WO2015182878A9 - Procédé de fabrication de particules de silice creuses, particules de silice creuses, et composition et feuille d'isolation thermique les comprenant - Google Patents

Procédé de fabrication de particules de silice creuses, particules de silice creuses, et composition et feuille d'isolation thermique les comprenant Download PDF

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WO2015182878A9
WO2015182878A9 PCT/KR2015/004057 KR2015004057W WO2015182878A9 WO 2015182878 A9 WO2015182878 A9 WO 2015182878A9 KR 2015004057 W KR2015004057 W KR 2015004057W WO 2015182878 A9 WO2015182878 A9 WO 2015182878A9
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particles
hollow silica
composition
silane
silica particles
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PCT/KR2015/004057
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Korean (ko)
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WO2015182878A1 (fr
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임형섭
유영철
권오성
송은영
김연주
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(주)석경에이티
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Priority claimed from KR1020150055981A external-priority patent/KR101790553B1/ko
Application filed by (주)석경에이티 filed Critical (주)석경에이티
Priority to US15/035,355 priority Critical patent/US20170073237A1/en
Priority to JP2016531653A priority patent/JP6218945B2/ja
Publication of WO2015182878A1 publication Critical patent/WO2015182878A1/fr
Publication of WO2015182878A9 publication Critical patent/WO2015182878A9/fr

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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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

Definitions

  • the present invention relates to hollow silica particles having complex properties, a method of manufacturing the same, and a composition and a heat insulating sheet including the hollow silica particles.
  • KR 101180040 describes a hollow composite in which magnesium fluoride is doped with silica, and a hollow composite having an average particle diameter of 20 to 500 nm is described.
  • the present invention relates to a method for producing hollow particles by a method of removing the core after preparing the core and shell of the silica particles by the sol-gel method.
  • KR 101359848 discloses the steps of synthesizing silver nanocrystals using a polyol solvent, synthesizing silver-silica core-shell nanoparticles by coating silica on the silver nanocrystals, and the silver core of the silver-silica core-shell nanoparticles.
  • hollow silica production techniques known to date have a problem that it is difficult to manufacture hollow silica particles that exhibit high visible light transmittance, high refractive index, low thermal conductivity, monodispersity, low oil absorption, and high porosity. .
  • the physical properties of the existing hollow silica is not enough to produce a transparent yet excellent heat insulating sheet.
  • the present invention has been proposed to solve the above problems, and an object of the present invention is to provide hollow silica particles having a combination of advantageous physical properties having a low refractive index and a low thermal conductivity. It is also an object of the present invention to provide a composition and a transparent insulating sheet containing the hollow silica particles.
  • the hollow silica particles of the present invention have a refractive index of 1.2 to 1.4, a thermal conductivity of less than 0.1 W / mK, an oil absorption of 0.1 ml / g or less, a porosity of 90% or more when mixed with resin, and a particle distribution variation coefficient (CV). Value) has a complex physical property of 10% or less.
  • grains is 1 micrometer or less
  • the inner diameter of a hollow part is 10 to 90% or more of the average diameter of a particle
  • the thickness of a shell is 5 to 45% of an average particle diameter.
  • the hollow silica particles have an average diameter of 500 nm or less and an inner diameter of the hollow portion of 40 nm or more. In order to maximize the filling rate of the particles in the production of the insulating sheet, it is preferable that the average diameter of the particles is 500 nm or less and the inner diameter of the hollow portion is 40 nm or more.
  • the hollow silica particles are formed from phenyl silane, and the surface of the particles has an advantage that the -OH group and the phenyl group exist as functional groups, and thus the strength of the particles is high.
  • the particles produced by the production method of the present invention have almost no pores on the surface, the oil absorption rate is 0.1 ml / g or less, and when mixed with the resin, the porosity is 90% or more.
  • particle characteristics such as sphericity, average particle diameter, refractive index, thermal conductivity, and the like remain stable without variation of hollow, and thus have suitable particle characteristics for high filling in binders such as resins.
  • the degree of sphericity of the hollow particles of the present invention is greater than or equal to 0.9 and at least 90% of the silica particles are spherical with uniform convex grain contours in which there are no flat faces, corners or recognizable recesses.
  • the hollow silica particles of the present invention is characterized by including the following steps.
