WO2012165766A2 - Composite creux à faible indice de réfraction, son procédé de fabrication et liquide de revêtement en contenant - Google Patents

Composite creux à faible indice de réfraction, son procédé de fabrication et liquide de revêtement en contenant Download PDF

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WO2012165766A2
WO2012165766A2 PCT/KR2012/003465 KR2012003465W WO2012165766A2 WO 2012165766 A2 WO2012165766 A2 WO 2012165766A2 KR 2012003465 W KR2012003465 W KR 2012003465W WO 2012165766 A2 WO2012165766 A2 WO 2012165766A2
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silica
composite
hollow
hydrotalcite
metal
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Korean (ko)
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WO2012165766A3 (fr
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신수철
김병만
임재환
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백산철강(주)
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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
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
    • C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
    • C01F7/785—Hydrotalcite
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/42—Clays
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B9/00—General methods of preparing halides
    • C01B9/08—Fluorides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/68—Particle size between 100-1000 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • 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

Definitions

  • the present invention relates to a fine composite particles of a hollow structure, and more particularly to a hollow composite having a low refractive index, a method for producing the hollow composite, a coating liquid and the adhesion substrate comprising the same.
  • nano-scale fine particles As it is possible to control the nano-scale fine particles, attempts to utilize such nano-sized particles in the drug delivery system and cosmetic raw materials, as well as the material of various electronic components using nano-sized particles are active.
  • hollow hollow particles are excellent in low density, high surface area, and optical properties, such as glasses, optical lenses, optical materials, solar cells,
  • image display devices such as transparent plastics, plastic films, cathode ray tubes (CRTs), liquid crystal displays (LCDs) and plasma displays (PDPs), UV transparent materials, deep UV, protective coatings, and phosphors Attention has been paid particularly to the next generation materials in the field of materials for imparting high functionality to semiconductor materials and cosmetics that require low dielectric constant materials such as matrix, insulation, drug carriers, catalyst materials, dyes, and interlayer insulating films. have.
  • hollow particles those based on metal oxides or metal fluorides are well known, and these hollow particles have a low refractive index, and thus are required as surfaces of display elements as well as optical materials, for example, antireflection such as antireflection.
  • porous particles are also utilized in an interlayer insulating film of a semiconductor by securing a low dielectric constant.
  • the image display surface must be provided with scratch resistance so as not to be scratched due to external impact or the like during handling, and at the same time, optical functions such as antireflection property and anti-glare property must be provided.
  • the anti-reflection treatment is performed by vacuum deposition or coating of a film or a coating liquid mainly composed of metal oxides or fluorides on the surface of the metal film.
  • a coating film made of silica or metal fluoride is formed on the outermost layer.
  • a hollow silica particle sol is used to realize low refractive index.
  • magnesium fluoride a vacuum is used by using a magnesium fluoride template. It is coated by a vapor deposition method and used as an antireflection film such as an optical lens.
  • the anti-reflective effect when applied on a silver film (coating a metal ceramic such as silica, alumina (Al 2 O 3 ), magnesium fluoride as a protective film material of the high reflection plate,
  • the coating has a low dielectric constant compared to magnesium fluoride, but the adhesion to the substrate and the durability against humidity are inferior to that of magnesium fluoride (Xueke Xu et al., The Study on the Interface Adhesion Comparison of the MgF 2 , Al 2 O 3 , SiO 2 and Ag thin flim, Applied Surface Science 245 (2005), 11-15).
  • the anti-reflection film of the lens of a low refractive index characteristic formed by using a silica hollow body particles having such properties, a transparent plastic, a plastic film, a diffuser film or the like is in, but has an excellent anti-reflection function, the hollow silica SiO 2 is air It is easy to adsorb moisture.
  • the film formed of silica particles is porous and has a large surface area, a large wavelength shift occurs, so that it can be used as an antireflection film of a display device, but it is difficult to use it for precision optical devices such as cameras and microscopes.
  • magnesium fluoride when a film mainly containing magnesium fluoride is formed on a substrate having a hydrophilic group on its surface, magnesium fluoride has a property that is difficult to adsorb moisture.
  • silica has an inherent low refractive index due to its sensitive properties to moisture, and when it is applied to a low antireflection film by forming a 100 nm thick coating film using hollow silica, the function of low refractive index is deteriorated. It has a disadvantage as a low refractive index substrate.
  • Patent Document 1 proposes hollow silica fine particles having excellent antireflection performance and scratch resistance by treatment with a perfluorogroup-containing (meth) acrylic acid ester resin having a specific structure and a silane coupling agent.
  • Patent Document 2 adds an aqueous solution of fluoride to a magnesium salt solution in a constant molar ratio to form a colloidal particle aggregate slurry of magnesium fluoride hydrate, and then removes salts as by-products in the slurry.
  • a method for producing an aqueous sol of magnesium fluoride hydrate obtained by a method of preparing is disclosed.
  • Patent Document 3 proposes a composite sol having a predetermined particle diameter in which silica and magnesium fluoride hydrates are mixed in a constant weight ratio so as to have a low refractive index of magnesium fluoride and a bonding property of silica sol.
  • the refractive index of the silica-magnesium fluoride composite sol thus synthesized is a combination of the refractive index of silica and the magnesium fluoride, it does not realize the low refractive index characteristics as desired, and also uses the silica-magnesium fluoride composite hydrate colloidal sol.
  • the film strength of the antireflection film is improved, but the original refractive index of magnesium fluoride is canceled out and the antireflection function is lowered.
  • Patent Document 4 discloses a silica core-magnesium fluoride solution by adding and stirring a fluoride raw material solution diluted with an organic solvent, a silica particle dispersion liquid as a mold dispersed in an organic solvent, and a magnesium raw material solution in which a magnesium raw material liquid and an organic solvent are mixed. After obtaining the particles of the coating film, it is revealed that hollow magnesium fluoride particles obtained by removing the silica core with caustic soda or the like were obtained.
  • sodium hydroxide and magnesium fluoride react to form magnesium hydroxide and sodium fluoride, and the magnesium fluoride melts in the process of dissolving and discharging silica used as a template, and thus, it is difficult to form hollow magnesium fluoride particles properly. Since the used silica still remains, it is difficult to secure a sufficiently good low refractive index characteristic, and due to the formation of a large diameter micropores in the magnesium fluoride film as the mold is discharged, durability is not only reduced, but also used as an antireflection coating liquid. In this case, since the solvent contained in the coating liquid penetrates into the hollow magnesium fluoride particles through the micropores, the low refractive index characteristic becomes more difficult to exhibit.
  • Korean Patent No. 10-0995401 discloses a method of preparing hollow magnesium fluoride as a method of reacting a magnesium precursor solution with a fluorine precursor solution in which an amine or ammonium additive is mixed.
  • Patent Document 5 there is a problem that not only a process for removing the salt generated as a by-product is required, but also the scratch resistance of the formed magnesium fluoride particles is not improved.
  • the method for producing porous silica particles which are representative porous metal particles
  • a method using a so-called sol-gel method has been proposed.
  • the method of forming hollow particles is a method in which an organic compound is used as a template to grow metal particles such as silica on its surface, and then the organic compound is removed by firing, or a metal oxide and silicate are mixed.
  • a method of removing metal oxides by producing silica-metal oxide particles and then treating the particles under acidic conditions using a strong acid such as hydrochloric acid or sulfuric acid is known.
  • the present invention has been proposed to solve the above-mentioned problems, and an object of the present invention is to provide hollow particles having excellent scratch resistance and ensuring low refractive index.
  • Another object of the present invention is to provide a method for producing hollow particles which can be easily and easily removed from the core.
  • Another object of the present invention is to provide a coating liquid containing the above-described hollow particles and a substrate to which the coating liquid is applied.
  • the hollow silica in order to compensate for the low refractive index deterioration due to moisture penetrating through the pores formed on the surface of the hollow silica, is made of metal fluoride having low refractive index and corrosion resistance, thermal stability, and high hardness. It is a composite hollow body filled with pores and formed of hollow silica and metal fluoride to lower the original low refractive index and lower the moisture absorption rate, thereby producing a composite hollow structure having low antireflection, scratch resistance and fingerprint resistance, coating solution and To provide a coating adhesion substrate.
