Barrier laminate and gas barrier film

Abstract

The present invention provides a barrier laminate including at least one inorganic barrier layer and at least one organic layer, wherein the organic layer is a layer formed of a polymerizable composition comprising a polymerizable compound represented by general formula (1) below; and a gas barrier film including the barrier laminate and a support that preferably contains a resin consisting of a polymer or a copolymer comprising a cyclic olefin within a repeating unit or a polycarbonate resin: ##STR00001##
wherein R represents hydrogen atom or methyl group, and Rs may be the same or different to each other.

Claims

1. A barrier laminate comprising at least one inorganic barrier layer and at least one organic layer, wherein the organic layer is a layer formed of a polymerizable composition comprising a polymerizable compound represented by general formula (1) below; ##STR00023## wherein R represents hydrogen atom or methyl group, and each R is the same or different to each other.

2. The barrier laminate according to claim 1, wherein each R represents hydrogen atom.

3. The barrier laminate according to claim 1, wherein the inorganic barrier layer comprises any one of metal compounds selected from a group consisting of a metal oxide, a metal nitride, a metal carbide, a metal oxynitride and a metal oxynitride carbide.

4. The barrier laminate according to claim 1, wherein the inorganic barrier layer comprises a silicon compound.

5. The barrier laminate according to claim 1, wherein the inorganic barrier layer comprises a nitride of silicon or an oxide of silicon.

6. The barrier laminate according to claim 1, wherein a proportion of the polymerizable compound relative to the total amount of polymerizable compounds in the polymerizable composition is 60 mass % or more.

7. The barrier laminate according to claim 1, wherein the organic layer and the inorganic barrier layer are adjacent to each other.

8. The barrier laminate according to claim 5, wherein the organic layer and the inorganic barrier layer are adjacent to each other.

9. A gas barrier film, wherein the barrier laminate according to claim 1 is provided on a support.

10. A gas barrier film, wherein the barrier laminate according to claim 8 is provided on a support.

11. The gas barrier film according to claim 9, wherein the support comprises a resin consisting of a polymer or a copolymer comprising a cyclic olefin within a repeating unit or a polycarbonate resin.

12. The gas barrier film according to claim 9, wherein the support is adjacent to the organic layer.

13. The gas barrier film according to claim 10, wherein the support is adjacent to the organic layer.

14. The gas barrier film according to claim 9, wherein the support and the inorganic barrier layer are adjacent to each other, and the inorganic barrier layer and the organic layer are adjacent to each other.

15. The gas barrier film according to claim 10, wherein the support and the inorganic barrier layer are adjacent to each other, and the inorganic barrier layer and the organic layer are adjacent to each other.

16. A device comprising the gas barrier film according to claim 9.

17. The device according to claim 16, wherein the device is an organic device for image display.

18. A production method of the gas barrier film according to claim 9, the method comprising applying, on the support, an application liquid that comprises a polymerizable compound represented by general formula (1) below, and water, an alkyl alcohol having 1 to 3 carbon atoms, or a mixture of water and an alkyl alcohol having 1 to 3 carbon atoms; ##STR00024## wherein R represents hydrogen atom or methyl group, and each R is the same or different to each other.

19. The production method according to claim 18, wherein each R represents hydrogen atom.

20. The production method according to claim 18, in which the application liquid comprises water and an alkyl alcohol having 1 to 3 carbon atoms.

Description

EXAMPLES

(1) Hereinafter, the present invention will be described more specifically through Example. Materials, amounts used, percentages, treatment contents, treatment procedures and the like shown in Example below can be changed appropriately as long as they do not depart from the gist of the present invention. Accordingly, the scope of the present invention is not limited to specific examples shown below.

Example 1

(2) [Preparation of Gas Barrier Films Having Structure of Support/Organic Layer/Inorganic Barrier Layer/Organic Layer]

(3) The gas barrier films of 1-1 to 1-19 having a laminated structure of the support/the organic layer/the inorganic barrier layer/the organic layer were prepared by changing a support, a polymerizable compound that is a precursor of a first organic layer, the type of the application solvent of a precursor composition and a polymerization initiator as shown in Table 1. The barrier performance, the flexibility and the interlayer adhesion of the prepared gas barrier films were evaluated.

