JP6582842B2 - Method for producing gas barrier film - Google Patents

Description

The present invention also relates to the manufacture how the gas barrier film. In particular, a configuration which comprises a gas barrier layer on both sides of the substrate, relates to the production how the gas barrier fill beam having excellent gas barrier performance and process suitability.

  In order to obtain high gas barrier performance as an electronic device application such as an organic electroluminescence (hereinafter also referred to as EL) element using a flexible substrate, various layer configurations of a gas barrier film have been studied.

  As an example, from the viewpoint of achieving both excellent gas barrier performance and suppression of interlayer film peeling due to dimensional variation, a configuration in which a gas barrier layer is installed on both sides of a plastic substrate has been studied (for example, (See Patent Documents 1 and 2.)

  When producing a gas barrier film having the above structure by forming a gas barrier layer on both surfaces of the substrate, or when producing an organic EL device in a vacuum environment using the gas barrier film having the above structure, the gas barrier layer It is necessary to protect the gas and prevent the gas barrier layers from sticking to each other. In order to protect the gas barrier layer and suppress sticking, after forming one gas barrier layer, before forming the other gas barrier layer, provide an antistatic layer on the one gas barrier layer. Can be considered.

  Up to now, a structure containing inorganic metal particles, metal oxide sol or the like has been used for the antistatic layer (see, for example, Patent Document 3), but the antistatic layer is applied to the gas barrier film having the above structure. Then, it became clear that deterioration of gas barrier performance (in-plane non-uniformity) occurred.

  This is due to the fact that inorganic metal particles and metal oxide sols are particles that are prone to agglomeration, and that repelling occurs due to the composition of the gas barrier layer and the presence of fine foreign substances unique to the gas barrier layer. This is presumably because non-uniformity of the layer film occurs. In addition, the restriction that the antistatic layer cannot be thickened from the viewpoint of optical properties (transparency) is also considered to be a cause of non-uniformity of the antistatic layer.

  Due to the non-uniformity of the antistatic layer due to these causes, in the gas barrier layer formed after the antistatic layer is provided, the energy such as excimer at the time of forming the gas barrier layer tends to concentrate on the nonuniform portion. It is considered that the gas barrier layer forming material cannot be uniformly applied, which adversely affects the formation of the gas barrier layer and deteriorates the gas barrier performance.

Special table 2007-523769 gazette Special table 2014-514981 gazette JP 2003-257254 A

The present invention has been made in view of the above problems or situation, the problem to be solved is a configuration including a gas barrier layer on both sides of the substrate, a gas barrier Phil beam having excellent gas barrier performance and process suitability it is to provide a manufacturing how.

As a result of investigating the cause of the above-mentioned problem in order to solve the above-mentioned problems relating to the present invention, a gas barrier film having a gas barrier layer on both sides of a substrate has a conductive polymer on one of the gas barrier layers. It has been found that a gas barrier film excellent in gas barrier performance and process suitability can be provided by laminating the antistatic layer to be contained.
That is, the subject concerning this invention is solved by the following means.

1 . A method for producing a gas barrier film comprising a gas barrier layer on both sides of a substrate,
Forming a second gas barrier layer on one surface of the substrate;
Forming an antistatic layer on the second gas barrier layer;
Forming a first gas barrier layer on the other surface of the base material by a CVD method after forming the antistatic layer. A method for producing a gas barrier film, comprising:

2 . Method for producing gas barrier film according to paragraph 1, characterized by forming the first gas barrier layer by a roll-to-roll method.

According to the present invention, a configuration comprising a gas barrier layer on both sides of the substrate, it is possible to provide a manufacturing how the gas barrier fill beam having excellent gas barrier performance and process suitability.
The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.
When a gas barrier layer is formed on both surfaces of a substrate by roll-to-roll method while unwinding and continuously transporting a long film substrate laminated in a roll shape, Since the gas barrier layers are rubbed or stuck to each other, the gas barrier layer may be scratched or foreign matter may adhere. In order to prevent this, it is considered effective to stack an antistatic layer on one of the gas barrier layers formed on both surfaces of the substrate. However, when an antistatic layer is formed using inorganic particles on the gas barrier layer, the antistatic layer film is uneven due to aggregation of inorganic particles, composition of the gas barrier layer, fine foreign matters on the gas barrier layer, and the like. Tends to occur. Therefore, gas barrier performance is achieved by forming an antistatic layer using a conductive polymer that does not cause aggregation on the gas barrier layer and is less likely to cause film non-uniformity due to the composition of the gas barrier layer and the presence of fine foreign matter. It is possible to obtain a gas barrier film that is excellent in protection and can achieve protection of the gas barrier layer and prevention of sticking.

Schematic sectional view showing an example of the configuration of the gas barrier film of the present invention Schematic diagram showing an example of an inter-roller discharge plasma CVD apparatus applicable to the formation of a gas barrier layer Schematic diagram showing an example of a roll-to-roll vacuum ultraviolet light irradiation apparatus applicable to the formation of a gas barrier layer

The method for producing a gas barrier film of the present invention is a method for producing a gas barrier film having a gas barrier layer on both surfaces of a substrate, and a step of forming a second gas barrier layer on one surface of the substrate. A step of forming an antistatic layer on the second gas barrier layer, and after forming the antistatic layer, a first gas barrier layer is formed on the other surface of the substrate by a CVD method. And a process. Thereby, the gas barrier film excellent in gas barrier performance and process aptitude can be manufactured.
Moreover, in the manufacturing method of the gas barrier film of this invention, it is preferable to form a said 1st gas barrier layer by a roll to roll system. Thereby, productivity of a gas barrier film can be improved, suppressing suitably sticking gas barrier layers by laminating | stacking in roll shape.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, "-" shown in this invention is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

<< Schematic configuration of gas barrier film >>
Gas barrier film according to the present invention is a gas barrier film on both sides of the substrate comprises a gas barrier layer, on one of the gas barrier layer, antistatic layer containing a conductive polymer that has been laminated.
Basic structure of the gas barrier film according to the present invention will be described sprinkled with FIG.

Fig.1 (a)-FIG.1 (c) are schematic sectional drawings which show an example of a structure of the gas barrier film 1 of this invention.
A gas barrier film 1 shown in FIG. 1A is provided with a first gas barrier layer 3 and a second gas barrier layer 4 on both surfaces of a base material 2. The antistatic layer 5 is provided on the opposite side. The antistatic layer 5 contains a conductive polymer having antistatic ability instead of containing inorganic particles.

  When the long base material provided with the gas barrier layer on both sides is wound up into a roll shape by the antistatic layer 5 formed by providing such a uniformly dissolved conductive polymer, An adverse effect caused by direct contact between the gas barrier layers on both sides can be prevented. Thereby, it can be set as the gas barrier film which has antistatic performance and improved transparency, abrasion resistance, and gas barrier property.

Moreover, in the gas barrier film of this invention, various structures can be taken.
For example, the configuration of the gas barrier film 1 shown in FIG. 1B shows an example in which the first gas barrier layer 3 is composed of two gas barrier layers 3A and 3B having different formation methods. For example, the lower gas barrier layer 3A may be formed by a discharge plasma chemical vapor deposition method, and the upper gas barrier layer 3B may be formed by a modification method using vacuum ultraviolet light irradiation.

  In the gas barrier film 1 shown in FIG.1 (c), with respect to the structure shown in FIG.1 (b), it is further between the base material 2 and 3 A of gas barrier layers, and the base material 2 and 2nd gas barrier. Clear hard coat layers 6 </ b> A and 6 </ b> B for realizing adhesion to the substrate 2 and smoothness of the layer formed thereon may be provided between the layers 4.

  In the configuration shown in FIGS. 1A to 1C, the first gas barrier layer 3, the gas barrier layers 3A and 3B, and the second gas barrier layer 4 have a single layer configuration. As needed, you may be comprised from the several layer by the same manufacturing method.

<Constituent elements of gas barrier film>
The basic configuration of the gas barrier film of the present invention mainly includes a base material, a gas barrier layer provided on both surfaces of the base material, and an antistatic layer provided on any one of the gas barrier layers. It is a configuration.
Hereinafter, the detail of the component of the gas barrier film of this invention is demonstrated.

"Base material"
The base material of the gas barrier film of the present invention is not particularly limited as long as it is a film-like material capable of holding at least the antistatic layer and the gas barrier layer.

  For example, acrylic ester, methacrylic ester, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP ), Polystyrene (PS), nylon (Ny), aromatic polyamide, polyether ether ketone, polysulfone, polyether sulfone, polyimide, polyetherimide, cycloolefin polymer, cycloolefin copolymer, and other resin films, organic-inorganic hybrid structures A heat-resistant transparent film (product name Sila-DEC, manufactured by Chisso Corporation) having a silsesquioxane having a basic skeleton as a basic skeleton, and two or more layers of the above resins are laminated. Lee Brides film or the like can be mentioned. From the viewpoint of cost and availability, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN) and the like are preferably used. From the viewpoint of low retardation, cycloolefin polymer, cycloolefin copolymer and polycarbonate (PC) are used. Preferably used. Further, in terms of optical transparency, heat resistance, and adhesion to the gas barrier layer and the antistatic layer, a heat-resistant transparent film having a basic skeleton of silsesquioxane having an organic-inorganic hybrid structure is preferably used. it can. In addition, it is also preferable to use polyimide or the like as the heat-resistant substrate. This is a manufacturing process of an electronic device to which the gas barrier film is applied by using a heat-resistant substrate (ex.Tg> 200 ° C.), and heating at a temperature of 200 ° C. or more is possible when forming an organic functional layer or an electrode. Thus, it is possible to achieve a reduction in resistance of the pattern layer using the transparent conductive layer or the metal nanoparticles necessary for increasing the area of the electronic device and improving the operation efficiency of the electronic device. As for the thickness of a base material, about 5-500 micrometers is preferable, More preferably, it is 15-250 micrometers.