  • the present invention is a hollow composite silica (SiO 2 ) and a metal fluoride compounded hollow composite, preferably a hollow composite having an average particle diameter of approximately 5 nm to 500 nm, for example, antireflection film, anti-fingerprint, scratch resistance It relates to a method for producing low refractive index composite hollow particles that can be used as a coating agent as a composite particle having a coating liquid and a coating substrate using the same.
  • a hollow composite composed of silica and a metal fluoride.
  • the metal fluoride may be an alkali metal fluoride or an alkaline earth metal fluoride, for example, the metal fluoride may be composed of CaF 2 , LiF 2 , BaF 2 , MgF 2 , NaF, AlF 3 and combinations thereof. Selected from the group.
  • the thickness of the shell portion constituting the hollow composite is characterized in that the range of approximately 5 ⁇ 50 nm.
  • preparing a composite sol of silica-metal fluoride Reacting the composite sol of silica-metal fluoride with a hydrotalcite sol to form inorganic fine particles comprising a shell of silica-metal fluoride and a core of hydrotalcite; Removing a hydrotalcite from the obtained inorganic fine particles provides a method for producing a hollow composite comprising the step of forming a hollow composite of silica-metal fluoride.
  • hydrotalcite is characterized in that it has a structure of formula (1).
  • M 2+ and M 3+ are mixed metal constituents of the positive charge layer, where M 2+ is Mg 2+ , Ca 2+ , Fe 2+ , Co 2+ , Ni 2+ or Zn 2+
  • a metal component that may have an oxidation number of +2, such as M 3+ is a metal component that may have an oxidation number of +3, such as Al 3+ (OH) component is a component constituting the upper and lower sides of the mixed metal component and, a n- is an interlayer anion having a valence of n as n is even possible that the anion exchange with other anions, CO 3 2-, NO 3-, SO 4 2-, OH -, F -, Cl -, Br -A silicon (Si) -containing oxygen acid anion comprising SiO 3 2- , a phosphorus (P) -containing oxygen acid anion comprising PO 4 3- , a boron (B) -containing oxygen acid anion comprising BO 3 2- , Selected from the group consisting of CrO
  • the surface of the hollow composite of the silica-metal fluoride formed can be surface treated using a fluorine-based organic compound or a silane coupling agent.
  • the hydrotalcite used as the core may be a structure partially dehydrated or a structure in which crystal water is removed.
  • hydrotalcite particles represented by Chemical Formula 1 when the hydrotalcite particles represented by Chemical Formula 1 are heat treated at a temperature of about 140 to 220 ° C., hydrotalcite particles from which crystal water is removed may be obtained. It may be represented by the formula (2).
  • hydrotalcite particles represented by Chemical Formula 1 when the hydrotalcite particles represented by Chemical Formula 1 are heat-treated at a temperature of about 220 to 260 ° C., partially dehydrated hydrotalcite particles from which a part of hydroxyl groups are released may be obtained.
  • Hydrotalcite particles may be, for example, represented by the following formula (3).
  • the oxidized hydrotalcite can be obtained by heat-treating the hydrotalcite of formula (1) at a temperature of about 500 °C or more, for example, at a temperature of about 500 ⁇ 1000 °C, preferably about 500 ⁇ 700 °C.
  • a coating liquid imparting antireflection and anti-fingerprint having a coating film containing the hollow composite described above.
  • the present invention provides an antireflection film coated with the coating liquid.
  • the composite hollow structure has a low refractive index property as it is, has an antireflection function, and is suitable as a coating agent and an adhesion substrate having anti-fingerprint properties.
  • the present invention fills the pores of hollow silica using magnesium fluoride having low refractive index, corrosion resistance, thermal stability, and high hardness, and forms a composite hollow body of hollow silica and magnesium fluoride to produce an organic solvent and a resin when preparing moisture and a coating agent.
  • Anti-reflective function and anti-reflection used to manufacture composite hollow particles that prevent hydrophobicity of magnesium fluoride and hydrophobic modification of hydrophilic silica particle surface by using hydrophobic property of magnesium fluoride
  • a coating liquid having properties and an adherent substrate coated or coated with such coating liquid can be prepared.
  • the size of the hollow composite particles having low refractive properties is about 5 to 500 nm, and the range of application varies.
  • the hollow composite structure with improved scratch resistance is an image display such as glasses, optical lens, optical filter, solar cell, transparent plastic, plastic film, cathode ray tube, liquid crystal display (LCD), plasma display (PDP), etc.
  • image display such as glasses, optical lens, optical filter, solar cell, transparent plastic, plastic film, cathode ray tube, liquid crystal display (LCD), plasma display (PDP), etc.
  • UV transparent materials UV and deep ultra violet range
  • protective coatings phosphors, phosphor coatings, insulating materials, drug carriers, dyes, low dielectric constant materials or cosmetics It is expected to be used as a material to add high functionality to the back.
  • FIG. 1 is a flow chart schematically illustrating a process for producing a hollow composite according to the present invention.
  • Example 2 is a TEM photograph of hydrotalcite particles used as cores according to one embodiment of the present invention (Example 1).
  • 3A and 3B are FE-SEM and TEM images of the silica-metal fluoride composite and the hollow composite prepared according to the embodiment of the present invention (Example 1), respectively.
  • Figure 4 is a TEM photograph of a hollow composite prepared according to another embodiment (Example 3) of the present invention.
  • the inventors of the present invention can exhibit an unexpected effect of a hollow composite containing a silicon oxide silica and a metal fluoride as an inorganic material for forming a shell, and in particular, it is easy to manufacture as a core and can control its components.
  • the present invention has been completed by focusing on solving the problems of the prior art by using hydrotalcite. EMBODIMENT OF THE INVENTION Below, this invention is demonstrated.
  • the hollow composite of the present invention compensates for the low refractive index deterioration due to moisture penetrating into the pores of the hollow silica surface and forms a composite hollow structure with a metal fluoride having a low refractive index, thereby lowering the original low refractive index and absorbing moisture. It is due to the urgent need to develop a composite hollow particle having a low refractive index that serves as an antireflection film by lowering the rate.
  • magnesium fluoride having low refractive index, corrosion resistance, thermal stability, and high hardness fills pores of hollow silica and forms a hollow composite of hollow silica and magnesium fluoride to infiltrate moisture, as well as organic solvent and It prevents the penetration of the resin and at the same time uses hydrophobic properties of magnesium fluoride to modify the surface of the hydrophilic silica particles with hydrophobicity, and to produce composite hollow particles that do not impair the original low refractive properties. to provide.
  • the hollow composite according to an aspect of the present invention is a hollow microparticle having a hollow structure, and forms a shell portion in which silica and metal fluoride are blended.
  • the term "hollow” is understood to mean the interior void space surrounded by the shell-forming inorganic composite (shell portion of the silica and metal fluoride composite), the term 'cavity' can be used simultaneously. have. In this sense, the term 'composite hollow shell' or 'composite hollow body' may be used interchangeably for the hollow composite composed of silica-metal fluoride.
  • the silica and metal fluoride constituting the hollow composite according to the present invention can be synthesized from a sol in which each precursor is dispersed in a suitable solvent as described below.
  • alkoxy silane is mentioned as a precursor for forming a silica, this invention is not limited to this.
  • a metal precursor in the form of a water-soluble metal salt and a fluorine compound in the form of a water-soluble fluorate may be used, but the present invention is not limited thereto.
  • any metal fluoride may be used as the metal fluoride, and fluorides of metals belonging to the periodic tables 1A to 3A are preferable, and fluorides of alkali metals or fluorides of alkaline earth metals are particularly preferable.
  • the metal fluoride constituting the hollow composite may be selected from the group consisting of CaF 2 , LiF 2 , BaF 2 , MgF 2 , NaF, AlF 3 and combinations thereof,
  • the metal fluorides according to the invention are not necessarily limited to these metal fluorides.