(4) Table 1

(5) TABLE-US-00001 Support First organic polymer layer Support Moisture Polymerization Sample No. name content (%) Polymerizable compound initiator Application solvent Remarks 1-1 ZEONOR <0.01 SR494 97 wt % DarocureTPO 3 wt % 2-butanone Comparative example 1-2 PET-30 97 wt % Comparative example 1-3 FF-214 59 wt % PET-30 38 wt % methanol Present invention 1-4 FF-214 97 wt % Present invention 1-5 TOPAS 0.02 SR494 97 wt % 2-butanone Comparative example 1-6 PET-30 97 wt % Comparative example 1-7 FF-214 59 wt % PET-30 38 wt % methanol Present invention 1-8 FF-214 97 wt % Present invention 1-9 ARTON 0.4 SR494 97 wt % 2-butanone Comparative example 1-10 PET-30 97 wt % Comparative example 1-11 FF-214 59 wt % PET-30 38 wt % methanol Present invention 1-12 FF-214 97 wt % Present invention 1-13 FF-214 97 wt % Irgacure2959 methanol/water = 5/5 Present invention 1-14 methanol/water = 1/9 Present invention 1-15 R140 0.2 SR494 97 wt % 2-butanone Comparative example 1-16 PET-30 97 wt % Comparative example 1-17 FF-214 59 wt % PET-30 38 wt % methanol Present invention 1-18 FF-214 97 wt % Present invention 1-19 FF-214 97 wt % Irgacure2959 methanol/water = 5/5 Present invention

(6) The thickness, the resin composition and the water absorption rate of the support in table 1 are as follows. ARTON: thickness of 70 ?m, resin compositioncyclic olefin polymer, water absorption rate0.4% ZEONOR: thickness of 100 ?m, resin compositioncyclic olefin polymer, water absorption rate<0.01% TOPAS: thickness of 100 ?m, resin compositioncyclic olefin polymer, water absorption rate0.02% R140: thickness of 100 ?m, resin compositionpolycarbonate, water absorption rate0.2%

(7) The manufacturers and the chemical structures of the polymerizable compounds in Table 1 are as follows. FF-214: it was synthesized by a method described in the synthesis of the exemplified compound (1a) disclosed in Example of Japanese Unexamined Patent Application Publication No. 2012-206992.

(8) Structural Formula

(9) ##STR00020##
In the formula, all Rs are hydrogen atoms. PET-30: manufactured by Nippon Kayaku Co., Ltd.

(10) ##STR00021## SR494: manufactured by Kayaku Sartomer Co., Ltd.

(11) ##STR00022##
(Formation of the First Organic Layer)

(12) The precursor composition was prepared by setting the solid proportion of the polymerizable compound to 97 mass % and the solid proportion of the polymerization initiator to 3 mass %, and dissolving each of the polymerizable compound and the polymerization initiator in the solvent shown in Table 1. The precursor composition was applied, by a spin coat method, onto the support subjected to a surface treatment with an atmospheric-pressure plasma in an air atmosphere, and then, the resultant applied material was dried at room temperature for 4 minutes. Subsequently, in an atmosphere of nitrogen having an oxygen content of 100 ppm or less, and at a temperature of 80? C., irradiation with ultraviolet rays having a main wavelength of 365 nm was performed at an irradiation amount of 0.6 J/cm.sup.2 to thereby cure the resultant material by photopolymerization, with the result that an organic layer was produced.

(13) Adequate adjustments of the solid concentration within a range of 15 to 35 mass % and the number of rotations of the spin coating within a range of 500 to 2000 rpm were made such that the film thickness after the polymerization and curing was 2 ?m.

(14) (Formation of Inorganic Barrier Layer)

(15) Through the use of a plasma CVD method using ammonia, silane and hydrogen as raw material gases, a film of silicon nitride (refractive index of 1.95) having a thickness of 35 nm was formed on the surface of the organic layer prepared as described above. 1 atm % of carbon and 25 atm % of hydrogen were contained in the film of silicon nitride.

