JP6295865B2 - Gas barrier film - Google Patents

Description

  The present invention relates to a gas barrier film. More specifically, the present invention relates to a technique for improving storage stability (particularly storage stability under high temperature and high humidity conditions) in a gas barrier film.

  In the fields of food, packaging materials, pharmaceuticals, etc., a gas barrier film that prevents the permeation of water vapor, oxygen, etc., which has been provided with a metal oxide deposition film or resin coating film on the surface of a resin film. It has been known. In recent years, in the field of electronic devices such as liquid crystal display elements (LCD), solar cells (PV), and organic electroluminescence (EL), resin substrates that are lighter and less likely to break than glass and the like have flexibility. There is a growing demand for gas-barrier films that use. These electronic devices are required to have a higher level of water vapor gas barrier properties that can withstand even under high temperature and high humidity, depending on their usage.

  As a method for producing such a gas barrier film, a gas barrier layer is mainly formed on a substrate such as a film by a plasma CVD method (Chemical Vapor Deposition) as a dry method. As a method for forming a gas barrier layer, a coating method containing polysilazane as a main component is applied on a substrate, and then a surface treatment (modification treatment) is performed on the coating film to form a gas barrier layer. Unlike the dry method, the wet method does not require large-scale equipment, is not affected by the surface roughness of the base material, and cannot be pinholed. Therefore, it has attracted attention as a method for obtaining a uniform gas barrier film with good reproducibility. Yes.

  For example, in Patent Document 1, a coating material formed by applying a polysilazane solution to which a transition metal compound (for example, tris (dibutylsulfide) rhodium chloride) is added on a substrate and drying it is substantially free of oxygen or moisture. Disclosed is a gas barrier film formed by irradiating energy rays (for example, vacuum ultraviolet light) in an atmosphere that is not contained. According to the document, by adding a transition metal compound, reforming proceeds in a short time, and a nitrogen high-concentration film having high gas barrier properties is formed.

JP 2012-148416 A

  However, the gas barrier film described in Patent Document 1 has a problem that the gas barrier performance deteriorates when exposed to high temperature and high humidity conditions.

  Therefore, an object of the present invention is to provide a gas barrier film excellent in storage stability (particularly, storage stability under high temperature and high humidity conditions).

The above object of the present invention is achieved by the following means.
1. A gas barrier film in which an inorganic barrier layer is laminated on a resin substrate,
The inorganic barrier layer is
A step of reacting a raw material polysilazane compound and a metal compound to prepare a coating solution;
Applying the coating solution on a substrate and drying to form a coating film;
Irradiating the coating film with vacuum ultraviolet light to perform a modification treatment;
Formed by a manufacturing method including
The dispersity Mw / Mn, which is the ratio of the weight average molecular weight Mw of the portion of the polysilazane compound corresponding to standard polystyrene having a number average molecular weight of 1000 or more, contained in the coating solution, to the number average molecular weight Mn is 6 or less. Gas barrier film.
2. The gas barrier film according to 1 above, wherein the step of performing the reforming treatment is performed in an atmosphere having an oxygen (O ₂ ) content of 200 to 10,000 ppm by volume.
3. The metal compound includes aluminum (Al), titanium (Ti), magnesium (Mg), boron, (B), iron (Fe), or copper (Cu), and a metal alkoxide and β-diketone as a ligand. 3. The gas barrier film according to 1 or 2 above, comprising at least one selected from the group consisting of metal chelate compounds.
4). In the reaction between the raw material polysilazane compound and the metal compound, the ratio of metal atoms contained in the metal compound is 2 to 20% with respect to the total number of silicon atoms (Si) contained in the raw material polysilazane compound. The gas-barrier film in any one of -3.
5. A method for producing a gas barrier film in which an inorganic barrier layer is laminated on a resin substrate,
Reacting a raw material polysilazane compound and a metal compound to prepare the coating liquid for forming the inorganic barrier layer;
Applying the coating solution on a substrate and drying to form a coating film;
Irradiating the coating film with vacuum ultraviolet light to perform a modification treatment;
Including
The dispersity Mw / Mn, which is the ratio of the weight average molecular weight Mw of the portion of the polysilazane compound corresponding to standard polystyrene having a number average molecular weight of 1000 or more, contained in the coating solution, to the number average molecular weight Mn is 6 or less. A method for producing a gas barrier film.
6). An electronic device body;
The gas barrier film according to any one of 1 to 4 or the gas barrier film obtained by the production method according to 5;
Having an electronic device.

  According to the present invention, it is possible to provide a gas barrier film barrier excellent in storage stability (particularly storage stability under high temperature and high humidity conditions).

It is a sectional view schematic diagram showing typically the layer composition of the gas barrier film concerning one embodiment of the present invention. It is a schematic diagram which shows an example of a vacuum ultraviolet irradiation device. It is a schematic diagram which shows an example of the manufacturing apparatus (vacuum plasma CVD apparatus) used for formation of the inorganic compound layer which concerns on this invention. It is a schematic diagram which shows an example of the other manufacturing apparatus used for formation of the inorganic compound layer which concerns on this invention.

  Embodiments of the present invention will be described below, but the technical scope of the present invention should be determined based on the description of the scope of claims, and is not limited to the following embodiments.

<Gas barrier film>
The gas barrier film according to one embodiment of the present invention is formed by laminating an inorganic barrier layer on a resin base material. The inorganic barrier layer comprises a step of reacting a raw material polysilazane compound and a metal compound to prepare a coating solution, a step of applying the coating solution on a substrate and drying to form a coating film; It is formed by a manufacturing method including a step of performing a modification treatment by irradiating vacuum ultraviolet light. And the dispersion degree Mw / Mn which is a ratio of the mass average molecular weight Mw of the polysilazane compound corresponding to the standard polystyrene having a number average molecular weight of 1000 or more and the number average molecular weight Mn contained in the coating solution is 6 or less. It is characterized by that.

  Moreover, according to the other one form of this invention, the manufacturing method of the gas-barrier film by which an inorganic barrier layer is laminated | stacked on the above resin base materials is provided. In the production method, a raw material polysilazane compound and a metal compound are reacted to prepare a coating solution for forming an inorganic barrier layer, and the coating solution is applied on a substrate and dried to form a coating film. And a step of irradiating the coating film with vacuum ultraviolet light to perform a modification treatment. And the dispersion degree Mw / Mn which is a ratio of the mass average molecular weight Mw of the polysilazane compound corresponding to the standard polystyrene having a number average molecular weight of 1000 or more and the number average molecular weight Mn contained in the coating solution is 6 or less. It is characterized by that.

  The gas barrier film of the present invention can exhibit excellent storage stability by adopting the above configuration. High gas barrier performance can be maintained even after exposure to high temperature and high humidity conditions. That is, the gas barrier film of the present invention is excellent in heat and moisture resistance.

  The inventors have intensively studied to solve the problems of the present invention. Among these, a detailed study was conducted focusing on the relationship between the preparation method of the coating liquid for forming the inorganic barrier layer and the storage stability of the gas barrier film. Surprisingly, the storage stability of the resulting gas barrier film can be obtained depending on whether the dilute solution of the raw material polysilazane is added to the dilute solution of the metal compound in a short period of time or when it is added little by little over a certain period of time. We found a significant difference in gender. Therefore, various analyzes were conducted on the properties of these coating solutions. From the results of gel permeation chromatography (GPC), in the coating solution prepared by gradually adding the raw polysilazane diluted solution to the metal compound diluted solution, It was found that the molecular weight distribution of was biased to a lower molecular weight range. On the other hand, it was also confirmed that the elemental composition of the polysilazane compound was hardly changed from the polysilazane compound before the reaction. From this result, it was considered that the slow addition of the raw material polysilazane compound and the metal compound caused some reaction to lower the molecular weight of the polysilazane compound.

  Furthermore, the present inventors examined the relationship between the molecular weight distribution of the polysilazane compound and the storage stability of the gas barrier film in the coating solution obtained by adding the raw material polysilazane diluent to the metal compound diluent. However, when the dispersity Mw / Mn, which is the ratio of the mass average molecular weight Mw of the polysilazane compound corresponding to the standard polystyrene having a number average molecular weight of 1000 or more and the number average molecular weight Mn, is 6 or less, high temperature and high humidity. The present inventors have found that a gas barrier film having sufficient gas barrier performance can be obtained even after exposure to conditions.

  Thus, although the detailed mechanism by which the gas barrier film excellent in storage stability is obtained by setting the Mw / Mn to 6 or less is not clear, the present inventors presume as follows. . The dispersion degree Mw / Mn, which is the ratio of the weight average molecular weight Mw of the polysilazane compound corresponding to the standard polystyrene having a number average molecular weight of 1000 or more in the coating solution, to the number average molecular weight Mn is 6 or less. It may mean that there are few coarse molecules of a polysilazane compound in a coating liquid. Thus, when there are few coarse molecules of a polysilazane compound, a metal compound can be disperse | distributed more uniformly with respect to a polysilazane compound. Since the reforming reaction is carried out using the metal atom as a base point, the modification of the polysilazane compound proceeds more uniformly, and a more homogeneous and dense gas barrier layer can be obtained. Therefore, even when exposed to high temperature and high humidity conditions, deterioration is unlikely to occur, and high gas barrier performance can be maintained. In addition, said mechanism is based on presumption and this invention is not limited to the said mechanism at all. Hereinafter, the basic layer structure of the gas barrier film of the present invention will be described.

  FIG. 1 is a schematic cross-sectional view schematically showing a layer structure of a gas barrier film according to an embodiment of the present invention. In the present invention, a layer configuration in which an inorganic barrier layer 12 formed by a specific manufacturing method is laminated on a resin base material 11 is essential as in the gas barrier film 10 of FIG. In addition to this, in the form of FIG. 1, an inorganic compound layer 13 having gas barrier properties different from the inorganic barrier layer 12 is provided between the resin base material 11 and the inorganic barrier layer 12. That is, the gas barrier film 10 has a configuration in which an inorganic compound layer 13 as a first barrier layer and an inorganic barrier layer 12 as a second barrier layer are sequentially laminated on a resin substrate 11. In the present invention, the inorganic compound layer 13 is an arbitrary member, but in order to provide a higher level of gas barrier performance, in addition to the inorganic barrier layer 12 essential to the present invention, one or two or more inorganic compounds are used. Layer 13 is preferably laminated as a barrier layer. Hereinafter, each component of the gas barrier film of the present invention will be described in detail.

[Resin substrate]
In the gas barrier film according to the present invention, a resin substrate (plastic film or sheet) is used as the substrate, and a film or sheet (resin substrate) made of a colorless and transparent resin is preferably used. In the present specification, “resin base material” is also simply referred to as “base material”. The resin base material is not particularly limited as long as it is a film that can hold an inorganic barrier layer, an optional hard coat layer, or the like, and can be appropriately selected according to the purpose of use. Specifically, as a resin material constituting the resin base material, polyester resin (for example, polyethylene terephthalate), (meth) acrylic resin, (meth) acrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide , Fluorinated polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, cellulose acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, Examples include thermoplastic resins such as polysulfone resins, cycloolefin copolymers, fluorene ring-modified polycarbonate resins, alicyclic ring-modified polycarbonate resins, fluorene ring-modified polyester resins, and (meth) acryloyl compounds. It is.

  In the present invention, the resin base materials disclosed in paragraphs “0056” to “0075” of JP2012-116101A, paragraphs “0124” to “0136” of JP2013-226758A are also appropriately used. Adopted.

  The thickness of the resin substrate used in the gas barrier film according to the present invention is not particularly limited because it is appropriately selected depending on the use, but is typically 1 to 800 μm, preferably 5 μm to 500 μm, more preferably. Is 25 to 250 μm.

  The resin base material preferably has a high surface smoothness. As the surface smoothness, those having an average surface roughness (Ra) of 2 nm or less are preferable. Although there is no particular lower limit, it is practically 0.01 nm or more. If necessary, both surfaces of the resin substrate, at least the side on which the barrier layer is provided, may be polished to improve smoothness.

