  • the silane compound may include alkoxysilane, chlorosilane, bromosilane and alkylsilane without particular limitation, and more specifically, useful is at least one selected from the group consisting of tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(b-methoxyethoxy)silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyld
  • the aluminum precursor may be an organic salt of aluminum or aluminum alkoxide.
  • the aluminum precursor is used as a component for forming the shell, and may be somewhat dissolved in the basic aqueous solution, as will be described later, whereby fine pores are formed in the shell, thus facilitating the discharge of the dissolved core material.
  • the kind of aluminum precursor is not particularly limited, and an organic salt of aluminum or aluminum alkoxide may be used.
  • the aluminosilicate shell contains X mol of Si and Y mol of Al, and the X/Y molar ratio may range from 7 to 15. If the X/Y molar ratio is less than 7, the dissolved core particles may become easy to discharge because of the large amount of aluminum, but a complete hollow shape is not formed due to the fine pores in the surface of the shell, thus deteriorating the strength of the particles, making it impossible to manufacture high-density hollow particles. Furthermore, since the refractive index of the resulting particles may increase due to the presence of aluminum, which is not dissolved in the shell particles, the particles are unsuitable for use in material fields requiring a low refractive index.
  • the amount of aluminum in the acidic aqueous solution or basic aqueous solution is low, and thus not only the surface aluminum of the shell particles but also the core particles are incompletely removed, undesirably increasing a refractive index or causing haze in the formation of the film.
  • the step of forming hollow aluminosilicate particles is performed in a manner in which the core-shell particles are reacted with a basic aqueous solution or an acidic aqueous solution, thus simultaneously forming fine pores in the shell and removing the core, thereby affording the hollow aluminosilicate particles.
  • the silane compound and the aluminum precursor are coupled with the core material, thus forming the shell containing a complex precursor of aluminum oxide and silica, resulting in core-shell particles.
  • the core-shell particles are reacted with the basic aqueous solution or the acidic aqueous solution, whereby a portion of the aluminum oxide of the complex oxide of aluminum and silica for the shell is removed, and fine pores are formed in the shell.
  • the kind of basic aqueous solution or acidic aqueous solution is not particularly limited, and specific examples of the basic aqueous solution may include sodium hydroxide, ammonium hydroxide, potassium hydroxide, hydroxyphosphate and mixed solutions thereof, and examples of the acidic aqueous solution may include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, and mixed solutions thereof.
  • the fine pores thus formed facilitate the entry and discharge of the dissolved organic polymer, and thus the organic polymer may be removed from the inside of the shell through a simple washing process.
  • the washing process functions to dissolve the organic polymer (the core material) inside the shell, and the dissolved organic polymer may be discharged to the outside through the fine pores in the shell by washing.
  • the solvent that is used in the washing process may include distilled water, alcohol, glycol, glycol ester or mixtures thereof.
  • the alcohol may include methyl alcohol, ethyl alcohol and isopropyl alcohol
  • examples of the glycol may include ethylene glycol, propylene glycol and xylene glycol
  • examples of the glycol ester may include ethyl cellosolve and methyl cellosolve.
  • the step of performing the hydrothermal reaction is conducted in a manner in which a hydrothermal reaction is carried out so as to increase the density of the hollow aluminosilicate particles.
  • the particles In order to use hollow particles as an optical coating agent, the particles should be configured such that no external organic material enters the cavities thereof and such that abrasion resistance and adhesion are maintained. To this end, the pores formed in the shell should disappear, and the shell should have high density. Hence, the density of the hollow aluminosilicate particles may be increased through a hydrothermal reaction.
  • the hydrothermal reaction may be carried out at a temperature ranging from 160 to 250°C, and particularly from 160 to 200°C. If the temperature of the hydrothermal reaction is lower than 160°C, a density as high as desired cannot be obtained, making it difficult to apply the resulting particles to displays and lenses requiring physical properties such as scratch resistance and low-reflection properties including increased transmittance (DT%), low refractive index, low reflectance, and low haze.
  • DT% transmittance
  • refractive index low refractive index
  • low reflectance low haze
  • the hollow aluminosilicate nanoparticles may have an average particle size of 10 to 300 nm, and the shell may have a thickness ranging from 5 to 15 nm.
  • the average particle size of the hollow aluminosilicate nanoparticles may range from 10 to 100 nm. If the particle size exceeds 100 nm, the resulting film may become opaque due to scattering of light in the course of coating and substrate lamination. On the other hand, if the particle size is less than 10 nm, it is difficult to expect a low refractive index due to a hollow shape.
  • the hollow ratio of the hollow aluminum-silicate particles may range from 50 to 95%. Given the above range, it is easy to remove the core during the manufacturing of the particles.
  • the hollow aluminum oxide-silicate particles may contain silica and aluminum oxide in amounts of 0.1 to 30 wt%. Given the above amount range, the particles have superior properties. Also, fine pores may be formed in the shell. During the manufacturing of the particles, the core material that is dissolved may be easily discharged from the shell through the fine pores, resulting in hollow particles in which the core is empty.
  • the present invention addresses a composition for forming a film, which includes the hollow aluminosilicate particles.
  • the kind of component of the composition for forming a film is not particularly limited, and components of the composition for forming a film typically useful in the art may be easily used, with the exception that the hollow aluminum oxide-silicate particles manufactured according to the present invention are included.
  • the present invention addresses an anti-reflective film, which includes a transparent film formed through a coating process using the composition for forming a film.
  • the hollow aluminum silicate particles have as low reflectance as desired, and may thus be easily utilized for films.
  • the anti-reflective film may have a transmittance increase of at least 3%, a refractive index of 1.31 or less, a reflectance of 1.5 or less, and a haze of 1 or less, whereby the anti-reflective film may be employed in display panels requiring a low refractive index and high transmittance, optical coating materials, AR (Anti-Refraction) coating layers, BLUs (Back Light Units) for high-luminance LCD/PDP, and high-efficiency display polarizer plates and prism sheets.
  • Example 2 The hollow aluminosilicate particles of Example 2 were manufactured in the same manner as in Example 1, with the exception that 5 mL of 3% aluminum isopropoxide was used.
  • Example 3 The hollow aluminosilicate particles of Example 3 were manufactured in the same manner as in Example 1, with the exception that 6 mL of 3% aluminum isopropoxide was used.
  • the hollow aluminosilicate particles of Comparative Example 4 were manufactured in the same manner as in Example 1, with the exception that 3 mL of 3% aluminum isopropoxide was used.
  • the aluminosilicate particles of Comparative Example 5 were manufactured in the same manner as in Example 1, with the exception that 1 mL of 3% aluminum isopropoxide was used.
  • the aluminosilicate particles of Comparative Example 6 were manufactured in the same manner as in Example 1, with the exception that 3% aluminum isopropoxide was not used.
  • the aluminosilicate particles having a bead chain structure of Comparative Example 7 were manufactured in the same manner as in Example 1, with the exception that 7 mL of 3% aluminum isopropoxide was used.
  • the aluminosilicate particles having a bead chain structure of Comparative Example 8 were manufactured in the same manner as in Example 1, with the exception that 10 mL of 3% aluminum isopropoxide was used.
  • a core template was prepared in the same manner as in Example 1, after which the solution was surface-treated with PVP and added with 3 mL of 3% aluminum isopropoxide and 30 mL of ethanol containing TEOS, thus obtaining spherical particles including the core. These particles were reacted with 5% sodium hydroxide, washed with distilled water and alcohol, and dried, thus manufacturing the hollow aluminosilicate particles of Comparative Example 9.
  • FIGS. 2A to 2F show TEM images of the hollow aluminosilicate particles of the Example and Comparative Examples, FIG. 2A illustrating Example 1, FIG. 2B illustrating Comparative Example 4, FIG. 2C illustrating Comparative Example 5, FIG. 2D illustrating Comparative Example 6, FIG. 2E illustrating Comparative Example 8, and FIG. 2F illustrating Comparative Example 9.
