KR102825667B1 - Inorganic oxide particle-containing dispersion composition, method for preparing the same and article using the same - Google Patents

Abstract

The present invention relates to an inorganic oxide particle-containing dispersion composition, a method for producing the same, and a molded article produced using the same. An inorganic oxide particle-containing dispersion composition according to one embodiment of the present invention comprises: an inorganic oxide particle dispersion; and a monomer of an acrylate resin; wherein the conductivity of the inorganic oxide particle dispersion is 1 μS/cm to 20,000 μS/cm.

Description

INORGANIC OXIDE PARTICLE-CONTAINING DISPERSION COMPOSITION, METHOD FOR PREPARING THE SAME AND ARTICLE USING THE SAME

The present invention relates to an inorganic oxide particle-containing dispersion composition, a method for producing the same, and a molded article produced using the same.

Optically transparent polymer materials are widely used as optical coatings and optoelectronic materials because of their low cost, good processability, and high transmittance in the visible light range. Recently, high-refractive-index transparent materials have been used as materials for optical filters, lenses, reflectors, optical waveguides, antireflection films, solar cells, and light emitting diodes (LEDs). However, since these polymers have a refractive index (n) of 1.3 to 1.7, it is difficult to use the polymer materials alone. Therefore, research is being conducted to mix and disperse high-refractive-index inorganic materials (n = 1.5 to 2.7) into the polymers.

The substances commonly used as high-refractive inorganic materials include TiO ₂ (n = 2.5 ~ 2.7), ZrO ₂ (n = 2.1 ~ 2.2), ZnO (n = 2.0), SnO ₂ (n = 2.0), and SiO ₂ (n = 1.5). In particular, TiO ₂ is the most commonly used high-refractive inorganic material because it has a high refractive index, is non-toxic, and is inexpensive. However, TiO ₂ has a yellow color when manufactured into a film, and since the Abbe number, which indicates the degree of dispersion, decreases as the TiO ₂ content increases, it has the disadvantage of being limited for commercial use. In particular, in the case of TiO ₂ , a yellowing phenomenon occurs during film manufacturing, and this causes problems such as reduced color and visibility when applied to a display. In addition, other high refractive index inorganic materials such as ZnO, SnO ₂ , and SiO ₂ have the disadvantages of significantly low refractive index and high price.

In addition, in order to manufacture a polymer composite including a high-refractive-index inorganic material, it is necessary to include a high content of a high-refractive-index inorganic material. In general, a high-refractive-index inorganic sol is manufactured by adding a catalyst to an inorganic precursor having a high refractive index in an aqueous solution and stirring the mixture. However, such a high-refractive-index sol is not only phase unstable and opaque, but also difficult to add a high content of inorganic material, making it difficult to manufacture a uniform film.

Titania ( _TiO2 ) has recently found a wide range of applications, including improving indoor air quality using its photocatalytic properties, removing nitrogen oxides through road paving, photocatalytic coating of structures, and sterilization systems in hospitals. However, due to its yellowness, it is difficult to manufacture optical films. Therefore, there is a growing need for an optical dispersion composition that can have a high refractive index, low yellowing, and low viscosity by synthesizing composite particles while utilizing the high dielectric constant of titania.

The present invention is to solve the above-described problems, and the purpose of the present invention is to provide an inorganic oxide particle-containing dispersion composition capable of improving yellowing properties, high refractive index, and low viscosity by controlling electrical conductivity during synthesis of an inorganic oxide particle dispersion, a method for producing the same, and a molded article produced using the same.

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

An inorganic oxide particle-containing dispersion composition according to one embodiment of the present invention comprises: an inorganic oxide particle dispersion; and a monomer of an acrylate resin; wherein the inorganic oxide particle dispersion comprises inorganic oxide particles, and the conductivity of the inorganic oxide particle dispersion is 1 μS/cm to 20,000 μS/cm.

In one embodiment, the inorganic oxide particle dispersion further includes second inorganic oxide particles, and the second inorganic oxide particles may be different from the inorganic oxide particles.

In one embodiment, the inorganic oxide particles and the second inorganic oxide particles are, respectively, TiO ₂ , BaTiO ₃ , SrTiO ₃ , BaTiO ₃ , PbTiO ₃ , It may include at least one selected from the group consisting of PbZrO ₃ , Pb(Zr,Ti)O ₃ (PZT), Pb _1-x La _x Zr _1-y Ti _y O ₃ (PLZT), PB(Mg ₃ Nb _2/3 )O ₃ ^- PbTiO ₃ (PMN-PT), hafnia (HfO ₂ )SrTiO ₃ , Al ₂ O ₃ , ZrO ₂ , SiO ₂ , CeO ₂ , ZnO, BN and V ₂ O ₅ .

In one embodiment, the diameters of the inorganic oxide particles and the second inorganic oxide particles may each be from 1 nm to 500 nm.

In one embodiment, the specific surface areas of the inorganic oxide particles and the second inorganic oxide particles may be 1 m ² /g to 250 m ² /g, respectively.

In one embodiment, the inorganic oxide particles and the second inorganic oxide particles may each be 30 wt% to 50 wt% of the inorganic oxide particle-containing dispersion composition.

In one embodiment, the inorganic oxide particles may include titanium-based oxide and have an anatase crystal structure.

In one embodiment, the inorganic oxide particles may include titania surface-treated with an inorganic oxide.

In one embodiment, the inorganic oxide particle dispersion further comprises a buffer solution, wherein the buffer solution comprises potassium bicarbonate, ammonium acetate, sodium acetate, potassium acetae, ammonium phosphate, sodium phosphate, potassium phosphate, ammonium carbonate, ammonium bicarbonate, sodium bicarbonate, sodium carbonate, potassium carbonate, triethylammonium bicarbonate, ammonium chloride and ammonium hydroxide. It may include at least one selected from the group consisting of:

In one embodiment, the pH of the inorganic oxide particle dispersion may be in the range of 9.5 to 11.