  Moreover, you may form an anchor coat layer (easy-adhesion layer) on a resin base material. In addition, it is also possible to expect higher adhesion by forming a thin film of monomolecular level to nano level like a silane coupling agent and providing an anchor coat layer with a material capable of forming a molecular bond at the layer interface. It can be preferably used. In addition, a stress relaxation layer made of resin, etc., a smoothing layer for smoothing the surface of the resin substrate, and a bleed-out prevention layer for preventing bleed-out from the resin substrate are additionally provided on the resin substrate. May be.

  In the present invention, for the purpose of reducing mechanical and thermal damage to the resin base material, such as an inorganic barrier layer forming process and improving handling properties, a protective film is provided on the surface of the resin base material opposite to the inorganic barrier layer. They can be used together as appropriate. The protective film may be a film in which an adhesive layer or an adhesive layer is coated on an adhesive substrate. In the present invention, in the process of forming an inorganic barrier layer, it is preferable to use a protective film in which an adhesive layer is coated on a support from the viewpoints of both transport characteristics such as roll-to-roll tension and suppression of peeling during the process. it can.

  The resin constituting the base film used for the protective film is preferably a thermoplastic resin, and examples thereof include polyvinyl chloride, polyester, polyethylene, and stretched polypropylene. In consideration of handling properties such as waist strength and the presence or absence of deformation of the film when the protective film is peeled off, a polyester film is preferably used. The thickness is preferably 10 to 200 μm from the viewpoint of handling.

  When the adhesive layer is separately provided, the type of the adhesive is not particularly limited, but an acrylic adhesive is preferable from the viewpoints of durability, transparency, and ease of adjustment of adhesive properties. The acrylic pressure-sensitive adhesive uses an acrylic polymer that is mainly composed of alkyl acrylate and copolymerized with a polar monomer component. The alkyl acrylate ester is an alkyl ester of acrylic acid or methacrylic acid and is not particularly limited. For example, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, (meth ) Pentyl acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, and the like.

  In this step, the protective film obtained as described above and a support are attached. The method of sticking is not particularly limited, and examples thereof include a method using a laminator. Moreover, in the plasma CVD apparatus provided with the film-forming roller mentioned later, the method of sticking by providing the apparatus which sticks a protective film and a support body before the sending roll is also mentioned.

  Moreover, it is preferable that the adhesive force of the resin base material thru | or hard-coat surface of a gas barrier film mentioned above and the adhesion layer which a protective film has is 0.05-0.20N / 25mm, 0.08-0.16N / 25 mm (180 ° peel test, JIS Z 0237) is more preferable. If it is this range, when conveying the film for vapor deposition (support body + protective film) with a vacuum plasma apparatus etc., a support body and a protective film will become difficult to peel. The pressure-sensitive adhesive force can be controlled by appropriately selecting the type of pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer. Moreover, this adhesive force can be measured by the method as described in an Example.

[Inorganic barrier layer]
The gas barrier film of the present invention has an inorganic barrier layer on the resin substrate. And the said inorganic barrier layer is manufactured by the manufacturing method including the following processes, It is characterized by the above-mentioned. Step 1: A raw material polysilazane compound and a metal compound are reacted to prepare a coating solution. Step 2: A coating solution is applied on a substrate and dried to form a coating film. Step of performing modification treatment by irradiation with vacuum ultraviolet light Each step will be described in detail below.

(Step 1: A step of preparing a coating solution by reacting a raw material polysilazane compound and a metal compound)
First, in step 1, a raw material polysilazane compound and a metal compound are reacted to prepare a coating solution. By reacting the polysilazane compound and the metal compound, the high molecular weight polysilazane compound is reduced in molecular weight, and a polysilazane compound having a specific molecular weight distribution is obtained.

In the present invention, the polysilazane compound is a polymer having a silicon-nitrogen bond. Specifically, ceramic precursor inorganic polymers such as SiO ₂ , Si ₃ N ₄ , and both intermediate solid solutions SiO _x N _y have bonds such as Si—N, Si—H, and N—H in their structure. It is. In the present specification, the “raw material polysilazane compound” means a polysilazane compound before reacting (contacting) with a metal compound among polysilazane compounds. In the present specification, “polysilazane compound” is also abbreviated as “polysilazane”.

  Examples of the polysilazane used in the present invention are not particularly limited and include known ones. For example, those disclosed in paragraphs “0043” to “0058” of JP2013-022799A, paragraphs “0038” to “0056” of JP2013-226758A are appropriately adopted.

  Moreover, the polysilazane compound is marketed in the solution state melt | dissolved in the organic solvent, As a commercial item of a polysilazane solution, NN120-10, NN120-20, NAX120-20, NN110, NN310 by AZ Electronic Materials KK NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, SP140, and the like.

  Another example of the polysilazane compound that can be used in the present invention is not limited to the following. For example, a silicon alkoxide-added polysilazane obtained by reacting a silicon alkoxide with the above polysilazane (Japanese Patent Laid-Open No. 5-238827) and glycidol are reacted. Glycidol-added polysilazane (JP-A-6-122852) obtained by reaction, alcohol-added polysilazane (JP-A-6-240208) obtained by reacting an alcohol, and metal carboxylic acid obtained by reacting a metal carboxylate Obtained by adding a salt-added polysilazane (JP-A-6-299118), an acetylacetonate complex-added polysilazane (JP-A-6-306329) obtained by reacting a metal-containing acetylacetonate complex, and metal fine particles. Metal fine particle added Such as silazane (JP-A-7-196986), and a polysilazane compound to a ceramic at low temperatures.

  Among them, polysilazane is more preferable, and perhydropolysilazane (PHPS) is particularly preferable because the gas barrier performance is high and the gas barrier performance is maintained even when bent and under high temperature and high humidity conditions.

  In the present invention, the metal compound has a function of promoting the modification reaction of the polysilazane compound. Examples of the metal compound include a metal alkoxide compound and a metal chelate compound.

  The metal constituting the metal alkoxide compound and the metal chelate compound is not particularly limited. For example, aluminum (Al), titanium (Ti), zirconium (Zr), zinc (Zn), gallium (Ga), indium (In), Chromium (Cr), magnesium (Mg), boron (B), iron (Fe), tin (Sn), nickel (Ni), palladium (Pd), lead (Pb), manganese (Mn), lithium (Li), Metals such as germanium (Ge), copper (Cu), sodium (Na), potassium (K), calcium (Ca), and cobalt (Co) are preferred. These metals tend to form coordinate bonds with nitrogen atoms in polysilazane. Further, metal alkoxides and metal chelate compounds containing aluminum (Al), titanium (Ti), magnesium (Mg), boron, (B), iron (Fe), or copper (Cu) as metals in terms of high Lewis acidity. It is more preferable that

  Specific examples of the metal alkoxide compound include, for example, trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tri-tert-butyl borate, magnesium ethoxide. , Magnesium ethoxy ethoxide, magnesium methoxy ethoxide, aluminum trimethoxide, aluminum triethoxide, aluminum tri n-propoxide, aluminum triisopropoxide, aluminum tri n-butoxide, aluminum tri sec-butoxide, aluminum tri tert- Butoxide, acetoalkoxyaluminum diisopropylate, aluminum diisopropylate monosec-butyrate, aluminum oxide isopropoxide trimer, aluminum Oxide octylate trimer, calcium methoxide, calcium ethoxide, calcium isopropoxide, titanium tetramethoxide, titanium tetraethoxide, titanium tetranormal propoxide, titanium tetraisopropoxide, titanium tetranormal butoxide, titanium tetraisobutoxide, Titanium diisopropoxy dinormal butoxide, titanium di tert-butoxy diisopropoxide, titanium tetra tert-butoxide, titanium tetraisooctyloxide, titanium tetrastearyl alkoxide, chromium n-propoxide, chromium isopropoxide, manganese methoxide, Iron methoxide, iron ethoxide, iron n-propoxide, iron isopropoxide, cobalt isopropoxide, copper methoxide, copper ethoxide, copper iso Lopoxide, zinc ethoxide, zinc ethoxide, zinc methoxyethoxide, gallium methoxide, gallium ethoxide, gallium isopropoxide, germanium methoxide, germanium ethoxide, germanium isopropoxide, germanium n-butoxide, germanium tert-butoxide , Ethyltriethoxygermanium, zirconium ethoxide, zirconium n-propoxide, zirconium isopropoxide, zirconium butoxide, zirconium tert-butoxide, indium isopropoxide, indium isopropoxide, indium n-butoxide, indium methoxyethoxide, tin Examples thereof include n-butoxide and tin tert-butoxide. Especially, it is preferable to use the said aluminum alkoxide from a viewpoint of making a reforming reaction advance more efficiently and forming a precise | minute gas barrier layer.

  Among these metal alkoxide compounds, a compound having a branched alkoxy group is preferable from the viewpoint of reactivity and solubility, and a compound having a 2-propoxy group or a sec-butoxy group is more preferable. More preferred metal alkoxide compounds are specifically aluminum trisec-butoxide, aluminum diisopropylate monosec-butyrate, and titanium tetraisopropoxide.

  On the other hand, the metal chelate compound is not particularly limited, but is a metal chelate compound having a β-diketone as a ligand in that the reforming reaction can proceed more efficiently and a dense gas barrier layer can be formed. Is preferred.

  Examples of the β-diketone include acetylacetone, ethyl acetoacetate, 2,4-hexanedione, 3,5-heptanedione, 2,4-octanedione, 2,4-decanedione, 2,4-tridecanedione, 5 , 5-dimethyl-2,4-hexanedione, 2,2-dimethyl-3,5-nonanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,3-cyclopentanedione, 1,3-cyclohexanedione, 1-cyclohexyl-1,3-butanedione and the like can be mentioned.

  Specific examples of the metal chelate compound having β-diketone as a ligand include, for example, magnesium acetylacetonate, aluminum acetylacetonate, aluminum ethylacetoacetate diisopropylate, aluminum ethylacetoacetate di n-butyrate Aluminum diethyl acetoacetate mono n-butyrate, aluminum bisethyl acetoacetate monoacetyl acetonate, aluminum tris acetyl acetonate, aluminum trisethyl acetoacetate, bis (ethyl acetoacetate) (2,4-pentanedionato) aluminum, Aluminum alkyl acetoacetate diisopropylate, calcium acetylacetonate, titanium diisopropoxybis (acetylacetate) Nate), titanium tetraacetylacetonate, tris (2,4-pentanedionato) chromium, tris (2,4-pentanedionato) manganese, tris (2,4-pentandedionato) iron, tris (2,4 -Pentandionato) cobalt, nickel acetylacetonate, bis (2,4-pentandionato) copper, gallium acetylacetonate, tetrakis (2,4-pentandionato) zirconium, palladium acetylacetonate, tris (2, 4-pentandionato) indium, tin acetylacetonate and the like.

  Among metal chelate compounds having a β-diketone as a ligand, metal compounds having an acetylacetonate group or an ethylacetoacetate group are preferable. These groups are preferable because they have an interaction with the central element of the alkoxide compound due to the carbonyl structure, and thus handleability becomes easy. More preferably, a compound having a plurality of alkoxide groups, ethyl acetoacetate groups or acetylacetonate groups is more preferable from the viewpoints of reactivity and film composition.

  More preferable metal chelate compounds are specifically, aluminum ethyl acetoacetate diisopropylate, aluminum ethyl acetoacetate di n-butyrate, aluminum diethyl acetoacetate mono n-butyrate, aluminum bisethyl acetoacetate monoacetyl acetonate, Titanium diisopropoxybis (acetylacetonate), bis (2,4-pentandionato) copper (II) (copper acetylacetonate), tris (2,4-pentandionato) iron (III) (iron acetylacetate) Nate).

As the chelate compound having a metal alkoxide compound or β-diketone as a ligand, a commercially available product or a synthesized product may be used. As a specific example of a commercially available product, for example,
Examples of the metal alkoxide compound include AMD (aluminum diisopropylate monosec-butyrate), ASBD (aluminum secondary butyrate), Preneact (registered trademark) AL-M (acetoalkoxyaluminum diisopropylate, manufactured by Ajinomoto Fine Chemical Co., Ltd.), Olga Chicks series (Matsumoto Fine Chemical Co., Ltd.) etc. are mentioned. Commercially available metal chelate compounds having β-diketone as a ligand include ALCH (aluminum ethyl acetoacetate / diisopropylate), ALCH-TR (aluminum trisethyl acetoacetate), aluminum chelate M (aluminum alkyl acetoacetate).・ Diisopropylate), aluminum chelate D (aluminum bisethyl acetoacetate monoacetylacetonate), aluminum chelate A (W) (aluminum trisacetylacetonate) (above, manufactured by Kawaken Fine Chemical Co., Ltd.), ORGATIX series ( Matsumoto Fine Chemical Co., Ltd.).