  • step (c) adding a base aqueous solution to the reaction solution of step (b) to form primary particles by bonding between silane droplets;
  • the particles to be finally produced are characterized in that the average diameter is 1 ⁇ m or less, the inner diameter of the hollow portion is 10 to 90% or more of the average diameter of the particles.
  • the pH of the reaction solution after the addition of the acid in step (b) is 1 ⁇ 5 and the hydration time in step (b) is characterized in that 1-10 minutes.
  • the basic aqueous solution is characterized in that the pH 10 or more and the polymerization reaction proceeds so that the thickness of the insoluble shell is 5 ⁇ 45% of the average particle diameter.
  • the silane is at least one selected from the group consisting of phenyl silanes, TEOS, TMOS, SiCl 4 , and silanes having organic groups other than phenyl groups, or mixtures thereof.
  • phenyl silanes TEOS, TMOS, SiCl 4
  • silanes having organic groups other than phenyl groups or mixtures thereof.
  • the base solution in step (d) is characterized in that the inorganic base of the NH 4 OH or alkylamine type, the alkylamine is NH 4 OH, or tetramethyl ammonium hydroxide (TMAH), octylamine (octylamine, OA, CH 3 ( CH 2 ) 6 CH 2 H 2 ), dodecylamine, DDA, CH 3 (CH 2 ) 10 CH 2 NH 2 ), hexadecylamine, HDA, CH 3 (CH 2 ) 14 CH 2 NH 2 ), 2-aminopropanol, 2- (methylphenylamino) ethanol, 2- (ethylphenylamino) ethanol, 2-amino-1-butanol, (diisopropylamino) ethanol, 2-diethylaminoethanol, 4-amino Phenylaminoisopropanol, N-ethylaminoethanol, monoethanolamine, diethanolamine, triethanolamine,
  • the reaction temperature in the step (b) and (d) is preferably 40 ⁇ 80 °C, and after the filtration in the step (f) (g) further comprising the step of sonicating the filtrate (surface) It can be produced more smoothly.
  • Drying after filtration is preferably performed at 250 ° C or lower, preferably at 150 ° C or lower.
  • step (f) it may further comprise the step of (i) modifying the surface of the hollow silica particles and can be expanded the use of the particles by adding a functional group of the particle surface.
  • composition comprising a hollow silica particles, a resin, and a solvent of the present invention. It is preferable that the hollow silica particles are 30 to 80 wt% and the resin is 20 to 70 wt% based on the total composition.
  • the resin preferably has a refractive index of less than 1.5, and at least one selected from acrylate polymer resin, polyimide (PI) resin, C-PVC resin, PVDF resin, ABS resin, CTFE, or a mixture thereof. It is preferable to use.
  • composition may further include one or more selected from a hard coating agent, a UV blocker, or an IR blocker to impart additional functionality.
  • the present invention is to prepare a substrate, the composition is applied to the substrate to form a coating layer and the coating layer is cured by visible light transmittance of 70% or more, thermal conductivity of less than 0.1w / mk and hollow silica particles filling rate of 30 ⁇ 80% It provides a heat insulating sheet, characterized in that.
  • the coating layer may further have a UV blocking and IR blocking function, and a sheet of a polymer material, a fiber, a film, or glass may be used as the substrate of the insulating sheet.
  • the refractive index is 1.2 to 1.4
  • the thermal conductivity is less than 0.1 W / mK
  • the oil absorption is 0.1 ml / g or less
  • the porosity is 90% or more when mixed with resin
  • the particle distribution coefficient of variation (CV value) is Hollow silica particles having a property of 10% or less can be provided by a simple and stable production method.
  • composition comprising the hollow silica particles having the above physical properties, so that the visible light transmittance of 70% or more, the thermal conductivity is less than 0.1w / mk, the particle filling rate of 30-80%, transparent and excellent thermal insulation function Sheets can be provided.
  • the refractive index is 1.2 to 1.4
  • the thermal conductivity is less than 0.1 W / mK
  • the oil absorption is 0.1 ml / g or less
  • the porosity is 90% or more when mixed with resin
  • the particle distribution coefficient of variation (CV value) is Hollow silica particles having a property of 10% or less can be provided by a simple and stable production method.