  Moreover, it is preferable that the base material which concerns on this invention is transparent. Since the base material is transparent and the layer formed on the base material is also transparent, it becomes possible to make a transparent gas barrier film, so that it becomes possible to make a transparent substrate for an organic EL element. It is.

  Moreover, the base material using the above-described resins or the like may be an unstretched film or a stretched film.

  The base material used in the present invention can be produced by a conventionally known general method. For example, a melt casting method for producing an unstretched substrate that is substantially amorphous and not oriented by melting a resin as a material with an extruder, extruding with an annular die or a T-die, and quenching, A solution casting method in which a material is dissolved in a solvent or the like to prepare a dope and then cast on a metal belt to form a film can be used. In addition, the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, etc. A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the base material, but is preferably 2 to 10 times in each of the vertical axis direction and the horizontal axis direction. Moreover, in the base material which concerns on this invention, you may perform surface treatments, such as a corona treatment, before forming an antistatic layer and a gas barrier layer.

<Antistatic layer>
The antistatic layer is provided on one of the gas barrier layers (second gas barrier layer) provided on both surfaces of the base material, and contains a conductive polymer having antistatic ability. Moreover, it is preferable that the conductive polymer contained in the antistatic layer is a conjugated polymer or an ionic polymer.

  The antistatic layer according to the present invention does not contain inorganic particles, specifically, metal oxide particles or the like as an antistatic agent. The term “not containing metal oxide particles” as used in the present invention means that the content of metal oxide particles with respect to the total mass of the antistatic layer is 5% by mass or less, preferably 2% by mass or less, particularly preferably at all. It is a configuration that does not.

Examples of the metal oxide particles not contained in the antistatic layer according to the present invention include SiO ₂ , ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, BaO, MoO ₂ and V ₂ O. ₅ or a complex oxide thereof.

The antistatic layer is preferably configured such that the surface resistivity of the gas barrier film is in the range of 1 × 10 ⁶ to 1 × 10 ¹¹ Ω / □. For example, the surface resistivity of the gas barrier film can be adjusted by changing the type of the conductive polymer contained in the antistatic layer or adjusting the layer thickness of the antistatic layer.

Further, the antistatic layer is configured so that the surface resistivity of the gas barrier film is in the range of 1 × 10 ⁶ to 1 × 10 ¹¹ Ω / □, so that the first gas barrier is provided after the antistatic layer. When the layer is formed, the first gas barrier layer is suitably formed, and the gas barrier property of the gas barrier film can be improved. When the antistatic layer is configured such that the surface resistivity is 1 × 10 ¹¹ Ω / □ or less, for example, when the first gas barrier layer is formed by the discharge plasma chemical vapor deposition method described later, It can suppress that a prevention layer affects the film-forming electrode of the discharge plasma CVD apparatus between rollers. On the other hand, when the antistatic layer is configured so that the surface resistivity is 1 × 10 ⁶ Ω / □ or more, for example, when the first gas barrier layer is formed by the discharge plasma chemical vapor deposition method, Occurrence of film unevenness can be suppressed. The same applies to the case where the first gas barrier layer is formed by sputtering. Further, even when the first gas barrier layer is formed by the coating method, the antistatic layer is configured so that the surface resistivity is within the above range, so that uneven filming may occur due to uniform charging. It is suppressed.

  In the present invention, the surface resistivity of the gas barrier film can be obtained by measuring the antistatic layer side surface of the gas barrier film with Hiresta UX MCP-HT800 manufactured by Mitsubishi Analytech.

  The layer thickness of the antistatic layer according to the present invention is preferably in the range of 0.5 to 5.0 μm, for example.

(1) Conductive polymer The conductive polymer used as the organic antistatic agent in the present invention has a function of preventing the base material or the gas barrier layer from being charged during the production or handling of the gas barrier film.

The conductive polymer referred to in the present invention has antistatic ability, and when the antistatic layer is formed, the surface resistivity of the gas barrier film is 1 × 10 ¹³ Ω / □ or less, preferably 1 × 10 ¹¹ Ω / □. □ or less, more preferably 1 × 10 ¹⁰ Ω / □ or less.

  The conductive polymer is preferably a material that is intended to be antistatic by forming a layer containing an ionic conductive substance or the like when the antistatic layer is formed. Here, the ionic conductive substance is an electrically conductive substance. It is a substance that contains ions, a carrier that carries electricity and carries electricity. Examples of such a conductive polymer include conjugated polymers and ionic polymers.

(1-1) Conjugated polymer As the conjugated polymer,
1) Aliphatic conjugated system: a polymer that is continuously long in a carbon-carbon conjugated system such as polyacetylene, such as polyacetylene, poly (1,6-heptadiene), etc.
2) Aromatic conjugated system: a polymer in which a conjugation in which aromatic hydrocarbons are bonded long, such as poly (paraphenylene), is developed. For example, polyparaphenylene, polynaphthalene, polyanthracene, etc.
3) Heterocyclic conjugated system: a polymer in which a conjugated system is developed by combining heterocyclic compounds such as polypyrrole and polythiophene, such as polypyrrole and its derivatives, polyfuran and its derivatives, polythiophene and its derivatives, polyisothio Naphthene and its derivatives, polyselenophene and its derivatives, etc.
4) Heteroatom-containing conjugated system: A polymer in which an aliphatic or aromatic conjugated system is bonded with a heteroatom such as polyaniline. Poly (paraphenylene sulfide) and its derivatives, poly (paraphenylene oxide) ) And its derivatives, poly (paraphenylene selenide) and its derivatives, and poly (vinylene sulfide), poly (vinylene oxide), poly (vinylene selenide), etc. in aliphatic systems,
5) Mixed conjugated system: a conjugated polymer having a structure in which the structural units of the conjugated system are alternately bonded, such as poly (phenylene vinylene). For example, poly (paraphenylene vinylene) and its derivatives, poly (pyrrole vinylene) ) And derivatives thereof, poly (thiophene vinylene) and derivatives thereof, poly (furanylene) and derivatives thereof, poly (2,2′-thienylpyrrole) and derivatives thereof,
6) Double-chain conjugated system: a conjugated system having a plurality of conjugated chains in the molecule and having a structure close to an aromatic conjugated system, such as polyperinaphthalene.
7) Metal phthalocyanine series: Metal phthalocyanines or polymers in which these molecules are bonded with a hetero atom or a conjugated system, such as metal phthalocyanine,
8) Conductive composite: A polymer obtained by polymerizing the conjugated polymer in a saturated polymer and a polymer obtained by graft copolymerization of the conjugated polymer chain with a saturated polymer. For example, a polythiophene (derivative) of 3) ), Polypyrrole (including derivatives), 4) polyaniline (including derivatives), etc., and 5) poly (paraphenylenevinylene) (including derivatives thereof), poly (thiophene vinylene) (including derivatives thereof) ) And the like in the side chain through a connecting group.

(1-2) Ionic polymer Examples of the ionic polymer include anionic polymers such as those described in JP-B-49-23828, JP-B-49-23827, JP-B-47-28937, and the like. Compound: JP-B-55-734, JP-A-50-54672, JP-B-59-14735, JP-B-57-18175, JP-B-57-18176, JP-B-57-56059 Ionene type polymers having a dissociation group in the main chain as seen in each publication such as JP-B-53-13223, JP-B-57-15376, JP-B-53-45231, and JP-B-55 No. -145783, Japanese Patent Publication No. 55-65950, Japanese Patent Publication No. 55-67746, Japanese Patent Publication No. 57-11342, Japanese Patent Publication No. 57-197 No. 35, Japanese Patent Publication No. 58-56858, Japanese Patent Publication No. Sho 61-27853, Japanese Patent Publication No. 62-9346, etc., which have a cationic dissociation group in the side chain. A pendant type polymer etc. can be mentioned.

(1-3) Other Examples of the conductive polymer other than the conjugated polymer and the ionic polymer include, for example, an ionene conductive polymer as described in JP-A-9-203810, or an intermolecular crosslinker. A quaternary ammonium cation conductive polymer etc. can be mentioned.

  Further, for example, antistatic hard coat agents described in JP-A-2006-265271, JP-A-2007-70456, JP-A-2009-62406, and the like can also be used. Moreover, it can also obtain as a commercial item, for example, can select and use suitably the antistatic agent etc. which are marketed by Aika Industry.

(2) Material for forming antistatic layer In addition to the above-described conductive polymer, materials contained in the antistatic layer according to the present invention will be described below.

(2-1) Binder resin The binder resin used to hold the conductive polymer according to the present invention at the time of forming the antistatic layer according to the present invention includes, for example, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate. Rate, cellulose acetate phthalate, cellulose derivatives such as cellulose nitrate, polyvinyl acetate, polystyrene, polycarbonate, polybutylene terephthalate, or polyester such as copolybutylene / tere / isophthalate, polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, polyvinyl butyral, Or polyvinyl alcohol derivatives such as polyvinyl benzal, norbornene polymers containing norbornene compounds, polymethyl methacrylate, polyester An acrylic resin such as til methacrylate, polypropyl butyl methacrylate, polybutyl methacrylate, and polymethyl acrylate, or a copolymer of an acrylic resin and another resin can be used, but the resin material is not particularly limited to these examples. Among these, a cellulose derivative or an acrylic resin is preferable, and an acrylic resin is most preferably used.