Next, a method for preparing a coating solution by reacting the above raw material polysilazane compound and a metal compound will be described. In the method of reacting the raw material polysilazane compound and the metal compound, the molecular weight distribution of the polysilazane compound after the reaction is in a specific range (that is,
The dispersion degree Mw / Mn, which is the ratio of the weight average molecular weight Mw of the polysilazane compound in the portion corresponding to the standard polystyrene having a number average molecular weight of 1000 or more and the number average molecular weight Mn contained in the coating solution, is 6 or less. If it is such a method, it will not be restrict | limited in particular.

  As described above, when the raw material polysilazane compound and the metal compound are brought into contact with each other under a certain condition, the present inventors react the raw material polysilazane compound and the metal compound to reduce the coarse molecular weight of the polysilazane compound (aggregation or cross-linking). It was found that the dispersity in the high molecular weight range is reduced by loosening the link). As a result of the study by the present inventors, the rate at which the raw material polysilazane compound and the metal compound are brought into contact with each other (that is, the addition rate) is important as a condition for causing such low molecular weight. Although the detailed reason is unknown, when the raw material polysilazane compound and the metal compound are contacted over a long period of time, the polysilazane compound is confirmed to have a low molecular weight, whereas when contacted in a short time, On the contrary, it has been confirmed that the molecules of the polysilazane compound are coarsened and a sufficient gas barrier performance cannot be obtained.

  In the present invention, the ratio of the weight average molecular weight Mw of the polysilazane compound in the portion corresponding to the standard polystyrene having a number average molecular weight of 1000 or more contained in the coating liquid obtained in this step (1) is the ratio of the number average molecular weight Mn. It is essential that the degree of dispersion Mw / Mn is 6 or less. In addition, the value of the dispersion degree Mw / Mn, which is the ratio between the mass average molecular weight Mw of the polysilazane compound and the number average molecular weight Mn in the present specification, is a value obtained by a measurement method using GPC described in Examples described later. Shall be adopted. If the value of Mw / Mn is greater than 6, the polysilazane compound having a number average molecular weight of more than 1000 in the coating solution contains many coarse molecular weight components, so that the polysilazane compound and the metal compound are uniformly dispersed in the coating solution. Some parts may not remain. When an inorganic barrier layer is formed using such a coating solution, there is a possibility that a homogeneous and dense film may not be formed, and the gas barrier performance after exposure to high temperature and high humidity conditions may not be sufficient. From the viewpoint of further improving the storage stability under high temperature and high humidity conditions, the value of Mw / Mn is preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less. On the other hand, the lower limit of Mw / Mn is not particularly limited, but is 1.2 or more.

  As specific means for reducing the molecular weight of the polysilazane compound in this manner, (i) the raw material polysilazane compound and / or the metal compound is sufficiently diluted and then contacted; (ii) the raw material polysilazane compound (or the raw material polysilazane compound) And a metal compound (or a diluted solution of the metal compound) are slowly brought into contact (increase the addition time); (iii) When the raw material polysilazane compound and the metal compound are brought into contact with each other, the mixture is sufficiently stirred; And the like.

  (I) In the case of adopting a method in which the raw material polysilazane compound and / or metal compound is brought into contact after sufficiently diluting, the degree of dilution varies depending on the scale used in preparing the coating liquid and the apparatus used, and thus varies depending on those skilled in the art. It can be adjusted appropriately. Usually, the concentration of the dilute solution of the starting polysilazane compound is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass. The lower limit is not particularly limited, but is preferably 2% by mass or more in consideration of the necessary concentration of the polysilazane compound in the final coating solution. On the other hand, the concentration of the diluted solution of the metal compound is usually preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass. The lower limit is not particularly limited, but is preferably 0.5% by mass or more in consideration of reactivity with the raw material polysilazane compound. In addition, either the raw material polysilazane compound or the metal compound may be used as a diluent, or both may be used as a diluent. However, in order to sufficiently reduce the molecular weight of the raw material polysilazane compound, It is preferable that both are brought into contact after being used as a diluent.

  The solvent used for diluting the raw material polysilazane compound and / or metal compound is not particularly limited as long as it can dissolve these compounds, but water and reactive groups (for example, hydroxyl groups) that easily react with the polysilazane compound. Or an amine group) and an inert organic solvent with respect to the silicon compound is preferred, and an aprotic organic solvent is more preferred. Specifically, as the solvent, an aprotic solvent; for example, pentane, 2,2,4-trimethylpentane, hexane, cyclohexane, toluene, xylene, solvesso, turben, aliphatic hydrocarbon, alicyclic carbonization, etc. Hydrocarbon solvents such as hydrogen and aromatic hydrocarbons; Halogen hydrocarbon solvents such as methylene chloride and trichloroethane; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone and methyl ethyl ketone; Dibutyl ether, dioxane, tetrahydrofuran, mono- And aliphatic ethers such as polyalkylene glycol dialkyl ethers (diglymes) and ethers such as alicyclic ethers. The solvent is selected according to purposes such as the solubility of the silicon compound and the evaporation rate of the solvent, and may be used alone or in the form of a mixture of two or more.

  (Ii) The addition time when the raw material polysilazane compound (or the diluted solution of the raw material polysilazane compound) and the metal compound (or the diluted solution of the metal compound) are brought into contact slowly (the addition time is increased) is prepared as the coating solution. Since it differs depending on the scale and the device used, it can be adjusted appropriately by those skilled in the art. Usually, when it is performed on a small scale (for example, the total amount of polysilazane compound (diluent) in the coating solution is 10 liters or less), the time from the start of addition to the end of addition is preferably 1 minute or more, and 5 minutes More preferably, it is more preferably 10 minutes or more. When performing on a large scale (for example, the total amount of polysilazane compound (diluent) in the coating solution is 10 liters or more), it is preferable to further increase the addition time. Specifically, the time from the start of addition to the end of addition Is preferably 5 minutes or longer, more preferably 10 minutes or longer, and even more preferably 15 minutes or longer. The upper limit of the addition time is not particularly limited, but considering productivity, it is preferably 60 minutes or less, and more preferably 30 minutes or less. In addition, the addition in this case may be performed continuously by a fixed amount or may be added in a plurality of divided portions.

  Further, the order of addition is not particularly limited, and a mode in which a dilute solution of the raw material polysilazane compound and a dilute solution of the metal compound are mixed at the same time is preferable, but after the raw material polysilazane compound (or dilute solution of the raw material polysilazane compound) is charged. The metal compound (or a diluted solution of the metal compound) may be slowly added thereto; after the metal compound (or the diluted solution of the metal compound) is charged, the raw material polysilazane compound (or the diluted raw material polysilazane compound) is added thereto. Liquid) may be added slowly. From the viewpoint of this molar reaction, it is preferable to employ a method in which a raw material polysilazane compound (or a diluted solution of the raw material polysilazane compound) is charged and then a metal compound (or a diluted solution of the metal compound) is slowly added thereto.

  (Iii) When the raw material polysilazane compound and the metal compound are brought into contact with each other, the stirring method in the case of sufficient stirring also varies depending on the scale used when preparing the coating liquid and the apparatus used, and can be appropriately adjusted by those skilled in the art. . Usually, the rotation speed of the stirrer when using a stirrer is preferably 100 to 1,000 rpm, and more preferably 200 to 500 rpm. If it is this range, a raw material polysilazane compound and a metal compound can fully be made to react.

  The methods (i) to (iii) may be used alone or in combination of two or three. From the viewpoint of sufficiently reacting the raw material polysilazane compound and the metal compound and surely reducing the molecular weight of the polysilazane compound, it is preferable to use a combination of two or three of the methods (i) to (iii). , (I) to (iii) are most preferably used in combination.

  The reaction temperature for reacting (contacting) the raw material polysilazane compound with the metal compound is not particularly limited. According to the study by the present inventors, it has been confirmed that the polysilazane compound is sufficiently lowered in molecular weight even at room temperature without particularly requiring heating or cooling. A preferred temperature range is 15 to 35 ° C., but the polysilazane compound can have a predetermined molecular weight distribution even at other temperatures.

Moreover, it is preferable that after the raw material polysilazane compound and the metal compound are reacted (contacted), the mixed solution is further heated for a certain time while stirring. By heating the mixed solution, —SiH ₃ located at the end of the polysilazane compound is eliminated, and silane gas can be generated. Thereby, it can suppress that silane gas is discharge | released continuously, and can stabilize the performance and the safety | security of a process. The heating temperature and heating time at this time are not particularly limited as long as the silane gas can be sufficiently removed. Although depending on the scale for preparing the coating solution, the preferred heating temperature is 60 to 100 ° C, more preferably 70 to 90 ° C. On the other hand, the heating time can also be appropriately set depending on the scale, but is preferably 10 to 180 minutes, and more preferably 30 to 90 minutes.

  The concentration of the polysilazane compound contained in the coating solution is not particularly limited and varies depending on the film thickness of the inorganic barrier layer and the pot life of the coating solution, but is preferably 1 to 20% by mass, more preferably 2 to 15% by mass. %, Particularly preferably 5 to 10% by mass. In order to obtain such a concentration of the polysilazane compound, the amount of the dilution solvent used in the coating solution may be appropriately adjusted.

  In addition, the amount of the metal compound added when preparing the coating liquid (that is, during the reaction between the polysilazane compound and the metal compound) can be appropriately adjusted according to the type of metal compound or polysilazane compound used. However, from the viewpoint of sufficiently progressing the modification reaction of the polysilazane compound and obtaining a gas barrier film having high gas barrier performance, the ratio of metal atoms contained in the metal compound is the total number of silicon atoms (Si) contained in the polysilazane compound. On the other hand, it is preferably 2 to 20%, more preferably 5 to 15%, and further preferably 7 to 10%. The said ratio is adjusted with the preparation amount of the polysilazane compound and metal compound at the time of preparing a coating liquid. In addition, since the ratio of metal atoms to silicon atoms in the coating solution does not change even after modification, it should be confirmed by analyzing the elemental composition of the inorganic barrier layer using X-ray photoelectron spectroscopy (XPS). Is possible.

  The coating solution preferably contains a catalyst in order to promote reforming. As the catalyst applicable to the present invention, a basic catalyst is preferable, and in particular, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N ', N'-tetramethyl-1,3-diaminopropane, amine catalysts such as N, N, N', N'-tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, propion Examples thereof include metal catalysts such as Pd compounds such as acid Pd, Rh compounds such as Rh acetylacetonate, and N-heterocyclic compounds. Of these, it is preferable to use an amine catalyst. The concentration of the catalyst added at this time is preferably in the range of 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, based on the polysilazane compound. By setting the amount of the catalyst to be in this range, it is possible to avoid excessive silanol formation due to rapid progress of the reaction, reduction in film density, increase in film defects, and the like. In addition, the addition method of the catalyst at the time of preparing a coating liquid is not restrict | limited, A conventionally well-known method can be employ | adopted suitably.

  In the coating solution, the following additives can be used as necessary. For example, cellulose ethers, cellulose esters; for example, ethyl cellulose, nitrocellulose, cellulose acetate, cellulose acetobutyrate, etc., natural resins; for example, rubber, rosin resin, etc., synthetic resins; Aminoplasts, especially urea resins, melamine formaldehyde resins, alkyd resins, acrylic resins, polyesters or modified polyesters, epoxides, polyisocyanates or blocked polyisocyanates, polysiloxanes, and the like.

The step of preparing the above coating solution, in order to prevent decomposition of the polysilazane compound and the metal compound is preferably carried out in an atmosphere substantially free of oxygen (O ₂₎ and moisture. Specifically, the oxygen concentration in the atmosphere when preparing the coating solution is preferably 0 to 200 ppm, preferably 0 to 100 ppm, and more preferably 0 to 30 ppm. Similarly, the moisture concentration in the atmosphere when preparing the coating solution is preferably 0 to 200 ppm, preferably 0 to 100 ppm, and more preferably 0 to 30 ppm.

