KR102555934B1 - Hollow silica particle, method of preparing the same, dispersion composition including the same, diffusion film for display and optical element for display - Google Patents

Abstract

The present invention relates to a hollow silica particle, a method for preparing the same, a dispersion composition for a display including the same, a diffusion film, and an optical member for a display. The hollow silica particle according to an embodiment of the present invention is a hollow core modified with cations. ; and a silica shell surrounding the core.

Description

Hollow silica particles, manufacturing method thereof, dispersion composition for display including the same, diffusion film and optical member for display

The present invention relates to hollow silica particles, a method for preparing the same, a dispersion composition for a display including the same, a diffusion film, and an optical member for a display.

Silica is a base material used in various application fields, and hollow silica particles having hollow spaces in the core portion can support various useful materials in the hollow portion, and thus have high applicability in various industrial fields. Hollow silica particles containing an air layer in the silica shell can be coated on the outermost layer of the display with a low refractive index material to achieve anti-reflection and anti-glare effects.

As a method for producing hollow silica particles, there is a method for producing a hollow composite in which silica is doped with magnesium fluoride, and has an average particle diameter of 20 to 500 nm. This relates to a method of manufacturing hollow particles by preparing a core and a shell of silica particles by a sol-gel method and then removing the core.

In addition, synthesizing silver nanocrystals using a polyol solvent, coating silica on the silver nanocrystals to synthesize silver-silica core-shell nanoparticles, and etching the silver core of the silver-silica core-shell nanoparticles There is also a method for producing hollow silica particles consisting of the steps of.

Hollow silica particles are a low refractive index material that can be coated on the outermost layer of a display to produce antireflection and antiglare effects. In order to exhibit characteristics of transparent coating and low reflectance, hollow silica particle size of 100 nm or less is required, The silica shell must be dense.

However, the currently known hollow silica particle manufacturing technology has a dense silica shell and is not suitable for manufacturing nanometer (nm) level nanoparticles.

Accordingly, it is necessary to develop a method for producing nanometer-level hollow silica particles having a dense silica shell.

The present invention is to solve the above-mentioned problems, and an object of the present invention is a dense silica shell, a nanometer-level hollow silica particle, a manufacturing method thereof, a dispersion composition for a display comprising the same, a diffusion film, and an optical display for a display. to provide absence.

However, the problem to be solved by the present invention is not limited to those mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

Hollow silica particles according to an embodiment of the present invention, the hollow core modified with cations; and a silica shell surrounding the core.

In one embodiment, the hollow core modified with the cation includes a cationic group derived from a cationic surfactant, and the cationic surfactant is cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTAC) , cetylpyridinium chloride (CPC), dodecyltrimethylammonium bromide (DTAB), tetradecyltrimethylammonium bromide (TTAB), tetratrimethylammonium bromide (TMB), dioctadecyldimethylammonium bromide (DODAB) and dimethyldioctadecylammonium It may include at least one selected from the group consisting of chloride (DODMAC).

In one embodiment, the average diameter of the hollow silica particles may be 30 nm to 100 nm.

In one embodiment, the core may have an average diameter of 30 nm to 60 nm, and the silica shell may have an average thickness of 1 nm to 20 nm.

In one embodiment, the porosity of the silica shell may be 40% to 70%.

In one embodiment, the specific surface area of the hollow silica particles may be 320 m ² /g or more.

A method for producing hollow silica particles according to another embodiment of the present invention includes preparing polystyrene particles surface-modified with cations; Preparing core-shell particles by forming a silica shell on the surface-modified polystyrene particles with the cation; and removing the core by firing the core-shell particle.

In one embodiment, the step of preparing the surface-modified polystyrene particles with cations, preparing a cationic surfactant solution by dissolving the cationic surfactant in distilled water; Forming a nitrogen atmosphere while raising the temperature of the cationic surfactant solution to a temperature range of 50 ℃ to 90 ℃; purifying the styrene monomer; preparing a mixture by adding the purified styrene monomer to the cationic surfactant solution under a nitrogen atmosphere and stirring; Injecting a polymerization initiator under a nitrogen atmosphere after heating the stirred styrene monomer to a temperature range of 50 ° C to 90 ° C; preparing a polymerization solution by reacting the styrene monomer into which the polymerization initiator was added overnight at a temperature range of 50 °C to 90 °C; and washing the formed polymerization solution several times with an organic solvent.

In one embodiment, the cationic surfactant is cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTAC), cetylpyridinium chloride (CPC), dodecyltrimethylammonium bromide (DTAB), tetradecyltrimethylammonium It may contain at least one selected from the group consisting of bromide (TTAB), tetratrimethylammonium bromide (TMB), dioctadecyldimethylammonium bromide (DODAB), and dimethyldioctadecylammonium chloride (DODMAC).

In one embodiment, the step of preparing a cationic surfactant solution by dissolving the cationic surfactant in the distilled water may include 0.001% to 50% by weight of the cationic surfactant compared to the styrene monomer.

