JPWO2015108086A1 - Gas barrier film and electronic device including the same - Google Patents

Abstract

A gas barrier film having high adhesion strength between a gas barrier layer containing a polyimide substrate and a silicon compound is provided. A gas barrier film in which at least a polyimide base material, a metal oxide layer containing a metal oxide, and a gas barrier layer containing a silicon compound are laminated in this order. [Selection figure] None

Description

<Technical field>
The present invention relates to a gas barrier film and an electronic device including the same.

<Related technologies>
Conventionally, a gas barrier film in which a thin film (gas barrier layer) containing a metal oxide such as aluminum oxide, magnesium oxide, or silicon oxide is formed on the surface of a plastic substrate or film is used for packaging articles in the fields of food, medicine, etc. It is used for. By using the gas barrier film, it is possible to prevent alteration of the article due to gas such as water vapor or oxygen.

  In recent years, with regard to such a gas barrier film that prevents permeation of water vapor, oxygen, and the like, development for electronic devices such as an organic electroluminescence (EL) element and a liquid crystal display (LCD) element has been requested, and many studies have been made. . When using a gas barrier film for an electronic device, a high gas barrier property, for example, a gas barrier property comparable to a glass substrate is required.

  As such a gas barrier film having a high gas barrier property, a gas barrier layer is formed on a substrate such as polypropylene (PP) or polyethylene terephthalate (PET) by physical vapor deposition or chemical vapor deposition. A gas barrier film produced by a so-called dry film forming method (see, for example, Patent Document 1) or a coating liquid containing polysilazane is applied on a substrate, and the resulting polysilazane coating film is modified to form a gas barrier. A gas barrier film produced by a so-called wet film forming method for forming a layer (for example, see Patent Document 2) is known. In Patent Document 1, the main component of the gas barrier layer in the gas barrier film produced by the dry film forming method is silicon oxide, and in Patent Document 2, the gas barrier in the gas barrier film produced by the wet film forming method. The main component of the layer is a modified polysilazane, and any gas barrier layer contains a silicon compound.

  By the way, when manufacturing an electronic device, a film is bonded to carrier glass or the like, and a device is formed by sequentially forming a functional layer or the like on the film by roll-to-roll or the like, and finally the device is formed from carrier glass or the like. A so-called device forming process of separation is preferably employed because of its excellent productivity. At this time, in the device formation process, the process may be exposed to a high temperature environment of 300 ° C. or higher, and the film to be used needs to have heat resistance. A polyimide base material is mentioned as a film provided with such heat resistance.

JP-A-11-240102 JP 2012-86436 A

<Outline of the invention>
Since the conventional gas barrier film mainly uses a thermoplastic resin such as PP or PET, it cannot be applied to a device forming process exposed to a high temperature environment.

  Further, it has been found that when a gas barrier layer containing a silicon compound is formed on a polyimide substrate, the adhesion (adhesive strength) between the polyimide substrate and the gas barrier layer becomes insufficient under a high temperature environment. As a result, in the device formation process, when separating the device from the carrier glass or the like during the process or after the device formation process, the gas barrier layer may be peeled off from the polyimide base material, making it difficult to apply to the device formation process. It becomes.

  Then, an object of this invention is to provide the gas-barrier film with the high adhesiveness of the gas barrier layer containing a polyimide base material and a silicon compound. Thereby, the gas-barrier film which concerns on this invention can be applied suitably for a device formation process.

  As a result of diligent research, the present inventors have found that the above problem can be solved by providing a metal oxide layer between a polyimide base material and a gas barrier layer containing a silicon compound, and the present invention has been completed. I came to let you.

  That is, in order to achieve at least one of the above-described objects, a gas barrier film reflecting one aspect of the present invention, an electronic device including the same, and a method for manufacturing the electronic device include the following.

(1) A gas barrier film in which at least a polyimide base material, a metal oxide layer containing a metal oxide, and a gas barrier layer containing a silicon compound are laminated in this order;
(2) The gas barrier film according to (1), wherein the polyimide is a polymer containing biphenyltetracarboxylic dianhydride and p-phenylenediamine as monomers;
(3) (1) or (2), wherein the metal oxide includes at least one selected from the group consisting of aluminum oxide, titanium oxide, tin oxide, cerium oxide, and zinc oxide. The gas barrier film according to the description;
(4) The gas barrier film according to any one of (1) to (3), wherein a thermal expansion coefficient at 200 to 300 ° C. is 15 ppm / K or less;
(5) The gas barrier film according to any one of (1) to (4), wherein the gas barrier layer has a two-layer structure;
(6) An electronic device comprising the gas barrier film according to any one of (1) to (5);
(7) A method for manufacturing the electronic device according to (6), which includes a step performed in an environment of 200 to 500 ° C.

It is a schematic diagram which shows an example of the manufacturing apparatus used for formation of the gas barrier layer by plasma CVD method.

<Description of Preferred Embodiment>
Hereinafter, embodiments for carrying out the present invention will be described in detail. In addition, this invention is not limited only to the following embodiment. In this specification, “X to Y” indicating a range means “X or more and Y or less”. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%. Moreover, the ratio of drawing may be exaggerated for description.

<Gas barrier film>
The gas barrier film according to the present embodiment is formed by laminating at least a polyimide base material, a metal oxide layer containing a metal oxide, and a gas barrier layer containing a silicon compound in this order. According to the configuration of such an embodiment, a gas barrier film having high adhesion of a gas barrier layer containing a polyimide base material and a silicon compound can be provided.

  Since the polyimide base material generally has excellent heat resistance, it can withstand the high temperature environment of the device forming process and can be used for the device forming process. However, it is known that the polyimide base material has low adhesion to other materials, and in particular, the adhesion to the gas barrier layer containing a silicon compound in a high temperature environment has been found to be very low. Therefore, when a gas barrier film including a polyimide base material and the gas barrier layer is applied to a device forming process, the polyimide base material and the gas barrier layer are peeled off when the device is separated from the carrier glass during the process or after the device formation. sell. As a result, a desired device cannot be formed.

  In contrast, in the gas barrier film according to this embodiment, a metal oxide layer is disposed between a gas barrier layer containing a polyimide base material and a silicon compound. Although the detailed mechanism is not clear, the gas barrier layer containing the silicon compound is disposed on the polyimide base material via the metal oxide layer, thereby improving the adhesion between the polyimide base material and the gas barrier layer in a high temperature environment. Can be. As a result, peeling of the polyimide base material and the gas barrier layer in the device forming process can be prevented, and the method can be suitably applied to the device forming process.

  The adhesive strength of the polyimide base material and the gas barrier layer of the gas barrier film according to this embodiment is preferably 1.3 N / cm or more, more preferably 4 N / cm or more, and 8 N / cm or more. Further preferred. In the present specification, “adhesive strength between a polyimide base material and a gas barrier layer” means an adhesive strength between a polyimide base material and a gas barrier layer containing a silicon compound. At this time, in this specification, the value measured in accordance with the 180 degree peeling method of JIS C6471: 1995 is adopted as the value of “adhesive strength of the polyimide base material and the gas barrier layer”. More specifically, a predetermined adhesive tape is affixed to the outermost surface of the manufactured gas barrier film. Next, the end of the tape was pulled at a speed of 30 mm / min using FGS-50E (manufactured by Nidec Shinpo Co., Ltd.) which is an electric vertical force gauge stand, and the polyimide base material, the gas barrier layer, Check if the peels off. Under the present circumstances, peel strength can be measured with the kind of adhesive tape to be used. For example, sealing masking tape No. 2541 (adhesive strength: 1.3 N / cm, manufactured by Nichiban Co., Ltd.), the polyimide base material and the gas barrier layer did not peel off, and cello tape (registered trademark) No. When 5511 (adhesive strength: 2.7 N / cm, manufactured by Nichiban Co., Ltd.) is used, when the polyimide substrate and the gas barrier layer are peeled off, the adhesive strength of the polyimide substrate and the gas barrier layer is 1.3 N / cm. It becomes less than super 2.7 N / cm.

The water vapor permeability of the gas barrier film is preferably 0.01 g / (m ² · 24 h) or less, and more preferably 0.0001 g / (m ² · 24 h) or less. In addition, in this specification, the value measured by the method based on JISK7129-1992 shall be employ | adopted for the value of "water vapor permeability". Measurement conditions are temperature: 60 ± 0.5 ° C. and relative humidity (RH): 90 ± 2%.

  The coefficient of thermal expansion (CTE) at 200 to 300 ° C. of the gas barrier film (that is, all the components such as the base material / metal oxide layer / silicon compound layer) is preferably 40 ppm / K or less, and 35 ppm / K or less. More preferably, it is 25 ppm / K or less, more preferably 15 ppm / K or less, and still more preferably 12 ppm / K or less.

