Organic-inorganic-hybrid thin film and method of manufacturing the same

Abstract

Provided is an organic-inorganic-hybrid thin film, which is provided in the form of a layered structure to prevent the scratching of the surface of a variety of kinds of displays, such as those of smartphones, tablet PCs, and laptop computers, and to fabricate ITO hard coating films, gas-barrier plates for flexible displays, and cover windows, and to a method of manufacturing the same, and more particularly, the organic-inorganic-hybrid thin film is provided in the form of a layered structure exhibiting the high light transmittance, mechanically flexible properties, lightweightness, and chemical resistance of a curable resin, and also ensuring the scratch resistance, heat dissipation performance, gas-barrier properties, and inherent refractive index matching of inorganic particles, thus exhibiting optical compensation effects, thereby increasing final surface hardness and satisfying barrier properties and index matching properties.

Claims

1. An organic-inorganic-hybrid thin film, comprising: a substrate having an upper surface and a lower surface; a coating layer formed on either or both of the upper surface and the lower surface of the substrate; and an adhesive layer formed on a surface of the coating layer opposite to a surface of the coating layer applied on the substrate, wherein the coating layer comprises an organic-inorganic-hybrid material, the organic-inorganic-hybrid material comprising 50.0 to 70.0 wt % of a hexafunctional acrylate monomer, 15.0 to 30.0 wt % of a trifunctional or tetrafunctional acrylate monomer, 15.0 to 30.0 wt % of an acrylate oligomer, and 14 to 50 wt % of nanomaterial particles or surface-modified nanomaterial particles, wherein the nanomaterial particles or surface-modified nanomaterial particles comprise alumina nanoparticles.

2. The organic-inorganic-hybrid thin film of claim 1, wherein the surface-modified nanomaterial particles are surface modified with a surface-treating agent including at least one selected from among 3-(trimethoxysilyl)propyl vinyl carbamate, 3-(trimethoxysilyl)propyl acrylate, 3-(trimethoxysilyl)propyl methacrylate, and 3-(2,3-epoxypropyloxy)propyl triethoxysilane so as to increase bondability between the surface-modified nanomaterial particles.

3. The organic-inorganic-hybrid thin film of claim 1, wherein the coating layer comprises 80.0 to 99.7 wt % of the organic-inorganic-hybrid material, 0.2 to 5.0 wt % of a photoinitiator, 0.1 to 5 wt % of an additive, and 0.1 to 10 wt % of a leveler.

4. The organic-inorganic-hybrid thin film of claim 1, wherein the coating layer has a film thickness after curing ranging from 1 nm to 300 μm.

5. The organic-inorganic-hybrid thin film of claim 1, wherein the nanomaterial particles or the surface-modified nanomaterial particles of the coating layer have a particle size ranging from 1 nm to 200 nm.

6. The organic-inorganic-hybrid thin film of claim 1, wherein the nanomaterial particles or the surface-modified nanomaterial particles are used in an amount ranging from 20 vol % to less than 30 vol %.

7. The organic-inorganic-hybrid thin film of claim 1, wherein the nanomaterial particles or the surface-modified nanomaterial particles are used in an amount ranging from 30 vol % to 100 vol %.

8. A printed circuit board, comprising the organic-inorganic-hybrid thin film of claim 1.

9. A glass board, comprising the organic-inorganic-hybrid thin film of claim 1.

10. A film or device for a display, comprising the organic-inorganic-hybrid thin film of claim 1.

11. A protective film, comprising the organic-inorganic-hybrid thin film of claim 1.

12. An electronic product, comprising the organic-inorganic-hybrid thin film of claim 1.

13. A plastic board, comprising the organic-inorganic-hybrid thin film of claim 1.

14. An electronic package module, comprising the organic-inorganic-hybrid thin film of claim 1.

15. A product for a car, comprising the organic-inorganic-hybrid thin film of claim 1.

16. A method of manufacturing an organic-inorganic-hybrid thin film of claim 1, comprising: providing a substrate having an upper surface and a lower surface; forming an adhesive layer on a surface of a coating layer opposite to a surface of the coating layer applied on the substrate; and forming the coating layer including the nanomaterial particles or the surface-modified nanomaterial particles on at least one surface selected from among the upper surface and the lower surface of the substrate; and wherein the coating layer comprises an organic-inorganic-hybrid material, the organic-inorganic-hybrid material, comprising 50.0 to 70.0 wt % of a hexafunctional acrylate monomer, 15.0 to 30.0 wt % of a trifunctional or tetrafunctional acrylate monomer, 15.0 to 30.0 wt % of an acrylate oligomer, and 14 to 50 wt % of nanomaterial particles or surface-modified nanomaterial particles, wherein the nanomaterial particles or surface-modified nanomaterial particles comprise alumina nanoparticles.