  As a method of preparing the coating solution in such an environment that does not contain oxygen or moisture, a method of preparing in a glove box filled with nitrogen or argon is preferable.

(Step 2: A step of applying a coating solution on a substrate and drying to form a coating film)
In the next step 2, the coating liquid prepared in the above step 1 is applied onto a substrate and dried to form a coating film. As a method for applying the coating solution, a conventionally known appropriate wet coating method may be employed. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.

  The coating thickness can be appropriately set according to the purpose. For example, the coating thickness per inorganic barrier layer is preferably about 10 nm to 1,000 nm after drying, more preferably 15 nm to 500 nm, and further preferably 20 to 300 nm. preferable. When the film thickness is 10 nm or more, sufficient gas barrier properties can be obtained, and when the film thickness is 1,000 nm or less, stable coating properties can be obtained during layer formation, and high light transmittance can be realized.

  After applying the coating solution, it is preferable to dry the coating film. By drying the coating film, a solvent such as an organic solvent contained in the coating film can be removed. At this time, all of the solvent contained in the coating film may be dried or may be partially left. Even when a part of the solvent is left, a suitable inorganic barrier layer can be obtained. The remaining solvent can be removed later.

  Although the drying temperature of a coating film changes also with the base material to apply, it is preferable that it is 50-200 degreeC. For example, when a polyethylene terephthalate substrate having a glass transition temperature (Tg) of 70 ° C. is used as the substrate, the drying temperature is preferably set appropriately in consideration of deformation of the substrate due to heat. The temperature can be set by using a hot plate, oven, furnace or the like. The drying time is preferably set to a short time, for example, preferably set to about 1 to several minutes at 80 ° C. The drying atmosphere may be any condition such as an air atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, or a reduced pressure atmosphere with a controlled oxygen concentration.

  The coating film obtained by applying the coating solution may include a step of removing moisture before or during the modification treatment. As a method for removing moisture, a form of dehumidification while maintaining a low humidity environment is preferable. Since humidity in a low-humidity environment varies depending on temperature, a preferable form is shown for the relationship between temperature and humidity by defining the dew point temperature. A preferable dew point temperature is 4 ° C. or lower (temperature 25 ° C./humidity 25%), a more preferable dew point temperature is −5 ° C. (temperature 25 ° C./humidity 10%) or lower, and the maintained time is the film thickness of the inorganic barrier layer. It is preferable to set appropriately. Under the condition that the film thickness of the inorganic barrier layer is 1.0 μm or less, it is preferable that the dew point temperature is −5 ° C. or less and the maintaining time is 1 minute or more. The lower limit of the dew point temperature is not particularly limited, but is usually −50 ° C. or higher and preferably −40 ° C. or higher. By removing water before or during the modification treatment, the dehydration reaction of the added silanol can be promoted.

(Step 3: A step of performing a modification treatment by irradiating the coating film with vacuum ultraviolet light)
In this step, the polysilazane compound is converted into silicon oxide, silicon oxynitride, or the like by irradiating the coating film formed in step 2 with vacuum ultraviolet light (vacuum ultraviolet light) and performing a modification treatment. Here, the reforming treatment is a treatment for forming an inorganic thin film at a level that can contribute to the development of gas barrier properties (water vapor permeability of 1 × 10 ⁻³ g / m ² · day or less) as a whole. Say.

  In the present invention, as the modification process, a process (excimer irradiation process) by vacuum ultraviolet irradiation is performed. The treatment by vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy with a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and bonds the atoms with only photons called photon processes. This is a method of forming a silicon oxide film at a relatively low temperature (about 200 ° C. or lower) by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by action.

  The radiation source in the present invention may be any radiation source that generates light having a wavelength of 100 to 180 nm, but preferably an excimer radiator (for example, a Xe excimer lamp) having a maximum emission at about 172 nm, and an emission line at about 185 nm. Low pressure mercury vapor lamps, and medium and high pressure mercury vapor lamps having a wavelength component of 230 nm or less, and excimer lamps having maximum emission at about 222 nm.

  Among these, the Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen.

  Moreover, it is known that the energy of light having a short wavelength of 172 nm has a high ability to dissociate organic bonds. Due to the high energy possessed by the active oxygen, ozone and ultraviolet radiation, the polysilazane coating can be modified in a short time.

  Since the excimer lamp has high light generation efficiency, it can be turned on with low power. In addition, light having a long wavelength that causes a temperature increase due to light is not emitted, and energy is irradiated in the ultraviolet region, that is, in a short wavelength, so that the increase in the surface temperature of the target object is suppressed. For this reason, it is suitable for flexible film materials such as PET that are easily affected by heat.

Oxygen is required for the reaction at the time of ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process tends to decrease. It is preferable to carry out in a state where the water vapor concentration is low. That is, the oxygen (O ₂ ) concentration at the time of vacuum ultraviolet irradiation is preferably 200 to 10,000 volume ppm, more preferably 500 to 5,000 volume ppm, still more preferably 700 volume ppm to 2, 000 ppm by volume. Also, the water vapor concentration during the conversion process is preferably in the range of 1,000 to 4,000 volume ppm. With such an oxygen concentration / water vapor concentration, the reforming reaction of the polysilazane compound can sufficiently proceed.

  As the gas satisfying the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays, it is preferable to use a dry inert gas, and argon gas and nitrogen gas are preferable, but dry nitrogen gas is particularly preferable from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

In vacuum ultraviolet irradiation step, more that illuminance of the vacuum ultraviolet rays in the coated surface of the polysilazane coating film is subjected is preferable to be ^{1mW / cm 2 ~10W / cm 2} , a 30mW / cm ² ~200mW / cm 2 ^preferably, further preferably at ^{50mW / cm 2 ~160mW / cm 2} . If it is 1 mW / cm ² or more, sufficient reforming efficiency is obtained, and if it is 10 W / cm ² or less, it is difficult to cause ablation in the coating film and damage the substrate.

Irradiation energy amount of the VUV in the coated surface (integrated quantity of light) is preferably 100~10000mJ / cm ^2, more preferably 500~8,000mJ / cm ^2, 700~6,000mJ / cm ² is more preferable. If it is 100 mJ / cm ² or more, the modification can proceed sufficiently. If it is 10,000 mJ / cm ² or less, generation of cracks due to excessive modification and thermal deformation of the substrate are difficult to occur.

Further, the vacuum ultraviolet light used for the modification may be generated by plasma formed from a gas containing at least one of CO, CO ₂ and CH ₄ (in this case, irradiation in a vacuum chamber is included). Further, as the gas containing at least one of CO, CO ₂ and CH ₄ (hereinafter also referred to as carbon-containing gas), the carbon-containing gas may be used alone, but carbon containing rare gas or H ₂ as the main gas. It is preferable to add a small amount of the contained gas. Examples of plasma generation methods include capacitively coupled plasma.

  In addition, although it can select suitably as temperature of the coating film in the modification | reformation process by vacuum ultraviolet light by a base material kind, it is preferable to adjust suitably in the range of 50-250 degreeC, and is the range of 50-120 degreeC. It is more preferable.

[Inorganic compound layer (other gas barrier layers)]
The gas barrier film of the present invention may have an inorganic compound layer as a gas barrier layer in addition to the inorganic barrier layer. By laminating an inorganic compound layer instead of the inorganic barrier layer, a gas barrier film having a higher level of gas barrier performance can be obtained.

  The position at which the inorganic compound layer is formed is not particularly limited, and may be on the side opposite to the surface on which the inorganic barrier layer of the resin substrate is formed, or between the resin substrate and the inorganic barrier layer. Alternatively, the surface of the inorganic barrier layer opposite to the surface on which the resin base material is located may be used, or a combination thereof may be used.

  Moreover, the inorganic compound layer formed in each position may be only one layer, and may be two or more layers.

In the present invention, as a preferred layer structure in the case where an inorganic compound layer is formed, a form in which an inorganic compound layer and an inorganic barrier layer are sequentially laminated on a resin substrate as shown in FIG. It is done. This is because the effect of the present invention is more remarkably exhibited in such a layer configuration. That is, when manufacturing a gas barrier film having such a layer structure, an inorganic barrier layer is formed on an inorganic compound layer formed on a resin substrate, but the modification at the stage of forming the inorganic barrier layer is performed. In the quality treatment, oxygen (O ₂ ) and moisture may not be sufficiently supplied to the coating film through the resin base material due to the presence of the already formed inorganic compound layer. In this case, the reforming does not proceed uniformly, and not only the heat and moisture resistance but also the initial gas barrier performance may not be sufficient. However, according to the present invention, even such a layer structure has an advantage that a more uniform and dense inorganic barrier layer can be obtained. Actually, in the examples described later, the inorganic barrier layer (second inorganic barrier layer) is formed on the inorganic compound layer (first gas barrier layer) formed on the resin substrate. It has been shown that a gas barrier film having heat resistance and heat-and-moisture resistance can be obtained.

  The formation method of the inorganic compound layer is not particularly limited, and is a vacuum film formation method such as physical vapor deposition (PVD) or chemical vapor deposition (CVD), or a liquid containing an inorganic compound, preferably a silicon compound. And a method of reforming and forming a coating film formed by applying a liquid containing a liquid (hereinafter also simply referred to as a coating method). Among these, for the inorganic compound layer, physical vapor deposition or chemical vapor deposition is more preferable, and chemical vapor deposition is particularly preferable. Hereinafter, vacuum film forming methods (physical vapor deposition method and chemical vapor deposition method) will be described.

  The physical vapor deposition method (PVD method) is a method of depositing a target material, for example, a thin film such as a carbon film, on the surface of the material in a gas phase by a physical method. Examples thereof include a DC sputtering method, an RF sputtering method, an ion beam sputtering method, and a magnetron sputtering method, a vacuum deposition method, and an ion plating method.

  Sputtering is a method in which a target is placed in a vacuum chamber, a rare gas element (usually argon) ionized by applying a high voltage is collided with the target, and atoms on the target surface are ejected and adhered to the substrate. . At this time, a reactive sputtering method may be used in which an inorganic layer is formed by causing nitrogen and oxygen gas to flow into the chamber to react nitrogen and oxygen with an element ejected from the target by argon gas. .

  Chemical vapor deposition (CVD) is a method in which a raw material gas containing a target thin film component is supplied onto a substrate and a film is deposited by a chemical reaction on the substrate surface or in the gas phase. It is. In addition, for the purpose of activating the chemical reaction, there is a method of generating plasma or the like. Known CVD such as thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, vacuum plasma CVD method, atmospheric pressure plasma CVD method, etc. The method etc. are mentioned. Although not particularly limited, it is preferable to apply the plasma CVD method from the viewpoint of film forming speed and processing area.

  The inorganic compound layer obtained by the vacuum plasma CVD method or the plasma CVD method under atmospheric pressure or near atmospheric pressure has conditions such as the raw material (also referred to as raw material) metal compound, decomposition gas, decomposition temperature, input power, etc. This is preferable because the desired compound can be produced. For details of the conditions for forming the barrier layer by the plasma CVD method, for example, the conditions described in paragraphs “0033” to “0051” of International Publication No. 2012/067186 may be appropriately employed. The inorganic compound layer formed by such a method is preferably a layer containing an oxide, nitride, oxynitride or oxycarbide.

  Hereinafter, a vacuum plasma CVD method, which is a preferred form among the CVD methods, will be specifically described.

  FIG. 3 is a schematic view showing an example of a vacuum plasma CVD apparatus used for forming the inorganic compound layer according to the present invention.

  In FIG. 3, the vacuum plasma CVD apparatus 101 has a vacuum chamber 102, and a susceptor 105 is disposed on the bottom surface inside the vacuum chamber 102. Further, a cathode electrode 103 is disposed on the ceiling side inside the vacuum chamber 102 at a position facing the susceptor 105. A heat medium circulation system 106, a vacuum exhaust system 107, a gas introduction system 108, and a high-frequency power source 109 are disposed outside the vacuum chamber 102. A heat medium is disposed in the heat medium circulation system 106. The heat medium circulation system 106 stores a pump for moving the heat medium, a heating device for heating the heat medium, a cooling device for cooling, a temperature sensor for measuring the temperature of the heat medium, and a set temperature of the heat medium. A heating / cooling device 160 having a storage device is provided. For the details of the vacuum plasma CVD apparatus described in FIG. 3, International Publication No. WO12 / 014653 can be referred to.