  When the CTE at 200 to 300 ° C. is particularly 9 ppm / K or less, the polyimide base material is balanced with both the metal oxide film to be laminated and the silicon compound to be laminated on the metal oxide in the high temperature environment of the device forming process. And a gas barrier layer containing a silicon compound is preferable because it is easy to prevent peeling. The lower limit is preferably 0 ppm / K or more, and more preferably 1 ppm / K or more, from the viewpoint of the same behavior as CTE and several ppm of the laminated film (thermal expansion rather than thermal contraction). It is particularly preferable from the viewpoint of adhesion (adhesive strength) that it is 3 ppm / K or more.

  In addition, the thermal expansion coefficient of the gas barrier film may be appropriately changed depending on the components, film thickness, layer structure (single layer, laminated layer, etc.), etc., of the polyimide substrate, metal oxide layer, gas barrier layer, etc. constituting the gas barrier film. Can be controlled. In this specification, the value measured by the method described in the Examples is adopted as the value of “CTE at 200 to 300 ° C.”.

[Polyimide substrate]
The polyimide substrate is generally a resin film obtained by polymerizing a monomer containing tetracarboxylic dianhydride and diamine.

  Although it does not restrict | limit especially as tetracarboxylic dianhydride, Aliphatic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride are mentioned.

  Examples of the aliphatic tetracarboxylic dianhydride include bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] octane. -2,3,5,6-tetracarboxylic dianhydride, 5- (dioxotetrahydrofuryl-3-methyl) -3-cyclohexene-1,2-dicarboxylic anhydride, 4- (2,5-di Oxotetrahydrofuran-3-yl) -tetralin-1,2-dicarboxylic anhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, bicyclo-3,3 ', 4,4'-tetracarboxylic Acid dianhydride, 3c-carboxymethylcyclopentane-1r, 2c, 4c-tricarboxylic acid 1,4,2,3-dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1, 2 3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, and the like.

  Examples of the aromatic tetracarboxylic dianhydride include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3 ′, 3,4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, oxydiphthalic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3 , 3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, m-terphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, 4,4 ′-(2,2- Hexafluoroisopropylene) diphthalic dianhydride, 2,2′-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, Screw (3,4- Carboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7 -Naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3 3-hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, (1,1 ′: 3 ', 1 "-terphenyl) -3,3", 4,4 "-tetracarboxylic dianhydride, 4,4'-(dimethylsiladiyl) diphthalic dianhydride, 4,4 '-(1, 4-phenylenebis (oxy)) diphthalic dianhydride That.

  Among the above-mentioned tetracarboxylic dianhydrides, from the viewpoint of obtaining a polyimide base material having excellent chemical and physical properties, it is preferably an aromatic tetracarboxylic dianhydride, pyromellitic dianhydride, More preferably, it is biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyl More preferred are tetracarboxylic dianhydride and 2,3 ′, 3,4′-biphenyltetracarboxylic dianhydride.

  Moreover, the above-mentioned tetracarboxylic dianhydride may be used independently or may be used in combination of 2 or more type.

  Although it does not restrict | limit especially as diamine, Aliphatic diamine and aromatic diamine are mentioned.

  Examples of the aliphatic diamine include diaminobutane, diaminopentane, diaminohexane, diaminoheptane, diaminooctane, diaminononane, diaminodecane, diaminoundecane, diaminododecane, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,2 -Diaminocyclohexane, 3-methyl-1,4-diaminocyclohexane, 3-methyl-, 3-aminomethyl-, 5,5-dimethylcyclohexylamine, 1,3-bisaminomethylcyclohexane, bis (4,4'- Aminocyclohexyl) methane, bis (3,3′-methyl-4,4′-aminocyclohexyl) methane, bis (aminomethyl) norbornane, bis (aminomethyl) -tricyclo [5,2,1,0] decane, isophorone Diamine, 1,3 Diamino adamantane.

  Examples of the aromatic diamine include p-phenylenediamine, metaphenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3, 4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4, 4'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-bis (4-aminophenyl) sulfide, 4,4'-diaminodiphenyl sulfone, 4,4'- Diaminobenzanilide, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4- Minophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 2,2- Bis (4-aminophenoxyphenyl) propane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-amino) Phenoxy) phenyl] hexafluoropropane.

  Of the above diamines, aromatic diamines are preferable from the viewpoint of obtaining a polyimide base material having excellent chemical and physical properties, and 4,4′-diaminodiphenyl ether and p-phenylenediamine are more preferable. preferable.

  Moreover, the above-mentioned diamine may be used independently or may be used in combination of 2 or more type.

  Of these, the polyimide substrate is preferably biphenyltetracarboxylic dianhydride or pyromellitic dianhydride and p-phenylenediamine or 4,4'-diaminodiphenyl ether.

  As described above, the polyimide base material can be obtained by polymerizing a monomer containing tetracarboxylic dianhydride and diamine. More specifically, (1) a polyamic acid is synthesized by reacting tetracarboxylic dianhydride and diamine in an organic solvent, and (2) a polyimide substrate is produced by imidizing the obtained polyamic acid. can do.

(1) Synthesis of polyamic acid A polyamic acid can be synthesized by reacting a tetracarboxylic dianhydride and a diamine in an organic solvent. The reaction is preferably performed by dissolving diamine in an organic solvent and gradually adding tetracarboxylic dianhydride while stirring the obtained diamine solution.

  The organic solvent that can be used is not particularly limited, but amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide; γ-butyrolactone, cyclic ester solvents such as γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone; carbonate solvents such as ethylene carbonate and propylene carbonate; glycol solvents such as triethylene glycol; Phenolic solvents such as m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol; acetophenone; 1,3-dimethyl-2-imidazolidinone; sulfolane; dimethyl sulfoxide and the like. Also, phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, tetrahydrofuran, dimethoxyethane, diethoxyethane, General solvents such as dibutyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, terpene, mineral spirit, petroleum naphtha solvents An organic solvent may be used. Of these, it is preferable to use an amide solvent. In addition, said organic solvent may be used independently or may be used in combination of 2 or more type.

  The molar ratio of tetracarboxylic dianhydride and diamine used in the reaction (tetracarboxylic dianhydride / diamine) can be appropriately set according to the viscosity of the polyamic acid, but is 0.90 to 1.10. Is more preferable, and 0.95 to 1.05 is more preferable.

  The reaction temperature is preferably 0 to 100 ° C. The reaction time is preferably 1 to 72 hours.

(2) Production of polyimide substrate A polyimide substrate can be produced by imidizing the polyamic acid obtained in (1) above.

  In one embodiment, the production of the polyimide base material can be performed by casting a solution containing polyamic acid on a support and heating.

  The solution containing the polyamic acid contains a polyamic acid and an organic solvent. If necessary, it may further contain an imidization catalyst, an organic phosphorus-containing compound, inorganic fine particles and the like.

  As the polyamic acid, the one obtained in the above (1) is used. Under the present circumstances, polyamic acid may be used independently or may be used in combination of 2 or more type. Moreover, it is preferable that content of a polyamic acid is 10-30 mass% with respect to the solution whole quantity containing a polyamic acid.

  As the solvent, those described above can be used.

  The imidization catalyst has a function of improving the physical properties (elongation, end tear resistance, etc.) of the polyimide film.

  Although it does not restrict | limit especially as an imidation catalyst, A substituted or unsubstituted nitrogen-containing heterocyclic compound and this N-oxide compound; A substituted or unsubstituted amino acid compound; Aromatic hydrocarbon compound which has a hydroxyl group; Aromatic heterocyclic Compounds.

  Specific imidization catalysts include 1,2-dimethylimidazole, N-methylimidazole, N-benzyl-2-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 5-methylbenzimidazole, N-benzyl-2-methylimidazole, isoquinoline, 3,5-dimethylpyridine, 3,4-dimethylpyridine, 2,5-dimethylpyridine, 2,4-dimethylpyridine, 4-n-propylpyridine and the like can be mentioned.

  The amount of the imidization catalyst used is preferably 0.01 to 2 equivalents, more preferably 0.02 to 1 equivalents relative to the amic acid unit of the polyamic acid.

  The organic phosphorus-containing compound is not particularly limited, but is monocaproyl phosphate ester, monooctyl phosphate ester, monolauryl phosphate ester, monomyristyl phosphate ester, monocetyl phosphate ester, monostearyl phosphate ester, triethylene Monophosphate ester of glycol monotridecyl ether, monophosphate ester of tetraethylene glycol monolauryl ether, monophosphate ester of diethylene glycol monostearyl ether, dicaproyl phosphate ester, dioctyl phosphate ester, dicapryl phosphate ester, dilauryl phosphate ester, dimyristyl Diphosphate ester of phosphate ester, dicetyl phosphate ester, distearyl phosphate ester, tetraethylene glycol mononeopentyl ether Ter, diethylene phosphate of triethylene glycol monotridecyl ether, diphosphate ester of tetraethylene glycol monolauryl ether, diphosphate ester of diethylene glycol monostearyl ether, amine salts of these phosphate esters can be used . Amine salts include ammonia, monomethylamine, monoethylamine, monopropylamine, monobutylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, monoethanolamine, diethanolamine, triamine. Examples include amine salts such as ethanolamine. These organic phosphorus-containing compounds may be used alone or in combination of two or more.

