KR20210025989A - Method for preparing surface-treated titania particle, surface-treated titania particle theby, titania particle-dispersion composition and composition for coating - Google Patents

Abstract

The present invention relates to a production method of surface-treated titania particles having high thermal stability, to surface-treated titania particles produced thereby, to a titania particle-dispersion composition, and to a composition for a film. The production method of surface-treated titania particles according to an embodiment of the present invention comprises a step of performing surface-treatment by mixing a phosphate-based surface treatment agent and treating the surfaces of the titania particles with the same.

Description

Manufacturing method of surface-treated titania particles, surface-treated titania particles produced thereby, titania particles-dispersion composition and composition for films AND COMPOSITION FOR COATING}

The present invention relates to a method for preparing a surface-treated titania particle, a surface-treated titania particle, titania particle-dispersion composition, and a composition for a film produced thereby.

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 region. Recently, high refractive 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, and it is difficult to use only polymer materials, research is being conducted to mix and disperse an inorganic material (n = 1.5 to 2.7) having a high refractive index in the polymer.

Materials used as high refractive inorganic materials are TiO ₂ (n=2.5~2.7), ZrO ₂ (n=2.1~2.2), ZnO(n=2.0), SnO ₂ (n=2.0), SiO ₂ (n=1.5) Materials such as are commonly used. In particular, TiO ₂ has a high refractive index, is non-toxic, and is inexpensive, so it is the most commonly used high refractive inorganic material. However, TiO ₂ has a disadvantage in that it has a yellow color when prepared as a film, and is limited in commercial use because the Abbe number representing the degree of dispersion decreases as the content of _{TiO 2 increases.} In particular, in _{the case of TiO 2} , a yellowing phenomenon occurs during film production, and thus, when applied to a display, there is a problem in that the color feel and visibility are deteriorated. In addition, other high refractive inorganic materials such as ZnO, SnO ₂ , SiO ₂ have disadvantages that the refractive index is significantly lower and the price is high.

In addition, in order to manufacture a polymer composite including a high refractive inorganic material, it is necessary to contain a high content of a high refractive inorganic material. In general, high refractive inorganic sols are prepared through stirring by adding a catalyst to an inorganic precursor having high refractive index in an aqueous solution, and such a high refractive sol has difficulty in adding a high content inorganic material as well as unstable phase and opacity. For this reason, it is difficult to manufacture a uniform film.

Titania (TiO ₂ ) has recently been greatly increased in the range of applications such as improvement of indoor air quality using photocatalytic properties, nitrogen oxide removal through road pavement, photocatalytic coating of structures, and sterilization systems in hospitals. However, there is a growing need for an optical composition that uses a high dielectric constant of titania, but can have a high refractive index, low yellowing property, and low viscosity by synthesizing composite particles.

The present invention is to solve the above-described problems, and an object of the present invention is to provide a method for producing surface-treated titania particles having high thermal stability and surface-treated titania particles produced thereby.

Another object of the present invention is to provide a titania dispersant particle-titania particle-dispersion composition and a composition for a film comprising the same, which require high light scattering property and light efficiency.

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

A method of manufacturing the surface-treated titania particles according to an embodiment of the present invention includes a step of mixing a phosphate-based surface treatment agent on the surface of the titania particles to treat the surface.

In one embodiment, the phosphate-based surface treatment agent is sodium orthophosphate, sodium pyrophosphate, potassium pyrophosphate, sodium tripolyphosphate, sodium metaphosphate, acid sodium phosphate, acid sodium pyrophosphate, orthophosphate, metaphosphate, ultraphosphate, It may include at least one selected from the group consisting of pyrophosphate, fluorinated phosphate, tripolyphosphate, tetrapolyphosphate, and sodium hexametaphosphate.

In one embodiment, the phosphate-based surface treatment agent may be 0.1 mol% to 5 mol% relative to the titania particles.

In one embodiment, the surface-treated titania particles may have an average particle size of 5 nm to 100 nm.

In one embodiment, after the step of surface treatment by mixing a phosphate-based surface treatment agent on the surface of the titania particles, calcining the surface-treated titania particles at a temperature range of 700° C. to 1000° C.; I can.

In one embodiment, the average primary particle size of the surface-treated titania particles after the step of calcining the surface-treated titania particles at a temperature range of 700°C to 1000°C is 20 nm to 100 nm, and the secondary particles The average particle size may be 100 nm to 500 nm.