  As a preferred embodiment of the inorganic compound layer formed by the CVD method according to the present invention, the inorganic compound layer preferably contains carbon, silicon, and oxygen as constituent elements. A more preferable form is a layer that satisfies the following requirements (i) to (ii).

(I) The distance (L) from the surface of the inorganic compound layer in the film thickness direction of the inorganic compound layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atom ratio of silicon) A silicon distribution curve showing a relationship, an oxygen distribution curve showing a relationship between the L and the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atomic ratio of oxygen), and the L and silicon atoms , Oxygen atoms, and a carbon distribution curve showing a relationship with a ratio of the amount of carbon atoms to the total amount of carbon atoms (atom ratio of carbon), the carbon distribution curve has at least two extreme values,
(Ii) The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 3 at% or more.

  Having such a composition is preferable from the viewpoint of achieving both high gas barrier properties and flexibility.

  Furthermore, in the region of 90% or more of the total thickness of the inorganic compound layer, the average atomic ratio of each atom with respect to the total amount of silicon atoms, oxygen atoms and carbon atoms (100 at%) is expressed by the following formula (A) or (B): It is preferable from the point of the further improvement of bending tolerance to have the magnitude relationship of the order represented by these.

  The preferred embodiment will be described below.

  (I) The distance (L) from the surface of the inorganic compound layer in the film thickness direction of the inorganic compound layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (silicon atomic ratio) A distribution curve showing the relationship between L and the oxygen distribution curve showing the relationship between the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atomic ratio of oxygen); In the carbon distribution curve showing the relationship with the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (carbon atomic ratio), the carbon distribution curve preferably has at least two extreme values. The inorganic compound layer preferably has at least three extreme values in the carbon distribution curve, more preferably at least four extreme values, but may have five or more. When the carbon distribution curve has at least two extreme values, the carbon atom ratio continuously changes with a concentration gradient, and the gas barrier performance during bending is enhanced. The upper limit of the extreme value of the carbon distribution curve is not particularly limited, but is preferably 30 or less, more preferably 25 or less, for example. Since the number of extreme values is also caused by the film thickness of the gas barrier layer, it cannot be defined unconditionally.

  Here, in the case of having at least three extreme values, from the surface of the inorganic compound layer in the film thickness direction of the inorganic compound layer at one extreme value of the carbon distribution curve and the extreme value adjacent to the extreme value. The absolute value of the difference in distance (L) (hereinafter also simply referred to as “distance between extreme values”) is preferably 200 nm or less, more preferably 100 nm or less, and 75 nm or less. Is particularly preferred. If the distance is between such extreme values, the inorganic compound layer has a portion having a large carbon atom ratio (maximum value) with an appropriate period, so that the inorganic compound layer is provided with appropriate flexibility and gas barrier properties. Generation of cracks when the film is bent can be more effectively suppressed / prevented. In this specification, the extreme value means the maximum value or the minimum value of the atomic ratio of the element to the distance (L) from the surface of the inorganic compound layer in the film thickness direction of the inorganic compound layer. In this specification, the maximum value is a point where the value of the atomic ratio of an element (oxygen, silicon, or carbon) changes from increasing to decreasing when the distance from the surface of the inorganic compound layer is changed, and The value of the atomic ratio of the element at the position where the distance from the surface of the inorganic compound layer in the film thickness direction of the inorganic compound layer from the point is further changed within the range of 4 to 20 nm rather than the value of the atomic ratio of the element at that point This is the point where the value decreases by 3 at% or more. That is, when changing in the range of 4 to 20 nm, the atomic ratio value of the element should be reduced by 3 at% or more in any range. This varies depending on the film thickness of the inorganic compound layer. For example, when the inorganic compound layer is 300 nm, it is preferable that the atomic ratio value of the element at a position where the distance from the surface of the inorganic compound layer in the film thickness direction of the inorganic compound layer is changed by 20 nm is reduced by 3 at% or more. . Further, in this specification, the minimum value is a point where the value of the atomic ratio of an element (oxygen, silicon or carbon) changes from decrease to increase when the distance from the surface of the inorganic compound layer is changed, and The value of the atomic ratio of the element at the position where the distance from the surface in the film thickness direction of the inorganic compound layer from the point in the film thickness direction of the inorganic compound layer is further changed in the range of 4 to 20 nm than the value of the atomic ratio of the element at the point. The point that increases by 3 at% or more. That is, when changing in the range of 4 to 20 nm, the atomic ratio value of the element only needs to increase by 3 at% or more in any range. Here, the lower limit of the distance between the extreme values in the case of having at least three extreme values is particularly high because the smaller the distance between the extreme values, the higher the effect of suppressing / preventing crack generation when the gas barrier film is bent. Not limited.

  Further, in the inorganic compound layer, (ii) the absolute value of the difference between the maximum value and the minimum value of the carbon atomic ratio in the carbon distribution curve is preferably 3 at% or more, and more preferably 5 at% or more. And more preferably 7 at% or more. When the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 3 at% or more, the gas barrier performance during bending is enhanced. In the present specification, the “maximum value” is the maximum atomic ratio of each element in the distribution curve of each element, and is the highest value among the maximum values. Similarly, in this specification, the “minimum value” is an atomic ratio of each element that is minimum in the distribution curve of each element, and is the lowest value among the minimum values.

  Further, in the region of 90% or more (upper limit: 100%) of the film thickness of the inorganic compound layer, (atomic ratio of oxygen), (atomic ratio of silicon), and (atomic ratio of carbon) increase in this order (atomic ratio is O> Si> C) is preferred. By satisfying such conditions, the resulting gas barrier film has sufficient gas barrier properties and flexibility. Here, in the carbon distribution curve, the relationship between the above (atomic ratio of oxygen), (atomic ratio of silicon) and (atomic ratio of carbon) is at least 90% or more (upper limit: 100%) of the film thickness of the gas barrier layer. ) And more preferably at least 93% or more (upper limit: 100%). Here, the term “at least 90% or more of the film thickness of the gas barrier layer” does not need to be continuous in the gas barrier layer.

  The silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve are obtained by using X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon in combination. Thus, it can be created by so-called XPS depth profile measurement in which surface composition analysis is sequentially performed while exposing the inside of the sample. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time). In the element distribution curve with the horizontal axis as the etching time, the etching time is generally correlated with the distance (L) from the surface of the inorganic compound layer in the film thickness direction of the inorganic compound layer. Therefore, as the “distance from the surface of the inorganic compound layer in the film thickness direction of the inorganic compound layer”, the surface of the inorganic compound layer calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement The distance from can be adopted. The silicon distribution curve, oxygen distribution curve, carbon distribution curve, and oxygen carbon distribution curve can be prepared under the following measurement conditions.

(Measurement condition)
Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide equivalent value): 0.05 nm / sec
Etching interval (SiO ₂ equivalent value): 10 nm
X-ray photoelectron spectrometer: Model name "VG Theta Probe", manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and its size: 800 × 400 μm oval.

  The film thickness (dry film thickness) of the inorganic compound layer formed by the plasma CVD method is not particularly limited. For example, the film thickness per layer of the inorganic compound layer is preferably 20 to 3000 nm, more preferably 50 to 2500 nm, and particularly preferably 30 to 1000 nm. With such a film thickness, the gas barrier film can exhibit excellent gas barrier properties and the effect of suppressing / preventing cracking during bending. In addition, when the inorganic compound layer formed by said plasma CVD method is comprised from 2 or more layers, it is preferable that each inorganic compound layer has a film thickness as mentioned above.

  In the present invention, from the viewpoint of forming an inorganic compound layer having a uniform and excellent gas barrier property over the entire film surface, the inorganic compound layer is substantially in the film surface direction (direction parallel to the surface of the inorganic compound layer). Preferably it is uniform. Here, the fact that the inorganic compound layer is substantially uniform in the film surface direction means that the oxygen distribution curve, the carbon distribution curve, and the carbon distribution curve at any two measurement points on the film surface of the inorganic compound layer by XPS depth profile measurement. When an oxygen carbon distribution curve is created, the number of extreme values of the carbon distribution curve obtained at any two measurement points is the same, and the maximum and minimum carbon atomic ratios in each carbon distribution curve The absolute value of the difference between the values is the same as each other or within 5 at%.

  Furthermore, in the present invention, it is preferable that the carbon distribution curve is substantially continuous. Here, the carbon distribution curve is substantially continuous means that the carbon distribution curve does not include a portion where the atomic ratio of carbon changes discontinuously. Specifically, the carbon distribution curve is calculated from the etching rate and the etching time. Between the distance (x, unit: nm) from the surface of the inorganic compound layer in the film thickness direction of at least one of the inorganic compound layers to be applied and the atomic ratio of carbon (C, unit: at%) Means satisfying the condition represented by the following formula 1.

  In the gas barrier film according to the present invention, the inorganic compound layer that satisfies all of the above conditions (i) to (ii) may include only one layer, or may include two or more layers. Furthermore, when two or more such inorganic compound layers are provided, the materials of the plurality of inorganic compound layers may be the same or different.

  In the present invention, the method for forming the inorganic compound layer is not particularly limited, and the conventional method and the method can be applied in the same manner or appropriately modified. The inorganic compound layer is preferably formed by a chemical vapor deposition (CVD) method, particularly a plasma chemical vapor deposition method (plasma CVD, PECVD (plasma-enhanced chemical vapor deposition), hereinafter, also simply referred to as “plasma CVD method”). More preferably, the substrate is formed by a plasma CVD method in which a base material is disposed on a pair of film forming rollers and plasma is generated by discharging between the pair of film forming rollers.

  In the following, a method for forming an inorganic compound layer on a base material by a plasma CVD method in which the base material is disposed on a pair of film forming rollers and plasma is generated by discharging between the pair of film forming rollers will be described. .

  As a method of forming the inorganic compound layer according to the present invention on the surface of the substrate, it is preferable to employ a plasma CVD method from the viewpoint of gas barrier properties. The plasma CVD method may be a Penning discharge plasma type plasma CVD method.

  Further, when plasma is generated in the plasma CVD method, it is preferable to generate plasma discharge in a space between a plurality of film forming rollers. A pair of film forming rollers is used, and each of the pair of film forming rollers is used. More preferably, a substrate is placed and discharged between a pair of film forming rollers to generate plasma. In this way, by using a pair of film forming rollers, placing a base material on the pair of film forming rollers, and discharging between the pair of film forming rollers, one film forming roller It is possible not only to produce a thin film efficiently because it is possible to form a film on the surface part of the base material existing in the film while simultaneously forming a film on the surface part of the base material present on the other film forming roller. The film formation rate can be doubled compared to the plasma CVD method without using any roller, and since it is possible to form a film having a structure that is substantially the same, it is possible to at least double the extreme value in the carbon distribution curve, It becomes possible to efficiently form a layer that satisfies all of the above conditions (i) to (ii).

  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. In the gas barrier film of the present invention, the inorganic compound layer is preferably a layer formed by a continuous film forming process.

  Moreover, it is preferable that the gas barrier film which concerns on this invention forms the said inorganic compound layer on the surface of the said base material by a roll-to-roll system from a viewpoint of productivity. In addition, an apparatus that can be used for manufacturing an inorganic compound 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 components. It is preferable that the apparatus has a configuration capable of discharging between the film rollers. For example, when the manufacturing apparatus shown in FIG. 4 is used, the apparatus is manufactured by a roll-to-roll method using the plasma CVD method. It is also possible to do.

  Hereinafter, with reference to FIG. 4, the base material is disposed on a pair of film forming rollers, and a method for forming an inorganic compound layer by a plasma CVD method in which plasma is generated by discharging between the pair of film forming rollers. This will be described in detail. FIG. 4 is a schematic view showing an example of a production apparatus that can be suitably used for producing an inorganic compound layer by this production method. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.

