JP2015127124A - Gas barrier film and gas barrier film manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new and improved gas barrier film in which gas barrier performance can be improved while utilizing high heat resistance which polyimide has, and a gas barrier film manufacturing method.SOLUTION: According to a certain view point of the present invention, provided is a gas barrier film featuring to include solvent-soluble polyimide. According to this view point, the solvent-soluble polyimide is used and this polyimide has high transparency, heat resistance and smoothness. And, a cording to this view point, coating liquid is prepared by dissolving the solvent-soluble polyimide in a solvent, and an organic layer is formed by applying this coating liquid on a coating surface and removing the solvent only. Therefore, high energy is not needed for forming the organic layer. For this reason, heat shrinkage of the organic layer is suppressed, and, in turn, crack generation in the gas barrier layer is suppressed. Therefore, gas barrier performance of the gas barrier film is improved.

Description

  The present invention relates to a gas barrier film and a method for producing the gas barrier film.

  A gas barrier film is used as a flexible substrate for an electronic device. The gas barrier film is obtained by alternately stacking a gas barrier layer made of a metal oxide or the like and an organic layer (binder layer) on a substrate. Conventionally, gas barrier films have been used for packaging of foods and the like, but have recently been used in electronic devices. For this reason, a dramatic improvement in gas barrier performance and heat resistance against gas molecules such as moisture and oxygen has been demanded.

  As a gas barrier film, for example, as disclosed in Patent Document 1, a gas barrier film using polyimide (PI) as an organic layer (binder layer) is known. Polyimide is one of the materials suitable for the organic layer of the gas barrier film because it has excellent gas barrier performance and heat resistance against gas molecules such as moisture and oxygen.

Japanese Patent Laid-Open No. 9-241892 US Pat. No. 6,268,695 Special table 2010-533087 gazette Japanese Patent Laid-Open No. 2007-21871

  However, in the conventional method for producing a gas barrier film, the organic layer is formed using polyimide that is insoluble in a solvent (solvent). Specifically, polyamic acid is formed by dissolving acid dianhydride and diamine in a solvent and reacting them in a solvent. Then, a coating layer is formed by coating a solution of polyamic acid on the gas barrier layer. Then, by heating the coating layer, the solvent is removed (that is, the coating layer is dried), and the polyamic acid is dehydrated and closed. Thereby, an organic layer made of polyimide is formed.

  Therefore, in the conventional method for producing a gas barrier film, since the polyamic acid is dehydrated and closed while removing the solvent, the polyamic acid is in a solid state, that is, the molecular motion of the polyamic acid is limited. For this reason, a great deal of energy is required to dehydrate and cyclize the polyamic acid. Specifically, the heating temperature of the coating layer had to be very high (for example, 300 ° C. or higher). As a result, the organic layer is thermally contracted, and cracks may be generated in the gas barrier layer due to the stress generated thereby. This crack becomes a passage for gas. Therefore, the gas barrier property of the gas barrier film is lowered.

  On the other hand, as disclosed in Patent Documents 2 to 4, gas barrier films using acrylic resin as an organic layer are also known. However, since acrylic resin is inferior in heat resistance, the gas barrier film using this has a problem in heat resistance. Specifically, when the process temperature when the gas barrier film is mounted on the electronic device becomes at least 100 ° C. or higher, the acrylic resin in the organic layer is decomposed. In addition, when process temperature becomes 100 degreeC or more, the case where a gas barrier film is used as a gas barrier film of organic EL, etc. are mentioned. In this case, a gas barrier film is laminated on a substrate, and a TFT and an OLED are sequentially laminated on the gas barrier film. When the TFT is laminated on the gas barrier film, the gas barrier film is exposed to a high temperature of 100 ° C. or higher. The thermal decomposition of the acrylic resin causes deterioration of the transparency of the gas barrier film and deterioration of the gas barrier property. Therefore, the gas barrier film using the acrylic resin as the organic layer does not satisfy the required level.

  Therefore, the present invention has been made in view of the above problems, and an object of the present invention is a novel and improved technique capable of improving gas barrier properties while utilizing high heat resistance of polyimide. Another object of the present invention is to provide a gas barrier film and a method for producing the gas barrier film.

  In order to solve the above-described problems, according to one aspect of the present invention, there is provided a gas barrier film including a solvent-soluble polyimide.

  According to this viewpoint, the solvent availability polyimide is used, and this polyimide has high transparency, heat resistance, and smoothness. Further, according to this aspect, a coating liquid is prepared by dissolving a solvent-soluble polyimide in a solvent, and an organic layer is formed simply by applying the coating liquid on the coating surface and removing the solvent. . Therefore, high energy is not required to form the organic layer. For this reason, the thermal contraction of the organic layer is suppressed, and as a result, the occurrence of cracks in the gas barrier layer is suppressed. Therefore, the gas barrier property of the gas barrier film is improved.

  Here, an organic layer containing a solvent-soluble polyimide and a gas barrier layer containing at least one of a group consisting of a metal oxide having a gas barrier property, a metal nitride, and a metal may be included. The gas barrier film according to this viewpoint has high transparency, heat resistance, smoothness, and gas barrier properties.

  Solvent-soluble polyimides are 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanoic acid dianhydride (2,2-bis (3,4-dicarboxylicboxyl phenyl) hexafluoropropanoic acid dianhydride), pyromellitic acid Dianhydride (1,2,4,5-Benzenetetracarboxylic anhydride), 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (3,3 ′, 4,4′-Benzophenonetetracarbox dihydride), 3, 3 ′, 4,4′-biphenyltetracarboxylic dianhydride (3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride), and 3 An acid dianhydride containing at least one member selected from the group consisting of 3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride (Bis- (3-phtalyl anhydride) ether) and 2,2'-bis (Trifluoromethyl) -4,4′-diaminebiphenyl (2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl), 3,3′-bis (trifluoromethyl) -4,4′-diamino Biphenyl, 2,2′-bis (trifluoromethyl) -5,5′-diaminobiphenyl, 3,3′-bis (trifluoromethyl) -5,5′-diaminobiphenyl, 2,2′-bis (tri Fluoromethyl) -4,4′-diaminebiphenyl, m-phenylenediamine (m-phenylenedia) ine), o-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide 4,4'-diaminobenzophenone (4,4'-Diaminobenzobenzone), 4,4'-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane (2,2- bis (4-aminophenoxy) propane), 1,4-bis (4-aminophenoxy) benzene (1,4-bis (4-aminophenoxy) benzene), 1,4-bis (4 Aminobenzoyl) benzene (1,4-bis (4-aminobenzoyl) benzone), 4,4′-bis (4-aminophenoxy) biphenyl (4,4-bis (4-aminophenoxy) biphenyl), 4,4 ′ -Diaminodiphenylhexafluoropropane (4,4'-Diaminodiphenylhexafluoropropane), 3,3'-diaminodiphenylhexafluoropropane, 2,2'-bis [4 (4-aminophenoxy) phenyl] hexafluoropropane (4-BDAF) ), 2,2′-bis [3 (3-aminophenoxy) phenyl] hexafluoropropane (3-BDAF), 1,3-bis (3-aminophenoxy) benzene (APB-133), 1,3-bis (4-amino Enoxy) benzene (APB-134) and 1,4-bis (4-aminophenoxy) benzene (APB-144) in the group consisting of at least one diamine may be used for condensation. .

  According to this viewpoint, the transparency, heat resistance, and smoothness of the gas barrier film are further improved.

