JP2014240462A - Gas barrier film, method for manufacturing gas barrier film, and apparatus for manufacturing gas barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve gas barrier properties and moist heat resistance of a gas barrier film while shortening its manufacturing time.SOLUTION: A method for manufacturing a gas barrier film of the present invention performs, in the following order: a droplet application step of applying a polysilazane-containing solution formed into droplets to one surface of a film substrate made of a resin in an atmosphere containing at least oxygen; a drying step of drying the solution, which has been applied to the one surface in the droplet application step, to form a polysilazane layer; and a modification step of subjecting the polysilazane layer to ultraviolet irradiation or plasma irradiation in a low oxygen concentration atmosphere to modify the polysilazane layer into a gas barrier layer.

Description

  The present invention relates to a gas barrier film, a gas barrier film manufacturing method, and a gas barrier film manufacturing apparatus. More specifically, a transparent gas barrier film excellent in flexibility, used for gas barrier of electronic devices such as liquid crystals, organic electroluminescence (organic EL), solar cells, and electronic paper, a method for producing the gas barrier film, and gas The present invention relates to a barrier film manufacturing apparatus.

  Conventionally, in the field of electronic devices, in addition to demands for weight reduction and size increase, long-term reliability, high degree of freedom of shape, and the ability to display curved surfaces have been added, resulting in large areas that are heavy and easy to break. Instead of difficult glass substrates, film substrates such as transparent plastics are beginning to be adopted.

However, a film substrate such as a transparent plastic has a problem that the gas barrier property is inferior to that of a glass substrate.
It has been found that when a base material with poor gas barrier properties is used, water vapor or oxygen penetrates and, for example, the function in the electronic device is deteriorated.

  Therefore, it is generally known that a film having gas barrier properties (hereinafter referred to as a gas barrier layer) is formed on a film substrate and the formed product is used as a gas barrier film. Polysilazane has attracted attention as a material for the gas barrier layer. Although polysilazane has almost no barrier property as it is, a smooth and highly barrier gas barrier layer can be formed by the wet method.

  In order to form a gas barrier layer using polysilazane, for example, a polysilazane layer is formed on a silicon oxide layer formed by plasma chemical vapor deposition and heated to 160 degrees. Thereby, gas barrier property is provided to the polysilazane layer, and a gas barrier layer is formed (for example, refer to Patent Document 1).

  However, in this technique, the heating temperature is set low because of the relationship with the heat resistant temperature of the film substrate, and the polysilazane layer cannot be made dense, so that it has sufficient gas barrier properties for use in organic EL devices and the like. Can't get.

Therefore, in recent years, techniques for densifying the polysilazane layer have been developed. For example, when the polysilazane layer is irradiated with vacuum ultraviolet rays or plasma, the polysilazane layer is modified and densified by reaction with O ₂ or H ₂ O in the atmosphere (see, for example, Patent Documents 2 and 3).

However, as a result of extensive research by the present inventors, it has been found that the techniques of Patent Documents 2 and 3 have the following problems.
That is, when the polysilazane layer is modified by these techniques, the modification of the polysilazane layer proceeds in order from the first arrival position of vacuum ultraviolet light or plasma energy (or ions or radicals generated by plasma), that is, from the outermost surface. Since the barrier property is high, in the region inside the outermost surface (region on the film substrate side), supply of O ₂ and H ₂ O necessary for the modification is hindered by the outermost surface, which is unstable. A state of polysilazane (hereinafter referred to as unstable polysilazane) is formed. Further, when another gas barrier layer is formed in advance as a base on the film base side than the polysilazane layer, the supply of O ₂ and H ₂ O from the film base side is also hindered. More stable polysilazane is formed. In the gas barrier film in which the unstable polysilazane is formed in the gas barrier layer in this way, a trace amount of H ₂ O permeates through the outermost surface of the gas barrier layer or the like and reaches the unstable polysilazane due to a wet heat environment or the like. When, by the reaction of H 2 _O and unstable polysilazane, thereby significantly degrading the performance of the gas barrier film.
On the other hand, in order to suppress the formation of unstable polysilazane, ultraviolet or plasma irradiation is performed in an O ₂ atmosphere, and when O ₂ is actively supplied to the polysilazane layer during the modification, O ₂ itself absorbs the energy of ultraviolet or plasma. As a result of absorption, the light energy is greatly reduced and the modification becomes insufficient, resulting in insufficient gas barrier properties or a long time for modification.

Japanese Patent Laid-Open No. 8-281186 JP 2009-255040 A JP 2007-237588 A

  The present invention has been made in view of the above-described problems and situations, and a solution to the problem is a method for producing a gas barrier film and a gas barrier film capable of improving gas barrier properties and wet heat resistance while shortening the production time. It is providing the manufacturing apparatus of this, and a gas barrier film.

In order to solve the above-mentioned problems, the present inventor forms a polysilazane layer while making polysilazane easy to come into contact with O ₂ or the like in the atmosphere in the process of examining the cause of the above-mentioned problems. It was found that the problem can be solved, and the present invention has been achieved.

  That is, the said subject which concerns on this invention is solved by the following means.

1. A droplet coating step of applying a solution containing polysilazane in a droplet form to one surface of a resin film substrate in an atmosphere containing at least oxygen; and
A drying step of forming the polysilazane layer by drying the solution applied to the one surface by the droplet application step;
A modification step of modifying the polysilazane layer to form a gas barrier layer by performing ultraviolet irradiation or plasma irradiation on the polysilazane layer in a low oxygen concentration atmosphere;
Are performed in this order.
2. In the droplet application step,
2. The method for producing a gas barrier film according to claim 1, wherein the solution is applied by a trace solvent coating method.
3. In the droplet application step,
3. The method for producing a gas barrier film according to claim 1, wherein the solution is applied by an electrostatic coating method.
4). Before the droplet applying process, the relative one surface, forming said unlike gas barrier layer, and a water vapor permeability of ^{1 × 10 -1 g / m 2} / 24h or less of another gas barrier layer The method for producing a gas barrier film according to any one of items 1 to 3, wherein a gas barrier layer forming step is performed.
5. The method for producing a gas barrier film according to any one of claims 1 to 4, wherein the thickness of the gas barrier layer is 50 nm or more.
6). A gas barrier film produced by the method for producing a gas barrier film according to any one of items 1 to 5.
7). A liquid droplet applying part for applying a solution containing polysilazane into liquid droplets on the one surface of the resin film base under an atmosphere containing at least oxygen; and
A drying unit for drying the solution applied to the one surface by the droplet application unit to form a polysilazane layer;
A modified portion that modifies the polysilazane layer to form a gas barrier layer by performing ultraviolet irradiation or plasma irradiation on the polysilazane layer in a low oxygen concentration atmosphere;
An apparatus for producing a gas barrier film, comprising:
8). The droplet applying part is
The apparatus for producing a gas barrier film according to claim 7, wherein the solution is applied by a micro solvent application method.
9. The droplet applying part is
The apparatus for producing a gas barrier film according to claim 7 or 8, wherein the solution is applied by an electrostatic coating method.
10. Wherein with respect to the one surface in the film substrate side of the gas barrier layer, different from the gas barrier layer, and the water vapor permeability of ^{1 × 10 -1 g / m 2} / 24h or less for other gas barrier layer The apparatus for producing a gas barrier film according to any one of Items 7 to 9, further comprising: a gas barrier layer forming unit that forms a gas.
11. The apparatus for producing a gas barrier film according to any one of Items 7 to 10, wherein the thickness of the gas barrier layer is 50 nm or more.

  By the above means of the present invention, gas barrier properties and wet heat resistance can be improved while shortening the production time of the gas barrier film.

  Although the expression mechanism or action mechanism of the effect of the present invention is not clarified, the present inventors infer as follows.

That is, since a solution containing polysilazane is applied as a droplet on one surface of a resin film substrate in an atmosphere containing at least oxygen, the polysilazane in the solution is actively added to O ₂ or the like in the atmosphere. It is thought that it is made to contact and land on a film base material. Then, the solution applied to the film substrate is dried to form a polysilazane layer, and the polysilazane layer is subjected to modification treatment by ultraviolet irradiation or plasma irradiation. This polysilazane is considered to be bonded to O _{2 by} hydrogen bonding or the like. Therefore, in this reforming treatment, the reforming of the polysilazane layer proceeds in order from the first arrival position of ultraviolet energy or plasma energy (or ions or radicals generated by ultraviolet radiation or plasma), that is, from the outermost surface, and the gas barrier property is high. Even in such a case, it is considered that O ₂ is supplied to the polysilazane in the inner region (region on the film substrate side) from the outermost surface, thereby preventing the formation of unstable polysilazane. Therefore, unlike the conventional case, a small amount of H ₂ O is prevented from permeating through the outermost surface of the gas barrier layer and reacting with unstable polysilazane, so that the performance of the gas barrier film is prevented from deteriorating. It is considered that the wet heat resistance is improved.
In addition, unlike the case of modifying the polysilazane layer while actively supplying O ₂ by irradiating plasma or ultraviolet light in an O ₂ atmosphere, the energy of plasma or ultraviolet light is not absorbed by O ₂ . It is considered that the polysilazane layer is reliably modified to improve the gas barrier property and the processing time is shortened.

It is a schematic diagram which shows the structure of a gas barrier film. It is the schematic which shows an example of the manufacturing apparatus of a gas barrier film. It is the schematic which shows the structure of the droplet coating device using ESD method. It is a figure for demonstrating operation | movement of the droplet coating apparatus using ESD method. It is a schematic diagram of the organic electroluminescent panel which comprised the gas barrier film. It is the schematic which shows the structure of the droplet coating apparatus using ESDUS method.

  The gas barrier film manufacturing method (and manufacturing apparatus) of the present invention is a droplet coating method in which a solution containing polysilazane is applied in a droplet form to one surface of a resin film substrate in an atmosphere containing at least oxygen. A step (droplet application portion), a drying step (drying portion) for drying the solution applied to the one surface by the droplet application step to form a polysilazane layer, and the atmosphere in a low oxygen concentration atmosphere. The polysilazane layer is subjected to (provided with) a modification step (modified portion) in this order by modifying the polysilazane layer to be a gas barrier layer by performing ultraviolet irradiation or plasma irradiation. . This feature is a technical feature common to the inventions according to claims 1 to 11.

  As an embodiment of the present invention, from the viewpoint of manifestation of the effects of the present invention, in the droplet coating process, it is possible to improve the gas barrier and wet heat resistance by applying the solution by a trace solvent coating method, preferably an electrostatic coating method. Can be preferred.

Further, in the present invention, prior to the droplet applying process, the relative one surface, unlike the gas barrier layer, and a water vapor permeability of ^{1 × 10 -1 g / m 2} / 24h or less of other It is preferable to perform the gas barrier layer forming step of forming the gas barrier layer because the gas barrier performance of the gas barrier film can be further improved. Moreover, it is preferable that the thickness of the gas barrier layer be 50 nm or more because the gas barrier performance of the gas barrier film can be further improved.

The “gas barrier property” as used in the present invention is a water vapor permeability (temperature: 60 ± 0.5 ° C., relative humidity (RH): 90 ± 2%) measured by a method according to JIS K 7129-1992. ) is not more than ^{3 × 10 -3 g / m 2} / 24h, the oxygen permeability measured by the method based on JIS K 7126-1987 is not more than ^{1 × 10 -3 ml / m 2} / 24h · atm Means that.

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

<1. Overview of Gas Barrier Film of the Present Invention>
The gas barrier film of the present invention includes a droplet coating step in which a solution containing polysilazane is applied as droplets on one surface of a resin film substrate in an atmosphere containing at least oxygen, and the droplet coating step The polysilazane layer is formed by drying the solution applied to the one surface to form a polysilazane layer, and performing ultraviolet irradiation or plasma irradiation on the polysilazane layer in a low oxygen concentration atmosphere. And a reforming step for reforming to form a gas barrier layer in this order.

<1-1. Configuration of gas barrier film>
Although the structure of the gas barrier film of this invention is not specifically limited, An example is shown in FIG. The gas barrier film 1 in the present embodiment includes a film base 10 and gas barrier layers 11 and 12 (hereinafter referred to as a first gas barrier layer 11 and a second gas barrier layer 12) laminated on the film base 10. And). A curable resin layer or a base layer (not shown) may be provided between the film substrate 10 and the first gas barrier layer 11, or an overcoat layer (on the second gas barrier layer 12). (Not shown) may be provided. In addition, a bleed-out prevention layer (not shown) may be provided on the surface (the lower surface in the drawing) opposite to the second gas barrier layer 12 in the film substrate 10. Further, the first gas barrier layer 11 may not be provided.

<1-2. Film base>
In this embodiment, the film base material 10 will not be specifically limited if it is produced with resin which can hold | maintain a gas barrier layer.