In one embodiment, preparing the core-shell particles by forming a silica shell on the polystyrene particles surface-modified with the cations includes preparing a dispersion by diluting the polystyrene particles surface-modified with the cations in distilled water; adjusting the pH by mixing an acidic substance with the dispersion; preparing a core-shell formation solution by heating the pH-adjusted dispersion to a temperature range of 40 °C to 80 °C and then introducing a silane compound; preparing a core-shell reaction solution by reacting the core-shell forming solution at a temperature range of 40 °C to 80 °C for 1 hour to 7 hours; and drying the core-shell reaction solution.

In one embodiment, the acidic substance is nitric acid, hydrochloric acid, phosphoric acid, sulfuric acid, hydrofluoric acid, hydrobromic acid, iodic acid, pimelic acid, malic acid, malonic acid, maleic acid, acetic acid, adipic acid, oxalic acid, succinic acid, tartaric acid , citric acid, lactic acid, glutaric acid, glycolic acid, formic acid, fumaric acid, propionic acid, butyric acid, hydroxybutyric acid, aspartic acid, itaconic acid, tricarbalic acid, suberic acid, benzoic acid, phenylacetic acid, naphthoic acid, mandelic acid, blood selected from the group consisting of cholic acid, nicotinic acid, isonicotinic acid, quinolinic acid, anthranilic acid, fujaric acid, phthalic acid, isophthalic acid, terephthalic acid, pyridinecarboxylic acid, salicylic acid, glutamic acid, polyacrylic acid, polyacrylic acid copolymer and polysulfonic acid It may contain at least any one.

In one embodiment, in the step of adjusting the pH by mixing an acidic material with the dispersion, the pH of the dispersion may be adjusted to a range of 1 to 6.

In one embodiment, the silane compound is tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra- sec-butoxysilane, tetra-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane , propyltriethoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-glycoxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ- methacryloyloxypropyltrimethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, trivinylmethoxysilane And it may include at least one selected from the group consisting of trivinylethoxysilane.

In one embodiment, the step of sintering the core-shell particles to remove the cores may be performed at a temperature range of 300 °C to 800 °C for 1 hour to 10 hours.

A dispersion composition for display according to another embodiment of the present invention includes hollow silica particles according to an embodiment of the present invention and hollow silica particles prepared by a method for manufacturing hollow silica particles according to another embodiment of the present invention. do.

A diffusion film according to another embodiment of the present invention includes a cured product of a dispersion composition for a display according to an embodiment of the present invention.

An optical member for a display according to another embodiment of the present invention includes a diffusion film according to an embodiment of the present invention.

Hollow silica particles according to an embodiment of the present invention are fine particles of 100 nm or less and are transparent and have low reflectance, which may be suitable for application as a low refractive index material.

In the method for producing hollow silica particles according to an embodiment of the present invention, a core may be synthesized by including and applying a cationic surfactant during polymerization, and hollow silica particles having a size of 100 nm or less may be prepared.

A dispersion composition for a display according to an embodiment of the present invention and a diffusion film including a cured product of the dispersion composition exhibit antireflection and antiglare efficiencies, thereby realizing excellent optical properties.

A diffusion film and an optical member for a display according to an embodiment of the present invention can be used to manufacture a diffusion film for a backlight unit of a mobile phone, tablet PC, PDP, laptop computer, monitor, or TV.

1 shows a schematic diagram of hollow silica particles according to an embodiment of the present invention.
2 is a flowchart schematically showing a manufacturing process of hollow silica particles according to an embodiment of the present invention.
FIG. 3 is a flowchart schematically illustrating a detailed process of preparing the surface-modified polystyrene particles of FIG. 2 .
FIG. 4 is a flowchart schematically illustrating a detailed process of preparing the core-shell particle of FIG. 2 .
5 is a TEM image of the hollow silica particles according to Examples 1 to 4 and Comparative Examples 1 and 2 of the present invention and a dispersion composition for a display comprising the same.

Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. However, since various changes can be made to the embodiments, the scope of the patent application is not limited or limited by these embodiments. It should be understood that all changes, equivalents or substitutes to the embodiments are included within the scope of rights.

Terms used in the examples are used only for descriptive purposes and should not be construed as limiting. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as "include" or "have" are intended to designate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that the presence or addition of numbers, steps, operations, components, parts, or combinations thereof is not precluded.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person of ordinary skill in the art to which the embodiment belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and unless explicitly defined in the present application, they should not be interpreted in an ideal or excessively formal meaning. don't

In addition, in the description with reference to the accompanying drawings, the same reference numerals are given to the same components regardless of reference numerals, and overlapping descriptions thereof will be omitted. In describing the embodiment, if it is determined that a detailed description of a related known technology may unnecessarily obscure the gist of the embodiment, the detailed description will be omitted.

In addition, in describing the components of the embodiment, terms such as first, second, A, B, (a), and (b) may be used. These terms are only used to distinguish the component from other components, and the nature, order, or order of the corresponding component is not limited by the term.

Components included in one embodiment and components having common functions will be described using the same names in other embodiments. Unless stated to the contrary, descriptions described in one embodiment may be applied to other embodiments, and detailed descriptions will be omitted to the extent of overlap.