  The inorganic fine particles are not particularly limited, but inorganic oxide powders such as fine particle titanium dioxide powder, silicon dioxide (silica) powder, magnesium oxide powder, aluminum oxide (alumina) powder, and zinc oxide powder; fine particle nitriding Examples thereof include inorganic nitride powders such as silicon powder and titanium nitride powder; inorganic carbide powders such as silicon carbide powder; inorganic salt powders such as particulate calcium carbonate powder, calcium sulfate powder and barium sulfate powder. These inorganic fine particles may be used alone or in combination of two or more. In addition, in order to disperse | distribute inorganic fine particles uniformly to the solution containing a polyamic acid, a means well-known per se can be applied.

  The support for casting a solution containing a polyamic acid is not particularly limited, and a known support such as a stainless steel substrate or a stainless steel belt can be used. Moreover, you may use the carrier glass used for a device formation process as a support body (in this case, since a polyimide base material is formed on a carrier glass, by manufacturing a gas barrier film using this, It can be applied to the device formation process as it is). At this time, the support is preferably smooth. The support is preferably an endless support such as an endless belt from the viewpoint of enabling continuous production.

  The method for casting the solution containing polyamic acid is not particularly limited, but is preferably extrusion coating or melt coating.

  When a solution containing a polyamic acid is cast on a support, a coating film having self-supporting properties can be obtained.

  Under the present circumstances, you may apply | coat the solution containing a surface treating agent to the single side | surface or both surfaces of the obtained coating film which has a self-supporting property as needed. In addition, in this specification, the process in the manufacturing process of the polyimide base material by the said surface treating agent is not included in the "surface treatment of a polyimide base material" mentioned later.

  The solution containing the surface treatment agent contains the surface treatment agent and an organic solvent.

  The surface treatment agent is not particularly limited, but silane coupling agents, borane coupling agents, aluminum coupling agents, aluminum chelating agents, titanate coupling agents, iron coupling agents, copper coupling agents and the like. Can be mentioned. Of these, silane coupling agents and titanate coupling agents are preferably used.

  The silane coupling agent is not particularly limited, but epoxy such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like. Silane coupling agents; vinyl silane coupling agents such as vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane; acrylic silane cups such as γ-methacryloxypropyltrimethoxysilane Ring agent: N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ -Aminopropylto Examples include aminosilane coupling agents such as limethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, and the like.

  The titanate coupling agent is not particularly limited, but is isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, isopropyl tris (dioctylpyrophosphate) titanate, tetraisopropylbis (dioctyl phosphite) titanate, tetra ( 2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyltricumyl Examples thereof include phenyl titanate.

  Of the above surface treatment agents, aminosilane coupling agents are preferably used, and γ-aminopropyl-triethoxysilane, N-β- (aminoethyl) -γ-aminopropyl-triethoxysilane, N- (aminocarbonyl). ) -Γ-aminopropyltriethoxysilane, N- [β- (phenylamino) -ethyl] -γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-amino More preferably, propyltrimethoxysilane is used, and N-phenyl-γ-aminopropyltrimethoxysilane is more preferably used.

  The above surface treatment agents may be used alone or in combination of two or more.

  Although content in particular of the surface treating agent in the solution containing a surface treating agent is not restrict | limited, It is preferable that it is 0.5 mass% or more with respect to the whole solution containing a surface treating agent, and is 1-100 mass%. Is more preferable, it is more preferable that it is 3-60 mass%, and it is especially preferable that it is 5-55 mass%.

  As the organic solvent, the same organic solvents used for the synthesis of the polyamic acid described above can be used.

  Examples of the coating method having a self-supporting solution containing a surface treatment agent include a gravure coating method, a spin coating method, a silk screen method, a dip coating method, a spray coating method, a bar coating method, and a knife coating method. And a known coating method such as a roll coating method, a blade coating method, and a die coating method.

The coating amount of the coating film having a self-supporting of the solution containing the surface treatment agent is not particularly limited, is preferably from 1 to 50 g / m ^2, more preferably from 2 to 30 g / m ² 3 to 20 g / m ² is particularly preferable.

  In this embodiment, imidation of polyamic acid is performed by heating the obtained coating film having self-supporting property, or the coating film obtained by applying a solution containing the coating film having self-supporting property and the surface treatment agent. And a polyimide substrate can be produced.

  The heating temperature for imidization is not particularly limited as long as imidization proceeds, but is preferably 100 to 550 ° C, and more preferably 100 to 400 ° C. At this time, the heating is preferably performed stepwise. For example, the heating is performed at 100 to 170 ° C. as the first heat treatment, the heating is performed at 170 to 220 ° C. as the second heat treatment, and 220 is performed as the third heat treatment. It can heat at -400 degreeC and can heat at 400-550 degreeC as a 4th heat processing.

  During heating, the film may be stretched as necessary. Thereby, physical properties, such as a thermal expansion coefficient of a polyimide base material, can be controlled suitably. At this time, the stretching method may be biaxial stretching such as sequential biaxial stretching and simultaneous biaxial stretching, or uniaxial stretching. The draw ratio is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction, respectively. In addition, you may perform a relaxation process after extending | stretching from a viewpoint of improving the dimensional stability of a polyimide base material.

  In one embodiment, the imidization of the polyamic acid can be performed by chemical imidation instead of or in addition to the above heating.

  Although the specific method of chemical imidation is not particularly limited, for example, a solution obtained by further adding a dehydrating agent and a catalyst to the solution containing the polyamic acid described above is cast on a support and heated. It can be carried out.

  The dehydrating agent is not particularly limited, and examples thereof include aliphatic acid anhydrides, aromatic acid anhydrides, alicyclic acid anhydrides, and heterocyclic acid anhydrides. Specific examples include acetic anhydride, propionic anhydride, butyric anhydride, formic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, picolinic anhydride, and the like. Of these, acetic anhydride is preferably used. In addition, the said dehydrating agent may be used independently or may be used in combination of 2 or more type.

  The addition amount of the dehydrating agent is preferably 0.5 mol or more with respect to 1 mol of the amic acid bond of the polyamic acid.

  The catalyst is not particularly limited, and examples thereof include aliphatic tertiary amines, aromatic tertiary amines, and heterocyclic tertiary amines. Specific examples include trimethylamine, triethylamine, dimethylaniline, pyridine, β-picoline, isoquinoline, quinoline and the like. Of these, isoquinoline is preferably used.

  It is preferable that the addition amount of a catalyst is 0.1 mol or more with respect to 1 mol of the amic acid bond of a polyamic acid.

  About the casting to a support body and heating, a polyimide base material can be manufactured by performing by the method similar to the above-mentioned.

  In addition to what was mentioned above as a polyimide base material, you may use the well-known polyimide base material manufactured by making tetracarboxylic dianhydride and diisocyanate react, for example.

  The polyimide base material may be further subjected to a surface treatment. Specific examples of the surface treatment include corona treatment, plasma treatment, UV ozone treatment, and excimer treatment.

  Modification, washing, and the like can be performed by surface-treating the polyimide base material. By the modification, an active group such as a hydroxyl group, a carboxy group, or an amino group can be introduced on the surface of the polyimide substrate. In addition, the wettability can be improved by the washing. Furthermore, by performing the surface treatment, the surface roughness can be increased and the anchor effect and the like can be expressed. By the action based on these at least one surface treatment, the adhesive strength between the polyimide base material and the gas barrier layer can be improved via the metal oxide layer.

Corona treatment Corona treatment is a method for surface modification using corona discharge that is excited by applying an alternating high voltage to a pair of electrodes in an atmospheric pressure state.

Plasma treatment Plasma treatment is a method in which oxygen gas or a mixed gas of oxygen gas and inert gas is ionized by arc discharge, and surface modification is performed using the plasma gas generated thereby.

  Examples of the inert gas that can be used include nitrogen gas, argon gas, and helium gas.

  As a method for generating plasma, for example, a direct current glow discharge, a high frequency discharge, a microwave discharge, or the like can be used.

  The supply amount of oxygen gas is preferably 1 to 50 sccm (0 ° C., 1 atm standard), more preferably 10 to 30 sccm.

  As a vacuum degree of a vacuum chamber, it is preferable that it is 0.5-50 Pa, and it is more preferable that it is 1-10 Pa.

  The applied power from the power source for generating plasma is preferably 50 to 500W.

  The frequency of the power source for generating plasma is preferably 5 to 50 kHz, and more preferably 10 to 20 kHz.

UV ozone treatment UV ozone treatment is a method in which ultraviolet rays (UV) are irradiated, oxygen in the air is converted into ozone, and surface modification is performed using ozone and ultraviolet rays.

  Examples of the light source used for the UV ozone treatment include a low-pressure mercury lamp (185 nm, 254 nm).

  The irradiation time is preferably 0.5 to 30 minutes, and more preferably 0.5 to 10 minutes.

Excimer treatment Excimer treatment is a method in which excimer light is irradiated, oxygen in the air is converted to ozone, and surface modification is performed using ozone and excimer light.