  • composition comprising the hollow silica particles having the above physical properties, so that the visible light transmittance of 70% or more, the thermal conductivity is less than 0.1w / mk, the particle filling rate of 30-80%, transparent and excellent thermal insulation function Sheets can be provided.
  • FIG. 1 is a diagram illustrating the structure of hydrated PTMS droplets, primary particles, and particles in which a shell is formed during the manufacturing process of the present invention
  • TEM 2 is a transmission electron microscope (TEM) of hollow silica particles having an average diameter of 100 nm according to an embodiment of the present invention
  • FIG. 4 is a TEM photograph after etching the silica particles according to an embodiment of the present invention after hydrolysis for 60 seconds, 30 seconds,
  • FIG. 5 is a TEM photograph of particles after sonicating the particles of FIG. 4;
  • FIG. 6 is a transmission electron micrograph (TEM) of particles after polymerizing, washing, dispersing, and etching PPSQ of the present invention.
  • the hollow silica particles of the present invention are made of silane as a starting material, stirred in an aqueous solution to form a droplet, and then hydrated by adding an acid, followed by addition of a basic aqueous solution to form primary particles by bonding between the droplets, followed by polymerization and shelling. After forming the hollow inside the shell by etching with an organic solvent to form a hollow hollow silica particle powder through filtration, drying.
  • the method may further include the step of sonicating the filtrate.
  • a raw material of the hollow silica particles at least one selected from the group consisting of phenyl silane, TEOS, TMOS, SiCl 4 , and silane having an organic group other than a phenyl group, or a mixture thereof may be used.
  • a mixture of phenyl silane and other silanes it is preferable to use a mixture of phenyl silane at least 80% by weight and other silanes at 20% by weight or less.
  • the phenyl silane the structure of Formula 1 It is preferable to use PTMS (phenyltrimethoxysilane, C 9 H 14 O 3 Si) for the branch.
  • the concentration of silane should be 0.1 mol% or less in the aqueous solution to obtain small particles of 1 ⁇ m or less.
  • silane When 0.1 to 2 mol% of silane is added to the aqueous solution, the silane is not mixed with the aqueous solution, and thus layer separation occurs. If the stirring is continued, silane droplets are formed and dispersed in the aqueous solution.
  • the -OR group of the silane is replaced with the -OH group by the role of the acid as shown in FIG. 1 (a).
  • the acid is preferably HCl, HNO 3, H 2 SO 4 and the like and the pH of the reaction solution is 0.5 ⁇ 5.
  • the lower the pH of the reaction solution the smaller the size of the particles due to the breakage of the chain of silane. Therefore, when the pH is strongly acidic, the amount of silane should be used in small amounts. This is because control of particle generation is difficult because no hollow is formed in the inside.
  • the pH is 5 or more, when a small amount of silane is used, particles and hollows are not formed.
  • the stirring time is preferably between 0.5 and 10 minutes, more preferably between 1 and 5 minutes.
  • the droplet size is not different when the stirring speed exceeds 200rpm when the size of the stirrer is about 80% compared to the reactor, but when the stirring speed is 200rpm or less, the particle size increases, so the stirring speed is preferably 200rpm or more, and the size of the hydrated droplet is 8 to 12 It is preferable that the thickness is ⁇ m and the final particle size is determined according to the size of the droplets.
  • the temperature of reaction 40-80 degreeC is preferable. It is difficult to produce particles at less than 40 °C, it is easy to agglomerate particles in a high concentration to form a gel, the thickness of the shell is thickened, there is a problem that the size of the hollow is reduced, if the temperature exceeds 80 °C the base volatilize the reaction conditions It is difficult to control, and the inside of the shell does not melt and no hollow particles are made.
  • the hydration scheme of PTMS is as follows.
  • the base solution is a base such as NaOH, Ca (OH) 2 , KOH, NH 4 OH, preferably NH 4 OH or an alkylamine type inorganic base so that the total reaction solution is at least pH 10.