  Examples of the material of the film substrate 10 include polyacrylate ester, polymethacrylate ester, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, poly Polyethylene copolymers such as vinyl chloride (PVC), polyethylene (PE), ethylene-cyclic olefin, polypropylene (PP), polystyrene (PS), polyamide (PA), polyether ether ketone, polysulfone, polyether sulfone, polyimide, Polymers such as polyetherimide, cellulose triacetate (TAC), cycloolefin polymer (COP, product name ZEONEX, manufactured by Nippon Zeon Co., Ltd.), Sil having an organic-inorganic hybrid structure Resistant transparent film substrate has a basic skeleton Sukiokisan (product name Sila-DEC, manufactured by Chisso Corporation), and further can be given substrate or the like formed by laminating the polymer of two or more layers.

  As the material for the film substrate 10, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polycarbonate (PC), and the like are preferably used in terms of cost and availability. Further, in terms of optical transparency, heat resistance, and adhesion to an inorganic layer, a heat resistant transparent film having a basic skeleton of silsesquioxane having an organic-inorganic hybrid structure is preferably used.

  The thickness of the film substrate 10 is preferably 5 to 500 μm, more preferably 25 to 250 μm, from the viewpoints of handleability and mechanical strength. In view of the case where the gas barrier film 1 of the embodiment of the present invention is used for a light-emitting element, the glass transition temperature (Tg) of the film substrate 10 is preferably 80 ° C. or higher. Moreover, it is preferable that a heat shrinkage rate is also low.

  Furthermore, the film substrate 10 is preferably transparent. When the film substrate 10 is transparent and the gas barrier layers 11 and 12 produced on the film substrate 10 are also transparent, the transparent gas barrier film 1 is obtained, so that transparent substrates such as solar cells and organic EL elements are used. This is because it becomes possible.

  Moreover, the film base material 10 using said polymer etc. may be an unstretched film, and may be a stretched film. Further, the surface of the film substrate 10 may be subjected to corona treatment.

  The film substrate 10 can be manufactured by a conventionally known general method. For example, an unstretched film substrate 10 that is substantially amorphous and not oriented can be produced by melting a polymer as a material with an extruder, extruding it with an annular die or a T-die, and quenching.

  In addition, the unstretched film is uniaxially stretched, by a known method such as tenter sequential biaxial stretching, tenter simultaneous biaxial stretching, tubular simultaneous biaxial stretching, or the like, the film flow direction (vertical axis direction), or The film substrate 10 can be produced as a stretched film by stretching in the direction perpendicular to the flow direction (horizontal axis direction). Although the draw ratio in this case can be suitably selected according to the polymer used as the material of the film substrate 10, it is preferably 2 to 10 times in each of the vertical axis direction and the horizontal axis direction.

<1-3. Gas barrier layer (first and second gas barrier layers)>
In the present embodiment, the gas barrier layer refers to a layer that can suppress the permeation of gases such as water molecules and oxygen molecules. As the gas barrier layer, a single layer or a plurality of similar films may be laminated, and the gas barrier property can be further improved by providing a plurality of layers.

<1-3-1. First gas barrier layer>
The first gas barrier layer 11 is another gas barrier layer in the present invention, and is provided on the film substrate 10 on the side of the film substrate 10 with respect to the second gas barrier layer 12. However, an underlayer (also referred to as a smooth layer or an anchor layer) may be interposed between the first gas barrier layer 11 and the film substrate 10.

The first gas barrier layer 11 is water vapor transmission rate is not more than ^{1 × 10 -1 g / m 2} / 24h, the layer thickness is 10 to 1000 nm, preferably has a 10 to 300 nm.

  As a material for forming the first gas barrier layer 11, a silicon compound, a titanium compound, and an aluminum compound are useful. In particular, by forming a thin film of silicon oxide such as silicon dioxide, silicon oxynitride or silicon oxycarbide on the film substrate, excellent gas barrier properties can be imparted to the film substrate 10.

  As a method for manufacturing the first gas barrier layer 11, a method using an inorganic film forming method by a vapor phase method is known. As an inorganic film-forming method by the vapor phase method, a metal (tetraethoxysilane (TEOS)) is typically formed on a substrate such as a film by a plasma CVD method (Chemical Vapor Deposition). A method of forming an inorganic film (gas barrier layer) by vaporizing while oxidizing with an oxygen plasma, or evaporating a metal using a semiconductor laser or the like and depositing on the substrate in the presence of oxygen. Examples thereof include a vacuum deposition method for depositing and a method for forming an inorganic film (gas barrier layer) by a sputtering method.

  Chemical vapor deposition (Chemical Vapor Deposition) is a method of depositing a film on a substrate by supplying a source gas containing components of a target thin film and performing a chemical reaction in the surface of the substrate or in the gas phase. It is. In addition, there is a method of generating plasma for the purpose of activating a chemical reaction. Known CVD methods such as thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, vacuum plasma CVD method, atmospheric pressure plasma CVD method, etc. Etc. Although not particularly limited, it is preferable to apply the plasma CVD method from the viewpoint of the film formation speed and the processing area. Forming the first gas barrier layer 11 by chemical vapor deposition is advantageous in terms of gas barrier properties.

The gas barrier layer obtained by the vacuum plasma CVD method or the plasma CVD method under atmospheric pressure or near atmospheric pressure is a condition such as a raw material (also referred to as a raw material) metal compound, decomposition gas, decomposition temperature, input power, etc. Is preferred because the desired compound can be produced.
For example, if a silicon compound is used as a raw material compound and oxygen is used as the decomposition gas, silicon oxide is generated. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.

As a raw material compound, a silicon compound, a titanium compound, and an aluminum compound are used.
Among these, as silicon compounds, silane, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetra t-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Diethyldimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, hexamethyldisiloxane, bis (dimethylamino) dimethylsilane Bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) carbodiimide, di Tylaminotrimethylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetrakisdimethylaminosilane, tetraisocyanatosilane, tetramethyldisilazane , Tris (dimethylamino) silane, triethoxyfluorosilane, allyldimethylsilane, allyltrimethylsilane, benzyltrimethylsilane, bis (trimethylsilyl) acetylene, 1,4-bistrimethylsilyl-1,3-butadiyne, di-t-butylsilane, 1,3-disilabutane, bis (trimethylsilyl) methane, cyclopentadienyltrimethylsilane, phenyldimethylsilane, phenyltrimethylsilane, Pargyltrimethylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetramethyl Examples thereof include cyclotetrasiloxane, hexamethylcyclotetrasiloxane, M silicate 51, and the like.

Examples of the titanium compound include titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium tetraisoporooxide, titanium n-butoxide, titanium diisopropoxide (bis-2,4-pentanedionate), titanium. Examples thereof include diisopropoxide (bis-2,4-ethylacetoacetate), titanium di-n-butoxide (bis-2,4-pentanedionate), titanium acetylacetonate, and butyl titanate dimer.
Examples of the aluminum compound include aluminum ethoxide, aluminum triisopropoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum s-butoxide, aluminum t-butoxide, aluminum acetylacetonate, and triethyl dialumonium tri-s-butoxide. Can be mentioned.

In addition, as a decomposition gas for decomposing a raw material gas containing these metals to obtain an inorganic compound, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, nitrous oxide Examples include gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, and water vapor. Further, the decomposition gas may be mixed with an inert gas such as argon gas or helium gas.
A desired barrier layer can be obtained by appropriately selecting a source gas containing a source compound and a decomposition gas. The first gas barrier layer 11 formed by chemical vapor deposition is an oxide, nitride, oxynitride, or oxycarbide.

<1-3-2. Second gas barrier layer>
The second gas barrier layer 12 is a layer provided on the first gas barrier layer 11. However, another layer may be interposed between the first gas barrier layer 11 and the second gas barrier layer 12.
The second gas barrier layer 12 preferably has a thickness of 50 nm or more.
Polysilazane is used as a material for forming the second gas barrier layer 12.

<1-3-2 (1). Polysilazane>
Polysilazane is a polymer having a silicon-nitrogen bond, and ceramics such as SiO ₂ , Si ₃ N ₄ , and both intermediate solid solutions SiO _x N _y having bonds such as Si—N, Si—H, and N—H. It is a precursor inorganic polymer.
Specifically, the polysilazane preferably has a structure represented by the following general formula (I).

Formula (I):
-[Si (R ₁ ) (R ₂ ) -N (R ₃ )] n-

In the general formula (I), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. . At this time, R ₁ , R ₂ and R ₃ may be the same or different. Here, as an alkyl group, a C1-C8 linear, branched or cyclic alkyl group is mentioned. More specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n -Hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like. Moreover, as an aryl group, a C6-C30 aryl group is mentioned. More specifically, non-condensed hydrocarbon groups such as phenyl group, biphenyl group, terphenyl group; pentarenyl group, indenyl group, naphthyl group, azulenyl group, heptaenyl group, biphenylenyl group, fluorenyl group, acenaphthylenyl group, preadenenyl group , Condensed polycyclic hydrocarbon groups such as acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceantrirenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, etc. Can be mentioned. Examples of the (trialkoxysilyl) alkyl group include an alkyl group having 1 to 8 carbon atoms having a silyl group substituted with an alkoxy group having 1 to 8 carbon atoms. More specifically, 3- (triethoxysilyl) propyl group, 3- (trimethoxysilyl) propyl group and the like can be mentioned. The substituent optionally present in R _{1 to} R ₃ is not particularly limited. For example, an alkyl group, a halogen atom, a hydroxy group (—OH), a mercapto group (—SH), a cyano group (—CN), There are a sulfo group (—SO ₃ H), a carboxy group (—COOH), a nitro group (—NO ₂ ), and the like. In addition, the substituent which exists depending on the case does not become the same as R < ₁ > -R < ₃ > to substitute. For example, when R _{1 to} R ₃ are alkyl groups, they are not further substituted with an alkyl group. Of these, R ₁ , R ₂ and R ₃ are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a phenyl group, a vinyl group, 3 -(Triethoxysilyl) propyl group or 3- (trimethoxysilylpropyl) group.

Moreover, in the said general formula (I), n is an integer, and it is preferable to determine so that the polysilazane which has a structure represented by general formula (I) may have a number average molecular weight of 150-150,000 g / mol.
In the compound having the structure represented by the general formula (I), one of preferred embodiments is perhydropolysilazane in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms.

Or as polysilazane, you may use what has a structure represented by the following general formula (II).
General formula (II):
_{- [Si (R 1 ')} (R 2') -N (R 3 ')] n' - [Si (R 4 ') (R 5') -N (R 6 ')] p-

In the general formula (II), R ₁ ′, R ₂ ′, R ₃ ′, R ₄ ′, R ₅ ′ and R ₆ ′ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, An aryl group, a vinyl group or a (trialkoxysilyl) alkyl group. At this time, R ₁ ′, R ₂ ′, R ₃ ′, R ₄ ′, R ₅ ′ and R ₆ ′ may be the same or different. The substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the above is the same as the definition of the general formula (I), and thus the description is omitted.

  In the general formula (II), n ′ and p are integers, and the polysilazane having the structure represented by the general formula (II) is determined to have a number average molecular weight of 150 to 150,000 g / mol. Is preferred. Note that n ′ and p may be the same or different.

Among the polysilazanes of the general formula (II), R ₁ ′, R ₃ ′ and R ₆ ′ each represent a hydrogen atom, and R ₂ ′, R ₄ ′ and R ₅ ′ each represent a methyl group; R ₁ Compounds in which ', R ₃ ' and R ₆ 'each represent a hydrogen atom, R ₂ ' and R ₄ 'each represent a methyl group, and R ₅ ' represents a vinyl group; R ₁ ', R ₃ ', R ₄ A compound in which 'and R ₆ ' each represents a hydrogen atom and R ₂ 'and R ₅ ' each represents a methyl group is preferred.

Or as polysilazane, you may use what has a structure represented by the following general formula (III).
General formula (III):
_{- [Si (R 1 ")} (R 2") -N (R 3 ")] n" - [Si (R 4 ") (R 5") -N (R 6 ")] p" - [Si ( _{R 7 ") (R 8"} ) -N (R 9 ")] q-

In the general formula (III), R ₁ ″, R ₂ ″, R ₃ ″, R ₄ ″, R ₅ ″, R ₆ ″, R ₇ ″, R ₈ ″ and R ₉ ″ are independently A hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group, wherein R ₁ ″, R ₂ ″, R ₃ ″, R ₄ ″, R ₅ ″. , R ₆ ″, R ₇ ″, R ₈ ″ and R ₉ ″ may be the same or different. The substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the above is the same as the definition of the general formula (I), and thus the description is omitted.

  In the general formula (III), n ″, p ″ and q are integers, and the polysilazane having the structure represented by the general formula (III) has a number average molecular weight of 150 to 150,000 g / mol. Preferably, it is defined. Note that n ″, p ″, and q may be the same or different.

Of the polysilazanes of the general formula (III), R ₁ ″, R ₃ ″ and R ₆ ″ each represent a hydrogen atom, and R ₂ ″, R ₄ ″, R ₅ ″ and R ₈ ″ each represent a methyl group. , R ₉ ″ represents a (triethoxysilyl) propyl group, and R ₇ ″ represents an alkyl group or a hydrogen atom.