(16) (Formation of the Second Organic Layer)

(17) In the solid proportion, 73 mass % of 3-functional acrylate monomer: Aronix M-308 (manufactured by Toa Gosei Co., Ltd.), 20 mass % of silane coupling agent: KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.), 5 mass % of phosphoric acid group-containing 1-functional acrylate monomer: PM-21 (manufactured by Nippon Kayaku Co., Ltd.) and 2 mass % of polymerization initiator: DarocureTPO (manufactured by Ciba Specialty Chemicals Inc.) were dissolved in 2-butanone solvent at a solid concentration of 22 mass %, and thus the polymerizable composition was prepared. Spin-coating was performed by adequate adjustments of the number of rotations of the spin coating within a range of 800 to 1600 rpm such that the film thickness after the film formation was 1 ?m, and then, the resultant material was dried at room temperature for 4 minutes. Subsequently, in an atmosphere of nitrogen having an oxygen content of 100 ppm or less, and at a temperature of 80? C., irradiation with ultraviolet rays having a main wavelength of 365 nm was performed at an irradiation amount of 0.6 J/cm.sup.2 to thereby cure the resultant material by photopolymerization, with the result that an organic layer was produced.

(18) (Performance Evaluation of Gas Barrier Film)

(19) The barrier performance (water vapor transmission rate), the flexibility and the interlayer adhesion after wet heat aging were evaluated for the obtained gas barrier films, by the following method.

(20) [Barrier Performance Evaluation]

(21) Evaluation was performed in terms of the water vapor transmission rate (g/m.sup.2/day) measured using a method described in pages 1435 to 1438 of SID Conference Record of the International Display Research Conference by G. NISATO, P. C. P. BOUTEN, P. J. SLIKKERVEER, et al. The atmosphere on the supply side of water vapor was set to 40? C., and the relative humidity was set to 90%.

(22) [Flexibility Evaluation]

(23) Evaluation was performed using a cylindrical mandrel bending test. A test sample was wound around a mandrel for bending test with the side where the organic layer and the inorganic barrier layer are laminated being directed outward, was folded by 180?, was held for 5 seconds and was then returned to an unfolded state. Whether a crack or a break is generated in the bent portion of the sample thus obtained was observed visually and with an optical microscope having a magnification of 100. The superiority or inferiority of the flexibility was evaluated depending on to what extent the test sample bears the bending test using a mandrel of a smaller diameter, without occurrence of a crack or a break when the diameter of the mandrel was gradually decreased.

(24) The results thereof are shown in Table 2.

(25) TABLE-US-00002 TABLE 2 The smallest bend diameter without Sample WVTR(g/m.sup.2/day) a crack (mm) @ No. @40 C. 90% RH cylindrical mandrel Remarks 1-1 3.5 ? 10.sup.?4 3 Comparative example 1-2 2.5 ? 10.sup.?4 3 Comparative example 1-3 1.8 ? 10.sup.?4 2 Present invention 1-4 1.2 ? 10.sup.?4 2 Present invention 1-5 3.0 ? 10.sup.?4 8 Comparative example 1-6 2.0 ? 10.sup.?4 8 Comparative example 1-7 1.5 ? 10.sup.?4 6 Present invention 1-8 1.0 ? 10.sup.?4 6 Present invention 1-9 5.0 ? 10.sup.?4 16 Comparative example 1-10 4.0 ? 10.sup.?4 20 Comparative example 1-11 1.5 ? 10.sup.?4 3 Present invention 1-12 1.0 ? 10.sup.?4 2 Present invention 1-13 1.0 ? 10.sup.?4 2 Present invention 1-14 1.2 ? 10.sup.?4 2 Present invention 1-15 6.0 ? 10.sup.?4 10 Comparative example 1-16 4.0 ? 10.sup.?4 16 Comparative example 1-17 1.7 ? 10.sup.?4 3 Present invention 1-18 1.0 ? 10.sup.?4 2 Present invention 1-19 1.2 ? 10.sup.?4 2 Present invention

