Fluorescent light diffusion / low-reflection composition using hollow-fluorescent organic ligand structure, and substrate and device which use same

Abstract

The present invention provides a fluorescent light diffusion / low-reflection composition, and a substrate and a device which use same, the composition implementing both light diffusion / low reflection and fluorescence properties through a primary coating by using fluorescent hollow particles of 0.03-3 μm. A hollow silica-fluorescent organic ligand structure composition of the present invention can provide a light diffusion effect, prevention of optical properties deterioration, and optical properties (blue, red and green are all possible but, particularly, deterioration of a blue property is prevented through a blue coating).

Description

Fluorescent light diffusion / low-reflection composition utilizing hollow-fluorescent organic ligand structure and substrate and device using the same

[0001] The present disclosure relates to a fluorescent light diffusion / low-reflection composition utilizing a hollow-fluorescent organic ligand structure, a substrate and device using the same, and a method for manufacturing the same.

[0002] Conventional display devices have adopted various anti-glare treatments. One such treatment is roughening the surface of hard coating films used in polarizing plates in liquid crystal displays and hard coating films used for various display protection. Anti-glare treatment methods for hard coating films can generally be broadly divided into two: (1) a method of physically roughening the surface during curing to form a hard coating layer, and (2) a method of incorporating fillers into the hard coating agent used to form the hard coating layer. After producing an anti-glare film, a low-reflection material is further coated on its surface to produce a low-reflection anti-glare film. Of these two methods, the latter method of incorporating fillers into the hard coating agent is the mainstream, and the filler primarily used is silica particles. Silica particles are used because they not only suppress the whiteness of the hard coating film, but also do not cause a decrease in hardness and exhibit good dispersibility when mixed into the coating agent. However, recent displays are moving toward high definition to achieve high image quality, and the current anti-glare treatment methods for hard coating films are inadequate to meet this demand. While attempts are being made to incorporate aggregates of colloidal silica particles into the hard coating layer (Japanese Patent Application Laid-Open No. 10-180950), higher clarity is still desired.

[0003] AR film, short for Anti-Reflection Film, literally reduces the light reflectance of liquid crystals. Anti-glare film (AG film) aims to achieve a similar effect. While AR film achieves its effect through light interference, AG film applies a hard coating layer with particles deposited on the surface of the base film substrate, creating a surface roughness and reducing the reflection of ambient light through diffuse reflection. Combining AR and AG films is also possible to further reduce the reflection of light from uneven surfaces, as well as ambient light.

[0004] Hollow silicas produced by the sol-gel method are being used. Sol-gel silica is silica obtained by removing the solvent and drying the silica sol suspension produced by hydrolysis and condensation of alkoxy silane in an organic solvent with water using a catalyst. It is characterized by having the form of a single spherical particle.

[0005] The present invention aims to provide a substrate having a fluorescent characteristic when irradiated with UV at 365 nm by using a method of injecting a structure produced by hollow silica-organic ligand hybridization into a silica sol manufactured by a conventional sol-gel method, hydrophobicizing the structure, drying and crushing the structure, and then coating the structure on the surface of a substrate, and a method of injecting carbon dots into a hollow silica sol manufactured by a conventional sol-gel method, hydrophobicizing the structure, and then coating the structure on the surface of a substrate.

[0006] Alternatively, a composition manufactured by mixing the above two methods can be manufactured, and another method is to manufacture a substrate having fluorescent properties by mixing raw materials, i.e., binder resin, wax, pigment, and CCA (charge control agent), inside the substrate.

[0007] The present invention makes it possible to increase luminous efficiency and control the amount of charge through a silica-organic ligand structure, since it is not easy to control the charging characteristics of a substrate when only carbon quantum dots are used.

[0008] As in the DNP Diffusion film of Fig. 2, a diffusion film is generally a multi-layer film consisting of a primary coating layer (AG) containing a 0.5 to 2㎛-grade diffusion agent, a secondary coating layer (AR layer), and finally a scratch-prevention coating.

[0009] However, the present invention features a fluorescent optical acid / low-reflection composition that simultaneously provides light diffusion / low-reflection and fluorescent properties through a first coating by utilizing fluorescent hollow particles in the range of 0.03 to 3 ㎛, and a substrate and device using the same.

[0010] In the present invention, the hollow particle range is 0.03 to 3㎛, and the hollowness is characterized by 20 to 80%.

[0011] In addition, the material of the hollow particles is characterized by being hollow particles such as silica, MgF2, and polymer (PMMA, PS, PC).

[0012] In the case of a substrate coated with a fluorescent light-diffusing / low-reflection composition utilizing a hollow-fluorescent organic ligand structure, the coating thickness is characterized as being 0.1 to 10 ㎛, and the curing method is characterized as being thermal curing or UV curing.

[0013] In addition, the coating composition of the present invention is composed of hollow particles + binder + solvent, and at this time, it is preferable that the hollow particles are 0.1 to 10%, the binder is 1 to 60%, and the remainder is solvent.