  • the content of the metal fluoride is lower than this, it is difficult to secure a desired low refractive index effect. If the content of the metal fluoride is higher than this, the strength of the film may be insufficient or the film thickness may be uneven when the coating liquid is applied to the substrate.
  • the hollow composite prepared according to the present invention has an average particle diameter of about 5 to 500 nm, preferably about 10 to 400 nm, more preferably about 20 to 100 nm. If the average particle diameter is smaller than the above-mentioned, it may not be possible to obtain sufficient cavity therein, and thus the effect of low refractive index may not be secured. If the average particle diameter exceeds the above-mentioned range, it is not only difficult to obtain a stable dispersion but also according to the present invention. This is because unevenness may occur on the surface of the substrate coated with the coating liquid containing the hollow fine particles of the composite structure.
  • the average thickness of the outer shell, ie the shell portion, of the hollow composite according to the invention is approximately 5 to 50 nm, preferably approximately 5 to 100 nm, more preferably approximately 10 to 50 nm. This is because if the thickness of the shell portion is smaller than this, it is difficult to maintain the shape of the particles, and if it is larger than this, it may be difficult to manufacture it.
  • a composite sol of silica and metal fluoride constituting the shell portion of the hollow composite is prepared (s110).
  • the silica sol can be, for example, silica whose surface is preserved in sol form with siloxane groups or silanol groups.
  • Silica sol comprising siloxane groups can be dispersed in water to form colloidal silica.
  • Suitable precursors for forming the silica sol include alkoxy silanes, silanes to which functional groups are attached, or glass water.
  • dialkoxysilanes such as dimethyldimethoxysilane, diethyldimethoxysilane, methylethyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, Methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, phenyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloylpropyltrimethoxysilane, gamma- ( Trialkoxysilanes such as 2-aminoethyl) aminopropyltrimethoxysilane, methyltriethoxysilane and phenyltriethoxysilane, tetramethoxysilane,
  • a hydrogen type strong acid cation exchange resin and an organic solvent are added to the aqueous silica sol, followed by stirring to allow the metal ions contained in the aqueous silica sol to be adsorbed onto the exchange resin, and then the reaction mixture is filtered to remove the exchange resin.
  • a sol in which silica is dispersed in a mixed solvent of water and an organic solvent is obtained.
  • the metal ion is sodium, aluminum, iron, etc., attached to the surface of the silica and present in the form of Si-O-M +, causing the silica to aggregate when the organic solvent is added.
  • treatment of the aqueous silica sol with a hydrogen type strongly acidic cation exchange resin not only increases the dispersion stability of the silica sol, but also converts the silica surface to Si-OH, which reacts favorably with the silane coupling agent in a subsequent process.
  • the aqueous silica sol has an average particle diameter of about 5 to 150 nm, preferably about 8 to 100 nm in consideration of the physical properties and storage stability of the sol.
  • the aqueous silica sol has a concentration of about 5 to 50%, preferably about 20 to 30% in consideration of economical efficiency and stability. At this time, if the concentration is less than 5%, the amount of the organic solvent substituted with water of the silica aqueous sol in the subsequent process is not economically increased by that amount, and if the concentration exceeds 50%, the viscosity of the aqueous silica sol increases to recover and By increasing the pressure of the filtration membrane, not only the life of the membrane is shortened, but also the stability is lowered.
  • the aqueous silica sol is a colloidal silica aqueous sol in which silica sol is dispersed in water, and is directly purchased or commercially available.
  • the aqueous silica sol provides a very economical advantage by making sodium ions removed from the water glass.
  • the commercially available aqueous silica sol generally has a pH of 9 to 11, so that additional ion exchange should be performed in the subsequent step of removing water, using an aqueous silica sol stabilized in an acidic region. It is desirable to.
  • Stirring is performed by adding an organic solvent to the aqueous silica sol, and the amount of the organic solvent added is determined according to the concentration of the aqueous silica sol, and preferably, 100 parts by weight of water contained in the aqueous silica sol. It is used at about 0.5 to 200 parts by weight relative to. Accordingly, organic bases or silane coupling agents which may be added in the steps described below increase the compatibility in the water phase.
  • the hydrogen-type strongly acidic cation exchange resin is used to remove metal ions contained in the aqueous silica sol.
  • the hydrogen type strong acid cation exchange resin is a sulfonic acid exchanger, and the support is polystyrene and / or divinylbenzene, and Diaion SKTM, Zeorex SATM, Dowex 50TM, Amberlite IR-120TM and IR-112TM series are used. Used.
  • the metal precursor constituting the metal fluoride used as the structural shell of the hollow composite according to the present invention can be used a metal compound in the form of a water-soluble organic salt or inorganic salt.
  • a metal compound in the form of a water-soluble organic salt or inorganic salt for example, if magnesium is used, one or more magnesium compounds selected from the group consisting of magnesium acetate, magnesium chloride, magnesium bromide, magnesium citrate, magnesium oxalate, magnesium nitrate, magnesium sulfate and their hydrates can be used. Can be.
  • a fluorine compound in the form of a water-soluble fluoride may be used, for example, hydrofluoric acid (HF), sodium fluoride (NaF), potassium fluoride (KF), cesium fluoride (CsF), and ammonium fluoride (NH 4).
  • HF hydrofluoric acid
  • NaF sodium fluoride
  • KF potassium fluoride
  • CsF cesium fluoride
  • NH 4 ammonium fluoride
  • F at least one fluorine compound selected from the group consisting of acidic ammonium fluoride (HF-NH 4 F) and tetra-ammonium fluoride can be used.
  • HF-NH 4 F acidic ammonium fluoride
  • the magnesium precursor solution and the fluorine precursor solution each contain an amount such that the molar ratio of magnesium (Mg) to fluorine (F) does not exceed approximately 1: 3.
  • the molar ratio of magnesium (Mg): fluorine (F) may be reacted in an amount of about 1: 1.5 to 1: 2, more preferably about 1: 1.9 to 1: 2.
  • the thickness of the desired shell portion can be controlled by adjusting the amount of the alkoxy silane, the metal precursor and the fluorine precursor, a person skilled in the art can select appropriately.
  • water and / or an organic solvent are used as a dispersion medium with respect to the precursor which exists in a sol state.
  • Preferred dispersion medium is distilled pure water.
  • organic solvents polar, nonpolar and aprotic solvents are preferred.
  • Examples include aliphatic alcohols having 1 to 6 carbon atoms, in particular methanol, ethanol and lower alcohols such as n- and I-propanol and butanol; Polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, diethylene glycol and triethylene glycol; Ketones such as acetone, methyl ethyl ketone, butanone, and esters such as ethyl acetate; Ethers such as diethyl ether, detrahydrofuran and tetrahydropyran; Amides such as dimethylacetamide and dimethylformamide; Sulfoxides and sulfones such as sulfolane and dimethyl sulfoxide; Aliphatic (optionally halogenated) hydrocarbons such as pentane, hexane and cyclohexane; And mixtures thereof. Preferably it has a boiling point which can be easily removed by distillation, for example, it
  • the silica precursor / metal fluoride precursor which will form a shell part is mixed with a suitable solvent, and binding and hydrolysis reaction of a precursor are performed.
  • the kind of solvent is not particularly limited, and various aqueous and organic solvents known in the art can be used.
  • a mixed solvent of water and alcohol is used.
  • water plays a role of conducting a hydrolysis reaction of the added silica precursor.
  • a hydroxyl group capable of carrying out the condensation and gelation reaction described below is introduced into the silicon atom in the silica precursor.
  • Silica precursors are usually used in admixture with a suitable organic solvent, such as alcohol, because they do not dissolve well in water.
  • the alcohol may dissolve both water and the silica precursor, and accordingly, the hydrolysis reaction may proceed by homogeneously mixing the water and the silica precursor.
  • the blending ratio of water and alcohol is not particularly limited, and a person skilled in the art can easily select a suitable blending ratio.
  • the hydrolysis reaction of the silica precursor may be carried out by a general method of stirring under reflux conditions, for example, or by an acidic catalyst (HCl, CH 3 COOH, etc.) or a basic catalyst (NaOH, KOH, NH 4).