Hollow silica particles according to an embodiment of the present invention, the hollow core modified with cations; and a silica shell surrounding the core.

In the present invention, "hollow silica particles" are particles including a hollow space (hollow) of a core and a silica shell, and have a structure in which a porous shell of silica surrounds the inner hollow. In the present invention, the silica shell has a plurality of small pores in the wall portion of the silica shell, and thus, the hollow silica particle has an inner core hollow and a plurality of mesopores are dispersed in the silica shell. Since the core particles modified with the cationic surfactant were removed during the manufacture of the hollow silica particles, some cationic surfactants exist and are dispersed in the outer surface of the silica shell, the inner surface, or the empty space of the mesopores of the silica shell. do.

1 shows a schematic diagram of hollow silica particles according to an embodiment of the present invention.

Referring to FIG. 1, a hollow silica particle 100 according to an embodiment of the present invention includes a hollow core 110 and a silica shell 120 surrounding the core 110, and the core 110 ) includes spaces modified with cations 130. Since the core particles modified with the cationic surfactant are removed from the core 110 during preparation of the hollow silica particles, some cationic surfactant may be present without being completely removed.

In one embodiment, the hollow core 110 modified with the cation may include a cationic group derived from a cationic surfactant.

In one embodiment, the cationic surfactant in the core 110 is 1 ppm to 500 ppm, 1 ppm to 450 ppm, 1 ppm to 400 ppm, 1 ppm to 350 ppm, 1 ppm to 300 ppm, 1 ppm to 400 ppm 250 ppm, 1 ppm to 200 ppm, 1 ppm to 150 ppm, 1 ppm to 100 ppm, 1 ppm to 50 ppm, 1 ppm to 30 ppm, 1 ppm to 10 ppm, 10 ppm to 500 ppm, 30 ppm to 500 ppm , 50 ppm to 500 ppm, 100 ppm to 500 ppm, 150 ppm to 500 ppm, 200 ppm to 500 ppm, 250 ppm to 500 ppm, 300 ppm to 500 ppm, 350 ppm to 500 ppm, 400 ppm to 500 ppm or 450 ppm to 500 ppm, which may be present.

In one embodiment, the cationic surfactant is cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTAC), cetylpyridinium chloride (CPC), dodecyltrimethylammonium bromide (DTAB), tetradecyltrimethylammonium It may contain at least one selected from the group consisting of bromide (TTAB), tetratrimethylammonium bromide (TMB), dioctadecyldimethylammonium bromide (DODAB), and dimethyldioctadecylammonium chloride (DODMAC).

In one embodiment, the average diameter of the hollow silica particles may be 30 nm to 100 nm. Preferably, the hollow silica particles are 30 nm to 90 nm, 30 nm to 80 nm, 30 nm to 70 nm, 30 nm to 60 nm, 30 nm to 50 nm, 30 nm to 40 nm, 40 nm to 90 nm , 50 nm to 90 nm, 60 nm to 90 nm, 70 nm to 90 nm or 80 nm to 90 nm average diameter.

In one embodiment, when the average diameter of the hollow silica particles is less than 30 nm, the refractive index of the hollow silica particles may increase, and it may be difficult to control dispersibility due to aggregation of the particles. If it exceeds 100 nm, haze (haze) is increased, the transparency is lowered, and the strength of the silica shell is lowered, so there is a concern that the silica shell is broken when filling the film. In one embodiment, the core may have an average diameter of 30 nm to 60 nm. Preferably, the core has a thickness of 30 nm to 55 nm, 30 nm to 50 nm, 30 nm to 45 nm, 30 nm to 40 nm, 30 nm to 35 nm, 35 nm to 60 nm, 40 nm to 60 nm, 45 nm. nm to 60 nm, 50 nm to 60 nm or 55 nm to 60 nm average diameter.

In one embodiment, when the average diameter of the core is less than 30 nm, the refractive index of the hollow silica particles may increase, and it may be difficult to control the dispersibility due to aggregation of the particles. If it exceeds 60 nm, the haze increases and the transparency decreases, and the strength of the shell decreases, so the shell may be broken when filling the film. The average diameter of the hollow silica to be finally manufactured is determined according to the average diameter of the core, and the average diameter of the hollow silica to be finally manufactured can be controlled by controlling the average diameter of the core.

In one embodiment, the silica shell may have an average thickness of 1 nm to 20 nm. Preferably, the silica shell has a thickness of 1 nm to 20 nm, 1 nm to 17 nm, 1 nm to 15 nm, 1 nm to 13 nm, 1 nm to 10 nm, 1 nm to 7 nm, 1 nm to 5 nm, Average thickness of 1 nm to 3 nm, 3 nm to 20 nm, 5 nm to 20 nm, 7 nm to 20 nm, 10 nm to 20 nm, 13 nm to 20 nm, 15 nm to 20 nm or 17 nm to 20 nm have

In one embodiment, when the average thickness of the silica shell is less than 1 nm, a problem of being removed as the core is removed during manufacturing of the hollow silica particles may occur, and when the average thickness of the silica shell is greater than 20 nm, the refractive index of the hollow silica particles may increase. .