  In addition, the metal oxide includes silicon oxide, silicon oxynitride film, aluminum oxide film, zirconium oxide film, titanium oxide film, tin oxide film, indium (Indium). ) At least one kind may be included from the group consisting of an alloy oxide film and a magnesium (Magnesium) oxide film.

  According to this viewpoint, the gas barrier property of the gas barrier film is further improved.

  Further, the metal nitride may contain at least one or more of the group consisting of silicon nitride, aluminum nitride, and titanium nitride.

  According to this viewpoint, the gas barrier property of the gas barrier film is further improved.

  Moreover, the metal may contain at least 1 or more types among the group which consists of aluminum, silver, nickel, copper, titanium, and alloy steel.

  According to this viewpoint, the gas barrier property of the gas barrier film is further improved.

  Moreover, the laminated film formed by laminating the organic layer and the gas barrier layer may have heat resistance with a weight loss of 5% or less in the range up to 500 ° C.

  According to this viewpoint, the heat resistance of the gas barrier film is further improved.

  Moreover, 50 nm-10 micrometers may be sufficient as the thickness of an organic layer.

  According to this viewpoint, the gas barrier film is made thinner.

  Further, the thickness of the gas barrier layer may be 10 nm to 1 μm.

  According to this viewpoint, the gas barrier film is made thinner.

  According to another aspect of the present invention, a step of forming a coating layer by coating a coating solution in which a solvent-soluble polyimide is dissolved on the coating surface, and removing the solvent from the coating layer, Forming an organic layer containing a soluble polyimide, and a method for producing a gas barrier film is provided.

  According to this viewpoint, a gas barrier film having high transparency, heat resistance, smoothness, and gas barrier properties is produced.

  Here, a step of alternately stacking a gas barrier layer including at least one of a group consisting of a metal oxide having a gas barrier property, a metal nitride, and a metal film and an organic layer on the substrate may be included.

  According to this viewpoint, a gas barrier film having high transparency, heat resistance, smoothness, and gas barrier properties is produced.

  The gas barrier layer may be formed by a step of applying a polysilazane solution in which a polysilazane material is dissolved on a coating surface and a step of forming a gas barrier layer by converting the polysilazane material into silica.

  According to this viewpoint, a gas barrier film having high transparency, heat resistance, smoothness, and gas barrier properties is produced.

  As described above, according to the present invention, a gas barrier film having high transparency, heat resistance, smoothness and gas barrier properties is produced according to this aspect.

It is sectional drawing which shows the structure of the gas barrier film which concerns on embodiment of this invention. It is sectional drawing which shows the modification of a gas barrier film.

  Exemplary embodiments of the present invention will be described below in detail with reference to the accompanying drawings. In addition, in this specification and drawing, about the component which has the substantially same function structure, duplication description is abbreviate | omitted by attaching | subjecting the same code | symbol.

(1. Configuration of gas barrier film)
First, based on FIG. 1, the structure of the gas barrier film 10 which concerns on this embodiment is demonstrated. The gas barrier film 10 is obtained by alternately laminating organic layers 11 and gas barrier layers 12 on a substrate 100. The number of stacked layers (the number of units 10a including the organic layer 11 and the gas barrier layer 12) is not particularly limited. In FIG. 1, the organic layer 11 and the gas barrier layer 12 are formed in this order on the substrate 100, but the order of stacking may be reversed as shown in FIG. 2.

(1-1. Configuration of Organic Layer)
The organic layer 11 functions as a binder for fixing the gas barrier layers 12 to each other or the gas barrier layer 12 and the substrate 100. The organic layer 11 includes a solvent-soluble polyimide. The solvent-soluble polyimide is a polyimide that dissolves in a solvent (solvent).

(1-2. Configuration of Gas Barrier Layer)
The gas barrier layer 12 is a layer having gas barrier properties. The gas barrier layer 12 includes at least one selected from the group consisting of metal oxides having metal barrier properties, metal nitrides, and metals.

  Specifically, the gas barrier layer 12 is a thin film in which at least one of the group consisting of metal oxide, metal nitride, and metal is made amorphous. Examples of the metal oxide, metal nitride, and metal include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), and boron. (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) and other metals, and oxides and nitrides of the metals.

  Preferable examples of the metal oxide include silicon oxide, silicon oxynitride film, aluminum oxide film, zirconium oxide film, titanium oxide film, tin oxide film, indium alloy oxide film, and magnesium oxide film.

Note that the structure of the metal oxide is expressed as MO _X. M represents a metal element. The value of X varies depending on the type of metal element. The value of X is 0-2 for silicon, 0-1.5 for aluminum, 0-1 for magnesium, 0-1 for calcium, 0-0.5 for potassium, 0-2 for tin, 0-2 for sodium, 0 to 0.5, boron is 0 to 1.5, titanium is 0 to 2, lead is 0 to 1, zirconium is 0 to 2, and yttrium is a real number within the range of 0 to 1.5. In the above, when X = 0, it is a complete metal and is not transparent, and the upper limit of the range of X is a completely oxidized value. The value of X is preferably 1.0 to 2.0 when M is silicon, and is preferably within the range of 0.5 to 1.5 when M is aluminum.

  Preferable examples of the metal nitride include a silicon nitride film, an aluminum nitride film, and a titanium nitride film.

  Preferable examples of the metal film include aluminum, silver, nickel, copper, titanium, and alloy steel.

  The material of the gas barrier layer 12 may be selected from one or more of the above metal oxides according to the use of the gas barrier film 10 and the like. For example, when the gas barrier film 10 is used as a gas barrier film of a display, the material of the gas barrier layer 12 is preferably silicon oxide, aluminum oxide, or the like.

  The layer thickness of the gas barrier layer 12 varies depending on the type of metal material used for the gas barrier layer 12, but is preferably in the range of, for example, about 5 to 1000 nm, and when the metal material is aluminum oxide or silicon oxide, A range of about 400 nm is desirable.

(1-3. Configuration of substrate)
The substrate 100 is not particularly limited, and can be suitably used in this embodiment as long as it can be used as a substrate of a conventional gas barrier film. Examples of the substrate 100 include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), and polyimide (PI). The substrate 100 is preferably subjected to a charging process before the organic layer 11 and the gas barrier layer 12 are laminated. This is to improve the binding force between the substrate 100 and the organic layer 11 and the gas barrier layer 12.

(2. Manufacturing method of gas barrier film)
Next, the manufacturing method of the gas barrier film 10 is demonstrated. The gas barrier film 10 is produced by alternately laminating (forming) organic layers 11 and gas barrier layers 12 on the substrate 100.

(2-1. Step of forming organic layer)
The step of forming the organic layer 11 includes a step of preparing a polyimide solution in which a solvent-soluble polyimide is dissolved, that is, a coating solution, and applying the coating solution to the coating surface (the surface of the substrate 100 or the gas barrier layer 12). The step of forming a coating layer and the step of forming an organic layer containing solvent-soluble polyimide by removing the solvent from the coating layer are roughly divided.

(2-1-1. Step of preparing polyimide solution)
The polyimide solution is produced by the following method. That is, a solution of diamine and acid dianhydride is prepared by dissolving diamine and acid dianhydride in a solvent. Then, the diamine and acid dianhydride are reacted (polymerized) in the solution. Thereby, a polyamic acid is produced. In addition, as temperature which makes diamine and acid dianhydride react in a solution, 0-80 degreeC is preferable and 40-60 degreeC is more preferable.