  • a JEOL Model JEM-1200EX was used as the TEM.
  • the uniformity of formation of the shell on the surface of the core was varied depending on the amount of aluminum isopropoxide that was added, and when no aluminum isopropoxide was added, the hollow shape could not be obtained.
  • the amount of aluminum isopropoxide was increased to the level of a Si/Al ratio of 7 or less, hollow particles were able to result, but aggregation of the particles increased, making it impossible to manufacture monodisperse particles.
  • Example 1 20 g of the particles of Example 1 and 80 g of distilled water were subjected to ultrasonic dispersion using an ultrasonic disperser for 1 hr, thus preparing an aqueous aluminosilicate dispersion which was stably dispersed in water.
  • This dispersion was placed in a 1L hydrothermal reactor and allowed to react at 180°C for 10 hr, followed by precipitation and drying, thereby manufacturing hollow aluminosilicate particles having increased shell density.
  • Hollow aluminosilicate particles having increased shell density were manufactured in the same manner as in Example 1_H180, with the exception that the particles of Example 2 were used.
  • Hollow aluminosilicate particles having increased shell density were manufactured in the same manner as in Example 1_H180, with the exception that the particles of Example 3 were used.
  • Aluminosilicate particles having increased shell density were manufactured in the same manner as in Example 1_H180, with the exception that the particles of Comparative Example 4 were used.
  • Aluminosilicate particles having increased shell density were manufactured in the same manner as in Example 1_H180, with the exception that the particles of Comparative Example 5 were used.
  • Aluminosilicate particles having increased shell density were manufactured in the same manner as in Example 1_H180, with the exception that the particles of Comparative Example 6 were used.
  • Aluminosilicate particles having increased shell density were manufactured in the same manner as in Example 1_H180, with the exception that the particles of Comparative Example 7 were used.
  • Aluminosilicate particles having increased shell density were manufactured in the same manner as in Example 1_H180, with the exception that the particles of Comparative Example 8 were used.
  • Hollow aluminosilicate particles having increased shell density were manufactured in the same manner as in Example 1_H180, with the exception that the particles of Comparative Example 9 were used.
  • Hollow aluminosilicate particles having increased shell density were manufactured in the same manner as in Example 1_H180, with the exceptions that the particles of Example 1 were used and the hydrothermal reaction was carried out at 150°C.
  • Hollow aluminosilicate particles having increased shell density were manufactured in the same manner as in Example 1_H180, with the exception that the particles of Example 1 were used and the hydrothermal reaction was carried out at 130°C.
  • Hollow aluminosilicate particles having increased shell density were manufactured in the same manner as in Example 1_H180, with the exception that the particles of Example 1 were used and the hydrothermal reaction was carried out at 100°C.
  • Hollow aluminosilicate particles having increased shell density were manufactured in the same manner as in Example 1_H180, with the exception that the particles of Example 2 were used and the hydrothermal reaction was carried out at 150°C.
  • Hollow aluminosilicate particles having increased shell density were manufactured in the same manner as in Example 1_H180, with the exception that the particles of Example 3 were used and the hydrothermal reaction was carried out at 150°C.
  • Table 3 below shows changes in the density of the shell before and after the hydrothermal reaction of Examples 1 to 3. As shown in Table 3, the density can be confirmed to increase in response to the hydrothermal reaction.
  • FIGS. 3A to 3F show the TEM images of hollow aluminosilicate particles of the Example and Comparative Examples after the high-density reaction, FIG. 3A illustrating Example 1_H180, FIG. 3B illustrating Comparative Example 4_H180, FIG. 3C illustrating Comparative Example 5_H180, FIG. 3D illustrating Comparative Example 6_H180, FIG. 3E illustrating Comparative Example 8_H180, and FIG. 3F illustrating Comparative Example 9_H180.
  • Example 1_H180 to Example 3_H180 in which the Si/Al ratio of the aluminosilicate shell was 7 to 15 and the hydrothermal reaction was carried out at 180°C, the hollow shape was maintained and the shell thickness was 8 to 10 nm.
  • Comparative Example 1_H150 to Comparative Example 3_H150 in which the aluminosilicate particles of Examples 1 to 3 were subjected to a hydrothermal reaction at a temperature lower than 180°C, the hollow shape was maintained and the shell thickness was 8 to 10 nm.
  • Comparative Example 4 in which the Si/Al ratio of the aluminosilicate shell was 15.9, the hollow shape was formed before the hydrothermal reaction but was partially broken during the hydrothermal reaction. Depending on the amount of aluminum isopropoxide that was added, the uniformity of formation of the shell on the surface of the core became different. If the Si/Al ratio of the aluminosilicate shell was greater than 15, the hollow particles were able to result, but the hollow shape was difficult to maintain during the hydrothermal reaction.
  • Example 1--_H180 The particles of Example 1--_H180 were substituted with ethanol and MIBK, thus preparing an aluminosilicate MIBK dispersion having a solid content of 10%.
  • This dispersion was surface-treated via the addition of an acid-catalyzed acryl silane (KBM-503) hydrolysate, after which pentaerythritol tritetraacrylate (Cytec) was added and the photoinitiator Irgacure 184 (available from Miwon Commercial) was further added, thus preparing a photocurable coating solution.
  • This coating solution was uniformly applied on a PET film using a Meyer bar coating process and then cured with UV light, thereby forming a transparent film.
  • a transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Example 2_H180 were used.
  • a transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Example 3_H180 were used.
  • a transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Comparative Example 4_H180 were used.
  • a transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Comparative Example 5_H180 were used.
  • a transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Comparative Example 6_H180 were used.
  • a transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Comparative Example 7_H180 were used.
  • a transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Comparative Example 8_H180 were used.
  • a transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Comparative Example 9_H180 were used.
  • a transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Example 1 were used.
  • a transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Comparative Example 1_H150 were used.
  • a transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Comparative Example 1_H130 were used.
  • a transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Comparative Example 1_H100 were used.
  • a transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Comparative Example 2_H150 were used.
  • a transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Comparative Example 3_H150 were used.
  • the transmittance increase (DT%) was determined by analyzing the total light transmittance (380 to 1100 nm) of the coating film and measuring the difference in transmittance thereof from that of a substrate (a PET film).
  • the transmittance analyzer was a model J-570, available from Jasco.
  • the refractive index was evaluated by coating a silicon wafer with the coating solution, curing it, and measuring the refractive index (200 to 1100 nm) through spectroscopic ellipsometry using an ellipsometer, available from Ellipso Technology.
  • Reflectance was analyzed by attaching a black film to the rear surface of the coating film to prevent the additional reflection of light.
  • Haze was measured by analyzing the coating film using an integrating sphere of J-570, available from Jasco.
  • Adhesion was evaluated in a manner in which cuts, forming squares in a 10x10 grid, were made in the coating surface, after which a piece of tape was attached to the coating surface and then detached therefrom to thus count the number of detached pieces.
  • the case where the number of detached pieces was zero was evaluated to be ⁇
  • the case where the number of detached pieces was less than 10 was evaluated to be D
  • the case where most of the pieces were removed was evaluated to be X.
  • Abrasion resistance was evaluated in a manner in which 150 g of steel wool (#0000) was reciprocated 10 times on the coating film.
  • the case where the number of scratch lines was less than 5 was evaluated to be ⁇
  • the case where the number of scratch lines was less than 20 was evaluated to be D
  • the case where the number of scratch lines was 20 or more was evaluated to be X.
  • Table 5 shows the results of evaluation of transmittance increase (DT%), refractive index (RI), reflectance, haze, adhesion and abrasion resistance of the transparent film formed using the aluminosilicate particles.