  Examples of the light source used for the UV ozone treatment include a Xe excimer lamp (172 nm), a krypton lamp (146 nm), and an argon lamp (126 nm). Among these, it is preferable to use a Xe excimer lamp.

Illuminance ^is preferably ^{1mW / cm 2 ~100kW / cm 2} , more preferably ^{100mW / cm 2 ~10W / cm 2} .

Cumulative exposure amount is preferably 10~1000mJ / cm ^2, and more preferably 50 to 500 mJ / cm ^2.

  The irradiation time is preferably 0.1 to 500 seconds, and more preferably 0.1 to 60 seconds.

  The film thickness of the polyimide base material is preferably 5 to 500 μm from the viewpoint of flexibility, more preferably 30 to 250 μm, and particularly preferably 25 to 150 μm from the viewpoint of CTE and handleability. preferable.

  Moreover, it is preferable that the thermal expansion coefficient (CTE) in 200-300 degreeC of a polyimide base material is 20 ppm / K or less, and it is more preferable that it is 10 ppm / K or less. It is preferable that the thermal expansion coefficient at 200 to 300 ° C. of the polyimide base material is 20 ppm / K or less because peeling of the polyimide base material and the gas barrier layer can be prevented or suppressed. In general, a polyimide base material tends to thermally expand in a high temperature environment. Moreover, the thermal expansion coefficient of a polyimide base material changes with compositions (monomer component) of a polyimide base material. Furthermore, the smaller the film thickness of the polyimide substrate, the lower the thermal expansion coefficient. Therefore, the thermal expansion coefficient of the polyimide base material can be controlled by appropriately changing the configuration of the polyimide base material.

  The polyimide substrate preferably has a visible light (400 to 700 nm) light transmittance of 80% or more, more preferably 90% or more. When the light transmittance is 80% or more, when a gas barrier film is applied to an electronic device such as a liquid crystal display (LCD panel), it is preferable because high luminance can be obtained. In the present specification, the “light transmittance” is a spectrophotometer (visible ultraviolet spectrophotometer UV-2500PC: manufactured by Shimadzu Corporation), and is based on the ASTM D-1003 standard. It means the average transmittance in the visible light range, which is calculated by measuring the total transmitted light amount with respect to the incident light amount.

  The polyimide base material preferably has a 10-point average surface roughness Rz defined by JIS B 0601 (2001) of 1 to 1500 nm, more preferably 5 to 400 nm, and further preferably 300 to 350 nm. preferable. In addition, the polyimide base material preferably has a center line average roughness Ra defined by JIS B 0601 (2001) of 0.5 to 12 nm, and more preferably 1 to 8 nm. It is preferable that Rz and Ra are within the above ranges since the coating property of the coating liquid is improved. If necessary, the polyimide base material may be polished on one side or both sides to improve smoothness.

  The elastic modulus of the polyimide base material is preferably 1 GPa or more, and more preferably 2 to 10 GPa. It is preferable for the elastic modulus of the polyimide base material to be 1 GPa or more because it has high dimensional stability and can be suitably applied to a device formation step. In addition, in this specification, the value measured based on ASTM D882-97 shall be employ | adopted for the value of "elastic modulus".

  In addition, the polyimide base material used by this invention may be prepared by purchasing a commercial item, for example, UPILEX-50SGA, UPILEX-50S (above, Ube Industries, Ltd. make), Kapton (trademark), (Toray Du Pont Co., Ltd.), XENOMAX (Toyobo), etc. are preferable from the viewpoint of CTE.

[Metal oxide layer]
The metal oxide layer includes a metal oxide. However, the metal oxide does not include a silicon-containing metal oxide such as silicon oxide.

  By providing the metal oxide layer between the polyimide base material and the gas barrier layer containing the silicon compound, the adhesion between the polyimide base material and the gas barrier layer can be enhanced. As described above, although the detailed mechanism that can improve the adhesion is not clear, the following mechanism is presumed as at least one factor. That is, it is considered that a polyimide base material having low adhesion to other materials is particularly incompatible with a silicon compound, and particularly has low adhesion to a silicon compound. As a result, even if a gas barrier layer containing a silicon compound is formed on a polyimide substrate, desired adhesion cannot be obtained. Therefore, by providing a metal oxide layer, which is a heat-resistant material other than a silicon compound, between the polyimide substrate and the gas barrier layer, the adhesion between the polyimide substrate and the metal oxide layer, and the metal oxide layer and the gas barrier are provided. It is considered that the adhesion of the layer can be improved, and as a result, the adhesion between the polyimide substrate and the metal oxide layer can be improved. Note that the above mechanism is just an estimate, and even if the adhesion is improved for other reasons, it is included in the technical scope of the present invention.

Accordingly, the metal oxide does not include a silicon-containing metal oxide such as silicon oxide. Therefore, the metal oxide is not particularly limited as long as it is other than a silicon-containing metal oxide, aluminum oxide such as aluminum oxide (Al ₂ O ₃ ); titanium oxide such as titanium oxide (TiO ₂ ); tin oxide Examples thereof include tin oxides such as (SnO ₂ , SnO, SnO ₃ ); cerium oxides such as cerium oxide (CeO ₂ ); zinc oxides such as zinc oxide (ZnO).

  Preferably, at least one selected from the group consisting of aluminum oxide, titanium oxide, tin oxide, cerium oxide, and zinc oxide is included, and among these, the film forming method is not selected and the production form is more matched. From the viewpoint of selecting a method, at least one selected from the group consisting of aluminum oxide, titanium oxide, tin oxide, and zinc oxide is included. These metal oxides may be used alone or in combination of two or more.

  From the viewpoint of optical properties, the thickness of the metal oxide layer is preferably 50 nm or less, more preferably 4 to 45 nm, and also preferably 5 to 30 nm. Since the metal oxide layer is preferably a thin film, it does not show or hardly shows gas barrier properties.

  In addition, as a method of forming a metal oxide layer, a physical vapor deposition method, a chemical vapor deposition method, or a combination thereof can be usually performed. Or the method of apply | coating and baking the solution containing the metal oxide used as the raw material of a metal oxide layer on a polyimide base material may be sufficient.

  Examples of the physical vapor deposition method include vapor deposition methods such as a resistance heating method, an electron beam vapor deposition method, and a molecular beam epitaxy method; an ion plating method; a sputtering method and the like.

  Examples of the chemical vapor deposition method include a thermal CVD method, a catalytic chemical vapor deposition method, a photo CVD method, and a plasma CVD method.

[Gas barrier layer]
The gas barrier layer contains a silicon compound.

  The film thickness of the gas barrier layer is preferably 10 to 500 nm, and more preferably 20 to 300 nm. The thickness of the gas barrier layer is preferably 10 nm or more, since the thickness can be made uniform and high gas barrier properties can be obtained. On the other hand, it is preferable that the thickness of the gas barrier layer is 500 nm or less because cracks can be suppressed. In addition, the film thickness of a gas barrier layer shall mean the total thickness, when a gas barrier layer consists of two or more layers.

The water vapor permeability of the gas barrier layer is preferably 1 × 10 ⁻³ g / (m ² · 24 h) or less, and more preferably 1 × 10 ⁻⁴ g / (m ² · 24 h) or less.

  Examples of the gas barrier layer containing a silicon compound include a gas barrier layer formed by a dry film forming method and a gas barrier layer formed by a wet film forming method.

(Gas barrier layer formed by dry film formation method)
The gas barrier layer formed by the dry film forming method contains silicon oxide that is a silicon compound.

  The gas barrier layer formed by the dry film formation method includes zinc disulfide, aluminum oxide, indium oxide, tin oxide, gallium oxide, indium tin oxide (ITO), aluminum-added zinc oxide (AZO), zinc-tin composite oxide ( ZTO), non-silicon metal oxides such as aluminum nitride and silicon carbide may further be included.

(Gas barrier layer formed by wet film formation method)
The gas barrier layer formed by the wet film forming method includes a polysilazane modified product that is a silicon compound. In addition, additives such as amine catalysts and metal catalysts may be included as necessary.

Polysilazane modified product The polysilazane modified product means a modified product obtained by modifying polysilazane.

  The polysilazane modified product contains silicon oxide obtained by modifying polysilazane. In addition, silicon nitride and / or silicon oxynitride obtained by modifying polysilazane may be included.

Polysilazane Polysilazane is a polymer having a bond such as Si—N, Si—H, or N—H in its structure.

  The polysilazane is not particularly limited, but in consideration of performing the modification treatment, it is preferably a compound that is ceramicized at a relatively low temperature and denatured into silica. For example, as described in JP-A-8-112879 A compound having a main skeleton composed of units represented by the following general formula is preferable.

In the above general formula, R ¹ , R ² , and R ³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, or an alkoxy group. .