(26) As is clear from the above results, it is found that the gas barrier film containing the organic layer formed of the polymerizable composition containing the polymerizable compound (FF-214) represented by general formula (1) are excellent in barrier performance and flexibility. It is also clear that the polymerizable composition containing the polymerizable compound represented by general formula (1) can be applied not only to a support of a cyclic olefin copolymer satisfying the requirements of a film support disclosed in Japanese Unexamined Patent Application Publication No. 2012-213938 and having a water absorption rate of 0.1% or less, but also to a film of a cyclic olefin polymer having a water absorption rate of 0.4% and a polycarbonate film. Furthermore, for the film of the cyclic olefin polymer having a water absorption rate of 0.4%, when the organic layer in comparative examples is used, the barrier performance and the flexibility were inferior to those for the film of the cyclic olefin copolymer having a water absorption rate of 0.1% or less, but when the organic layer formed of the polymerizable composition containing the polymerizable compound represented by general formula (1) is used, the barrier performance and the flexibility were substantially equal to those for the film of the cyclic olefin copolymer having a water absorption rate of 0.1% or less, with the result that the total of the barrier performance and the flexibility was superior to those for the film of the cyclic olefin copolymer having a water absorption rate of 0.1% or less.

Example 2

(27) [Preparation of Gas Barrier Films Having Structure of Support/Inorganic Barrier Layer/Organic Layer/Inorganic Barrier Layer/Organic Layer]

(28) The gas barrier films of 2-1 to 2-14 having a multilayer structure of the support/the inorganic barrier layer/the organic layer/the inorganic barrier layer/the organic layer were prepared by changing a polymerizable compound, the type of an application solvent of a precursor composition and a polymerization initiator as shown in Table 3, in the preparation of a support and the first and the second organic layers. The barrier performance and the haze of the prepared gas barrier films were evaluated.

(29) TABLE-US-00003 TABLE 3 Support First organic polymer layer Sample No. Support name Moisture content (%) Polymerizable compound Polymerization initiator Application solvent 2-1 ARTON 0.4 SR494 78 wt % DarocureTPO 3 wt % 2-butanone KBM-5103 20 wt % 2-2 PET-30 78 wt % KBM-5103 20 wt % 2-3 FF-214 59 wt % methanol PET-30 39 wt % KBM-5103 20 wt % 2-4 FF-214 78 wt % KBM-5103 20 wt % 2-5 FF-214 78 wt % KBM-5103 20 wt % 2-6 FF-214 78 wt % Irgacure2959 methanol/water = 5/5 KBM-5103 20 wt % 2-7 FF-214 78 wt % methanol/water = 1/9 KBM-5103 20 wt % 2-8 FF-214 78 wt % KBM-5103 20 wt % 2-9 R140 0.2 SR494 78 wt % DarocureTPO 3 wt % 2-butanone KBM-5103 20 wt % 2-10 PET-30 78 wt % KBM-5103 20 wt % 2-11 FF-214 59 wt % methanol PET-30 39 wt % KBM-5103 20 wt % 2-12 FF-214 78 wt % KBM-5103 20 wt % 2-13 FF-214 78 wt % KBM-5103 20 wt % 2-14 FF-214 78 wt % Irgacure2959 methanol/water = 5/5 KBM-5103 20 wt % Second organic polymer layer Sample No. Polymerizable compound Polymerization initiator Application solvent Remarks 2-1 PET-30 73 wt % DarocureTPO 2 wt % 2-butanone Comparative example KBM-5103 20 wt % PM-21 5 wt % 2-2 PET-30 73 wt % Comparative example KBM-5103 20 wt % PM-21 5 wt % 2-3 PET-30 73 wt % Present invention KBM-5103 20 wt % PM-21 5 wt % 2-4 PET-30 73 wt % Present invention KBM-5103 20 wt % PM-21 5 wt % 2-5 FF-214 73 wt % methanol Present invention KBM-5103 20 wt % PM-21 5 wt % 2-6 PET-30 73 wt % 2-butanone Present invention KBM-5103 20 wt % PM-21 5 wt % 2-7 PET-30 73 wt % Present invention KBM-5103 20 wt % PM-21 5 wt % 2-8 FF-214 73 wt % Irgacure2959 2 wt % methanol/water = 1 Present invention KBM-5103 20 wt % PM-21 5 wt % 2-9 PET-30 73 wt % DarocureTPO 2 wt % 2-butanone Comparative example KBM-5103 20 wt % PM-21 5 wt % 2-10 PET-30 73 wt % Comparative example KBM-5103 20 wt % PM-21 5 wt % 2-11 PET-30 73 wt % Present invention KBM-5103 20 wt % PM-21 5 wt % 2-12 PET-30 73 wt % Present invention KBM-5103 20 wt % PM-21 5 wt % 2-13 FF-214 73 wt % methanol Present invention KBM-5103 20 wt % PM-21 5 wt % 2-14 PET-30 73 wt % 2-butanone Present invention KBM-5103 20 wt % PM-21 5 wt %

(30) The thickness of the support, the resin composition and the water absorption rate in Table 3 are the same as those in Table 1.