In one embodiment, the inorganic oxide particle dispersion may be hydrophilic solvent-free.

In one embodiment, the monomer of the acrylate-based resin may include at least one selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, sec-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, and tetradecyl (meth)acrylate.

In one embodiment, the monomer of the acrylate resin may be 45 wt% to 65 wt% of the inorganic oxide particle-containing dispersion composition.

In one embodiment, the composition may further include an additive including the silica-based surface treatment agent, the phosphate-based dispersant, or both.

In one embodiment, the inorganic oxide particle dispersion may include inorganic oxide particles surface-treated with the silica-based surface treatment agent.

In one embodiment, the silica-based surface treatment agent includes at least one selected from the group consisting of silane, alkyl silane having 1 to 20 carbon atoms, alkyloxy silane, alkoxy silane, isocyanate silane, amino silane, epoxy silane, acrylic silane, mercapto silane, fluorine silane, methacroxy silane, vinyl silane, phenyl silane, chloro silane, and silazane, and the silica-based surface treatment agent may be included in an amount of 10 to 25 parts by weight per 100 parts by weight of the inorganic oxide particles.

In one embodiment, the silica-based surface treatment agent may be present in an amount of 5 wt% to 20 wt% of the inorganic oxide particle-containing dispersion composition.

In one embodiment, the phosphate-based dispersant includes at least one selected from the group consisting of sodium diphosphate, sodium orthophosphate, sodium pyrophosphate, potassium pyrophosphate, sodium tripolyphosphate, sodium metaphosphate, sodium acid phosphate, sodium acid pyrophosphate, orthophosphate, metaphosphate, ultraphosphate, pyrophosphate, fluorophosphate, tripolyphosphate, tetrapolyphosphate, and sodium hexametaphosphate, and the phosphate-based dispersant may be included in an amount of 10 to 20 parts by weight per 100 parts by weight of the inorganic oxide particles.

In one embodiment, the phosphate-based dispersant may be present in an amount of 5 wt% to 20 wt% of the inorganic oxide particle-containing dispersion composition.

In one embodiment, the refractive index of the inorganic oxide particle-containing dispersion composition may be 1.70 or more, and the viscosity may be 2,000 cP or less.

In one embodiment, the inorganic oxide particle-containing dispersion composition may have a yellowness index (Y.I) of 2.2 or less.

A molded article according to another embodiment of the present invention is manufactured from an inorganic oxide particle-containing dispersion composition according to one embodiment of the present invention.

In one embodiment, the molded body may be a film or a sheet.

A method for producing an inorganic oxide particle-containing dispersion composition according to another embodiment of the present invention comprises the steps of: preparing an inorganic oxide particle dispersion; and adding and mixing a monomer of an acrylate resin to the inorganic oxide particle dispersion.

In one embodiment, the step of preparing the inorganic oxide particle dispersion may include a step of preparing an inorganic gel dispersion by adding a buffer solution to an inorganic precursor; a step of preparing a mixture by mixing a silica-based surface treatment agent, a phosphate-based dispersing agent, or both, into the inorganic gel dispersion; and a step of heat-treating the mixture at a temperature of 25° C. to 100° C.

In one embodiment, the inorganic precursor further comprises a second inorganic precursor, and the second inorganic precursor may be different from the inorganic precursor.

In one embodiment, after the step of preparing a mixture by mixing a silica-based surface treatment agent, a phosphate-based dispersant, or both into the inorganic gel dispersion, the method may further include a step of drying the mixture at a temperature of 25° C. to 100° C.

In one embodiment, after the step of adding and mixing a monomer of an acrylate resin into the inorganic oxide particle dispersion, the method may further include a step of removing a solvent.

An inorganic oxide particle-containing dispersion composition according to one embodiment of the present invention can improve the yellowing and viscosity of the composition while maintaining high transparency and high refractive index by changing the electrical conductivity of the solution during synthesis of an inorganic oxide particle dispersion.

According to one embodiment of the present invention, various optical products such as films with improved optical properties of low yellowing and low viscosity can be provided using the inorganic oxide particle-polymer dispersion composition.

By a method for producing an inorganic oxide particle-containing dispersion composition according to one embodiment of the present invention, an inorganic oxide particle-containing dispersion composition with improved dispersibility and inhibition of yellowing can be provided.

Figure 1 is an X-ray diffraction result showing the anatase crystal structure of titania particles and titania particles according to an embodiment of the present invention.
Figure 2 is a SEM image of titania particles according to an embodiment of the present invention.
Figure 3 is a TEM image of titania particles manufactured in an embodiment of the present invention.
Figure 4 shows an image of the dispersion composition of Example 1 of the present invention.
Figure 5 shows an image of the dispersion composition of Comparative Example 1 of the present invention.
FIG. 6 is an image of monomer dispersion compositions according to Examples 1 to 3 and Comparative Example 5 of the present invention.

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

The terms used in the examples are for the purpose of description only and should not be construed as limiting. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this specification, the terms "comprises" or "has" and the like are intended to specify the presence of a feature, number, step, operation, component, part or combination thereof described in the specification, but should be understood to not exclude in advance the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts or combinations thereof.

Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the embodiments belong. Terms defined in commonly used dictionaries, such as those defined in common dictionaries, should be interpreted as having a meaning consistent with the meaning they have in the context of the relevant art, and shall not be interpreted in an idealized or overly formal sense, unless expressly defined in this application.