  As the binder resin used for forming the antistatic layer, the thermoplastic resin having a weight average molecular weight of 400,000 or more and a glass transition temperature in the range of 80 to 110 ° C. has optical characteristics and an antistatic layer to be formed. It is preferable in terms of surface quality.

  The glass transition temperature can be determined by the method described in JIS K7121. The binder resin used here is 60% by mass or more, more preferably 80% by mass or more of the total resin mass constituting the antistatic layer, and an actinic ray curable resin or thermosetting resin is applied as necessary. You can also

(2-2) Organic solvent The antistatic layer according to the present invention is prepared, for example, by dissolving a conductive polymer and a binder resin in a suitable organic solvent to prepare a coating solution for forming an antistatic layer in a solution state. It can be formed by applying and drying on a substrate by a wet application method.

  As the organic solvent used for the preparation of the coating solution for forming the antistatic layer, for example, hydrocarbons, alcohols, ketones, esters, glycol ethers and the like can be appropriately mixed and used. It is not limited to.

  In the organic solvent applicable to the present invention, examples of hydrocarbons include benzene, toluene, xylene, hexane, cyclohexane and the like, and examples of alcohols include methanol, ethanol, n-propyl alcohol, isopropyl alcohol. N-butanol, 2-butanol, tert-butanol, pentanol, 2-methyl-2-butanol, cyclohexanol and the like. Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the esters include methyl formate, ethyl formate, methyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, ethyl lactate, and methyl lactate. Examples of glycol ethers (1 to 4 carbon atoms) include methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether (abbreviation: PGME), propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol. Examples include monoisopropyl ether and propylene glycol monobutyl ether. Examples of the propylene glycol mono (C1-4) alkyl ether esters include propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate. Examples of other solvents include N-methylpyrrolidone. The organic solvent according to the present invention is not particularly limited to these, but a solvent in which these are appropriately mixed is also preferably used.

  As a method for applying the coating solution for forming an antistatic layer according to the present invention on a substrate, doctor coating, extrusion coating, slide coating, roll coating, gravure coating, wire bar coating, reverse coating, curtain coating, extrusion coating, Alternatively, an extrusion coating method using a hopper described in US Pat. No. 2,681,294 may be mentioned. By appropriately using these wet coating methods, an antistatic layer having a dry layer thickness in the range of 0.1 to 20 μm, preferably in the range of 0.2 to 5 μm, can be formed on the substrate.

《First gas barrier layer》
The 1st gas barrier layer which concerns on this invention is a gas barrier layer by which the antistatic layer is not provided among the gas barrier layers provided in both surfaces of the base material. There is no restriction | limiting in particular as a 1st gas barrier layer, Any structure may be sufficient. For example, a plurality of layers may be laminated to form the first gas barrier layer, and in that case, each layer may be formed by a different film forming method.

  The layer thickness of the first gas barrier layer according to the present invention is preferably in the range of 5 to 800 nm, more preferably in the range of 10 to 600 nm, and further in the range of 50 to 600 nm. The range of 100 to 400 nm is particularly preferable.

[Method for forming first gas barrier layer]
Examples of the method for forming the first gas barrier layer according to the present invention include a dry method and a wet method.

  Examples of the dry method include a vapor deposition method, and more specifically, a physical vapor deposition method (PVD method) or a chemical vapor deposition method (CVD method).

  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.

  Chemical vapor deposition (CVD) is a method of depositing a film on a substrate by a chemical reaction on the surface of the substrate or in the vapor phase by supplying a raw material gas containing a target thin film component onto the substrate. 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, a method of forming by a discharge plasma chemical vapor deposition method is preferable from the viewpoint of film forming speed and processing area.

  In addition, as a wet method, after applying a polysilazane layer-forming coating solution containing polysilazane and drying to form a precursor layer, the precursor layer is subjected to a modification process using vacuum ultraviolet light to form a first gas. A method of forming a barrier layer is preferred.

[1] Formation of first gas barrier layer by dry method [1-1] Reactive vapor deposition method Reactive vapor deposition method introduces reactive gas into a vacuum vessel and reacts atoms and molecules evaporated from the evaporation source. In order to accelerate the reaction, an excitation source such as plasma can be introduced. As typical raw materials, silicon, silicon nitride, silicon oxide, silicon oxynitride and the like are used as a deposition source, and nitrogen, hydrogen, ammonia, oxygen and the like are used as reactive gases.

[1-2] Sputtering method The sputtering method is a method of depositing constituent atoms of a sputtered target on a substrate by utilizing a sputtering phenomenon in which high-energy ions accelerated by an electric field are incident on the target and knocking out constituent atoms of the target. is there. The reactive sputtering method is a method in which a reactive gas is introduced into a vacuum vessel and reacted with constituent atoms of a sputtered target to be deposited on a substrate. As typical raw materials, silicon, silicon nitride, silicon oxide, silicon oxynitride and the like are used as target materials, and nitrogen, hydrogen, ammonia, oxygen and the like are used as reactive gases.

[1-3] Chemical Vapor Deposition Method In chemical vapor deposition, a material gas containing a constituent element of a film is introduced into a vacuum vessel and excited by a chemical reaction by exciting the material gas with a specific excitation source. A method of forming seeds and depositing them on a substrate. As typical raw materials, monosilane, hexamethyldisilazane, ammonia, nitrogen, hydrogen, oxygen and the like are used.

  The chemical vapor deposition method is a more promising method because it can form a film at a high speed and has a better covering property on the substrate than a sputtering method or the like. In particular, a catalytic chemical vapor deposition (Cat-CVD) method using a very high temperature catalyst as an excitation source and a plasma chemical vapor deposition (PECVD) method using plasma as an excitation source are preferable methods.

[1-4] Discharge Plasma Chemical Vapor Deposition Method Hereinafter, formation of the first gas barrier layer by the discharge plasma chemical vapor deposition method, which is one of the chemical vapor deposition methods that can be suitably used in the present invention. The method will be described in detail.

  In the present invention, the discharge plasma chemical vapor deposition method is more preferably a discharge plasma chemical vapor phase having a discharge space between rollers to which a magnetic field is applied using a source gas containing an organosilicon compound and an oxygen gas. A method of forming the first gas barrier layer using a growth apparatus is preferable.

  That is, in the formation of the first gas barrier layer according to the present invention, a substrate is wound around a pair of film forming rollers using a discharge plasma processing apparatus between rollers to which a magnetic field is applied, and is formed between the pair of film forming rollers. It is preferably formed by a plasma chemical vapor deposition apparatus that forms a thin film by plasma discharge while supplying a film gas. Further, when discharging while applying a magnetic field between the pair of film forming rollers, it is preferable to reverse the polarity between the pair of film forming rollers alternately.

  In a discharge plasma chemical vapor deposition method (hereinafter also referred to as plasma CVD method) in which a first gas barrier layer is formed while supplying a film forming gas between rollers to which a magnetic field is applied according to the present invention, plasma is generated. In this case, it is preferable to generate a plasma discharge in the formed discharge space while applying a magnetic field between the plurality of film forming rollers. In the present invention, a pair of film forming rollers is used, a substrate is wound around each of the pair of film forming rollers, and a plasma is generated by discharging in a state where a magnetic field is applied between the pair of film forming rollers. It is preferable.

  In addition, it is possible to simultaneously form the surface portion of the resin base material existing on the other film forming roller while forming the surface portion of the base material existing on one film forming roller at the time of film formation. Thus, not only can the thin film be produced efficiently, but also the film formation rate can be doubled and a film having the same structure can be formed, so that the gas barrier layer can be formed efficiently.

  Moreover, it is preferable that the gas barrier film of this invention forms a 1st gas barrier layer on the surface of a base material by a roll to roll system from a viewpoint of productivity.

  In addition, as an apparatus that can be used when manufacturing a gas barrier film by such a plasma chemical vapor deposition method, a film forming roller having at least a pair of magnetic field applying apparatuses and a plasma power source are provided. And it is the apparatus which becomes a structure which can be discharged between a pair of film-forming rollers.

  FIG. 2 is a schematic view showing an example of a discharge plasma chemical vapor deposition apparatus having a pair of rollers to which a magnetic field that can be suitably used in the production of the gas barrier film of the present invention is applied.

  An inter-roller discharge plasma CVD apparatus 31 (hereinafter also referred to as a plasma CVD apparatus) to which a magnetic field shown in FIG. 2 is applied mainly includes a feeding roller 32, transport rollers 33, 34, 35, and 36, and a film forming roller. 39, 40, a film forming gas supply pipe 41, a plasma generating power source 42, magnetic field generators 43, 44 installed inside the film forming rollers 39, 40, and a take-up roller 45. Further, in such a plasma CVD apparatus 31, at least the film forming rollers 39 and 40, the film forming gas supply pipe 41, the plasma generating power source 42, and the magnetic field generating apparatuses 43 and 44 are disposed in the vacuum chamber C. Is arranged. Further, in such a plasma CVD apparatus 31, the chamber C is connected to the vacuum pump 17, and the pressure in the chamber C can be appropriately adjusted by the vacuum pump 17.