In one embodiment, the specific surface area of the surface-treated titania particles after the step of calcining the surface-treated titania particles in a temperature range of 700 °C to 1000 °C is 1 m ² /g to 250 m ² /g Can be.

In one embodiment, the surface-treated titania particles after the step of calcining the surface-treated titania particles at a temperature range of 700°C to 1000°C have an anatase crystal structure of 98% by weight or more in the total particles, and , The rest may exist in a rutile crystal structure.

The surface-treated titania particles according to another embodiment of the present invention are manufactured by the method of manufacturing the surface-treated titania particles according to one aspect.

A titania particle-dispersion composition according to another embodiment of the present invention includes a surface-treated titania particle according to an aspect; And an 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, trimethylphosphate, 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 mono Ethyl 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 di Ethyl 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-me Tyl-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, carbonic acid It may include at least one selected from the group consisting of butyl, benzene, toluene, xylene, cyclohexanone, ethylene glycol, diethylene glycol, tetrahydrofuran, 1,4-dioxane, and glycerin.

In one embodiment, the surface-treated titania particles may be from 30% to 50% by weight of the titania particle-dispersion composition.

Composition for a film according to another embodiment of the present invention, titania particles according to an embodiment-dispersion composition; UV photoinitiator; And UV curing monomers.

In one embodiment, the UV photoinitiator may include a photocationic initiator selected from an onium salt-based, diazonium salt-based, sulfonium salt-based compound, and an imidazole-based compound; And thioxanthone-based, phosphorus-based, triazine-based, benzophenone-based, benzoin-based, oxime-based, propanone-based, amino ketone-based, ketone-based, benzoin ether acetophenone-based, anthraquinone-based and aromatic phosphine oxide-based compound. It may include at least one selected from the group consisting of; a radical photoinitiator.

In one embodiment, the UV curing monomer is glycidyl acrylate, glycidyl methacrylate, glycidyl methacrylate, glycidyl-alpha-ethyl acrylate, glycidyl-alpha-ene -Propyl acrylate, glycidyl-alpha-butyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxybutyl acrylate, 6,7-epoxypeptyl methacrylate, 6,7-epoxyheptyl Acrylate, 6,7-epoxyheptyl-alpha-ethylacrylate, 2 Hydroxy propyl acrylate (2HPA), 2 Hydroxy ethylacrylate (2HEA), tetrahydrofurfuryl acrylic Tetrahydrofurfuryl acrylate (THFA), Isobonyl acrylate (IBOA), 2 Hydroxy ethyl methacrylate (2HEMA), Tripropylene glycol diacrylate (TPGDA), D At least selected from the group consisting of propylene glycol diacrylate (DPGDA), 1,6 hexanediol diacrylate (1,6 Hexanediol diacrylate; 1,6HDDA) and trimethylopropane triacrylate (TMPTA) It may include any one.

In one embodiment, the refractive index of the film composition may be 1.70 or more, and the viscosity of the film composition may be 1000 cPs or less.

A film according to another embodiment of the present invention is prepared from the composition for a film according to an embodiment of the present invention.

In one embodiment, the film may have a total transmittance of 80% to 90%, a diffuse transmittance of the film of 5% to 20%, and a haze of the film of 10% to 20%.

The surface-treated titania particles produced by the method for producing surface-treated titania particles according to an embodiment of the present invention are subjected to a phase transition of titania particles from anatase to rutile through surface modification using a phosphate-based additive. It can exhibit high thermal stability that suppresses.

The titania particle-dispersion composition according to an embodiment of the present invention includes the titania particles surface-treated by including the surface-treated titania particles according to an embodiment of the present invention, so that the light stability is high and the photocatalytic property is lowered. Yellowing is suppressed, and a film exhibiting high light scattering property and light efficiency can be implemented.

1 is an X-ray diffraction result showing anatase and rutile crystal structures of titania particles subjected to phosphoric acid surface treatment according to Examples 1 to 5 and Comparative Example 2 of the present invention.
FIG. 2 is an X-ray diffraction result showing anatase and rutile crystal structures of titania particles without surface treatment, which were calcined at a temperature of 800° C. for 1 hour.
3 is an SEM image of titania particles subjected to phosphoric acid surface treatment according to Example 1 of the present invention.
4 shows the particle size distribution of titania particles subjected to phosphoric acid surface treatment according to Example 1 of the present invention.

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

The terms used in the examples are used for illustrative purposes only and should not be construed as limiting. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present specification, terms such as "comprise" or "have" are intended to designate the presence of features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, but one or more other features. It is to be understood that the presence or addition of elements or numbers, steps, actions, components, parts, or combinations thereof does not preclude in advance.