  • Alkylamines are NH 4 OH, or tetramethyl ammonium hydroxide (TMAH), octylamine, OA, CH 3 (CH 2 ) 6 CH 2 H 2 ), dodecylamine, DDA, CH 3 (CH 2 ) 10 CH 2 NH 2 ), hexadecylamine, HDA, CH 3 (CH 2 ) 14 CH 2 NH 2 ), 2-aminopropanol, 2- (methylphenylamino) ethanol, 2- (ethylphenylamino) ethanol, 2 -Amino-1-butanol, (diisopropylamino) ethanol, 2-diethylaminoethanol, 4-aminophenylaminoisopropanol, N-ethylaminoethanol, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, Diisopropanolamine, triisopropanolamine, methyldiethanolamine, dimethyl monoethanol
  • the reaction is difficult to produce hollow particles because the particles are easily aggregated together to form a gel at less than 40 °C, the thickness of the shell is too thick, there is a problem that the size of the hollow is reduced, if the base exceeds 80 °C volatilized It is preferable to proceed at 40 ⁇ 80 °C because it is difficult to control the reaction conditions, the inside of the shell does not melt and hollow particles are not made.
  • the aqueous solution to which the base solution is added is stirred to polymerize the primary particles by siloxane bonds to form a shell insoluble in the organic solvent.
  • the thickness of the shell is preferably 5 to 45% of the average diameter of the silica particles.
  • Silane oligomer and unreacted droplets are present in the insoluble shell, and the hollow inside is etched by using an organic solvent.
  • the organic solvent may be generally used, including ethanol or methanol.
  • impurities on the surface of the particles may be removed to make the surface of the particles smoother, and the sonication may be performed within 5 seconds to 40 minutes. Do.
  • the filtrate is dried at less than 250 °C, more preferably less than 150 °C 1 to 10 hours in a vacuum oven to evaporate or sublimate moisture at a temperature corresponding to the degree of vacuum to dry.
  • the step of modifying the surface of the particles by a known method such as nitrification, sulfonation, amination, halogenation by treating the silane coupling agent to the resulting hollow silica particles may be further applied.
  • a silane coupling agent can use a silane type, aluminum type, titanium type, zirconium type coupling agent.
  • the surface modified hollow silica particles can be applied to various fields such as functional ceramics, microcapsules, nanoreactors, DDS, catalysts, sensors, and the like. In this way, the treatment with the surface treatment agent improves the dispersibility to hydrophobic dispersion mediums such as resins and organic solvents, and improves adhesion to resins, peel strength, and the like.
  • Hollow silica particles prepared by the above production method has a refractive index of 1.2 to 1.4, a thermal conductivity of less than 0.1 W / m ⁇ K, an oil absorption of 0.1 ml / g or less, a porosity of 90% or more when mixed with resin, and a particle distribution variation.
  • the coefficient (CV value) has a monodispersity of 10% or less.
  • the average diameter of the particles is 1 ⁇ m or less
  • the inner diameter of the hollow portion is 10 to 90% of the average diameter of the particles
  • the shell thickness is 5 to 45% of the average particle diameter and spherical particles having a sphericity of 0.9 or more.
  • the hollow silica is first dispersed in sorbitol syrup (70% sorbitol) / water mixture. After 1 hour of degassing, the light transmittance of the dispersion is measured using a spectrophotometer at 589 nm, and water is used as a blind sample. The refractive index of each dispersion is measured using an Abbe refractometer. From the graph of the transmittance
  • the measurement of thermal conductivity first cuts out the center part of the thermal insulation sheet of 30 cm long, 30 cm wide, and 5 cm thick to square shape of 24 cm and 24 cm, and forms a frame.
  • An aluminum foil of 30 cm in length and 30 cm in width is bonded to one side of the frame to form a concave portion, and a sample is taken.
  • the surface covered with aluminum foil is made into the bottom surface of a sample stand, and the other surface with respect to the thickness direction of a heat insulation sheet is made into the ceiling surface.
  • the thermal conductivity at 30 ° C. was measured using a heat flow meter HFM 436 Lambda (trade name, manufactured by NETZSCH).
  • the calibration is carried out in accordance with JIS A1412-2 using a standard plate for calibration of NIST SRM 1450c with a density of 163.12 kg / m 3 and thickness of 25.32 mm, on the condition that the temperature difference between the high temperature side and the low temperature side is 20 ° C., 15, 20, 24, 30 , 40, 50, 60, 65 °C in advance.
  • Thermal conductivity in 800 degreeC is measured based on the method of JISA1421-1.
  • Two sheets of a heat insulating sheet having a diameter of 30 cm and a disc shape having a thickness of 20 mm were used as measurement samples, and a protective heat plate method thermal conductivity measuring device (manufactured by Eiko Seiki Co., Ltd.) was used as the measuring device.