  • Example 1 In Comparative Example 1, in which the hydrothermal reaction was not carried out, all of the transmittance increase (DT%), refractive index, reflectance, haze, adhesion and abrasion resistance were poor compared to Example 1_H180_3-1, in which the same hollow aluminosilicate particles were used and the hydrothermal reaction was carried out at 180°C.
  • the particles should be configured such that external organic material does not enter cavities thereof and abrasion resistance and adhesion are maintained. To this end, the pores formed in the shell should disappear, and the shell should have high density.
  • Comparative Example 1 in which the hydrothermal reaction was not carried out, the density was not sufficient, and poor results were obtained for all evaluation items. Also, in Comparative Example 1_H150_3-1 to Comparative Example 3_H150_3-1, in which the hydrothermal reaction was carried out at 150°C or less, sufficient density was not obtained, and thus results similar to those of Comparative Example 1 were afforded.
  • Comparative Example 9_H180_3-1 in which the surface treatment was performed using a polymer electrolyte such as PVP, the hollow shape was maintained by virtue of strong cations by the addition of the polymer electrolyte, but the cations were left behind after the formation of the hollow silica, making it impossible to perform additional surface treatment, undesirably deteriorating dispersibility upon binder addition and solvent substitution, resulting in an opaque film.
  • a polymer electrolyte such as PVP
  • the transparent films which were formed using the aluminosilicate particles of Example 1_H180_3-1 to Example 3_H180_3-1, in which the Si/Al ratio of the aluminosilicate shell was 7 to 15 and the hydrothermal reaction was carried out at 180°C, exhibited a transmittance increase (DT%) of at least 3%, a refractive index of 1.31 or less, a reflectance of 1.5 or less, a haze of 1 or less, and superior adhesion and abrasion resistance.
  • DT% transmittance increase
  • the anti-reflective film can satisfy properties suitable for display materials, and can thus be employed in display panels requiring a low refractive index and high transmittance, optical coating materials, AR (Anti-Refraction) coating layers, BLUs (Back Light Units) for high-luminance LCD/PDPs, and high-efficiency display polarizer plates and prism sheets.
  • the hollow aluminosilicate particles are manufactured in a manner in which an aluminosilicate shell is formed on a core composed of an organic polymer and the organic polymer is removed from the inside of the shell without high-temperature sintering, thus exhibiting a low degree of aggregation and high dispersibility, and high density thereof can be obtained through a hydrothermal reaction.
  • the method of manufacturing hollow aluminosilicate particles enables the formation of a uniform shell even without additional core surface treatment by forming negative charges during the preparation of a complex oxide through the reaction of an aluminum precursor and a silica precursor upon forming a shell, resulting in hollow particles wherein the shell is not broken during the high-density reaction but is uniform.

Abstract

Disclosed are hollow aluminosilicate particles and a method of manufacturing the same. The method includes reacting a template core including an organic polymer in micelle or reverse micelle form with a silane compound and an aluminum precursor to synthesize core-shell particles having an aluminosilicate shell, which are then reacted with a basic or acidic aqueous solution, thus simultaneously forming fine pores in the shell and removing the core, thereby producing hollow aluminosilicate particles, and performing a hydrothermal reaction so as to increase the density of the hollow aluminosilicate particles. This method enables the formation of a uniform shell even without additional core surface treatment by forming negative charges during the preparation of a complex oxide through the reaction of an aluminum precursor and a silica precursor upon forming a shell, resulting in hollow particles wherein the shell is not broken during the high-density reaction but is uniform.

Description

HOLLOW ALUMINOSILICATE PARTICLES AND METHOD OF MANUFACTURING THE SAME
The present invention relates to hollow aluminosilicate particles and a method of manufacturing the same and, more particularly, to hollow aluminosilicate particles and a method of manufacturing the same, wherein an organic polymer in the shell may be removed without high-temperature sintering, as a consequence of which the hollow aluminosilicate particles may exhibit a low degree of aggregation and high dispersibility, and high density thereof may be obtained through a hydrothermal reaction.
Typically, hollow particles are used for displays and lenses requiring low reflectiveness, as indicated by a low refractive index, and may also be utilized in thermal insulation materials, drug delivery systems, and low dielectrics, which are required to have a hollow shape and a low refractive index.
Particles having a hollow shape with a particle diameter of 0.03 to 380 mm, especially hollow silica particles, are manufactured in a manner in which active silica is reacted on a core (made of a material other than silica) in an acidic or alkaline metal aqueous solution to form a silica shell, and the core is removed without breaking the silica shell.
Specifically, the aforementioned manufacturing method is performed by forming a silica shell using water glass or a silane polycondensation material on template core particles composed of acid- or base-soluble zinc, iron oxide or aluminum silicate oxide, and then dissolving the internal material (i.e. the core) with a strong acid or a strong base to discharge it. However, this method makes it difficult to control the size of the hollow structure, and is disadvantageous in that processing uses ion exchange resin or ultrafiltration, which is complicated, undesirably increasing manufacturing costs.
Accordingly, there are devised methods of manufacturing hollow silicate particles by forming a core using a polymer such as an epoxy polymer, growing a silicate shell on the core, and removing the core (the polymer). The particles thus manufactured are configured such that the silica shell is dense, and thus, it is not easy to remove the polymer from the inside of the shell using water or other solvents.
Hence, methods of manufacturing hollow silica by burning and removing the template polymer at a high temperature have been proposed. However, since hollow silica particles may aggregate during the high-temperature burning, it is difficult to redisperse the manufactured particles in the solution. Furthermore, when such particles are applied to an optical coating, the resulting coating film may be very hazy or have low transmittance.
The process of manufacturing hollow particles using the template polymer as the core may include the formation of strong cations by adding a polymer electrolyte, such as polyvinyl pyrrolidone (PVP), polycyclic aromatic hydrocarbon (PAH), AIBN (PS core) and a metal salt, in order to uniformly form the shell material on the surface of the core. In this case, however, the cations may be left behind after the preparation of hollow silica, and thus additional surface treatment cannot be performed, undesirably deteriorating dispersibility upon binder addition and solvent substitution.
Korean Patent No. 1461203 discloses a method of manufacturing hollow particles, in which a metal oxide is added to silicate particles and dissolved using a basic or acidic solution to prepare a shell having fine pores, whereby the dissolved core materials are discharged through the fine pores. However, this method is problematic because shell particles may be non-uniformly produced due to the fine pores formed in the shell, and the shell may break down during the process of increasing the density of the shell, making it difficult to form uniform hollow particles having high density.
There is thus a need for techniques regarding hollow particles and a method of manufacturing the same, in which the particles have fine pores with smooth and less aggregated uniform structure to thus facilitate the removal of the core and realize the uniform shell.
[Citation List]
[Patent Literature]
(Patent Document 1) Japanese Patent Application Publication No. 2011-042527
(Patent Document 2) Japanese Patent Application Publication No. 2010-131593
(Patent Document 3) Korean Patent No. 1461203
Accordingly, the present invention has been made keeping in mind the problems encountered in the related art, and the present invention is intended to provide hollow aluminosilicate particles, in which an aluminosilicate shell is formed on a core composed of an organic polymer, after which the organic polymer is removed from the inside of the shell without high-temperature sintering, so the particles may exhibit a low degree of aggregation and high dispersibility, and high density thereof may be obtained through a hydrothermal reaction.
Particularly, upon the formation of silicate shell particles, the amount of aluminum for forming fine pores is adjusted, whereby high-density hollow particles may result upon hydrothermal reaction without breaking the shell particles.
In addition, the present invention is intended to provide a method of manufacturing hollow aluminosilicate particles, which enables the formation of a uniform shell even without additional core surface treatment by forming negative charges during the preparation of a complex oxide through the reaction of an aluminum precursor and a silica precursor upon forming a shell, resulting in hollow particles wherein the shell is not broken during the high-density reaction but is uniform.
The roughness of the shell and degree of agglomeration is severely affected by the amount of aluminum used for the formation of complex oxide shell.
