Gas barrier film with protective coating layer containing inorganic particles

Abstract

A gas barrier film with a protective layer including inorganic particles is provided. A gas barrier effect of the gas barrier film is improved by including inorganic nanoparticles in a protective layer when a protective coating is performed to protect a gas barrier layer.

Claims

1. A gas barrier film consisting of: a substrate layer; a barrier layer; an intermediate layer between the barrier layer and the substrate layer, the intermediate layer having a thickness of 0.3 m to 2 m and comprising a silica component comprising a hydrolysis reaction product of tetraethyl orthosilicate or tetraethoxy orthosilicate and a silane containing a substituent selected from the group consisting of vinyl, phenyl, gamma-glycidoxypropyl, gamma-methacryloxypropyl and methyl; and a cured protective layer formed on the barrier layer so as to be in contact with the barrier layer, wherein the cured protective layer is a curing reaction product of a coating composition that contains spherical nanoparticles, an initiator and a binder, wherein: the nanoparticles are present in an amount of 40 wt % to 70 wt % based on the total weight of the nanoparticles and the binder; the nanoparticles have an average diameter of 10 to 20 nm; and the binder is selected from the group consisting of 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, tripropylene glycol diacrylate, dicyclopentanyl diacrylate, butylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, propionoxide modified trimethylolpropane triacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, caprolactone modified dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, polyester acrylate, polyether acrylate, urethane acrylate, epoxy acrylate, polyol acrylate and a combination thereof.

2. The gas barrier film of claim 1, wherein the nanoparticles are silica particles, alumina particles, titania particles, zirconia particles, antimony oxide particles, or zinc oxide particles.

3. The gas barrier film of claim 1, wherein the initiator is a radical initiator or a cationic initiator.

4. The gas barrier film of claim 1, wherein the cured protective layer has a thickness of 0.2 m to 2 m.

5. The gas barrier film of claim 1, wherein the barrier layer includes SiO.sub.2, A1.sub.2O.sub.3, ZnO, ZnS, HfO.sub.2, HfON, AlN, or Si.sub.3N.sub.4.

6. The gas barrier film of claim 1, wherein the barrier layer is an atomic layer deposition layer.

7. The gas barrier film of claim 1, wherein the barrier layer has a thickness of 2 nm to 100 nm.

8. The gas barrier film of claim 1, wherein the silica component in the intermediate layer is a hydrolysis reaction product of tetraethoxy orthosilicate with 3-glycidoxypropyltrimethoxysilane.

9. A method of preparing the gas barrier film of claim 1, comprising: applying on a substrate an intermediate layer an intermediate layer having a thickness of 0.3 m to 2 m and comprising a silica component comprising a hydrolysis reaction product of tetraethyl orthosilicate or tetraethoxy orthosilicate and a silane containing a substituent selected from the group consisting of vinyl, phenyl, gamma-glycidoxypropyl gamma-methacyloxypropyl and methyl; applying a barrier layer on the intermediate layer; applying on the barrier layer a coating composition which contains spherical nanoparticles, an initiator and a binder, wherein: the nanoparticles are present in an amount of 40 wt % to 70 wt % based on the total weight of the nanoparticles and the binder and have an average diameter of 10 to 20 nm; and the binder is selected from the group consisting of 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, tripropylene glycol diacrylate, dicyclopentanyl diacrylate, butylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, propionoxide modified trimethylolpropane triacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, caprolactone modified dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, polyester acrylate, polyether acrylate, urethane acrylate, epoxy acrylate, polyol acrylate and a combination thereof; and initiating a curing reaction of the coating composition to form a protective layer.

10. The method of claim 9, wherein the barrier layer is formed by atomic layer deposition.

11. The method of claim 9, wherein the silica component in the intermediate layer is a hydrolysis reaction product of tetraethoxy orthosilicate with 3-glycidoxypropyltrimethoxysilane.

12. An electronic device comprising the gas barrier film of claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a diagram showing a gas barrier film according to one example of the present invention; and

(2) FIG. 2 is a diagram showing a structure of a gas barrier film according to another example of the present invention.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

(3) Hereinafter, the present invention will be described in detail through Examples which follow the present invention and Comparative Examples which do not follow the present invention, but scope of the present invention is not limited to the following Examples.