  Subsequently, the ring closing condensation of the polyamic acid is carried out in a polyamic acid solution. As described above, this embodiment is different from the conventional production method in that the ring-closing condensation of the polyamic acid is performed in the polyamic acid solution (that is, in the solvent). Since the polyimide which concerns on this embodiment melt | dissolves in a solvent, it becomes possible to perform ring-closing condensation of a polyamic acid in a polyamic acid solution. If an attempt is made to produce a polyimide that does not dissolve in a solvent by the above method, the produced polyimide will precipitate from the solvent. In this case, polyimide cannot be used as a material for the organic layer.

  Thus, in this embodiment, the polyamic acid dissolved in the solvent is subjected to ring-closing condensation. Therefore, when the polyamic acid molecule is subjected to ring-closing condensation, it dissolves in the solvent, and thus moves more freely than the solid state polyamic acid molecule. For this reason, the energy required for the ring-closing condensation of the polyamic acid is lowered.

  For example, as a method of ring-closing condensation of polyamic acid, a method of ring-closing condensation of polyamic acid by heating a polyamic acid solution, a method of ring-closing condensation of polyamic acid using a catalyst (so-called chemical imidization), and the like can be mentioned. . In the former case, the heating temperature of the polyamic acid solution, that is, the reaction temperature is preferably 80 to 210 ° C, and more preferably 130 to 200 ° C. By setting it as such reaction temperature, a favorable reaction rate is obtained and it becomes possible to obtain a polyimide efficiently. Thus, in this embodiment, the heating temperature of the polyamic acid solution can be suppressed to 200 ° C. or lower.

  In the latter method, the ring closing condensation of the polyamic acid can proceed at room temperature, so that the polyamic acid can be subjected to the ring closing condensation with lower energy. Examples of the catalyst used for the chemical imidization include tertiary amines such as imidazole, trialkylamine, pyridine, and picoline. By using these catalysts, it becomes possible to produce polyimide more efficiently. In addition, since the reaction sufficiently occurs even when the reaction temperature is lower than that of the method of heating the polyamic acid solution, it is possible to greatly suppress side reactions caused by high temperature conditions.

  In addition, since water is produced when the polyamic acid is subjected to ring-closing condensation, it is necessary to remove water by any method. The method for removing water is not particularly limited. Examples of the method for removing water include a method of adding acetic anhydride to the polyamic acid solution, a method using a solvent azeotropic with water, such as toluene or xylene, and a method of passing a nitrogen stream through the polyamic acid solution. .

  In order to prepare a polyimide solution, that is, a solvent-soluble polyimide, it is necessary to appropriately select the starting materials, acid dianhydride and diamine. In this embodiment, a solvent-soluble diamine can be produced by combining the acid dianhydrides and diamines listed below.

  Examples of the acid dianhydride that can be used in this embodiment include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanoic acid dianhydride, 4,4′-sulfonyldiphthalic acid dianhydride, 3-fluoropyromellitic dianhydride, 3-chloropyromellitic dianhydride, 3-bromopyromellitic dianhydride, 3-trifluoromethylpyromellitic dianhydride, 3-trichloromethylpyromellitic acid dianhydride Anhydride, 3-tribromomethylpyromellitic dianhydride, 3,6-difluoropyromellitic dianhydride, 3,6-dichloropyromellitic dianhydride, 3,6-dibromopyromellitic dianhydride 3,6-bistrifluoromethylpyromellitic dianhydride, 3,6-bistrichloromethylpyromellitic dianhydride, 3,6-bistribromomethyl pyrome Tsu doo dianhydride, and the like. Among these, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanoic acid dianhydride is more preferable in terms of imparting solubility in various organic solvents.

  In this embodiment, it is preferable to use at least one of the above acid dianhydrides. However, the following acid dianhydrides can be used in combination with or in place of the acid dianhydrides as appropriate. It is. Examples of such acid dianhydrides include 9,9-bis (3,4-dicarboxyphenyl) fluorenic dianhydride and 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl. ] Fluorenoic acid dianhydride, 4,4'-biphenylenebis (trimellitic acid monoester acid anhydride), p-phenylenebis (trimellitic acid monoester acid anhydride), p-methylphenylenebis (trimellitic acid monoester) Ester acid anhydride), p- (2,3-dimethylphenylene) bis (trimellitic acid monoester acid anhydride) 1,4-naphthalene bis (trimellitic acid monoester acid anhydride), 2,6-naphthalene bis (Trimellitic acid monoester anhydride), biphenyltetracarboxylic dianhydride, 2,2-bis [4- (trimellitic acid monoester anhydride) Phenyl] propane, 2,2-bis [4- (trimellitic acid monoester anhydride) phenyl] hexafluoropropane, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′ , 4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3 5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,3-bis ( 3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, 1- (2,3-dicarboxyphenyl) -3- (3,4-dicarboxyphenyl) -1 , 1, , 3-Tetramethyldisiloxane dianhydride, 4,4′-biphthalic anhydride, pyromellitic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6, 7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4 '-Benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyl ether tetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5 , 6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 4,4′-sulfonyldiphthalic dianhydride, 1-trifluoromethyl-2,3 5,6-benzene Tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenyltetracarboxylic dianhydride, 2,2-bis (3 , 4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-Dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2 , 3 4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2,3,2 ′, 3-benzophenone tetracarboxylic dianhydride, 2,3,3 ′ , 4′-benzophenonetetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2, 3,4,5-tetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,4,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2 , 3,2 ′, 3′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methylphenylsilane dianhydride Bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4-dicarboxy) Phenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitic anhydride), ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic acid Anhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5 6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 4,4′-bis ( 3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4 ′-(4,4′isopropylidenediphenoxy) -bis (phthalic anhydride), tetrahydrofuran-2,3,4,5-tetracarboxylic And acid dianhydride, bis (exobicyclo (2,2,1) heptane-2,3-dicarboxylic dianhydride) sulfone, and the like. Examples of the aliphatic tetracarboxylic dianhydride include cyclobutane-1,2,3,4-tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, dicyclohexyl-3, 3 ′, 4,4′-tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid-1,2: 4,5-dianhydride, 1,2,3,4-cyclobutanetetra Preferable examples include carboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3; 5,6-tetracarboxylic dianhydride and the like. These can be used alone or in combination.