The technical problem according to the present invention is merely exemplary and the spirit of the present invention is not limited thereto.
Therefore, the present invention provides a method of manufacturing hollow aluminosilicate particles, comprising: reacting a template core composed of an organic polymer in micelle or reverse micelle form with a silane compound and an aluminum precursor, thus synthesizing core-shell particles having an aluminosilicate shell; reacting the core-shell particles with a basic aqueous solution or an acidic aqueous solution, thus simultaneously forming fine pores in the shell and removing the core, thereby producing hollow aluminosilicate particles; and performing a hydrothermal reaction so as to increase the density of the hollow aluminosilicate particles.
In some embodiments of the present invention, the aluminosilicate shell may include X mol of Si and Y mol of Al, and the X/Y molar ratio may range from 7 to 15.
In some embodiments of the present invention, the hydrothermal reaction may be carried out at a temperature ranging from 160 to 230°C.
In some embodiments of the present invention, the hollow aluminosilicate particles may have an average particle size ranging from 10 to 300 nm, and the shell may have a thickness of 5 to 15 nm.
In some embodiments of the present invention, the organic polymer may be a copolymer or a block copolymer including a polymer selected from the group consisting of polyoxyethylene, polyoxyethylene glycol, polyoxypropylene alkyl ether, polyoxypropylene monoalkylether, polyoxypropylene alkyl, polyoxyethylene tallow amine, polyoxyethylene oleyl amine, polyoxyethylene stearyl amine, polyoxyethylene lauryl amine, polyoxyethylene sorbitan ester, polyoxyethylene octyl ether, polyoxyethylene glycerin ether, polyacrylic acid, polysulfonic acid, polyacryl amine, and triethylene amine.
In some embodiments of the present invention, the silane compound may be represented by Chemical Formula 1 below.
Chemical Formula 1
Figure PCTKR2016014721-appb-I000001
(wherein R1, R2, R3 and R4 are each independently an alkyl group, an alkoxy group, a phenyl group, a vinyl group, a halogen group, an epoxy group, a glycidoxy group, an amino group or a mercapto group.)
In some embodiments of the present invention, the aluminum precursor may be an organic salt of aluminum or aluminum alkoxide.
In some embodiments of the present invention, the basic aqueous solution may be sodium hydroxide, ammonium hydroxide, potassium hydroxide, hydroxyphosphate or a mixed solution thereof, and the acidic aqueous solution may be hydrochloric acid, nitric acid, sulfuric acid, acetic acid or a mixed solution thereof.
In addition, the present invention provides a composition for forming a film, comprising the aforementioned hollow aluminosilicate particles.
In some embodiments of the present invention, the hollow aluminosilicate particles may have an average particle size ranging from 10 to 300 nm, and the shell may have a thickness of 5 to 15 nm.
In addition, the present invention provides an anti-reflective film, comprising a transparent film formed through a coating process using the aforementioned composition.
In some embodiments of the present invention, the anti-reflective film may have a transmittance increase of at least 3%, a refractive index of 1.31 or less, a reflectance of 1.5 or less, and a haze of 1 or less.
According to the present invention, hollow aluminosilicate particles can result from forming an aluminosilicate shell on a core composed of an organic polymer and then removing the organic polymer from the inside of the shell without high-temperature sintering, thus exhibiting a low degree of aggregation and high dispersibility, and also high density thereof can be obtained through a hydrothermal reaction.
Also, according to the present invention, a method of manufacturing hollow aluminosilicate particles enables the formation of a uniform shell even without additional core surface treatment by forming charges during the preparation of a complex oxide through the reaction of an aluminum precursor and a silica precursor upon forming a shell, resulting in hollow particles with smooth surface wherein the shell is not broken and less aggregated during the high-density reaction but is uniform.
The aforementioned effects of the present invention are exemplarily described, and the scope of the present invention is not limited thereby.
FIG. 1 schematically shows a process of manufacturing hollow aluminosilicate particles according to the present invention;
FIGS. 2A to 2F show transmission electron microscope (TEM) images of hollow aluminosilicate particles, manufactured in Example of the present invention and Comparative Examples; and
FIGS. 3A to 3F show TEM images of hollow aluminosilicate particles, manufactured in Example of the present invention and Comparative Examples and subjected to a high-density reaction.
Hereinafter, a detailed description will be given of preferred embodiments of the present invention with reference to the accompanying drawings. The embodiments of the present invention are provided to more fully explain the spirit of the present invention to those skilled in the art, may be modified into different forms, and are not construed as limiting the scope of the present invention. Rather, these embodiments are provided to thoroughly explain the disclosure and to sufficiently transfer the spirit of the present invention to those skilled in the art. Throughout the specification, the term "and/or" may include any one of the listed items and any combination of one or more thereof, and the same reference numerals designate the same elements. Throughout the drawings, various elements and regions are schematically depicted, and thus, the spirit of the present invention is not limited by the relative sizes or gaps illustrated in the drawings.
FIG. 1 schematically shows the process of manufacturing hollow aluminosilicate particles according to the present invention. The method of manufacturing hollow aluminosilicate particles according to the present invention includes the steps of synthesizing core-shell particles, forming hollow aluminosilicate particles, and performing a hydrothermal reaction.
The step of synthesizing core-shell particles is performed in a manner in which a template core comprising an organic polymer in micelle or reverse micelle form is reacted with a silane compound and an aluminum precursor, thus synthesizing core-shell particles having an aluminosilicate shell.
The template core may be provided in the form of a micelle or reverse micelle in the solvent. The micelle or reverse micelle is prepared from the organic polymer. The organic polymer exhibits amphoteric functional characteristics, that is, hydrophobic and hydrophilic properties, and such amphoteric functional characteristics are manifested as functional groups having the same properties becoming attached to each other. Thus, when a hydrophobic functional group is formed in an inward direction, the counterpart functional group, namely a hydrophilic functional group, is formed in an outward direction. Conversely, when a hydrophilic functional group is formed in an inward direction, a hydrophobic functional group is formed in an outward direction, thus forming a micelle. Such functional characteristics may vary depending on the polarity of the solvent that is added upon preparation of the micelle and on the molecular weight of the functional group.
The organic polymer forms micelle- or reverse micelle-type particles which are uniform in a specific solvent, is easily dispersed in the solvent, and is bondable to the silane compound so as to form a shell.
The organic polymer may include a copolymer or block copolymer of the polymer. The copolymer or block copolymer of the polymer may typically function as a surfactant. Specific examples of the polymer may include polyoxyethylene, polyoxyethylene glycol, polyoxypropylene alkyl ether, polyoxypropylene monoalkylether, polyoxypropylene alkyl, polyoxyethylene tallow amine, polyoxyethylene oleyl amine, polyoxyethylene stearyl amine, polyoxyethylene lauryl amine, polyoxyethylene sorbitan ester, polyoxyethylene octyl ether, polyoxyethylene glycerin ether, polyacrylic acid, polysulfonic acid, polyacryl amine, and triethylene amine.
More specifically, the copolymer or block copolymer of the polymer may include a polyoxyethylene-polyoxyethylene block copolymer, or may include at least one selected from the group consisting of polyoxyethylene glycol, polyoxyethylene-polyoxypropylene alkyl ether, polyoxyethylene-polyoxypropylene monoalkylether, polyoxyethylene-polyoxypropylene alkyl copolymer, polyoxyethylene tallow amine, polyoxyethylene oleyl amine, polyoxyethylene stearyl amine, polyoxyethylene lauryl amine, polyoxyethylene sorbitan ester, polyoxyethylene octyl ether, and polyoxyethylene glycerin ether. In the present invention, useful as the organic polymer is a mixture of polyacrylic acid and polystyrene sulfonic acid.