In addition, when describing with reference to the attached drawings, the same components will be given the same reference numerals regardless of the drawing numbers, and redundant descriptions thereof will be omitted. When describing an 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 thereof will be omitted.

Hereinafter, the inorganic oxide particle-containing dispersion composition of the present invention, the method for producing the same, and the molded article produced using the same will be specifically described with reference to examples and drawings. However, the present invention is not limited to these examples and drawings.

An inorganic oxide particle-containing dispersion composition according to one embodiment of the present invention comprises: an inorganic oxide particle dispersion; and a monomer of an acrylate resin; wherein the inorganic oxide particle dispersion comprises inorganic oxide particles, and the conductivity of the inorganic oxide particle dispersion is 1 μS/cm to 20,000 μS/cm.

According to one embodiment of the present invention, an inorganic oxide particle-containing dispersion composition has a conductivity of 1 μS/cm to 20,000 μS/cm before and after synthesis of the inorganic oxide particle dispersion, thereby changing the electrical conductivity of the solution during synthesis of the inorganic oxide particle dispersion, thereby improving the yellowing and viscosity of the composition while maintaining high transparency and high refractive index. The present invention is a method for dramatically lowering the yellowing by controlling the electrical conductivity, although there is a disadvantage in that the yellowing is high when a dispersion is prepared using titania alone without controlling the electrical conductivity and mixed with a coating solution during UV curing.

According to one embodiment of the present invention, the inorganic oxide particle-containing dispersion composition may have a difference in conductivity of 60 μS/cm or less, 50 μS/cm or less, or 40 μS/cm or less before and after synthesis of the inorganic oxide particle dispersion.

In one embodiment, the inorganic oxide particle dispersion further includes second inorganic oxide particles, and the second inorganic oxide particles may be different from the inorganic oxide particles.

In one embodiment, the inorganic oxide particles and the second inorganic oxide particles are, respectively, TiO ₂ , BaTiO ₃ , SrTiO ₃ , BaTiO ₃ , PbTiO ₃ , It may include at least one selected from the group consisting of PbZrO ₃ , Pb(Zr,Ti)O ₃ (PZT), Pb _1-x La _x Zr _1-y Ti _y O ₃ (PLZT), PB(Mg ₃ Nb _2/3 )O ₃ ^- PbTiO ₃ (PMN-PT), hafnia (HfO ₂ )SrTiO ₃ , Al ₂ O ₃ , ZrO ₂ , SiO ₂ , CeO ₂ , ZnO, BN and V ₂ O ₅ . Preferably, it may include TiO ₂ particles. The TiO ₂ particles are a high-k material, may have a high dielectric constant, and may be fine particles having a high refractive index. TiO ₂ particles may be prepared as commercially available particles, or may be synthesized by any one of the synthetic methods selected from the group consisting of a sol-gel method, a hydrothermal method, a solid-state method, and a supercritical method. For example, TiO ₂ particles prepared by the sol-gel method may have thermal stability and high refractive index and transmittance.

In one embodiment, the inorganic oxide particles may include titanium-based oxide and have an anatase crystal structure. The anatase crystal structure can be applied to numerous fields and is the most widely used material. For this reason, it is important to include inorganic oxide particles having a stable anatase crystal structure.

In one embodiment, the inorganic oxide particle may include titania surface-treated with an inorganic oxide. For example, the inorganic oxide may be formed by reacting a precursor of the inorganic oxide on the surface of the titania particle to form a shell layer of the inorganic oxide. The inorganic oxide may include at least one selected from the group consisting of alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), silica (SiO ₂ ), ceria (CeO ₂ ), zinc oxide (ZnO), boron nitride (BN), barium titanate (BaTiO ₃ ), and vanadia (V ₂ O ₅ ).

In one embodiment, the diameters of the inorganic oxide particles and the second inorganic oxide particles may be 1 nm to 500 nm, respectively. This may be the diameter of inorganic oxide particles that have not been surface-treated with a silica-based surface treatment agent. When the diameter of the inorganic oxide particles is less than 1 nm, there may be a problem that dispersion becomes difficult due to an increase in the surface energy of the nanoparticles, and when it exceeds 500 nm, there is a problem that the thickness of the film becomes thick. In the case of inorganic oxide particles surface-treated with a silica-based surface treatment agent, the size may be the same as or smaller than the size of the inorganic oxide particles in order to form a core/shell structure.

In one embodiment, the specific surface areas of the inorganic oxide particles and the second inorganic oxide particles may each be from 1 m ² /g to 250 m ² /g. Inorganic oxide particles having a specific surface area in the above range can have little or no agglomeration or can have reduced agglomeration.

In one embodiment, the inorganic oxide particles and the second inorganic oxide particles may each be 30 wt% to 50 wt% of the inorganic oxide particle-containing dispersion composition. If the surface-treated titania particles are less than 30 wt% of the inorganic oxide particle-containing dispersion composition, the relative proportion of the particles in the dispersion may decrease, thereby decreasing the refractive index and brightness of the dispersion, and if they are more than 50 wt%, there is a problem that the film appears yellowish.

In one embodiment, the inorganic oxide particle dispersion may further include a buffer solution. The buffer solution may be a powder obtained by controlling the conductivity properties through hydrothermal synthesis with a precursor material of the inorganic oxide particles.

In one embodiment, the buffer solution may include at least one selected from the group consisting of potassium bicarbonate, ammonium acetate, sodium acetate, potassium acetae, ammonium phosphate, sodium phosphate, potassium phosphate, ammonium carbonate, ammonium bicarbonate, sodium bicarbonate, sodium carbonate, potassium carbonate, triethylammonium bicarbonate, ammonium chloride, and ammonium hydroxide.

In one embodiment, when the precursor of the inorganic oxide particle is Ti(OH) ₄ and the buffer solution is ammonium bicarbonate, the following reaction formula is shown.