17. The method of claim 16, further comprising subjecting the coating layer to chemical etching or plasma etching, after the forming the coating layer.

Description

DESCRIPTION OF DRAWINGS

(1) FIGS. 1A and 1B are a perspective view showing an organic-inorganic-hybrid thin film according to an embodiment of the present invention;

(2) FIG. 2 shows the structure of the organic-inorganic-hybrid thin film according to the present invention;

(3) FIG. 3 shows the candidates for a surface-treating agent for nanoparticles according to the present invention;

(4) FIG. 4 shows the structure in which an adhesive layer is coated with alumina;

(5) FIG. 5 shows an improvement in the roughness of the organic-inorganic-hybrid thin film according to the present invention;

(6) FIG. 6 shows an organic-inorganic-hybrid thin film according to a modified embodiment of the present invention; and

(7) FIGS. 7A and 7B show an organic-inorganic-hybrid thin film according to another modified embodiment of the present invention.

(8) TABLE-US-00001 <Description of the Reference Numerals in the Drawings> 10: substrate 20: coating layer 21: first organic/inorganic layer 21′: second organic/inorganic layer 21″: third organic/inorganic layer 22: organic layer 23: inorganic layer or surface-modified inorganic layer 30: adhesive layer 40: adhesive layer or UV-blocking layer

BEST MODE

(9) Hereinafter, a detailed description will be given of an organic-inorganic-hybrid thin film having a layered structure and a method of manufacturing the same according to embodiments of the present invention.

(10) For a surface-modified alumina coating layer, alumina (Al.sub.2O.sub.3) particles were prepared in Preparation Example. As the amount of NH.sub.4OH that was added was changed, two kinds of alumina particles having different particle diameters were obtained.

Preparation Example 1. (Preparation of Al.SUB.2.O.SUB.3.)

(11) 100 ml of anhydrous ethanol (C.sub.2H.sub.5OH) was placed in a 250 ml three-neck flask, after which 2.5 g of AIP (Aluminum Isopropoxide, Al[OCH(CH.sub.3).sub.2]) was added, and the reaction mixture was stirred at room temperature for 3 hr at 400 rpm using a mechanical stirrer, thus preparing a 0.12 M AIP solution. Into the 0.12 M AIP solution, which was stirred at 400 rpm using a mechanical stirrer, 0.52 ml of 0.07 to 0.21 M NH.sub.4OH was added dropwise, and the reaction was carried out at room temperature for 4 hr. The powder thus synthesized was filtered, washed, dried and then thermally treated, thereby yielding alumina particles having a particle size ranging from 20 to 60 nm.

(12) As shown in Table 1 below, inorganic particles were prepared depending on the kind of precursor thereof, and alumina particles having a particle size of about 20 nm were confirmed at different ammonia concentrations.

(13) TABLE-US-00002 TABLE 1 Properties of inorganic particles depending on the kind of precursor Ammonia concentration Particle size No. Precursor (M) (nm) 1-1 Aluminum isopropoxide (AIP) 0.07 60 1-2 0.14 40 1-3 0.21 20 1-4 TEOS 0.07 50 1-5 0.14 35 1-6 0.21 25 1-7 Titanium (IV) isopropoxide 0.21 20 (TTIP) 1-8 Tetraethyl orthotitanate (TEOT) 0.21 20

Preparation Example 2. (Preparation of Inorganic Particle Dispersion)

(14) Inorganic particle dispersions were prepared by milling the inorganic particles of Preparation Example 1 for 5 hr. Here, the dispersion solvent was an alcoholic organic solvent such as isopropyl alcohol, and the dispersions shown in Table 2 below were obtained.