  • a suitable catalyst such as OH may be used to promote the hydrolysis reaction.
  • caustic soda, ammonium chloride or the like can be used to promote hydrolysis of the silane compound as a silica precursor.
  • the pH is adjusted in the range of about 9 to 10 and a mixed solvent of water and alcohol is used as the solvent used for the hydrolysis, the mixed solvent / silane is used in the range of about 2 to 6, preferably about 3.5 Range from ⁇ 5.
  • a hydrotalcite sol is used as a core for forming the hollow composite from the aforementioned precursor complex sol solution (step s120).
  • a sol state hydrotalcite is dispersed in a suitable solvent, for example, the above-mentioned solvent.
  • Hydrotalcite are anionic clays, layered double hydroxides (layered double hydroxide, LDH), the layer as the layer complex hydroxide, also known as mixed metal hydroxide, mixed-metal component and a hydroxyl group (OH -) anion between the layer and the layer made of the It means a material having a fixed structure.
  • the hydrotalcite has a tetrahedral or trivalent metal cation centered on it, and typically has six octahedron structures in which six hydroxide ions (OH-) surround these metal cations, and the octahedral unit repeats. As a result, it has a double layer structure that forms two layers, and an anion and water molecules are positioned between the double layers to maintain an equilibrium of charge amount, and can be generally represented by the following general formula.
  • Such hydrotalcite may be represented by the following Chemical Formula 1.
  • M 2+ and M 3+ are each a mixed metal component constituting the center of the positive charge layer.
  • M 2+ is Mg 2+ , Ca 2+ , Fe 2+ , Co 2+ , Ni.
  • M 3+ is composed of Al 3+ , Fe 3+ , Ga 3+, and Y 3+ .
  • (OH) is a component constituting the upper and lower sides of the mixed metal component
  • a n- is an interlayer anion having a valence of n and the other anion.
  • n is also as anion is exchangeable, for example, CO 3 2-, NO 3-, SO 4 2-, OH -, F -, Cl -, Br -, silicon containing SiO 3 2- (Si ))-Containing oxygen acid anion, phosphorus (P) -containing oxygen acid anion including PO 4 3- , boron (B) -containing oxygen acid anion containing BO 3 2- , consisting of CrO 4 2- , CrO 7 2- Can be selected from the group x is M 2+ surname
  • the fraction of the fraction and the M 3+ component the total charge of the hydrotalcite of this structure is determined according to the fraction value of the M 3+ component, which is usually in the range of 0.20 ⁇ x ⁇ 0.50, preferably 0.20 ⁇ x ⁇ 0.36, while 0 ⁇ m ⁇ 1)
  • the addition or mixing of the metal raw material component, the anion source and the alkali component used as the core according to the present invention is not particularly limited, and according to the present invention by adjusting the input amount of the raw material of the aforementioned metal component, hydroxide ion and interlayer anion
  • the content of each metal component can be adjusted, and the mole fraction adjustment of magnesium (Mg), which is a main component of the divalent metal component, and aluminum (Al), which is a trivalent metal component, is well known.
  • the value of x which is a mole fraction of Al, which is a trivalent metal component in the layered composite metal hydrate in the form of hydrotalcite particles represented by Formula 1, is usually about 0.20 or more and 0.50 or less, preferably about 0.20 or more and 0.40 or less. More preferably, they are about 0.20 or more and 0.36 or less. If this value is less than 0.20 or more than 0.50, there may be a problem that it is difficult to obtain hydrotalcite particles in the form of a single phase.
  • Hydrotalcite particles according to the present invention may be prepared according to any one of a coprecipitation method and a hydrothermal synthesis method. Although the hydrothermal synthesis method was used in the embodiment of the present invention, the present invention is not limited to the hydrotalcite particles obtained according to this specific production method.
  • calcium (Ca) As a source of calcium (Ca), salts, hydroxides, oxides, and chlorides of calcium may be used.
  • CaCl 2 calcium chloride
  • Ca (NO 3 ) 2 calcium nitrate
  • Ca SO 4 calcium sulfate
  • Materials selected from calcium hydroxide (Ca (OH) 2 ), calcium sulfate (CaSO 4 ), calcium oxide (CaO) and the like can be used.
  • zinc oxides, hydroxides, chlorides, and salts of zinc (Zn) may be used as the source, and specifically, zinc oxide (ZnO), zinc hydroxide (Zn (OH) 2 ), zinc chloride (ZnCl 2 ), and zinc sulfate (ZnSO 4 ), zinc nitrate (Zn (NO 3 ) 2 ), and the like.
  • Al aluminum oxide
  • Al (OH) 3 aluminum hydroxide
  • Al (OH) 3 aluminum hydroxide
  • Al (CO 3 ) 3 Aluminum carbonate
  • Al sulfate Al 2 (SO 4 ) 3
  • Al nitrate Al (NO 3 ) 3
  • Al phosphate AlPO 4
  • AlCl 3 aluminum chloride
  • an alkali metal hydroxide may be used as a source for providing the hydroxyl group (OH ⁇ ) between the above-described metal layers.
  • ammonia, urea solution, as well as caustic soda (sodium hydroxide, NaOH) or potassium hydroxide (KOH) Etc. can be used.
  • caustic soda sodium hydroxide, NaOH
  • KOH potassium hydroxide
  • a n- it is already known to form the interlayer anion of hydrotalcite particles using various raw materials for each anion, and thus any known material can be used.
  • the addition or mixing component of a metal raw material component, an anion source and an alkali component as a component for producing hydrotalcite particles used as a core material for forming the hollow composite of the present invention is not particularly limited, and according to the present invention
  • the content of each metal component can be adjusted by adjusting the input amounts of the raw materials of metal components, hydroxide ions and interlayer anions, and adjusting the mole fraction of magnesium (Mg), which is the main component of the divalent metal component, and aluminum (Al), which is the trivalent metal component.
  • Mg mole fraction of magnesium
  • Al aluminum
  • the value of x which is a mole fraction of Al, which is a trivalent metal component in the layered composite metal hydrate in the form of hydrotalcite particles represented by Formula 1, is usually about 0.20 or more and 0.50 or less, preferably about 0.20 or more and 0.40 or less. More preferably, they are about 0.20 or more and 0.36 or less. If the value of this mole fraction is less than or above the above-mentioned range, there may be a problem that it is difficult to obtain hydrotalcite particles in the form of a single phase.
  • the hydrotalcite according to the present invention may be hydrotalcite in which all or part of water molecules are removed by heat treatment, in addition to the above-described formula (1).
  • heat treatment of hydrotalcite to approximately 140 to 180 ° C. leads to a dehydration reaction in which water molecules, ie, crystal water, are removed between the layers of hydrotalcite, resulting in a dehydration intermediate (metahydrotalcite-D, HT-D) is formed, and heat treatment at approximately 240 to 260 ° C.
  • partially dehydrated hydrotalcite is hydrotalcite containing crystallized water at high temperature to remove the crystallized water contained in hydrotalcite, and some hydroxide ions contained in hydrotalcite are converted into water and oxide ions.
  • Dehydration reaction (2OH- ⁇ H 2 O + O 2- ) is decomposed hydrotalcite, which is partially dehydrated hydrotalcite is octahedral with six hydroxide ions surrounding the metal cation due to dehydration Part of the structure disappears, converting four hydroxide ions into a tetrahedron structure surrounding the metal cation, resulting in a mixture of octahedral and tetrahedral structures within the double layer (see above; Ts.
  • hydrotalcite used in the present invention includes not only the compound of Formula 1 described above, but also partially dehydrated hydrotalcite, or hydrotalcite in which the crystal water is completely removed.
  • the hydrotalcite particles from which the crystal water is removed may have a hydrotalcite particle represented by Chemical Formula 1 at a temperature of about 140 to 220 ° C., preferably about 140 to 200 ° C., more preferably about 140 to 180 ° C. It may be obtained by heat treatment at, it may be represented by the formula (2).