[Reaction Formula 1]

Ti(OH) ₄ → TiO ₂ + 2H ₂ O

[Reaction Formula 2]

NH ₄ HCO ₃ (Ammonium bicarbonate) → NH ₄ ⁺ + HCO ₃ ^- → NH ₃ + H ₂ O + CO ₂

The effect of reducing conductivity can be seen because the buffer solution exists in the dispersion by being decomposed as in the above reaction scheme 2 (does not exist as NH ₄ ⁺ + OH ^- ).

The acidity (pK _a ) of NH ₃ is 10.5, and the acidity (pK _a ) of NH ₄ ⁺ is 9.25.

In one embodiment, by including the buffer solution, the pH and electrical conductivity of the inorganic oxide particle-containing dispersion composition can be controlled without a separate pH regulator or additive.

In one embodiment, the pH of the inorganic oxide particle dispersion may be in the range of 9.5 to 11. By synthesizing the inorganic oxide particle dispersion at the pH in the above range, an inorganic oxide sol with improved stability can be obtained.

In one embodiment, the inorganic oxide particle dispersion may be a hydrophilic solvent-free. The solvent of the inorganic oxide particle dispersion is a solvent of each component or a dispersible organic solvent.

In one embodiment, the organic solvent is ethanol (EtOH), methanol (MeOH), propanol (PrOH), butanol (BuOH), isopropyl alcohol (IPA), isopropyl alcohol propanol, isobutyl alcohol, hexanol, cyclohexanol, dimethylacetamide (DMAC), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), triethylene phosphate, trimethyl phosphate, hexane, benzene, toluene, xylene, acetone, methyl ethyl ketone (MEK), ethyl isobutyl ketone (EIBK), methyl isobutyl ketone (MIBK), diethyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, dioxane, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-Methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, benzene, It may contain at least one selected from the group consisting of toluene, xylene, cyclohexanone, ethylene glycol, diethylene glycol, tetrahydrofuran, 1,4-dioxane, and glycerin.

In one embodiment, the monomer of the acrylate resin can maintain high transmittance and low haze as an optical adhesive.

In one embodiment, the monomer of the acrylate resin is an example of a UV paint used for optical films, etc., and is an ultraviolet-curable acrylate resin. The photoinitiator is activated by ultraviolet rays to crosslink the oligomer and the monomer to form a coating film, and there are no particular limitations as long as it can be cured at low temperatures and has a fast curing speed.

In one embodiment, the monomer of the acrylate-based resin may include at least one selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, sec-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, and tetradecyl (meth)acrylate.

In one embodiment, the monomer of the acrylate resin may be a multifunctional acrylate resin, for example, a difunctional to hexafunctional (having 2 to 6 acrylate groups) acrylate resin.

In one embodiment, the monomer of the acrylate resin is a saturated hydrocarbon polymer without a double bond in the molecule, and thus has excellent resistance to oxidation due to its inherent properties, and thus may have excellent weather resistance.

In one embodiment, the number average molecular weight of the monomer of the acrylate resin may be preferably in the range of 10,000 to 1,000,000, more preferably in the range of 100,000 to 500,000.

In one embodiment, the monomer of the acrylate resin preferably has a glass transition temperature of 0° C. or higher, more preferably 25° C. to 70° C., and even more preferably 40° C. to 66° C. When the glass transition temperature is within this range, the inorganic oxide particle-containing dispersion composition of the present invention can have improved yellowing. In one embodiment, the monomer of the acrylate resin may be 45 wt% to 65 wt% in the inorganic oxide particle-containing dispersion composition. When the monomer of the acrylate resin is less than 45 wt% in the inorganic oxide particle-containing dispersion composition, the content of particles in the dispersion system may increase, which may cause a problem in that the viscosity of the dispersion may increase, and when it exceeds 65 wt%, the content of particles may decrease, which may cause a problem in that the refractive index, yellowing, and brightness characteristics of the film may deteriorate when forming the film. For example, when the content of inorganic oxide particles is 30 wt%, the additive may be 5 wt% to 10 wt% and the monomer of the acrylate resin may be 60 wt% to 65 wt%, and when the content of inorganic oxide particles is 40 wt%, the additive may be 10 wt% to 15 wt% and the monomer of the acrylate resin may be 40 wt% to 50 wt%.

In one embodiment, the composition may further include an additive including the silica-based surface treatment agent, the phosphate-based dispersant, or both.

In one embodiment, the inorganic oxide particle dispersion may include inorganic oxide particles surface-treated with the silica-based surface treatment agent. The inorganic oxide particle dispersion including the surface-treated inorganic oxide particles has a denaturation-inhibiting effect while maintaining a high refractive index.

In one embodiment, the silica-based surface treatment agent may include at least one selected from the group consisting of silane, alkyl silane having 1 to 20 carbon atoms, alkyloxy silane, alkoxy silane, isocyanate silane, amino silane, epoxy silane, acrylic silane, mercapto silane, fluorine silane, methacroxy silane, vinyl silane, phenyl silane, chloro silane, and silazane.

In one embodiment, the silica-based surface treatment agent may be included in an amount of 10 to 25 parts by weight per 100 parts by weight of the inorganic oxide particles.

In one embodiment, the silica-based surface treatment agent may be present in an amount of 5 wt% to 20 wt% of the inorganic oxide particle-containing dispersion composition.

In one embodiment, when the silica-based surface treatment agent is included within the above range, it can improve the dispersibility of inorganic oxides and help improve yellowing and viscosity.

In one embodiment, the phosphate-based dispersant can improve dispersibility by surface-treating an inorganic oxide together with the silane coupling agent.