(15) TABLE-US-00003 TABLE 2 Preparation of inorganic particle dispersion No. Inorganic particles Average particle size (nm) 2-1 1-1 80 2-2 1-2 55 2-3 1-3 40 2-4 1-4 70 2-5 1-5 50 2-6 1-6 40 2-7 1-7 33 2-8 1-8 38

Preparation Example 3. (Preparation of Surface-Modified Inorganic Particles and Dispersion)

(16) Each of the inorganic particle dispersions of Preparation Example 2 was added with a surface-treating agent, as shown in Table 3 below, and reacted at room temperature for 3 hr. A dispersant made by BYK was added in an amount of 10% based on the amount of the surface-modified inorganic particles, followed by milling using a nanomill for 5 hr, thus obtaining 30% surface-modified nanomaterial dispersions as shown in Table 3 below.

(17) TABLE-US-00004 TABLE 3 Conditions of Preparation Example 3 and average particle size in dispersion Average particle size Preparation (nm) in Example No. Dispersion Surface-treating agent dispersion 3-1 2-3 3-(Trimethoxysilyl)propyl vinyl 40 carbamate 3-2 2-5 3-(Trimethoxysilyl)propyl vinyl 50 carbamate 3-3 2-6 3-(Trimethoxysilyl)propyl vinyl 40 carbamate 3-4 2-7 3-(Trimethoxysilyl)propyl vinyl 33 carbamate 3-5 2-8 3-(Trimethoxysilyl)propyl vinyl 38 carbamate 3-6 2-3 3-(Trimethoxysilyl)propyl acrylate 40 3-7 2-6 3-(Trimethoxysilyl)propyl acrylate 40 3-8 2-8 3-(Trimethoxysilyl)propyl acrylate 38 3-9 2-3 3-(Trimethoxysilyl)propyl 40 methacrylate 3-10 2-6 3-(Trimethoxysilyl)propyl 40 methacrylate 3-11 2-8 3-(Trimethoxysilyl)propyl 38 methacrylate 3-12 2-3 3-(2,3-Epoxypropyloxy)propyl 40 triethoxysilane 3-13 2-6 3-(2,3-Epoxypropyloxy)propyl 40 triethoxysilane 3-14 2-8 3-(2,3-Epoxypropyloxy)propyl 38 triethoxysilane

(18) The properties of the surface-modified nanomaterial inorganic particle thin films according to the present invention were as follows.

(19) 1) Light Transmittance and Haze

(20) Total transmittance and haze were measured using a spectrophotometer (made by Nippon Denshoku, Japan, NDH700).

(21) 2) Reflectance

(22) Reflectance was measured using a color measurement system (CM-5).

(23) 3) Pencil Hardness

(24) Pencil hardness was measured under a load of 750 g using a pencil hardness tester according to ASTM D3502.

(25) 4) Adhesion

(26) Onto a 5 mm thick glass board having a piece of double-sided tape attached thereto, the nanomaterial inorganic particle thin film of each of the Examples and Comparative Examples was adhered such that the coating layer thereof was positioned outwards. Subsequently, lattice pattern cuts forming 100 squares were made in the thin film ranging from the coating layer to the substrate using a cutter guide having a gap interval of 2 mm. Then, a piece of adhesive tape (made by Nichiban, No. 405; width 24 mm) was attached to the surface of the lattice pattern cuts. The air remaining at the interface upon attachment was completely removed using an eraser and thus the adhesive tape was completely adhered, after which the adhesive tape was forcibly vertically detached, and the adhesion was observed with the naked eye based on the following Equation. Also, the case of a square having partial detachment was combined to count the number of detached squares.
Adhesion (%)=(1−number of detached squares/100)×100
⊚: Adhesion (%) of 90 to 100%
◯: Adhesion (%) of 80 to 89%
x: Adhesion (%) of 0 to 79%

Example 1

(27) In the coating layer of the surface-modified inorganic particles of Preparation Example 3-1 having a solid content of 50 wt %, an organic binder having a solid content of 50 wt % (the organic binder includes an oligomer, a hexafunctional monomer, and a tetrafunctional monomer) was used and 2,2-dimethoxy-1,2-diphenyl ethanone as a photoinitiator was added in an amount of 1 wt %, thus preparing a coating composition for a 30% surface-modified nanomaterial inorganic particle thin film, as shown in Table 4 below.

(28) The coating composition was applied on a PET film, dried at 50° C., and cured with UV light in air using a high-pressure mercury lamp (0.5 J/cm.sup.2), thereby manufacturing a surface-modified nanomaterial inorganic particle thin film as shown in Table 4 below.