Example 1

(4) A polycarbonate film having a thickness of about 100 m and a water vapor transmission rate (WVTR) of about 4 g/m.sup.2/day was used as a substrate layer. 50 g of tetraethoxy orthosilicate and 50 g of 3-glycidoxypropyltrimethoxysilane were diluted with 150 g of ethanol, 56.4 g of water and 1.6 g of 0.1 N HCl were added thereto, and then the mixture was reacted for one day at room temperature to form a coating composition solution in a sol state. The coating composition solution was coated on the substrate layer by bar coating, and thermally cured for 10 minutes at 120 C. to form a flattened coating layer having a thickness of about 0.6 m.

(5) Subsequently, an Al.sub.2O.sub.3 layer was formed as a barrier layer to have a thickness of about 15 nm on the flattened layer by atomic layer deposition (ALD). Specifically, trimethyl aluminum (TMA) and H.sub.2O were respectively deposited and reacted in a pulse shape for 5 seconds on an intermediate layer to form a film having a thickness of 15 nm, followed by purging with argon gas to remove un-reacted H.sub.2O and byproducts. Such processes were set to one cycle, and the cycle was performed 40 times to form a barrier layer. Subsequently, a coating liquid including pentaerythritol triacrylate and a 3-isocyanatopropyltriethoxysilane adduct as a binder and spherical silica particles having an average diameter of about 15 nm and an initiator (Irgacure 127) (an amount of the silica particles was about 50 wt % based on the total weight of the binder and the silica particles) was prepared, the coating liquid was applied on the barrier layer and cured through UV curing to form a protective layer having a thickness of about 0.5 m, and thus a gas barrier film was prepared.

Example 2

(6) A gas barrier film was prepared in the same manner as in Example 1 except that the amount of the silica particles was about 60 wt % based on the total weight of the binder and the silica particles in a coating solution used when a protective layer was formed.

Example 3

(7) A gas barrier film was prepared in the same manner as in Example 1 except that spherical silica particles having an average diameter of about 50 nm were used when a protective layer was formed.

Example 4

(8) A gas barrier film was prepared in the same manner as in Example 1 except that the amount of the silica particles was about 40 wt % based on the total weight of the binder and the silica particles in a coating solution used when a protective layer was formed.

Example 5

(9) A gas barrier film was prepared in the same manner as in Example 1 except that a solution in which pentaerythritol triacrylate, 3-isocyanatopropyltriethoxysilane adduct and 3-gylcidoxypropyltrimethoxysilane were provided as a binder and an initiator (Irgacure 127 and Irgacure 250) (an amount of the silica was about 50 wt % based on the total weight of the binder and the silica particles) was used.

Comparative Example 1

(10) A gas barrier film was prepared in the same manner as in Example 1 except that silica particles were not used when the protective layer was formed.

Comparative Example 2

(11) A gas barrier film was prepared in the same manner as in Example 1 except that the amount of the silica particles was about 30 wt % based on the total weight of the binder and the silica particles in a coating solution used when a protective layer was formed.

Comparative Example 3

(12) A gas barrier film was prepared in the same manner as in Example 1 except that the amount of the silica particles was about 80 wt % based on the total weight of the binder and the silica particles in a coating solution used when a protective layer was formed.

Experimental Example 1

(13) WVTRs, light transmittances, and hazes of the gas barrier films prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were measured by the following methods.

(14) 1) WVTR: WVTR was measured for 48 hours at 38 C. and 100% of relative humidity by an ASTM F 1249 method using Aquatran Model 1.

(15) 2) Light transmittance (Tt): Light transmittance was measured in a visible region of 380 to 780 nm using UV-3600 manufactured by Shimadzu corporation.

(16) (3) Haze: Haze was measured using HM-150 manufactured by Murakami Color Research Laboratory.

(17) TABLE-US-00001 TABLE 1 Tt (%) Haze WVTR (g/m.sup.2 .Math. day) Example 1 92.8 0.1 0.0021 Example 2 92.8 0.1 0.0030 Example 3 92.0 0.3 0.0052 Example 4 92.6 0.1 0.0049 Comparative 92.8 0.1 0.0124 Example 1 Comparative 92.8 0.1 0.0073 Example 2 Comparative 92.7 0.1 0.0092 Example 3

(18) TABLE-US-00002 Description of Reference Numerals 10, 20: Gas barrier film structure 11, 21: Protective layer 12, 22: Barrier layer 13, 23: Intermediate layer 14, 24: Substrate layer