The polysilazane is particularly preferably perhydropolysilazane (hereinafter, also referred to as “PHPS”) in which all of R ¹ , R ² , and R ³ are hydrogen atoms from the viewpoint of the denseness of the resulting gas barrier layer.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on a 6-membered ring and an 8-membered ring. Its molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), and can be a liquid or solid substance depending on the molecular weight. As the perhydropolysilazane, a commercially available product may be used, and examples of the commercially available product include NN120, NN110, NAX120, NAX110, NL120A, NL110A, NL150A, NP110, NP140 (manufactured by AZ Electronic Materials Co., Ltd.). .

  As another example of the polysilazane that is ceramicized at a low temperature, a silicon alkoxide-added polysilazane obtained by reacting a polysilazane represented by the above general formula with a silicon alkoxide (for example, JP-A-5-238827), glycidol is reacted. Glycidol-added polysilazane (for example, JP-A-6-122852) obtained by reaction, alcohol-added polysilazane (for example, JP-A-6-240208) obtained by reacting alcohol, and metal carboxylate Metal silicic acid salt-added polysilazane (for example, JP-A-6-299118), acetylacetonate complex-added polysilazane (for example, JP-A-6-306329) obtained by reacting a metal-containing acetylacetonate complex, metal Add fine particles Are fine metal particles added polysilazane (e.g., JP-A-7-196986 JP), and the like.

Modified polysilazane is converted by modification to produce silicon oxide.

  The modification mechanism of polysilazane to silicon oxide includes modification of polysilazane by hydrolysis of water. Specifically, the Si—N bond of polysilazane is hydrolyzed with water, whereby the polymer main chain is cleaved to form Si—OH. When two Si—OH are dehydrated and condensed under the reforming conditions, Si—O—Si bonds are formed and cured to produce silicon oxide.

  In addition, when polysilazane is modified particularly by irradiation with vacuum ultraviolet light, modification to silicon oxide by direct oxidation of polysilazane can occur together with or instead of the modification mechanism to silicon oxide. Specifically, when polysilazane is irradiated with vacuum ultraviolet light, H or N in the polysilazane is directly replaced with O by vacuum ultraviolet light, ozone activated by the vacuum ultraviolet light, active oxygen, or the like (that is, Forming Si—O—Si bonds (without going through silanol) and curing results in silicon oxide (the action of photons called photon processes).

  At this time, in the modification of polysilazane by irradiation with vacuum ultraviolet light, modification to silicon nitride and / or silicon oxynitride can occur in addition to or instead of modification of the polysilazane to silicon oxide by direct oxidation. Specifically, when polysilazane is irradiated with vacuum ultraviolet light, the Si—H bond or N—H bond in the polysilazane is relatively easily cleaved by excitation or the like, and recombines as Si—N in an inert atmosphere. Thereby, silicon nitride and silicon oxynitride can be generated.

  When polysilazane is modified by irradiation with vacuum ultraviolet light, the polysilazane is directly oxidized, so a modified film with high density and few defects can be formed, and a gas barrier layer having high gas barrier properties is formed. Can be done. In this specification, “vacuum ultraviolet light (VUV light)” means ultraviolet light having a high energy with a wavelength of 200 nm or less.

  The above reforming mechanism is just an estimation, and even when polysilazane is produced by silicon oxide, silicon nitride, or silicon oxynitride by a mechanism different from the above mechanism, it is included in the technical scope of the present invention.

Amine catalyst and metal catalyst The gas barrier layer formed by the wet film-forming method may contain an amine catalyst and / or a metal catalyst.

  The amine catalyst is not particularly limited, but N, N-dimethylethanolamine, N, N-diethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N ′, N′-tetra Examples include methyl-1,3-diaminopropane, N, N, N ′, N′-tetramethyl-1,6-diaminohexane.

  The metal catalyst is not particularly limited, and examples thereof include platinum compounds such as platinum acetylacetonate, palladium compounds such as palladium propionate, and rhodium compounds such as rhodium acetylacetonate.

  By adding the amine catalyst and / or the metal catalyst, the modification of polysilazane can be promoted.

  Two or more of the above gas barrier layers (a gas barrier layer formed by a dry film forming method and a gas barrier layer formed by a wet film forming method) may be laminated.

<Method for producing gas barrier film>
The manufacturing method of a gas barrier film includes the process of forming a metal oxide layer on a polyimide base material, and the process of forming a gas barrier layer on a metal oxide layer. In addition, the process of preparing a base material is included as needed.

  In a preferred embodiment, the method for producing a gas barrier film includes a step of preparing a substrate, a step of forming a metal oxide layer, and a step of forming a gas barrier layer in this order.

[Process for preparing polyimide base material]
This step includes preparing a polyimide substrate. If necessary, a surface treatment of the polyimide base material may be included.

(Preparation of polyimide substrate)
Preparation of a polyimide base material can be performed by manufacturing a polyimide base material itself. Moreover, you may purchase commercially available polyimide.

  There is no restriction | limiting in particular about the manufacturing method of the said polyimide base material, The above-mentioned description can be referred suitably.

(Surface treatment of polyimide substrate)
From the viewpoint of improving the adhesive strength between the polyimide substrate and the gas barrier layer, it is preferable to perform a surface treatment of the polyimide substrate.

  Examples of the surface treatment include corona treatment, plasma treatment, UV ozone treatment, and excimer treatment as described above. The specific surface treatment method is not particularly limited, and a known technique can be used. For example, the above description can be referred to appropriately.

[Step of forming metal oxide layer]
This step includes forming a metal oxide layer on the polyimide substrate.

  The method for forming the metal oxide layer is not particularly limited, and for example, the physical vapor deposition method and the chemical vapor deposition method can be applied as described above, and the raw material for the metal oxide layer on the polyimide substrate. A method of applying and baking a solution containing a metal oxide to be used can also be applied.

[Step of forming gas barrier layer]
This step includes forming a gas barrier layer on the metal oxide layer. At this time, the gas barrier layer includes a silicon compound.

  As described above, the gas barrier layer containing a silicon compound is formed by a dry film formation method and / or a wet film formation method.

(Dry film forming method)
Examples of the dry film forming method include physical vapor deposition and chemical vapor deposition. Thereby, a gas barrier layer containing silicon oxide and, if necessary, a non-silicon metal oxide can be formed.

  The physical vapor deposition method is a method in which a thin film of a target substance is deposited on the surface of the substance by a physical method in a gas phase. A vapor deposition method (resistance heating method, electron beam evaporation method, molecular beam epitaxy method). ), Ion plating method, sputtering method and the like. On the other hand, the chemical vapor deposition method (chemical vapor deposition method, CVD method) is a method in which a raw material gas containing a target thin film component is supplied onto a substrate or the like, and a film is formed by a chemical reaction on the substrate surface or in the gas phase. The thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, plasma CVD method and the like can be mentioned. Of these, the sputtering method and the plasma CVD method are preferably used, and the plasma CVD method is more preferably used.

  Hereinafter, the plasma CVD method will be described as an example.

  When generating plasma in the plasma CVD method, it is preferable to generate a plasma discharge in a space between a plurality of film forming rollers. A pair of film forming rollers is used, and a film is applied to each of the pair of film forming rollers. More preferably, the plasma is generated by discharging between the pair of film forming rollers. Thus, by using a pair of film forming rollers, placing a film on the pair of film forming rollers, and discharging between the pair of film forming rollers, one film forming roller is placed on the film forming roller. While forming an existing film, it is possible to form a film on the surface of the substrate on the other film forming roller at the same time, so that a thin film can be produced efficiently and a normal roller is not used. Compared with the plasma CVD method, the film formation rate can be doubled, and a film having a substantially identical structure can be formed.

  Further, when discharging between the pair of film forming rollers in this way, it is preferable to reverse the polarities of the pair of film forming rollers alternately. Further, the film forming gas used in such a plasma CVD method preferably includes an organic silicon compound and oxygen, and the content of oxygen in the film forming gas is determined by the organosilicon compound in the film forming gas. It is preferable that the amount of oxygen be less than the theoretical oxygen amount necessary for complete oxidation. The gas barrier layer formed by the dry film forming method is preferably a layer formed by a continuous film forming process. Alternatively, it is also preferable that an organic silicon compound is included as a film forming gas, an oxygen gas is included as a reactive gas, and these are mixed gas to be supplied to the discharge region.

  From the viewpoint of productivity, it is preferable to form a gas barrier layer on the metal oxide layer by a roll-to-roll method. An apparatus that can be used when forming a gas barrier layer by such a plasma CVD method is not particularly limited, and includes at least a pair of film forming rollers and a plasma power source, and the pair of film forming films. It is preferable that the apparatus is configured to be capable of discharging between rollers. For example, when the manufacturing apparatus shown in FIG. 1 is used, a roll-to-roll system is used while using a plasma CVD method. It can also be manufactured.

  Hereinafter, with reference to FIG. 1, when a substrate is used, a gas barrier by a plasma CVD method in which the substrate is disposed on a pair of film forming rollers and plasma is generated by discharging between the pair of film forming rollers. The method for forming the layer will be described in more detail. FIG. 1 is a schematic view showing an example of a manufacturing apparatus that can be suitably used for forming a gas barrier layer by this method. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.