Examples 2 to 14

(29) Respective thin films as shown in Table 4 below were manufactured in the same manner as in Example 1, with the exception that Preparation Examples 3-2 to 3-14 of Table 3 were used.

Comparative Examples 1 to 8

(30) Respective thin films as shown in Table 4 below were manufactured in the same manner as in Example 1, with the exception that the nanomaterial particle dispersion of Preparation Example 2 was used.

(31) TABLE-US-00005 TABLE 4 Thermal Coating Light Reflectance Pencil conductivity thick. (μm) transmittance (%) Haze (%) hardness (H) Adhesion (W/mK) Ex. 1 8.4 91 1.2 0.91 9 ⊚ 8.3 Ex. 2 8.7 92 1.3 0.87 8 ⊚ 8.4 Ex. 3 8.6 93 1.2 0.84 8 ⊚ 8.9 Ex. 4 8.5 94 1.2 0.82 8 ⊚ 9.1 Ex. 5 8.9 93 1.3 0.93 9 ⊚ 9.0 Ex. 6 9.1 93 1.1 0.94 9 ⊚ 8.7 Ex. 7 9.2 91 1.2 0.84 8 ⊚ 8.6 Ex. 8 7.8 93 1.0 0.83 9 ⊚ 8.5 Ex. 9 7.9 92 0.9 0.86 9 ⊚ 8.4 Ex. 10 8.4 93 1.2 0.87 8 ⊚ 8.2 Ex. 11 8.6 94 1.1 0.91 8 ⊚ 8.9 Ex. 12 8.9 93 1.0 1.01 9 ⊚ 9.0 Ex. 13 9.1 93 1.3 0.98 8 ⊚ 9.1 Ex. 14 9.2 92 1.0 0.92 9 ⊚ 9.0 C. Ex. 1 10 87 3.4 3.0 6 ⊚ 3.5 C. Ex. 2 12 89 3.2 3.2 5 ◯ 5.0 C. Ex. 3 13 88 3.1 3.4 4 ◯ 5.4 C. Ex. 4 11 87 3.0 3.5 4 ◯ 5.8 C. Ex. 5 12 87 2.9 3.1 6 ◯ 6.0 C. Ex. 6 13 88 2.7 2.9 5 ◯ 7.1 C. Ex. 7 11 87 3.2 2.8 4 ◯ 4.8 C. Ex. 8 10 85 4.0 4.1 5 ◯ 3.9

Examples 15 to 28

(32) Respective thin films as shown in Table 5 below were manufactured in the same manner as in Examples 1 to 14, with the exception that the transparent PI film was used.

Comparative Examples 9 to 16

(33) Respective thin films as shown in Table 5 below were manufactured in the same manner as in Comparative Examples 1 to 8, with the exception that the transparent PI film was used.

(34) TABLE-US-00006 TABLE 5 Thermal Coating Light Reflectance Pencil conductivity thick. (μm) transmittance (%) Haze (%) hardness (H) Adhesion (W/mK) Ex. 15 7.1 91.5 1.1 0.93 9 ⊚ 8.6 Ex. 16 6.8 91.3 1.2 0.82 9 ⊚ 8.5 Ex. 17 6.7 92.1 1.2 0.81 9 ⊚ 8.7 Ex. 18 6.1 93.4 1.1 0.80 9 ⊚ 9.2 Ex. 19 6.8 92.1 1.2 0.92 9 ⊚ 9.3 Ex. 20 6.3 92.5 1.0 0.91 9 ⊚ 8.4 Ex. 21 6.4 92.4 1.1 0.81 9 ⊚ 8.6 Ex. 22 6.5 92.9 1.0 0.82 9 ⊚ 8.7 Ex. 23 6.2 92.3 0.8 0.81 9 ⊚ 8.8 Ex. 24 5.1 93.1 1.1 0.81 9 ⊚ 8.3 Ex. 25 8.0 92.5 1.1 0.90 9 ⊚ 8.6 Ex. 26 7.5 93.2 1.0 1.00 9 ⊚ 9.2 Ex. 27 7.6 92.8 1.2 0.91 9 ⊚ 9.3 Ex. 28 6.8 93.2 1.2 0.94 9 ⊚ 9.1 C. Ex. 9 9.4 89.6 3.8 3.2 7 ⊚ 3.2 C. Ex. 10 9.8 89.2 3.6 3.6 6 ◯ 4.5 C. Ex. 11 10.1 88.4 3.8 3.5 6 ◯ 4.6 C. Ex. 12 9.5 87.3 3.7 3.4 5 ◯ 5.1 C. Ex. 13 9.6 87.4 2.2 3.7 7 ◯ 5.2 C. Ex. 14 9.8 88.2 2.3 2.8 5 ◯ 6.2 C. Ex. 15 9.7 87.4 3.4 2.9 5 ◯ 4.2 C. Ex. 16 9.5 85.6 4.5 4.5 6 ◯ 3.2