As mentioned above, the organic polymer is able to form a micelle or a reverse micelle in the solvent. Here, the kind of solvent is not particularly limited, and may be selected depending on the properties of the organic polymer. Specifically, the solvent may include an alcohol, glycol ester, ketone or a mixture thereof. Examples of the alcohol may include methyl alcohol, ethyl alcohol and isopropyl alcohol, examples of the glycol ester may include methyl cellosolve and ethyl cellosolve, and examples of the ketone may include methyl ethyl ketone and methyl isobutyl ketone.
The amount of the organic polymer is not particularly limited, and may be set within the range of 1 to 50 parts by weight based on 100 parts by weight of the solvent. Given the above amount range, it is easy to form the micelle or reverse micelle, and high dispersibility may result.
In the present invention, the shell is formed from the silane compound and the aluminum precursor, and is specifically formed in a manner in which the silane compound and the aluminum precursor are added to the solvent containing the core comprising the organic polymer in micelle or reverse micelle form.
The silane compound may be easily coupled with the organic polymer that forms a template core. This coupling may be performed through a St?ber method (Werner, 1968) known in the art. In the preparation of the shell using a sol-gel process through the St?ber method, a stable shell may be manufactured through hydrolysis and polycondensation synthesis using an acidic solution or a basic solution contained in the solvent.
The silane compound may be represented by Chemical Formula 1 below.
<Chemical Formula 1>
Figure PCTKR2016014721-appb-I000002
In Chemical Formula 1, R1, R2, R3 and R4 are each independently an alkyl group, an alkoxy group, a phenyl group, a vinyl group, a halogen group, an epoxy group, a glycidoxy group, an amino group or a mercapto group. Specifically, the silane compound may include alkoxysilane, chlorosilane, bromosilane and alkylsilane without particular limitation, and more specifically, useful is at least one selected from the group consisting of tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(b-methoxyethoxy)silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, b-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, g-glycidoxytripropyltrimethoxysilane, g-glycidoxypropylmethyldiethoxysilane, g-glycidoxypropyltriethoxysilane, g-methacryloxypropylmethyldimethoxysilane, g-methacryloxypropyltrimethoxysilane, g-methacryloxypropylmethyldiethoxysilane, g-methacryloxypropyltriethoxysilane, N-b(aminoethyl)-g-aminopropylmethyldimethoxysilane, N-b(aminoethyl)-g-aminopropyltrimethoxysilane, N-b(aminoethyl)-g-aminopropyltriethoxysilane, g-aminopropyltrimethoxysilane, g-aminopropyltriethoxysilane, N-phenyl-g-aminopropyltrimethoxysilane, g-mercaptopropyltrimethoxysilane, acryloxypropyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, vinyltrichlorosilane, trimethylbromosilane, and diethylsilane.
The aluminum precursor may be an organic salt of aluminum or aluminum alkoxide. The aluminum precursor is used as a component for forming the shell, and may be somewhat dissolved in the basic aqueous solution, as will be described later, whereby fine pores are formed in the shell, thus facilitating the discharge of the dissolved core material. The kind of aluminum precursor is not particularly limited, and an organic salt of aluminum or aluminum alkoxide may be used.
The aluminosilicate shell contains X mol of Si and Y mol of Al, and the X/Y molar ratio may range from 7 to 15. If the X/Y molar ratio is less than 7, the dissolved core particles may become easy to discharge because of the large amount of aluminum, but a complete hollow shape is not formed due to the fine pores in the surface of the shell, thus deteriorating the strength of the particles, making it impossible to manufacture high-density hollow particles. Furthermore, since the refractive index of the resulting particles may increase due to the presence of aluminum, which is not dissolved in the shell particles, the particles are unsuitable for use in material fields requiring a low refractive index. On the other hand, if the X/Y molar ratio exceeds 15, the amount of aluminum in the acidic aqueous solution or basic aqueous solution is low, and thus not only the surface aluminum of the shell particles but also the core particles are incompletely removed, undesirably increasing a refractive index or causing haze in the formation of the film.
The step of forming hollow aluminosilicate particles is performed in a manner in which the core-shell particles are reacted with a basic aqueous solution or an acidic aqueous solution, thus simultaneously forming fine pores in the shell and removing the core, thereby affording the hollow aluminosilicate particles.
The silane compound and the aluminum precursor are coupled with the core material, thus forming the shell containing a complex precursor of aluminum oxide and silica, resulting in core-shell particles. The core-shell particles are reacted with the basic aqueous solution or the acidic aqueous solution, whereby a portion of the aluminum oxide of the complex oxide of aluminum and silica for the shell is removed, and fine pores are formed in the shell.
The kind of basic aqueous solution or acidic aqueous solution is not particularly limited, and specific examples of the basic aqueous solution may include sodium hydroxide, ammonium hydroxide, potassium hydroxide, hydroxyphosphate and mixed solutions thereof, and examples of the acidic aqueous solution may include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, and mixed solutions thereof.
The fine pores thus formed facilitate the entry and discharge of the dissolved organic polymer, and thus the organic polymer may be removed from the inside of the shell through a simple washing process. The washing process functions to dissolve the organic polymer (the core material) inside the shell, and the dissolved organic polymer may be discharged to the outside through the fine pores in the shell by washing.
The solvent that is used in the washing process may include distilled water, alcohol, glycol, glycol ester or mixtures thereof. Examples of the alcohol may include methyl alcohol, ethyl alcohol and isopropyl alcohol, examples of the glycol may include ethylene glycol, propylene glycol and xylene glycol, and examples of the glycol ester may include ethyl cellosolve and methyl cellosolve.
The step of performing the hydrothermal reaction is conducted in a manner in which a hydrothermal reaction is carried out so as to increase the density of the hollow aluminosilicate particles. In order to use hollow particles as an optical coating agent, the particles should be configured such that no external organic material enters the cavities thereof and such that abrasion resistance and adhesion are maintained. To this end, the pores formed in the shell should disappear, and the shell should have high density. Hence, the density of the hollow aluminosilicate particles may be increased through a hydrothermal reaction.
The hydrothermal reaction may be carried out at a temperature ranging from 160 to 250°C, and particularly from 160 to 200°C. If the temperature of the hydrothermal reaction is lower than 160°C, a density as high as desired cannot be obtained, making it difficult to apply the resulting particles to displays and lenses requiring physical properties such as scratch resistance and low-reflection properties including increased transmittance (DT%), low refractive index, low reflectance, and low haze.
The hollow aluminosilicate nanoparticles may have an average particle size of 10 to 300 nm, and the shell may have a thickness ranging from 5 to 15 nm. When the particle size falls in the above range, a low refractive index and high transparency may result. In particular, the average particle size of the hollow aluminosilicate nanoparticles may range from 10 to 100 nm. If the particle size exceeds 100 nm, the resulting film may become opaque due to scattering of light in the course of coating and substrate lamination. On the other hand, if the particle size is less than 10 nm, it is difficult to expect a low refractive index due to a hollow shape. The hollow ratio of the hollow aluminum-silicate particles may range from 50 to 95%. Given the above range, it is easy to remove the core during the manufacturing of the particles.
The hollow aluminum oxide-silicate particles may contain silica and aluminum oxide in amounts of 0.1 to 30 wt%. Given the above amount range, the particles have superior properties. Also, fine pores may be formed in the shell. During the manufacturing of the particles, the core material that is dissolved may be easily discharged from the shell through the fine pores, resulting in hollow particles in which the core is empty.
In addition, the present invention addresses a composition for forming a film, which includes the hollow aluminosilicate particles. The kind of component of the composition for forming a film is not particularly limited, and components of the composition for forming a film typically useful in the art may be easily used, with the exception that the hollow aluminum oxide-silicate particles manufactured according to the present invention are included.
In addition, the present invention addresses an anti-reflective film, which includes a transparent film formed through a coating process using the composition for forming a film. In the present invention, the hollow aluminum silicate particles have as low reflectance as desired, and may thus be easily utilized for films. In particular, the anti-reflective film may have a transmittance increase of at least 3%, a refractive index of 1.31 or less, a reflectance of 1.5 or less, and a haze of 1 or less, whereby the anti-reflective film may be employed in display panels requiring a low refractive index and high transmittance, optical coating materials, AR (Anti-Refraction) coating layers, BLUs (Back Light Units) for high-luminance LCD/PDP, and high-efficiency display polarizer plates and prism sheets.