  On the other hand, the organopolysilazane in which a part of the hydrogen atom portion bonded to Si is substituted with an alkyl group or the like has improved adhesion to the base material as a base by having an alkyl group such as a methyl group and is hard. The ceramic film made of brittle polysilazane can be toughened, and there is an advantage that the occurrence of cracks can be suppressed even when the (average) film thickness is increased. For this reason, perhydropolysilazane and organopolysilazane may be selected as appropriate according to the application, and may be used in combination.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. The molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), and there are liquid or solid substances, and the state varies depending on the molecular weight.

  Polysilazane is commercially available in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as a coating solution for forming a polysilazane layer. As a commercial product of this coating liquid, AZ Electronic Materials Co., Ltd. Aquamica (registered trademark) NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, SP140 etc. are mentioned.

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

<1-3-2 (2). Polysilazane coating solution>
The above polysilazane is applied to the film substrate 10 in the form of a solution (hereinafter referred to as a polysilazane coating solution 120 (see FIG. 4)), dried, and then modified to thereby modify the second gas barrier layer 12. Form. In the present invention, the solution may not necessarily be a solute dissolved, but may be a colloidal solution in which a solute is dispersed in a solvent.

The content of polysilazane in the polysilazane coating solution 120 varies depending on the desired layer thickness of the second gas barrier layer 12, the pot life of the coating solution, etc., but is 0.2 mass relative to the total amount of the polysilazane coating solution 120. It is preferable that it is% -35 mass%.
The polysilazane coating solution 120 contains the following solvent, and preferably further contains the following catalyst.

<1-3-2 (3). Solvent>
Specific examples of organic solvents that can be used to prepare the polysilazane coating solution 120 include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, halogenated hydrocarbon solvents, And ethers such as aliphatic ethers and alicyclic ethers. Specifically, there are hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, ethers such as dibutyl ether, dioxane and tetrahydrofuran. These organic solvents may be selected according to characteristics such as the solubility of the polysilazane compound material and the evaporation rate of the organic solvent, and a plurality of organic solvents may be mixed.

<1-3-2 (4). Catalyst>
In order to modify the polysilazane layer into a gas barrier layer, a catalyst that promotes a reaction for converting at least a part of the polysilazane in the polysilazane layer into a silicon oxide compound may be used.

  The catalyst preferably used in the present invention is at least one selected from the group of nickel, titanium, platinum, rhodium, cobalt, iron, ruthenium, osmium, palladium, iridium, and aluminum described in JP-A-10-279362. Metal carboxylates obtained by reacting metal carboxylates containing these metals, acetylacetonate complexes containing nickel, platinum, palladium or aluminum, and fine particles of metals including Au, Ag, Pd, Ni, Also, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, tributylamine, pentylamine, dipentylamine, tripentylamine Emissions, hexylamine, dihexylamine, trihexylamine, heptylamine, diheptylamine, triheptyl, octylamine, dioctylamine, trioctylamine, phenylamine, diphenylamine, triphenylamine, and the like. The hydrocarbon chain contained in these amine compounds may be a straight chain or a branched chain.

  The addition amount of these catalysts with respect to polysilazane is 0.1 ppm or more and less than 5.0% as a mass ratio with respect to the total mass of polysilazane as a solid content concentration ratio in the coating liquid for gas barrier layer formation containing polysilazane. preferable. More preferably, it is the range of 100 ppm or more and 3.0% or less.

<1-4. Curable resin layer>
The gas barrier film 1 according to the present invention preferably has a curable resin layer formed by curing a curable resin on the film substrate 10. The curable resin is not particularly limited, and the active energy ray curable resin or the thermosetting material obtained by irradiating the active energy ray curable material with an active energy ray such as ultraviolet ray to be cured is heated. The thermosetting resin etc. which are obtained by curing by the above method. These curable resins may be used alone or in combination of two or more.

  Such a curable resin layer (1) smoothes the surface of the film substrate 10, (2) relaxes the stress of the upper layer to be laminated, and (3) adhesion between the film substrate 10 and the upper layer. It has at least one function of enhancing. For this reason, the curable resin layer may also be used as a smooth layer and an anchor coat layer (an easy adhesion layer) described later.

  Examples of the active energy ray-curable material include a composition containing an acrylate compound, a composition containing an acrylate compound and a mercapto compound containing a thiol group, epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene Examples thereof include compositions containing polyfunctional acrylate monomers such as glycol acrylate and glycerol methacrylate. Specifically, it is possible to use a UV curable organic / inorganic hybrid hard coating material OPSTAR (registered trademark) series (compound obtained by bonding an organic compound having a polymerizable unsaturated group to silica fine particles) manufactured by JSR Corporation. it can. It is also possible to use any mixture of the above-mentioned compositions, and an active energy ray-curable material containing a reactive monomer having at least one photopolymerizable unsaturated bond in the molecule. If there is no restriction in particular.

  Examples of reactive monomers having at least one photopolymerizable unsaturated bond in the molecule include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and n-pentyl. Acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclo Pentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycy Acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, Ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexadiol diacrylate, 1,3-propanediol acrylate, 1,4-cyclohexanediol Diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripropylene Glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol triacrylate, ethylene oxide modified pentaerythritol tetraacrylate, propion Oxide modified pentaerythritol triacrylate, propion oxide modified pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimethylolpropane triacrylate, butylene glycol diacrylate, 1,2,4-butanediol triacrylate, 2,2, 4-to Limethyl-1,3-pentadiol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, pentaerythritol hexaacrylate, and acrylate replaced with acrylate, γ-methacryloxypropyltrimethoxysilane, Examples thereof include 1-vinyl-2-pyrrolidone and the like. Said reactive monomer can be used as a 1 type, 2 or more types of mixture, or a mixture with another compound.

It is preferable that the composition containing an active energy ray-curable material contains a photopolymerization initiator.
Examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino acetophenone, 4,4-dichloro. Benzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p- tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzylmethoxyethyl acetal, benzoy Methyl ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (p-azide Benzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (O-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxy , Michler's ketone, 2-methyl [4- (methylthio) phenyl] -2-monoforino-1-propane, 2-benzyl-2-dimethylamino-1- (4-monoforinophenyl) -butanone-1, naphthalenesulfonyl chloride , Quinolinesulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenyl sulfone, benzoin peroxide And combinations of photoreducing dyes such as eosin and methylene blue and reducing agents such as ascorbic acid and triethanolamine. These photopolymerization initiators can be used alone or in combination of two or more. .

  Specific examples of thermosetting materials include TutProm Series (Organic Polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Coat, Nanohybrid Silicone manufactured by Adeka, Unicom manufactured by DIC, Inc. Dick (registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat resistant epoxy resin), silicon resin X-12-2400 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., Nitto Boseki Co., Ltd. Inorganic / organic nanocomposite material SSG coating, thermosetting urethane resin consisting of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicon resin, polyamidoamine-epichlorohydrin resin And the like.

  The method for forming the curable resin layer is not particularly limited, but a coating solution containing a curable material is applied to a spin coating method, a spray method, a blade coating method, a dipping method, a gravure printing method or other wet coating method, or a vapor deposition method. After applying the dry coating method to form a coating film, irradiation with active energy rays such as visible rays, infrared rays, ultraviolet rays, X-rays, α rays, β rays, γ rays, electron rays and / or heating are performed. A method of forming the film by curing is preferred. As a method of irradiating active energy rays, for example, an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a metal halide lamp or the like is preferably used to irradiate ultraviolet rays in a wavelength region of 100 to 400 nm, more preferably 200 to 400 nm. Alternatively, a method of irradiating an electron beam having a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator can be used.

  Solvents used when forming a curable resin layer using a coating solution in which a curable material is dissolved or dispersed in a solvent include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol, and the like. Alcohols, terpenes such as α- or β-terpineol, etc., ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, toluene, xylene, tetramethyl Aromatic hydrocarbons such as benzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ester -Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carb Acetic esters such as tall acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, cyclohexyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate , Diethylene glycol dialkyl ether, dipro Glycol dialkyl ethers, ethyl 3-ethoxypropionate, methyl benzoate, N, N- dimethylacetamide, N, may be mentioned N- dimethylformamide.

  The curable resin layer can contain additives such as a thermoplastic resin, an antioxidant, an ultraviolet absorber, and a plasticizer, if necessary, in addition to the above-described materials. In addition, an appropriate resin or additive may be used for improving the film formability and preventing the film from generating pinholes. Examples of the thermoplastic resin include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, and methylcellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof, and the like. Examples include resins, acetal resins such as polyvinyl formal and polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, and polycarbonate resins.

Although it does not restrict | limit especially as thickness of a curable resin layer, The range of 0.1-10 micrometers is preferable.
As for the smoothness of the curable resin layer, the centerline average surface roughness (Ra) is preferably 0.3 to 2.0 nm, and more preferably 0.3 to 1.0 nm. If it is such a range, the objective of the curable resin layer of smoothing the surface of the film base material 10 can be achieved. The centerline average surface roughness (Ra) can be measured by a conventionally known method (for example, a method using a scanning probe microscope (AFM)).

  The elastic modulus of the curable resin layer is preferably 2 to 20 Pa. If it is such a range, the hard coat property of a film surface will improve and the objective of the curable resin layer that can relieve | moderate the stress by upper layer lamination | stacking can be achieved. The elastic modulus can be obtained by a conventionally known elastic modulus measuring method, for example, a method of measuring under a condition in which a constant strain is applied at a constant frequency (Hz) using Vibron DDV-2 manufactured by Orientec. , Using RSA-II (manufactured by Rheometrics) as a measuring device, forming a curable resin layer on the film substrate 10, and then obtaining a measured value obtained by changing applied strain at a constant frequency, or In addition, it can be measured by a nano indenter to which the nano indentation method is applied, for example, a nano indenter (Nano IndenterTM XP / DCM) manufactured by MTS System.

<1-5. Underlayer>
The gas barrier film 1 of the present invention may have a base layer (smooth layer, primer layer, anchor layer) on the surface having the gas barrier layers 11 and 12. The underlayer is provided in order to flatten the rough surface of the film substrate 10 on which protrusions and the like exist. Such an underlayer is basically formed by curing an active energy ray curable material or a thermosetting material. The underlying layer may basically have the same configuration as the curable resin layer as long as it has the above function.

  Examples of the active energy ray curable material and the thermosetting material, and the formation method of the base layer are the same as those described in the column of the curable resin layer, and thus the description thereof is omitted here.

Although it does not restrict | limit especially as thickness of a base layer, The range of 0.1-10 micrometers is preferable.
The smooth layer may be used as the following anchor coat layer.

(Anchor coat layer)
On the surface of the film substrate 10 in the present invention, an anchor coat layer may be formed as an easy-adhesion layer for the purpose of improving adhesion (adhesion) with the barrier layer. Examples of the anchor coating agent used in this anchor coat layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. One type or two or more types can be used in combination. A commercially available product may be used as the anchor coating agent. Specifically, a siloxane-based UV curable polymer solution (manufactured by Shin-Etsu Chemical Co., Ltd., 3% isopropyl alcohol solution of “X-12-2400”) can be used.

Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on the film substrate 10 by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, and the like, and is applied by drying and removing the solvent, diluent and the like. can do. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state). A commercially available base material with an easy-adhesion layer may be used.
Alternatively, the anchor coat layer can be formed by a vapor phase method such as physical vapor deposition or chemical vapor deposition. For example, as described in JP-A-2008-142941, an inorganic film mainly composed of silicon oxide can be formed for the purpose of improving adhesion and the like.
The thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10.0 μm.

<1-6. Bleed-out prevention layer>
In the gas barrier film 1 of the present invention, a bleed-out prevention layer can be provided. When a film having a curable resin layer / smooth layer is heated, the bleed-out prevention layer moves unreacted oligomers and the like from the film base material 10 to the surface, so that the contact surface to the film base material 10 is provided. For the purpose of suppressing the phenomenon of contamination, the film substrate 10 is provided on the surface opposite to the curable resin layer / smooth layer. The bleed-out prevention layer may basically have the same configuration as the curable resin layer / smooth layer as long as it has this function.

The hard coat agent that can be included in the bleed-out prevention layer is a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule, or one polymerizable unsaturated in the molecule. Examples thereof include monounsaturated organic compounds having a group.
Here, as the polyunsaturated organic compound, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, 1,4-butanediol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dicyclopentanyl di (meth) acrylate, pentaerythritol tri (meta ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, ditrimethylolpropane Tiger (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate.

  Examples of unit unsaturated organic compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, and lauryl. (Meth) acrylate, stearyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( (Meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-eth Ciethoxy) ethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2- Examples include methoxypropyl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate. .

As other additives, a matting agent may be contained. As the matting agent, inorganic particles having an average particle diameter of about 0.1 to 5 μm are preferable.
As such inorganic particles, one or more of silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like can be used in combination. .