  On the other hand, examples of the diamine that can be used in the present embodiment include 2,2′-difluoro-4,4′-diaminobiphenyl, 3,3′-difluoro-4,4′-diaminobiphenyl, and 2,2′-. Difluoro-5,5′-diaminobiphenyl, 3,3′-difluoro-5,5′-diaminobiphenyl, 2,2′-dichloro-4,4′-diaminobiphenyl, 3,3′-dichloro-4,4 '-Diaminobiphenyl, 2,2'-dichloro-5,5'-diaminobiphenyl, 3,3'-dichloro-5,5'-diaminobiphenyl, 2,2'-dibromo-4,4'-diaminobiphenyl, 3,3′-dibromo-4,4′-diaminobiphenyl, 2,2′-dibromo-5,5′-diaminobiphenyl, 3,3′-dibromo-5,5′-diaminobiphenyl, 2, '-Bis (trifluoromethyl) -4,4'-diaminebiphenyl, 3,3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -5 , 5′-diaminobiphenyl, 3,3′-bis (trifluoromethyl) -5,5′-diaminobiphenyl, 2,2′-bis (trichloromethyl) -4,4′-diaminebiphenyl, 3,3 ′ -Bis (trichloromethyl) -4,4'-diaminobiphenyl, 2,2'-bis (trichloromethyl) -5,5'-diaminobiphenyl, 3,3'-bis (trichloromethyl) -5,5'- Diaminobiphenyl, 2,2′-bis (tribromomethyl) -4,4′-diaminebiphenyl, 3,3′-bis (tribromomethyl) -4,4′-diaminobiphenyl, 2, 2′-bis (tribromomethyl) -5,5′-diaminobiphenyl, 3,3′-bis (tribromomethyl) -5,5′-diaminobiphenyl, bis (4-aminophenyl) sulfone, bis (3 -Aminophenyl) sulfone, bis (5-fluoro-4-aminophenyl) sulfone, bis (5-fluoro-3-aminophenyl) sulfone, bis (5-chloro-4-aminophenyl) sulfone, bis (5-chloro) -3-aminophenyl) sulfone, bis (5-bromo-4-aminophenyl) sulfone, bis (5-bromo-3-aminophenyl) sulfone, bis (5-trifluoromethyl-4-aminophenyl) sulfone, bis (5-trifluoromethyl-3-aminophenyl) sulfone, bis (5-trichloromethyl-4-aminophenyl) sulfone Bis (5-trichloromethyl-3-aminophenyl) sulfone, bis (5-tribromomomethyl-4-aminophenyl) sulfone, bis (5-tribromomethyl-3-aminophenyl) sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (5-fluoro-4-aminophenoxy) phenyl] sulfone, bis [4- (5-fluoro -3-aminophenoxy) phenyl] sulfone, bis [4- (5-chloro-4-aminophenoxy) phenyl] sulfone, bis [4- (5-chloro-3-aminophenoxy) phenyl] sulfone, bis [4- (5-Bromo-4-aminophenoxy) phenyl] sulfone, bis [4- (5-bromo-3-aminophenoxy) Enyl] sulfone, bis [4- (5-trifluoromethyl-4-aminophenoxy) phenyl] sulfone, bis [4- (5-trifluoromethyl-3-aminophenoxy) phenyl] sulfone, bis [4- (5 -Trichloromethyl-4-aminophenoxy) phenyl] sulfone, bis [4- (5-trichloromethyl-3-aminophenoxy) phenyl] sulfone, bis [4- (5-tribromomethyl-4-aminophenoxy) phenyl] Sulfone, bis [4- (5-tribromomethyl-3-aminophenoxy) phenyl] sulfone, 4,4′-diaminodiphenylhexafluoropropane, 3,3′-diaminodiphenylhexafluoropropane, 2,2′-bis [4 (4-Aminophenoxy) phenyl] hexafluoropropane (4-B AF), 2,2'-bis [3 (3-aminophenoxy) phenyl] hexafluoropropane (3-BDAF), and the like. These are preferable in terms of solubility in a solvent. Of these, 2,2'-bis (trifluoromethyl) -4,4'-diaminebiphenyl is more preferred.

  Moreover, in this embodiment, aliphatic diamine can also be used conveniently. Examples of the aliphatic diamine that can be used in the present embodiment include trans-1,4-diaminocyclohexane, cis-1,4-diaminocyclohexane, 1,6-hexamethylenediamine, and 1,10-deca. Examples include methylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, and polyoxypropylenediamine having a weight average molecular weight of 500 or less.

  In this embodiment, it is preferable to use at least one of the above diamines. However, the following diamines can be used in combination with or in place of the above diamines. Examples of such diamines include m-phenylene diamine, o-phenylene diamine, p-phenylene diamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfide, and 4,4′-diamino. Benzophenone, 4,4′-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminobenzoyl) benzene, 4 , 4′-bis (4-aminophenoxy) biphenyl, 1,3-bis (3-aminophenoxy) benzene (APB-133), 1,3-bis (4-aminophenoxy) benzene (APB-134), 1 , 4-bis (4-aminophenoxy) benzene (APB-144), bis [4- (4-aminophenoxy) Phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] methane, 2, 2-bis [4- (4-aminophenoxy) phenyl] propane, 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene, diaminopolysiloxane, 4,4′-diamino-benzophenone, 4,4 '-Bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) benzophenone, 4,4'-diaminodiphenyl ether, 4,4 '-Bis (4-aminophenoxy) diphenyl ether, 3,3'-diaminodiphenyl sulfone, 2,2-bi [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) ) Phenyl] methane, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ketone, 1,3 -Bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2'-dimethylbiphenyl-4,4'-diamine, 2,6,2 ', 6'-tetramethyl -4,4'-diamine, 5,5'-dimethyl-2,2'-sulfonyl-biphenyl-4,4'-diamine, (4,4'-diamino) diphe Nyl ether, (4,4′-diamino) diphenylsulfone, (4,4′-diamino) benzophenone, (3,3′-diamino) benzophenone, (4,4′-diamino) diphenylmethane, (4,4′-diamino) ) Diphenyl ether, (3,3′-diamino) diphenyl ether, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 4,4′-diamino- 2,2′-dimethyl-5,5′-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (4-amino-2-hydroxy) Phenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3) Hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) ether, bis (4-amino-3-hydroxyphenyl) ether, bis (4-amino-2-methyl-5hydroxyphenyl) ether, 3,5 -Diaminobenzoic acid, 2,4-diaminobenzoic acid, 5,5'-methylenebisanthranilic acid and the like. These diamines can be used alone or in combination.

  Moreover, in this embodiment, since a polyimide solution is produced, a polyimide solution can be used as a coating liquid of the organic layer 11 as it is. Accordingly, the solvent preferably has a low boiling point. As will be described later, in the present embodiment, the organic layer 11 is formed simply by removing the solvent from the coating layer made of the polyimide solution. Therefore, the lower the boiling point of the solvent, the lower the thermal shrinkage of the organic layer 11, and This is because the occurrence of cracks in the gas barrier layer 12 is suppressed.

  Solvents that can be preferably used in the present embodiment include, for example, ureas such as tetramethylurea, N, N-dimethylethylurea, sulfoxides or sulfones such as dimethylsulfoxide, diphenylsulfone, and tetramethylsulfone, N, Such as N-dimethylacetamide (DMAc), N, N-dimethylformamide (DMF), N, N′-diethylacetamide, N-methyl-2-pyrrolidone (NMP), γ-butyllactone, hexamethylphosphoric triamide Amido or aprotic solvent of phosphorylamide, alkyl halides such as chloroform and methylene chloride, aromatic hydrocarbons such as benzene, toluene, p-xylene, m-xylene and mesitylene, phenol and cresol Phenols, dimethyl Ether, ethers such as diethyl ether, p- cresol methyl ether, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), may be mentioned ketones such as acetone and diethyl ketone. Two or more of these solvents can be used in combination.

  In this embodiment, polyimide may be extracted from the obtained polyimide solution. For example, the polyimide is deposited by adding a precipitation solvent (a solvent in which the polyimide does not dissolve) to the polyimide solution. And the polyimide is collect | recovered by filtering the mixed solution in which the polyimide precipitated with a filter. In addition, since polyimide may be dissolved in the filtrate, the above treatment may be repeated on the filtrate. When a polyimide lump is formed when the polyimide is precipitated, a wet or dry pulverizer can be used in combination.

  The mass of the precipitation solvent used to actually precipitate the polyimide (the total of the mass added to the polyimide solution and the mass added to the filtrate) is 1.5 times or more of the original polyimide solution. It is preferable in terms of controlling the body shape.

  In addition, it is preferable to remove the catalyst and acetic anhydride described above by washing the recovered polyimide in terms of suppressing the deterioration of the polyimide. The solvent used for washing is not particularly limited, and may be a solvent used as a precipitation solvent, a solvent used during imidization, or the like.

  Thereafter, the solvent is removed by drying the polyimide. As a drying method, for example, vacuum drying or hot air drying can be used. As the drying temperature, coloring may occur at 120 ° C. or higher in the presence of oxygen, and it is clearly colored at 150 ° C. Therefore, the drying temperature is preferably 120 ° C. or lower. It is desirable to carry out at 120 ° C. or lower even in vacuum or in an inert gas atmosphere.