In one embodiment, the average particle diameter of the hollow silica particles can be understood as the average diameter of all the particles in all the hollow silica particles. It may be to collect a representative sample of the hollow silica particles and measure the diameter of the hollow silica particles with a scanning electron microscope (SEM). In addition, the inner diameter of the hollow portion may be measured by transmission electron micrograph (TEM).

In one embodiment, the porosity of the silica shell may be 40% to 70%. Preferably, the silica shell has a porosity of 50% to 65%.

In one embodiment, the specific surface area of the hollow silica particles may be 320 m ² /g or more. Preferably, the specific surface area of the hollow silica particles may be 320 m ² /g to 500 m ² /g.

Hollow silica particles according to an embodiment of the present invention are fine particles of 100 nm or less and are transparent and have low reflectance, which may be suitable for application as a low refractive index material.

A method for producing hollow silica particles according to another embodiment of the present invention includes preparing polystyrene particles surface-modified with cations; Preparing core-shell particles by forming a silica shell on the surface-modified polystyrene particles with the cation; and removing the core by firing the core-shell particle.

2 is a flowchart schematically showing a manufacturing process of hollow silica particles according to an embodiment of the present invention.

Referring to FIG. 2 , the method for manufacturing hollow silica particles according to an embodiment of the present invention includes preparing polystyrene particles surface-modified with cations (210), preparing core-shell particles (220), and removing cores (230). ).

In one embodiment, the step of preparing the surface-modified polystyrene particles with cations, preparing a cationic surfactant solution by dissolving the cationic surfactant in distilled water; Forming a nitrogen atmosphere while raising the temperature of the cationic surfactant solution to a temperature range of 50 ℃ to 90 ℃; purifying the styrene monomer; preparing a mixture by adding the purified styrene monomer to the cationic surfactant solution under a nitrogen atmosphere and stirring; Injecting a polymerization initiator under a nitrogen atmosphere after heating the stirred styrene monomer to a temperature range of 50 ° C to 90 ° C; preparing a polymerization solution by reacting the styrene monomer into which the polymerization initiator was added overnight at a temperature range of 50 °C to 90 °C; and washing the formed polymerization solution several times with an organic solvent.

FIG. 3 is a flowchart schematically illustrating a detailed process of preparing the surface-modified polystyrene particles of FIG. 2 .

Referring to FIG. 3, the step of preparing the polystyrene particles surface-modified with cations of the present invention includes preparing a cationic surfactant solution (211), raising the temperature and forming a nitrogen atmosphere (212), purifying the styrene monomer (213), and mixing A preparation step (214), a polymerization initiator input step (215), a polymerization solution preparation step (216), and a washing step (217) are included.

In one embodiment, the cationic surfactant solution preparation step 211 is a step of preparing a cationic surfactant solution by dissolving the cationic surfactant in distilled water.

In one embodiment, the step of preparing a cationic surfactant solution by dissolving the cationic surfactant in the distilled water may include 0.001% to 50% by weight of the cationic surfactant compared to the styrene monomer. Preferably, it may be 4% by weight to 26% by weight. If the cationic surfactant is less than 0.001% by weight relative to the styrene monomer, the shape of the hollow silica may be non-uniform, and if it is greater than 50% by weight, it may cause high viscosity of the polymerization solution.

In one embodiment, the cationic surfactant is cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTAC), cetylpyridinium chloride (CPC), dodecyltrimethylammonium bromide (DTAB), tetradecyltrimethylammonium It may contain at least one selected from the group consisting of bromide (TTAB), tetratrimethylammonium bromide (TMB), dioctadecyldimethylammonium bromide (DODAB), and dimethyldioctadecylammonium chloride (DODMAC).

In one embodiment, the step of raising the temperature and forming a nitrogen atmosphere (212) is a step of forming a nitrogen atmosphere while raising the temperature of the cationic surfactant solution to a temperature range of 50 °C to 90 °C (reflux). Preferably, a nitrogen atmosphere may be formed while raising the temperature to a temperature range of 60 °C to 80 °C, most preferably, to 70 °C.

In one embodiment, the styrene monomer purification step 213 is a step of purifying the styrene monomer.

In one embodiment, the mixture preparation step 214 is a step of preparing a mixture by adding the purified styrene monomer to the cationic surfactant solution under a nitrogen atmosphere and stirring it.

In one embodiment, the polymerization initiator input step 215 is a step of heating the stirred styrene monomer to a temperature range of 50 °C to 90 °C and then introducing a polymerization initiator under a nitrogen atmosphere. Preferably, the temperature range of 60 ℃ to 80 ℃, most preferably, it may be to introduce a polymerization initiator under a nitrogen atmosphere after reaching 70 ℃.