  4 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. Details regarding the apparatus can be referred to conventionally known documents, for example, Japanese Patent Application Laid-Open No. 2011-73430.

  As described above, as a more preferable aspect of the present embodiment, the inorganic compound layer according to the present invention is formed by the plasma CVD method using the plasma CVD apparatus (roll-to-roll method) having the counter roll electrode shown in FIG. Film. This is excellent in flexibility (flexibility) and mechanical strength, especially when transported by 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 an inorganic compound layer having both gas barrier performance and gas 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.

[Anchor coat layer (anchor layer)]
On the surface of the resin substrate according to the present invention, an anchor coat layer (anchor layer) may be formed as an easy adhesion layer for the purpose of improving adhesiveness (adhesion). The anchor coating agent used in this anchor coat layer includes polyester resin, isocyanate resin, urethane resin, (meth) acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl. Titanate etc. can be used 1 type or in combination of 2 or more types. A commercially available product may be used as the anchor coating agent. Specifically, a siloxane-based UV curable polymer solution (manufactured by Shin-Etsu Chemical Co., Ltd., 3% isopropyl alcohol solution of “X-12-2400”) can be used.

Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on a substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, and the like, and is coated by drying and removing the solvent, diluent, etc. Can do. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state). A commercially available base material with an easy-adhesion layer may be used.

  Alternatively, the anchor coat layer can be formed by a vapor phase method such as physical vapor deposition or chemical vapor deposition. For example, as described in JP-A-2008-142941, an inorganic film mainly composed of silicon oxide can be formed for the purpose of improving adhesion and the like.

  The thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10.0 μm.

[Bleed-out prevention layer]
The gas barrier film of the present invention may have a bleed-out prevention layer on the base material surface opposite to the surface on which the barrier layer is provided.

  The bleed-out prevention layer is provided for the purpose of suppressing a phenomenon that, when the film is heated, unreacted oligomers and the like are transferred from the film to the surface and contaminate the contact surface. The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.

  As the constituent material, forming method, film thickness and the like of the bleed-out prevention layer, the materials and methods disclosed in paragraphs “0249” to “0262” of JP2013-52561A are appropriately employed.

  The gas barrier film of the present invention may have other functional layers such as a transparent conductive layer and a primer layer in addition to the anchor coat layer or the bleed-out prevention layer. As the functional layer, in addition to those described above, those described in paragraphs “0036” to “0039” of JP-A-2006-289627 can be preferably employed.

<Use of gas barrier film>
The gas barrier film of the present invention can be preferably used for performance deterioration due to chemical components in the air (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.). Therefore, this invention also provides the electronic device containing the electronic device main body and the gas barrier film which concerns on this invention, or the gas barrier film manufactured by the method of this invention.

  Examples of devices include electronic devices such as organic EL elements, liquid crystal display elements (LCD), thin film transistors, touch panels, electronic paper, and solar cells (PV). From the viewpoint that the effect of the present invention can be obtained more efficiently, it is preferably used for an organic EL device or a solar cell, and particularly preferably used for an organic EL device.

  The gas barrier film of the present invention can also be used for device film sealing. That is, the present invention also provides an electronic device including the electronic device body and the gas barrier film of the present invention. Specifically, the gas barrier film of the present invention is provided on the surface of the device itself as a support. Note that the device may be covered with a protective layer before providing the gas barrier film.

  The gas barrier film of the present invention can also be used as a device substrate or a film for sealing by a solid sealing method. The solid sealing method is a method in which after a protective layer is formed on a device, an adhesive layer and a gas barrier film are stacked and cured. Although there is no restriction | limiting in particular in an adhesive agent, A thermosetting epoxy resin, a photocurable acrylate resin, etc. are illustrated.

(Organic EL device)
An example of an organic EL element using a gas barrier film is described in detail in Japanese Patent Application Laid-Open No. 2007-30387.

(Liquid crystal display element)
The reflective liquid crystal display device has a configuration including a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a λ / 4 plate, and a polarizing film in order from the bottom. The gas barrier film in the present invention can be used as the transparent electrode substrate and the upper substrate. In the case of color display, it is preferable to further provide a color filter layer between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode. The transmissive liquid crystal display device includes, in order from the bottom, a backlight, a polarizing plate, a λ / 4 plate, a lower transparent electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, an upper transparent electrode, an upper substrate, a λ / 4 plate, and a polarization It has the structure which consists of a film | membrane. In the case of color display, it is preferable to further provide a color filter layer between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode. The type of the liquid crystal cell is not particularly limited, but more preferably TN type (Twisted Nematic), STN type (Super Twisted Nematic), HAN type (Hybrid Aligned Nematic), VA type (Vertically Alignment), ECB type (Electrically Controlled Birefringence) OCB type (Optically Compensated Bend), IPS type (In-Plane Switching), and CPA type (Continuous Pinwheel Alignment) are preferable.

(Solar cell)
The gas barrier film of the present invention can also be used as a sealing film for solar cell elements. Here, the gas barrier film of the present invention is preferably sealed so that the barrier layer is closer to the solar cell element. The solar cell element in which the gas barrier film of the present invention is preferably used is not particularly limited. For example, it is a single crystal silicon solar cell element, a polycrystalline silicon solar cell element, a single junction type, or a tandem structure type. Amorphous silicon-based solar cell elements, III-V compound semiconductor solar cell elements such as gallium arsenide (GaAs) and indium phosphorus (InP), II-VI compound semiconductor solar cell elements such as cadmium tellurium (CdTe), I / III- such as copper / indium / selenium system (so-called CIS system), copper / indium / gallium / selenium system (so-called CIGS system), copper / indium / gallium / selenium / sulfur system (so-called CIGS system) Group VI compound semiconductor solar cell element, dye-sensitized solar cell element, organic solar cell element, etc. And the like. In particular, in the present invention, the solar cell element includes a copper / indium / selenium system (so-called CIS system), a copper / indium / gallium / selenium system (so-called CIGS system), copper / indium / gallium / selenium / A sulfur-based (so-called CIGSS-based) I-III-VI group compound semiconductor solar cell element or organic solar cell element is preferable.

(Other)
As other application examples, the thin film transistor described in JP-A-10-512104, the touch panel described in JP-A-5-127822, JP-A-2002-48913, etc., described in JP-A-2000-98326. And an optical member for display described in JP 2013-554018 A.

  The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples. Further, in the examples, “part” or “%” is used, but “part by mass” or “% by mass” is expressed unless otherwise specified. Moreover, in the following operation, unless otherwise specified, the measurement of the operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.

(Comparative Example 1: Production of gas barrier film 101)
[Formation of inorganic compound layer (first barrier layer) (plasma CVD method)]
A PET base material (125 μm thick) provided with Kimoto's clear hard coat was set in a manufacturing apparatus 31 as shown in FIG. 4 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. Next, a film forming gas (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, A gas barrier thin film (inorganic compound layer containing silicon, oxygen, and carbon, first barrier layer) was formed by plasma CVD, and the thickness of the inorganic compound layer was 150 nm.

The film formation conditions were as follows:
(Deposition conditions)
Source gas supply: 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: 2Pa
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.

[Formation of inorganic barrier layer (second barrier layer) (coating method)]
(Preparation and film formation of polysilazane-containing coating solution)
The polysilazane-containing coating solution was prepared in a glove box filled with nitrogen (oxygen concentration <10 ppm, moisture concentration <10 ppm environment). The barrier layer was formed by coating in a normal atmospheric environment (specifically, an environment of 25 ° C. and 60% RH).

  A dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (PHPS) (manufactured by AZ Electronic Materials, Aquamica (registered trademark) NN120-20), and an amine catalyst (N, N, N ′, N′— A perhydropolysilazane 20 mass% dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., Aquamica (registered trademark) NAX120-20) containing 5 mass% of tetramethyl-1,6-diaminohexane (TMDAH)) and 4 1 (mixing ratio) (stirring speed: 200 rpm), and a solvent mixed so that the mass ratio of dibutyl ether and 2,2,4-trimethylpentane is 65:35. The coating liquid (1) was prepared so that the solid content (perhydropolysilazane concentration) was 2.7% by mass. And the.

  The molecular weight distribution of perhydropolysilazane can be measured by gel permeation chromatography (GPC). The measurement conditions are as follows.

Solvent: THF (tetrahydrofuran)
Column: Three Tskel G2000HxL (manufactured by Tosoh Corporation) and one G4000 are connected and used.

Column temperature: 40 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (GL Science Co., Ltd.)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0 ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation), number average molecular weight (Mn) = 1.0 × 10 ^{5 to} 1.0 × 10 ² Standard calibration curves are used. Thirteen samples were selected at approximately equal intervals.

  Here, GPC measurement was performed on the coating solution (1) as described above.

The mass average molecular weight (Mw) and the number average molecular weight (Mn) of the portion corresponding to standard polystyrene having a number average molecular weight of 1,000 or more were determined, and the degree of dispersion (Mw / Mn) was calculated.
As a result, Mw / Mn was 10.

  The coating solution obtained above is formed on the inorganic compound layer with a spin coater so that the thickness (dry film thickness) is 80 nm, and subjected to additional heat treatment for 1 minute on an 80 ° C. hot plate. A polysilazane coating film (precursor layer) was formed.

After forming the polysilazane coating film, the inorganic barrier layer (second barrier layer) is irradiated with a vacuum ultraviolet ray of 172 nm so as to be 6000 mJ / cm ² according to the following method to form an inorganic compound layer (first barrier layer). ) Formed on top. Thus, the gas barrier film 101 was produced.

<Measurement of vacuum ultraviolet irradiation conditions and irradiation energy>
The vacuum ultraviolet irradiation was performed using the apparatus schematically shown in FIG. In FIG. 2, reference numeral 21 denotes an apparatus chamber, which supplies appropriate amounts of nitrogen and oxygen from a gas supply port (not shown) to the inside and exhausts gas from a gas discharge port (not shown), thereby substantially removing water vapor from the inside of the chamber. The oxygen concentration can be maintained at a predetermined concentration. Here, vacuum ultraviolet irradiation was performed with the oxygen concentration adjusted to 1,000 ppm by volume. The oxygen concentration in the chamber was measured using an oxygen concentration meter (zirconia oxygen concentration meter LC-450A manufactured by Toray Engineering Co., Ltd.). Reference numeral 22 denotes an Xe excimer lamp having a double tube structure that irradiates vacuum ultraviolet rays of 172 nm, and reference numeral 23 denotes an excimer lamp holder that also serves as an external electrode. Reference numeral 24 denotes a sample stage. The sample stage 24 can be reciprocated horizontally at a predetermined speed in the apparatus chamber 21 by a moving means (not shown). The sample stage 24 can be maintained at a predetermined temperature by a heating means (not shown). Here, the temperature was set to 100 ° C. Reference numeral 25 denotes a sample on which a polysilazane coating film is formed. When the sample stage moves horizontally, the height of the sample stage is adjusted so that the shortest distance between the surface of the sample coating layer and the excimer lamp tube surface is 6 mm. Reference numeral 26 denotes a light shielding plate, which prevents the application layer of the sample from being irradiated with vacuum ultraviolet light during aging of the Xe excimer lamp 22.

  The energy irradiated to the coating film surface in the vacuum ultraviolet irradiation process was measured using a 172 nm sensor head using a UV integrating photometer: C8026 / H8025 UV POWER METER manufactured by Hamamatsu Photonics Co., Ltd. In the measurement, the sensor head is placed in the center of the sample stage 24 so that the shortest distance between the Xe excimer lamp tube surface and the measurement surface of the sensor head is 6 mm, and the atmosphere in the apparatus chamber 21 is irradiated with vacuum ultraviolet rays. Nitrogen and oxygen were supplied so that the oxygen concentration was the same as that in the process, and the sample stage 24 was moved at a speed of 0.5 m / min (V in FIG. 2) for measurement. Prior to the measurement, in order to stabilize the illuminance of the Xe excimer lamp 12, an aging time of 10 minutes was provided after the Xe excimer lamp was turned on, and then the sample stage was moved to start the measurement.

Based on the irradiation energy obtained by this measurement, adjustment was made so that the irradiation energy was 2.0 J / cm ² by adjusting the moving speed of the sample stage. The vacuum ultraviolet irradiation during the reforming treatment was performed after aging for 10 minutes as in the case of measuring the irradiation energy.