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 embodiment belongs. Terms as defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related technology, and should not be interpreted as an ideal or excessive formal meaning unless explicitly defined in this application. Does not.

In addition, in the description with reference to the accompanying drawings, the same reference numerals are assigned to the same components regardless of the reference numerals, and redundant descriptions thereof will be omitted. In describing the embodiments, when it is determined that a detailed description of related known technologies may unnecessarily obscure the subject matter of the embodiments, the detailed description thereof will be omitted.

Hereinafter, the method for preparing the surface-treated titania particles of the present invention, the surface-treated titania particles, titania particles-dispersion composition, and film composition prepared by the method of the present invention will be described in detail with reference to Examples and drawings. However, the present invention is not limited to these examples and drawings.

A method of manufacturing the surface-treated titania particles according to an embodiment of the present invention includes a step of mixing a phosphate-based surface treatment agent on the surface of the titania particles to treat the surface.

In one embodiment, the titania particles are high dielectric materials, may have a high dielectric constant, and may be fine particles having a high refractive index.

In one embodiment, the titania particles may be prepared commercially available particles, or the particles are synthesized by any one synthesis method selected from the group consisting of a sol-gel method, a hydrothermal method, a solid phase method, and a supercritical method. May be.

In one embodiment, the titania particles prepared by the sol-gel method may have thermal stability, high refractive index, and transmittance.

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

In one embodiment, the phosphate-based surface treatment agent is sodium orthophosphate, sodium pyrophosphate, potassium pyrophosphate, sodium tripolyphosphate, sodium metaphosphate, acid sodium phosphate, acid sodium pyrophosphate, orthophosphate, metaphosphate, ultraphosphate, It may include at least one selected from the group consisting of pyrophosphate, fluorinated phosphate, tripolyphosphate, tetrapolyphosphate, and sodium hexametaphosphate.

In one embodiment, the phosphate-based surface treatment agent may be 0.1 mol% to 5 mol% relative to the titania particles. When the phosphate-based surface treatment agent is less than 0.1 mol% of the titania particles, the surface modification effect for improving the dispersibility of the titania particles may be lowered, yellowing cannot be suppressed, and when it exceeds 5 mol%, phosphate Since the system surface treatment agent is not sufficiently dissolved in the solvent, the surface modification effect may decrease, and the viscosity of the dispersion may increase. The pH of the phosphate-based surface treatment agent is basic at a level of 10, and the solubility of the phosphate-based surface treatment agent may be about 6.7 g/mL (25°C). A surface treatment agent may be included.

In one embodiment, the surface-treated titania particles may have an average particle size of 5 nm to 100 nm. When the average particle size of the surface-treated titania particles is less than 5 nm, dispersion may be difficult due to an increase in the surface energy of the nanoparticles, and when it is more than 100 nm, there is a problem that the thickness of the film becomes thick.

In one embodiment, after the step of surface treatment by mixing a phosphate-based surface treatment agent on the surface of the titania particles, calcining the surface-treated titania particles at a temperature range of 700° C. to 1000° C.; I can. The rutile crystal structure is most abundantly produced in nature, and the anatase crystal structure can be applied to many fields, and is the most widely used material. For this reason, it is necessary to transform the most abundant rutile form into a stable anatase crystal structure.

In one embodiment, when the calcination temperature is less than 700° C., crystal grain growth may not occur, and when the calcination temperature is higher than 1000° C., the phase transition from an anatase crystal structure to a rutile crystal structure is suppressed. It can be difficult.

In one embodiment, the average primary particle size of the surface-treated titania particles after the step of calcining the surface-treated titania particles at a temperature range of 700°C to 1000°C is 20 nm to 100 nm, and the secondary particles The average particle size may be 100 nm to 500 nm. The diffraction degree of the surface-treated titania particles in the above range is superior to that of the single crystal particles.

In one embodiment, the specific surface area of the surface-treated titania particles after the step of calcining the surface-treated titania particles in a temperature range of 700 °C to 1000 °C is 1 m ² /g to 250 m ² /g Can be. Surface-treated titania particles having a specific surface area within the above range have little or no aggregation, or aggregation can be reduced.

In one embodiment, the surface-treated titania particles have an average primary particle size of 20 nm to 100 nm, and an average secondary particle size of 100 nm to 500 nm and a specific surface area of 1 m ² /g to 250 m ^{In the case of 2} /g, it has a high refractive index, and crystal grains grow during heat treatment, so that it may be easy to form a separated crystal grain structure.