  The recovered polyimide may be processed into a desired shape after drying. For example, polyimide can be processed into various shapes such as powder and flakes. The average particle diameter of the processed polyimide particles is not particularly limited, but is preferably 5 mm or less, more preferably 3 mm or less, and particularly preferably 1 mm or less. The average particle diameter is, for example, an arithmetic average value of particle diameters (diameters) when polyimide particles are regarded as spheres. The average particle size may be calculated based on the result of measuring the particle size distribution using, for example, a laser diffraction scattering type particle size particle size distribution measuring device.

  When the recovered polyimide is used as a material for the organic layer 11, it is dissolved again in the above-described solvent to form a polyimide solution, that is, a coating solution.

(2-1-2. Step of applying coating liquid to coated surface)
Next, the coating layer is formed by coating the coating liquid on the coating surface (the surface of the substrate 100 or the gas barrier layer 12). The coated surface is the surface of the substrate 100 when the unit 10a is not formed on the substrate 100, and the surface of the gas barrier layer 12 when the unit 10a is formed on the substrate 100.

(2-1-3. Step of removing the solvent from the coating layer)
Subsequently, the organic layer 11 containing a solvent-soluble polyimide is formed by removing the solvent from the coating layer. In this embodiment, since the organic layer 11 can be formed only by removing the solvent from the coating layer, the organic layer 11 can be formed with low energy, that is, a low heating temperature. Therefore, thermal contraction of the organic layer 11 is suppressed, and as a result, generation of cracks in the gas barrier layer 12 is suppressed.

(2-2. Step of forming a gas barrier layer)
The gas barrier layer 12 is formed on the organic layer 11. The method for forming the gas barrier layer 12 is not particularly limited, but when the gas barrier layer 12 is composed of silicon oxide, the method of converting polysilazane to silica is most preferable. Hereinafter, this method will be described.

  In this method, a polysilazane solution is coated on a coating surface (the surface of the organic layer 11) and dried to prepare a coating layer, and the coating layer is used in an atmosphere in which at least one of oxygen and water vapor exists. Irradiating the substrate with ultraviolet rays to convert the polysilazane in the coating layer into silica.

(2-2-1. Step of applying and drying polysilazane solution on substrate)
First, a polysilazane solution is applied on the organic layer 11 and dried to prepare a coating layer. The method for applying the polysilazane solution on the coated surface is not particularly limited, and a known method is arbitrarily applied. Examples of the coating method include polysilazane solution, spin coating method, roll coating method, flow coating method, ink jet method, spray coating method, printing method, dipping coating method, casting film forming method, bar coating method, gravure printing method. Etc. The thickness of the coating solution on the organic layer 11, that is, the coating thickness can be appropriately set according to the purpose. For example, the coating thickness can be set such that the thickness after drying, that is, the thickness of the coating layer is about 30 nm to 750 nm, more preferably about 40 nm to 600 nm, and most preferably about 45 nm to 500 nm.

Polysilazane is a photocurable inorganic polymer having a silicon-nitrogen bond, and has a bond such as Si—N, Si—H, or N—H. Polysilazane serves as a precursor of SiO ₂ , Si ₃ N ₄ and both intermediate solid solutions SiO _x N _y . Specifically, polysilazane has a repeating unit represented by the following Chemical Formula 1 or Chemical Formula 2, and can be dissolved in various solvents.

  In Chemical Formula 2, R1 and R2 are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, an alkoxy group, or the like. In the present embodiment, perhydropolysilazane (PHPS) in which all of R1 and R2 are hydrogen atoms is particularly preferable from the viewpoint of the denseness of the barrier film.

  Perhydropolysilazane is presumed to have at least one of a linear structure and a ring structure centered on 6- and 8-membered rings. Each perhydropolysilazane is commercially available in a solution state dissolved in an organic solvent. In this embodiment, a commercially available product can be used as it is as a polysilazane solution.

  The solvent of the polysilazane solution may be any solvent other than a solvent that easily reacts with polysilazane (for example, alcohols and water). Examples of such solvents include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, and ethers such as halogenated hydrocarbon solvents, aliphatic ethers, and alicyclic ethers. it can. More specifically, examples of such solvents include pentane, hexane, cyclohexane, toluene, xylene, aromatic solvents (such as Solvesso), methylene chloride, trichloroethylene, dibutyl ether, dioxane, and tetrahydrofuran. These solvents may be selected according to the solubility of polysilazane, the evaporation rate of the solvent, and the like. A plurality of solvents may be mixed.

  Moreover, in this embodiment, in order to accelerate | stimulate the silica conversion of polysilazane, you may add various catalysts to a coating liquid. Examples of such a catalyst include amines and metal carboxylates. Such catalysts are listed, for example, in JP-A-11-116815 and JP-A-9-31333, and in this embodiment, the catalysts listed in these documents can be used.

  Specific examples of the polysilazane solution include Aquamica NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials Co., Ltd. Among these, NN120 and NN110 made of perhydropolysilazane containing no catalyst are preferable as the coating liquid for producing the barrier film of this embodiment. By using these coating liquids, a denser barrier film having a higher barrier property can be produced.

(2-2-2. Step of irradiating the coating layer with ultraviolet rays)
Next, the coating layer is irradiated with ultraviolet rays in an atmosphere in which at least one of oxygen and water vapor exists. Thereby, the silica conversion process of a coating layer is performed.

  Here, the silica conversion treatment will be briefly described. Polysilazane becomes silicon nitride by sintering at high temperature in a nitrogen or ammonia atmosphere, while it is converted to silica by irradiating polysilazane with ultraviolet light in an atmosphere in which at least one of oxygen and water vapor exists. It has been reported. Polysilazane has also been reported to be converted to silica by sintering at a low temperature from room temperature to 450 ° C. in an atmosphere containing at least one of oxygen and water vapor.

  An ultraviolet irradiation treatment is preferably used in this embodiment. By irradiating polysilazane with ultraviolet light in an atmosphere in which at least one of oxygen and water vapor exists, active oxygen and ozone are generated, and these active oxygen and ozone can promote the silica conversion reaction of polysilazane. .

  Active oxygen and ozone are very reactive. For example, the polysilazane-containing coating layer becomes a gas barrier layer 12 with higher density and fewer defects by being directly oxidized by active oxygen and ozone without passing through silanol.

  In the case of a water vapor atmosphere, it is presumed that hydroxyl radicals are also generated. Hydroxyl radicals are also very reactive, as are active oxygen and ozone.

  Here, ozone in the vicinity of the coating layer may be insufficient during irradiation with ultraviolet rays. Therefore, in this embodiment, ozone may be produced by a device different from the ultraviolet irradiation device, and this ozone may be introduced into the reaction region of the coating layer.

  Although the wavelength of an ultraviolet-ray is not specifically limited, 100 nm-450 nm are preferable, 150 nm-300 nm are more preferable, 100 nm-200 nm are more preferable, 150 nm-200 nm are the most preferable. When the wavelength of the ultraviolet ray is within this range, the photon energy of the ultraviolet ray is increased, so that the silica conversion reaction is further promoted.

  That is, when the wavelength of the ultraviolet light is 100 to 200 nm, the photon energy of the ultraviolet light is larger than the interatomic bonding force in the compound, so that active oxygen, ozone, and hydroxyl radicals are easily generated from oxygen and water vapor, and Each bond in polysilazane tends to be broken. Then, the active oxygen, ozone, and oxygen from the hydroxyl radical are inserted into the bond portion cleaved within the polysilazane, so that the silica conversion reaction proceeds. Thereby, the silica conversion reaction proceeds at a relatively low temperature.