(Comparative Example 2: Production of gas barrier film 102)
In Comparative Example 1, a gas barrier film 102 was produced in the same manner as Comparative Example 1, except that the coating liquid (2) prepared by the following method was used instead of the coating liquid (1).

  The coating solution (2) was dissolved by adding 17 parts by mass of dibutyl ether (manufactured by Kanto Chemical Co., Inc.) to 0.2 parts by mass of ALCH (produced by Kawaken Fine Chemical Co., Ltd., aluminum ethyl acetoacetate / diisopropylate). . Furthermore, a dibutyl ether solution containing 20% by mass of perhydropolysilazane (PHPS) (manufactured by AZ Electronic Materials, Aquamica (registered trademark) NN120-20) and an amine catalyst (N, N, N ′, N′-tetra) 20% by mass of a perhydropolysilazane containing 5% by mass of methyl-1,6-diaminohexane (TMDAH) (manufactured by AZ Electronic Materials Co., Ltd., Aquamica (registered trademark) NAX120-20) 1.6 parts by mass of the liquid mixed at a ratio of 1 (mass ratio) was added all at once and stirred (stirring speed: 200 rpm). The amount of Al atoms derived from ALCH was about 10 mol% with respect to the total number of moles of Si atoms derived from the starting polysilazane compound. While stirring the above mixed liquid, the temperature was raised to 80 ° C. (temperature rising rate was 3 ° C./min), and the mixture was allowed to react with stirring for 1 hour, followed by cooling to apply a solid content concentration of about 2.7% by mass. Liquid (2) was prepared.

  In addition, the said reaction was performed in the atmosphere whose water vapor | steam density | concentration and oxygen concentration are 10 volume ppm or less, respectively. Here, the oxygen concentration in the reaction system was measured using an oxygen concentration meter (zirconia type oxygen concentration meter LC-450A manufactured by Toray Engineering Co., Ltd.). In addition, the water vapor concentration in the reaction system was determined by measuring the dew point using a dew point meter (manufactured by Vaisala, DMT type dew point meter), and obtaining the water vapor concentration from the measured dew point.

  The coating solution (2) was subjected to GPC measurement as described above, and the mass average molecular weight (Mw) and the number average molecular weight (Mn) of the portion corresponding to standard polystyrene having a number average molecular weight of 1,000 or more were determined. When (Mw / Mn) was calculated, it was 7.0.

Further, the XPS analysis was performed on the second barrier layer as described below, and the element composition was examined. As a result, the proportion of Al atoms contained in the layer was about 10 mol% with respect to the Si atoms.
(XPS analysis)
The composition in the thickness direction of the gas barrier layer was measured under the following conditions.
・ Device: QUANTERASXM (manufactured by ULVAC-PHI Co., Ltd.)
・ X-ray source: Monochromatic Al-Kα
Measurement area: Si2p, C1s, N1s, O1s
・ Sputtering ion: Ar (2 keV)
Depth profile: Repeat measurement after sputtering for 1 minute Data processing: MultiPak (manufactured by ULVAC-PHI Co., Ltd.)
Quantification: The background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area.

Regarding the length in the thickness direction of the region in the XPS analysis, the following correction was performed. That is, first, the composition in the thickness direction and the length in the thickness direction of the gas barrier layer are obtained from the etching rate converted to SiO ₂ by XPS analysis. On the other hand, TEM analysis is performed on the same sample, and the thickness of the gas barrier layer is obtained from the cross-sectional image. Then, the cross-sectional image of the TEM was compared with the composition distribution in the thickness direction of the gas barrier layer obtained from XPS analysis, and the composition distribution in the thickness direction was specified.

(Example 1: Production of gas barrier film 103)
In Comparative Example 2, a gas barrier film 103 was produced in the same manner as in Comparative Example 2, except that the coating liquid (3) prepared by the following method was used instead of the coating liquid (2).

  A dibutyl ether solution containing 20% by mass of perhydropolysilazane (PHPS, manufactured by AZ Electronic Materials, Aquamica (registered trademark) NN120-20), and an amine catalyst (N, N, N ′, N′-tetramethyl-) 20% by mass of a perhydropolysilazane containing 5% by mass of 1,6-diaminohexane (TMDAH) (manufactured by AZ Electronic Materials Co., Ltd., Aquamica (registered trademark) NAX120-20) A liquid A was obtained by diluting 12 parts by mass of dibutyl ether to 5 parts by mass of the liquid mixed at a ratio (mass ratio). Subsequently, 17 parts by mass of dibutyl ether (manufactured by Kanto Chemical Co., Inc.) was added to 0.035 parts by mass of ALCH (manufactured by Kawaken Fine Chemical Co., Ltd., aluminum ethyl acetoacetate diisopropylate) to obtain a solution B. The amount of Al atoms derived from ALCH was about 0.5 mol% with respect to the total number of Si atoms derived from the starting polysilazane compound.

  Next, liquid B was added over 10 minutes while stirring the liquid A produced above at room temperature (stirring speed: 400 rpm). After stirring at room temperature for 10 minutes, the temperature of the reaction solution was raised to 80 ° C. (temperature increase rate was 3 ° C./minute). After stirring for 1 hour, the solution was cooled to prepare a liquid having a solid content of about 5% by mass. . Dibutyl ether was further added to adjust the solid content to 2.7% by mass to obtain a coating solution (3).

  The coating solution (3) was subjected to GPC measurement as described above, and the mass average molecular weight (Mw) and the number average molecular weight (Mn) of the portion corresponding to standard polystyrene having a number average molecular weight of 1,000 or more were determined. When (Mw / Mn) was calculated, it was 5.8.

  Moreover, when XPS analysis was performed about the 2nd barrier layer and the elemental composition was investigated, the ratio of the Al atom contained in the said layer was about 0.5 mol% with respect to Si atom.

(Example 2: Production of gas barrier film 104)
In Example 1, a gas barrier film 104 was produced in the same manner as in Example 1 except that the coating liquid (4) prepared by the following method was used instead of the coating liquid (3).

  The coating liquid (4) is a solid similar to the coating liquid (3) except that the coating liquid (3) ALCH (made by Kawaken Fine Chemical Co., Ltd., aluminum ethyl acetoacetate diisopropylate) is 0.14 parts by mass. The amount was made 2.7% by mass. The amount of Al atoms derived from ALCH was about 2.0 mol% with respect to the total number of moles of Si atoms derived from the starting polysilazane compound.

  The coating solution (4) was subjected to GPC measurement as described above, and the mass average molecular weight (Mw) and the number average molecular weight (Mn) of the portion corresponding to standard polystyrene having a number average molecular weight of 1,000 or more were determined. When (Mw / Mn) was calculated, it was 3.5.

  Moreover, when XPS analysis was performed about the 2nd barrier layer and the elemental composition was investigated, the ratio of the Al atom contained in the said layer was about 2.0 mol% with respect to the Si atom.

(Example 3: Production of gas barrier film 105)
In Example 1, a gas barrier film 105 was produced in the same manner as in Example 1 except that the coating liquid (5) prepared by the following method was used instead of the coating liquid (3).

  The coating liquid (5) is a solid similar to the coating liquid (3) except that 0.7 parts by mass of ALCH (aluminum ethyl acetoacetate diisopropylate manufactured by Kawaken Fine Chemical Co., Ltd.) of the coating liquid (3) is used. The coating solution (5) was prepared with the content of 2.7% by mass. The amount of Al atoms derived from ALCH was about 10 mol% with respect to the total number of moles of Si atoms derived from the starting polysilazane compound.

  The coating solution (5) was subjected to GPC measurement as described above, and the mass average molecular weight (Mw) and the number average molecular weight (Mn) of the portion corresponding to standard polystyrene having a number average molecular weight of 1,000 or more were determined. It was 2.1 when (Mw / Mn) was calculated.

  Further, when XPS analysis was performed on the second barrier layer and the elemental composition was examined, the proportion of Al atoms contained in the layer was about 10 mol% with respect to Si atoms.

(Example 4: Production of gas barrier film 106)
In Example 1, a gas barrier film 106 was produced in the same manner as in Example 1 except that the coating liquid (6) prepared by the following method was used instead of the coating liquid (3).

  The coating solution (6) is replaced with ALCH (made by Kawaken Fine Chemical Co., Ltd., aluminum ethyl acetoacetate diisopropylate), and titanium (IV) isopropoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) is used. A coating solution (6) was prepared with a solid content of 2.7% by mass in the same manner as the coating solution (3) except that the amount was 0.73 parts by mass. The amount of Ti atom derived from titanium (IV) isopropoxide was about 10 mol% with respect to the total number of Si atoms derived from the raw material polysilazane compound.

  The coating solution (6) was subjected to GPC measurement as described above, and the mass average molecular weight (Mw) and the number average molecular weight (Mn) of the portion corresponding to standard polystyrene having a number average molecular weight of 1,000 or more were determined. When (Mw / Mn) was calculated, it was 4.7.

  Further, when XPS analysis was performed on the second barrier layer and the elemental composition was examined, the proportion of Ti atoms contained in the layer was about 10 mol% with respect to Si atoms.

(Example 5: Production of gas barrier film 107)
In Example 1, a gas barrier film 107 was produced in the same manner as in Example 1 except that the coating liquid (7) prepared by the following method was used instead of the coating liquid (3).

  The coating solution (7) was replaced with ALCH (aluminum ethyl acetoacetate diisopropylate manufactured by Kawaken Fine Chemical Co., Ltd.) in the coating solution (3) and 1.68 magnesium ethoxide (manufactured by Wako Pure Chemical Industries, Ltd.). A coating solution (7) was prepared with a solid content of 2.7% by mass in the same manner as in the coating solution (3) except that the content was changed to parts by mass. The amount of Mg atoms derived from magnesium ethoxide was about 10 mol% with respect to the total number of moles of Si atoms derived from the starting polysilazane compound.

  The coating solution (7) was subjected to GPC measurement as described above, and the mass average molecular weight (Mw) and the number average molecular weight (Mn) of the portion corresponding to standard polystyrene having a number average molecular weight of 1,000 or more were determined. When (Mw / Mn) was calculated, it was 5.0.

  Moreover, when XPS analysis was performed about the 2nd barrier layer and the elemental composition was investigated, the ratio of Mg atom contained in the said layer was about 10 mol% with respect to Si atom.

(Example 6: Production of gas barrier film 108)
In Example 1, a gas barrier film 108 was produced in the same manner as in Example 1 except that instead of the coating liquid (3), the coating liquid (8) prepared by the following method was used.

  The coating solution (8) is obtained by replacing trial borate (manufactured by Wako Pure Chemical Industries, Ltd.) with 1. A coating solution (8) was produced with a solid content of 2.7% by mass in the same manner as the coating solution (3) except that the amount was 0 parts by mass. The amount of B atoms derived from triisopropyl borate was about 10 mol% with respect to the total number of moles of Si atoms derived from the starting polysilazane compound.

  The coating solution (8) was subjected to GPC measurement as described above, and the mass average molecular weight (Mw) and the number average molecular weight (Mn) of the portion corresponding to standard polystyrene having a number average molecular weight of 1,000 or more were determined. The calculated (Mw / Mn) was 5.2.

  Moreover, when XPS analysis was performed about the 2nd barrier layer and the elemental composition was investigated, the ratio of the B atom contained in the said layer was about 10 mol% with respect to Si atom.

(Example 7: Production of gas barrier film 109)
In Example 2, the oxygen concentration in the chamber is adjusted by supplying appropriate amounts of nitrogen and oxygen from a gas supply port (not shown) to the inside of the apparatus chamber in FIG. 2 and adjusting the amount discharged from a gas discharge port (not shown). A gas barrier film 109 was produced in the same manner as in Example 2 except that the vacuum ultraviolet irradiation was performed with the content adjusted to 100 ppm by volume.

  When the XPS analysis was performed on the second barrier layer and the elemental composition was examined, the proportion of Al atoms contained in the layer was about 2.0 mol% with respect to the Si atoms.