In one embodiment, the polymerization initiator is 2,2'-azobis (2-methylpropionamide) dihydrochloride (2,2'-azobis (2-methylpropionamide) dihydrochloride; AIBA), N, N'-azo Bisisobutyronitrile (N,N'-azobisisobutyronitrile; AIBN), 2,2'-azobisisoheptonitrile (2,2'-azobisisoheptonitrile; ABVN), 2,2'-azobis-2-methylbutyro Nitrile (2,2'-azobis-2-methylbutyronitrile; AMBN), 1,1'-azobis (cyclohexane-1-carbonitrile) (1,1'-azobis (cyclohexane-1-carbonitrile); ACCN), 1-[cyano-1-methylethyl)azo]formamide; CABN), dimethyl 2,2'-azobis (2-methylpropionate) (dimethyl 2,2'-azobis (2-methylpropionate); AIBME), 2,2'-azobis [2- (2-imine Dazolin-2-yl)propane] dihydrochloride (2,2'-azobis [2-(2-imidazolin-2-yl)propane] dihydrochloride; AIBI), benzoyl peroxide (BPO), dicumyl Dicumyl peroxide (DCP), lauroyl peroxide (LPO), methyl ethyl ketone peroxide (MEKPO) and t-butyl cumyl peroxide (tBCP) It may include at least one selected from the group consisting of.

In one embodiment, the polymerization solution preparation step 216 is a step of preparing a polymerization solution by reacting the styrene monomer into which the polymerization initiator is introduced at a temperature range of 50 °C to 90 °C overnight. Preferably, the temperature range of 60 ℃ to 80 ℃, most preferably, it may be to react overnight at 70 ℃.

In one embodiment, the washing step 217 is a step of washing the formed polymerization solution several times with an organic solvent.

In one embodiment, the organic solvent may include at least one selected from the group consisting of ethanol, methanol, chloroform, chloromethane, dichloromethane, trichloroethane, and dimethylsulfoxide. Preferably, the polymerization solution may be washed with ethanol to obtain polystyrene particles surface-modified with cations.

In one embodiment, preparing the core-shell particles by forming a silica shell on the polystyrene particles surface-modified with the cations includes preparing a dispersion by diluting the polystyrene particles surface-modified with the cations in distilled water; adjusting the pH by mixing an acidic substance with the dispersion; preparing a core-shell formation solution by heating the pH-adjusted dispersion to a temperature range of 40 °C to 80 °C and then introducing a silane compound; preparing a core-shell reaction solution by reacting the core-shell forming solution at a temperature range of 40 °C to 80 °C for 1 hour to 7 hours; and drying the core-shell reaction solution.

FIG. 4 is a flowchart schematically illustrating a detailed process of preparing the core-shell particle of FIG. 2 .

Referring to FIG. 4, the core-shell particle preparation step of the present invention includes a dispersion solution preparation step (221), a pH adjustment step (222), a core-shell forming solution preparation step (223), and a core-shell reaction solution preparation step ( 224), and drying the core-shell reaction solution (225).

In one embodiment, the dispersion preparation step 221 is a step of preparing a dispersion solution by diluting the polystyrene particles surface-modified with the cation in distilled water.

In one embodiment, the pH adjusting step 222 is a step of adjusting the pH by mixing an acidic material with the dispersion.

In one embodiment, the acidic substance is nitric acid, hydrochloric acid, phosphoric acid, sulfuric acid, hydrofluoric acid, hydrobromic acid, iodic acid, pimelic acid, malic acid, malonic acid, maleic acid, acetic acid, adipic acid, oxalic acid, succinic acid, tartaric acid , citric acid, lactic acid, glutaric acid, glycolic acid, formic acid, fumaric acid, propionic acid, butyric acid, hydroxybutyric acid, aspartic acid, itaconic acid, tricarbalic acid, suberic acid, benzoic acid, phenylacetic acid, naphthoic acid, mandelic acid, blood selected from the group consisting of cholic acid, nicotinic acid, isonicotinic acid, quinolinic acid, anthranilic acid, fujaric acid, phthalic acid, isophthalic acid, terephthalic acid, pyridinecarboxylic acid, salicylic acid, glutamic acid, polyacrylic acid, polyacrylic acid copolymer and polysulfonic acid It may contain at least any one.

In one embodiment, in the step of adjusting the pH by mixing an acidic material with the dispersion, the pH of the dispersion may be adjusted to a range of 1 to 6. Preferably, the pH of the dispersion may be 2 to 5.

In one embodiment, in the preparing of the core-shell forming solution (223), the pH-adjusted dispersion is heated to a temperature range of 40 ° C to 80 ° C, and then a silane compound is introduced to prepare a core-shell forming solution. It is a step. Preferably, the temperature range of 50 ℃ to 70 ℃, most preferably, it may be to inject the silane compound after reaching 60 ℃.

In one embodiment, the silane compound is tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra- sec-butoxysilane, tetra-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane , propyltriethoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-glycoxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ- methacryloyloxypropyltrimethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, trivinylmethoxysilane And it may include at least one selected from the group consisting of trivinylethoxysilane.

In one embodiment, the core-shell reaction solution preparation step (224) prepares a core-shell reaction solution by reacting the core-shell forming solution at a temperature range of 40 ° C. to 80 ° C. for 1 hour to 7 hours. It is a step. Preferably, it may be to react at a temperature range of 50 ℃ to 70 ℃, most preferably, 60 ℃ for 3 hours to 6 hours.