In one embodiment, the phosphate-based dispersant is not particularly limited as long as it satisfies the acid conditions for securing dispersibility, but may preferably be an organic acid or an inorganic acid.

In one embodiment, the phosphate-based dispersant may include at least one selected from the group consisting of sodium diphosphate, sodium orthophosphate, sodium pyrophosphate, potassium pyrophosphate, sodium tripolyphosphate, sodium metaphosphate, sodium acid phosphate, sodium acid pyrophosphate, orthophosphate, metaphosphate, ultraphosphate, pyrophosphate, fluorophosphate, tripolyphosphate, tetrapolyphosphate, and sodium hexametaphosphate.

In one embodiment, the phosphate-based dispersant may be included in an amount of 10 to 20 parts by weight per 100 parts by weight of the inorganic oxide particles.

In one embodiment, the phosphate-based dispersant may be present in an amount of 5 wt% to 20 wt% of the inorganic oxide particle-containing dispersion composition.

In one embodiment, if the phosphate-based surface treatment agent is less than the above range, the dispersing effect of the inorganic oxide particles may be reduced and yellowing may not be suppressed, and if the phosphate-based surface treatment agent is more than the above range, the phosphate-based surface treatment agent may not sufficiently dissolve in the solvent, thereby reducing the dispersing effect and increasing the viscosity of the dispersion.

In one embodiment, the pH of the phosphate-based dispersant is alkaline at the pH level of 10, and the solubility of the phosphate-based surface treatment agent may be about 6.7 g/mL (25°C). Since the problem of not dissolving may occur when an excessive amount is added, the phosphate-based surface treatment agent may be included within the above range.

In one embodiment, the refractive index of the inorganic oxide particle-containing dispersion composition may be 1.70 or more or 1.80 or more, and the viscosity may be 2,000 cP or less, 1,800 cP or less, 1,600 cP or less, 1,400 cP or less, 1,200 cP or less, 1,000 cP or less, 800 cP or less, or 500 cP or less.

In one embodiment, the inorganic oxide particle-containing dispersion composition may have a yellowness (Y.I) of 2.2 or less or 2.15 or less.

An inorganic oxide particle-containing dispersion composition according to one embodiment of the present invention can improve the yellowing and viscosity of the composition while maintaining high transparency and high refractive index by changing the electrical conductivity of the solution during synthesis of an inorganic oxide particle dispersion.

A molded article according to another embodiment of the present invention is manufactured from an inorganic oxide particle-containing dispersion composition according to one embodiment of the present invention.

In one embodiment, the molded body may be a film or a sheet. Specifically, the inorganic oxide particle-containing dispersion composition can provide a sheet, film, or the like having a high refractive index, and thus can be applied to a high refractive index hard coating, an antireflection film, a prism sheet, or the like for a display (flat panel, flexible).

In one embodiment, the total transmittance of the film or sheet may be 80% to 90%, the diffuse transmittance of the film may be 5% to 20%, and the haze of the film may be 10% to 20%. A high haze value is required to have high light scattering properties. When the haze of the film is in the range of 10% to 20%, therefore, a film including surface-treated titania particles according to one embodiment of the present invention may realize higher dispersibility and light scattering properties under the same conditions.

A method for producing an inorganic oxide particle-containing dispersion composition according to another embodiment of the present invention comprises the steps of: preparing an inorganic oxide particle dispersion; and adding and mixing a monomer of an acrylate resin to the inorganic oxide particle dispersion.

By a method for producing an inorganic oxide particle-containing dispersion composition according to one embodiment of the present invention, an inorganic oxide particle-containing dispersion composition with improved dispersibility and inhibition of yellowing can be provided.

In one embodiment, the step of preparing the inorganic oxide particle dispersion may include a step of preparing an inorganic gel dispersion by adding a buffer solution to an inorganic precursor; a step of preparing a mixture by mixing a silica-based surface treatment agent, a phosphate-based dispersing agent, or both into the inorganic gel dispersion; and a step of heat-treating the mixture at 25° C. to 100° C.

In one embodiment, the heat treatment step may be performed by heat treating the mixture in an atmosphere containing at least one of oxygen, air, and an inert gas or a vacuum atmosphere for 10 minutes or more, 30 minutes or more, 1 hour or more, or 3 hours to 24 hours to form a surface-treated inorganic oxide. As another example, the mixture may be dispersed in a solvent, and the mixture may be reacted at a temperature of 25° C. to 100° C. for 1 hour or more, or 3 hours to 24 hours to form a surface-treated inorganic oxide particle.

In one embodiment, the inorganic precursor further comprises a second inorganic precursor, and the second inorganic precursor may be different from the inorganic precursor.

In one embodiment, after the step of preparing a mixture by mixing a silica-based surface treatment agent, a phosphate-based dispersant, or both into the inorganic gel dispersion, the method may further include a step of drying the mixture at a temperature of 25° C. to 100° C.

In one embodiment, the mixture can be dried at a temperature of 25° C. to 100° C. or a temperature of 50° C. to 100° C. in a vacuum or in an atmosphere containing at least one of oxygen, air and an inert gas.

In one embodiment, after the step of adding and mixing a monomer of an acrylate resin into the inorganic oxide particle dispersion, the method may further include a step of removing a solvent.

In one embodiment, the step of removing the solvent is to remove the solvent of the mixture formed after the addition of the monomer of the acrylate resin, and may be performed by drying or using a degassing process in a vacuum or an atmosphere containing at least one of oxygen, air, and an inert gas at a temperature of 25° C. to 50° C. or 50° C. to 100° C.

Hereinafter, the present invention will be described in detail with reference to the following examples and comparative examples. However, the technical idea of the present invention is not limited or restricted thereto.