(31) The manufacturers and the chemical structures of the respective polymerizable compounds in Table 3 are the same as those in Table 1 in Example 1.

(32) (Formation of the First Inorganic Barrier Layer)

(33) A film of silicon nitride (refractive index of 1.95) having the same thickness (35 nm) was formed under the same conditions as those of the inorganic barrier layer in Example 1.

(34) (Formation of the First Organic Layer)

(35) The polymerizable composition was prepared by setting solid proportion of the polymerizable compound to 98 mass % and the solid proportion of the polymerization initiator to 2 mass %, and dissolving each of the polymerizable compound and the polymerization initiator in the solvent shown in Table 1. Among 98 mass % of the polymerizable compound, 20 mass % was applied to silane coupling agent: KBM-5103, and 78 mass % of the remainder was changed for each sample. The polymerizable composition was applied, by a spin coating method, onto the support obtained by forming the first inorganic barrier layer, and the resultant material was dried at a temperature of 110? C. for 3 minutes. The same condition as that of the first organic layer in Example 1 was used in the curing process with the subsequent ultraviolet ray irradiation, to prepare the organic layer.

(36) Adequate adjustments of the solid concentration within a range of 15 to 35 mass % and the number of rotations of the spin coating within a range of 500 to 2000 rpm were made such that the film thickness after the polymerization and curing was 2 ?m.

(37) (Formation of the Second Inorganic Barrier Layer)

(38) A film of silicon nitride (refractive index of 1.95) having the same thickness (35 nm) was formed under the same conditions as those of the first inorganic barrier layer.

(39) (Formation of the Second Organic Layer)

(40) The polymerizable composition was prepared by setting the solid proportion of the polymerizable compound to 98 mass % and the solid proportion of the polymerization initiator to 2 mass %, and dissolving each of the polymerizable compound and the polymerization initiator in the solvent shown in Table 1. In 98 mass % of the polymerizable compound, 20 mass % was applied to silane coupling agent: KBM-5103, and 5 mass % to phosphoric acid group-containing 1-functional acrylate monomer: PM-21, and 73 mass % of the remainder was changed for each sample. The polymerizable composition was applied, by a spin coating method, onto the support obtained by forming the second inorganic barrier layer, and the resultant material was dried at room temperature for 4 minutes. The same condition as that of the first organic layer in Example 1 was used in the curing process with the subsequent ultraviolet ray irradiation, to prepare the organic layer. Adequate adjustments of the solid concentration within a range of 15 to 25 mass % and the number of rotations of the spin coating within a range of 500 to 2000 rpm were made such that the film thickness after the film formation was 1 ?m.

(41) [Barrier Performance Evaluation]

(42) Evaluation was performed by the same method as in Example 1.

(43) [Evaluations on Haze and Total Light Transmittance]

(44) Haze to a D65 light source was measured through the use of NDH2000 manufactured by Nippon Denshoku Industries Co. Ltd, in accordance with JIS-K7136 and JIS-K7361. The results thereof are shown in Table 4.

(45) TABLE-US-00004 TABLE 4 Sample WVTR(g/m.sup.2/day) Haze (%) @D65 No. @40 C. 90% RH light source Remarks 2-1 2.5 ? 10.sup.?4 1.45 Comparative example 2-2 2.0 ? 10.sup.?4 1.43 Comparative example 2-3 7.4 ? 10.sup.?5 0.30 Present invention 2-4 4.9 ? 10.sup.?5 0.30 Present invention 2-5 4.7 ? 10.sup.?5 0.27 Present invention 2-6 5.0 ? 10.sup.?5 0.30 Present invention 2-7 5.2 ? 10.sup.?5 0.32 Present invention 2-8 5.0 ? 10.sup.?5 0.28 Present invention 2-9 2.9 ? 10.sup.?4 1.88 Comparative example 2-10 2.0 ? 10.sup.?4 1.75 Comparative example 2-11 8.4 ? 10.sup.?5 0.63 Present invention 2-12 5.0 ? 10.sup.?5 0.59 Present invention 2-13 4.8 ? 10.sup.?5 0.60 Present invention 2-14 5.2 ? 10.sup.?5 0.61 Present invention