A better understanding of the present invention will be obtained through the following examples and test examples.
1. Manufacture of hollow aluminosilicate particles
1-1. Formation of core-shell depending on amount of added aluminum
Example 1
Into a 500 mL three-neck round-bottom flask, 0.086 g of polyacrylic acid (PAA), 0.043 g of polystyrene sulfonic acid (PSS), and 1.5 mL of ammonium hydroxide were added, and 30 mL of ethanol was further added, thus preparing a core template for forming hollow particles. While the resulting solution was vigorously stirred, 4 mL of 3% aluminum isopropoxide and 30 mL of ethanol containing tetraethoxy silane (TEOS) were added using a syringe pump, thus obtaining spherical particles including the core. These particles were reacted with 5% sodium hydroxide, washed with distilled water and alcohol, and dried, thus manufacturing the hollow aluminosilicate particles of Example 1.
Example 2
The hollow aluminosilicate particles of Example 2 were manufactured in the same manner as in Example 1, with the exception that 5 mL of 3% aluminum isopropoxide was used.
Example 3
The hollow aluminosilicate particles of Example 3 were manufactured in the same manner as in Example 1, with the exception that 6 mL of 3% aluminum isopropoxide was used.
Comparative Example 4
The hollow aluminosilicate particles of Comparative Example 4 were manufactured in the same manner as in Example 1, with the exception that 3 mL of 3% aluminum isopropoxide was used.
Comparative Example 5
The aluminosilicate particles of Comparative Example 5 were manufactured in the same manner as in Example 1, with the exception that 1 mL of 3% aluminum isopropoxide was used.
Comparative Example 6
The aluminosilicate particles of Comparative Example 6 were manufactured in the same manner as in Example 1, with the exception that 3% aluminum isopropoxide was not used.
Comparative Example 7
The aluminosilicate particles having a bead chain structure of Comparative Example 7 were manufactured in the same manner as in Example 1, with the exception that 7 mL of 3% aluminum isopropoxide was used.
Comparative Example 8
The aluminosilicate particles having a bead chain structure of Comparative Example 8 were manufactured in the same manner as in Example 1, with the exception that 10 mL of 3% aluminum isopropoxide was used.
Comparative Example 9
A core template was prepared in the same manner as in Example 1, after which the solution was surface-treated with PVP and added with 3 mL of 3% aluminum isopropoxide and 30 mL of ethanol containing TEOS, thus obtaining spherical particles including the core. These particles were reacted with 5% sodium hydroxide, washed with distilled water and alcohol, and dried, thus manufacturing the hollow aluminosilicate particles of Comparative Example 9.
1-2. Test results
Table 1 below shows the Si/Al ratio of the formed core-shell depending on the amount of added aluminum, and Table 2 below shows the maintenance of the hollow shape of the core-shell depending on the amount of added aluminum and the shell thickness. FIGS. 2A to 2F show TEM images of the hollow aluminosilicate particles of the Example and Comparative Examples, FIG. 2A illustrating Example 1, FIG. 2B illustrating Comparative Example 4, FIG. 2C illustrating Comparative Example 5, FIG. 2D illustrating Comparative Example 6, FIG. 2E illustrating Comparative Example 8, and FIG. 2F illustrating Comparative Example 9. Here, a JEOL Model JEM-1200EX was used as the TEM.
Core material Shell material
PAA(g) PSS(g) Ammonium hydroxide (mL) Ethanol(mL) Al mol Si mol Si/Al ratio
Ex.1 0.086 0.043 1.5 30 5.9*e-4 0.007 11.86
Ex.2 0.086 0.043 1.5 30 7.3*e-4 0.007 9.58
Ex.3 0.086 0.043 1.5 30 8.8*e-4 0.007 7.95
C.Ex.4 0.086 0.043 1.5 30 4.4*e-4 0.007 15.90
C.Ex.5 0.086 0.043 1.5 30 1.5*e-4 0.007 46.67
C.Ex.6 0.086 0.043 1.5 30 - 0.007 -
C.Ex.7 0.086 0.043 1.5 30 0.00102 0.007 6.87
C.Ex.8 0.086 0.043 1.5 30 0.00147 0.007 4.76
C.Ex.9 0.086 0.043 1.5 30(PVP) 4.4*e-4 0.007 15.90
Average particle size (nm) Maintenance of Hollow shape Shell thickness (nm)
Ex.1 60 to 100 Hollow shape 10 to 15
Ex.2 60 to 100 Hollow shape 10 to 15
Ex.3 60 to 100 Hollow shape 10 to 15
C.Ex.4 60 to 100 Hollow shape 10 to 15
C.Ex.5 60 to 100 Hollow shape not formed -
C.Ex.6 60 to 100 Hollow shape not formed -
C.Ex.7 60 to 100 Hollow bead chain structure -
C.Ex.8 60 to 100 Hollow bead chain structure -
C.Ex.9 60 to 100 Hollow shape 10 to 15
When 3% aluminum isopropoxide was added in an amount ranging from 3 to 6 mL, the aluminosilicate formed in Examples 1 to 3 and Comparative Examples 4 and 9, having the Si/Al ratio of 7 to 16, was observed to be hollow particles having a particle size of about 60 to 100 nm and a shell thickness of 10 to 15 nm.
The uniformity of formation of the shell on the surface of the core was varied depending on the amount of aluminum isopropoxide that was added, and when no aluminum isopropoxide was added, the hollow shape could not be obtained. When the amount of aluminum isopropoxide was increased to the level of a Si/Al ratio of 7 or less, hollow particles were able to result, but aggregation of the particles increased, making it impossible to manufacture monodisperse particles.
2. High-density reaction of hollow aluminosilicate particles
2-1. Hydrothermal synthesis reaction of manufactured particles
Example 1_H180
20 g of the particles of Example 1 and 80 g of distilled water were subjected to ultrasonic dispersion using an ultrasonic disperser for 1 hr, thus preparing an aqueous aluminosilicate dispersion which was stably dispersed in water. This dispersion was placed in a 1L hydrothermal reactor and allowed to react at 180°C for 10 hr, followed by precipitation and drying, thereby manufacturing hollow aluminosilicate particles having increased shell density.
Example 2_H180
Hollow aluminosilicate particles having increased shell density were manufactured in the same manner as in Example 1_H180, with the exception that the particles of Example 2 were used.
Example 3_H180
Hollow aluminosilicate particles having increased shell density were manufactured in the same manner as in Example 1_H180, with the exception that the particles of Example 3 were used.
Comparative Example 4_H180
Aluminosilicate particles having increased shell density were manufactured in the same manner as in Example 1_H180, with the exception that the particles of Comparative Example 4 were used.
Comparative Example 5_H180
Aluminosilicate particles having increased shell density were manufactured in the same manner as in Example 1_H180, with the exception that the particles of Comparative Example 5 were used.
Comparative Example 6_H180
Aluminosilicate particles having increased shell density were manufactured in the same manner as in Example 1_H180, with the exception that the particles of Comparative Example 6 were used.
Comparative Example 7_H180
Aluminosilicate particles having increased shell density were manufactured in the same manner as in Example 1_H180, with the exception that the particles of Comparative Example 7 were used.
Comparative Example 8_H180
Aluminosilicate particles having increased shell density were manufactured in the same manner as in Example 1_H180, with the exception that the particles of Comparative Example 8 were used.
Comparative Example 9_H180
Hollow aluminosilicate particles having increased shell density were manufactured in the same manner as in Example 1_H180, with the exception that the particles of Comparative Example 9 were used.