  • Hollow silica particles of the present invention is characterized in that the spherical surface is substantially smooth even after the separate firing and surface treatment.
  • smooth it is meant that there are very few fine pores on the surface and that the surface of the shell is free of any irregularities such as pits, gaps, nicks, cracks, protrusions, grooves and the like. Such surface properties are not seen in the hollow silica particles obtained by the conventional manufacturing method.
  • the smoothness of the particles of the present invention can be measured by scanning electron microscopy and can be confirmed through oil absorption, porosity when mixed with resin, and the like.
  • Oil absorption was measured using the rub-out method (ASTM D281). This method is based on the principle of mixing linseed oil with silica by rubbing the linseed oil / silica mixture with a spatula on a smooth surface until a stiff putty-type paste is formed. By measuring the amount of oil required to have a paste mixture that is curled when sprayed, the oil absorption of silica can be calculated, indicating the volume of oil required per unit weight of silica to saturate the silica adsorption capacity. . High levels of oil absorption indicate that there are many pores on the surface or that the pores are large in size, while lower values indicate that there are few pores on the shell surface of the silica particles. Oil absorption can be determined from the equation:
  • Oil absorption rate oil volume ml / silica 100g
  • the amount of resin permeated into the hollow interior can be confirmed.
  • the amount of resin penetrated into the hollow is measured in the same manner as the oil absorption rate, and as the amount of the resin is smaller, the hollow inside is maintained.
  • the structure of the particles having a smooth surface and almost no pores increases the porosity because the resin or oil constituting the binder does not penetrate into the hollow of the particles when the hollow silica particles are filled in the resin. It means that it is possible to increase the transparent heat insulating performance of the heat insulating sheet coated with the composition containing the particles and exhibiting transparent and low thermal conductivity.
  • Characterization of the silica particles of the present invention as a very round shape is measured by a scanning electron microscope (SEM) photograph showing the cross-sectional structure of the particles and expressed as the ratio of the short diameter (DS) to the long diameter (DL) (DS / DL). do.
  • Representative samples of silica particles were collected and tested by scanning electron microscopy (SEM).
  • SEM scanning electron microscopy
  • S 80 the sphericity degree of the particles of the present invention is 0.9 or more, which is very spherical particles.
  • S 80 is defined and calculated as follows.
  • a representative 20,000-fold magnified SEM image of the silica particle sample is loaded into photo imaging software and the contour (two-dimensional) of each particle is traced. Particles close to each other but not attached to each other should be considered as separate particles for evaluation.
  • the contoured particles are then filled with color, and the image is taken with particle characterization software (e.g. MAGE-PRO PLUS available from Media Cybernetics, Inc. (Bethesda, Maryland)) that can determine the particle's perimeter and product. It is called.
  • the degree of sphericity of the particles can then be calculated according to the following equation.
  • the perimeter is the software measurement perimeter derived from the contoured tracking of the particle and the area is the software measurement area within the particle's tracked perimeter.
  • the calculation is performed for each suitable particle as a whole in the SEM image. These values are then classified according to their values, and the lower 20% of these values are discarded. The remaining 80% of these values are averaged to obtain S 80 .
  • the sphericity coefficient S 80 for the particles of FIG. 2 was found to be 0.98.
  • Average diameter is understood as the diameter averaged over all particles in a sample.
  • Representative samples of silica particles were collected and the diameter of the silica particles was measured by scanning electron microscopy (SEM). The inner diameter of the hollow portion was measured by transmission electron micrograph (TEM).
  • SEM scanning electron microscopy
  • TEM transmission electron micrograph
  • the average diameter of the hollow particles of the present invention is generally 1 ⁇ m or less, preferably 500 nm or less, and more preferably 100 nm or less. If the average diameter exceeds 1 ⁇ m, the filling rate may not be completely filled in the thickness of the coating layer during the production of the insulating sheet, and thus the filling rate may be lowered.
  • the hollow silica particles of the present invention are particles having an average diameter of 1 ⁇ m or less and an inner diameter of the hollow portion of 10 to 90% of the average diameter of the particles. In the case of particles with an average diameter of 100 nm, the inner diameter of the hollow portion was good at more than 40 nm. In addition, since the thickness of the shell is 5 to 45% of the average particle diameter and is stable during the reaction, hollow silica particles may be used as a heat insulating material.