  In such a plasma CVD apparatus, the film forming rollers 39 and 40 are connected to the plasma generating power source 42 so that the pair of film forming rollers 39 and 40 can function as a pair of counter electrodes. ing. By supplying electric power to the pair of film forming rollers 39, 40 from the plasma generating power source 42, it becomes possible to discharge into the space between the film forming roller 39 and the film forming roller 40, thereby forming the film forming rollers. Plasma can be generated in a space (also referred to as a discharge space) between 39 and the film forming roller 40. In addition, since the film forming rollers 39 and 40 are used as electrodes in this way, materials and designs that can be used as electrodes may be appropriately changed. Moreover, in such a plasma CVD apparatus 31, it is preferable to arrange | position a pair of film-forming rollers 39 and 40 so that the central axis may become substantially parallel on the same plane. In this way, by arranging the pair of film forming rollers 39 and 40, the film forming rate can be doubled.

  The film forming rollers 39 and 40 are characterized in that magnetic field generators 43 and 44 fixed so as not to rotate even if the film forming roller rotates are provided.

  Furthermore, as the film forming rollers 39 and 40, known rollers can be appropriately used. As the film forming rollers 39 and 40, those having the same diameter are preferably used from the viewpoint of more efficiently forming a thin film. Further, the diameters of the film forming rollers 39 and 40 are preferably in the range of 100 to 1000 mmφ, particularly in the range of 100 to 700 mmφ, from the viewpoint of discharge conditions, the space of the chamber C, and the like. If the diameter is 100 mmφ or more, it is preferable that the plasma discharge space is not reduced, the productivity is not deteriorated, the total amount of heat of the plasma discharge can be prevented from being applied to the film in a short time, and the residual stress is hardly increased. On the other hand, a diameter of 1000 mmφ or less is preferable because practicality can be maintained in terms of device design including uniformity of the plasma discharge space.

  Further, as the feeding roller 32 and the transport rollers 33, 34, 35, and 36 used in such a plasma CVD apparatus, known rollers can be appropriately selected and used. The take-up roller 45 is not particularly limited as long as it can take up the base material 2 on which the gas barrier layer is formed, and a known roller can be used as appropriate.

  As the film forming gas supply pipe 41, a pipe capable of supplying or discharging the source gas and the oxygen gas at a predetermined rate can be appropriately used. Further, as the plasma generating power source 42, a power source of a conventionally known plasma generating apparatus can be used. Such a plasma generating power source 42 supplies power to the film forming rollers 39 and 40 connected thereto, and makes it possible to use these as counter electrodes for discharge. As such a plasma generation power source 42, it is possible to more efficiently carry out the plasma CVD method, and therefore, a power source capable of alternately reversing the polarity of a pair of film forming rollers (for example, an AC power source). Etc.) is preferred. Moreover, as such a plasma generating power source 42, it is possible to perform the plasma CVD method more efficiently, so that the applied power can be in the range of 100 W to 10 kW, and the AC frequency is 50 Hz. It is more preferable that it can be in the range of ˜500 kHz. As the magnetic field generators 43 and 44, known magnetic field generators can be used as appropriate.

  Using the plasma CVD apparatus as shown in FIG. 2, for example, the type of source gas, the power of the electrode drum of the plasma generator, the strength of the magnetic field generator, the pressure in the chamber C, the diameter of the film forming roller, and the resin The gas barrier film of the present invention can be produced by appropriately adjusting the conveyance speed of the substrate. That is, using the plasma CVD apparatus shown in FIG. 2, plasma discharge is performed while a magnetic field is generated between the pair of film forming rollers 39 and 40 while supplying a film forming gas (raw material gas or the like) into the chamber C. Thus, the film forming gas (raw material gas or the like) is decomposed by plasma, and the first gas according to the present invention is formed on the surface of the base material 2 on the film forming roller 39 and on the surface of the base material 2 on the film forming roller 40. The gas barrier layer 3 is formed by plasma CVD. In such film formation, the substrate 2 is conveyed by the feed roller 32, the film formation roller 39, and the like, respectively, so that the surface of the substrate 2 is formed by a roll-to-roll continuous film formation process. A first gas barrier layer 3 is formed thereon.

  As a method for forming the first gas barrier layer according to the present invention, a method in which the transport direction is reversed in the transport direction A and the transport direction B shown in FIG. Can be taken.

[1-4-1] Film Formation Gas In the formation of the first gas barrier layer by the discharge plasma chemical vapor deposition method, the source gas constituting the film formation gas used for film formation is an organic material containing at least silicon. It is preferable to use a silicon compound.

  Examples of the organosilicon compound applicable to the present invention include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, and trimethyl. Examples thereof include silane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling in film formation and gas barrier properties of the obtained gas barrier layer. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.

  The film-forming gas contains oxygen gas as a reaction gas in addition to the source gas. The oxygen gas is a gas that reacts with the raw material gas to become an inorganic compound such as an oxide.

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

  When such a film forming gas contains a source gas containing an organosilicon compound containing silicon and an oxygen gas, it is preferable to appropriately adjust the ratio of the source gas to the oxygen gas.

Hereinafter, as a representative example, a system of hexamethyldisiloxane (organosilicon compound: HMDSO: (CH ₃ ) ₆ Si ₂ O :) as a source gas and oxygen (O ₂ ) as a reaction gas will be described.

A film-forming gas containing hexamethyldisiloxane (HMDSO, (CH ₃ ) ₆ Si ₂ O) as a source gas and oxygen (O ₂ ) as a reaction gas is reacted by a plasma CVD method to form silicon- When an oxygen-based thin film is formed, a reaction represented by the following reaction formula (1) occurs by the film forming gas, and a thin film made of silicon dioxide SiO ₂ is formed.

Reaction formula (1): (CH ₃ ) ₆ Si ₂ O + 12O ₂ → 6CO ₂ + 9H ₂ O + 2SiO ₂
In such a reaction, the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. Therefore, in the initial stage of film formation, a silicon dioxide film having a high oxygen atom ratio and a uniform composition can be obtained by completely reacting by adding 12 mol or more of oxygen to 1 mol of hexamethyldisiloxane in the film forming gas. However, it is possible to increase the ratio of SiOC by controlling the gas flow rate ratio of the raw material during the film formation to the latter stage to a flow rate that is less than the theoretical raw material ratio, thereby performing the incomplete reaction. It is also good.

  In the actual reaction in the chamber C of the plasma CVD apparatus, the raw material hexamethyldisiloxane and the reaction gas, oxygen, are supplied from the gas supply unit to the film formation region for film formation. Even if the molar amount (flow rate) of the catalyst is 12 times the molar amount (flow rate) of the raw material hexamethyldisiloxane, the reaction cannot actually proceed completely. It is considered that the reaction is completed only when the content is supplied in a large excess compared to the stoichiometric ratio. For example, in order to obtain silicon oxide by complete oxidation by a CVD method, the molar amount (flow rate) of oxygen may be about 20 times or more the molar amount (flow rate) of hexamethyldisiloxane as a raw material. In the present invention, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of the raw material hexamethyldisiloxane is an amount of 12 times or less (more preferably 10 times or less) which is the stoichiometric ratio. It is preferable. By containing hexamethyldisiloxane and oxygen in such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are taken into the gas barrier layer to form a desired gas barrier layer. This makes it possible to exhibit excellent gas barrier properties and bending resistance in the obtained gas barrier film. If the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of hexamethyldisiloxane in the deposition gas is too small, unoxidized carbon atoms and hydrogen atoms will be excessively taken into the gas barrier layer. become.

[1-4-2] Degree of vacuum The pressure (degree of vacuum) in the chamber C can be appropriately adjusted according to the type of the raw material gas, but is preferably in the range of 0.5 to 100 Pa.

[1-4-3] Roller Film Formation In the plasma CVD method using a plasma CVD apparatus or the like as shown in FIG. 2, in order to discharge between the film formation rollers 39 and 40, it is connected to a plasma generation power source 42. The electric power applied to the electrode drum (installed in the film forming rollers 39 and 40 in FIG. 2) can be appropriately adjusted according to the type of source gas, the pressure in the chamber C, and the like. However, it is preferable to set it within the range of 0.1 to 10 kW. If the applied power is in such a range, no generation of particles (illegal particles) is observed, and the amount of heat generated during film formation is within the control range. There is no thermal deformation of the material, performance deterioration due to heat, or generation of wrinkles during film formation. In addition, damage to the film forming roller due to melting of the base material by heat and generation of a large current discharge between the bare film forming rollers can be prevented.

  The conveyance speed (line speed) of the base material can be appropriately adjusted according to the type of source gas, the pressure in the chamber, etc., but is preferably in the range of 0.25 to 100 m / min. More preferably, it is within the range of 5 to 20 m / min. If the line speed is within the above range, wrinkles due to the heat of the resin base material hardly occur, and the thickness of the formed gas barrier layer can be sufficiently controlled.

[2] Formation of First Gas Barrier Layer by Wet Method As a method for forming the first gas barrier layer according to the present invention, a coating liquid for forming a polysilazane layer containing polysilazane is applied and dried to form a precursor layer. A method of forming a gas barrier layer by subjecting the precursor layer to a modification treatment with vacuum ultraviolet light after the formation can also be preferably used.

  The polysilazane modification treatment in the present invention refers to a reaction in which a part or all of the polysilazane compound is converted into silicon oxide or silicon oxynitride.

