GAS BARRIER FILM AND METHOD OF PRODUCING GAS BARRIER FILM

Abstract

A gas barrier film includes, in order, a film substrate, an organic layer, and a silica layer, in which the silica layer includes a silica polymer having at least a covalent bond between a silicon atom and an oxygen atom, and a concentration of carbon atoms of the organic layer is 50% or more. A method of producing a gas barrier film includes forming an organic layer having a concentration of carbon atoms of 50% or more on a film substrate, applying a coating liquid including a silicon compound to the organic layer to form a layer including the silicon compound, and irradiating the layer including the silicon compound with vacuum ultraviolet rays to form a silica layer including a silica polymer having at least a covalent bond between a silicon atom and an oxygen atom.

Claims

1. A gas barrier film comprising, in order: a film substrate; a first organic layer; and a silica layer, wherein the silica layer includes a silica polymer having at least a covalent bond between a silicon atom and an oxygen atom, and a concentration of carbon atoms of the first organic layer is 50% or more.

2. The gas barrier film according to claim 1, wherein the first organic layer is in direct contact with the silica layer.

3. The gas barrier film according to claim 1, further comprising: an inorganic layer, wherein the first organic layer is in direct contact with the inorganic layer.

4. The gas barrier film according to claim 1, further comprising: an inorganic layer, wherein the film substrate, the first organic layer, the silica layer, and the inorganic layer are provided in this order.

5. The gas barrier film according to claim 3, wherein the inorganic layer is a vapor deposition layer.

6. The gas barrier film according to claim 4, wherein the inorganic layer is a vapor deposition layer.

7. The gas barrier film according to claim 1, wherein an atomic number ratio of the first organic layer is O/C=0.050 to 1.0 and Si/C=0.00 to 0.10.

8. The gas barrier film according to claim 1, wherein a film thickness of the first organic layer is 0.5 to 10 m.

9. The gas barrier film according to claim 1, wherein a film thickness of the silica layer is 50 to 1000 nm.

10. The gas barrier film according to claim 1, wherein an atomic number ratio of the silica layer is Si:O:N=1:0.1 to 1.2:0.5 to 1.5.

11. The gas barrier film according to claim 1, further comprising: an inorganic layer; and a second organic layer, wherein the film substrate, the first organic layer, the silica layer, the inorganic layer, and the second organic layer are provided in this order, and a concentration of carbon atoms of the second organic layer is 50% or more.

12. A method of producing a gas barrier film comprising: forming an organic layer having a concentration of carbon atoms of 50% or more on a film substrate; applying a coating liquid including a silicon compound to the organic layer to form a coating layer including the silicon compound; and irradiating the coating layer including the silicon compound with vacuum ultraviolet rays to form a silica layer including a silica polymer having at least a covalent bond between a silicon atom and an oxygen atom.

13. The method of producing a gas barrier film according to claim 12, wherein the applying of the coating liquid includes applying the coating liquid to a surface of the organic layer, and the method further comprises forming an inorganic layer on a surface of the silica layer by a vapor deposition method or a sputtering method.

14. The method of producing a gas barrier film according to claim 12, further comprising: forming an inorganic layer on a surface of the organic layer by a vapor deposition method or a sputtering method, wherein the applying of the coating liquid includes applying the coating liquid to a surface of the inorganic layer.

15. The method of producing a gas barrier film according to claim 13, wherein the inorganic layer is formed by a chemical vapor deposition method.

16. The method of producing a gas barrier film according to claim 14, wherein the inorganic layer is formed by a chemical vapor deposition method.

17. The method of producing a gas barrier film according to claim 12, wherein the silicon compound is perhydropolysilazane.

18. The method of producing a gas barrier film according to claim 12, wherein an atomic number ratio of the organic layer is O/C=0.050 to 1.0 and Si/C=0 to 0.1.

Description

EXAMPLES

[0141] The present invention is described with greater specificity below through Examples. The materials, amounts used, ratios, processing contents, processing procedures, and the like that are indicated in the Examples below can be suitably modified without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited by the specific examples given below.

[0142] <Preparation of Gas Barrier Film of Example 1>

[0143] [Formation of Organic Layer]

[0144] To polyethylene naphthalate film (PEN, TEONEX Q65FA, manufactured by Teijin DuPont, thickness: 100 m), a polymerizable composition including a polymerizable compound (TMPTA: trimethylol propane triacrylate, manufactured by Daicel-Allnex Ltd.), a photopolymerization initiator (IRGACURE 819, manufactured by BASF SE), and a 2-butanone (TMPTA:IRGACURE 819:2-butanone=19.4:0.6:80 at a mass ratio) was applied with a wire bar and the polymerizable composition was dried at 80 C. for 3 minutes. Next, the dried polymerizable composition was irradiated with ultraviolet rays using a high pressure mercury lamp (irradiation dose: 0.5 J/cm.sup.2) in a nitrogen atmosphere at an oxygen content of 100 ppm or less to cure the polymerizable composition. Thus, an organic layer having a thickness of 4 m was prepared.