Here, the matting agent composed of inorganic particles is 2 parts by mass or more, preferably 4 parts by mass or more, more preferably 6 parts by mass or more and 20 parts by mass or less, preferably 100 parts by mass of the solid content of the hard coating agent. It is desirable that they are mixed in a proportion of 18 parts by mass or less, more preferably 16 parts by mass or less.
In addition, the bleed-out prevention layer may contain a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator, and the like as other components of the hard coat agent and the mat agent.

  Examples of such thermoplastic resins include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, methylcellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof. Vinyl resins such as polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, polycarbonates Examples thereof include resins.

Moreover, as a thermosetting resin, the thermosetting urethane resin which consists of an acrylic polyol and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, a silicon resin etc. are mentioned.
In addition, as an ionizing radiation curable resin, ionizing radiation (ultraviolet rays or electron beams) is irradiated to an ionizing radiation curable coating material in which one or more of photopolymerizable prepolymer or photopolymerizable monomer is mixed. Those that cure can be used. Here, as the photopolymerizable prepolymer, an acrylic prepolymer having two or more acryloyl groups in one molecule and having a three-dimensional network structure by crosslinking and curing is particularly preferably used. As this acrylic prepolymer, urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate and the like can be used. Further, as the photopolymerizable monomer, the polyunsaturated organic compounds described above can be used.

  Examples of the photopolymerization initiator include acetophenone, benzophenone, Michler's ketone, benzoin, benzylmethyl ketal, benzoin benzoate, hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl). ) -1-propane, α-acyloxime ester, thioxanthone and the like.

  The bleed-out prevention layer as described above is blended with a hard coat agent and other components as necessary, and is prepared as a coating solution using a diluent solvent as necessary. After coating on the surface by a conventionally known coating method, it can be formed by irradiating with ionizing radiation and curing. In addition, as a method of irradiating with ionizing radiation, ultraviolet rays in a wavelength region of preferably 100 to 400 nm, more preferably 200 to 400 nm, emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp or the like are irradiated. Alternatively, the irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator.

The thickness of the bleed-out prevention layer is 1 to 10 μm, preferably 2 to 7 μm. By making it 1 μm or more, it becomes easy to make the heat resistance as a film sufficient, and by making it 10 μm or less, it becomes easy to adjust the balance of optical properties of the smooth film, and the curable resin layer / smooth layer is transparent. The curl of the gas barrier film 1 when it is provided on one surface of the polymer film can be easily suppressed.
The gas barrier film 1 of the present invention can be further provided with functionalized layers such as another organic layer, a protective layer, a hygroscopic layer, and an antistatic layer as necessary.

<2. Gas barrier film manufacturing equipment>
Then, the manufacturing apparatus of the gas barrier film 1 is demonstrated.
As shown in FIG. 2, the gas barrier film 1 manufacturing apparatus 5 (hereinafter referred to as a gas barrier film manufacturing apparatus 5) includes a transport apparatus 50, a first gas barrier layer forming apparatus 51, and a second gas barrier layer forming apparatus. Device 52.

<2-1. Transport device>
The transport device 50 is a device that transports the film substrate 10 in the transport direction X.
The transport device 50 includes a delivery roller (original winding roller) 500 on the upstream side in the transport direction X and a winding roller 501 on the downstream side in the transport direction X.

The delivery roller 500 is a roller around which the film substrate 10 is wound, and is disposed rotatably.
The winding roller 501 is a roller for winding up the film substrate 10 on which the first gas barrier layer 11 and the second gas barrier layer 12 are formed, that is, the gas barrier film 1, and is rotatably disposed. ing. Note that a driving source (not shown) such as a motor for rotating the winding roller 501 is connected to the winding roller 501 in the present embodiment.

A plurality of transport rollers 503 are disposed along the transport direction X between the feed roller 500 and the take-up roller 501. Each of these transport rollers 503 is rotatably arranged, and transports the film substrate 10 in the transport direction X while applying a predetermined tension to the film substrate 10.
In addition, as the above conveying apparatus 50, a conventionally well-known conveying apparatus can be used.

<2-2. First gas barrier layer forming apparatus>
The first gas barrier layer forming apparatus 51 is a gas barrier layer forming unit in the present invention, and forms the first gas barrier layer 11 on the upper surface of the film substrate 10. As the first gas barrier layer forming apparatus 51, a conventionally known apparatus such as a vacuum plasma CVD apparatus can be used.

<2-3. Second gas barrier layer forming apparatus>
The second gas barrier layer forming apparatus 52 is configured to form the second gas barrier layer 12 on the upper surface of the film substrate 10, in the present embodiment, on the upper surface of the first gas barrier layer 11.
The second gas barrier layer forming apparatus 52 includes a droplet applying unit 520, a drying unit 521, and a modifying unit 522.

<2-3-1. Droplet application section>
The droplet applying unit 520 applies the above-described polysilazane coating solution 120 in the form of droplets to the upper surface of the film substrate 10.

The droplet applying unit 520 includes a chamber 520A and a droplet applying device 6 disposed in the chamber 520A.
The chamber 520 </ b> A maintains the interior in an atmosphere containing at least oxygen, so that the polysilazane is brought into contact with oxygen when the polysilazane coating solution 120 is applied. Here, the atmosphere containing oxygen is specifically an atmosphere containing oxygen at a concentration of 1% or more, and preferably an atmosphere containing oxygen at a concentration of 10% or more. In addition, from the viewpoint of surely modifying polysilazane in the modifying section described later, it is preferable to contact polysilazane with water in addition to oxygen when applying the polysilazane coating liquid 120. It may be included. Here, the atmosphere containing water is specifically an atmosphere containing water at a concentration of 20% or more, preferably an atmosphere containing water at a concentration of 50% or more.

  In the present embodiment, the droplet applying apparatus 6 applies the polysilazane coating solution 120 by a trace solvent coating method.

  Here, the “trace solvent coating method” in the present invention refers to forming a droplet by spraying a solution obtained by dissolving and / or dispersing a material in a solvent, or a liquid obtained by volatilizing the solvent in the droplet. Depositing droplets on a substrate or on a thin film provided on the substrate. Specifically, as a trace solvent coating method, ESD method (Electro Spray Deposition method: electrostatic spray deposition, electrostatic coating method), ESDUS method (Evaporative Spray Deposition from Ultra-dilute Solution method: ultra-dilute solution concentrated spray deposition method) ).

Hereinafter, in the present embodiment, the droplet applying device 6 will be described as applying the polysilazane coating solution 120 using the ESD method.
That is, the droplet coating apparatus 6 in the present embodiment is an apparatus for applying a spray by charging the polysilazane coating solution 120 by applying a voltage. For example, as shown in FIG. 3, a flat coating made of a conductor such as a metal is used. A support 60 is provided.

  This support body 60 supports the film base material 10 from the back surface side, and is arrange | positioned horizontally in this Embodiment. A capillary 61 is disposed at a position facing the support 60 (upward in the present embodiment).

  The capillary 61 is a fine tube filled with the polysilazane coating solution 120, and is disposed with the opening at the tip (hereinafter referred to as a spray port) facing the support 60. The spray port of the capillary 61 can send out the polysilazane coating solution 120, and the polysilazane coating solution 120 sent out from the spray port is formed into liquid droplets and dispersed as described later. It will land. The droplet immediately before landing is preferably in the form of aerosol particles, and specifically, it is preferably in the form of particles having a particle size of less than 1 μm.

  The capillary 61 can be made of a conductor such as metal. The inner diameter of the spray port of the capillary 61 is not particularly limited and can be appropriately set according to the flow rate of the polysilazane coating liquid 120, the size of the droplet to be formed, etc., but is preferably in the range of 10 to 300 μm, more Preferably it exists in the range of 30-50 micrometers. In addition, the distance Da from the spray port of the capillary 61 to the film formation surface (upper surface in the present embodiment) of the film substrate 10 may be set as appropriate so that the solvent from the polysilazane coating solution 120 can be volatilized well. it can. As the distance Da increases, the solvent evaporates and the droplets easily dry. However, since the droplets are widely distributed and the film formation area is enlarged, it takes time to form a desired layer thickness. From such a tendency, the distance Da is not particularly limited, but is preferably in the range of 3 to 20 cm, more preferably in the range of 5 to 10 cm. Only one capillary 61 may be provided in the droplet applying device 6, or a plurality of capillaries 61 may be provided in order to increase productivity.

The capillary 61 is supplied with the polysilazane coating solution 120 from the solution supply unit 62.
The solution supply unit 62 stores the polysilazane coating solution 120 and supplies it to the capillary 61, and can appropriately set the flow rate and speed of the supplied polysilazane coating solution 120. Note that the viscosity of the polysilazane coating solution 120 used by the droplet coating apparatus 6 is preferably 100 mPa · s or less, and more preferably 5 mPa · s or less. This viscosity is a value measured according to JIS Z 8803 with a viscometer DV-II + Pro (manufactured by Brookfield) at 25 ° C. Moreover, the solid content concentration of the polysilazane coating solution 120 used by the droplet coating apparatus 6 is preferably 2% by mass or less, and preferably in the range of 0.01 to 1.0% by mass.

Further, a linearly formed electrode 610 is disposed in the tube of the capillary 61 described above.
The voltage application units 650 and 651 are connected to the electrode 610 and the support 60 described above.

  The voltage application unit 650 applies a voltage to the electrode 610 in the capillary 61, and the voltage application unit 651 applies a voltage to the support 60, so that the polysilazane coating solution 120 in the capillary 61 and the film base on the support 60 are applied. The material 10 is charged to the opposite polarity. In the present embodiment, a positive voltage is applied to the electrode 610 of the capillary 61, and a negative voltage is applied to the support 60. However, instead of applying a negative voltage to the support 60, the support 60 may be grounded, or a negative voltage may be applied to the electrode 610 of the capillary 61 to apply a positive voltage to the support 60. . The voltage (V) to be applied is not particularly limited, and can be appropriately set according to the relationship between the distance Da from the spray port of the capillary 61 to the film substrate 10 and the spray amount of the polysilazane coating solution 120, preferably 5 It is in the range of ˜20 kV, more preferably in the range of 10 to 15 kV.

A control unit 65 is connected to the voltage application units 650 and 651 and the solution supply unit 62 described above.
The control unit 65 includes a CPU (Central Processing Unit), a RAM (Random Access Memory), a nonvolatile memory such as a hard disk, and the like, by reading and executing a control program stored in the nonvolatile memory, The operation of each part of the droplet applying device 6 is controlled. For example, the control unit 65 controls the voltage applied by the voltage application units 650 and 651, the liquid supply speed at which the solution supply unit 62 supplies liquid to the capillary 61, and the like.

  In the droplet applying apparatus 6 described above, as shown in FIG. 4, when the voltage applying units 650 and 651 apply a voltage between the electrode 610 of the capillary 61 filled with the polysilazane coating solution 120 and the support 60, The polysilazane coating solution 120 in the capillary 61 is charged with a positive polarity, and the film substrate 10 placed on the support 60 is charged with a negative polarity. In this state, when the polysilazane coating solution 120 is sent out from the capillary 61, the polysilazane coating solution 120 is repelled by the Coulomb force and split into droplets each having a positive charge. At this time, the solvent in the polysilazane coating solution 120 is volatilized by the splitting, and the charge density is increased by the volatilization. Therefore, the droplets are further repelled and repeat the splitting. Then, the droplets which are finely divided by repeating the division are attracted to the film substrate 10 having a negative polarity, and adhere to the film substrate 10 to form a coating film. Since the solvent is almost volatilized by the time it reaches the film substrate 10, there is almost no solvent in the formed organic layer, and a dry organic layer is formed.

<2-3-2. Drying section>
As shown in FIG. 2 described above, the drying unit 521 forms a polysilazane layer by drying the coating solution applied to the upper surface of the film substrate 10 by the droplet applying unit 520, that is, the coating film.
The drying unit 521 is a conventionally known drying apparatus, and drying processing conditions (temperature, humidity, processing time, etc.) are appropriately set according to a method such as heat treatment to be applied. Here, the temperature of the drying process is preferably a high temperature from the viewpoint of rapid processing. However, considering the heat damage to the film substrate 10 which is a resin film, the temperature to be applied is preferably set appropriately in consideration of the time of the drying process. For example, when a polyethylene terephthalate film (hereinafter abbreviated as PET film) having a glass transition temperature (Tg) of 70 ° C. is used as the film substrate 10, the drying treatment temperature is preferably set to 150 ° C. or less.
The time for the drying treatment is preferably set to a short time so that the solvent is removed and the thermal damage to the substrate is reduced. If the drying treatment temperature is 150 ° C. or lower, the drying treatment time is set within 30 minutes. It is preferable to do.
The atmosphere during the drying treatment preferably contains oxygen. The atmosphere is preferably controlled at a relatively low humidity, but the humidity in a low humidity environment varies depending on the temperature. Therefore, the relationship between the temperature and the humidity is indicated by a dew point temperature. A preferable dew point temperature is 4 ° C. or less (temperature 25 ° C./humidity 25%), a more preferable dew point temperature is −8 ° C. (temperature 25 ° C./humidity 10%) or less, and a more preferable dew point temperature is −31 ° C. (temperature 25 ° C./temperature). Humidity 1%) or less. Moreover, in order to make it easy to remove moisture, the drying unit 521 may perform drying under reduced pressure. The pressure in vacuum drying can be selected in the range of normal pressure to 0.1 MPa.