  For this modification treatment, a known method based on the conversion reaction of polysilazane can be selected. Formation of a silicon oxide film or a silicon oxynitride film by a substitution reaction of a polysilazane compound requires a high temperature of 450 ° C. or more, and is difficult to adapt to a flexible substrate using a resin film as a base material. Therefore, when producing the gas barrier film of the present invention, a method using ultraviolet light capable of conversion reaction at a lower temperature is preferable from the viewpoint of adaptation to a plastic substrate.

  In the method for producing a gas barrier film in the present invention, the polysilazane coating film from which moisture has been removed is modified by treatment with ultraviolet light irradiation. Ozone and active oxygen atoms generated by ultraviolet light (synonymous with ultraviolet light) have high oxidation ability, and can form silicon oxide films or silicon oxynitride films with high density and insulation at low temperatures. It is.

This ultraviolet light irradiation excites and activates O ₂ and H ₂ O, UV absorbers, and polysilazane itself that contribute to ceramicization. And the ceramicization of the excited polysilazane is promoted, and the resulting ceramic film becomes dense. Irradiation with ultraviolet light is effective at any time after the formation of the coating film.

  For the vacuum ultraviolet light irradiation treatment in the present invention, a commonly used ultraviolet ray generator can be used. In addition, the ultraviolet light as used in the field of this invention means the ultraviolet light containing the electromagnetic wave which has a wavelength of 10-200 nm generally called vacuum ultraviolet light.

  In the irradiation with vacuum ultraviolet light, it is preferable to set the irradiation intensity and the irradiation time within a range in which the base material carrying the pre-modified polysilazane layer to be irradiated is not damaged.

For example, when a plastic film is used as the substrate, for example, a 2 kW (80 W / cm × 25 cm) lamp is used, and the strength of the substrate surface is 20 to 300 mW / cm ² , preferably 50 to 200 mW / cm. The distance between the substrate and the ultraviolet irradiation lamp is set so as to be ^2, and irradiation can be performed for 0.1 second to 10 minutes.

  In general, when the temperature of the base material during the ultraviolet irradiation treatment is 150 ° C. or higher, the properties of the base material are impaired in the case of a plastic film or the like, for example, the base material is deformed or its strength is deteriorated. . However, in the case of a film having high heat resistance such as polyimide, a modification treatment at a higher temperature is possible. Accordingly, there is no general upper limit for the substrate temperature at the time of ultraviolet irradiation, and it can be appropriately set by those skilled in the art depending on the type of substrate. Moreover, there is no restriction | limiting in particular in ultraviolet irradiation atmosphere, What is necessary is just to implement in air.

  Examples of such ultraviolet ray generating means include, but are not limited to, a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a xenon arc lamp, a carbon arc lamp, an excimer lamp, and a UV light laser. In addition, when the polysilazane layer before modification is irradiated with the generated ultraviolet light, the polysilazane before modification is reflected after reflecting the ultraviolet light from the generation source with a reflector from the viewpoint of improving efficiency and uniform irradiation. It is desirable to hit the layer.

  The ultraviolet irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be used. When the substrate having the polysilazane modified layer is in the form of a long film, it is converted into ceramics by continuously irradiating ultraviolet rays in the drying zone equipped with the ultraviolet ray generation source as described above while being conveyed. Can do. The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although depending on the base material used and the composition and concentration of the polysilazane modified layer.

  Moreover, it is preferable to make oxygen concentration into 300-10000 ppm (1%) at the time of irradiating a vacuum ultraviolet light (VUV), More preferably, it is 500-5000 ppm. By adjusting to such an oxygen concentration range, it is possible to prevent the formation of an oxygen-excess gas barrier layer and to prevent deterioration of gas barrier properties.

  A dry inert gas is preferably used as a gas other than oxygen at the time of vacuum ultraviolet light (VUV) irradiation, and dry nitrogen gas is particularly preferable from the viewpoint of cost.

  The oxygen concentration can be adjusted by measuring the flow rates of oxygen gas and inert gas introduced into the irradiation apparatus and changing the flow rate ratio.

  The treatment by vacuum ultraviolet light irradiation uses light energy of 100 to 200 nm, preferably light energy having a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and the bonding of atoms is called a photon process called a photon process. This is a method in which a silicon oxide film is formed at a relatively low temperature by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by only the action. As a vacuum ultraviolet light source required for this, a rare gas excimer lamp is preferably used.

In the vacuum ultraviolet light irradiation step of the present invention, the illuminance of the vacuum ultraviolet light in the coating film surface for receiving the polysilazane coating film is more preferably 30~200mW / cm ^2, is 50~160mW / cm ² And more preferred. If it is 30 mW / cm ² or more, the reforming efficiency can be sufficiently expressed, and if it is 200 mW / cm ² or less, problems such as ablation of the coating film or damage to the substrate are prevented. be able to.

Irradiation energy amount of the vacuum ultraviolet light in the polysilazane coating film surface is preferably 10~30000mJ / cm ^2, more preferable to be 100~15000mJ / cm ^2, further preferably a 200~12000mJ / cm ^2. If 10 mJ / cm ² or more is sufficient as the modification effect can if 30000mJ / cm ² or less, to suppress the occurrence of thermal deformation of cracks and substrate.

  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. In addition, it is known that the energy of light having a short wavelength of 172 nm for dissociating the bonds of organic substances has high ability. Due to the high energy of the active oxygen, ozone and ultraviolet radiation, the polysilazane film can be modified in a short time. Therefore, compared to low-pressure mercury lamps with wavelengths of 185 nm and 254 nm and plasma cleaning, shortening process time and equipment area associated with high throughput, irradiation to organic materials, plastic substrates, resin films, etc. that are easily damaged by heat. It is possible.

  In addition, 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 of a single wavelength is irradiated in the ultraviolet region, so that an increase in the surface temperature of the irradiation object is suppressed. For this reason, it is suitable for the irradiation to the gas barrier film which uses resin films, such as a polyethylene terephthalate considered to be easily influenced by heat, as a base material.

  In the formation of the first gas barrier layer, any appropriate wet coating method can be applied as a coating method for coating a gas barrier layer forming coating solution containing a polysilazane compound. Examples thereof include a roller 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 thickness of the coating film can be set according to the purpose of use of the gas barrier film and is not particularly limited. For example, the thickness of the coating film is preferably 0.01 to 1 μm as the thickness after drying. More preferably, it is in the range of 20 to 600 nm, and most preferably in the range of 40 to 400 nm.

The “polysilazane compound” preferably used in the present invention is a polymer having a silicon-nitrogen bond in the structure, and is composed of Si—N, Si—H, N—H, etc., SiO ₂ , Si ₃ N _4, and an intermediate between them. It is a ceramic precursor inorganic polymer such as solid solution SiO _x N _y .

In order to apply so as not to damage the film substrate, a polysilazane compound which is modified to SiO _x N _y at a relatively low temperature is preferable, as described in JP-A-8-112879.

As such a polysilazane compound, those having the following structure are preferably used.
—Si (R ₁ ) (R ₂ ) —N (R ₃ ) —
In the formula, R ₁ , R ₂ and R ₃ each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group.

In the present invention, from the viewpoint of the denseness of the resulting gas barrier layer as a film, perhydropolysilazane (abbreviation: PHPS) in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms is particularly preferable.

  On the other hand, the organopolysilazane in which the hydrogen part bonded to Si is partially substituted with an alkyl group or the like has an alkyl group such as a methyl group, so that the adhesion to the base substrate is improved and the polysilazane which is hard and brittle As a result, it is possible to impart toughness to the ceramic film, and there is an advantage that generation of cracks can be suppressed even when the film thickness is increased.

  These perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and can also be mixed and used.

  Perhydropolysilazane is presumed to have a structure in which a linear structure and a ring structure centered on a 6-membered ring or an 8-membered ring coexist.

  The molecular weight of polysilazane is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), is a liquid or solid substance, and varies depending on the molecular weight.

  These polysilazanes are commercially available in the form of a solution dissolved in an organic solvent, and commercially available products can be used as they are as a polysilazane-containing coating solution.

  Other examples of the polysilazane compound that is converted to ceramics at a low temperature include silicon alkoxide-added polysilazane obtained by reacting silicon alkoxide with the above polysilazane (Japanese Patent Laid-Open No. 5-238827), glycidol-added polysilazane obtained by reacting glycidol ( JP-A-6-122852), an alcohol-added polysilazane obtained by reacting an alcohol (JP-A-6-240208), a metal carboxylate-added polysilazane obtained by reacting a metal carboxylate (JP-A-6-6240) 299118), acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (JP-A-6-306329), metal fine particle-added polysilazane obtained by adding metal fine particles (JP-A-7) -1 JP) or the like 6986 and the like.

  As an organic solvent for preparing a coating solution containing a polysilazane compound, it is preferable to avoid using an alcohol or water-containing one that easily reacts with polysilazane.

  Examples of the organic solvent include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbon solvents, or ethers such as aliphatic ethers or alicyclic ethers. Can be used.

  Specific examples include hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso or turben, halogen hydrocarbons such as methylene chloride or trichloroethane, or ethers such as dibutyl ether, dioxane or tetrahydrofuran. It is done.

  These organic solvents may be selected according to purposes such as the solubility of polysilazane and the evaporation rate of the solvent, and a plurality of organic solvents may be mixed.

  The concentration of the polysilazane compound in the polysilazane compound-containing coating solution is about 0.2 to 35% by mass, although it varies depending on the layer thickness of the target gas barrier layer and the pot life of the coating solution.