In one embodiment, the step of drying the core-shell reaction solution (225) may be to obtain core-shell particles by drying the core-shell reaction solution.

In one embodiment, the step 230 of removing the core by firing the core-shell particles may be performed for 1 hour to 10 hours at a temperature range of 300 ° C to 800 ° C. . Preferably, the reaction may be performed at a temperature range of 400 °C to 700 °C, most preferably at 600 °C for 3 hours to 6 hours to obtain hollow silica particles from which the core is removed.

A dispersion composition for display according to another embodiment of the present invention includes hollow silica particles according to an embodiment of the present invention and hollow silica particles prepared by a method for manufacturing hollow silica particles according to another embodiment of the present invention. do.

As used herein, "dispersion composition for display" refers to any liquid, liquefiable or mastic composition comprising hollow silica that is converted to a solid film after application to a substrate. The dispersion composition for display may be applied to the inside or outside of the surface of any structure.

The dispersion composition for a display of the present invention may be prepared by mixing hollow silica particles having high transparency, low reflectivity, and anti-glare effects as described above with a resin, an organic solvent, and the like.

In one embodiment, the organic solvent is propylene glycol monomethyl ether acetate (PGMEA), cyclohexanone or ethyl lactate, glycol ether derivatives, ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol dimethyl ether, propylene glycol n-propyl ether, or diethylene glycol dimethyl ether; glycol ether ester derivatives, ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycolmonomethyl ether acetate (PGMEA); carboxylates, ethyl acetate, n-butyl acetate and amyl acetate; carboxylates, diethyloxylates and diethylmalonates of dibasic acids; dicarboxylates of glycols, ethylene glycol diacetate and propylene glycol diacetate; and hydroxycarboxylates, methyl lactate, ethyl lactate, ethyl glycolate, and ethyl-3-hydroxy propionate; ketone esters, methyl pyruvate or ethyl pyruvate; alkoxycarboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate, or methylethoxypropionate; ketone derivatives, methyl ethyl ketone, acetyl acetone, cyclopentanone, cyclohexanone or 2-heptanone; ketone ether derivatives, diacetone alcohol methyl ether; ketone alcohol derivatives, acetol or diacetone alcohol; ketals or acetals, 1, 3-dioxalane and diethoxypropane; lactones, butyrolactone and gamma valerolactone; amide derivatives, dimethylacetamide or dimethylformamide, anisole; And it may be any one selected from the group consisting of mixtures thereof.

In one embodiment, the hollow silica particles in the display dispersion composition may be 5% to 20% by weight. When the amount of the hollow silica particles is less than 5% by weight, antireflection and antiglare effects cannot be sufficiently achieved, and when it is greater than 20% by weight, transparency is reduced and the content of the resin is reduced, so curing efficiency may be reduced.

In one embodiment, the resin in the dispersion composition for display may be 20% by weight to 70% by weight. In order to make a transparent composition by adjusting the refractive index of the hollow silica particles, the refractive index of the resin is preferably less than 1.5, and it is preferable to select and use a resin having a refractive index similar to that of the hollow particles among UV curable resins.

In one embodiment, the UV curable resin may include at least one selected from the group consisting of a urethane resin, an acrylic resin, a polyester resin, and an epoxy resin.

In one embodiment, the dispersion composition for display may further include a hard coating agent, a UV blocker, or an IR blocker, and the known additives are used, and if necessary, an additive providing additional functions is further included. can do.

In one embodiment, the dispersion composition for display may be any coating composition and may be applied to any substrate.

The dispersion composition for a display of the present invention can be used to manufacture an optical member for a display such as a polarizing film, a prism sheet, or an AR sheet.

The dispersion composition for a display according to an embodiment of the present invention can realize optically excellent properties by exhibiting antireflection and antiglare efficiencies.

A diffusion film according to another embodiment of the present invention includes a cured product of a dispersion composition for a display according to an embodiment of the present invention.

In one embodiment, a cured body may be prepared by preparing a substrate, laminating or applying the dispersion composition for display according to an embodiment of the present invention on the substrate, and UV curing to form a coating layer.

In one embodiment, the coating method comprises gravure coating, offset gravure coating, 2 and 3 roll pressure coating, 2 and 3 roll reverse coating, dip coating, 1 and 3 roll pressure coating. 2 rollkiss coatings, trailing balde coating, nip coating, flexographic coating, inverted knife coating, polishing bar coating And it may include at least one selected from the group consisting of wire wound doctor coating. After coating, the coating layer is cured with UV rays, and the curing treatment may be completed for 10 seconds to 1 hour.

In one embodiment, the thickness of the diffusion film may be 0.1 μm to 5 μm. When the thickness is less than 0.1 μm, the anti-reflection and anti-glare effects do not appear, and when the thickness exceeds 5 μm, a problem in which the refractive index is increased may occur.

The diffusion film according to an embodiment of the present invention can be used to manufacture a diffusion film for a backlight unit of a mobile phone, tablet PC, PDP, laptop computer, monitor, or TV.