<2-3-3. Reformer>
The modifying unit 522 modifies the polysilazane layer to form the second gas barrier layer 12, and performs modification by irradiating the polysilazane layer with ultraviolet rays or plasma in an atmosphere of low oxygen concentration. It is like that.

The reformer 522 includes a chamber 522A and an irradiation device 522B disposed in the chamber 522A.
The chamber 522A is configured to maintain the internal atmosphere at a low oxygen concentration. Here, the low oxygen concentration specifically means an atmosphere containing oxygen at a concentration of less than 1% or not containing oxygen. More specifically, the oxygen concentration in the environment irradiated with vacuum ultraviolet light (VUV) is preferably in the range of 300 ppm or more and less than 10000 ppm (1%), more preferably in the range of 500 to 5000 ppm. . By adjusting the oxygen concentration within such a range, it is possible to prevent the generation of the oxygen-rich gas barrier layer 12 and to prevent the deterioration of the barrier property. As the gas other than oxygen in the atmosphere at the time of irradiation with vacuum ultraviolet light (VUV), it is preferable to use a dry inert gas, and it is particularly preferable to apply dry nitrogen gas from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the chamber 522A and changing the flow rate ratio.

The irradiation device 522B modifies the polysilazane layer by irradiation with ultraviolet rays or plasma.
As the chamber 522A and the irradiation device 522B as described above, conventionally known ones can be used.
Hereinafter, the reforming process performed by the reforming unit 522 will be described.

<2-3-3 (1). Modification of polysilazane>
The modification of polysilazane in the present invention refers to a reaction that converts part or all of a polysilazane compound into silicon oxide or silicon oxynitride.
In this modification treatment, from the viewpoint of adaptation to the film substrate 10, a conversion reaction using ultraviolet light is preferably used so that a conversion reaction at a lower temperature is possible.

<2-3-3 (2). Vacuum ultraviolet light irradiation treatment>
In the gas barrier film manufacturing apparatus 5 in the present invention, the polysilazane coating film (polysilazane layer) 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, that is, the second gas barrier layer 12 becomes dense. Irradiation with ultraviolet light is effective at any time after the formation of the coating film.

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

In the irradiation with vacuum ultraviolet light, it is preferable to appropriately set the irradiation intensity and the irradiation time within a range in which the film substrate 10 carrying the pre-modified polysilazane layer to be irradiated is not damaged.
Taking the case where a plastic film is used as the film substrate 10, for example, a 2 kW (80 W / cm × 25 cm) lamp is used as the light source of the irradiation device 522B, and the strength of the surface of the film substrate 10 is 20 to 300 mW / cm. ² , Preferably, the distance between the substrate and the ultraviolet irradiation lamp is set so as to be within the range of 50 to 200 mW / cm ² , and irradiation can be performed within the range of 0.1 second to 10 minutes.

  In general, when the temperature of the film substrate 10 during the ultraviolet irradiation treatment is 150 ° C. or higher, when the film substrate 10 is a plastic film or the like, the film substrate 10 is deformed or its strength is deteriorated. The characteristics of the film substrate 10 will be impaired. However, in the case of a film having high heat resistance such as polyimide, a modification treatment at a higher temperature is possible. Therefore, there is no general upper limit as 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 the film substrate 10.

Examples of such ultraviolet ray generating means, that is, a light source 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 ultraviolet light from the generation source is reflected by the reflector and then applied to the polysilazane layer from the viewpoint of improving efficiency and uniform irradiation. It is desirable.
The ultraviolet irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the film substrate 10 to be used. When the film substrate 10 having a polysilazane layer is a long film, it is converted into ceramics by continuously irradiating ultraviolet rays in the drying zone having the ultraviolet ray generation source as described above while being conveyed. be able to. The time required for ultraviolet irradiation depends on the composition and concentration of the film substrate 10 and the polysilazane modified layer (polysilazane layer, second gas barrier layer 12) to be used, but is generally 0.1 seconds to 10 minutes, preferably Within the range of 0.5 seconds to 3 minutes.

As described above, the preferred polysilazane layer modification method in the present invention is treatment by vacuum ultraviolet light irradiation. Here, 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 bonds the atoms to the photon process. This is a method of forming a silicon oxide film at a relatively low temperature by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by the action of photons only. As a vacuum ultraviolet light source required for this, a rare gas excimer lamp is preferably used.
Note that rare gas atoms such as Xe, Kr, Ar, and Ne are called inert gases because they are chemically bonded and do not form molecules. However, rare gas atoms (excited atoms) that have gained energy by discharge or the like can be combined with other atoms to form molecules.

<2-3-3 (3). Plasma treatment>
Moreover, in the gas barrier film manufacturing apparatus 5 in this invention, the polysilazane coating film (polysilazane layer) from which the water | moisture content was removed may be modified | reformed by the process by plasma irradiation.
Plasma treatment that can be used as the modification treatment in the present invention includes capacitively coupled plasma (CCP), magnetron combined plasma (JP-A-11-61416, etc.), inductively coupled plasma (ICP), and microwave plasma (JP 2006-269151 or JP-A-2007-317499, etc.) can be used, but at or near atmospheric pressure as described in Japanese Patent No. 4000830 and Japanese Patent No. 4433680 A plasma processing apparatus for forming plasma can also be preferably used. The atmospheric pressure or the pressure in the vicinity thereof is about 20 to 110 kPa, and 93 to 104 kPa is preferable in order to obtain a good effect described in the present invention. The atmospheric pressure plasma CVD method does not need to be reduced in pressure and has high productivity as compared with the plasma CVD method under vacuum, and also has a high reforming speed due to high plasma density, and further, normal CVD. Compared with the conditions of the method, under the high pressure condition under atmospheric pressure, the mean free path of gas is very short, so that a very homogeneous reforming effect can be obtained.
In the case of atmospheric pressure plasma treatment, nitrogen gas or 18th group atom of the periodic table, specifically helium, neon, argon, krypton, xenon, radon or the like is used as the discharge gas. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.
Further, a gas such as CO, CO ₂ , or N ₂ may be added to the atmosphere for generating plasma. Since these gases strongly generate light having a wavelength of 150 to 180 nm in plasma, in addition to modification by radicals, ions, and electrons formed by plasma, modification by strong vacuum ultraviolet light can be simultaneously performed.

<3. Manufacturing method of gas barrier film>
Then, the manufacturing method of the gas barrier film 1 using the above gas barrier film manufacturing apparatus 5 is demonstrated.

  First, in a state where the transport device 50 transports the film base material 10 in the transport direction X, the first gas barrier layer forming device 51 forms the first gas barrier layer 11 on the upper surface of the film base material 10 ( First gas barrier layer forming step).

  Next, the second gas barrier layer forming device 52 forms the second gas barrier layer 12 in the region where the first gas barrier layer 11 is formed on the upper surface of the film substrate 10 (second gas). Barrier layer forming step).

  Specifically, in the second gas barrier layer forming step, first, the droplet applying unit 520 forms the polysilazane coating solution 120 into droplets by an electrostatic coating method in an atmosphere containing at least oxygen. It is applied to the upper surface (droplet application process). Next, the drying unit 521 forms a polysilazane layer by drying the coating solution applied to the upper surface of the film substrate 10, that is, the coating film (drying step). Next, the reforming unit 522 performs ultraviolet irradiation or plasma irradiation on the polysilazane layer in an atmosphere having a low oxygen concentration, thereby modifying the polysilazane layer to form the second gas barrier layer 12 (modification step). .

  And the above-mentioned 1st gas barrier layer formation process and the 2nd gas barrier layer formation process are performed in this order with respect to each area | region of the film base material 10, The film base material 10 over the whole area of a length direction A first gas barrier layer 11 and a second gas barrier layer 12 are formed on the upper surface of the substrate, and the gas barrier film 1 is manufactured.

<4. Electronic device to which gas barrier film is applied>
The gas barrier film 1 of the present invention is preferably used as a film for an organic element device. Examples of the organic element device include an organic electroluminescence element (hereinafter abbreviated as an organic EL element), an organic photoelectric conversion element, and a liquid crystal element.

<Organic EL panel as an electronic device>
The gas barrier film 1 of the present invention can be used as a sealing film for sealing solar cells, liquid crystal display elements, organic EL elements and the like.

  An example of the organic EL panel P which is an electronic device using the gas barrier film 1 as a sealing film is shown in FIG.

  As shown in FIG. 5, the organic EL panel P is formed on the gas barrier film 1, the transparent electrode 100 such as ITO formed on the gas barrier film 1, and the transparent electrode 100. An organic EL element 101 that is a main body of the electronic device, and a counter film 102 disposed via an adhesive layer 103 so as to cover the organic EL element 101. The transparent electrode 100 may form part of the organic EL element 101.

  A transparent electrode 100 and an organic EL element 101 are formed on the surface of the gas barrier film 1 on the second gas barrier layer 12 side.

  In this organic EL panel P, since the organic EL element 101 is suitably sealed by the gas barrier film 1 so as not to be exposed to water vapor and hardly deteriorated, the organic EL panel P can be used for a long time. It becomes possible, and the lifetime of the organic EL panel P is extended.

  The counter film 102 may be a gas barrier film according to the present invention in addition to a metal film such as an aluminum foil. When a gas barrier film is used as the counter film 102, the surface on which the second gas barrier layer 12 is formed may be attached to the organic EL element 101 with the adhesive layer 103.

As described above, according to the present embodiment, since the polysilazane coating liquid 120 is applied as droplets to one surface of the resin film substrate 10 in an atmosphere containing at least oxygen, the polysilazane is added to the O in the atmosphere. _The film substrate 10 can be landed by positive contact with ₂ etc. Therefore, by drying the polysilazane coating solution 120 applied to the film substrate 10 to form a polysilazane layer, the polysilazane in the polysilazane layer can be brought into a state bonded to O _{2 by} hydrogen bonding or the like. Therefore, by performing a modification process on the polysilazane layer formed in this way, the initial arrival position of ultraviolet energy or plasma energy (or ions or radicals generated by ultraviolet or plasma) in this modification process, That is, even when the modification of the polysilazane layer proceeds in order from the outermost surface and the gas barrier property becomes higher, O ₂ is supplied to the polysilazane in the region inside the outermost surface (region on the film base material 10 side), The formation of unstable polysilazane will be prevented. Therefore, unlike the conventional case, it is possible to prevent a trace amount of H ₂ O from passing through the outermost surface of the second gas barrier layer 12 and reacting with the unstable polysilazane, so that the performance of the gas barrier film 1 is deteriorated. Can be prevented, and resistance to moist heat can be improved.
In addition, unlike the case of modifying the polysilazane layer while actively supplying O ₂ by irradiating plasma or ultraviolet light in an O ₂ atmosphere, the energy of plasma or ultraviolet light is not absorbed by O ₂ . The polysilazane layer can be reliably modified to improve the gas barrier property and the processing time can be shortened.

In addition, since the polysilazane coating solution 120 is applied by a trace solvent coating method in the droplet coating step, the droplets can be dispersed and uniformly coated. In addition, since the droplet diameter can be reduced by supplying the droplets to the substrate while volatilizing the solvent, the solute concentration in the droplets increases and the specific surface area of the droplets increases. Become. Therefore, since the polysilazane in each droplet can be reliably brought into contact with O ₂ or the like in the atmosphere and landed on the film substrate 10, it is possible to reliably improve wet heat resistance. In addition, since the polysilazane layer having a uniform layer thickness and thus the second gas barrier layer 12 can be formed by dispersing and uniformly applying the droplets, the layer thickness of the second gas barrier layer 12 can be increased. Compared with a non-uniform case, the gas barrier property can be improved.

In addition, since the polysilazane coating solution 120 is applied by an electrostatic coating method such as a trace solvent coating method in the droplet coating step, the droplets can be reliably and uniformly dispersed. Therefore, since the polysilazane in the droplet can be reliably brought into contact with O ₂ or the like in the atmosphere and landed on the film substrate 10, the wet heat resistance can be more reliably improved. In addition, since the polysilazane layer having a uniform layer thickness and thus the second gas barrier layer 12 can be formed by dispersing and uniformly applying the droplets, the layer thickness of the second gas barrier layer 12 can be increased. Compared with the non-uniform case, the gas barrier property can be further improved.