  An amine or a metal catalyst may be added to the coating solution in order to promote modification to the silicon oxide compound. Specific examples include Aquamica NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials Co., Ltd.

  The addition amount of these catalysts is preferably adjusted to 2% by mass or less with respect to the polysilazane compound in order to avoid excessive silanol formation by the catalyst, decrease in film density, increase in film defects, and the like.

  In addition to the polysilazane compound, the coating liquid containing the polysilazane compound can contain an inorganic precursor compound. The inorganic precursor compound other than the polysilazane compound is not particularly limited as long as the coating solution can be prepared. For example, paragraphs 0140 to 0142 of International Publication No. 2012/090644 and International Publication No. 2013/002026 Examples thereof include compounds containing silicon and polysilsesquioxanes described in paragraph numbers 0112 to 0114 and paragraph numbers 0072 to 0074 of JP-A-2015-33764.

The formation of the first gas barrier layer by a wet method can also be performed using a vacuum ultraviolet light irradiation apparatus shown in FIG.
FIG. 3 is a schematic diagram illustrating an example of a roll-to-roll type vacuum ultraviolet light irradiation apparatus.

  The vacuum ultraviolet light irradiation apparatus 50 described in FIG. 3 is an apparatus that forms a gas barrier layer on the substrate 2 by a roll-to-roll continuous production method.

  The vacuum ultraviolet light irradiation apparatus 50 shown in FIG. 3 applies a coating portion containing a polysilazane compound on the substrate 2 by feeding a feeding portion 54 for feeding the substrate 2 from a state in which the substrate 2 is laminated in a roll shape. A coater 55 equipped with a coating section for forming, a drying section 56 for drying the polysilazane layer formed on the substrate 2, and a polysilazane layer on the substrate 2 is irradiated with excimer light to modify the polysilazane layer. An excimer light irradiation unit 57, and a winding unit 58 that winds up the gas barrier film obtained by the reforming process into a roll shape. A barrier layer is formed.

As a specific method, the base material 2 is fed out from the feeding roller 54 from a laminating roller in which the long base materials 2 are laminated in a roll shape. Next, using a coater 55 of a wet coating method equipped in the coating unit, a coating liquid having a polysilazane compound is applied on the substrate 2 with a desired wet layer thickness while controlling the supply amount to the coater 55, A wet polysilazane layer is formed on the substrate 2. Next, the formed wet polysilazane layer is moved to the drying unit 56, and the polysilazane layer on the substrate 2 is dried by a dryer using warm air, a heater, or the like.
The dried polysilazane layer moves to the excimer light irradiation unit 57 which is the next step.

  The excimer light irradiation unit 57 that irradiates the excimer light and performs surface modification treatment on the polysilazane layer includes a plurality of excimer light irradiation units U1 to U30 each having an excimer lamp 51 and a transport unit for transporting the substrate 2. (Not shown). Further, a pipe (not shown) for supplying nitrogen gas and water vapor to each of the excimer light irradiation units U1 to U30 and a water vapor concentration in the excimer light irradiation unit 57 are adjusted to form nitrogen gas and a water vapor atmosphere. A gas and water vapor inlet 59 and a nitrogen gas and water vapor outlet 60 are provided. A vapor concentration measurement sensor (not shown) is provided inside the excimer light irradiation unit 57, and the water vapor concentration in the mixed gas of nitrogen gas and water vapor is controlled to a predetermined condition according to the measurement information.

《Second gas barrier layer》
Of the gas barrier layers provided on both surfaces of the substrate 2, the second gas barrier layer provided on the opposite side of the first gas barrier layer has any configuration as long as it has gas barrier properties. It may be the same as that of the first gas barrier layer. The second gas barrier layer may have a gas barrier property lower than that of the first gas barrier layer from the viewpoint of cost reduction. The antistatic layer is provided on the second gas barrier layer of the two gas barrier layers.

  The method for forming the second gas barrier layer is not particularly limited. For example, physical vapor deposition (PVD) such as vacuum deposition, sputtering, or ion plating, or reduced pressure chemical vapor deposition. And chemical vapor deposition (CVD: Chemical Vapor Deposition) such as plasma chemical vapor deposition.

  Moreover, as a layer thickness of the 2nd gas barrier layer based on this invention, it is preferable that it is the range of 5-800 nm, for example, and it is more preferable that it is 30-150 nm.

《Other constituent layers》
(Clear hard coat layer)
In the gas barrier film of the present invention, it is preferable to provide a clear hard coat layer between the base material and the gas barrier layer.

  As the clear hard coat layer, a curable resin such as a thermosetting resin or an active energy ray curable resin can be used. Of these, active energy ray-curable resins are preferred because they are easy to mold.

  The thermosetting resin is not particularly limited, and examples thereof include various thermosetting resins such as epoxy resins, cyanate ester resins, phenol resins, bismaleimide-triazine resins, polyimide resins, acrylic resins, and vinylbenzyl resins. .

  As an epoxy resin, those having an average of two or more epoxy groups per molecule may be used. Specifically, bisphenol A type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol type epoxy are used. Resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus-containing epoxy resin, bisphenol S type epoxy resin, aromatic glycidylamine type epoxy resin (specifically, for example, tetraglycidyldiaminodiphenylmethane, triglycidyl-p-amino Phenol, diglycidyl toluidine, diglycidyl aniline, etc.), cycloaliphatic epoxy resin, aliphatic chain epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac type Poxy resin, epoxy resin having butadiene structure, phenol aralkyl type epoxy resin, epoxy resin having dicyclopentadiene structure, diglycidyl etherified product of bisphenol, diglycidyl etherified product of naphthalenediol, glycidyl etherified product of phenol, alcohol Examples thereof include diglycidyl etherified products, alkyl-substituted products of these epoxy resins, halides, hydrogenated products, and the like. These may be used alone or in combination of two or more.

The active energy ray-curable resin is a resin that is cured through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays and electron beams.
Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, and among them, an ultraviolet curable resin is preferable.

  Examples of the ultraviolet curable resin include an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. Can do.

  In addition, about the other details of a clear hard-coat layer, the conditions described in the paragraph numbers 0230-0246 grade of Unexamined-Japanese-Patent No. 2015-33764 etc. can be selected suitably, and can be employ | adopted, for example.

(Bleed-out prevention layer)
The bleed-out prevention layer is a layer provided for the purpose of suppressing a phenomenon in which unreacted oligomers and the like migrate from the base material to the surface and contaminate the contact surface when the base material is heated. The bleed-out layer may have the same configuration as the clear hard coat layer as long as it has this function.

  For the detailed structure of the bleed-out prevention layer, reference can be made to, for example, paragraph numbers 0247 to 0261 of JP-A-2015-33764.

<< Method for producing gas barrier film >>
The method for producing a gas barrier film of the present invention is a method for producing a gas barrier film comprising a gas barrier layer on both surfaces of a substrate, and a step of forming a second gas barrier layer on one surface of the substrate; A step of forming an antistatic layer on the second gas barrier layer, and a step of forming the first gas barrier layer by CVD on the other surface of the substrate after forming the antistatic layer. Have.

  The first gas barrier layer, the second gas barrier layer, and the antistatic layer are preferably formed by a roll-to-roll method.

  Moreover, as a manufacturing method of the gas barrier film of the present invention, the second gas barrier layer, the antistatic layer, and the first gas barrier layer are formed in this order, and the gas barrier film of the present invention is obtained. For this purpose, the antistatic layer may be formed on the second gas barrier layer after the first and second gas barrier layers are formed on both surfaces of the substrate.

《Electronic device》
The gas barrier film of the present invention can be preferably used for an electronic device whose performance can be deteriorated by chemical components in the air (for example, oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.). That is, this invention provides the electronic device which has an electronic device main body and the gas barrier film of this invention, or the gas barrier film obtained by the manufacturing method of this invention.

  Examples of electronic devices include organic EL elements, liquid crystal display elements (LCD), thin film transistors, touch panels, electronic paper, solar cells (PV), and the like. 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.

  Moreover, the gas barrier film of this invention can be used for film | membrane sealing of an electronic device. That is, it is a method of providing the gas barrier film of the present invention on the surface of the electronic device itself as a support. 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 substrate for electronic devices or as a film for sealing by a solid sealing method. The solid sealing method is a method in which after forming a protective layer 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)
The gas barrier film of the present invention can be applied to an organic EL device. Regarding the outline of the organic EL element applicable to the present invention, for example, JP2013-157634A, JP2013-168552A, JP2013-177361A, JP2013-187221A, JP JP 2013-191644 A, JP 2013-191804 A, JP 2013-225678 A, JP 2013-235994 A, JP 2013-243234 A, JP 2013-243236 A, JP 2013-2013 A. JP 242366, JP 2013-243371, JP 2013-245179, JP 2014-003249, JP 2014-003299, JP 2014-013910, JP 2014-014933 Gazette, JP, 2014-017494, A It can be mentioned configurations described in.

(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 of the present invention can be used as a substrate for a transparent electrode or an 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 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 in order from the bottom. 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 upper transparent electrode.
The type of the liquid crystal cell is not particularly limited, but more preferably, a TN type (Twisted Nematic), an STN type (Super Twisted Nematic), a HAN type (Hybrid Aligned Nematic), a VA type (Vertical Alignment Ecntl Ecntl, an EC type Bt) 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 first gas barrier layer opposite to the antistatic layer is on the side close 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 phosphide (InP), II-VI group 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. That. In particular, in the present invention, the solar cell element is a copper / indium / selenium system (so-called CIS system), a copper / indium / gallium / selenium system (so-called CIGS system), copper / indium / gallium / selenium / sulfur. It is preferable that it is an I-III-VI group compound semiconductor solar cell element, such as a system (so-called CIGSS system).