(46) As apparent from the results of Table 4, the barrier performance was satisfactory and the haze was low, in the gas barrier film including the organic layer formed of the polymerizable composition containing the monomer represented by general formula (1). In the test samples with haze exceeding 1%, which use the organic layer of comparative examples, minute wrinkles were generated in the vicinity of the interface between the support and the first inorganic layer.

(47) <Evaluation on Organic EL Light-Emitting Element>

(48) In order to evaluate a barrier property, an organic EL element that generates a black spot (dark spot) defect by water vapor or oxygen was produced, and a module obtained by sealing the element with the gas barrier film of Example 2 was evaluated. First, a conductive glass substrate (surface resistivity 10?/? (?/sq., ohms per square)) including an ITO film was washed with 2-propanol, and then, UV-ozone processing was performed for 10 minutes. The following compound layers were sequentially deposited on the substrate (positive electrode), by a vacuum deposition method. (First Hole Transport Layer) Copper phthalocyanine: film thickness of 10 nm (Second Hole Transport Layer) N,N-diphenyl-N,N-dinaphthylbenzidine: film thickness of 40 nm (Light-Emitting Layer and Electron Transport Layer) Tris(8-hydroxyquinolinato) aluminum: film thickness of 60 nm (Electron Injection Layer) Lithium fluoride: film thickness of 1 nm

(49) Deposition of 100 nm of metal aluminum thereon forms a negative electrode, and a silicon nitride film having a thickness of 1.5 ?m was provided thereon using a plasma CVD method, with the result that the organic EL element was prepared.

(50) Then, each of the gas barrier films produced as described above was stuck onto the prepared organic EL element through the use of a thermosetting adhesive (Epotec 310, Daizo Nichimori Co. Ltd.) such that the barrier layer were placed on the side of the organic EL element, and the adhesive was cured by heating at 65? C. for 3 hours. The organic EL element sealed in this manner was prepared, and a voltage of 7V was applied to the organic EL element to make it emit light, through the use of a source measure unit (SMU2400 type, manufactured by Keithley Inc.). When the light-emitting surface was observed with a microscope, it was found that the organic EL element sealed with the gas barrier film of the present invention uniformly emitted light without any dark spot even after it was left for 24 hours under an environment of 60? C. and 90% relative humidity.

(51) <Preparation of Solar Battery>

(52) A solar battery module was prepared by using the gas barrier film prepared in Example 1 described above. Specifically, ethylene-vinyl acetate copolymer of a standard cure type was used as a filler for the solar battery module. On a reinforced glass of 10 cm square, an amorphous silicon solar battery cell was sandwiched and filled by the ethylene-vinyl acetate copolymer having a thickness of 450 ?m, and furthermore, the gas barrier film was stuck thereon to prepare the solar battery module. The installation conditions were vacuuming at 150? C. for 3 minutes, and then crimping for 9 minutes. The solar battery module to which the gas barrier film of the present invention was stuck was satisfactorily operable and exhibited satisfactory electrical output characteristics even under an environment of 85? C. and 85% relative humidity.

(53) Since the gas barrier film of the present invention has a high barrier performance and a high transparency, the film can be applied to various types of electronic devices, and preferably to the sealing of the front side of an organic EL or a solar battery. Since it is possible to produce a gas barrier film having high wet heat durability, the film can be particularly preferably used for protecting an electronic device used outdoors.

(54) While the present invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof. All the publications referred to in the present specification are expressly incorporated herein by reference in their entirety. The foregoing description of preferred embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or to limit the invention to the precise form disclosed. The description was selected to best explain the principles of the invention and their practical application to enable others skilled in the art to best utilize the invention in various embodiments and various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention not be limited by the specification, but be defined claims set forth below.