  • the partially dehydrated hydrotalcite particles may be obtained by heat-treating the hydrotalcite particles represented by Chemical Formula 1 at a temperature of about 220 to 260 ° C., preferably about 240 to 260 ° C. Can be displayed.
  • the oxidized hydrotalcite that is, the hydrotalcite from which the interlayer anion has been removed, has a hydrotalcite of Formula 1 at a temperature of about 500 ° C. or more, for example, a temperature of about 500 to 1000 ° C., preferably about 500 to 700 ° C. It can be obtained by heat treatment at.
  • step s130 the silica-metal fluoride composite sol prepared in step s110 and the hydrotalcite sol prepared in step s120 are reacted to form a shell of the core of the hydrotalcite and a composite of silica-metal fluoride (step s130).
  • a gelation reaction is performed by condensation of the hydrolyzed silica precursor and the metal fluoride to form a shell portion, through which the hydrolyzed precursor forms a siloxane bond (-Si-O-Si-) and condensation and gelation. do.
  • Such condensation reactions can be classified into dehydration condensation and alcohol condensation reactions.
  • the dehydration condensation reaction water is removed while forming a siloxane bond through the hydroxy bond introduced into the precursor during the hydrolysis reaction.
  • alcohol condensation reaction alcohol is removed while forming a siloxane bond through the bonding of a hydroxy group and an alkoxy group.
  • the method of advancing such condensation and gelation reaction is not specifically limited, For example, it can carry out by stirring a mixture under suitable temperature conditions.
  • the metal fluoride forms a composite structure in the form of penetrating into the pores formed in the silica.
  • step s140 the step of removing the core is performed (step s140).
  • Hydrotalcite used as a core in accordance with the present invention can be removed in strong acidic conditions such as hydrochloric acid or sulfuric acid, for example pH 1 to 3 atmosphere.
  • strong acidic conditions such as hydrochloric acid or sulfuric acid, for example pH 1 to 3 atmosphere.
  • metal oxide used as a template it is difficult to exert low refractive properties as the metal oxide used as a template remains, but according to the present invention It was confirmed that the hydrotalcite used as was easily and completely removed under strong acid conditions.
  • a surface treatment using an appropriate coupling agent or the like is performed (step s150). It should be noted that the surface treatment step may be performed immediately after the core is removed, but may also be performed immediately after each of the cleaning step (s160), the aging step (s170), and the solvent replacement step (s180) described below. .
  • the coupling agent may be, for example, a silane-based, aluminum-based, titanium-based, or zirconium-based coupling agent.
  • silane-based coupling agent examples include 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxy.
  • Silane vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxy-ethoxy) -silane, 2- (acryloxyethoxy) trimethylsilane, N- (3-acryloxy-2-hydro Oxypropyl) -3-aminopropyltriethoxysilane, (3-acryloxypropyl) dimethylmethoxysilane, (3-acryloxypropyl) methyl bis- (trimethylsiloxy) silane, (3-acryloxypropyl) methyl Dimethoxysilane, 3- (N-arylamino) propyltrimethoxysilane, aryldimethoxysilane, aryltriethoxysilane, butenyltriethoxysilane, 2- (chloromethyl) aryltrimethoxysilane, [2 -(3-cyclohexenyl) ethyl] trimethoxysilane, 5- (bicycloheptenyl
  • a mixture of a fluorine-based organic material or a mixture of a silane coupling agent and a silane coupling agent having a phenyl group is preferably about 0.5 to 50% by weight with respect to the composite hollow body for the purpose of securing anti-fingerprint to the silica-metal fluoride composite hollow powder.
  • it may be used in the range of about 0.1 to 20% by weight.
  • a sol-gel method is used under a catalyst using a fluorine-based organic compound or a mixture of a silane coupling agent and a silane coupling agent having a phenyl group in the range of about 0.1 to 10% by weight.
  • Composite prepared using is used in the range of approximately 0.1 to 7% by weight using a surface bond with the composite hollow particles.
  • fluorine acrylate monomer used in the present invention examples include trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl acrylate, tetrafluoropropyl methacrylate, and hexafluoropropyl methacrylate.
  • the fluorine silane used in the present invention is tridecafluorooctyltriethoxysilane, trifluoropropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane (heptadecafluorodecyltrimethoxysilane ) And heptadecafluorodecyltriisopropoxysilane.
  • a washing step (s160) of removing the by-products and impurities of the reaction, and the hollow composite powder from which the reaction by-products and the impurities have been removed are placed in, for example, a high pressure reactor, approximately 100.
  • Step of aging for 5 to 24 hours in the range ⁇ ⁇ 180 °C (s170) the solvent replacement to adjust the content of Na ions to 100 ppm or less, for example by removing impurities using the cation and anionic resin in the aged hollow composite powder Step s180 may be performed.
  • the substrate to which the hollow composite of the present invention may be attached may be formed on the surface of the substrate alone or in combination with other coatings, including the hollow composite of the present invention and the film-forming matrix.
  • Such substrates include glass, polycarbonate, acrylic resins, polyethylene glycol (PET), plastic sheets such as triacetyl cellulose (TAC), plastic films, plastic lenses, substrates such as plastic panels, CRTs, and liquid crystal display devices. And a film formed on the display surface.
  • it may be a protective film, a hard coat film, a planarization film, an insulating film, a low dielectric constant film, a thermal barrier film, a conductive metal fine particle film, etc. on the desired substrate, and such a film may be formed by spin coating a coating liquid or a coating liquid for film formation. It can apply
  • Composite hollow particles prepared according to the present invention has a low refractive index and can be utilized in components for imparting anti-glare function to prevent reflection of light and / or projection of external light in a display device. That is, using the hollow composite prepared according to the present invention as a raw material for anti-glare or anti-reflection, has a function of diffusely reflecting the external light source through excellent scratch resistance (scratch resistance), high light transmittance to external stimuli It may be contained in the coating liquid.
  • the anti-glare coating solution includes ultraviolet curable resins such as methyl acrylate, methyl methacrylate, methoxy polyethylene methacrylate, cyclohexyl methacrylate, and dipenta, which have a light transmittance of 80% or more.
  • ultraviolet curable resins such as methyl acrylate, methyl methacrylate, methoxy polyethylene methacrylate, cyclohexyl methacrylate, and dipenta, which have a light transmittance of 80% or more.
  • UV-curable resins such as rititolitol hexaacrylate and trimethyl propane triacrylate, 1-hydroxy cyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, 3-methylaceto Photoinitiators such as phenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, and the like.
  • Alcohol such as methanol, ethanol, a propanol, butanol, benzyl alcohol, ethylene glycol
  • Ketones such as methyl ethyl ketone, cyclohexanone and methylcyclohexanone
  • Esters such as methyl acetate / ethyl / propyl / butyl, ethyl formate and butyl formate
  • Amides such as dimethylformamide and n-methylpyrrolidone
  • ethers such as propylene glycol monoethyl ether, dioxane, tetrahydrofuran and ethylene glycol dimethyl ether.
  • the surface of the hollow composite described above may be utilized for drug delivery as modified by using a biocompatible polymer.
  • the biocompatible polymer has a weight average molecular weight of approximately 100 to 100,000, and polyalkylene glycol (PAG), polyetherimide (PEI) such as polyethylene glycol (PEG) and / or monomethoxy polyethylene glycol (mPEG).
  • PAG polyalkylene glycol
  • PEI polyetherimide
  • PEG polyethylene glycol
  • mPEG monomethoxy polyethylene glycol
  • biodegradable polymers selected from the group consisting of polyvinylpyrilidone (PVP), hydrophilic vinyl polymers and copolymers of two or more thereof may be used, but are not limited thereto.
  • Such biocompatible polymer is preferably included in about 5 to 50% by weight based on the hollow composite particles.
  • aqueous magnesium chloride solution (MgCl 2 , 30%) was completely dissolved in 1000 kg of water to prepare a solution (B).
  • Solution (C) was prepared by dissolving 10.25 kg of sodium bicarbonate (NaHCO 3 , 99.99%) in 1500 kg of water.