In one embodiment, the surface-treated titania particles after the step of calcining the surface-treated titania particles at a temperature range of 700°C to 1000°C have an anatase crystal structure of 98% by weight or more in the total particles, and , The rest may exist in a rutile crystal structure. The calcined surface-treated titania particles may be maintained at a constant temperature for a time depending on the calcining treatment temperature until the rutile ratio is less than 2% by weight with respect to the total weight of the particles. In the above-mentioned constant temperature range, the time for the calcination treatment is usually 40 to 300 minutes.

Anatase titania fraction: Xa (%)=100/(1+1.265 Ir/Ia)

Rutile titania fraction: Xr (%)=100/(1+0.8 Ia/Ir)

Ia: Anatase particle XRD Intensity (2θ: ~25.4˚), Ir: Rutile particle XRD Intensity (2θ: ~27.5˚)

The surface-treated titania particles according to another embodiment of the present invention are manufactured by the method of manufacturing the surface-treated titania particles according to one aspect.

The surface-treated titania particles according to an embodiment of the present invention may have thermal stability, high refractive index, and transmittance.

A titania particle-dispersion composition according to another embodiment of the present invention includes a surface-treated titania particle according to an aspect; And an organic solvent;

The titania particle-dispersion composition according to an embodiment of the present invention may improve yellowing of the dispersion composition and film by including the surface-treated titania particles according to an embodiment of the present invention.

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, trimethylphosphate, 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 mono Ethyl 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 di Ethyl 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-me Tyl-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, carbonic acid It may include at least one selected from the group consisting of butyl, benzene, toluene, xylene, cyclohexanone, ethylene glycol, diethylene glycol, tetrahydrofuran, 1,4-dioxane, and glycerin.

In one embodiment, the surface-treated titania particles may be from 30% to 50% by weight of the titania particle-dispersion composition. When the surface-treated titania particles are less than 30% by weight of the titania particles-dispersion composition, the relative proportion of particles in the dispersion decreases, so that the refractive index and luminance of the dispersion may decrease, and when it exceeds 50% by weight, the yellowish film is yellowish. ) Appears.

Composition for a film according to another embodiment of the present invention, titania particles according to an embodiment-dispersion composition; UV photoinitiator; And UV curing monomers.

In one embodiment, the UV photoinitiator may include a photocationic initiator selected from an onium salt-based, diazonium salt-based, sulfonium salt-based compound, and an imidazole-based compound; And thioxanthone-based, phosphorus-based, triazine-based, benzophenone-based, benzoin-based, oxime-based, propanone-based, amino ketone-based, ketone-based, benzoin ether acetophenone-based, anthraquinone-based and aromatic phosphine oxide-based compound. It may include at least one selected from the group consisting of; a radical photoinitiator.

In one embodiment, the photoinitiator may include a photocationic initiator, a radical photoinitiator, or both.

In one embodiment, the photocationic initiator may include at least one selected from the group consisting of an onium salt-based, a diazonium salt-based, a sulfonium salt-based compound, and an imidazole-based compound. For example, the photocationic initiator, diphenyliodonium, 4-methoxydiphenyliodonium, bis (4-methylphenyl) iodonium (bis (4-methylphenyl) iodonium), bis (4-tert-butylphenyl) iodonium (bis(4-tert-butylphenyl)iodonium), bis(dodecylphenyl)iodonium (bis(dodecylphenyl)iodonium), (4-methylphenyl)[(4-(2- Diaryliodonium, such as methylpropyl)phenyl)iodonium (4-methylphenyl)[(4-(2-methylpropyl)phenyl)iodonium], triphenylsulfonium, diphenyl-4-thiophenylphenylsulfonium Triarylsulfoniums such as (diphenyl-4-thiophenylphenylsulfonium) and diphenyl-4-thiophenoxyphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide ( bis [4- (diphenylsulfonio) phenyl] sulfide) of a cation and hexafluoro such as phosphate (PF ₆ ^-), tetrafluoroborate (BF ₄ ^-), anti-hexafluoro-Mo carbonate (SbF ₆ ^-), hexafluorophosphate are Senate (AsF ₆ ^-), hexachloro antimonate (SbCl ₆ ^-), and onium salts containing anions such as, triarylsulfonium perfluoroalkyl sulfonate, triarylsulfonium triflate, triaryl alcohol It may be phonium nonaflate, diaryliodonium nonaflate, succinimidyl triflate, 2,6-dinitrobenzyl sulfonate, and the like, but is not limited thereto.