[Example 1]

Conductivity controlled TiO ₂ Preparation of monomer dispersion containing single particles

A titanium gel dispersion was prepared by adding 20.45 g of NH ₄ HCO ₃ (ammonium bicarbonate) as a buffer solution to 499.7 g of Ti(OH) ₄ as a titanium precursor.

The reaction equation within the dispersion is as follows.

[Reaction Formula 1]

Ti(OH) ₄ → TiO ₂ + 2H ₂ O

[Reaction Formula 2]

NH ₄ HCO ₃ (Ammonium bicarbonate) → NH ₄ ⁺ + HCO ₃ ^- → NH ₃ + H ₂ O + CO ₂

The effect of reducing conductivity can be seen because the buffer solution exists in the dispersion by being decomposed as in the above reaction scheme 2 (does not exist as NH ₄ ⁺ + OH ^- ).

The acidity (pK _a ) of NH ₃ is 10.5, and the acidity (pK _a ) of NH ₄ ⁺ is 9.25.

A mixture was prepared by adding 50 g of tetrahydrofuran (THF), 5 g (12.5% content) of methacryl silane as a coupling agent, and 5 g of a dispersant to a 250 mL paint shaker container.

The above mixture was mixed for 5 minutes using a stirrer bar at a temperature of 25°C. Thereafter, 40 g of titania was added to the mixture, and the mixture was formed for 30 minutes using a stirrer bar at a temperature of 25°C.

Thereafter, 200 g of 0.05 mm beads were added to the mixture containing the titania and dispersed for 3 hours using a paint shaker to obtain a titania-THF dispersion. At this time, the beads are zirconia with a size of 0.05 mm.

Afterwards, the titania-THF dispersion, an acrylate resin monomer, a silane surface treatment agent, and sodium diphosphate (SDP) as a phosphate dispersant were mixed, and the solvent was removed under vacuum and reduced pressure to obtain a 43 wt% titania-monomer dispersion.

[Comparative Example 1]

Preparation of dispersions with uncontrolled conductivity

A titania-THF dispersion was prepared in the same manner as in Example 1, except that 0.5 mol% of sodium diphosphate (SDP), a phosphate-based dispersing agent, was added instead of the buffer solution of Example 1.

Thereafter, the titania-THF dispersion, the acrylate resin monomer, and the silane surface treatment agent were mixed, and the solvent was removed under vacuum and reduced pressure to obtain a 43 wt% titania-monomer dispersion.

[Comparative Example 2]

Preparation of dispersions with uncontrolled conductivity

A titania-THF dispersion was prepared in the same manner as in Example 1, except that 1 mol% of sodium diphosphate (SDP), a phosphate-based dispersing agent, was added instead of the buffer solution of Example 1.

Thereafter, the titania-THF dispersion, the acrylate resin monomer, and the silane surface treatment agent were mixed, and the solvent was removed under vacuum and reduced pressure to obtain a 43 wt% titania-monomer dispersion.

[Comparative Example 3]

Preparation of dispersions with uncontrolled conductivity

A titania-monomer dispersion was prepared in the same manner as in Example 1, except that 22.16 g of NH ₄ HCO ₃ (Ammonium bicarbonate) was added as a buffer solution.

Thereafter, the titania-THF dispersion, acrylate resin monomer, silane surface treatment agent, and phosphate dispersant sodium diphosphate (SDP) were mixed, and the solvent was removed under vacuum and reduced pressure to obtain a 43 wt% titania-monomer dispersion.

[Comparative Example 4]

Preparation of dispersions with uncontrolled conductivity

A titania-monomer dispersion was prepared in the same manner as in Example 1, except that 23.85 g of NH ₄ HCO ₃ (Ammonium bicarbonate) was added as a buffer solution.

Thereafter, the titania-THF dispersion, acrylate resin monomer, silane surface treatment agent, and phosphate dispersant sodium diphosphate (SDP) were mixed, and the solvent was removed under vacuum and reduced pressure to obtain a 43 wt% titania-monomer dispersion.

Fig. 1 is an X-ray diffraction result showing the anatase crystal structure of titania particles and titania particles according to an embodiment of the present invention. As shown in Fig. 1, it was confirmed that the titania particles according to an embodiment of the present invention mostly have an anatase crystal structure.

FIG. 2 is a SEM image of titania particles according to Example 1 of the present invention, and FIG. 3 is a TEM image of titania particles manufactured in Example 1 of the present invention. As shown in FIGS. 2 and 3, it can be seen that the titania particles according to Example 1 of the present invention are well synthesized with uniform sizes.

Table 1 below shows the conductivity, pH, refractive index (R.I.), yellowness (Y.I.), and viscosity of dispersions according to Example 1 and Comparative Examples 1 to 4 of the present invention, and FIG. 4 shows an image of the dispersion of Example 1 of the present invention, and FIG. 5 shows an image of the dispersion of Comparative Example 1 of the present invention.

Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 conductivity
(μS/cm) Before synthesis 7.1 10.9 13.6 9.4 14.0 After synthesis 39.8 79.5 104.9 112.3 132.4 pH Before synthesis 7.24 7.00 6.87 7.09 7.03 After synthesis 9.97 9.73 9.22 9.39 9.02 Refractive index (R.I.) 1.703 1.701 1.70 1.706 1.707 Yellowness (Y.I.) 2.03 2.11 2.29 2.32 2.38 Viscosity (cP) 472 916 996.2 408.4 676.1

Looking at Table 1, Figures 4 and 5, the pH, yellowness (Y.I.) and viscosity of the optical film were observed, and it was confirmed that as the conductivity after synthesis decreased, the pH increased, the viscosity improved, and the yellowness (Y.I.) also improved. This shows that there are changes in pH and conductivity due to the degree of decomposition of the buffer solution, and that the yellowness decreases accordingly.