  • the prepared A, B, C solution was added dropwise to the 20 m 3 reactor capable of stirring more than 3000 rpm at a temperature of 80 ⁇ 100 °C for 1 to 24 hours to prepare a hydrotalcite sol (D) having a solid content of 1%.
  • An SEM photograph of the hydrotalcite particles prepared according to this example is shown in FIG. 2.
  • a solution (E) dissolved in 1000 kg of water was prepared.
  • Solution (F) was prepared by dissolving 191.48 kg of ammonium fluoride (NH 4 F, 98%) completely in 2000 kg of water.
  • 126.00 kg of water glass (SiO 2 solid content 30%) constituting silica was completely dissolved in 1000 kg of water to prepare a solution (G).
  • the prepared solutions E, F, and G were added to a 20 m 3 reactor and added dropwise in a range of 60 to 90 ° C. for 1 to 24 hours using a metering pump to prepare a sol (H) constituting the composite hollow body.
  • the hydrotalcite sol (D) prepared above and the sol (H) constituting the composite hollow body were dropped into a 20 m 3 reactor in a range of 60 to 90 ° C. for 1 to 24 hours using a metering pump.
  • the formed multiparticulate (I) was prepared.
  • hydrochloric acid was added thereto until the pH became 3 or less, followed by stirring at room temperature for 24 hours to prepare a hollow composite from which the core was removed. Reaction byproducts and impurities were removed using a filtration device.
  • Hollow composites from which reaction products and impurities were removed were placed in a high pressure reactor in order to increase the crystal structure and purity, and were aged for 5 to 24 hours in the range of 100 to 200 ° C.
  • the crystallized composite hollow structure was adjusted to a Na content of 100 ppm or less by removing impurities using a cation and anionic resin.
  • Example 2 The same procedure and conditions as in Example 1 were repeated except that 167 kg of aqueous magnesium chloride solution (MgCl 2 , 30%) was completely dissolved in 1000 kg of water as a raw material of the magnesium component to prepare a solution (B).
  • the hollow shell was prepared.
  • aqueous magnesium chloride solution (MgCl 2 , 30%) was completely dissolved in 1000 kg of water to prepare a solution (B), and 12.25 kg of sodium nitrate (NaNO 3 , 99.99%) was dissolved in 1500 kg of water.
  • the same procedure and conditions as in Example 1 were repeated except that the solution (C) was prepared, thereby preparing a composite hollow shell.
  • Hollow composites were prepared using partially dehydroxylated hydrotalcite as the sol.
  • Mg 0.67 Al 0.33 (OH) 2 (CO 3) in order to use the hydrotalcite particles determines the number of removal of 0.167 structure of a core hydroxide as a raw material of the aluminum component constituting the hydrotalcite crystal can remove aluminum (Al ( OH) 3 , 99.9%) 13.49 kg of sodium hydroxide and 49.32 kg of caustic soda (NaOH, 50%) and 1000 kg of water were added to a 1 m 3 reactor and heated at 100 ° C. for 1 to 5 hours to dissolve sodium Aluminate solution (A) was prepared.
  • Magnesium chloride aqueous solution (MgCl 2 , 30%) was completely dissolved in 1000 kg of water as a raw material of the magnesium component to prepare a solution (B).
  • Solution (C) was prepared by dissolving 10.25 kg of sodium bicarbonate (NaHCO 3 , 99.99%) in 1500 kg of water.
  • the prepared A, B, C solution was added dropwise to the 20 m 3 reactor capable of stirring more than 3000 rpm at a temperature of 80 ⁇ 100 °C for 1 to 24 hours to prepare a hydrotalcite sol (D) having a solid content of 8%. Filtered with distilled water and dried.
  • the composite hollow shell was prepared by repeating the same procedure and conditions as those described in Example 1 except that the hydrotalcite prepared was heat-treated at about 180 to 220 ° C. and partially dehydrated.
  • Composite hollow shells were prepared using partially dehydrated hydrotalcite as a core.
  • Magnesium chloride aqueous solution (MgCl 2 , 30%) was completely dissolved in 1000 kg of water as a raw material of the magnesium component to prepare a solution (B).
  • Solution (C) was prepared by dissolving 10.25 kg of sodium bicarbonate (NaHCO 3 , 99.99%) in 1500 kg of water.
  • the prepared A, B, C solution was added dropwise to the 20 m 3 reactor capable of stirring more than 3000 rpm at a temperature of 80 ⁇ 100 °C for 1 to 24 hours to prepare a hydrotalcite sol (D) having a solid content of 8%. Filtered with distilled water and dried.
  • a composite hollow shell was prepared by repeating the same procedure and conditions as those indicated in Example 1 except that the hydrotalcite prepared was partially dehydrated in the vicinity of 220 to 250 ° C.
  • Composite hollow shells were prepared using calcined hydrotalcite particles as the core. Mg 0.67 Al 0.33 (OH) 2 (CO 3) 0.167 ⁇ 0.5H to produce the hydrotalcite particles in the structure of the 2 O, aluminum (Al (OH) hydroxide as a raw material of the aluminum component constituting the particles 3, 99.9 %) Add 13.21 kg and 49.32 kg of caustic soda (NaOH, 50%) and 1000 kg of water as a raw material of hydroxide ions in a 1 m 3 reactor, and dissolve by heating at 100 ° C for 1 to 5 hours to dissolve sodium aluminate solution (A ) Was prepared.
  • CaOH caustic soda
  • Magnesium chloride aqueous solution (MgCl 2 , 30%) was completely dissolved in 1000 kg of water as a raw material of the magnesium component to prepare a solution (B).
  • Solution (C) was prepared by dissolving 10.25 kg of sodium bicarbonate (NaHCO 3 , 99.99%) in 1500 kg of water.
  • the prepared A, B, C solution was added dropwise to the 20 m 3 reactor capable of stirring more than 3000 rpm for 1 to 24 hours at a temperature of 80 ⁇ 100 °C to prepare a hydrotalcite particles of 8% solids. Filtered with distilled water and dried.
  • the composite hollow shell was prepared by repeating the same procedure and conditions as those described in Example 1 except that the prepared hydrotalcite was calcined at 500 ° C. or higher to remove carbonate ions, which are interlayer anions.
  • the divalent metal used as the core used Zn dihydrotalcite particles as the core.
  • aluminum hydroxide (Al (OH) 3 , 99.9%) as a raw material of the aluminum component 11.11 kg and 41.51 kg of caustic soda (NaOH, 50%) and 1000 kg of water were added to a 1 m 3 reactor as a raw material for hydroxide ions, and heated and dissolved at 100 ° C. for 1 to 5 hours to dissolve sodium aluminate solution (A). Prepared.
  • a zinc chloride aqueous solution (ZnCl 2 , 99%) was completely dissolved in 1000 kg of water to prepare a solution (B).
  • a composite hollow shell was prepared by repeating the same procedures and conditions as in Example 1 except that 10.25 kg of sodium bicarbonate (NaHCO 3 , 99.99%) was dissolved in 1500 kg of water to prepare a solution (C).
  • Hydrotalcite whose divalent metal used as a core is Mg and Ca was used as a core.
  • aluminum hydroxide (Al (Al ( OH) 3 , 99.9%) 15.24 kg and 52.64 kg of caustic soda (NaOH, 50%) and 1000 kg of water were added to a 1 m 3 reactor as a raw material for hydroxide ions, and heated and dissolved at 100 ° C. for 1 to 5 hours.
  • An aluminate solution (A) was prepared.
  • aqueous calcium chloride solution (CaCl 2 , 99%) was completely dissolved in 1000 kg of water to prepare a solution (B).
  • a solution (C) was prepared by dissolving 10.25 kg of sodium bicarbonate (NaHCO 3 , 99.99%) in 1500 kg of water.
  • the prepared A, B, C solution was added dropwise to a 20 m 3 reactor capable of stirring at 3000 rpm or more at a temperature of 80 to 100 ° C. for 1 to 24 hours, except that a hydrotalcite sol (D) having a solid content of 1% was prepared. And repeating the same procedures and conditions as in Example 1, to prepare a composite hollow shell.