An optical member for a display according to another embodiment of the present invention includes a diffusion film according to an embodiment of the present invention.

The diffusion film according to an embodiment of the present invention may be applied as an optical member for a backlight unit of a mobile phone, tablet PC, PDP, laptop computer, monitor, or TV.

Hereinafter, the present invention will be described in more detail by examples and comparative examples.

However, the following examples are only for illustrating the present invention, and the content of the present invention is not limited to the following examples.

[Production Example]

Preparation of polystyrene particles

The cationic surfactant was dissolved in distilled water with stirring. A nitrogen atmosphere was created while the temperature was raised to 70 °C (reflux). The styrene monomer was then purified. Purified styrene monomer was introduced under a nitrogen atmosphere. Styrene monomer was stirred for 30 minutes to mix well. After reaching 70 °C, a polymerization initiator was added under a nitrogen atmosphere. Reacted overnight at 70 °C. The polymerization solution was washed several times with ethanol.

Styrene core-silica shell fabrication

Polystyrene was diluted in distilled water. Titrate to pH 4 using acetic acid. After reaching 60 ℃, the silica material was added. Reacted at 60 °C for 5 hours.

Core - polystyrene removal

The reaction solution in the form of core-polystyrene and shell-silica was dried. The core-shell particles in a solid state were heat-treated in an electric furnace at 600° C. for 5 hours to remove the core.

Dispersion composition preparation

An organic solvent and 10% to 30% by weight of a silane coupling agent compared to the powder were put in a 100 mL paint shaker container and mixed for 10 minutes using a stirrer bar at a temperature of 25 °C. 5% to 20% by weight of hollow silica powder was added to the solution, and a mixed solution was formed for 30 minutes using a stirrer bar at a temperature of 25 °C. 100 g of 0.1 mm zirconia beads were added to the mixture and dispersed for 2 hours using a paint shaker to obtain a hollow silica dispersion composition.

[Example 1]

Hollow silica particles prepared using polystyrene as a core polymerized by including 4.18% by weight of the cationic surfactant compared to the styrene monomer in the preparation example and a display dispersion composition containing the hollow silica particles were prepared

[Example 2]

Hollow silica particles and a dispersion containing the hollow silica particles were prepared in the same manner as in Example 1, except that the cationic surfactant was included in 8.36% by weight of the styrene monomer in Example 1.

[Example 3]

Hollow silica particles and a dispersion containing the hollow silica particles were prepared in the same manner as in Example 1, except that the cationic surfactant was included in 16.72% by weight of the styrene monomer in Example 1.

[Example 4]

Hollow silica particles were prepared in the same manner as in Example 1, except that the cationic surfactant was included in 25.08% by weight of the styrene monomer in Example 1.

[Comparative Example 1]

In Example 1, hollow silica particles were prepared in the same manner as in Example 1, except that the polystyrene polymerized by including 40% by weight of a nonionic surfactant relative to the styrene monomer was prepared as a core instead of a cationic surfactant.

[Comparative Example 2]

Hollow silica particles were prepared in the same manner as in Comparative Example 1, except that the polystyrene polymerized by including 40% by weight of a nonionic surfactant of a different type from the surfactant applied in Comparative Example 1 was used as a core.

Hollow silica particle analysis

Specific surface area (BET) analysis: When nitrogen gas was adsorbed as a monomolecular layer on the surface and pores of the sample using 0.2 g to 0.3 g of hollow silica powder, the adsorption amount was measured and analyzed.

TEM analysis: hollow silica powder was diluted in ethanol, and particle size and shell thickness were analyzed through images at each magnification.

5 is a TEM image of hollow silica particles according to Examples 1 to 4 and Comparative Examples 1 and 2 of the present invention and a dispersion composition for a display comprising the same, and Table 1 below shows Examples 1 to 4 and Comparative Examples of the present invention It shows the physical properties of the hollow silica particles according to 1 and 2 and the display dispersion composition containing them.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 specific surface area
(m ² /g) 323 329 332 424 457 411 core average
diameter
(nm) 60 50 40 30 100 100 hollow silica mean diameter
(nm) 70 60 50 40 122 - Dispersion particle size D ₅₀ (nm) 235 208 185 - - -

10% by weight Hollow SiO ₂ in PGMEA Dispersion Referring to particle size 5 and Table 1, as a result of Examples 1 to 4, it is possible to synthesize hollow silica particles of 100 nm or less by using a cationic surfactant, and the specific surface area of the particles It can be confirmed that is 320 m ² /g or more.

It can be seen that as the content of the cationic surfactant increases, the core polystyrene particles are synthesized in a smaller size, and the size of the hollow silica particles to which they are applied is also reduced.

In addition, it can be seen that the smaller the primary particle size of the hollow silica, the smaller the particle size D ₅₀ of the dispersion.

As described above, although the embodiments have been described with limited drawings, those skilled in the art can apply various technical modifications and variations based on the above. For example, the described techniques may be performed in an order different from the method described, and/or the components of the described system, structure, device, circuit, etc. may be combined or combined in a different form than the method described, or other components may be used. Or even if it is replaced or substituted by equivalents, appropriate results can be achieved.