  • the particles when used as a raw material, the particles have -OH groups and phenyl groups as functional groups, and the phenyl group has a refractive index higher than that of other silica particles, and thus has a refractive index similar to that of resin, thereby minimizing the difference between the resin and the refractive index. Therefore, a transparent insulation sheet can be made.
  • Coating composition comprising hollow silica particles and resin
  • composition for forming a transparent heat insulating coating layer on a substrate is provided.
  • the composition of the present invention may be prepared by mixing hollow silica particles having a complex physical property as described above, resin, an organic solvent and the like.
  • the hollow silica particle in the whole composition of this invention 30 to 80 weight% is preferable. If less than 30% by weight can not sufficiently achieve the thermal insulation performance of the coating layer, if it exceeds 80% by weight because the transparency is reduced and the content of the resin is less hardening efficiency is lowered.
  • the resin in the total composition of the present invention can be mixed in 20-70% by weight.
  • the refractive index of the resin is preferably less than 1.5 to adjust the refractive index with the silica particles, and preferably, a resin similar to the refractive index with the hollow particles is selected from among UV curable resins.
  • UV curable resins include, but are not limited to, urethane resins, acrylic resins, polyester resins, epoxy resins, and mixtures thereof, and are resins having low thermal conductivity, such as acrylate-based polymer resins, polyimide (PI) resins, C -It can use 1 or more types or mixed from PVC resin, PVDF resin (heat-resistant temperature about 300 degreeC), ABS resin, CTFE, etc.
  • composition may further include a hard coating agent, a UV blocker, or an IR blocker
  • additive may further include an additive that uses a known one and additionally provides additional functions if necessary.
  • composition refers to any liquid, liquefiable or mastic composition comprising silica that is converted to a solid film after application to a substrate.
  • the composition can be applied inside or outside the surface of any structure.
  • the composition comprises a hollow silica particle product and the silica product described herein has specific particle properties including hardness, sphericity, refractive index, oil absorption rate, thermal conductivity, and the like, which are useful for adiabatic, imparting transparency to the composition.
  • the composition can be any coating composition and can be applied to any substrate.
  • the compositions are useful as coatings for houses, constructions, automotive windows, and the like, such as insulation sheets, glass windows, as they exhibit excellent transparency and thermal insulation while maintaining the integrity of the polymer and pigment matrix that may be present in the coating.
  • the compositions described herein are useful in plastic compound and masterbatch formulations, as well as exhibiting good thermal and transparent properties as well as enhancing the physical properties of the formulation.
  • a heat insulating sheet may be prepared by preparing a substrate, and laminating or applying the composition of the present invention to the substrate to UV-cure to form a coating layer.
  • the coating method may use any suitable coating method known in the art, and examples of known methods are gravure coating, offset gravure coating, two and three roll pressure coating, two and three rolleys. Roll reverse coating, immersion coating, 1 and 2 roll kiss coating, trailing balde coating, nip coating, flexographic coating, inverted knife coating ( inverted knife coating, polishing bar coating and wire wound doctor coating. After coating, the coating layer is cured with UV light and curing is usually completed in a relatively short period of time from about 1 to about 60 seconds.
  • the base material which forms a coating layer by the said composition is not specifically limited,
  • the organic base material represented by resin is mentioned. It is preferably a sheet of a polymer material, a fiber, a film, a glass or the like, in particular the film substrate may be a film that can be commonly applied, such as PET, PE.
  • the same base material may be independent, and the heterogeneous material may be laminated
  • at least 1 layer or more of another layer may be previously formed in the base material surface.
  • an ultraviolet curable hard cord layer, an electron beam hardening type hard cord layer, and a thermosetting hard cord layer are mentioned as another layer.
  • the thickness of the coating layer can be arbitrarily selected and adjusted according to the product and the use, and preferably coated with a thickness of 1 ⁇ 500 ⁇ m, if out of the above range may increase the thermal conductivity or the visible light transmittance.
  • the coating layer may further have a UV blocking and IR blocking function, and may be prepared by laminating a UV blocking layer and an IR blocking layer separately on the coating layer.
  • the insulating sheet using the composition according to the present invention has a filling rate of 30-80% and a visible light transmittance of 70% or more, and exhibits a thermal conductivity of less than 0.1w / m.k, thus enabling transparent insulating properties.