In one embodiment, a photocationic initiator; And thioxanthone-based, phosphorus-based, triazine-based, benzophenone-based, benzoin-based, oxime-based, propanone-based, amino ketone-based, ketone-based, benzoin ether acetophenone-based, anthraquinone-based and aromatic phosphine oxide-based compound. It may include at least one selected from the group. For example, the radical photoinitiator is benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylanino acetophenone , 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone , 2-hydroxy-2-methyl-1-phenylpropan-1one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane- 1-one, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, benzophenone, 4,4-diaminobenzophenone, p-phenylbenzophenone, 4,4' -Diethylaminobenzophenone, 4,4-dimethoxyacetophenone, dichlorobenzophenone, 3-methylacetophenone, 4-chronoloacetophenone, anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2- t-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, Benzyldimethylketal, acetophenone dimethylketal, p-dimethylamino benzoic acid ester, oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone], bis(2,4, 6-trimethylbenzoyl)-phenyl-phosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]2-morpholinepropanone- 1, diphenyl ketone benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenyl-1-one, 4-hydroxycyclophenyl ketone, dimethoxy-2-phenylatetophenone, fluorene, triphenylamine , Carbazole, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone, 2-benzyl-2- (Dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone, benzoin methyl ether, benzoin isopropyl ether, anisoin methyl ether, 2-methyl-2-hydroxypropy Ophenone, bis (2, 4, 6-trimethylbenzoyl) phenyl phosphine oxide, 2-naphthalene-sulfonyl chloride, 1-phenyl-1,2-propanedione-2 ( O-ethoxycarbonyl) oxime, and the like, but is not limited thereto.

In one embodiment, the mass ratio of the photocationic initiator to the radical photoinitiator may be a mixture of 99:0.1 to 0.1:99. When included in the mixing ratio, it is possible to absorb various wavelengths to promote reactivity to increase curing speed, and to improve light transmittance and curl properties after curing of the coating composition.

In one embodiment, the photoinitiator may be 2% to 5% by weight of the coating composition. If the photoinitiator is less than 2% by weight of the coating composition, it is difficult to secure adequate hardness due to insufficient curing of the coating composition, and if it exceeds 5% by weight, cracks and cracks after curing of the coating composition due to curing shrinkage Peeling, etc. may occur.

In one embodiment, the UV curing monomer may include an acrylate-based resin.

According to one aspect, as the UV curing monomer, the acrylate-based resin may be one that maintains high transmittance and low haze as an optical pressure-sensitive adhesive, and may have corrosion resistance to ITO.

According to one aspect, the acrylate-based resin is a saturated hydrocarbon-based polymer without intramolecular double bonds, and has excellent resistance to oxidation in terms of its inherent properties, and thus may have excellent weather resistance.

In one embodiment, the UV curing monomer is an example of a UV coating used in an optical film, etc., and a photoinitiator is activated by ultraviolet rays to crosslink the oligomer and the monomer to form a coating film, and low temperature curing is possible, If the curing speed is fast, it is not particularly limited.

In one embodiment, the UV curing monomer is glycidyl acrylate, glycidyl methacrylate, glycidyl methacrylate, glycidyl-alpha-ethyl acrylate, glycidyl-alpha-ene -Propyl acrylate, glycidyl-alpha-butyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxybutyl acrylate, 6,7-epoxypeptyl methacrylate, 6,7-epoxyheptyl Acrylate, 6,7-epoxyheptyl-alpha-ethylacrylate, 2 Hydroxy propyl acrylate (2HPA), 2 Hydroxy ethylacrylate (2HEA), tetrahydrofurfuryl acrylic Tetrahydrofurfuryl acrylate (THFA), Isobonyl acrylate (IBOA), 2 Hydroxy ethyl methacrylate (2HEMA), Tripropylene glycol diacrylate (TPGDA), D At least selected from the group consisting of propylene glycol diacrylate (DPGDA), 1,6 hexanediol diacrylate (1,6 Hexanediol diacrylate; 1,6HDDA) and trimethylopropane triacrylate (TMPTA) It may include any one.

The composition for a film according to an embodiment of the present invention may improve the color of the film from yellowing.

In one embodiment, the composition for a film may further include an acrylic resin.