  • a solution (E) was prepared in which 177.3 kg was dissolved in 1000 kg of water, and 41.48 kg of ammonium fluoride (NH 4 F, 98%) was completely dissolved in 2000 kg of water to prepare a solution (F).
  • SiO 2 solids 30% A composite hollow shell was prepared by repeating the same procedure and conditions as those indicated in Example 1, except that 550.61 kg of the solution (G) was prepared by completely dissolving 550.61 kg in 1000 kg of water.
  • a solution (E) was prepared by dissolving 351.49 kg in 1000 kg of water, and 82.04 kg of ammonium fluoride (NH 4 F,, 98%) was completely dissolved in 2000 kg of water to prepare a solution (F), which constituted silica.
  • a composite hollow shell was prepared by repeating the same procedure and conditions as those indicated in Example 1, except that 436.60 kg of water glass (30% of SiO 2 solids) was completely dissolved in 1000 kg of water to prepare a solution (G).
  • a solution (E) was prepared in which 856.89 kg was dissolved in 1000 kg of water, 168.10 kg of ammonium fluoride (NH 4 F, 98%) was completely dissolved in 2000 kg of water to prepare a solution (F), and the water glass constituting silica. (SiO 2 solids 30%)
  • a composite hollow shell was prepared by repeating the same procedure and conditions as those indicated in Example 1, except that 106.33 kg was completely dissolved in 1000 kg of water to prepare a solution (G).
  • a solution (E) was prepared by dissolving 690.28 kg in 1000 kg of water, 161.11 kg of ammonium fluoride (NH 4 F, 98%) was completely dissolved in 2000 kg of water to prepare a solution (F), and the water glass constituting silica. (SiO 2 solids 30%)
  • a composite hollow shell was prepared by repeating the same procedure and conditions as those indicated in Example 1, except that 214.51 kg was completely dissolved in 1000 kg of water to prepare a solution (G).
  • the raw material constituting the calcium fluoride as the metal fluoride is magnesium chloride (MgCl 2, 30%)
  • a solution (F) was prepared by completely dissolving 810 kg in 2500 kg of water and 250 kg of calcium fluoride (CaF 2 , 98%) in 1000 kg of water to prepare a solution (F).
  • the composite hollow shell was prepared by repeating the procedure and conditions of Example 1 except that 176.8 kg was completely dissolved in 1000 kg of water to prepare a solution (G).
  • a composite hollow shell was prepared by repeating the procedure and conditions of Example 1 except that 176.8 kg of the constituent water glass was completely dissolved in 1000 kg of water to prepare a solution (G).
  • a composite hollow shell was prepared by repeating the procedure and conditions of Example 1 except that 176.8 kg of the constituent water glass was completely dissolved in 1000 kg of water to prepare a solution (G).
  • the composite hollow shells prepared in Examples 1 to 20, respectively were substituted with organic solvents of alcohols such that the content of solids was 20%, and the content of moisture was adjusted to 0.5% or less.
  • An organosol was prepared.
  • organosol IPA, 20% solids
  • 3-methacryloxypropyltrimethoxysilane 3-Methaacryl trimethoxysilane, Shin-Etsu, Japan, trade name; KBM 503
  • catalyst 0.1N hydrochloric acid
  • 4 kg of water were added dropwise to react for 24 hours at a reaction temperature of 50 ° C. to treat the organosol of the composite hollow structure with a silane coupling agent.
  • Examples 61 to 80 preparing a coating liquid having a low reflection coating liquid and anti-fingerprint properties
  • a composite hollow shell was prepared by repeating the same procedure and conditions as in Example 1, except that 660.39 kg of the solution (G) was prepared by completely dissolving 660.39 kg in 2500 kg of water.
  • the surface-treated organosol was prepared by repeating the same procedure as in 21 to Example 60, and the same procedure as in Examples 61 to 80 was repeated to prepare a coating solution.
  • a solution (E) was prepared in which 1010 kg was dissolved in 1500 kg of water, 235.74 kg of ammonium fluoride (NH 4 F, 98%) was completely dissolved in 2000 kg of water to prepare a solution (F), and water glass constituting silica.
  • a composite hollow shell was prepared and carried out by repeating the same procedure and conditions as those described in Example 1, except that solution (G) was prepared by completely dissolving (65% of SiO 2 solids), 5.65 kg in 1000 kg of water.
  • solution (G) was prepared by completely dissolving (65% of SiO 2 solids), 5.65 kg in 1000 kg of water.
  • the same procedure as in Example 21 to Example 60 was repeated to prepare a surface-treated organosol, and then the same procedure as in Examples 61 to 80 was repeated to prepare a coating solution.
  • a composite hollow shell was prepared and carried out by repeating the same procedure and conditions as in Example 1, except that 667.00 kg of water glass (30% of SiO 2 solids) was completely dissolved in 1000 kg of water to prepare a solution (G). The same procedure as in Example 21 to Example 60 was repeated to prepare a surface-treated organosol, and then the same procedure as in Examples 61 to 80 was repeated to prepare a coating solution.
  • preparing (F) the same procedure and conditions as in Example 1 were repeated to prepare a composite hollow shell, and the same procedure as in Examples 21 to 60 was repeated to surface treated orgas. After the preparation of the nosol, the same procedure as in Examples 61 to 80 was repeated to prepare a coating solution.
  • Example 41 to Example 60 The same procedure as in Example 41 to Example 60 was carried out except that 1250 kg of hollow silica 80 nm-IPA substituted 20% organosol from Japan H Company was used in place of the composite hollow shell synthesized according to the present invention. After the surface-treated organosol was prepared, the same procedure as in Examples 61 to 80 was repeated to prepare a coating solution.
  • the organosol of the hollow silica and the hollow fluoride-silica prepared in Comparative Example 3 to Comparative Example 4 is a metal fluoride / silica (MF a / (SiO 2 ) b molar ratio of 8: 2 by weight of solids
  • MF a / (SiO 2 ) b molar ratio of 8: 2 by weight of solids The same procedure as described in Example 1, except that 880.25 kg of hollow fluoride sol (solid content 20%, IPA) and 191.70 kg of hollow silica sol (solid content 20%, IPA) were quantified to prepare a mixed sol. And the conditions were repeated to prepare a composite hollow shell, and the same procedure as in Example 21 to Example 60 was repeated to prepare a surface-treated organosol, and then the same procedure as in Examples 61 to 80 was repeated. To prepare a coating solution.
  • the molar ratio of solid fluoride metal fluoride / silica is 8: 2 and silica solid particles were 191.7 kg of DuPont's LUDOX 30nm (IPA, 20%).
  • the magnesium fluoride solid particles were prepared without the hydrotalcite core used in Example 1, to prepare a solution (E) in which 1700 kg of magnesium chloride (MgCl 2 , 30% aqueous solution) was dissolved in 2000 kg of water, and ammonium fluoride (NH 4 F, 98%) After completely dissolving 296.30 kg in 1000 kg of water, and reacted at 80 °C for 1 to 24 hours to prepare a magnesium fluoride sol having an average particle size of 30 nm Examples 21 to The same procedure as in 60 was repeated to prepare a surface-treated organosol, and the same procedure as in Examples 61 to 80 was performed to prepare a coating solution.
  • E 1700 kg of magnesium chloride
  • NH 4 F ammonium fluoride
  • trifluoropropyl trimethoxysilane in 200 kg of the surface-treated composite hollow structure prepared in Example 1 (20% sol substituted with IPA (isopropyl alcohol)) In the same manner as in Examples 61 to 80, except that 1 kg of catalyst (0.1 N hydrochloric acid) and 2 kg of water were added dropwise to 10 kg and 5 kg of polydimethyl siloxane, and the reaction was not carried out at a reaction temperature of 50 ° C. for 24 hours. A coating solution was prepared.
  • trifluoropropyl trimethoxysilane was prepared in 200 kg of the surface-treated composite hollow structure prepared in Example 2 (20% sol substituted with IPA (isopropyl alcohol)). Same as Examples 61 to 80, except that 1 kg of catalyst (0.1 N hydrochloric acid) and 2 kg of water were added dropwise to 10 kg and 5 kg of polydimethyl siloxane and not reacted at a reaction temperature of 50 ° C. for 24 hours. To prepare a coating solution.