[0145] [Formation of Silica Layer]

[0146] A coating liquid A was applied to the surface of the organic layer by a spin coating method and then the coating layer was dried at 80 C. for 1 minute. The dried coating layer was subjected to an irradiation treatment under Condition A and thus a laminate provided with a silica layer having a thickness of 250 nm was obtained.

[0147] (Coating Liquid A)

[0148] A perhydropolysilazane (PHPS) solution (PHPS: 20% by mass, dibutyl ether: 80% by mass) and an amine solution (N,N,N,N-tetramethyl-1,6-diaminohexane: 5% by mass, dibutyl ether: 95% by mass) were mixed to prepare a coating solution such that the mass ratio between perhydropolysilazane and N,N,N,N-tetramethyl-1,6-diaminohexane was 100:1. Then, the mixture was diluted with dibutyl ether such that the mass percent of the coating liquid A became 10% by mass. Thus, a coating liquid A was obtained.

[0149] (Condition A)

[0150] Using a stage movable Xenon excimer irradiation device (MECL-M-1-200, manufactured by M.D. Excimer Inc.), the irradiation treatment was performed under the following conditions. In addition, the oxygen concentration was adjusted according to a nitrogen gas/oxygen gas flow ratio of a gas to be introduced into an irradiation chamber obtained by measuring the flow rate of nitrogen gas and oxygen gas to be introduced in the irradiation chamber using a flow meter.

[0151] Irradiance: 140 mW/cm.sup.2 (main peak emission wavelength: 172 nm)

[0152] Stage temperature: 100 C.

[0153] Distance between sample and light source: 1 mm

[0154] Treatment environment: dry nitrogen gas atmosphere

[0155] Oxygen concentration of treatment environment: 0.1% by volume

[0156] Stage moving speed: 10 mm/sec

[0157] Excimer exposure light cumulative amount: 6500 mJ/cm.sup.2

[0158] [Preparation of Inorganic Layer]

[0159] An inorganic layer having a thickness of 250 nm was provided on the surface of the silica layer under Condition B to obtain a laminate (Condition B).

[0160] Polyethylene naphthalate film (PEN, TEONEX Q65FA, manufactured by Teijin DuPont) was bonded to the laminate in the longitudinal direction to prepare a roll. The inorganic layer was provided on the surface of the silica layer using a device shown in FIG. 1 of JP2012-97291A under the following film formation conditions.

[0161] (Film Formation Conditions)

[0162] Supply amount of raw material gas (HMDSO: hexamethyldisiloxane): 25 ml/min

[0163] Supply amount of oxygen gas (O.sub.2): 500 ml/min

[0164] Vacuum degree in vacuum chamber: 2 Pa

[0165] Application power from power source for generating plasma: 1.2 kW

[0166] Frequency of power source for generating plasma: 80 kHz

[0167] Transport speed of film: 0.5 m/min

[0168] <Preparation of Gas Barrier Films of Examples 2 to 7 and Comparative Examples 1 and 2>

[0169] Gas barrier films of Examples 2 to 7 and Comparative Examples 1 and 2 were prepared in the same procedure as in the preparation of the gas barrier film of Example 1 except that the organic layer was formed as follows.

Example 2

[0170] A gas barrier film was prepared in the same manner as in Example 1 except that the polymerizable compound of the organic layer was changed from TMPTA to A-DCP manufactured by Shin-Nakamura Chemical Co., Ltd.

Example 3

[0171] A gas barrier film was prepared in the same manner as in Example 1 except that the polymerizable compound of the organic layer was changed to a mixed compound of TMPTA and KBM5103 manufactured by Shin-Etsu Chemical Co., Ltd. (TMPTA:KBM5103=80:20 in mass ratio).

Example 4

[0172] A gas barrier film was prepared in the same manner as in Example 1 except that the polymerizable compound of the organic layer was changed to a mixed compound of A-DCP and KBM5103 (A-DCP:KBM5103=80:20 in mass ratio).

Example 5

[0173] A gas barrier film was prepared in the same manner as in Example 1 except that the polymerizable compound of the organic layer was changed from TMPTA to M-305 manufactured by Toagosei Co., Ltd.

Example 6

[0174] A gas barrier film was prepared in the same manner as in Example 1 except that the polymerizable compound of the organic layer was changed to a mixed compound of TMPTA and KBM5103 manufactured by Shin-Etsu Chemical Co., Ltd. (TMPTA:KBM5103=50:50 in mass ratio).