  • the generated particles are monodisperse spherical particles and hollow particles having bright hollows therein.
  • Table 1 shows the refractive index, thermal conductivity, oil absorption rate, porosity when mixing with resin, and particle distribution variation coefficient (CV value) of the particles.
  • Example 2 Hollow silica particles were obtained in the same manner as in Example 1 except that the silane was used by mixing phenyltrimethoxysilane (PTMS) (0.8 ml) and TEOS (0.2 ml) in Example 1, and the physical properties of the resulting particles were obtained. Table 1 shows.
  • PTMS phenyltrimethoxysilane
  • TEOS 0.2 ml
  • Example 3 particles were prepared by adding an acidic solution in Example 1 to 9 minutes of stirring time. The resulting particles formed spherical monodispersed hollow particles as shown in Figure 4, the physical properties are shown in Table 1.
  • Example 4 was further subjected to the sonication in Example 1 to prepare a particle.
  • the resulting particles formed spherical monodisperse hollow particles as shown in FIG. 5 and exhibited a smooth and spherical shape with almost no surface impurities than the particles in Example 3.
  • Physical properties are shown in Table 1.
  • Comparative Example 3 was stirred for 15 minutes after the addition of the acidic solution described in Example 1 and the reaction results are shown in Table 1.
  • the final particles gelled and did not produce hollow particles, probably due to the aggregation of small particles due to the excessively long stirring time.
  • the hollow silica particles prepared according to Example 1 were prepared by mixing 60% by weight of the total composition, 30% by weight of polyimide (PI) resin, and the remaining organic solvent and initiator.
  • the prepared composition was applied to one side of the PET film by bar coating, and irradiated with UV for 20 seconds using a UV lamp to prepare a heat insulating sheet having a coating layer having a thickness of 125 ⁇ m.
  • Table 2 shows the results of measuring physical properties of the insulation sheet.
  • Examples 6 and 7 were prepared by mixing the hollow silica particles in Example 5 at a ratio of 30% by weight and 80% by weight of the total composition, respectively, to prepare a heat insulating sheet, and the results of measuring physical properties are shown in Table 2. It was.
  • Example 5 the composition was prepared using the mixing ratio of the hollow silica particles in 20% by weight and 90% by weight of the total composition, respectively, and when the content of the hollow particles was 50% or more, the viscosity of the crude liquid was high and the coating was difficult.
  • Table 2 shows the results of measuring the physical properties of the insulating sheet after adjusting the viscosity by using a solvent MEK.
  • Insulation sheet was prepared in the same manner as in Example 5 using hollow particles having a diameter of 200 nm and a hollow portion of 100 nm in the hollow part prepared using a conventional mold synthesis method. Shown in The insulating sheet could not be dispersed in the composition during coating and UV curing to escape from the resin to form a coating layer.
  • the particles produced by Comparative Example 7 had large pores on the surface.

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Abstract

La présente invention concerne des particules de silice creuses qui ont un indice de réfraction de 1,2 à 1,4, une conductivité thermique inférieure à 0,1 W/m·K, un taux d'absorption d'huile de inférieur ou égal à 0,1 ml/g, une porosité d'au moins 90 % lorsqu'elles sont mélangées avec une résine, et un coefficient de variation de distribution de particules (valeur CV) inférieur ou égal à 10 %. En outre, la présente invention peut concerner une composition comprenant les particules de silice creuses, et peut concerner une feuille d'isolation thermique transparente qui présente une transmittance de la lumière visible d'au moins 70 %, une conductivité thermique inférieure à 0,1 W/m·K, et un taux de remplissage de particules de 30 à 80 %.
PCT/KR2015/004057 2014-05-30 2015-04-23 Procédé de fabrication de particules de silice creuses, particules de silice creuses, et composition et feuille d'isolation thermique les comprenant WO2015182878A1 (fr)

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US15/035,355 US20170073237A1 (en) 2014-05-30 2015-04-23 Method for manufacturing hollow silica particles, hollow silica particles, and composition and thermal insulation sheet comprising same
JP2016531653A JP6218945B2 (ja) 2014-05-30 2015-04-23 中空シリカ粒子の製造方法、中空シリカ粒子及びそれらを含む組成物、並びに断熱シート

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