(Other)
As other application examples, the thin film transistor described in JP 10-512104 A, the touch panel described in JP 5-127822 A, JP 2002-48913 A, JP 2000-98326 A, etc. The electronic paper described in the above.

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

<< Preparation of gas barrier film 101 >>
(1) Preparation of base material Transparent resin base material (manufactured by Kimoto Co., Ltd., polyethylene terephthalate (abbreviation: PET) film with clear hard coat layer (CHC)) and clear hard coat layer made of acrylic resin. A composition made of UV curable resin as a main component and a PET thickness of 125 μm) was prepared.

(2) Formation of second gas barrier layer (SiO ₂ layer) On one surface of the base material, vapor phase method / DC sputtering (magnetron sputtering apparatus, manufactured by Canon Anelva: Model EB1100 (hereinafter, the same apparatus for sputtering) In this way, a second gas barrier layer having a layer thickness of 30 nm was formed. The sputtering apparatus used is capable of two-way simultaneous sputtering.
A polycrystalline Si target was used as a target, and Ar and O ₂ were used as process gases. Film formation was performed by adjusting the oxygen partial pressure so that the composition of the layer was SiO ₂ . In addition, the condition of the composition was determined by adjusting the oxygen partial pressure by film formation using a glass substrate in advance, and the condition in which the composition near the depth of 10 nm from the surface layer was SiO ₂ was found, and the condition was applied. . Also, regarding the layer thickness, after taking the data of the change in the layer thickness with respect to the film forming time in the range of 100 to 300 nm, calculating the layer thickness to be formed per unit time, the film forming time to be the set layer thickness The layer thickness was adjusted by setting. Hereinafter, the film formation by sputtering similarly finds the condition that the composition near the depth of 10 nm from the surface layer becomes a desired composition, further calculates the thickness of the film formed per unit time, and determines the condition. Applicable.

(3) Formation of antistatic layer Polyoxyalkylene fatty acid ester antistatic with respect to 100 parts by mass of UV curable resin (Opstar Z7527, manufactured by JSR) as a binder resin on the second gas barrier layer of the base material After coating and drying 0.2 parts by weight of the agent under the condition that the layer thickness after drying is 1 μm, an antistatic layer is formed by performing an ultraviolet irradiation treatment under the condition of 300 mJ using an 80 W / cm ² mercury lamp. did.

(4) Formation of first gas barrier layer (plasma CVD method)
A first gas barrier layer was formed on the surface of the substrate opposite to the surface on which the second gas barrier layer was formed according to the following method.

  Using the discharge plasma chemical vapor deposition apparatus shown in FIG. 2, the substrate was set in the plasma CVD apparatus 31 and continuously conveyed by a roll-to-roll method. A magnetic field is applied between the film forming roller 39 and the film forming roller 40, and electric power is supplied to each of the film forming rollers 39 and 40 to discharge between the film forming roller 39 and the film forming roller 40 to generate plasma. To generate a discharge region. Next, a mixed gas of hexamethyldisiloxane (HMDSO), which is a raw material gas, and oxygen gas (which also functions as a discharge gas), which is a reactive gas, is used as a film forming gas in the formed discharge region. The first gas barrier layer having a layer thickness of 120 nm was formed on the surface of the substrate opposite to the surface on which the second gas barrier layer was formed under the following conditions. The film forming operation is performed in the transport direction A by feeding the base material from the feed roller 32 → film formation → winding the base material by the take-up roller 45, and further in the transport direction B by the base material from the take-up roller 45. The operation of unwinding → film formation → winding around the unwinding roller 32 was divided into five times.

(Deposition conditions)
Feed rate of source gas (hexamethyldisiloxane, HMDSO): 50 sccm (Standard Cubic Centimeter per Minute)
Reaction gas (O ₂ ) supply amount: 500 sccm
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Film transport speed: 0.8 m / min
The first gas barrier layer formed according to the above method was composed of silicon oxide (SiOC), and the layer thickness was 270 nm.

  In this way, a gas barrier film 101 was produced.

<< Preparation of gas barrier film 102 >>
In the production of the gas barrier film 101, a gas barrier film 102 was produced in the same manner except that the formation method of the antistatic layer and the first gas barrier layer was changed as follows.

(Formation of antistatic layer)
On the second gas barrier layer of the base material, a mixture of phosphorus-doped tin oxide (manufactured by Nissan Chemical Industries, Cellax CX-S204IP) and a UV curable resin (OPSTAR Z7527, manufactured by JSR) as a binder resin ( After applying and drying the solid content mass ratio = 1: 1) under the condition that the layer thickness after drying is 4 μm, using an 80 W / cm ² mercury lamp, ultraviolet irradiation treatment is performed under the condition of 300 mJ, thereby preventing antistatic. A layer was formed.

(Formation of first gas barrier layer (coating method))
<Preparation of polysilazane-containing coating solution>
A dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (manufactured by AZ Electronic Materials Co., Ltd., NN120-20) and a dibutyl ether solution containing 20% by mass of perhydropolysilazane containing amine catalyst (AZ Electronic Materials ( Co., Ltd., NAX120-20) was mixed at a ratio of 4: 1, and further diluted with a dibutyl ether solvent so that the solid content of the coating solution was 10% by mass, and a polysilazane-containing coating solution was prepared. Prepared.

<Application of polysilazane-containing coating solution and UV irradiation>
The prepared polysilazane compound-containing coating solution was mounted on the coating portion on the surface opposite to the surface on which the second gas barrier layer of the substrate was formed, using the vacuum ultraviolet light irradiation apparatus 50 shown in FIG. After coating continuously at a line speed of 1.0 m / min using the coater 55, the drying unit 56 is dried for 1 minute at a drying temperature of 50 ° C. and a dew point of 10 ° C. of the drying atmosphere. The polysilazane layer having a layer thickness of 250 nm was formed after drying at a dew point of 5 ° C. for 2 minutes.

  Next, the polysilazane layer formed through the drying unit 56 was transferred to the excimer light irradiation unit 57 and subjected to surface modification treatment by excimer light irradiation.

Excimer light irradiation uses, as an excimer lamp, a xenon excimer lamp (wavelength: 172 nm, peak illuminance: 120 mW / cm ² ) manufactured by MD Excimer, as shown in FIG. Thirty excimer lamps (U1 to U30) were arranged. The installation position of the excimer lamp was adjusted so that the shortest distance between the excimer lamp tube surface and the surface of the substrate being conveyed was 3 mm. The energy applied to the surface of the sample coating layer in the vacuum ultraviolet light irradiation step was measured using a 172 nm sensor head using an ultraviolet integrated light meter: C8026 / H8025UVPOWERMETER manufactured by Hamamatsu Photonics. In the measurement, the shortest distance between the Xe excimer lamp tube surface and the measurement surface of the sensor head was set to 3 mm.

<< Preparation of gas barrier film 103 >>
A gas barrier film 103 was produced in the same manner as in the production of the gas barrier film 101 except that the formation method of the antistatic layer and the first gas barrier layer was changed as follows.

(Formation of antistatic layer)
On the second gas barrier layer of the base material, the conductive polymer 1 (lithium salt acrylate-based monomer, Sanko Chemical Co., Ltd., Sanconol A600-50R) was applied and dried under the condition that the layer thickness after curing was 2 μm. Then, using an 80 W / cm < ² > mercury lamp, the ultraviolet irradiation process was performed on the conditions of 300 mJ, and the antistatic layer was formed.

(Formation of first gas barrier layer (sputtering method)
A first gas barrier layer having a layer thickness of 30 nm was formed on the surface of the substrate opposite to the surface on which the second gas barrier layer was formed by the same method as the method for forming the second gas barrier layer. .

<< Production of gas barrier film 104 >>
In the production of the gas barrier film 103, a gas barrier film 104 was produced in the same manner except that the formation method of the first gas barrier layer was changed to the coating method in the production of the gas barrier film 102.

<< Preparation of gas barrier film 105 >>
In the production of the gas barrier film 103, a gas barrier film 105 was produced in the same manner except that the formation method of the first gas barrier layer was changed to the plasma CVD method in the production of the gas barrier film 101.

<< Production of Gas Barrier Film 106 >>
In the production of the gas barrier film 105, a gas barrier film 106 was produced in the same manner except that the conductive polymer 1 used for forming the antistatic layer was changed to polythiophene (conductive polymer 2) which is a conjugated polymer. .

<< Production of Gas Barrier Film 107 >>
In the production of the gas barrier film 105, except that the conductive polymer 1 used for forming the antistatic layer was changed to poly (1,6-heptadiene) (conductive polymer 3) which is a conjugated polymer, A gas barrier film 107 was produced.

<< Production of gas barrier film 108 >>
In the production of the gas barrier film 105, the gas barrier film 108 was formed in the same manner except that the layer thickness of the antistatic layer was changed so that the surface resistivity obtained by the measurement method described later becomes the value shown in Table 1. Produced.