  1 includes a feed roller 32, transport rollers 33, 34, 35, and 36, film forming rollers 39 and 40, a gas supply pipe 41, a plasma generating power source 42, and a film forming roller 39. And magnetic field generators 43 and 44 installed inside 40 and a winding roller 45. In such a manufacturing apparatus, at least the film forming rollers 39 and 40, the gas supply pipe 41, the plasma generating power source 42, and the magnetic field generating apparatuses 43 and 44 are arranged in a vacuum chamber (not shown). ing. Further, in such a manufacturing apparatus 31, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.

  Using such a manufacturing apparatus 31 shown in FIG. 1, for example, the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roller, and the film (base material, etc.) The gas barrier layer can be formed by appropriately adjusting the transport speed. That is, using the manufacturing apparatus 31 shown in FIG. 1, a discharge is generated between a pair of film forming rollers (film forming rollers 39 and 40) while supplying a film forming gas (raw material gas, etc.) into the vacuum chamber. As a result, the film forming gas (raw material gas or the like) is decomposed by plasma, and the gas barrier layer is formed on the surface of the base material on the film forming roller 39 and the surface of the base material on the film forming roller 40 by plasma CVD. It is formed by. In such film formation, the substrate and the like are conveyed by the delivery roller 32 and the film formation roller 39, respectively, so that they are formed on the surface of the substrate and the like by a roll-to-roll continuous film formation process. A gas barrier layer is formed.

  As the film forming gas (such as source gas) supplied from the gas supply pipe 41 to the facing space, source gas, reaction gas, carrier gas, and discharge gas may be used alone or in combination of two or more. The source gas in the film forming gas used for forming the gas barrier layer can be appropriately selected and used according to the material of the gas barrier layer to be formed. As such a source gas, for example, an organic silicon compound containing silicon or an organic compound gas containing carbon can be used. Examples of such organosilicon compounds include hexamethyldisiloxane (HMDSO), hexamethyldisilane (HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, and hexamethyldisilane. , Methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltriethoxy Examples include silane and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of properties such as the handleability of the compound and the gas barrier properties of the resulting gas barrier layer. These organosilicon compounds can be used alone or in combination of two or more. Examples of the organic compound gas containing carbon include methane, ethane, ethylene, and acetylene. As these organosilicon compound gas and organic compound gas, an appropriate source gas is selected according to the type of the gas barrier layer.

  Further, as the film forming gas, a reactive gas may be used in combination with the source gas. As such a reactive gas, a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used. As a reaction gas for forming an oxide, for example, oxygen or ozone can be used. Moreover, as a reactive gas for forming nitride, nitrogen and ammonia can be used, for example. These reaction gases can be used alone or in combination of two or more. For example, when forming an oxynitride, a reaction gas for forming an oxide and a reaction gas for forming a nitride can be used in combination.

  As the film forming gas, a carrier gas may be used as necessary to supply the source gas into the vacuum chamber. Further, as the film forming gas, a discharge gas may be used as necessary in order to generate plasma discharge. As such carrier gas and discharge gas, known ones can be used as appropriate, for example, rare gases such as helium, argon, neon, xenon; hydrogen can be used.

  When such a film-forming gas contains a source gas and a reactive gas, the ratio of the source gas and the reactive gas is the reaction gas that is theoretically necessary for completely reacting the source gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive rather than the ratio of the amount. By not making the ratio of the reaction gas excessive, it is excellent in that excellent barrier properties and bending resistance can be obtained by the formed gas barrier layer. Further, when the film forming gas contains the organosilicon compound and oxygen, the amount is less than the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas. It is preferable.

  The supply amount of the source gas is preferably about 5 to 200 sccm. The supply amount of oxygen gas is preferably about 100 to 1000 sccm.

  Moreover, although the pressure (vacuum degree) in a vacuum chamber can be suitably adjusted according to the kind etc. of source gas, it is preferable to set it as the range of 0.5 Pa-50 Pa.

  In such a plasma CVD method, in order to discharge between the film forming roller 39 and the film forming roller 40, an electrode drum connected to the plasma generating power source 42 (in this embodiment, the film forming roller 39) is used. The electric power to be applied to the power source can be adjusted as appropriate according to the type of the raw material gas, the pressure in the vacuum chamber, etc. It is preferable to be in the range. If such applied power is 100 W or more, generation of particles can be sufficiently suppressed, and if it is 10 kW or less, the amount of heat generated during film formation can be suppressed, and the film surface during film formation can be suppressed. It is possible to suppress an increase in temperature. Therefore, it is excellent in that wrinkles can be prevented during film formation without losing heat to the film.

  As described above, as a more preferable aspect of the present embodiment, the gas barrier layer is formed by the plasma CVD method using the plasma CVD apparatus (roll-to-roll method) having the counter roll electrode shown in FIG. It is. This is excellent in flexibility (flexibility) and mechanical strength, especially in roll-to-roll, when mass-produced using a plasma CVD apparatus (roll-to-roll method) having a counter roll electrode. This is because it is possible to efficiently produce a gas barrier layer having both durability at the time and barrier performance. Such a manufacturing apparatus is also excellent in that it can inexpensively and easily mass-produce gas barrier films that are required for durability against temperature changes used in solar cells and electronic components.

(Wet deposition method)
The wet film-forming method includes modifying a polysilazane by applying a coating solution containing polysilazane on the metal oxide layer. Thereby, the gas barrier layer containing the polysilazane modified product can be obtained.

Coating liquid containing polysilazane A coating liquid containing polysilazane (hereinafter, also simply referred to as “coating liquid”) contains polysilazane and a solvent. In addition, additives such as an amine catalyst and a metal catalyst may be included as necessary.

Polysilazane Polysilazane can be used in the same manner as described above, and the description thereof is omitted here.

  The content of polysilazane in the coating solution varies depending on the desired film thickness of the gas barrier layer, the pot life of the coating solution, and the like, but is preferably 0.2 to 35% by mass with respect to the total amount of the coating solution.

Solvent The solvent is not particularly limited as long as it does not react with polysilazane, and a known solvent can be used. Specific examples include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons; ether solvents such as aliphatic ethers and alicyclic ethers. More specifically, examples of the hydrocarbon solvent include pentane, hexane, cyclohexane, toluene, xylene, solvesso, turben, methylene chloride, trichloroethane, and the like. Examples of ether solvents include dibutyl ether, dioxane, and tetrahydrofuran. These solvents can be used alone or in admixture of two or more.

Amine catalyst and metal catalyst As the amine catalyst and the metal catalyst, the same ones as described above can be used, so that the description thereof is omitted here.

  Among these, when a coating liquid contains an amine catalyst and / or a metal catalyst, it is preferable that the said amine catalyst and / or a metal catalyst contain 0.1-10 mass% with respect to polysilazane. Especially about an amine catalyst, it is more preferable to contain 0.5-5 mass% with respect to polysilazane from a viewpoint of improvement of applicability | paintability and shortening of reaction time.

  Moreover, in one Embodiment, it is preferable that content of an amine catalyst is less than 2 mass% with respect to polysilazane. It is preferable that the content of the amine catalyst is less than 2% by mass because components that do not contribute to the gas barrier property itself in the gas barrier layer are reduced and high gas barrier property is obtained. Further, when heating is included in the polysilazane modification method described later, the entire coating film is modified. Therefore, in such a case, when the content of the amine catalyst is less than 2% by mass, the modification rate of the polysilazane is reduced, and the modification proceeds while following the base material. Since the gas barrier layer tends to take a thermodynamically stable form, the adhesion between the polyimide base material and the gas barrier layer is improved, and the occurrence of cracks in the gas barrier layer can be prevented.

Application In application, an application liquid is applied onto the metal oxide layer to form a coating film.

  As a coating method of the coating solution, a known method can be adopted as appropriate. Specific examples include spin coating methods, roll coating methods, flow coating methods, ink jet methods, spray coating methods, printing methods, dip coating methods, cast film forming methods, bar coating methods, and gravure printing methods.

  The coating amount of the coating solution is not particularly limited, but can be appropriately adjusted so as to be the desired thickness of the gas barrier layer.

Modification of polysilazane The modification method of polysilazane is not particularly limited, and a known method can be applied. Specific methods for modifying polysilazane include ultraviolet light irradiation, plasma irradiation, heating, and combinations thereof.

  The irradiation of the ultraviolet light can be performed by irradiating the ultraviolet light by a known method. Polysilazane can be modified by irradiation with ultraviolet light. In addition, “irradiation with ultraviolet light” includes setting an environment in which ultraviolet light is irradiated onto a coating film obtained by applying a coating liquid. Therefore, “irradiation with ultraviolet light” includes standing the coating film in an environment such as a fluorescent lamp or a yellow lamp. Of these, irradiation with ultraviolet light is preferably performed in an oxidizing gas atmosphere and in a low humidity environment.