  The ultraviolet light source is not particularly limited, and examples thereof include a rare gas excimer lamp, a low pressure mercury lamp, a deuterium lamp, a metal halide lamp, and a plasma cleaning lamp. Of these light sources, a rare gas excimer lamp is particularly preferred. This is because the rare gas excimer lamp can output ultraviolet rays having a wavelength of 100 to 200 nm. Among rare gas excimer lamps, xenon excimer lamps are particularly preferable.

  Here, the rare gas excimer lamp emits ultraviolet rays from the rare gas by applying energy to the rare gas by discharge or the like. That is, noble gas atoms such as Xe, Kr, Ar, and Ne are chemically bonded and do not form molecules, so they are called inert gases. However, noble gas atoms (excited atoms) that have gained energy by discharge or the like can form molecules by combining with other noble gas atoms. When the rare gas atom becomes a xenon atom, it becomes a xenon molecule through the processes shown in the following chemical formulas 3 and 4.

Then, the excited excimer molecule Xe ₂ * emits 172 nm excimer light, that is, ultraviolet light when transitioning to the ground state. As a feature of the rare gas excimer lamp, radiation concentrates on one wavelength, and radiation of other wavelengths is hardly emitted, so that the efficiency of the silica conversion reaction is increased.

  In addition to the above features, the xenon excimer lamp has the advantage that the luminous efficiency is higher than that of other rare gases and that a lamp for irradiating a large area can be made of quartz glass. Furthermore, ultraviolet light having a wavelength of 172 nm emitted from a xenon excimer lamp has a large oxygen absorption coefficient. For this reason, radical oxygen atomic species (that is, active oxygen) and ozone can be generated at a high concentration with a small amount of oxygen. In addition, ultraviolet light having a wavelength of 172 nm can efficiently cut the interatomic bond of organic substances. Therefore, by using a xenon excimer lamp as a light source, high-concentration ozone and active oxygen can be generated efficiently, and polysilazane interatomic bonds can be efficiently cut, so silica conversion can be achieved in a short time. The reaction can proceed. Furthermore, although the polysilazane and the organic layer 11 are easily damaged by heat, since the silica conversion reaction can proceed in a short time, excessive heat generation of the polysilazane and the organic layer 11 can be prevented. Furthermore, since the silica conversion reaction using a xenon excimer lamp proceeds efficiently, a reduction in equipment area can be expected.

  Other rare gas excimer lamps can output ultraviolet rays having a wavelength of 100 to 200 nm, but cannot be as effective as xenon. Therefore, in this embodiment, a xenon excimer lamp is particularly preferable.

The output of the light source, the illuminance, and the irradiation energy are not particularly limited as long as the above-described effects can be obtained. For example, the output of the light source may be about 400 W to 30 kW. The illuminance may be about 5 mW / cm ^{2 to} 100 kW / cm ² , but 1 mW / cm ^{2 to} 10 W / cm ² is preferable. The irradiation energy is ^preferably from ^{1mJ / cm 2 ~5000mJ / cm 2} , 10mJ / cm 2 ~2000mJ / cm 2 is more preferable. In addition to continuous irradiation, a plurality of times of irradiation may be performed, or a plurality of times of irradiation may be pulsed irradiation in a short time.

  Other methods for forming the gas barrier layer 12 include, for example, a physical vapor deposition method such as a vacuum deposition method, a sputtering method, and an ion plating method, a plasma chemical vapor deposition method, and the like. In this embodiment, as a method for forming a metal oxide, metal nitride, or metal vapor-deposited film, the above-described metal oxide, metal nitride, or metal is used as a raw material, and heated and vapor-deposited on a substrate. Or an oxidation reaction vapor deposition method in which a metal oxide, a metal nitride or a metal is used as a raw material and is oxidized by introducing oxygen gas to deposit on the substrate, a metal oxide, a metal nitride or a metal Use as a target material, introduce argon gas, oxygen gas, sputtering, sputtering method to deposit on the substrate, metal oxide or metal nitride or metal heated by plasma beam generated by plasma gun, When depositing an ion plating method for vapor deposition on a substrate or a vapor deposition film of silicon oxide, The machine silicon compound can be formed by a plasma chemical vapor deposition method as a raw material.

  As the silicon oxide thin film, a vapor deposition film formed by using a low temperature plasma chemical vapor deposition method using an organosilicon compound as a raw material can be used. For example, 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, Tetramethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, etc. can be used. In the present invention, among the organosilicon compounds as described above, it is preferable to use tetramethoxysilane or hexamethyldisiloxane from the viewpoints of handleability and vapor deposition film characteristics.

Example 1
In Example 1, an organic layer made of soluble polyimide and a gas barrier layer made of silicon oxide (SiO ₂ ) were alternately laminated on a substrate.

1) Cleaning of substrate (resin film) Ube Industries, Ltd. (0.125 mm thick polyimide film) was prepared as a substrate. The substrate was washed with a detergent and pure water, and then dried by air blow.

2) Charging treatment The substrate was UV / ozone treated for 5 minutes.

3) Preparation of solvent-soluble polyimide solution (varnish) In a separable flask, 223.0 g of N-methylpyrrolidone (NMP) (manufactured by Mitsubishi Chemical) was charged as a solvent for polymerization, and 2,2′-bis (trifluoro) was added thereto. Methyl) -4,4′-diaminobiphenyl (0.125 mol) (manufactured by Daikin Industries) was dissolved. To this solution, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanoic acid dianhydride (0.125 mol) (manufactured by Daikin Industries) was added and stirred to dissolve completely. After complete dissolution, the mixture was stirred to increase the polymerization viscosity to 80 Pa · s. The solution was heated to 180 ° C. by a Dean-Stark tube filled with toluene (manufactured by Wako Pure Chemical Industries), and the generated water was removed from the system. When heated for 5 hours, no water was observed from the system. After cooling, a soluble polyimide solution was obtained.

4) Formation of organic layer The soluble polyimide varnish produced in 3) was spin coated. The coating film was dried and cured at 180 ° C. for 5 minutes using a hot plate (PC-400D manufactured by ASONE). Thus, an organic layer having a thickness of 1.0 μm was formed on the substrate.

5) Formation of Gas Barrier Layer 5-1) Formation of Coating Layer A washed substrate was spin coated with Aquanica NN110 manufactured by AZ Electronic Materials as a perhydropolysilazane-containing coating solution. This coating solution does not contain a catalyst. Next, the coating solution was dried at 100 ° C. for 15 minutes. Thereby, a polysilazane (PHPS) coating layer was formed on the substrate.
5-2) SiO ₂ conversion treatment Next, a SiO ₂ conversion treatment was performed using a xenon excimer lamp (manufactured by MD Excimer). The processing conditions are as follows. The film thickness of SiO ₂ was about 100 nm.

Processing conditions UV wavelength: 172 nm
UV illuminance: 20 mW / cm ²
Distance between coating film and light source: 4mm
UV irradiation time: 2 minutes 30 seconds Reaction atmosphere: air

6) Lamination of organic layer and gas barrier layer The above 4) and 5) were repeated in order to form three pairs (three units) of the organic layer and the gas barrier layer on the substrate.

(Example 2)
In Example 2, an organic layer made of soluble polyimide and a gas barrier layer made of silicon oxide (SiO ₂ ) were alternately laminated on the substrate. However, in Example 2, the produced polyimide was once precipitated and collected in a solution, and then dissolved in a low boiling point solvent. The specific processing is as follows.