In one embodiment, the acrylic resin is hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), hexanediol diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA), ethylene Glycol diacrylate (EGDA), trimethylolpropane triacrylate (TMPTA), trimethylolpropaneethoxy triacrylate (TMPEOTA), glycerin propoxylated triacrylate (GPTA), pentaerythritol tetraacrylate (PETA) , Benzyl methacrylate, phenyl acrylate, diphenyl acrylate, biphenyl acrylate, 2-biphenylyl acrylate, 2-([1,1'-biphenyl]-2-yloxy)ethyl acrylate, Phenoxybenzylacrylate, 3-phenoxybenzyl-3-(1-naphthyl)acrylate, phenylmethacrylate, biphenylmethacrylate, 2-nitrophenylacrylate, 4-nitrophenylacrylate, 2- It may include at least one selected from the group consisting of nitrophenyl methacrylate, 4-nitrophenyl methacrylate, and dipentaerythritol hexaacrylate (DPHA).

In one embodiment, the acrylic resin may preferably have 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. If the glass transition temperature is within this range, the titania particle-dispersion composition of the present invention can be improved in yellowing.

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

In one embodiment, the acrylic resin may be 50% to 70% by weight of the titania particle-dispersion composition. If the acrylic resin is less than 50% by weight of the titania particle-dispersion composition, the content of the particles in the dispersion system may increase, resulting in a problem of increasing the viscosity of the dispersion, and if it exceeds 70% by weight, the content of the particles is lowered to form a film. There is a problem that the refractive index and luminance characteristics of the image are deteriorated.

In one embodiment, by blending the acrylic resin, a titania particle-dispersion composition and film excellent in moldability, processability, and mechanical properties can be obtained.

In one embodiment, the refractive index of the film composition may be 1.70 or more, and the viscosity of the film composition may be 1000 cPs or less. By including the surface-treated titania particles, yellowing is suppressed, and a film exhibiting high light scattering property and light efficiency can be implemented.

A film according to another embodiment of the present invention is prepared from the composition for a film according to an embodiment of the present invention.

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

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 limited thereby.

[Production Example]

Phosphoric acid surface-treated titania particle dispersion preparation

In a 250 mL container for a paint shaker, 50 g of tetrahydrofuran (THF) and 5 g (12.5 content%) of methacrylic silane were added as a coupling agent, and 5 g of a dispersant was added.

The solution was mixed for 5 minutes using a stirrer bar at a temperature of 25 °C.

Thereafter, 40 g of phosphoric acid surface-treated titania was added to the mixture, and a 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 mixed solution further containing titania and dispersed for 3 hours using a paint shaker to obtain a titania-THF dispersion.

In this case, the bead is zirconia having a size of 0.05 mm.

Thereafter, a titania-THF dispersion and an acrylate-based resin monomer were mixed to remove the solvent under vacuum to obtain a titania-monomer dispersion of 43 wt%.

[Example 1]

The phosphoric acid surface-treated titania particles prepared in Preparation Example were calcined for 1 hour at a temperature of 800°C.

[Example 2]

The phosphoric acid surface-treated titania particles prepared in Preparation Example were calcined for 3 hours at a temperature of 750°C.

[Example 3]

The phosphoric acid surface-treated titania particles prepared in Preparation Example were calcined for 2 hours at a temperature of 800°C.

[Example 4]

The phosphoric acid surface-treated titania particles prepared in Preparation Example were calcined for 3 hours at a temperature of 800°C.

[Example 5]

The phosphoric acid surface-treated titania particles prepared in Preparation Example were calcined for 2 hours at a temperature of 900°C.

[Comparative Example 1]

The titania particles without phosphoric acid surface treatment were calcined for 1 hour at a temperature of 800°C.

[Comparative Example 2]

The phosphoric acid surface-treated titania particles prepared in Preparation Example were calcined for 2 hours at a temperature of 1000°C.

The phosphoric acid surface-treated titania particles after calcining according to Examples 1 to 5 are grown of colon particles so that the primary particle average particle size is 20 nm to 100 nm, and the secondary particle average particle size dispersed in the organic solvent is 100 nm to It was 500 nm.

1 is an X-ray diffraction result showing the anatase and rutile crystal structures of titania particles subjected to phosphoric acid surface treatment according to Examples 1 to 5 and Comparative Example 2 of the present invention, and FIG. 2 is a temperature of 800° C. for 1 hour. X-ray diffraction results showing the anatase and rutile crystal structures of titania particles without calcined surface treatment.