<< Production of gas barrier film 109 >>
A gas barrier film 109 was produced in the same manner as in the production of the gas barrier film 105 except that the conductive polymer 1 used for forming the antistatic layer was changed to the following conductive polymer 4.
Conductive polymer 4: Coating composition (2) which is an ion conductive polymer described in Examples of JP-A-2006-104458 (copolymer of methyl methacrylate / dimethylaminoethyl methacrylate (76% conductive segment, weight) Average molecular weight: 23000))

<< Production of Gas Barrier Film 110 >>
In the production of the gas barrier film 105, the gas barrier film 110 was formed in the same manner except that the layer thickness of the antistatic layer was changed so that the surface resistivity obtained by the measurement method described later becomes the value shown in Table 1. Produced.

<< Production of organic EL element >>
Each constituent layer described below was formed on each of the first gas barrier layers of the produced gas barrier films 101 to 110 to produce an organic EL element.

(Formation of the first electrode)
On the first gas barrier layer of each gas barrier film, ITO (indium tin oxide) having a thickness of 150 nm was formed by sputtering, and patterned by photolithography to form a first electrode. The pattern was such that the light emission area was 50 mm square.

(Formation of hole transport layer)
Before applying the coating liquid for forming the hole transport layer, a cleaning surface modification treatment of the gas barrier film was performed 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. For the charge removal treatment, a static eliminator using weak X-rays was used.

  Next, a solution obtained by diluting polyethylene dioxythiophene / polystyrene sulfonate (PEDOT / PSS, Baytron PAI4083 manufactured by Bayer) with 65% pure water and 5% methanol was used as a coating solution for forming a hole transport layer.

  On the first electrode layer of the gas barrier film, a hole transport layer forming coating solution was applied by an extrusion coater in the atmosphere at 25 ° C. and in a relative humidity of 50% RH. The hole transport layer forming coating solution was applied so that the layer thickness after drying was 50 nm.

  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)
As a host material, 1.0 g of the following HA, 100 mg of the following DA as a dopant material, 0.2 mg of the following DB, and 0.2 mg of the following DC are dissolved in 100 g of toluene. Thus, a white light emitting layer forming coating solution was obtained.

  On the hole transport layer of the gas barrier film, a white light emitting layer forming coating solution was applied by an extrusion coater in an atmosphere having a nitrogen gas concentration of 99% or more. The coating temperature was 25 ° C. and the coating speed was 1 m / min. The white light emitting layer forming coating solution was applied so that the layer thickness after drying was 40 nm.

  After the white light emitting layer forming coating solution was applied, the solvent was removed at a height of 100 mm toward the film forming surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C. Next, heat treatment was performed at a temperature of 130 ° C. to form a light emitting layer that emits white light.

(Formation of electron transport layer)
The following EA was dissolved in 2,2,3,3-tetrafluoro-1-propanol to obtain a 0.5 mass% solution, which was used as a coating solution for forming an electron transport layer.

  On the light emitting layer, the electron transport layer forming coating solution was applied by an extrusion coater in an atmosphere having a nitrogen gas concentration of 99% or more. The coating temperature was 25 ° C., and the coating speed was 1 m / min. The coating solution for forming an electron transport layer was applied so that the layer thickness after drying was 30 nm.

  After applying the electron transport layer forming coating solution, the solvent was removed at a height of 100 mm toward the film forming surface, a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 60 ° C. Next, in the heat treatment section, heat treatment was performed at a temperature of 200 ° C. to form an electron transport layer.

(Formation of electron injection layer)
The gas barrier film on which each of the constituent layers was formed was put into a vacuum chamber, and the pressure was reduced to 5 × 10 ⁻⁴ Pa. In advance, cesium fluoride prepared in a tantalum vapor deposition boat in a vacuum chamber was heated to form an electron injection layer having a thickness of 3 nm on the electron transport layer.

(Formation of second electrode)
Except for the portion constituting the extraction electrode of the first electrode, aluminum is used as the second electrode forming material on the formed electron injection layer under a vacuum of 5 × 10 ⁻⁴ Pa, and vapor deposition is performed so as to have the extraction electrode. Then, a mask pattern was formed so that the light emission area was 50 mm square, and a second electrode having a thickness of 100 nm was laminated.

(Cutting)
The gas barrier film formed up to the second electrode was moved again under a nitrogen atmosphere and cut using an ultraviolet laser so as to have a prescribed size.

(Electrode lead connection)
An anisotropic conductive film DP3232S9 manufactured by Sony Chemical & Information Device Co., Ltd. was used for the produced laminate, and a flexible printed circuit board (base film: polyimide 12.5 μm, rolled copper foil 18 μm, coverlay: polyimide 12.5 μm). , Surface-treated NiAu plating). The pressure bonding conditions were a temperature of 170 ° C. (ACF temperature of 140 ° C. measured using a separate thermocouple), a pressure of 2 MPa, and 10 seconds.

(Sealing)
As a sealing member, an adhesive for dry lamination (two-component reaction type urethane adhesive) is used, and a polyethylene terephthalate (PET) film (12 μm thick) is formed on a 30 μm thick aluminum foil (manufactured by Toyo Aluminum Co., Ltd.). ) (Adhesive layer thickness 1.5 μm) was used.

  Using a dispenser, a thermosetting adhesive was uniformly applied at a thickness of 20 μm along the adhesive surface (shiny surface) of the aluminum foil of the sealing member. As the thermosetting adhesive, a mixture of bisphenol A diglycidyl ether (DGEBA), dicyandiamide (DICY), and an epoxy adduct curing accelerator (epoxy adhesive) was used.

The sealing member is closely attached and arranged so as to cover other than the extraction electrode and the electrode lead provided on the produced laminate, and the pressure roller temperature is 120 degrees, the pressure is 0.5 MPa, by a commercially available roller laminating apparatus. Close sealing was performed at an apparatus speed of 0.3 m / min.
In this way, an organic EL element was produced.

<< Evaluation of gas barrier films 101-110 >>
About the gas barrier films 101-110 produced as mentioned above, the following surface resistivity measurement and gas barrier property evaluation were performed. Moreover, the dark spot evaluation of the following organic EL element was performed about the organic EL element produced using the gas barrier films 101-110. Each evaluation result is shown in Table 1.

(1) Measurement of surface resistivity of gas barrier film The surface resistivity of the antistatic layer side surface of each gas barrier film was measured using Hiresta UX MCP-HT800 manufactured by Mitsubishi Analytech.

(2) Evaluation of gas barrier properties Using a vacuum vapor deposition apparatus (vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.), the surface of the first gas barrier layer of the produced gas barrier film is passed through a mask with a metal calcium size of 12 mm × 12 mm. Was evaporated. 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 the gas barrier film on which the metal calcium was vapor-deposited for 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 under a high temperature and high humidity of 85 ° C. and 85% using a constant temperature and humidity oven (YamatoHumicic Chamber IG47M), and the state of corrosion of metallic calcium with respect to the storage time was observed. The time at which the area where metal calcium corrodes with respect to the metal calcium vapor deposition area of 12 mm × 12 mm was 50% was obtained by interpolating from the observation results with a straight line, and evaluated according to the following criteria. If it is 3 or more in the following criteria, it can be determined that there is no practical problem.

5: More than 200 hours 4: 150 hours or more and less than 200 hours 3: 100 hours or more and less than 150 hours 2: 50 hours or more and less than 100 hours 1: Less than 50 hours

(3) Evaluation of Dark Spot (Black Spot) of Organic EL Element Each of the organic EL elements produced above was subjected to an accelerated deterioration process for 100 hours in an environment of 85 ° C. and 85% RH, and then was not subjected to the accelerated deterioration process. Along with each organic EL element, a dark spot (abbreviated as DS in Table 1) was evaluated.

A current of 1 mA / cm ² was applied to the organic EL element subjected to the accelerated deterioration treatment and the organic EL element not subjected to the accelerated deterioration treatment to emit light continuously for 24 hours. ) A part of the panel was enlarged with Moritex MS-804 and lens MP-ZE25-200), and photographing was performed. The photographed image was cut out in 2 mm square, the area ratio of dark spots (black spots) was determined, the element deterioration resistance rate was calculated according to the following formula, and evaluated according to the following criteria. If it is 3 or more in the following criteria, it can be determined that there is no practical problem.

  Element degradation tolerance ratio = (area of black spots generated in organic EL elements not subjected to accelerated degradation processing / area of black spots generated in organic EL elements subjected to accelerated degradation processing) × 100 (%)

5: Element deterioration resistance rate is 98% or more 4: Element deterioration resistance ratio is 90% or more and less than 98% 3: Element deterioration resistance ratio is 60% or more and less than 90% 2: Element Deterioration resistance ratio is 20% or more and less than 60% 1: Element deterioration resistance ratio is less than 20%

  As shown in Table 1, it can be seen that the gas barrier film of the present invention is superior in gas barrier properties to the gas barrier film of the comparative example, and the occurrence of dark spots is suppressed by applying it to the organic EL device. .

DESCRIPTION OF SYMBOLS 1 Gas barrier film 2 Base material 3 1st gas barrier layer 3A, 3B Gas barrier layer 4 2nd gas barrier layer 5 Antistatic layer

Claims (2)

A method for producing a gas barrier film comprising a gas barrier layer on both sides of a substrate,
Forming a second gas barrier layer on one surface of the substrate;
Forming an antistatic layer on the second gas barrier layer;
Forming a first gas barrier layer on the other surface of the base material by a CVD method after forming the antistatic layer. A method for producing a gas barrier film, comprising: The method for producing a gas barrier film according to claim 1 , wherein the first gas barrier layer is formed by a roll-to-roll method.

Images