  • trifluoropropyl trimethoxysilane in 200 kg of the surface-treated composite hollow structure prepared in Example 3 (20% sol substituted with IPA (isopropyl alcohol)) ) 1 kg of catalyst (0.1 N hydrochloric acid) and 2 kg of water are added dropwise to 10 kg and 5 kg of polydimethyl siloxane, and the reaction is not performed for 24 hours at a reaction temperature of 50 ° C.
  • IPA isopropyl alcohol
  • the refractive index of the hollow composite prepared through the above example was measured by the following method.
  • the refractive index of the particles of the composite hollow body is dried at 120 ° C. after evaporating the dispersion medium using the composite hollow sol with an evaporator.
  • a standard refractive liquid with a known refractive index is added dropwise onto two or three drops of glass plates, and the powder is mixed with the standard refractive liquid, and the refractive index of the standard refractive liquid when the mixed liquid becomes transparent is used as the refractive index of the fine particles. Shall be.
  • the hydrotalcite particle form used as the core of the composite hollow shell prepared in Examples 1 to 16 and Comparative Examples 1 to 8, the average particle size of the composite hollow shell, and the metal fluoride-silica The molar ratio and shell thickness of the composite hollow shell were measured.
  • Mass-spectrometer particle size analyzer was used to investigate the composition of hydrotalcite particles used as cores.
  • the average particle diameter and the shell thickness of the hollow composite shell was measured by particle size distribution measurement by laser diffraction scattering method, the average particle diameter was taken as the average secondary particle diameter MV value obtained after the particle size distribution measurement.
  • the synthesized hollow shell particles were photographed by scanning electron microscope (FE-SEM) and FEM.
  • Table 1 The analytical results for each of the hydrotalcite particles and the hollow composite shell analyzed in this example are shown in Table 1 below.
  • Figure 2 is a TEM picture of the core of the composite hollow body used as a core in Example 1
  • Figure 3a and Figure 3b is a FE-SEM and TEM picture of the hollow composite shell prepared according to Example 1
  • Figure 4 SEM photograph of the hollow composite shell prepared in Example 3
  • Figure 5 is a SEM photograph of the hollow composite shell prepared in Comparative Example 1
  • Figure 6 is a TEM photograph of the hollow composite shell prepared in Comparative Example 2. . It can be seen that the hollow composite shell produced according to the invention has a good hollow structure.
  • the coating liquid prepared in Examples 49 to 64 and the coating liquid prepared in Comparative Examples 7 to 12 were placed on a triacetylcellulose film (hereinafter referred to as TAC film). After coating, heat drying at 70 ° C. for 1 minute, and curing under UV light, physical properties were measured. Each physical property was measured according to the method described in Korean Patent Publication No. 10-2007-0080820, and specific measuring methods are as follows.
  • the coating solution containing the composite hollow particles prepared in the above-described examples was left in a 60 ° C. dryer for 7 days to evaluate storage stability and dispersion stability. When left for 7 days or more, the degree of clouding and gelation was visually evaluated.
  • the total light transmittance and haze of the low reflection films prepared in Examples and Comparative Examples were measured using a spectrophotometer (HZ-1, Japanese SUGA). When the total light transmittance (%) is 95% or more, 5, 93% or more, 4, 90% or more, 3, 85% or more, 2, 80% or more, and 1 is indicated.
  • the reflectance of the low reflection film prepared in the above-mentioned Examples and Comparative Examples was measured using a UV spectrometer (UV-Spectrophotometer, Japan SHIMADZU).
  • the wavelength region measures the visible light region of 380 ⁇ 780 nm.
  • the minimum reflectance (%) of the low reflection film was obtained from the obtained reflectance spectrum.
  • Rubbing of the low reflection film coated with the coating liquid prepared in the above-mentioned Examples and Comparative Examples by reciprocating 10 times under 1 kg / (2 cm x 2 cm) using a steel wool tester (WT-LCM100, PROTECH Korea) Test for constancy.
  • Steel wool uses # 0000. 0 scratches were marked as A, 1 to 10 scratches as A ', 11 to 20 scratches as B, 21 to 30 scratches as C, and 31 scratches as D.
  • n number of rectangles that do not peel out of the entire rectangle
  • Fingerprints were applied to the surface of the coating film to visually observe the degree of burial at about 20 ° angle and evaluated by the following method.
  • the hollow composite particles synthesized according to the present invention had good dispersion stability, transmittance, reflectance, pencil hardness, fingerprint resistance, scratch resistance and adhesion.

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Geology (AREA)
  • Nanotechnology (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Silicon Compounds (AREA)
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  • Paints Or Removers (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'un composite particulaire utilisant de l'hydrotalcite comme noyau et caractérisé par la présence d'une enveloppe creuse composite constituée d'un oxyde métallique et d'un fluorure métallique présentant un faible indice de réfraction. L'invention concerne également un liquide de revêtement et une base adhésive utilisant ledit composite, ce qui permet d'éviter la réflexion et de modifier les propriétés superficielles, avec pour résultat une amélioration des propriétés physiques. Ladite enveloppe composite creuse agit au niveau de l'indice de réfraction et a pour fonction d'éviter une faible réfraction et les traces de doigt, ce qui la rend adaptée à une utilisation en tant qu'agent de revêtement ou base adhésive. Lorsque le liquide de revêtement contenant le composite creux selon la présente invention est appliqué, par exemple sur un film plastique ou une surface d'affichage d'images d'un dispositif d'affichage d'images, les propriétés anti-réflexion et anti-traces de doigt de ladite surface peuvent s'en trouver améliorées.
PCT/KR2012/003465 2011-05-30 2012-05-03 Composite creux à faible indice de réfraction, son procédé de fabrication et liquide de revêtement en contenant WO2012165766A2 (fr)

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WO2015084097A1 (fr) * 2013-12-05 2015-06-11 삼성에스디아이 주식회사 Film de résine et procédé de fabrication de film de résine
CN105793741A (zh) * 2013-12-05 2016-07-20 三星Sdi株式会社 树脂膜以及树脂膜的制造方法
CN113856707A (zh) * 2021-09-18 2021-12-31 深圳市东有新材料科技有限公司 一种高催化效率的中空纳米氟化铝球及其制备方法
JP2023026979A (ja) * 2021-08-16 2023-03-01 公立大学法人大阪 ハイドロタルサイト化合物及び光活性触媒

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KR101735052B1 (ko) * 2014-12-11 2017-05-12 한국외국어대학교 연구산학협력단 메조포러스 실리카 나노입자 및 이의 제조방법
KR101764581B1 (ko) * 2015-09-23 2017-08-10 청운대학교산학협력단 내지문·내반사 필름 코팅제 제조방법
KR102644010B1 (ko) * 2021-09-03 2024-03-07 주식회사 케이씨텍 표면개질된 중공실리카 및 표면개질된 중공실리카 분산액
KR20240053717A (ko) 2022-10-17 2024-04-25 국립한국교통대학교산학협력단 카테콜 기반 양쪽성이온과 반응성 관능기로 개질된 중공실리카의 제조방법 및 이를 포함하는 리튬-황 전지용 기능화된 분리막 및 이의 제조 방법

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WO2015084097A1 (fr) * 2013-12-05 2015-06-11 삼성에스디아이 주식회사 Film de résine et procédé de fabrication de film de résine
CN105793741A (zh) * 2013-12-05 2016-07-20 三星Sdi株式会社 树脂膜以及树脂膜的制造方法
CN105793741B (zh) * 2013-12-05 2017-09-08 三星Sdi株式会社 树脂膜、树脂膜组成物以及树脂膜的制造方法
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JP7416441B2 (ja) 2021-08-16 2024-01-17 公立大学法人大阪 ハイドロタルサイト化合物及び光活性触媒
CN113856707A (zh) * 2021-09-18 2021-12-31 深圳市东有新材料科技有限公司 一种高催化效率的中空纳米氟化铝球及其制备方法

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