Example 7

[0175] A gas barrier film was prepared in the same manner as in Example 1 except that to the polymerizable composition used in Example 1, silica particle (MEK-ST-40, manufactured by Nissan Chemical Industries, Limited, particle diameter: 10 to 15 nm, solid content concentration: 40% by mass) were further added to form a polymerizable composition (TMPTA:MEK-ST-40:IRGACURE819:2-butanone=15.5:9.8:0.6:74.1 in mass ratio).

Comparative Example 1

[0176] A gas barrier film was prepared in the same manner as in Example 7 except that the polymerizable compound of the organic layer was changed from TMPTA to M-240 manufactured by Toagosei Co., Ltd.

Comparative Example 2

[0177] A gas barrier film was prepared in the same manner as in Example 7 except that the mass ratio in the polymerizable composition was changed to TMPTA:MEK-ST-40:IRGACURE819:2-butanone=9.7:24.3:0.6:65.4.

[0178] <Evaluation of Gas Barrier Film>

[0179] (Measurement of Water Vapor Transmission Rate)

[0180] The water vapor transmission rate [g/(m.sup.2.Math.day)] of each of the gas barrier films obtained was measured by a calcium corrosion method (a method described in JP2005-283561A). The water vapor transmission rate immediately after preparation was set to WVTR(0), and the water vapor transmission rate after the film was left to stand under an environment of 85 C. and 85% RH for 250 hours was set to WVTR(1). The results are shown in Table 1.

[0181] (Measurement of Atomic Number Ratio of Silica Layer (Si:O:N))

[0182] The surface of the silica layer before the inorganic layer was formed was used to measure the atomic number ratio of the silica layer by an XPS method. In the XPS, an ESCALAB-200R manufactured by VG Scientific was used. As an X-ray anode, Mg was used and measurement was performed at an output of 600 W (accelerating voltage: 15 kV, emission current: 40 mA). The results are shown in Table 1.

[0183] (Measurement of Atomic Number Ratio (Si:O:C) of Organic Layer)

[0184] The surface of the organic layer before the silica layer was formed was used to evaluate the atomic number ratio of the organic layer by an XPS method in the same manner as in the measurement of the atomic number ratio of the silica layer. In the table, the concentration of the carbon atoms of the organic layer is denoted as C percentage.

TABLE-US-00001 TABLE 1 C percentage O/C Si/C WVTR(0) WVTR(1) WVTR(0)/WVTR(1) Example 1 67 0.48 0.00 2 10.sup.5 6 10.sup.5 0.33 Example 2 82 0.22 0.00 2 10.sup.5 5 10.sup.5 0.40 Example 3 65 0.51 0.02 2 10.sup.5 6 10.sup.5 0.33 Example 4 78 0.27 0.02 2 10.sup.5 4 10.sup.5 0.50 Example 5 62 0.58 0.00 2 10.sup.5 1 10.sup.4 0.20 Example 6 64 0.52 0.05 2 10.sup.5 2 10.sup.4 0.10 Example 7 57 0.68 0.09 2 10.sup.5 2 10.sup.4 0.10 Comparative 45 1.09 0.14 2 10.sup.6 5 10.sup.4 0.04 Example 1 Comparative 39 1.20 0.35 2 10.sup.5 6 10.sup.4 0.03 Example 2

[0185] <Preparation of Gas Barrier Films of Examples 11 to 17 and Comparative Examples 11 and 12>

[0186] Gas barrier films of Examples 11 to 17 and Comparative Examples 11 and 12 were prepared respectively in the same manner as in the preparation of the gas barrier films of Examples 1 to 7 and Comparative Examples 1 and 2 except that instead of using the amine solution of the coating liquid A used for forming the silica layer, another amine solution (trihexylamine: 5% by mass, dibutyl ether: 95% by mass) was used and a coating liquid was prepared such that the mass ratio of perhydropolysilazane and trihexylamine became 100:1, and were evaluated in the same manner. The results are shown in Table 2.

TABLE-US-00002 TABLE 2 C percentage O/C Si/C WVTR(0) WVTR(1) WVTR(0)/WVTR(1) Example11 67 0.48 0.00 2 10.sup.5 5 10.sup.5 0.40 Example12 82 0.22 0.00 2 10.sup.5 4 10.sup.5 0.50 Example13 65 0.51 0.02 2 10.sup.5 4 10.sup.5 0.50 Example14 78 0.27 0.02 2 10.sup.5 3 10.sup.5 0.67 Example15 62 0.58 0.00 2 10.sup.5 8 10.sup.5 0.25 Example16 64 0.52 0.05 2 10.sup.5 8 10.sup.5 0.25 Example17 57 0.68 0.09 2 10.sup.5 1 10.sup.4 0.20 Comparative 45 1.09 0.14 2 10.sup.6 3 10.sup.4 0.07 Example 11 Comparative 39 1.20 0.35 2 10.sup.5 4 10.sup.4 0.05 Example 12