Moreover, since the thickness of the second gas barrier layer 12 is formed to be 50 nm or more, the gas barrier performance of the gas barrier film 1 can be further improved. In addition, when the layer thickness of the second gas barrier layer 12 is formed to be 50 nm or more in this way, when the polysilazane layer is modified to form the second gas barrier layer 12, the polysilazane inside the polysilazane layer is reduced. although O ₂ is not sufficiently supplied there is a risk, in the present invention, as described above, the polysilazane in the polysilazane coating liquid 120 is positively contacted with O ₂ and the like in the atmosphere in the droplet applying process film base Since the material 10 can be landed and the formation of unstable polysilazane can be prevented, the disadvantages of increasing the thickness of the second gas barrier layer 12 can be eliminated.

Moreover, before the droplet applying process, with respect to the upper surface of the film substrate 10, since the water vapor transmission rate to form a ^{1 × 10 -1 g / m 2} / 24h or less of the first gas barrier layer 11, the gas The gas barrier performance of the barrier film 1 can be further improved. When the first gas barrier layer 11 is formed in this way, when the polysilazane layer is modified to form the second gas barrier layer 12, the supply of O ₂ from the film substrate 10 side to the polysilazane layer is performed. In the present invention, as described above, the polysilazane in the polysilazane coating solution 120 is positively brought into contact with O ₂ or the like in the atmosphere to land on the film substrate 10 as described above. And the formation of the unstable polysilazane can be prevented, so that the disadvantages due to the formation of the first gas barrier layer 11 can be eliminated.

[Modification]
Then, the modification of the said embodiment is demonstrated. In addition, the same code | symbol is attached | subjected to the component similar to said embodiment, and the description is abbreviate | omitted.

As shown in FIG. 2, the gas barrier film manufacturing apparatus 5 </ b> A in the present modification includes a droplet applying apparatus 6 </ b> A instead of the droplet applying apparatus 6.
This droplet coating apparatus 6A is configured to apply the polysilazane coating solution 120 using the ESDUS method. Here, the ESDUS method is a method in which an aerosol of a solution in which a material is dissolved or dispersed in a solvent is formed, and the aerosol is heated and sprayed to form a thin film layer on a substrate. One of the features of the ESDUS method is that a thin film can be formed even when the material concentration in the solution is extremely low.

The droplet applying apparatus 6A includes a flat support 67A as shown in FIG. 6, for example.
The support 67A supports the film base 10 from the back side. The support 67A is disposed inside the chamber 65A.

  The chamber 65A has an opening at a position facing the surface of the film substrate 10 supported by the support 67A (the surface on the side opposite to the support 67A), and the opening has a cylindrical chamber 64A. One end of is inserted.

  The inside of the chamber 64A is heated by the heating unit 66A. The chamber 64A is formed in a bottomless cylindrical shape (a cylindrical shape with both ends open), and the opening at one end is tapered and inserted into the chamber 65A, and faces the film base 10. Yes. In addition, an aerosol forming portion 63A connected to the gas supply portion 61A and the solution supply portion 62A is fitted into the opening at the other end of the chamber 64A.

The gas supply unit 61A supplies the carrier gas to the aerosol forming unit 63A. However, the gas supply unit 61A may directly supply the carrier gas also to the chamber 64A. As the carrier gas, a gas such as nitrogen, argon, helium, or air can be used.
The solution supply unit 62A stores the polysilazane coating solution 120 and sends it to the aerosol forming unit 63A.

  The aerosol forming unit 63A floats the supplied polysilazane coating liquid 120 as liquid particles in the carrier gas to form an aerosol. The aerosol forming means by the aerosol forming portion 63A is not particularly limited, and conventionally known means can be used. For example, the aerosol forming unit 63A may form the aerosol by mixing the solution and the carrier gas and then spraying from the sprayer at a high speed. Alternatively, the solution may be atomized using an ultrasonic vibrator and suspended in the carrier gas. An aerosol may be formed.

  In the droplet applying apparatus 6A described above, when the aerosol forming unit 63A forms an aerosol and sprays it into the chamber 64A, the sprayed aerosol is a carrier gas (a carrier gas used for aerosol formation in the aerosol forming unit 63A, Or it is conveyed by the carrier gas directly supplied to the chamber 64A) and passes through the chamber 64A heated by the heating unit 66A. At this time, the solvent in the aerosol particles is vaporized, and fine particles of the organic material are generated. The fine particles of the organic material are further transported into the chamber 65A by the transport gas and adhere onto the film substrate 10 to form a coating film of the polysilazane coating liquid 120. However, also in the droplet applying apparatus 6A using such an ESDUS method, the aerosol may be sprayed by applying the ESD method to charge the aerosol particles and the film base material 10 to opposite characteristics. In this case, finer particles can be formed by repulsion of electric charges.

  The same effect as the gas barrier film manufacturing apparatus 5 in the above embodiment can also be obtained by the gas barrier film manufacturing apparatus 5A having the droplet applying apparatus 6A as described above.

  It should be noted that the detailed configuration of each component of the gas barrier film 1 and the detailed configuration and detailed operation of each component of the gas barrier film manufacturing apparatus 5 in the above-described embodiment and modification do not depart from the spirit of the present invention. Of course, it can be appropriately changed within the range.

For example, in the above-described embodiments and modifications, the liquid droplet application unit 520 (the liquid droplet application apparatus 6 and 6A) has been described as applying the polysilazane coating liquid 120 to the upper surface of the film substrate 10 by a trace solvent coating method. However, it is good also as spray-coating by the 2 fluid spray method etc. Also in this case, since the droplets can be dispersed and uniformly applied, a polysilazane layer having a uniform layer thickness, and thus the second gas barrier layer 12 can be formed. Therefore, the gas barrier property can be improved as compared with the case where the thickness of the second gas barrier layer 12 is not uniform. Here, when the polysilazane coating solution 120 is spray-coated, it is preferable that the polysilazane coating solution 120 is spray-coated while being heated and dried. In this case, the particle size of the droplets can be further reduced, and the polysilazane can be more positively brought into contact with O ₂ or the like in the atmosphere and landed on the film substrate 10. Therefore, since formation of unstable polysilazane can be reliably prevented, the performance of the gas barrier film 1 can be surely prevented from being deteriorated, and the wet heat resistance can be further improved. As a two-fluid spray coating method, for example, as disclosed in FIG. 1 of JP-A-2001-297876, a method of forming a film by spraying a solution from a nozzle onto a substrate can be used. As a method for further miniaturizing droplets generated by the two-fluid spray method, a method described in Japanese Patent No. 3541294 (a method in which a droplet is heated and dried to vaporize a solvent) or the above-described electrostatic coating method (ESD method). ) Can be used. In order to form a uniform and flat thin film by the two-fluid spray method, it is preferable that variations in the number of droplets sprayed from the nozzle per unit volume and the size of the droplets are small. The spraying of the coating liquid may be performed in a state where the relative position between the substrate and the nozzle is kept constant, and the relative position between the substrate and the nozzle is moved by moving at least one of the substrate and the nozzle. It may be performed while fluctuating.

  In addition, the first gas barrier layer 11 and the second gas barrier layer 12 have been described as being formed on one surface (upper surface) of the film substrate 10, but are formed on both surfaces (upper surface and lower surface). It's also good.

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

<Production of gas barrier film>
[Preparation of substrate]
As a film substrate, a 125 μm thick polyester film (extra-low heat yield PET Q83, manufactured by Teijin DuPont Films Ltd.) with easy adhesion processing on both sides was used. An out-prevention layer having a smooth layer formed on the opposite surface was produced as a “substrate” of the gas barrier film. The gas barrier performance (water vapor permeability) of this substrate was measured by the same method as described later in “Measurement of water vapor permeability A” and [Measurement of water vapor permeability B]. was ^1g / m 2 / 24h.

<Formation of bleed-out prevention layer>
A UV curable organic / inorganic hybrid hard coat material OPSTAR Z7535 manufactured by JSR Corporation was applied to one side of the film substrate by a die coater under a condition that the layer thickness after drying was 4 μm, and then dried at 80 ° C., 3 ° C. Drying was performed for minutes, and a high pressure mercury lamp was used in an air atmosphere, and curing treatment was performed under curing conditions of 1.0 J / cm ² to form a bleed-out prevention layer.

<Smooth layer formation>
Next, a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation was applied to the opposite surface of the film substrate with a die coater under the condition that the layer thickness after drying was 4 μm, and then the drying condition 80 Drying was performed at 3 ° C. for 3 minutes, and a high pressure mercury lamp was used in an air atmosphere, and a curing treatment was performed under curing conditions of 1.0 J / cm ² to form a smooth layer. The obtained smooth layer had a maximum cross-sectional height Rt (p) of 16 nm. This maximum cross-sectional height (surface roughness) is calculated from an uneven cross-sectional curve continuously measured with a detector having a stylus with a minimum tip radius using an AFM (Atomic Force Microscope). The measurement was performed a number of times in a section having a measurement direction of 30 μm with a stylus, and the average roughness related to the amplitude of fine irregularities was obtained.

[Production of gas barrier film (1)]
(Preparation of polysilazane coating solution)
Dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (Aquamica NN120-20; manufactured by AZ Electronic Materials Co., Ltd.) and 5% by mass of amine catalyst (N, N, N ′, N′-tetramethyl- 1,6-diaminohexane) and a dibutyl ether solution containing 20% by mass of perhydropolysilazane (AQUAMICA NAX120-20; manufactured by AZ Electronic Materials Co., Ltd.) at a ratio of 4: 1, A polysilazane coating solution was prepared with dibutyl ether so that the solid content was 10% by mass. The obtained coating liquid was 1% by mass (solid content) of the amine catalyst.

(Application of polysilazane coating solution, drying)
The polysilazane coating solution prepared above is applied on the smooth layer of the substrate under the condition that the layer thickness after drying is 100 nm, and dried at 100 ° C. for 2 minutes in an atmosphere with an oxygen concentration of 21% to provide a polysilazane layer. A sample was obtained. The application was performed at room temperature using a spin coater.

(Modification process)
The sample on which the polysilazane layer is formed is fixed on the operation stage of the following reforming treatment apparatus, and then the reforming treatment is performed under the following conditions to form the polysilazane layer as a gas barrier layer (second gas barrier in the above embodiment). Gas barrier film (1). The “Pass number” in the modification treatment condition is the number of times that the sample passes through the excimer light (ultraviolet) irradiation region in modifying the polysilazane layer.

《Reforming treatment equipment》
Apparatus: Ex D irradiation apparatus MODEL manufactured by M.D. Com: MECL-M-1-200
Wavelength: 172 nm
Lamp filled gas: Xe

<Reforming treatment conditions>
Excimer light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 1mm
Stage heating temperature: 70 ° C
Oxygen concentration in the irradiation device: 0.1%
Film transport speed: 0.6 m / min
Pass number: 1 time Excimer irradiation time: 5 seconds Energy irradiated to polysilazane coating film at 1 Pass: 3.0 J / cm ²

[Production of gas barrier film (2)]
(Preparation of polysilazane coating solution)
Dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (Aquamica NN120-20; manufactured by AZ Electronic Materials Co., Ltd.) and 5% by mass of amine catalyst (N, N, N ′, N′-tetramethyl- 1,6-diaminohexane) and a dibutyl ether solution containing 20% by mass of perhydropolysilazane (AQUAMICA NAX120-20; manufactured by AZ Electronic Materials Co., Ltd.) at a ratio of 4: 1, A polysilazane coating solution was prepared with dibutyl ether so that the solid content was 1.0% by mass. The obtained coating liquid was 1% by mass (solid content) of the amine catalyst.

(Application of polysilazane coating solution, drying, modification)
The polysilazane coating solution prepared above was applied on the same smooth layer as the gas barrier film (1) under the following coating conditions and dried at 100 ° C. for 2 minutes in an atmosphere with an oxygen concentration of 21%. A sample provided with a polysilazane layer was obtained. For the application, a two-fluid spray film forming apparatus manufactured by Asahi Sunac Corporation was used.
Thereafter, the modification treatment was performed in the same manner as the gas barrier film (1) to produce the gas barrier film (2).

<< Application conditions (two-fluid spray method) >>
Spray flow rate from nozzle: 1.50 g / min
Air pressure during liquid feeding: 0.1 MPa
Relative speed between nozzle and substrate: 0.5m / sec
Distance from nozzle spray port to substrate: 50 mm
Oxygen concentration in the coating atmosphere: 21%
Temperature of application atmosphere: 25 ° C

[Production of gas barrier film (3)]
(Preparation of polysilazane coating solution)
Dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (Aquamica NN120-20; manufactured by AZ Electronic Materials Co., Ltd.) and 5% by mass of amine catalyst (N, N, N ′, N′-tetramethyl- 1,6-diaminohexane) and a dibutyl ether solution containing 20% by mass of perhydropolysilazane (AQUAMICA NAX120-20; manufactured by AZ Electronic Materials Co., Ltd.) at a ratio of 4: 1, A polysilazane coating solution was prepared with dibutyl ether so that the solid content was 1.0% by mass. The obtained coating liquid was 1% by mass (solid content) of the amine catalyst.