Therefore, other implementations, other embodiments, and equivalents of the claims are within the scope of the following claims.

Claims (18)

delete delete delete delete delete delete preparing polystyrene particles surface-modified with cations;
Preparing core-shell particles by forming a silica shell on the surface-modified polystyrene particles with the cation; and
removing the core by firing the core-shell particle;
including,
Preparing the surface-modified polystyrene particles with the cation,
Preparing a cationic surfactant solution;
preparing a mixture by adding a styrene monomer to the cationic surfactant solution and stirring; and
Injecting the styrene monomer and adding a polymerization initiator to the stirred mixture, followed by polymerization;
including,
Manufacturing method of hollow silica particles.
According to claim 7,
Preparing the surface-modified polystyrene particles with the cation,
Preparing a cationic surfactant solution by dissolving a cationic surfactant in distilled water;
Forming a nitrogen atmosphere while raising the temperature of the cationic surfactant solution to a temperature range of 50 ℃ to 90 ℃;
purifying the styrene monomer;
preparing a mixture by adding the purified styrene monomer to the cationic surfactant solution under a nitrogen atmosphere and stirring;
Injecting a polymerization initiator under a nitrogen atmosphere after heating the stirred styrene monomer to a temperature range of 50 ° C to 90 ° C;
preparing a polymerization solution by reacting the styrene monomer into which the polymerization initiator was added overnight at a temperature range of 50 °C to 90 °C; and
washing the formed polymerization solution several times with an organic solvent;
including,
Manufacturing method of hollow silica particles.
According to claim 8,
The cationic surfactant is cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTAC), cetylpyridinium chloride (CPC), dodecyltrimethylammonium bromide (DTAB), tetradecyltrimethylammonium bromide (TTAB), tetra To include at least one selected from the group consisting of trimethylammonium bromide (TMB), dioctadecyldimethylammonium bromide (DODAB) and dimethyldioctadecylammonium chloride (DODMAC),
Manufacturing method of hollow silica particles.
According to claim 8,
Preparing a cationic surfactant solution by dissolving the cationic surfactant in the distilled water,
It comprises 0.001% by weight to 50% by weight of the cationic surfactant relative to the styrene monomer,
Manufacturing method of hollow silica particles.
According to claim 7,
Preparing core-shell particles by forming a silica shell on the surface-modified polystyrene particles with the cation,
preparing a dispersion by diluting the surface-modified polystyrene particles with distilled water;
adjusting the pH by mixing an acidic substance with the dispersion;
preparing a core-shell forming solution by heating the pH-adjusted dispersion to a temperature range of 40° C. to 80° C. and then introducing a silane compound;
preparing a core-shell reaction solution by reacting the core-shell formation solution at a temperature range of 40 °C to 80 °C for 1 hour to 7 hours; and
drying the core-shell reaction solution;
including,
Manufacturing method of hollow silica particles.
According to claim 11,
The acidic substance is nitric acid, hydrochloric acid, phosphoric acid, sulfuric acid, hydrofluoric acid, hydrobromic acid, iodic acid, pimelic acid, malic acid, malonic acid, maleic acid, acetic acid, adipic acid, oxalic acid, succinic acid, tartaric acid, citric acid, lactic acid, glue Taric acid, glycolic acid, formic acid, fumaric acid, propionic acid, butyric acid, hydroxybutyric acid, aspartic acid, itaconic acid, tricarbalic acid, suberic acid, benzoic acid, phenylacetic acid, naphthoic acid, mandelic acid, picolinic acid, nicotinic acid, iso Nicotinic acid, quinolinic acid, anthranilic acid, fujaric acid, phthalic acid, isophthalic acid, terephthalic acid, pyridinecarboxylic acid, salicylic acid, glutamic acid, polyacrylic acid, polyacrylic acid copolymers, and polysulfonic acid containing at least one selected from the group consisting of will,
Manufacturing method of hollow silica particles.
According to claim 11,
The step of adjusting the pH by mixing an acidic substance with the dispersion,
The pH of the dispersion is adjusted to the range of 1 to 6,
Manufacturing method of hollow silica particles.
According to claim 11,
The silane compound,
tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-sec-butoxysilane, tetra-tert-part Toxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltrimethoxy Silane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-glycoxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, selected from the group consisting of dimethyldimethoxysilane, methylphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, trivinylmethoxysilane and trivinylethoxysilane Which includes at least one that is,
Manufacturing method of hollow silica particles.
According to claim 7,
The step of removing the core by firing the core-shell particle,
Carrying out the core-shell particles in the temperature range of 300 ℃ to 800 ℃ for 1 hour to 10 hours,
Manufacturing method of hollow silica particles.
A display dispersion composition comprising hollow silica particles prepared by the method of manufacturing hollow silica particles according to claim 7.
A diffusion film comprising a cured product of the dispersion composition for display of claim 16.
An optical member for a display comprising the diffusion film of claim 17.

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