  The wavelength of the ultraviolet light to be irradiated is not particularly limited, but is preferably 10 to 450 nm, more preferably 100 to 300 nm, still more preferably 100 to 200 nm, and particularly preferably 100 to 180 nm. preferable. Among these, the ultraviolet light to be irradiated is preferably vacuum ultraviolet light (ultraviolet light having a wavelength of 200 nm or less) from the viewpoint of proceeding the conversion reaction at a lower temperature and in a shorter time.

  As described above, since the polysilazane is directly oxidized without passing through silanol by irradiation with vacuum ultraviolet light (the action of photons called a photon process), there is little volume change in the oxidation process, and the defect density is high. Films containing a small amount of silicon compounds such as silicon oxide, silicon nitride, and silicon oxynitride can be obtained. Further, in vacuum ultraviolet light, ozone or active oxygen having high oxidation ability is generated from oxygen or the like present in the reaction atmosphere, and polysilazane reforming treatment can be performed by the ozone or active oxygen. As a result, denser films such as silicon oxide, silicon nitride, and silicon oxynitride can be obtained. Therefore, the gas barrier layer obtained by modifying polysilazane by irradiation with vacuum ultraviolet light can have high barrier properties. In addition, you may implement vacuum ultraviolet light irradiation at any time, if it is after coating-film formation.

  Although it does not restrict | limit especially as a light source of an ultraviolet light, A low pressure mercury lamp, a deuterium lamp, a xenon excimer lamp, a metal halide lamp, an excimer laser, etc. can be used. Further, as described above, a fluorescent lamp, a yellow lamp, or the like may be used. Among these, it is preferable to use a rare gas excimer lamp such as a xenon excimer lamp.

  As described above, a modified polysilazane containing silicon oxide can be obtained by modifying polysilazane by a method such as ultraviolet light irradiation, plasma irradiation, heating, or a combination thereof. In particular, when the modification includes irradiation with vacuum ultraviolet light, a polysilazane modified product containing silicon nitride and / or silicon oxynitride together with silicon oxide can be obtained.

<Electronic device>
According to one form of this invention, the electronic device containing an electronic device main body and the above-mentioned gas barrier film is provided.

[Electronic device body]
The electronic device body is not particularly limited, and examples thereof include known electronic device bodies to which a gas barrier film can be applied. For example, a solar cell (PV), a liquid crystal display element (LCD), an organic electroluminescence (EL) element, etc. are mentioned. There is no restriction | limiting in particular also about the structure of these electronic device main bodies, It can have a well-known structure. For example, the organic EL element can have a substrate, a negative electrode, an electron injection layer, an electron transport layer, a light emitting layer, a hole transport layer, a hole injection layer, a positive electrode, and the like.

[Gas barrier film]
The gas barrier film described above can be used as a substrate, a sealing material, and the like. As a base material, when used for a solar cell, for example, it can be applied as a resin support in which a transparent conductive thin film such as ITO is provided as a transparent electrode on a gas barrier film. In this case, the gas barrier film is incorporated in the electronic device body. When used as a sealing material, for example, an electronic device in which a liquid crystal display element is sealed can be obtained. The gas barrier film according to the present invention is preferably used for sealing an electronic device body as a sealing material.

<Method for manufacturing electronic device>
According to one embodiment of the present invention, a method for manufacturing an electronic device is provided. The manufacturing method of the electronic device includes a step of being exposed to an environment of 200 to 500 ° C.

  The gas barrier film described above has high adhesion strength of the gas barrier layer containing the polyimide base material and the silicon compound. Accordingly, the polyimide base material and the gas barrier layer are not peeled or hardly peeled even after a device forming process such as a baking process, which is in an environment of 200 to 500 ° C., preferably 250 to 400 ° C. Therefore, a desired electronic device can be manufactured while realizing high productivity.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "mass part" or "mass%" is represented.

<Manufacture of gas barrier film>
[Example 1]
(1) Base material UPILEX-50SGA (polyimide film, manufactured by Ube Industries, Ltd.) having a thickness of 50 μm was used as a base material.

  UPILEX-50SGA is a polymer containing biphenyltetracarboxylic dianhydride (BPDA) and p-phenylenediamine (PDA) as monomers.

(2) Formation of metal oxide layer A metal oxide layer containing titanium oxide (TiO ₂ ) having a thickness of 40 nm by sputtering on a base material using a sputtering apparatus (RFS200, manufactured by ULVAC Kiko Co., Ltd.). Formed.

(3) Formation of gas barrier layer (dry film formation: first layer) A gas barrier layer containing silicon oxide (dry film formation: first layer) was formed on the metal oxide layer by a dry film formation method.

  More specifically, the film obtained in (2) above was set in a production apparatus 31 as shown in FIG. 1 and conveyed. Next, a magnetic field is applied between the film forming roller 39 and the film forming roller 40, and electric power is supplied to the film forming roller 39 and the film forming roller 40, respectively. Was discharged to generate plasma. Subsequently, a film forming gas (a mixed gas of hexamethyldisiloxane (HMDSO) as a source gas and oxygen gas (which also functions as a discharge gas) as a source gas) is supplied to the formed discharge region, and a metal oxide layer A gas barrier layer (dry film formation: first layer) was formed thereon by plasma CVD, and the film thickness of the gas barrier layer (dry film formation: first layer) was 150 nm. It was street.

(Deposition conditions)
Supply amount of source gas: 50 sccm (Standard Cubic Centimeter per Minute, 0 ° C., 1 atm standard)
Oxygen gas supply amount: 500 sccm (0 ° C., 1 atm standard)
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Film conveyance speed: 1.0 m / min.

(4) Formation of gas barrier layer (second layer) A gas barrier layer containing a polysilazane modified product (wet film formation: second layer) was formed on the gas barrier layer (dry film formation: first layer) by a wet film formation method.

  More specifically, first, a coating solution containing polysilazane was prepared as follows.

  That is, an uncatalyzed perhydropolysilazane 20 wt% dibutyl ether solution (NN120-20, manufactured by AZ Electronic Materials Co., Ltd.) was converted into an amine catalyst (N, N, N ′, N′-tetramethyl-1,6-diamino). Hexane) was mixed with a perhydropolysilazane 20 wt% dibutyl ether solution (NAX120-20, manufactured by AZ Electronic Materials Co., Ltd.) containing 5 wt% of perhydropolysilazane. Next, by appropriately diluting with dibutyl ether, a coating liquid containing polysilazane was prepared as a dibutyl ether solution containing 1 wt% of the amine catalyst with respect to perhydropolysilazane.

  Next, the prepared coating liquid containing polysilazane was applied on the gas barrier layer (dry film formation: first layer) to form a coating film. More specifically, a coating liquid containing polysilazane was applied on the gas barrier layer (dry film formation: first layer) by spin coating, and then dried at 80 ° C. for 1 minute to form a coating film. The obtained coating film was irradiated with vacuum ultraviolet (VUV) light having a main peak emission wavelength of 172 nm under the following conditions to form a gas barrier layer (wet film formation: second layer) having a film thickness of 80 nm. The film thickness was confirmed by the fact that a clear interface was seen from a cross-sectional photograph of TEM (Transmission Electron Microscope).

(Vacuum ultraviolet (VUV light) irradiation treatment conditions)
Vacuum UV irradiation equipment: Stage movable xenon excimer irradiation equipment
(MD excimer, MECL-M-1-200)
Illuminance: 140 mW / cm ² (172 nm)
Stage temperature: 100 ° C
Processing environment: Under dry nitrogen gas atmosphere Oxygen concentration in processing environment: 0.1% by volume
Stage movable speed and number of times of transportation: 15 times of transportation at 10 mm / sec. Excimer light exposure integrated amount: 6500 mJ / cm ² .

  The sample was set so that the gap (Gap) between the lamp and the sample was 3 mm. Further, the irradiation time was changed by adjusting the movable speed of the movable stage. Regarding the adjustment of oxygen concentration during irradiation with vacuum ultraviolet rays (VUV light), the flow rate of nitrogen gas and oxygen gas introduced into the irradiation chamber is measured with a flow meter, and the nitrogen gas / oxygen gas flow ratio of the gas introduced into the chamber is measured. It was adjusted by controlling. Further, heat treatment is performed at 250 ° C. for 60 minutes, and a gas barrier property in which a polyimide base material-metal oxide layer-gas barrier layer (dry film formation: first layer) -gas barrier layer (wet film formation: second layer) are laminated in this order. A film was produced.

[Example 2]
Example except that Kapton having a thickness of 50 μm (a polyimide film having pyromellitic dianhydride and 4,4′-diaminodiphenyl ether as monomer components, manufactured by Toray DuPont Co., Ltd.) was used as a substrate. 1 was used to produce a gas barrier film.

  The obtained gas barrier film has a structure in which a polyimide base material-metal oxide layer-gas barrier layer (dry film formation: first layer) -gas barrier layer (wet film formation: second layer) are laminated in this order.

[Example 3]
(1) Base material UPILEX-50SGA (polyimide film, manufactured by Ube Industries, Ltd.) having a thickness of 50 μm was used as a base material.

(2) Formation of metal oxide layer By the method similar to Example 1, the metal oxide layer containing a 40-nm-thick titanium oxide was formed on the polyimide base material.