[0014] The present invention aims to express fluorescent properties in a substrate by adding a silica-organic ligand structure or carbon dots inside or outside the substrate. In addition, the basic properties of the substrate, such as charging, developing, transfer, and fixing properties, are maintained, and silica manufactured in a sol-gel type with a narrow particle size distribution is used, allowing size control of various silica particles, and has the advantage of easy particle size control from 10 nm to 200 nm. In addition, the difference in charging depending on the environment is minimized by performing hydrophobic silane treatment such as PDMS, HMDS, DMDES, and OTES.

[0015] To produce multi-color light emission such as red, green, blue, yellow, and orange, carbon dots were doped with nitrogen or acid-treated, and inorganic nano metal oxide particles with sizes ranging from several nm to several tens of nm were brought into proximity to increase electron mobility, thereby producing various multi-color light-emitting phosphors under UV light.

[0016] The above complex is characterized in that carbon dots having a diameter of 2 to 10 nm are bonded to the surface of carbon quantum dots by providing hydroxyl and carbxyl groups so that they can form clusters with inorganic nanoparticles having a diameter of 2 to 50 nm, and by controlling electrostatic attraction or repulsion and hydrogen bonding with the inorganic nanoparticles.

[0017] In addition, the above complex is characterized by exhibiting red, green, blue, yellow, and orange fluorescence characteristics depending on the content of carbon dots, the content of nitrogen, and the type and size of inorganic nanoparticles when irradiated with 365 nm UV.

[0018] Meanwhile, in the above complex, the carbon dot comprises polysaccharides such as biomass-based cellulose, hemicellulose, and lignin, monosaccharides or disaccharides such as glucose, sucrose, and xylose, and acids such as citric acid, and is characterized in that it is manufactured through a hydrothermal reaction in water using these raw materials as they are or after acid treatment. Biomass-based materials may be selected from the group consisting of pulp materials such as UNP (unbleached kraft pulp), BKP (bleached kraft pulp), and TMP (thermo mechanical pulp), recycled paper materials such as ONP (old news paper), OCC (old corrugated container), OMP (old magazine printing matters), MOP (mixed office paper), and milk cartons, and food-based recycled materials such as starch or citric acid, such as rice bran, coffee grounds, and fruit juice.

[0019] In order to increase the fluorescence intensity and express multi-color, the inorganic nanoparticles used for hybrid are spherical particles of 2 to 50 nm and are characterized by containing one or more components selected from the group consisting of Europium, SiO2, TiO2, ZnO, Fe2O3, CuO, MgO, Mg(OH)2, Al2O3, Nd2O3, Ce2O3, Er2O3, and Dy2O3.

[0020] The composition of the present invention

[0021] A step for manufacturing hollow silica manufactured by a sol-gel method;

[0022] A step of structuring the manufactured silica sol and organic ligand; and

[0023] It comprises a step of mixing the structured complex with a solvent.

[0024] The hollow silica-organic ligand structure or hollow silica-carbon dot structure of the present invention has optical properties with tunable excitation emission, and is highly attractive due to its high photochemical and colloidal stability, excellent biocompatibility, easy-to-use equipment synthesis process, and low raw material cost. As mentioned above, it is composed of only C, N, and O, making it a completely metal-free, eco-friendly material for safe, advanced applications. In addition to its use in surface treatment of substrates, this material has been extensively studied in a wide range of applications, including optoelectronics, light-emitting diodes, chemical and biosensing, bioimaging, drug delivery, photo- and electrocatalysis, latent fingerprint detection, and anti-counterfeiting.

[0025] The hollow silica-fluorescent organic ligand structure composition of the present invention can provide a light diffusion effect, prevent degradation of optical properties, and impart optical properties (blue, red, and green are all possible, but blue coating in particular prevents degradation of blue properties).

[0026] The present invention relates to a light diffusion / low-reflection composition and a substrate or optical element using the same, and more particularly, to a low-reflection optical film and an optical element using the same, which can maximize the display image effect by obtaining high anti-glareness without lowering the high-definition display image quality and reducing the reflectance of the surface by applying a low-reflection coating treatment to an anti-glare film on which a light diffusion coating layer is applied using hollow silica particles, and at the same time. In addition, the composition of the present invention can replace OLED, LED, QD Film, and LCD light diffusion Film.

[0027] Figure 1 is a schematic diagram of a light diffusion / low-reflection film of the present invention.

[0028] Figure 2 is a schematic diagram of a typical diffusion film.

[0029] To facilitate understanding of the present invention, preferred examples are presented below. However, the following examples are provided solely to facilitate understanding of the invention and are not intended to limit the scope of the present invention.