Example 29

(35) In the coating layer of the surface-modified inorganic particles of Preparation Example 3-1 having a solid content of 14 wt %, an organic binder having a solid content of 86 wt % (the organic binder includes an oligomer, a hexafunctional monomer, and a tetrafunctional monomer) was used and 2,2-dimethoxy-1,2-diphenyl ethanone as a photoinitiator was added in an amount of 1 wt %, thus obtaining a coating composition for a 30% surface-modified nanomaterial inorganic particle thin film.

(36) The coating composition was applied on a transparent PI film, dried at 50° C., and cured with UV light in air using a high-pressure mercury lamp (0.5 J/cm.sup.2), thereby manufacturing a surface-modified nanomaterial inorganic particle thin film as shown in Table 6 below.

Examples 30 to 42

(37) Respective thin films as shown in Table 6 below were manufactured in the same manner as in Example 29, with the exception that Preparation Examples 3-2 to 3-14 of Table 3 were used.

Comparative Examples 17 to 24

(38) Respective thin films as shown in Table 6 below were manufactured in the same manner as in Example 29, with the exception that the nanomaterial particle dispersion of Preparation Example 2 was used.

(39) TABLE-US-00007 TABLE 6 Thermal Coating Light Reflectance Pencil conductivity thick. (μm) transmittance (%) Haze (%) hardness (H) Adhesion (W/mK) Ex. 29 4.1 92.5 0.9 0.91 9 ⊚ 7.6 Ex. 30 4.3 93.3 1.0 0.84 9 ⊚ 7.5 Ex. 31 4.5 93.1 0.8 0.86 9 ⊚ 7.7 Ex. 32 4.4 94.4 0.9 0.83 9 ⊚ 8.2 Ex. 33 4.6 93.1 1.0 0.91 9 ⊚ 8.3 Ex. 34 4.8 94.5 0.9 0.93 9 ⊚ 7.4 Ex. 35 5.1 93.4 0.8 0.82 9 ⊚ 7.6 Ex. 36 5.0 92.9 1.0 0.85 9 ⊚ 7.7 Ex. 37 4.9 94.3 1.0 0.80 9 ⊚ 7.8 Ex. 38 4.8 93.5 0.9 0.85 9 ⊚ 7.3 Ex. 39 4.1 94.2 0.8 0.90 9 ⊚ 7.6 Ex. 40 4.2 94.1 1.0 0.97 9 ⊚ 8.2 Ex. 41 4.3 93.8 0.9 0.92 9 ⊚ 8.3 Ex. 42 4.5 93.6 0.9 0.90 9 ⊚ 8.1 C. Ex. 17 8.2 89.6 3.6 3.4 6 ⊚ 3.0 C. Ex. 18 8.4 89.2 3.8 3.0 5 ◯ 4.1 C. Ex. 19 8.1 88.4 4.2 3.1 7 ◯ 4.2 C. Ex. 20 8.3 87.3 5.1 3.7 7 ◯ 5.0 C. Ex. 21 8.2 87.4 6.0 3.4 5 ◯ 5.1 C. Ex. 22 8.3 88.2 4.8 2.2 5 ◯ 6.0 C. Ex. 23 8.4 87.4 4.9 2.3 6 ◯ 4.0 C. Ex. 24 8.5 85.6 5.3 4.1 6 ◯ 2.9

(40) As is apparent from Tables 1 to 6, in Examples 1 to 42, compared to Comparative Examples 1 to 24, the thickness of the coating layer was decreased, light transmittance was increased, and haze and reflectance were decreased. Also, superior pencil hardness and adhesion resulted, and thermal conductivity was increased.