(Example 8: Production of gas barrier film 110)
In Example 2, the oxygen concentration in the chamber is adjusted by supplying appropriate amounts of nitrogen and oxygen from a gas supply port (not shown) to the inside of the apparatus chamber in FIG. 2 and adjusting the amount discharged from a gas discharge port (not shown). A gas barrier film 110 was produced in the same manner as in Example 2 except that the vacuum ultraviolet irradiation was performed with the content adjusted to 200 ppm by volume.

  When the XPS analysis was performed on the second barrier layer and the elemental composition was examined, the proportion of Al atoms contained in the layer was about 2.0 mol% with respect to the Si atoms.

(Example 9: Production of gas barrier film 111)
In the second embodiment, an appropriate amount of nitrogen and oxygen are supplied to the inside of the apparatus chamber shown in FIG. 2 from a gas supply port (not shown) and the amount discharged from a gas discharge port (not shown) is adjusted. A gas barrier film 111 was produced in the same manner as in Example 2 except that the vacuum concentration was adjusted to 500 ppm by volume and the ultraviolet irradiation was performed.

  When the XPS analysis was performed on the second barrier layer and the elemental composition was examined, the proportion of Al atoms contained in the layer was about 2.0 mol% with respect to the Si atoms.

<< Evaluation of gas barrier property retention >>
About the gas barrier film produced above, each sample (sample after deterioration test) exposed to high temperature and high humidity of 60 ° C. and 90% RH for 500 hours is prepared. The indicated calcium corrosion time was evaluated, and the retention rate (%) was determined according to the following formula.

  As an index of retention rate, 70% or more was considered acceptable, and less than 70% was judged as nonconforming. The results of the retention rate (%) before and after the deterioration test are shown in Table 1.

(Metal calcium film forming equipment)
Vapor deposition apparatus: JEOL Ltd., vacuum vapor deposition apparatus JEE-400
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
(raw materials)
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
(Calculation method of calcium corrosion time)
Using a vacuum vapor deposition apparatus (vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.), metallic calcium was vapor-deposited with a size of 12 mm × 12 mm through the mask on the surface of the second barrier layer of the produced gas barrier film. At this time, the deposited film thickness was set to 80 nm.

  Thereafter, the mask was removed in a vacuum state, and aluminum was vapor-deposited on the entire surface of one side of the sheet to perform temporary sealing. Next, the vacuum state is released, and it is immediately transferred to a dry nitrogen gas atmosphere, and a quartz glass with a thickness of 0.2 mm is bonded to the aluminum vapor-deposited surface via an ultraviolet curing resin for sealing (manufactured by Nagase ChemteX Corporation). The water vapor barrier property evaluation sample was produced by irradiating ultraviolet rays to cure and adhere the resin to perform main sealing.

  The obtained sample was stored at a high temperature and high humidity of 85 ° C. and 85% RH, and the state in which the metal calcium was corroded with respect to the storage time was observed. The observation was obtained by extrapolating the time (calcium corrosion time) in which the area where the metal calcium was corroded with respect to the metal calcium vapor deposition area of 12 mm × 12 mm to 100% from the observation result by a straight line.

<< Production of organic thin film electronic devices >>
Using the gas barrier film produced above as a sealing film, an organic EL element which is an organic thin film electronic device was produced.

[Production of organic EL elements]
(Formation of first electrode layer)
A 150-nm-thick ITO (indium tin oxide) film formed by sputtering on an alkali-free glass was patterned by photolithography to form a first electrode layer. The pattern was such that the light emission area was 50 mm square.

(Formation of hole transport layer)
On the first electrode layer of each gas barrier film on which the first electrode layer is formed, the following coating liquid for forming a hole transport layer is extrusion coated in an environment of 25 ° C. and a relative humidity of 50% RH. After coating, the substrate was dried and heated under the following conditions to form a hole transport layer. The coating liquid for forming the hole transport layer was applied so that the thickness after drying was 50 nm.

Before applying the coating solution for forming the hole transport layer, the gas barrier film was subjected to cleaning surface modification using a low-pressure mercury lamp with a wavelength of 184.9 nm at an irradiation intensity of 15 mW / cm ² and a distance of 10 mm. The charge removal treatment was performed using a static eliminator with weak X-rays.

<Preparation of hole transport layer forming coating solution>
A solution prepared by diluting polyethylene dioxythiophene / polystyrene sulfonate (PEDOT / PSS, Baytron P AI 4083 manufactured by Bayer) with pure water at 65% and methanol at 5% was prepared as a coating solution for forming a hole transport layer.

<Drying and heat treatment conditions>
After applying the hole transport layer forming coating solution, the solvent is removed at a height of 100 mm toward the film formation surface, a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 100 ° C., followed by heat treatment. The back surface heat transfer type heat treatment was performed at a temperature of 150 ° C. using an apparatus to form a hole transport layer.

(Formation of light emitting layer)
On the hole transport layer formed above, the following coating solution for forming a white light emitting layer is applied by an extrusion coater under the following conditions, followed by drying and heat treatment under the following conditions to form a light emitting layer. did. The white light emitting layer forming coating solution was applied so that the thickness after drying was 40 nm.

<White luminescent layer forming coating solution>
As a host material, 1.0 g of a compound represented by the following chemical formula HA, 100 mg of a compound represented by the following chemical formula DA as a dopant material, and 0.1 mg of a compound represented by the following chemical formula DB as a dopant material. 2 mg of a compound represented by the following chemical formula DC as a dopant material was dissolved in 0.2 mg and 100 g of toluene to prepare a white light emitting layer forming coating solution.

<Application conditions>
The coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, a coating temperature of 25 ° C., and a coating speed of 1 m / min.

<Drying and heat treatment conditions>
After applying the white light emitting layer forming coating solution, the solvent was removed at a height of 100 mm toward the film formation surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C., and then a temperature of 130 ° C. A heat treatment was performed to form a light emitting layer.

(Formation of electron transport layer)
On the light emitting layer formed above, the following electron transport layer forming coating solution was applied by an extrusion coater under the following conditions, and then dried and heat-treated under the following conditions to form an electron transport layer. The coating solution for forming an electron transport layer was applied so that the thickness after drying was 30 nm.

<Application conditions>
The coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, the coating temperature of the electron transport layer forming coating solution was 25 ° C., and the coating speed was 1 m / min.

<Coating liquid for electron transport layer formation>
The electron transport layer was prepared by dissolving a compound represented by the following chemical formula EA in 2,2,3,3-tetrafluoro-1-propanol to obtain a 0.5 mass% solution as a coating liquid for forming an electron transport layer.

<Drying and heat treatment conditions>
After applying the electron transport layer forming coating solution, the solvent is removed at a height of 100 mm toward the film formation surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C. Then, heat treatment was performed at a temperature of 200 ° C. to form an electron transport layer.

(Formation of electron injection layer)
An electron injection layer was formed on the electron transport layer formed above. First, the substrate was put into a decompression chamber and decompressed to 5 × 10 ⁻⁴ Pa. In advance, cesium fluoride prepared in a tantalum vapor deposition boat was heated in a vacuum chamber to form an electron injection layer having a thickness of 3 nm.

(Formation of second electrode)
Aluminum is used as the second electrode forming material on the electron injection layer formed as described above, except for the portion that becomes the extraction electrode of the first electrode 22 under a vacuum of 5 × 10 ⁻⁴ Pa. A mask pattern was formed by vapor deposition so as to have an extraction electrode so that the light emission area was 50 mm square, and a second electrode having a thickness of 100 nm was laminated.

(Sealing)
The prepared gas barrier film was trimmed to a predetermined size, and a thermosetting adhesive was uniformly applied to the barrier layer surface side with a thickness of 20 μm using a dispenser to form an adhesive layer. At this time, an epoxy adhesive containing bisphenol A diglycidyl ether (DGEBA), dicyandiamide (DICY) and an epoxy adduct curing accelerator was used as the thermosetting adhesive.

  The gas barrier film is closely attached and arranged so that the extraction electrode (including the extraction electrodes of the first electrode and the second electrode) patterned on the first electrode is exposed, and the vacuum laminator is Used tightly sealed. After sealing, post-curing treatment was performed at 110 ° C. for 15 minutes to produce an organic EL element.

<< Evaluation of organic EL elements >>
About the produced organic EL element, durability was evaluated in accordance with the following method.

[Evaluation of durability]
(Accelerated deterioration processing)
Each of the produced organic EL devices was subjected to an accelerated deterioration treatment for 500 hours in an environment of 85 ° C. and 85% RH, and then the following dark spots were evaluated.

(Evaluation of dark spots (DS, black spots))
A current of 1 mA / cm ² is applied to the organic EL element subjected to the accelerated deterioration treatment, and a part of the panel is enlarged with a 100 × microscope (MORITEX MS-804, lens MP-ZE25-200). , Took a picture. The photographed image was cut out in a 20 mm square scale, the dark spot generation area ratio was determined, and the durability was evaluated according to the following criteria. When the evaluation rank was Δ, it was judged as a practical characteristic, when it was ○, a more practical characteristic, and when it was ◎, it was judged as a preferable characteristic having no problem at all.

A: Dark spot generation rate is less than 1% B: Dark spot generation rate is 1% or more and less than 2% Δ: Dark spot generation rate is 2% or more and less than 5% X: Dark spot generation The rate is 5% or more.

  As is clear from Table 1 above, it was shown that the gas barrier film of the present invention hardly deteriorates the gas barrier performance and is excellent in storage stability even after being exposed to high temperature and high humidity for a long time. .

In addition, the results of Examples 2 and 7 to 9 show that the storage stability is further improved by setting the oxygen (O ₂ ) content in the atmosphere during the reforming treatment to 200 ppm by volume or more. It was.

  Furthermore, from the results of Examples 1 to 3, the content of the metal atom contained in the metal compound used in preparing the coating solution is 2% or more with respect to the silicon atom (Si) contained in the raw material polysilazane compound. It was found that the storage stability was further improved.

  Moreover, it turned out that generation | occurrence | production of a dark spot is reduced from the said Table 1 by using the gas barrier film of this invention as a sealing film of an organic EL element. From this, it was shown that the gas barrier film of the present invention can be suitably used for various electric devices.

1, 10 gas barrier film,
2, 110 substrate,
3 first barrier layer,
11 resin base material,
12 Inorganic barrier layer,
13 Inorganic compound layer,
21 equipment chamber,
22 Xe excimer lamp,
23 holder,
24 Sample stage,
25 samples,
26 shading plate,
31 manufacturing equipment,
32 Feeding roller,
33, 34, 35, 36 transport rollers,
39, 40 Deposition roller,
41 gas supply pipe,
42 Power supply for plasma generation,
43, 44 Magnetic field generator,
45 take-up roller,
101 plasma CVD apparatus,
102 vacuum chamber,
103 cathode electrode,
105 susceptors,
106 heat medium circulation system,
107 vacuum exhaust system,
108 gas introduction system,
109 high frequency power supply,
160 Heating and cooling device.

Claims (4)

A method for producing a gas barrier film in which an inorganic barrier layer is laminated on a resin substrate,
Reacting a raw material polysilazane compound and a metal compound to prepare the coating liquid for forming the inorganic barrier layer;
Applying the coating solution on a substrate and drying to form a coating film;
Irradiating the coating film with vacuum ultraviolet light to perform a modification treatment;
Including
The dispersity Mw / Mn, which is the ratio of the weight average molecular weight Mw of the portion of the polysilazane compound corresponding to standard polystyrene having a number average molecular weight of 1000 or more, contained in the coating solution, to the number average molecular weight Mn is 6 or less. A method for producing a gas barrier film. The method for producing a gas barrier film according to claim 1, wherein the step of performing the modification treatment is performed in an atmosphere having an oxygen (O ₂ ) content of 200 to 10,000 ppm by volume.   The metal compound has a metal alkoxide and β-diketone containing aluminum (Al), titanium (Ti), magnesium (Mg), boron (B), iron (Fe), or copper (Cu) as a ligand. The method for producing a gas barrier film according to claim 1 or 2, comprising at least one selected from the group consisting of metal chelate compounds.   In the reaction between the raw material polysilazane compound and the metal compound, the ratio of metal atoms contained in the metal compound is 2 to 20% with respect to the total number of silicon atoms (Si) contained in the raw material polysilazane compound. The manufacturing method of the gas-barrier film of any one of 1-3.