(Application of polysilazane coating solution, drying, modification)
The polysilazane coating solution prepared above was applied on the same smooth layer as the gas barrier film (1) under the following coating conditions and dried at 100 ° C. for 2 minutes in an atmosphere with an oxygen concentration of 21%. A sample provided with a polysilazane layer was obtained. For coating, a droplet coating apparatus using the ESDUS method was used.
Thereafter, a modification treatment was performed in the same manner as in the gas barrier film (1) to produce a gas barrier film (3).

<< Application conditions (ESDUS method) >>
Spray flow rate from nozzle: 1.50 g / min
Air pressure during liquid feeding: 0.1 MPa
Relative speed between nozzle and substrate: 0.5m / sec
Distance from nozzle spray port to substrate: 50 mm
Oxygen concentration in the coating atmosphere: 21%
Temperature of coating atmosphere: 70 ° C

[Production of gas barrier film (4)]
(Preparation of polysilazane coating solution)
Dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (Aquamica NN120-20; manufactured by AZ Electronic Materials Co., Ltd.) and 5% by mass of amine catalyst (N, N, N ′, N′-tetramethyl- 1,6-diaminohexane) and a dibutyl ether solution containing 20% by mass of perhydropolysilazane (AQUAMICA NAX120-20; manufactured by AZ Electronic Materials Co., Ltd.) at a ratio of 4: 1, A polysilazane coating solution was prepared with dibutyl ether so that the solid content was 1.0% by mass. The obtained coating liquid was 1% by mass (solid content) of the amine catalyst.

(Application of polysilazane coating solution, drying, modification)
The polysilazane coating solution prepared above was applied on the same smooth layer as the gas barrier film (1) under the following coating conditions and dried at 100 ° C. for 2 minutes in an atmosphere with an oxygen concentration of 21%. A sample provided with a polysilazane layer was obtained. For coating, a droplet coating apparatus using an ESD method was used.
Thereafter, a modification treatment was performed in the same manner as in the gas barrier film (1) to produce a gas barrier film (4).

<< Application conditions (ESD method) >>
Inner diameter of capillary spray port: 40 μm
Liquid feeding speed to capillary: 10 μl / min
Distance from spray port to substrate: 5cm
Voltage applied between capillary and substrate: 10 kV
Oxygen concentration in the coating atmosphere: 21%

[Production of gas barrier film (5)]
A gas barrier layer (the first gas barrier layer in the above embodiment) was formed on the smooth layer of the same substrate as the gas barrier film (1) by the plasma CVD method under the following film forming conditions.
Thereafter, in the same manner as the gas barrier film (1), a polysilazane layer is formed and modified on the barrier layer, and the polysilazane layer is used as a gas barrier layer (second gas barrier layer in the above-described embodiment). A barrier film (5) was produced. Before the formation of the polysilazane layer, the gas barrier performance (water vapor permeability) of the laminate of the base material and the barrier layer is determined by “measurement of water vapor permeability A” and “measurement of water vapor permeability B” described later. was measured by the same method, the water vapor transmission rate by either method was 0.05g ^/ m 2 ^/ 24h.

(Deposition conditions by CVD method)
A SiOC film having a thickness of 50 nm was formed on the substrate using a vacuum plasma CVD apparatus. This vacuum plasma CVD apparatus includes a flat plate-like susceptor that supports a substrate from below, and a flat plate-like cathode electrode disposed above the susceptor so as to be parallel to the susceptor. Plasma is generated by applying a voltage between the cathode electrode and the susceptor while supplying source gas from a plurality of nozzles provided. As a power source for applying a voltage to the cathode electrode, a 27.12 MHz high frequency power source was used, and the distance between the electrodes (the distance between the cathode electrode and the susceptor) was 20 mm. Hexamethyldisiloxane (HMDSO) with a flow rate of 7.5 sccm was used as a source gas, and was introduced into the vacuum chamber together with an oxygen gas with a flow rate of 30 sccm. The substrate temperature at the start of film formation was set to 100 ° C., and the atmospheric pressure during film formation was set to 30 Pa.
Subsequently, using the same vacuum plasma CVD apparatus, a SiO ₂ film having a thickness of 50 nm is formed on the SiOC film, and a gas barrier is formed by these films (a SiOC film having a thickness of 50 nm and a SiO ₂ film having a thickness of 50 nm). A layer was formed. A 27.12 MHz high frequency power source was used as the power source, and the distance between the electrodes was 20 mm. Silane gas with a flow rate of 7.5 sccm was used as the source gas, and was introduced into the vacuum chamber together with oxygen gas with a flow rate of 30 sccm. The substrate temperature at the start of film formation was set to 100 ° C., and the atmospheric pressure during film formation was set to 30 Pa.

[Production of gas barrier film (6)]
(Preparation of polysilazane coating solution)
Dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (Aquamica NN120-20; manufactured by AZ Electronic Materials Co., Ltd.) and 5% by mass of amine catalyst (N, N, N ′, N′-tetramethyl- 1,6-diaminohexane) and a dibutyl ether solution containing 20% by mass of perhydropolysilazane (AQUAMICA NAX120-20; manufactured by AZ Electronic Materials Co., Ltd.) at a ratio of 4: 1, A polysilazane coating solution was prepared with dibutyl ether so that the solid content was 1.0% by mass. The obtained coating liquid was 1% by mass (solid content) of the amine catalyst.

(Application of polysilazane coating solution, drying, modification)
A gas barrier film (6) was produced in the same manner as the gas barrier film (5) except that the polysilazane layer was formed using the polysilazane coating solution prepared above under the following coating conditions. For coating, a droplet coating apparatus using an ESD method was used.

<< Application conditions (ESD method) >>
Inner diameter of capillary spray port: 40 μm
Liquid feeding speed to capillary: 10 μl / min
Distance from spray port to substrate: 5cm
Voltage applied between capillary and substrate: 10 kV
Oxygen concentration in the coating atmosphere: 21%

[Production of gas barrier film (7)]
A gas barrier film (7) was produced in the same manner as the gas barrier film (6) except that the spraying time was increased and the thickness of the polysilazane layer was changed to 800 nm.

[Production of gas barrier film (8)]
A gas barrier film (8) was produced in the same manner as the gas barrier film (6) except that the conditions for forming the barrier layer by plasma CVD were as follows. Before the formation of the polysilazane layer, the gas barrier performance (water vapor permeability) of the laminate of the base material and the barrier layer is determined by “measurement of water vapor permeability A” and “measurement of water vapor permeability B” described later. was measured by the same method, the water vapor transmission rate by any of the methods was 0.005g ^/ m 2 ^/ 24h.

(Deposition conditions by CVD method)
A SiOC film having a thickness of 50 nm was formed on the substrate using the same vacuum plasma CVD apparatus as that used for the production of the gas barrier film (5). A 27.12 MHz high frequency power source was used as the power source, and the distance between the electrodes was 20 mm. Hexamethyldisiloxane (HMDSO) with a flow rate of 7.5 sccm was used as a source gas, and was introduced into the vacuum chamber together with an oxygen gas with a flow rate of 30 sccm. The substrate temperature at the start of film formation was set to 100 ° C., and the atmospheric pressure during film formation was set to 30 Pa.
Subsequently, a SiO ₂ film having a thickness of 50 nm was formed on the SiOC film using the same vacuum plasma CVD apparatus. A 27.12 MHz high frequency power source was used as the power source, and the distance between the electrodes was 20 mm. Silane gas with a flow rate of 7.5 sccm was used as the source gas, and was introduced into the vacuum chamber together with oxygen gas with a flow rate of 30 sccm. The substrate temperature at the start of film formation was set to 100 ° C., and the atmospheric pressure during film formation was set to 30 Pa.
Subsequently, a SiOC film having a thickness of 200 nm was formed on the substrate using the same vacuum plasma CVD apparatus. A 27.12 MHz high frequency power source was used as the power source, and the distance between the electrodes was 20 mm. Hexamethyldisiloxane (HMDSO) with a flow rate of 7.5 sccm was used as a source gas, and was introduced into the vacuum chamber together with an oxygen gas with a flow rate of 30 sccm. The substrate temperature at the start of film formation was set to 100 ° C., and the atmospheric pressure during film formation was set to 30 Pa.
Subsequently, using the same vacuum plasma CVD apparatus, a SiO ₂ film having a thickness of 50 nm was formed on the SiOC film, and these films (a SiOC film having a thickness of 50 nm, a SiO ₂ film having a thickness of 50 nm, and a thickness of 200 nm were formed). The gas barrier layer was formed by a SiOC film and a SiO ₂ film having a thickness of 50 nm. A 27.12 MHz high frequency power source was used as the power source, and the distance between the electrodes was 20 mm. Silane gas with a flow rate of 7.5 sccm was used as the source gas, and was introduced into the vacuum chamber together with oxygen gas with a flow rate of 30 sccm. The substrate temperature at the start of film formation was set to 100 ° C., and the atmospheric pressure during film formation was set to 30 Pa.

[Production of gas barrier film (9)]
(Preparation of polysilazane coating solution)
Dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (Aquamica NN120-20; manufactured by AZ Electronic Materials Co., Ltd.) and 5% by mass of amine catalyst (N, N, N ′, N′-tetramethyl- 1,6-diaminohexane) and a dibutyl ether solution containing 20% by mass of perhydropolysilazane (AQUAMICA NAX120-20; manufactured by AZ Electronic Materials Co., Ltd.) at a ratio of 4: 1, A polysilazane coating solution was prepared with dibutyl ether so that the solid content was 1.0% by mass. The obtained coating liquid was 1% by mass (solid content) of the amine catalyst.

(Application of polysilazane coating solution, drying, modification)
A gas barrier film (9) was produced in the same manner as the gas barrier film (5) except that the polysilazane layer was formed using the polysilazane coating solution prepared above under the following coating conditions. For the application, a two-fluid spray film forming apparatus manufactured by Asahi Sunac Corporation was used.

<< Application conditions (two-fluid spray method) >>
Spray flow rate from nozzle: 1.50 g / min
Air pressure during liquid feeding: 0.1 MPa
Relative speed between nozzle and substrate: 0.5m / sec
Distance from nozzle spray port to substrate: 50 mm
Oxygen concentration in the coating atmosphere: 21%
Temperature of coating atmosphere: 70 ° C

[Production of gas barrier film (10)]
A gas barrier film (10) was produced in the same manner as the gas barrier film (6) except that the spraying time was shortened and the thickness of the polysilazane layer was changed to 50 nm.

[Production of gas barrier film (11)]
A gas barrier film (11) was produced in the same manner as the gas barrier film (6) except that the oxygen concentration in the coating atmosphere by the ESD method was adjusted to 10%.

[Production of gas barrier film (12)]
A gas barrier film (12) was produced in the same manner as the gas barrier film (6) except that the oxygen concentration in the coating atmosphere by the ESD method was adjusted to 0.5%.

[Preparation of gas barrier film (13)]
(Preparation of polysilazane coating solution)
Dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (Aquamica NN120-20; manufactured by AZ Electronic Materials Co., Ltd.) and 5% by mass of amine catalyst (N, N, N ′, N′-tetramethyl- 1,6-diaminohexane) and a dibutyl ether solution containing 20% by mass of perhydropolysilazane (AQUAMICA NAX120-20; manufactured by AZ Electronic Materials Co., Ltd.) at a ratio of 4: 1, A polysilazane coating solution was prepared with dibutyl ether so that the solid content was 2.0% by mass. The obtained coating liquid was 1% by mass (solid content) of the amine catalyst.

  A gas barrier film (13) was produced in the same manner as the gas barrier film (8) except that the polysilazane coating solution prepared above was used and the polysilazane layer was formed and modified as follows.

(Application of polysilazane coating solution, drying, modification)
A polysilazane coating solution prepared in the same manner as in the gas barrier film (1) was applied onto the smooth layer of the same substrate as in the gas barrier film (1) so that the layer thickness after drying was 25 nm, and an oxygen concentration of 21 A sample having a polysilazane layer was obtained by drying at 100 ° C. for 2 minutes in a% atmosphere. A spin coater was used for coating. Next, after fixing the sample on which the polysilazane layer was formed on the operation stage of the following reforming treatment apparatus, the reforming treatment was performed under the following conditions.
By repeating the coating, drying, and modification processes described above four times, a 100 nm polysilazane layer is formed and modified, and the polysilazane layer is used as a gas barrier layer (second gas barrier layer in the above embodiment). A barrier film (13) was produced.

《Reforming treatment equipment》
Apparatus: Ex D irradiation apparatus MODEL manufactured by M.D. Com: MECL-M-1-200
Wavelength: 172 nm
Lamp filled gas: Xe

<Reforming treatment conditions>
Excimer light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 1mm
Stage heating temperature: 70 ° C
Oxygen concentration in the irradiation device: 0.1%
Film transport speed: 2.4 m / min
Pass number: 1 time Excimer irradiation time: 0.312 seconds Energy irradiated to polysilazane coating film at 1 Pass: 0.75 J / cm ²

[Production of Gas Barrier Film (14)]
A gas barrier film (14) was formed in the same manner as the gas barrier film (6) except that the conditions for forming the barrier layer by plasma CVD were as follows. Before the formation of the polysilazane layer, the gas barrier performance (water vapor permeability) of the laminate of the base material and the barrier layer is determined by “measurement of water vapor permeability A” and “measurement of water vapor permeability B” described later. was measured by the same method, the water vapor transmission rate by either method was 0.5g ^/ m 2 ^/ 24h.