Comparative Example 1_H150
Hollow aluminosilicate particles having increased shell density were manufactured in the same manner as in Example 1_H180, with the exceptions that the particles of Example 1 were used and the hydrothermal reaction was carried out at 150°C.
Comparative Example 1_H130
Hollow aluminosilicate particles having increased shell density were manufactured in the same manner as in Example 1_H180, with the exception that the particles of Example 1 were used and the hydrothermal reaction was carried out at 130°C.
Comparative Example 1_H100
Hollow aluminosilicate particles having increased shell density were manufactured in the same manner as in Example 1_H180, with the exception that the particles of Example 1 were used and the hydrothermal reaction was carried out at 100°C.
Comparative Example 2_H150
Hollow aluminosilicate particles having increased shell density were manufactured in the same manner as in Example 1_H180, with the exception that the particles of Example 2 were used and the hydrothermal reaction was carried out at 150°C.
Comparative Example 3_H150
Hollow aluminosilicate particles having increased shell density were manufactured in the same manner as in Example 1_H180, with the exception that the particles of Example 3 were used and the hydrothermal reaction was carried out at 150°C.
2-2. Test results
Table 3 below shows changes in the density of the shell before and after the hydrothermal reaction of Examples 1 to 3. As shown in Table 3, the density can be confirmed to increase in response to the hydrothermal reaction.
Sample name Sample mass (g) Average volume (cm3) Average Density (g/cm3)
Before hydrothermal reaction (Examples 1 to 3) 0.450±0.005 0.218±0.005 2.065±0.005
After hydrothermal reaction (Examples 1_H180 to 3_H180) 0.505±0.005 0.234±0.005 2.150±0.005
Table 4 below shows the results of maintenance of the hollow shape and measurement of shell thickness in the aluminosilicate particles in which the shell density was increased through the hydrothermal reaction, and FIGS. 3A to 3F show the TEM images of hollow aluminosilicate particles of the Example and Comparative Examples after the high-density reaction, FIG. 3A illustrating Example 1_H180, FIG. 3B illustrating Comparative Example 4_H180, FIG. 3C illustrating Comparative Example 5_H180, FIG. 3D illustrating Comparative Example 6_H180, FIG. 3E illustrating Comparative Example 8_H180, and FIG. 3F illustrating Comparative Example 9_H180.
Test Example Maintenance of hollow shape Shell thickness
Ex.1_H180 Hollow shape 8 to 10 nm
Ex.2_H180 Hollow shape 8 to 10 nm
Ex.3_H180 Hollow shape 8 to 10 nm
C.Ex.4_H180 Partially Hollow shape 8 to 10 nm
C.Ex.5_H180 Most shell breakage -
C.Ex.6_H180 Spherical shape -
C.Ex.7_H180 Hollow shape and amorphous particulate form -
C.Ex.8_H180 Hollow shape and amorphous particulate form -
C.Ex.9_H180 Hollow shape 8 to 10 nm
C.Ex.1_H150 Hollow shape 8 to 10 nm
C.Ex.1_H130 Hollow shape 8 to 10 nm
C.Ex.1_H100 Hollow shape 8 to 10 nm
C.Ex.2_H150 Hollow shape 8 to 10 nm
C.Ex.3_H150 Hollow shape 8 to 10 nm
As is apparent from Table 4, in Example 1_H180 to Example 3_H180, in which the Si/Al ratio of the aluminosilicate shell was 7 to 15 and the hydrothermal reaction was carried out at 180°C, the hollow shape was maintained and the shell thickness was 8 to 10 nm. In Comparative Example 1_H150 to Comparative Example 3_H150, in which the aluminosilicate particles of Examples 1 to 3 were subjected to a hydrothermal reaction at a temperature lower than 180°C, the hollow shape was maintained and the shell thickness was 8 to 10 nm.
However, in Comparative Example 4, in which the Si/Al ratio of the aluminosilicate shell was 15.9, the hollow shape was formed before the hydrothermal reaction but was partially broken during the hydrothermal reaction. Depending on the amount of aluminum isopropoxide that was added, the uniformity of formation of the shell on the surface of the core became different. If the Si/Al ratio of the aluminosilicate shell was greater than 15, the hollow particles were able to result, but the hollow shape was difficult to maintain during the hydrothermal reaction.
3. Formation of low-reflection coating film using hollow aluminosilicate particles
3-1. Preparation of anti-reflective coating solution and coating film
Example 1_H180_3-1
The particles of Example 1--_H180 were substituted with ethanol and MIBK, thus preparing an aluminosilicate MIBK dispersion having a solid content of 10%. This dispersion was surface-treated via the addition of an acid-catalyzed acryl silane (KBM-503) hydrolysate, after which pentaerythritol tritetraacrylate (Cytec) was added and the photoinitiator Irgacure 184 (available from Miwon Commercial) was further added, thus preparing a photocurable coating solution. This coating solution was uniformly applied on a PET film using a Meyer bar coating process and then cured with UV light, thereby forming a transparent film.
Example 2_H180_3-1
A transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Example 2_H180 were used.
Example 3_H180_3-1
A transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Example 3_H180 were used.
Comparative Example 4_H180_3-1
A transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Comparative Example 4_H180 were used.
Comparative Example 5_H180_3-1
A transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Comparative Example 5_H180 were used.
Comparative Example 6_H180_3-1
A transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Comparative Example 6_H180 were used.
Comparative Example 7_H180_3-1
A transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Comparative Example 7_H180 were used.
Comparative Example 8_H180_3-1
A transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Comparative Example 8_H180 were used.
Comparative Example 9_H180_3-1
A transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Comparative Example 9_H180 were used.
Comparative Example 1_3-1
A transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Example 1 were used.
Comparative Example 1_H150_3-1
A transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Comparative Example 1_H150 were used.
Comparative Example 1_H130_3-1
A transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Comparative Example 1_H130 were used.
Comparative Example 1_H100_3-1
A transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Comparative Example 1_H100 were used.
Comparative Example 2_H150_3-1
A transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Comparative Example 2_H150 were used.
Comparative Example 3-H150_3-1
A transparent film was formed in the same manner as in Example 1_H180_3-1, with the exception that the particles of Comparative Example 3_H150 were used.
3-2. Test evaluation method
I. The transmittance increase (DT%) was determined by analyzing the total light transmittance (380 to 1100 nm) of the coating film and measuring the difference in transmittance thereof from that of a substrate (a PET film). The transmittance analyzer was a model J-570, available from Jasco.
II. The refractive index was evaluated by coating a silicon wafer with the coating solution, curing it, and measuring the refractive index (200 to 1100 nm) through spectroscopic ellipsometry using an ellipsometer, available from Ellipso Technology.
III. Reflectance was analyzed by attaching a black film to the rear surface of the coating film to prevent the additional reflection of light.
IV. Haze was measured by analyzing the coating film using an integrating sphere of J-570, available from Jasco.
V. Adhesion was evaluated in a manner in which cuts, forming squares in a 10x10 grid, were made in the coating surface, after which a piece of tape was attached to the coating surface and then detached therefrom to thus count the number of detached pieces. Here, the case where the number of detached pieces was zero was evaluated to be ◎, the case where the number of detached pieces was less than 10 was evaluated to be D, and the case where most of the pieces were removed was evaluated to be X.
VI. Abrasion resistance was evaluated in a manner in which 150 g of steel wool (#0000) was reciprocated 10 times on the coating film. Here, the case where the number of scratch lines was less than 5 was evaluated to be ◎, the case where the number of scratch lines was less than 20 was evaluated to be D, and the case where the number of scratch lines was 20 or more was evaluated to be X.
3-3. Test results
Table 5 below shows the results of evaluation of transmittance increase (DT%), refractive index (RI), reflectance, haze, adhesion and abrasion resistance of the transparent film formed using the aluminosilicate particles.