3 is an SEM image of titania particles subjected to phosphoric acid surface treatment according to Example 1 of the present invention, and Table 1 below is an XRD particle size, BET, and SEM image of titania particles subjected to phosphoric acid surface treatment according to Example 1 of the present invention. It shows the phase particle size.

Crystal structure XRD
(nm) BET
(nm) SEM
(nm) Anatase 27.1 102.3 50-140

4 shows the particle size distribution of titania particles subjected to phosphoric acid surface treatment according to Example 1 of the present invention.

As shown in Figs. 1 to 4, it was confirmed that most of the anatase crystal structures having an average particle size of 20 nm to 500 nm were found, and the diffraction degree of the P-surface-treated titania particles was superior to that of the titania particles. I could confirm.

1 to 4, it can be seen that the titania particles exhibit high thermal stability for suppressing the phase transition from anatase to rutile through surface modification using a phosphate-based additive.

The titania particle-dispersion composition of Example 1 of the present invention was mixed with 20% by weight as a UV photoinitiator and 50% by weight as a UV curing monomer and mixed for 30 minutes using a stirrer bar to prepare a coating coating. . The resulting product was coated for a PET film using a bar coater and then UV cured to measure film properties.

Powder analysis (specific surface area, particle size) of titania particles used in Comparative Examples 1 to 2 and Example 1 in Table 2, physical properties (viscosity, particle CR, NV) and film properties (total transmittance) of the dispersion to which titania particles are applied , Diffusion transmittance, Haze) were summarized.

Powder analysis Dispersion properties Film properties TiO ₂
particle Specific surface area
(m ² /g) Particle size
(BET, nm) Viscosity
(cP) particle
CR
(nm) NV
(%) all
Transmittance
(%) diffusion
Transmittance
(%) Haze
(%) Comparative example
One _{TiO 2} without surface treatment 1.09 1456.3 <10cp 514 27 89.2 3.4 3.9 Comparative example
2 P-surface treated TiO ₂ 1.26 1119 <10cp 840 16 90.3 1.4 1.5 Example
One P-surface treated TiO ₂ 13.86 102.3 <10cp 145 45 84.2 13.5 16.0 Example
2 P-surface treated TiO ₂ 18.57 85 <10cp 119 43 86.1 8.8 10.2

NV is an abbreviation of non-volatile, and is used as solid, solid, non-volatile, active, etc., and refers to the remaining powder content (non-volatile) when the solvent is volatilized by applying heat to the dispersion. You can check the wt% of the particles. It is judged that the higher the recovery rate of the powder put in the dispersion, the better the dispersion, and in Table 1, 50% was put as the target, so the closer to 50%, the better the dispersibility 　.

_{Referring to Table 2, it can be seen that in the case of TiO 2 that} is not surface-treated, the particle size is too large, so that the dispersibility is reduced under the same dispersion conditions as the surface-treated particles of the present invention (low CR value, NV value). In addition, it can be seen that the non-surface-treated TiO ₂ exhibits a high transmittance due to a low TiO _{2 content and a low haze value.}

Comparative Example 2 is a powder obtained by calcining the phosphoric acid surface-treated titania particles prepared in Preparation Example at a temperature of 1000° C. for 2 hours, and referring to the graph of FIG. 1, it was confirmed that the particles were phase-transferred to rutile. I can. As shown in Table 2, Comparative Example 2 exhibits a high C.R value and a low NV value because the dispersibility is poor. It can be seen that the diffusion transmittance and haze value are low, indicating low dispersibility and low light scattering property.

As described above, although the embodiments have been described by the limited drawings, a person of ordinary skill 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 from the described method, and/or the described components are combined or combined in a form different from the described method, or are replaced or substituted by other components or equivalents. Appropriate results can be achieved.

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

Claims (18)