As shown in Table 1, Examples 1 and 2 of the present invention can provide an inorganic oxide particle-containing dispersion composition having improved viscosity while maintaining an ultra-high refractive index and reducing yellowing by controlling electrical conductivity.

[Example 2]

Conductivity controlled titania-zinc oxide (TiO ₂ Manufacturing of @ZnO

Zinc Nitrate Hexahydrate was added to 400 mL of DI water in a 1 L flask and mixed at room temperature for 10 minutes. The same TiO ₂ powder as in Example 1 was added at a molar ratio of TiO ₂ :ZnO of 1:1 and mixed at room temperature for 10 minutes. Then, 0.1 M NaOH was added and mixed at room temperature for 5 hours. After mixing for 5 hours, the mixture was reacted at 97 ° C for 3 hours. After the reaction was completed, the mixture was washed 5 times with DI water and acetone solvent using a centrifuge and dried at room temperature for 12 hours to obtain titania-ZnO powder (TiO ₂ @ ZnO) is obtained.

Conductivity controlled titania-zinc oxide (TiO ₂ @ZnO)-Preparation of monomer dispersion

26.5 g of tetrahydrofuran (THF) and 3.5 g of silane were added to a paint shaker container with a capacity of 125 mL and mixed at a temperature of 25°C for 5 minutes. Then, 20 g of titania-ZnO powder (TiO ₂ @ ZnO) was added, and a mixture was formed at a temperature of 25 ℃ for 30 minutes. Thereafter, a phosphoric acid-based surface treatment agent as a high molecular weight surface treatment agent was added to the mixture, and 100 g of 0.05 mm beads were added and dispersed for 3 hours using a paint shaker to obtain a titania-THF dispersion. Thereafter, the titania-THF dispersion, an acrylate-based resin monomer, and a silane-based surface treatment agent were mixed, and the solvent was removed under vacuum and reduced pressure to obtain a titania-monomer dispersion.

[Example 3]

Conductivity-controlled titania-containing three-composite particles (TiO ₂ @ZnO+ZrO ₂ )-Preparation of monomer dispersion

The titania-zinc oxide (TiO ₂ @ZnO)-monomer dispersion of Example 2 and the zirconia (ZrO ₂ )-monomer dispersion of Comparative Example 5 below were mixed.

[Comparative Example 5]

Zirconia (ZrO ₂ )-Preparation of monomer dispersion

In a 125 mL paint shaker container, 27.5 g of tetrahydrofuran (THF) and 2.5 g of silane were placed and mixed at 25°C for 5 minutes. Thereafter, 20 g of zirconia powder was added to the solution, and a mixture was formed at 25°C for 30 minutes. Thereafter, a phosphoric acid-based surface treatment agent as a high molecular weight surface treatment agent was added to the mixture, and 100 g of 0.05 mm beads were added and dispersed using a paint shaker for 3 hours to obtain a zirconia-THF dispersion. Thereafter, the zirconia-THF dispersion, an acrylate-based resin monomer, and a silane-based surface treatment agent were mixed, and the solvent was removed under vacuum and reduced pressure to obtain a zirconia-monomer dispersion.

Table 2 below shows the refractive index (R.I.), yellowness (Y.I.), and viscosity of monomer dispersion compositions according to Examples 2, 3, and Comparative Example 5 of the present invention.

Example 2 Example 3 Comparative Example 5 Refractive index (R.I.) 1.702 1.700 1.700 Yellowness (Y.I.) 1.71 1.52 1.55 Viscosity (cP) 550 1510 3500

FIG. 6 is an image of monomer dispersion compositions according to Examples 1 to 3 and Comparative Example 5 of the present invention. Referring to FIG. 6, it can be confirmed that the yellowness (YI) gradually improves as the dispersion composition containing conductivity-controlled TiO ₂ particles contains composite particles and mixed particles of conductivity-controlled titania, and that the refractive index at this time is 1.7 or higher and the viscosity is 2,000 cP or lower. However, in the case of Comparative Example 5, although the yellowness (YI) value is low, it can be seen that the viscosity of the dispersion composition having a refractive index of 1.7 or higher is significantly high, resulting in poor compatibility.

Although the embodiments have been described with limited drawings as described above, those skilled in the art can apply various technical modifications and variations based on the above. For example, even if the described techniques are performed in a different order than the described method, and/or the described components are combined or combined in a different form than the described method, or are replaced or substituted by other components or equivalents, appropriate results can be achieved.

Therefore, other implementations, other embodiments, and equivalents to the claims are also included in the scope of the claims described below.

Claims (21)