(3) Formation of gas barrier layer (wet film formation: first layer) In the same manner as the formation of (4) gas barrier layer (wet film formation: second layer) in Example 1, metal oxidation is performed by a wet film formation method. A gas barrier layer (wet film formation: first layer) containing a 150 nm-thick polysilazane modification product was formed on the physical layer.

(4) Gas barrier layer (wet film formation: second layer)
In the same manner as in Example 1, a gas barrier layer (wet film formation: second layer) containing a polysilazane modified product having a film thickness of 40 nm is formed on the gas barrier layer (wet film formation: first layer) by a wet film formation method. did.

  The obtained gas barrier film has a structure in which a polyimide base material-metal oxide layer-gas barrier layer (wet film formation: first layer) -gas barrier layer (wet film formation: second layer) are laminated in this order.

[Example 4]
(1) Base material UPILEX-50SGA (polyimide film, manufactured by Ube Industries, Ltd.) having a thickness of 50 μm was used as a base material.

(2) Formation of metal oxide layer By the method similar to Example 1, the metal oxide layer containing a 40-nm-thick titanium oxide was formed on the polyimide base material.

(3) Formation of gas barrier layer (dry film formation: first layer) By repeating the same method as the formation of (3) gas barrier layer (dry film formation: first layer) in Example 1 three times, the film thickness is 250 nm. A gas barrier layer containing silicon oxide (dry film formation: first layer) was formed.

  The obtained gas barrier film has a configuration in which a polyimide substrate, a metal oxide layer, and a gas barrier layer (dry film formation: first layer) are laminated in this order.

[Example 5]
A gas barrier film was produced in the same manner as in Example 1 except that a metal oxide layer containing zinc oxide (ZnO) was formed as the metal oxide layer.

  Note that the metal oxide layer containing zinc oxide (ZnO) was formed as follows. That is, it was formed by applying a zinc acetate dihydrate solution and baking it.

  The obtained gas barrier film has a structure in which a polyimide base material-metal oxide layer-gas barrier layer (dry film formation: first layer) -gas barrier layer (wet film formation: second layer) are laminated in this order.

[Example 6]
A gas barrier film was produced in the same manner as in Example 1 except that a metal oxide layer containing tin oxide (SnO) was formed as the metal oxide layer.

  The metal oxide layer containing tin oxide (SnO) was formed as follows. That is, it was formed by baking after applying a solution of tin acetate.

  The obtained gas barrier film has a structure in which a polyimide base material-metal oxide layer-gas barrier layer (dry film formation: first layer) -gas barrier layer (wet film formation: second layer) are laminated in this order.

[Example 7]
A gas barrier film was produced in the same manner as in Example 1 except that a metal oxide layer containing aluminum oxide (Al ₂ O ₃ ) was formed as the metal oxide layer.

Note that the metal oxide layer containing aluminum oxide (Al ₂ O ₃ ) was formed as follows. That is, it was formed by applying and baking an aluminum acetate dihydrate solution.

  The obtained gas barrier film has a structure in which a polyimide base material-metal oxide layer-gas barrier layer (dry film formation: first layer) -gas barrier layer (wet film formation: second layer) are laminated in this order.

[Example 8]
A gas barrier film was produced in the same manner as in Example 1 except that UPILEX-25SGA (polyimide film, Ube Industries, Ltd.) having a thickness of 25 μm was used as the substrate.

  The obtained gas barrier film has a structure in which a polyimide base material-metal oxide layer-gas barrier layer (dry film formation: first layer) -gas barrier layer (wet film formation: second layer) are laminated in this order.

[Example 9]
A gas barrier film was produced in the same manner as in Example 1 except that UPILEX-100S (polyimide film, manufactured by Ube Industries, Ltd.) having a thickness of 100 μm was used as the base material.

  The obtained gas barrier film has a structure in which a polyimide base material-metal oxide layer-gas barrier layer (dry film formation: first layer) -gas barrier layer (wet film formation: second layer) are laminated in this order.

[Example 10]
A gas barrier film was produced in the same manner as in Example 1 except that XENOMAX (polyimide film, manufactured by Toyobo Co., Ltd.) having a thickness of 25 μm was used as the substrate.

  The obtained gas barrier film has a structure in which a polyimide base material-metal oxide layer-gas barrier layer (dry film formation: first layer) -gas barrier layer (wet film formation: second layer) are laminated in this order.

[Comparative Example 1]
A gas barrier film was produced in the same manner as in Example 1 except that polyethylene terephthalate (PET) having a thickness of 50 μm (product name: A4300, manufactured by Toyobo Co., Ltd.) was used as the substrate.

  The obtained gas barrier film has a configuration in which a PET base material-metal oxide layer-gas barrier layer (dry film formation: first layer) -gas barrier layer (wet film formation: second layer) are laminated in this order.

[Comparative Example 2]
A gas barrier film was produced in the same manner as in Example 1 except that the metal oxide layer was not formed. In Table 1, the column of the metal oxide layer or the like is “−” that the metal oxide layer was not formed.

  The obtained gas barrier film has a structure in which a polyimide base material-gas barrier layer (dry film formation: first layer) -gas barrier layer (wet film formation: second layer) are laminated in this order.

[Comparative Example 3]
A gas barrier film was produced in the same manner as in Example 1 except that a metal oxide layer containing silicon (SiO ₂ ) was formed as the metal oxide layer.

The obtained gas barrier film was formed by laminating a polyimide base material-metal oxide layer (SiO ₂ ) -gas barrier layer (dry film formation: first layer) -gas barrier layer (wet film formation: second layer) in this order. It has a configuration.

<Evaluation of gas barrier film>
Using the gas barrier films produced in Examples 1 to 10 and Comparative Examples 1 to 3, the performance of the gas barrier films was evaluated.

[Coefficient of thermal expansion (CTE)]
The coefficient of thermal expansion (CTE) of the gas barrier film was determined from the dimensional change during the temperature rising process at 200 to 300 ° C. under the following conditions by thermomechanical analysis (TMA).

Measuring device: TMA / SS6100 (manufactured by Hitachi High-Tech Science Co., Ltd.)
Measurement mode: Tensile mode, load 2g
Sample length: 15mm
Sample width: 4mm
Temperature rise start temperature: 25 ° C
Temperature rise end temperature: 500 ° C
Temperature drop end temperature: 25 ° C
Temperature increase / decrease rate: 20 ° C / min
Measurement atmosphere: nitrogen.

As shown below, since PET as a base material melts at 300 ° C., in Comparative Example 1, the value of CTE could not be obtained. Therefore, in Table 1, “-” is shown in the CTE column. In Comparative Examples 2 and 3, since the base material was polyimide, it was not melted. In Comparative Example 2, a metal oxide layer was not formed. In Comparative Example 3, the metal oxide layer was not formed. Instead, since an oxide layer containing silicon oxide (SiO ₂ ) is formed, the gas barrier layer peels off from the polyimide base material after the 300 ° C. 1 hour pretreatment of the peel test, and as a gas barrier film CTE could not be measured. Therefore, in Table 1, “measurement impossible” is indicated in the CTE column.

[Adhesion]
Each gas barrier film was heat-treated at 300 ° C. for 1 h, and after natural heat dissipation, was evaluated for adhesion by a cross-cut method.

×: 100/100 square peeled between gas barrier layer and PI substrate ○ △: 1-99 / 100 square peeled between gas barrier layer and PI substrate ○: 100/100 square peeled None (50 square percent to less than 90 square percent of each square is bonded)
(Double-circle): 100/100 mass does not peel (90 area% or more of each mass adhere | attaches).

  The obtained results are shown in Table 1 below.

  In addition, about Comparative Example 1, since PET which is a base material melts at 300 ° C., the adhesion could not be measured and evaluated.

  The obtained results are shown in Table 1.

  From the results of Table 1, the gas barrier films according to the examples all have high adhesive strength, and even when applied to the device forming process, the gas barrier layer does not peel off from the polyimide substrate, and the device forming process. It was found that the present invention can be suitably applied to.

  In addition, this application is based on the Japan patent application 2014-004582 for which it applied on January 14, 2014, The content of an indication is referred as a whole by reference.

Claims (6)

  A gas barrier film in which at least a polyimide base material, a metal oxide layer containing a metal oxide, and a gas barrier layer containing a silicon compound are laminated in this order.   The gas barrier film according to claim 1, wherein the polyimide is a polymer containing biphenyltetracarboxylic dianhydride or pyromellitic dianhydride and p-phenylenediamine or 4,4'-diaminodiphenyl ether as monomers.   The gas barrier film according to claim 1 or 2, wherein the metal oxide includes at least one selected from the group consisting of aluminum oxide, titanium oxide, tin oxide, cerium oxide, and zinc oxide. .   The gas barrier film according to any one of claims 1 to 3, wherein a thermal expansion coefficient at 200 to 300 ° C is 15 ppm / K or less.   The gas barrier film according to claim 1, wherein the gas barrier layer has a two-layer structure.   An electronic device comprising the gas barrier film according to claim 1.