Surface treatment by mixing a phosphate-based surface treatment agent on the surface of the titania particles;
Containing,
Method for producing surface-treated titania particles.
The method of claim 1,
The phosphate-based surface treatment agents include sodium orthophosphate, sodium pyrophosphate, potassium pyrophosphate, sodium tripolyphosphate, sodium metaphosphate, acid sodium phosphate, acid sodium pyrophosphate, orthophosphate, metaphosphate, ultraphosphate, pyrophosphate, fluorophosphate, Tripolyphosphate, tetrapolyphosphate, and sodium hexametaphosphate containing at least any one selected from the group consisting of,
Method for producing surface-treated titania particles.
The method of claim 1,
The phosphate-based surface treatment agent,
It is 0.1 mol% to 5 mol% relative to the titania particles,
Method for producing surface-treated titania particles.
The method of claim 1,
The surface-treated titania particles have an average particle size of 5 nm to 100 nm,
Method for producing surface-treated titania particles.
The method of claim 1,
After the step of surface treatment by mixing a phosphate-based surface treatment agent on the surface of the titania particles,
Calcining the surface-treated titania particles at a temperature range of 700°C to 1000°C;
Further comprising,
Method for producing surface-treated titania particles.
The method of claim 5,
After the step of calcining the surface-treated titania particles at a temperature range of 700°C to 1000°C, the average primary particle size of the surface-treated titania particles is 20 nm to 100 nm, and the secondary particle average particle size is 100 nm to 500 nm,
Method for producing surface-treated titania particles.
The method of claim 5,
The specific surface area of the surface-treated titania particles after the step of calcining the surface-treated titania particles at a temperature range of 700° C. to 1000° C. is 1 m ² /g to 250 m ² /g,
Method for producing surface-treated titania particles.
The method of claim 5,
The surface-treated titania particles after the step of calcining the surface-treated titania particles at a temperature range of 700°C to 1000°C have an anatase crystal structure of 98% by weight or more in the total particles, and the remainder is rutile ( rutile) exists as a crystal structure,
Method for producing surface-treated titania particles.
Surface-treated titania particles produced by the method for producing surface-treated titania particles according to any one of claims 1 to 8.
The surface-treated titania particles of claim 9; And
Organic solvent;
Containing,
Titania particle-dispersion composition.
The method of claim 10,
The organic solvent is ethanol (EtOH), methanol (MeOH), propanol (PrOH), butanol (BuOH), isopropyl alcohol (IPA), isopropyl alcohol propanol, isobutyl alcohol, hexanol, cyclohexanol, dimethylacet Amide (DMAC), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), triethylene phosphate (Triethylphosphate), trimethylphosphate, 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 mono Propyl 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 mono Methyl 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-methoxy Butyl 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 T, 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, toluene, xyl It contains at least any one selected from the group consisting of ene, cyclohexanone, ethylene glycol, diethylene glycol, tetrahydrofuran, 1,4-dioxane and glycerin,
Titania particle-dispersion composition.
The method of claim 10,
The surface-treated titania particles are from 30% to 50% by weight of the titania particle-dispersion composition,
Titania particle-dispersion composition.
The titania particle-dispersion composition of claim 10;
UV photoinitiator; And
UV curing monomer;
Containing,
Composition for films.
The method of claim 13,
The UV photoinitiator,
Photocationic initiators selected from onium salts, diazonium salts, sulfonium salt compounds and imidazoles; And
Thioxanthone, phosphorus, triazine, benzophenone, benzoin, oxime, propanone, amino ketone, ketone, benzoin ether acetophenone, anthraquinone, and aromatic phosphine oxide compounds. Radical photoinitiators;
It includes at least any one selected from the group consisting of,
Composition for films.
The method of claim 13,
The UV curing monomer,
Glycidyl acrylate, glycidyl methacrylate, glycidyl methacrylate, glycidyl-alpha-ethyl acrylate, glycidyl-alpha-ene-propyl acrylate, glycidyl-alpha-butylacrylic Rate, 3,4-epoxybutyl methacrylate, 3,4-epoxybutyl acrylate, 6,7-epoxypeptyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl-alpha-ethyl Acrylate, 2 Hydroxy propyl acrylate (2HPA), 2 Hydroxy ethylacrylate (2HEA), Tetrahydrofurfuryl acrylate (THFA), isobornyl acrylate ( Isobonyl acrylate; IBOA), 2 Hydroxy ethyl methacrylate (2HEMA), Tripropylene glycol diacrylate (TPGDA), Dipropylene glycol diacrylate (DPGDA), 1,6 hexanediol diacrylate (1,6 Hexanediol diacrylate; 1,6HDDA) and trimethylpropane triacrylate (Trimethylopropane triacrylate; TMPTA) containing at least any one selected from the group consisting of,
Composition for films.
The method of claim 13,
The refractive index of the composition for films is 1.70 or more,
The viscosity of the film composition is 1000 cPs or less,
Composition for films.
A film made of the composition for a film of claim 13.
The method of claim 17,
The total transmittance of the film is 80% to 90%,
The film has a diffuse transmittance of 5% to 20%,
The film has a haze of 10% to 20%,
film.

Images