Inorganic oxide particle dispersion; and
Monomer of acrylate resin;
In an inorganic oxide particle-containing dispersion composition comprising:
The above inorganic oxide particle dispersion contains inorganic oxide particles,
The above inorganic oxide particles contain titanium oxide and have an anatase crystal structure.
The conductivity of the above inorganic oxide particle dispersion is 1 μS/cm to 20,000 μS/cm,
The refractive index of the above inorganic oxide particle-containing dispersion composition is 1.70 or more, and the viscosity is 2,000 cP or less.
A dispersion composition containing inorganic oxide particles.
In the first paragraph,
The above inorganic oxide particle dispersion further comprises second inorganic oxide particles,
The second inorganic oxide particle is different from the inorganic oxide particle.
A dispersion composition containing inorganic oxide particles.
In the second paragraph,
The above inorganic oxide particles and the second inorganic oxide particles are, respectively, TiO ₂ , BaTiO ₃ , SrTiO ₃ , BaTiO ₃ , PbTiO ₃ , A composition comprising at least one selected from the group consisting of PbZrO ₃ , Pb(Zr,Ti)O ₃ (PZT), Pb _1-x La _x Zr _1-y Ti _y O ₃ (PLZT), PB(Mg ₃ Nb _2/3 )O ₃ ^- PbTiO ₃ (PMN-PT), hafnia (HfO ₂ )SrTiO ₃ , Al ₂ O ₃ , ZrO ₂ , SiO ₂ , CeO ₂ , ZnO, BN and V ₂ O ₅ .
A dispersion composition containing inorganic oxide particles.
In the second paragraph,
The diameters of the above inorganic oxide particles and the second inorganic oxide particles are each 1 nm to 500 nm,
The specific surface areas of the above inorganic oxide particles and the second inorganic oxide particles are, respectively, 1 m ² /g to 250 m ² /g,
The above inorganic oxide particles and the second inorganic oxide particles each account for 30 wt% to 50 wt% of the inorganic oxide particle-containing dispersion composition.
A dispersion composition containing inorganic oxide particles.
delete In the first paragraph,
The above inorganic oxide particles include titania surface-treated with an inorganic oxide.
A dispersion composition containing inorganic oxide particles.
In the first paragraph,
The above inorganic oxide particle dispersion further comprises a buffer solution;
The above buffer solution comprises at least one selected from the group consisting of potassium bicarbonate, ammonium acetate, sodium acetate, potassium acetae, ammonium phosphate, sodium phosphate, potassium phosphate, ammonium carbonate, ammonium bicarbonate, sodium bicarbonate, sodium carbonate, potassium carbonate, triethylammonium bicarbonate, ammonium chloride, and ammonium hydroxide.
A dispersion composition containing inorganic oxide particles.
In the first paragraph,
The pH of the above inorganic oxide particle dispersion is in the range of 9.5 to 11.
A dispersion composition containing inorganic oxide particles.
In the first paragraph,
The above inorganic oxide particle dispersion is hydrophilic solvent-free.
A dispersion composition containing inorganic oxide particles.
In the first paragraph,
The monomer of the above acrylate resin includes at least one selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, sec-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, and tetradecyl (meth)acrylate.
A dispersion composition containing inorganic oxide particles.
In the first paragraph,
The monomer of the above acrylate resin is 45 wt% to 65 wt% of the inorganic oxide particle-containing dispersion composition.
A dispersion composition containing inorganic oxide particles.
In the first paragraph,
The above inorganic oxide particle dispersion is,
Additives including a silica-based surface treatment agent, a phosphate-based dispersant, or both;
The above inorganic oxide particle dispersion contains inorganic oxide particles surface-treated with the silica-based surface treatment agent,
The above silica-based surface treatment agent comprises at least one selected from the group consisting of silane, alkyl silane having 1 to 20 carbon atoms, alkyloxy silane, alkoxy silane, isocyanate silane, amino silane, epoxy silane, acrylic silane, mercapto silane, fluorine silane, methacroxy silane, vinyl silane, phenyl silane, chloro silane and silazane.
The above silica-based surface treatment agent is included in an amount of 10 to 25 parts by weight per 100 parts by weight of the inorganic oxide particles.
The above silica-based surface treatment agent is 5 to 20 wt% of the inorganic oxide particle-containing dispersion composition,
The above phosphate dispersant comprises at least one selected from the group consisting of sodium diphosphate, sodium orthophosphate, sodium pyrophosphate, potassium pyrophosphate, sodium tripolyphosphate, sodium metaphosphate, sodium acid phosphate, sodium acid pyrophosphate, orthophosphate, metaphosphate, pyrophosphate, fluorophosphate, tripolyphosphate, tetrapolyphosphate and sodium hexametaphosphate.
The above phosphate-based dispersant is included in an amount of 10 to 20 parts by weight per 100 parts by weight of the inorganic oxide particles.
The above phosphate-based dispersant is 5 to 20 wt% of the inorganic oxide particle-containing dispersion composition.
A dispersion composition containing inorganic oxide particles.
delete In the first paragraph,
The above-mentioned inorganic oxide particle-containing dispersion composition has a yellowness index (YI) of 2.2 or less.
A dispersion composition containing inorganic oxide particles.
A molded article manufactured from a dispersion composition containing inorganic oxide particles according to any one of claims 1 to 4, 6 to 12, and 14.
In Article 15,
The above-mentioned molded body is a film or sheet,
Molded body.
A step of preparing a dispersion of inorganic oxide particles; and
A step of adding and mixing a monomer of an acrylate resin to the above-mentioned inorganic oxide particle dispersion;
Including,
The step of preparing the above inorganic oxide particle dispersion is:
A step of preparing an inorganic gel dispersion by adding a buffer solution to an inorganic precursor;
A step of preparing a mixture by mixing a silica-based surface treatment agent, a phosphate-based dispersant, or both into the above-mentioned inorganic gel dispersion; and
A step of heat treating the above mixture at a temperature of 25 ℃ to 100 ℃;
which includes,
A method for producing a dispersion composition containing inorganic oxide particles.
delete In Article 17,
The above inorganic precursor further comprises a second inorganic precursor,
The second inorganic precursor is different from the above inorganic precursor,
A method for producing a dispersion composition containing inorganic oxide particles.
In Article 17,
After the step of preparing a mixture by mixing a silica-based surface treatment agent, a phosphate-based dispersant, or both into the above-mentioned inorganic gel dispersion,
A step of drying the above mixture at a temperature of 25 ℃ to 100 ℃;
Including more,
A method for producing a dispersion composition containing inorganic oxide particles.
In Article 17,
After the step of adding and mixing the monomer of the acrylate resin to the above-mentioned inorganic oxide particle dispersion,
Step of removing the solvent;
Including more,
A method for producing a dispersion composition of inorganic oxide.

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