1) Cleaning of substrate (substrate) Ube Industries, Ltd. (0.125 mm thick polyimide film) was prepared as a substrate. The substrate was washed with a detergent and pure water, and then dried by air blow.

2) Charging treatment The substrate was UV / ozone treated for 5 minutes.

3) Preparation of solvent-soluble polyimide solution (varnish) In a separable flask, 223.0 g of N-methylpyrrolidone (NMP) (manufactured by Mitsubishi Chemical) was charged as a solvent for polymerization, and 2,2′-bis (trifluoro) was added thereto. Methyl) -4,4′-diaminobiphenyl (0.125 mol) (manufactured by Daikin Industries) was dissolved. To this solution, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanoic acid dianhydride (0.125 mol) (manufactured by Daikin Industries) was added and stirred to dissolve completely. After complete dissolution, the mixture was stirred to increase the polymerization viscosity to 80 Pa · s. The solution was heated to 180 ° C. by a Dean-Stark tube filled with toluene (manufactured by Wako Pure Chemical Industries), and the generated water was removed from the system. When heated for 5 hours, no water was observed from the system. After cooling, a soluble polyimide solution was obtained. This soluble polyimide solution was dropped into a large amount of methanol solution to perform reprecipitation. Vacuum drying was performed to obtain a filamentous soluble polyimide. This thread-like soluble polyimide was dissolved in MEK (manufactured by Wako Pure Chemical Industries, Ltd.) to a concentration of 10% by mass (10% by mass with respect to the total mass of the polyimide solution) to obtain a low-boiling solvent soluble polyimide solution. .

4) Formation of organic layer The soluble polyimide varnish produced in 3) was spin coated. The coating film was dried and cured at 150 ° C. for 5 minutes using a hot plate (PC-400D manufactured by ASONE). As a result, an organic layer having a thickness of 1.0 μm was formed on the substrate.

5) Formation of Gas Barrier Layer 5-1) Formation of Coating Layer A washed substrate was spin coated with Aquanica NN110 manufactured by AZ Electronic Materials as a perhydropolysilazane-containing coating solution. This coating solution does not contain a catalyst. Next, the coating solution was dried at 100 ° C. for 15 minutes. Thereby, a polysilazane (PHPS) coating layer was formed on the substrate.
5-2) SiO ₂ conversion treatment Next, a SiO ₂ conversion treatment was performed using a xenon excimer lamp (manufactured by MDI Excimer). The processing conditions are as follows. The film thickness was about 100 nm.
Processing conditions UV wavelength: 172 nm
UV illuminance: 20 mW / cm ²
Distance between coating film and light source: 4mm
UV irradiation time: 2 minutes and 30 seconds Reaction atmosphere: air 6) Lamination of organic layer and gas barrier layer The above 4) and 5) were repeated in order to form three pairs of laminated layers of organic layer and gas barrier layer on the substrate.

(Example 3)
The same treatment as in Example 2 was performed except that the above 4) and 5) were not repeated and one pair of laminated films was formed.

Example 4
Except for forming soluble polyimide with a film thickness of 200 nm and gas barrier layer SiO ₂ with a thickness of 400 nm and forming two pairs of organic films and gas barrier layers on the substrate, the same treatment as in Example 2 was performed.

(Example 5)
Except for forming soluble polyimide with a film thickness of 1000 nm and forming two pairs of organic films and gas barrier layers on the substrate, the same treatment as in Example 2 was performed.

(Example 6)
Except for forming the gas barrier layer with a film thickness of 800 nm and forming one pair of the organic film and the gas barrier layer on the substrate, the same treatment as in Example 2 was performed.

(Example 7)
The same treatment as in Example 2 was performed except that the steps 4) and 5) were replaced and the gas barrier layer and the organic layer were formed in this order.

(Example 8)
The same treatment as in Example 3 was performed except that the steps 4) and 5) were replaced and the gas barrier layer and the organic layer were formed in this order.

Example 9
The steps 4) and 5) above are interchanged to form a gas barrier layer and an organic layer in this order, and the process is exactly the same as that except that the thickness of the gas barrier layer is 400 nm and the thickness of the organic layer is 10000 nm. went.

(Example 10)
In Example 2, an organic layer made of soluble polyimide and a gas barrier layer made of SiO ₂ / SiN were alternately laminated on the substrate. Specifically, the same treatment as in Example 2 was performed except that Step 5) of Example 2 was performed as follows.

5 ′) Formation of Gas Barrier Layer An SiO ₂ film and a SiN film were formed on the substrate as a gas barrier film using a general CVD apparatus that performs film formation using a plasma CVD apparatus (manufactured by Samco).

Next, the substrate was set at a predetermined position in the vacuum chamber, and the vacuum chamber was closed. Next, the inside of the vacuum chamber was evacuated, and when the pressure reached 0.01 Pa, the reactive gas of the SiO ₂ film was introduced. A high-frequency power of 600 W was supplied to the electrode at a frequency of 13.56 MHz to generate plasma, thereby forming a gas barrier film SiO ₂ with a film thickness of 60 nm.

After forming the SiO ₂ film, the reaction gas and residues in the vacuum chamber are exhausted once. When the pressure reaches 0.01 Pa, the reaction gas of the SiN film is introduced, and a high frequency is applied in the same manner to generate plasma. The gas barrier film SiN was formed with a film thickness of 60 nm.

Reaction gas tetramethylenedisiloxane (TMDSO) / O ₂ / Ar for SiO ₂ film
Reaction gas of SiN film Nitrogen / Silane / Ammonia

  Two pairs of laminated layers of the organic layer and the gas barrier layer 5 ') were formed.

(Example 11)
In Example 11, an organic layer made of soluble polyimide and a gas barrier layer made of Al ₂ O ₃ were alternately laminated on a substrate. Specifically, the same treatment as in Example 2 was performed except that Steps 5) and 6) of Example 2 were as follows.

5 ″) Formation of gas barrier layer Using a sputtering apparatus (manufactured by ULVAC, Inc.), reaction is performed using Ar gas as the discharge gas and Al (manufactured by ULVAC TECHNO) as the target so as to have a composition ratio of Al ₂ O _3. A gas barrier layer having a thickness of 30 nm was formed by adding O2 gas as a gas to a pressure of 0.25 Pa, applying a high frequency of 400 W to the target, plasma discharge, and sputtering the target.

6 ′) Lamination of organic layer and gas barrier layer The above 4) and 5 ″) were repeated 5 times in order to form a laminated film.

(Comparative Example 1)
In Comparative Example 1, an organic layer made of polyvinyl alcohol and a gas barrier layer made of SiO ₂ were alternately laminated on the substrate. Specifically, the same treatment as in Example 1 was performed except that Step 4) of Example 1 was performed as follows.

4 ′) Formation of organic layer By spin coating, polyvinyl alcohol resin (PVA1400, manufactured by Kuraray Co., Ltd.) was applied with a thickness of 1.0 μm, and dried at 100 ° C. using a hot plate (PC-400D manufactured by ASONE). An organic layer was formed.

6 ″) Lamination of organic layer and gas barrier layer In the same manner as in Example 1, the organic layer and the gas barrier layer were sequentially repeated to form three pairs of laminated films on the substrate.

(Comparative Example 2)
In Comparative Example 1, an organic layer made of solvent-insoluble polyimide and a gas barrier layer made of SiO ₂ were alternately laminated on a substrate. Specifically, the same treatment as Comparative Example 1 was performed except that the organic layer of Comparative Example 1 was replaced with the following solvent-insoluble polyimide.