[0030] Example

[0031] 1. Preparation of hollow silica particles

[0032] Disperse 40 g of wet cake silica in water. Dissolve 15 g of CTAB in water to make a solution. Add the silica dispersed in water to the CTAB solution and stir for 30 minutes to coat the silica with CTAB. Meanwhile, dissolve 170 g of Na2CO3 in water to make a solution. Add the Na2CO3 solution to the CTAB-coated silica. Stir for 6 hours while maintaining the reaction temperature at 50°C. Once stirring is complete, filter the supernatant and separate the slurry. Disperse the separated slurry in water. Add the Na2CO3 solution to the dispersed slurry. Stir for 2 hours while maintaining the reaction temperature at 50°C. Once stirring is complete, filter the supernatant, wash with UP, and dry at 60°C. Once drying is complete, calcinate at 800°C for 4 hours.

[0033]

[0034] 2. Preparation of nano-hollow silica-organicligand structures

[0035] Organic ligand was dissolved in water at 1% and dispersed at 90°C for 1 hour with high-speed stirring (1000 rpm). The dispersed organic ligand was added to 10 nm silica sol at 1% of the silica solid content and stirred for 30 minutes to proceed with the reaction. The organic ligand reacted on the silica surface, and it was confirmed that the dispersion was maintained in a stable state due to electrostatic repulsion even after long-term standing due to the carboxyl group of the organic ligand.

[0036] The fluorescence characteristics of this nano hollow silica-organic ligand structure sol with good dispersibility were confirmed at UV 365 nm, and it exhibited blue luminescence characteristics as shown in Fig. 2.

[0037] The above structure was treated with one or more hydrophobic silanes, PDMS, HMDS, OTES, and DMDES, and then dried at 90°C for 24 hours. The dried structure was milled again to produce a final powder.

[0038]

[0039] 3. Preparation of carbon dot-nano hollow silica particles

[0040] 1) Manufacturing method through continuous process

[0041] During the above sol-gel silica manufacturing process, carbon dots were added to ensure uniform distribution of carbon dots within the silica. 1 mol of distilled water and 0.2 mol of NH3 were stirred at 300 rpm for 10 minutes. The mixture was heated to 48°C and 0.2 mol of TEOS was added dropwise. Carbon dots were added immediately after adding TEOS and aged for 2.5 hours before collecting samples.

[0042]

[0043] 2) Manufacturing method through two-step reaction

[0044] The two-step reaction method first produces nanoparticle silica using a sol-gel process and then proposes a method of bonding carbon dots onto the silica surface. First, 100 nm silica was produced using the above-mentioned nano-silica production method, and the silica solution was treated with N-2(aminoethyl)-3-aminoprophyl trimethoxy silane. The surface charge of the silica solution was confirmed to change positively from -30 mV to +20 mV when measuring the zeta potential by amino silane treatment. To the positively changed silica surface, 3% of negatively charged CD was added based on silica solid. After adding CD, the zeta potential was measured to be -10 to +5 mV. The final solution was centrifuged to remove the supernatant, and the remaining particles were dried at 100°C for 2 hours.

[0045]

[0046] 4. Preparation of fluorescent polymerization substrate

[0047] In addition to the method of manufacturing the above silica-organic ligand structure or carbon dot by agglomeration inside the substrate, the method of treating the outer surface of the substrate is as follows. First, the composition of the fluorescent silica (silica-organic ligand structure or carbon dot) manufactured in Manufacturing Examples 2 and 3, a binder, and a solvent was coated on the substrate. The composition of the coating composition of the present invention is hollow particles + binder + solvent, and at this time, it is preferable that the hollow particles are 0.1 to 10%, the binder is 1 to 60%, and the remainder is solvent. In the case of the substrate coated with the fluorescent light diffusion / low-reflection composition utilizing the hollow-fluorescent organic ligand structure, the coating thickness is characterized by being 0.1 to 10 μm. And the curing method was to harden the coating layer by thermal curing or UV curing.

[0048] Fluorescent Silica 100nm Fluorescent Silica 50nm Fluorescent Silica 10nm Fluorescent Characteristics Fluorescent Color Example 11○Blue Example 22○+Blue Example 31○Blue Example 42○+Blue Example 51○Blue Example 62○+Blue Comparative Example 7000XBlue

[0049] Method for coating the surface of a substrate with fluorescent silica

Claims

1. A fluorescent light-diffusing / low-reflection coating composition comprising hollow particles, a binder and a solvent.

2. A composition according to claim 1, characterized in that it comprises 0.1 to 10% of hollow particles and 1 to 60% of binder.

3. A composition according to claim 1, characterized in that the hollow particles are at least one selected from silica, MgF2, PMMA, PS, and PC.

4. A composition characterized in that the hollow particles in the first paragraph have a particle diameter of 0.03 to 3 ㎛ and a porosity of 20 to 80%.

5. A fluorescent optical acid / low-reflection composition substrate coated with any one of the compositions of clauses 1 to 4.

6. A substrate characterized in that the coating thickness in the fifth paragraph is 0.1 to 10 ㎛.

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