(Deposition conditions by CVD method)
A SiOC film having a thickness of 50 nm was formed on the substrate using the same vacuum plasma CVD apparatus as that used for the production of the gas barrier film (5). This vacuum plasma CVD apparatus includes a flat plate-like susceptor that supports a substrate from below, and a flat plate-like cathode electrode disposed above the susceptor so as to be parallel to the susceptor. Plasma is generated by applying a voltage between the cathode electrode and the susceptor while supplying source gas from a plurality of nozzles provided. As a power source for applying a voltage to the cathode electrode, a 27.12 MHz high frequency power source was used, and the distance between the electrodes (the distance between the cathode electrode and the susceptor) was 20 mm. Hexamethyldisiloxane (HMDSO) with a flow rate of 7.5 sccm was used as a source gas, and was introduced into the vacuum chamber together with an oxygen gas with a flow rate of 30 sccm. The substrate temperature at the start of film formation was set to 100 ° C., and the atmospheric pressure during film formation was set to 30 Pa.
Subsequently, using the same vacuum plasma CVD apparatus, a SiO ₂ film having a thickness of 10 nm is formed on the SiOC film, and a gas barrier is formed by these films (a SiOC film having a thickness of 50 nm and a SiO ₂ film having a thickness of 10 nm). A layer was formed. A 27.12 MHz high frequency power source was used as the power source, and the distance between the electrodes was 20 mm. Silane gas with a flow rate of 7.5 sccm was used as the source gas, and was introduced into the vacuum chamber together with oxygen gas with a flow rate of 30 sccm. The substrate temperature at the start of film formation was set to 100 ° C., and the atmospheric pressure during film formation was set to 30 Pa.

[Production of gas barrier film (15)]
A gas barrier film (15) was produced in the same manner as the gas barrier film (13) except that the film conveyance speed was changed to 2.4 m / min in the modification treatment of the polysilazane layer.

[Production of Gas Barrier Film (16)]
A gas barrier film (16) was produced in the same manner as the gas barrier film (5) except that the film conveyance speed was changed to 0.2 m / min in the modification treatment of the polysilazane layer.

<Evaluation of water vapor permeability degradation>
According to the following measurement methods, the water vapor permeability A before the wet heat test and the water vapor permeability B after the wet heat test of each gas barrier film (1) to (16) were measured.

[Water vapor barrier property evaluation sample preparation device]
Vapor deposition apparatus: manufactured by JEOL Ltd., vacuum vapor deposition apparatus JEE-400
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
<raw materials>
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)

[Preparation of water vapor barrier property evaluation sample]
Using a vacuum vapor deposition device (JEOL-made vacuum vapor deposition device JEE-400), the gas barrier layer forming surface of each of the produced gas barrier films (1) to (16) is passed through a mask and has a size of 12 mm × 12 mm in 9 locations. Calcium was deposited.

  Subsequently, the mask was removed in a vacuum state, and aluminum was vapor-deposited on the entire surface of one side of the sheet to perform temporary sealing. Next, the vacuum state is released, and it is quickly transferred to a dry nitrogen gas atmosphere, and the aluminum vapor deposition surface is made to face the quartz glass having a thickness of 0.2 mm through a sealing ultraviolet curable resin (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.

[Measurement of water vapor permeability A]
The obtained sample was stored under high temperature and high humidity of 60 ° C. and 90% RH, and based on the method described in Japanese Patent Application Laid-Open No. 2005-283561, the water vapor permeability A ( g / m ² · day) was calculated.

  In addition, in order to confirm that there is no permeation of water vapor from other than the gas barrier film surface, a sample obtained by depositing metallic calcium using a quartz glass plate having a thickness of 0.2 mm instead of the gas barrier film sample as a comparative sample Similarly, it was stored under high temperature and high humidity of 60 ° C. and 90% RH, and it was confirmed that corrosion of metallic calcium did not occur even after 1000 hours.

[Measurement of water vapor permeability B]
Separately, gas barrier films (1) to (16) were prepared and stored continuously in a high-temperature and high-humidity tank (constant temperature and humidity oven: Yamato Humidic Chamber IG47M) adjusted to 85 ° C. and 85% RH, The water vapor permeability B was measured. Other conditions were the same as the conditions for measuring the water vapor permeability A.

[Evaluation of water vapor permeability degradation]
When the degree of deterioration of water vapor permeability was calculated and ranked according to the following formula, it was as shown in Table 1 below. In addition, it shows that the change before and behind wet heat is so small that a rank is large, ie, it is excellent in wet heat tolerance. In Table 1, “polysilazane” means the second gas barrier layer in the embodiment, and “PE-CVD” means the first gas barrier layer.

B ÷ A = C
Rank4: C ≦ 3.0
Rank3: 3 <C <10.0
Rank2: 10.0 ≦ C <20.0
Rank1: 20.0 ≦ C

  As is clear from the results shown in Table 1, the gas barrier film as an example of the present invention, that is, the gas barrier films (2) to (4) and (6) to (6) coated with the polysilazane coating liquid in droplets. In 11) and (14), the water vapor permeability after the wet heat test is evaluated as compared with the gas barrier films (1), (5), (12) to (13), and (15) to (16) of the comparative example. It can be seen that the rank is increased and the wet heat resistance is improved.

  Further, focusing on the gas barrier films (2) to (4), (6) and (9), in the gas barrier films (3), (4) and (6) coated with a polysilazane coating solution by a trace solvent coating method. It can be seen that the wet heat resistance is improved as compared with the gas barrier films (2) and (9) coated with the polysilazane coating solution by the two-fluid spray method.

In addition, when focusing on the gas barrier films (2) to (4) and (6) to (9), the layer thickness of the second gas barrier layer is formed to be 50 nm or more in these gas barrier films. When modifying the polysilazane layer to form the second gas barrier layer, although there is a risk that unstable polysilazane is formed without sufficient supply of O ₂ to the polysilazane inside the polysilazane layer, Wet heat resistance is improved. From this, it can be seen that in these gas barrier films (2) to (4) and (6) to (9), there is no demerit caused by increasing the thickness of the second gas barrier layer.

When attention is paid to the gas barrier films (1) and (5) as comparative examples, the base material (here, the base material and the first gas barrier layer) before the polysilazane layer (second gas barrier layer) is formed. gas barrier film water vapor transmission rate of 0.05g ^/ m 2 ^/ 24h of the stack) (5), that is, the first gas barrier layer water vapor transmission rate is less than ^{1 × 10 -1 g / m 2} / 24h is In the gas barrier film (5) formed on the film substrate side, the wet heat resistance is deteriorated as compared with the gas barrier film (1) in which such a first gas barrier layer is not formed. This is because, in the gas barrier film water vapor transmission rate is to form a first gas barrier layer below ^{1 × 10 -1 g / m 2} / 24h (5), reformed second gas barrier polysilazane layer When forming a layer, it is presumed that the first gas barrier layer hinders the supply of O ₂ from the film substrate side to the polysilazane layer, and unstable polysilazane is formed.
In this regard, focusing on the gas barrier films (6) and (14) as examples, in the gas barrier film (6), the first gas barrier layer similar to the gas barrier film (5) is formed on the film substrate side. Although formed, a gas barrier film (14) (a gas barrier film in which a first gas barrier layer having a water vapor permeability greater than 1 × 10 ⁻¹ g / m ² / 24h is formed on the film substrate side. ) Has improved wet heat resistance to the same extent. Therefore, the gas barrier film (6), that there is no disadvantage due to the water vapor transmission rate to form a first gas barrier layer below ^{1 × 10 -1 g / m 2} / 24h to film substrate side I understand.

Further, when focusing attention on the gas barrier film (8) as an example and the gas barrier film (13) as a comparative example, the gas barrier film (13) is modified by modifying a thin polysilazane layer having a layer thickness of 25 nm. Since the second gas barrier layer having a total thickness of 100 nm is formed by repeating the process of forming the barrier layer (second gas barrier layer) four times, when the polysilazane layer is modified, O ₂ can be sufficiently supplied to the internal polysilazane. However, in this gas barrier film (13), since the irradiation energy at the time of modification is insufficient, each polysilazane layer is not sufficiently modified and the wet heat resistance is deteriorated. On the other hand, in the gas barrier film (8) of the example, the wet heat resistance is improved even when the modification is performed with the same amount of irradiation energy. From this, it can be seen that the gas barrier film (8) can improve the wet heat resistance with a small irradiation energy.

  Further, focusing on the gas barrier films (2) to (4) and (6) to (11) as examples and the gas barrier film (16) as a comparative example, the gas barrier film (16) of the comparative example In the gas barrier film (2) to (4) and (6) to (11) of the example, three times the irradiation energy is used for the modification treatment, but the gas barrier film of the example ( 2) to (4) and (6) to (11) are inferior to wet heat. From this, it can be seen that in the gas barrier films (2) to (4) and (6) to (11) of the examples, it is possible to improve the wet heat resistance with a small irradiation energy.

  Further, focusing on the gas barrier films (2) to (4) and (6) to (11) as examples and the gas barrier film (15) as a comparative example, the gas barrier film (15) of the comparative example Then, compared with the gas barrier films (2) to (4) and (6) to (11) of the examples, twice the irradiation energy is used for the reforming treatment, but the gas barrier films of the examples ( Only the lowest level of wet heat resistance in 2) to (4) and (6) to (11) can be obtained. Further, in the gas barrier film (15) of the comparative example, the process of applying, drying and modifying the thin polysilazane layer is repeated four times, which takes about four times as much labor and time as the gas barrier film of the example. However, although each polysilazane layer is in a state of being easily modified, only the lowest level of wet heat resistance in the gas barrier films (2) to (4) and (6) to (11) of the examples can be obtained. Absent. From this, it can be seen that the gas barrier films (2) to (4) and (6) to (11) of the examples can improve the wet heat resistance with low irradiation energy and high efficiency.

DESCRIPTION OF SYMBOLS 1 Gas barrier film 5,5A Gas barrier film manufacturing apparatus 10 Film base material 11 1st gas barrier layer (other gas barrier layers)
12 Second gas barrier layer (gas barrier layer)
51 1st gas barrier layer formation apparatus (gas barrier layer formation part)
520 Droplet application unit 521 Drying unit 522 Modification unit

Claims (11)

A droplet coating step of applying a solution containing polysilazane in a droplet form to one surface of a resin film substrate in an atmosphere containing at least oxygen; and
A drying step of forming the polysilazane layer by drying the solution applied to the one surface by the droplet application step;
A modification step of modifying the polysilazane layer to form a gas barrier layer by performing ultraviolet irradiation or plasma irradiation on the polysilazane layer in a low oxygen concentration atmosphere;
Are performed in this order. In the droplet application step,
The method for producing a gas barrier film according to claim 1, wherein the solution is applied by a trace solvent coating method. In the droplet application step,
The method for producing a gas barrier film according to claim 1 or 2, wherein the solution is applied by an electrostatic coating method. Before the droplet applying process, the relative one surface, forming said unlike gas barrier layer, and a water vapor permeability of ^{1 × 10 -1 g / m 2} / 24h or less of another gas barrier layer The method for producing a gas barrier film according to any one of claims 1 to 3, wherein a gas barrier layer forming step is performed.   The method for producing a gas barrier film according to any one of claims 1 to 4, wherein the thickness of the gas barrier layer is 50 nm or more.   A gas barrier film produced by the method for producing a gas barrier film according to any one of claims 1 to 5. A liquid droplet applying part for applying a solution containing polysilazane into liquid droplets on the one surface of the resin film base under an atmosphere containing at least oxygen; and
A drying unit for drying the solution applied to the one surface by the droplet application unit to form a polysilazane layer;
A modified portion that modifies the polysilazane layer to form a gas barrier layer by performing ultraviolet irradiation or plasma irradiation on the polysilazane layer in a low oxygen concentration atmosphere;
An apparatus for producing a gas barrier film, comprising: The droplet applying part is
8. The apparatus for producing a gas barrier film according to claim 7, wherein the solution is applied by a micro solvent application method. The droplet applying part is
The apparatus for producing a gas barrier film according to claim 7 or 8, wherein the solution is applied by an electrostatic coating method. Wherein with respect to the one surface in the film substrate side of the gas barrier layer, different from the gas barrier layer, and a water vapor permeability of ^{1 × 10 -1 g / m 2} / 24h or less of another gas barrier layer The apparatus for producing a gas barrier film according to any one of claims 7 to 9, further comprising: a gas barrier layer forming part that forms a gas.   The apparatus for producing a gas barrier film according to any one of claims 7 to 10, wherein the thickness of the gas barrier layer is 50 nm or more.

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