3 ') Preparation of non-soluble polyimide varnish In a separable flask, 223.0 g of N-methylpyrrolidone (NMP) was charged as a solvent for polymerization, and 24,4'-oxydianiline (4,4'-ODA) was added thereto. (0.125 mol) was dissolved. To this solution, pyromellitic anhydride (PMDA) (0.125 mol) was added and stirred to completely dissolve. After complete dissolution, the mixture was stirred to increase the polymerization viscosity to 80 Pa · s, and an insoluble polyimide solution was obtained.

4 ″) Formation of organic layer The insoluble polyimide varnish produced in 3 ′) was spin-coated. The coating film was dried and cured at 150 ° C. for 5 minutes using a hot plate (PC-400D manufactured by ASONE). Furthermore, in order to complete imidation, it dried and hardened at 250 degreeC for 30 minutes, 350 degreeC for 30 minutes, and 450 degreeC for 30 minutes using oven. Thus, an organic layer having a thickness of 1.0 μm was formed on the substrate.

(Comparative Example 3)
In Comparative Example 3, an organic layer made of solvent-insoluble polyimide and a gas barrier layer made of SiO ₂ were alternately laminated on the substrate. Specifically, the same treatment as in Comparative Example 2 was performed except that the organic layer and gas barrier layer of Comparative Example 2 were replaced.

(Comparative Example 4)
In Comparative Example 4, an organic layer made of methacrylate resin and a gas barrier layer made of SiO ₂ / SiN were alternately laminated on the substrate. Specifically, the same treatment as in Example 10 was performed except that the organic layer of Example 10 was replaced with the following methacrylate resin.

4 ″ ′) Formation of Organic Layer A methacrylate resin (TMPTA manufactured by Tokyo Chemical Industry Co., Ltd.) is applied at a film thickness of 1.0 μm by spin coating, and 100 ° C. using a hot plate (As One PC-400D). And dried to form an organic layer.

(Comparative Example 5)
In Comparative Example 5, an organic layer made of polyparaxylylene resin and a gas barrier layer made of Al ₂ O ₃ were alternately laminated on the substrate. Specifically, the same treatment as in Example 11 was performed except that the organic layer of Example 11 was replaced with the following polyparaxylylene resin.

4 ″ ″) Formation of organic layer An organic layer was formed with a polyparaxylylene resin (diX coating manufactured by Sansei Kasei Co., Ltd.) with a film thickness of 1.0 μm by vapor deposition polymerization (lab coater, manufactured by Parylene, Japan). .

(Gas barrier property measurement)
(WVTR measurement)
The WVTR of the barrier film was measured using a water vapor transmission rate measuring apparatus AQUATRAN manufactured by MOCON.
Since the lower limit of detection is 5 × 10 ⁻⁴ (g / m ² / day), those having a very low WVTR value were set to 5 × 10 ⁻⁴ (g / m ² / day).

(Heat resistance measurement)
The weight loss from room temperature to 500 ° C. was measured using a thermal analyzer (TG-DTA) manufactured by Rigaku Corporation.

(Flexibility measurement)
Using an automatic mandrel testing machine, each mandrel with a radius of 1, 3, 5, 10, 20 mm was bent 100,000 times, and then an optical microscope was used to observe whether the gas barrier layer was broken near the bent. The radius of the mandrel that did not break was taken as the breaking limit. The evaluation results are summarized in Table 1.

  According to Table 1, it turns out that the gas barrier film which concerns on a present Example is excellent in all of gas barrier property, heat resistance, and flexibility.

  As described above, according to the present embodiment, the gas barrier film is produced using the solvent availability polyimide. The solvent-soluble polyimide is excellent in transparency, heat resistance and smoothness. And by laminating | stacking the organic layer which consists of solvent availability polyimide on a gas barrier layer, it prevents that foreign materials, such as a particle, penetrate | invade into a gas barrier layer, and also prevents the pinhole of a gas barrier layer and improves gas barrier performance. Furthermore, it functions as stress relaxation of the gas barrier layer made of a fragile metal oxide, and the flexibility can be improved. Furthermore, the occurrence of cracks in the gas barrier layer is suppressed by stress relaxation.

  The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to such examples. It is obvious that a person having ordinary knowledge in the technical field to which the present invention pertains can come up with various changes or modifications within the scope of the technical idea described in the claims. Of course, it is understood that these also belong to the technical scope of the present invention.

10 gas barrier film 10a unit 11 organic layer 12 gas barrier layer

Claims (12)

  A gas barrier film comprising a solvent-soluble polyimide. An organic layer comprising the solvent-soluble polyimide;
2. The gas barrier film according to claim 1, comprising a gas barrier layer containing at least one kind selected from the group consisting of a metal oxide having a gas barrier property, a metal nitride, and a metal. The solvent-soluble polyimide is
2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanoic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 An acid dianhydride containing at least one of the group consisting of ', 4,4'-biphenyltetracarboxylic dianhydride and 3,3', 4,4'-biphenyl ether tetracarboxylic dianhydride; ,
2,2′-bis (trifluoromethyl) -4,4′-diaminebiphenyl, 3,3′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) ) -5,5′-diaminobiphenyl, 3,3′-bis (trifluoromethyl) -5,5′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminebiphenyl, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylmethane 2,2-bis (4-aminophenyl) propane, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminobenzoyl) Benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-diaminodiphenylhexafluoropropane, 3,3′-diaminodiphenylhexafluoropropane, 2,2′-bis [4 (4-amino Phenoxy) phenyl] hexafluoropropane (4-BDAF), 2,2′-bis [3 (3-aminophenoxy) phenyl] hexafluoropropane (3-BDAF), 1,3-bis (3-aminophenoxy) benzene (APB-133), 1,3-bis (4-aminophenoxy) benzene (APB-134), 1,4-bis (4-aminophenoxy) benzene (APB-144), at least one kind The gas barrier film according to claim 2, wherein the gas barrier film is produced by condensing a diamine containing   The metal oxide includes at least one selected from the group consisting of silicon oxide, silicon oxynitride film, aluminum oxide film, zirconium oxide film, titanium oxide film, tin oxide film, indium alloy oxide film, and magnesium oxide film. The gas barrier film according to claim 2, wherein the gas barrier film is contained.   The gas barrier according to any one of claims 2 to 4, wherein the metal nitride includes at least one of the group consisting of silicon nitride, aluminum nitride, and titanium nitride. the film.   The gas barrier film according to any one of claims 2 to 5, wherein the metal includes at least one of a group consisting of aluminum, silver, nickel, copper, titanium, and alloy steel. .   The laminated film formed by laminating the organic layer and the gas barrier layer has a heat resistance of 5% or less in weight reduction within a range of up to 500 ° C. The gas barrier film according to 1.   The thickness of the said organic layer is 50 nm-10 micrometers, The gas barrier film of any one of Claims 2-7 characterized by the above-mentioned.   The gas barrier film according to claim 2, wherein the gas barrier layer has a thickness of 10 nm to 1 μm. Forming a coating layer by applying a coating solution in which a solvent-soluble polyimide is dissolved on the coating surface;
Forming an organic layer containing the solvent-soluble polyimide by removing the solvent from the coating layer, and a method for producing a gas barrier film.   The method includes alternately stacking a gas barrier layer including at least one member selected from the group consisting of a metal oxide having a gas barrier property, a metal nitride, and a metal film and the organic layer on a substrate. The method for producing a gas barrier film according to 10. The gas barrier layer is
Applying a polysilazane solution in which a polysilazane-based material is dissolved on the coating surface;
The method for producing a gas barrier film according to claim 11, wherein the gas barrier layer is formed by converting the polysilazane-based material into silica.

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