Test Example DT% RI Reflectance Haze Adhesion Abrasion resistance
Ex.1_H180_3-1 3.06 1.31 0.4 0.5 ◎ ◎
Ex.2_H180_3-1 3.01 1.31 0.4 0.5 ◎ ◎
Ex.3_H180_3-1 3.01 1.31 0.4 0.5 ◎ ◎
C.Ex.4_H180_3-1 2.6 1.35 1.1 0.7 ◎ ◎
C.Ex.5_H180_3-1 1.7 1.38 1.6 1.2 ◎ ◎
C.Ex.6_H180_3-1 1.4 1.41 2.4 0.6 ◎ ◎
C.Ex.7_H180_3-1 2.5 1.32 2.0 2.1 ◎ ◎
C.Ex.8_H180_3-1 2.8 1.34 1.9 2.4 ◎ ◎
C.Ex.9_H180_3-1 - - - - - -
C.Ex.1_3-1 2.5 1.39 1.2 0.5 D X
C.Ex.1_H150_3-1 3.05 1.31 0.5 0.6 ◎ X
C.Ex.1_H130_3-1 3.04 1.31 0.5 0.4 D X
C.Ex.1_H100_3-1 3.02 1.31 0.5 0.4 X X
C.Ex.2_H150_3-1 3.01 1.31 0.5 0.4 ◎ X
C.Ex.3_H150_3-1 3.00 1.31 0.5 0.4 ◎ X
As is apparent from the test results of Table 5, in Comparative Example 4_H180_3-1 and Comparative Example 5_H180_3-1, in which the Si/Al ratio of the aluminosilicate shell was 15 or more, a partially hollow shape or shell breakage was exhibited, and in Comparative Example 6_H180_3-1 to Comparative Example 8_H180_3-1, in which the Si/Al ratio of the aluminosilicate shell was 7 or less, the spherical shape or amorphous particulate form was exhibited, and thus a partially hollow shape, shell breakage or amorphous particulate form resulted after the hydrothermal reaction, undesirably making it difficult to maintain the shape of the hollow silica and affording poor results in terms of transmittance increase (DT%), refractive index, reflectance and haze.
In Comparative Example 1, in which the hydrothermal reaction was not carried out, all of the transmittance increase (DT%), refractive index, reflectance, haze, adhesion and abrasion resistance were poor compared to Example 1_H180_3-1, in which the same hollow aluminosilicate particles were used and the hydrothermal reaction was carried out at 180°C.
In order to use hollow particles as an optical coating agent, the particles should be configured such that external organic material does not enter cavities thereof and abrasion resistance and adhesion are maintained. To this end, the pores formed in the shell should disappear, and the shell should have high density.
In Comparative Example 1, in which the hydrothermal reaction was not carried out, the density was not sufficient, and poor results were obtained for all evaluation items. Also, in Comparative Example 1_H150_3-1 to Comparative Example 3_H150_3-1, in which the hydrothermal reaction was carried out at 150°C or less, sufficient density was not obtained, and thus results similar to those of Comparative Example 1 were afforded.
In Comparative Example 9_H180_3-1, in which the surface treatment was performed using a polymer electrolyte such as PVP, the hollow shape was maintained by virtue of strong cations by the addition of the polymer electrolyte, but the cations were left behind after the formation of the hollow silica, making it impossible to perform additional surface treatment, undesirably deteriorating dispersibility upon binder addition and solvent substitution, resulting in an opaque film.
However, the transparent films, which were formed using the aluminosilicate particles of Example 1_H180_3-1 to Example 3_H180_3-1, in which the Si/Al ratio of the aluminosilicate shell was 7 to 15 and the hydrothermal reaction was carried out at 180°C, exhibited a transmittance increase (DT%) of at least 3%, a refractive index of 1.31 or less, a reflectance of 1.5 or less, a haze of 1 or less, and superior adhesion and abrasion resistance.
According to the present invention, the anti-reflective film can satisfy properties suitable for display materials, and can thus be employed in display panels requiring a low refractive index and high transmittance, optical coating materials, AR (Anti-Refraction) coating layers, BLUs (Back Light Units) for high-luminance LCD/PDPs, and high-efficiency display polarizer plates and prism sheets.
According to the present invention, the hollow aluminosilicate particles are manufactured in a manner in which an aluminosilicate shell is formed on a core composed of an organic polymer and the organic polymer is removed from the inside of the shell without high-temperature sintering, thus exhibiting a low degree of aggregation and high dispersibility, and high density thereof can be obtained through a hydrothermal reaction.
According to the present invention, the method of manufacturing hollow aluminosilicate particles enables the formation of a uniform shell even without additional core surface treatment by forming negative charges during the preparation of a complex oxide through the reaction of an aluminum precursor and a silica precursor upon forming a shell, resulting in hollow particles wherein the shell is not broken during the high-density reaction but is uniform.
Although preferred examples and test examples of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

Claims (11)

  1. A method of manufacturing hollow aluminosilicate particles, comprising:
    reacting a template core comprising an organic polymer in a micelle or reverse micelle form with a silane compound and an aluminum precursor at a Si/Al molar ratio of 7 to 15, thus synthesizing core-shell particles having an aluminosilicate shell;
    reacting the core-shell particles with a basic aqueous solution or an acidic aqueous solution, thus simultaneously forming fine pores in the shell and removing the core, thereby producing hollow aluminosilicate particles; and
    subjecting the hollow aluminosilicate particles to a hydrothermal reaction at a temperature ranging from 160 to 200°C so as to increase a density of the hollow aluminosilicate particles, thereby yielding the hollow aluminosilicate particles having a shell density of 2.150±0.005 g/cm3.
  2. The method of claim 1, wherein the hollow aluminosilicate particles have an average particle size ranging from 10 to 300 nm and the shell has a thickness ranging from 5 to 15 nm.
  3. The method of claim 1, wherein the organic polymer is a copolymer or a block copolymer including a polymer selected from the group consisting of polyoxyethylene, polyoxyethylene glycol, polyoxypropylene alkyl ether, polyoxypropylene monoalkylether, polyoxypropylene alkyl, polyoxyethylene tallow amine, polyoxyethylene oleyl amine, polyoxyethylene stearyl amine, polyoxyethylene lauryl amine, polyoxyethylene sorbitan ester, polyoxyethylene octyl ether, polyoxyethylene glycerin ether, polyacrylic acid, polysulfonic acid, polyacryl amine, and triethylene amine.
  4. The method of claim 1, wherein the silane compound is represented by Chemical Formula 1 below.
    Chemical Formula 1
    Figure PCTKR2016014721-appb-I000003
    (wherein R1, R2, R3 and R4 are each independently an alkyl group, an alkoxy group, a phenyl group, a vinyl group, a halogen group, an epoxy group, a glycidoxy group, an amino group or a mercapto group.)
  5. The method of claim 1, wherein the aluminum precursor is an organic salt of aluminum or aluminum alkoxide.
  6. The method of claim 1, wherein the basic aqueous solution is sodium hydroxide, ammonium hydroxide, potassium hydroxide, hydroxyphosphate or a mixed solution thereof, and the acidic aqueous solution is hydrochloric acid, nitric acid, sulfuric acid, acetic acid or a mixed solution thereof.
  7. Hollow aluminosilicate particles, manufactured by the method of claim 1 and each configured to include a hollow core and a shell containing silica and aluminum oxide, with a shell density of 2.150±0.005 g/cm3.
  8. The hollow aluminosilicate particles of claim 7, wherein the hollow aluminosilicate particles have an average particle size of 10 to 300 nm and the shell has a thickness of 5 to 15 nm.
  9. A composition for forming a film, comprising the hollow aluminosilicate particles of claim 7.
  10. An anti-reflective film, comprising a transparent film formed through a coating process using the composition of claim 9.
  11. The anti-reflective film of claim 10, wherein the anti-reflective film has a transmittance increase of at least 3%, a refractive index of 1.31 or less, a reflectance of 1.5 or less, and a haze of 1 or less.
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