JP5825016B2 - Barrier film manufacturing method - Google Patents

Description

The present invention relates to a method of manufacturing a bus rear film.

  Conventionally, a gas barrier film in which a metal oxide thin film (gas barrier layer) such as aluminum oxide, magnesium oxide, or silicon oxide is formed on the surface of a plastic substrate or film must block various gases such as water vapor and oxygen. It is widely used for packaging of articles and packaging for preventing deterioration of food, industrial goods, pharmaceuticals, and the like. In addition to the packaging applications described above, it is also used for sealing electronic devices such as solar cells, liquid crystal display elements, and organic EL elements in order to prevent deterioration due to various gases.

As a method for forming such a gas barrier film, a technique for forming a gas barrier layer by a plasma CVD method (Chemical Vapor Deposition or chemical vapor deposition) or a coating liquid mainly composed of polysilazane is applied. And the technique which forms a coating film is known (for example, refer patent documents 1-3).
In recent years, it is desired to produce a gas barrier film having high gas barrier performance at a low cost. Therefore, for example, as disclosed in Patent Document 3, a gas barrier layer is studied to be formed by a coating method with higher film formation efficiency, such as a roll-to-roll continuous production method under atmospheric pressure.
However, the current mainstream technique is a deposition method using CVD, which is a technique that requires a reduced pressure environment because of low film formation productivity. In addition, currently, there is no report on the mechanical properties of each layer in the gas barrier film produced by a coating method, and the gas barrier has a water vapor transmission rate (WVTR) of less than 1 × 10 ⁻² g / m ² / day. The current situation is that the film has not been realized.

  Furthermore, since the demand for mobile displays has increased rapidly in recent years, a plastic substrate or a thickness of about 100 μm is used as a substrate for a liquid crystal display (LCD), which has conventionally used a glass substrate for the purpose of weight reduction. Attempts have been made to use flexible and lightweight substrates such as thin glass, a glass cloth substrate formed by solidifying a glass fiber woven cloth with a resin, and a cellulose nanofiber substrate formed by molding cellulose nanofibers. From the viewpoint of not only weight reduction but also prevention of breakage at the time of dropping, a plastic substrate, a glass cloth substrate, and a cellulose nanofiber substrate are particularly promising.

When these substrates are used as substrates for LCDs, it is required to suppress the elution of impurity ions from the substrate and members on the substrate side into the liquid crystal so as not to affect the driving of the liquid crystal. For example, in Patent Document 4, a plurality of SiO ₂ insulating layers formed on an alkali glass substrate by sputtering are thermally diffused from the glass substrate during high-temperature treatment at 350 ° C. to 500 ° C. in the display manufacturing process. A technique for suppressing elution of coming sodium ions into the liquid crystal is disclosed.
However, in patent document 4, there is no description about the above-mentioned plastic base material etc., and since the glass base material is used, gas barrier property is not regarded as a problem. In addition, since the film is formed in a vacuum system by sputtering, continuous productivity is poor.

Further, Patent Document 5 discloses a technique aimed at improving productivity and achieving both ion elution preventing property and gas barrier property when a base material is plasticized for the purpose of weight reduction and damage prevention. In Patent Document 5, high productivity is realized by forming a gas barrier layer by applying polyvinyl alcohol (PVA) from which sodium acetate is removed by purification to a plastic base material (polycarbonate, etc.) and drying to form a gas barrier property. And prevention of alkali metal ion elution from the PVA.
However, in Patent Document 5, since PVA is used for the gas barrier layer, it is exposed to a high temperature close to 200 ° C. in the display driving circuit forming process and the color filter forming process in the amorphous Si-TFT manufacturing process which is currently mainstream. As a result, the gas barrier layer was damaged, and its performance could not be maintained. In addition, since PVA is a hydrophilic resin, the water vapor barrier property was not satisfactory.

On the other hand, a technique for forming an ion elution preventing layer by coating an inorganic material having excellent heat resistance is disclosed (for example, Patent Document 6). In Patent Document 6, a metal oxide layer is formed by a vapor deposition method such as sputtering between a color filter and a flattening layer for flattening the surface of the color filter, or polyamide, polyimide, A long-term stability of the color filter is realized by forming a layer made of siloxane or the like and suppressing deterioration of the flattening film.
However, in Patent Document 6, there is no detailed description regarding a manufacturing method of a layer mainly composed of a siloxane-based material or an inorganic skeleton, and a soda glass (blue plate glass) is used as a base material. There is no mention of sex.

JP 2008-56967 A JP 2009-255040 A Special table 2009-503157 JP 2000-26139 A Japanese Patent Laid-Open No. 9-15618 JP 9-189903 A

The present invention has been made in view of the above problems, and an object thereof is to provide a method of manufacturing a resolver rear film having a high barrier performance and ion elution prevention performance.

In order to solve the above problems, the invention described in claim 1
A method for producing a barrier film comprising a gas barrier layer and an ion barrier layer mainly composed of an inorganic skeleton on a substrate,
After forming a coating film containing polysilazane, forming the gas barrier layer by modifying the coating film by applying vacuum ultraviolet light; and
Forming a coating film containing polysiloxane, and then forming the ion barrier layer by modifying the coating film by irradiating it with vacuum ultraviolet light.
Providing the gas barrier layer in an arrangement covering the ion barrier layer;
The interface between the gas barrier layer and the ion barrier layer is an ion block surface.

The invention described in claim 2
A method for producing a barrier film comprising a gas barrier layer and an ion barrier layer mainly composed of an inorganic skeleton on a substrate,
After forming a coating film containing polysilazane, forming the gas barrier layer by modifying the coating film by applying vacuum ultraviolet light; and
Forming a coating film containing polysiloxane, and then forming the ion barrier layer by modifying the coating film by irradiating it with vacuum ultraviolet light.
The gas barrier layer is provided in an arrangement sandwiched between the paired ion barrier layers ,
The interface between the gas barrier layer and the ion barrier layer is an ion block surface .

The invention according to claim 3
A method for producing a barrier film comprising a gas barrier layer and an ion barrier layer mainly composed of an inorganic skeleton on a substrate,
After forming a coating film containing polysilazane, forming the gas barrier layer by modifying the coating film by applying vacuum ultraviolet light; and
Forming a coating film containing polysiloxane, and then forming the ion barrier layer by modifying the coating film by irradiating it with vacuum ultraviolet light.
The ion barrier layer is provided in an arrangement sandwiched between the gas barrier layers forming a pair ,
The interface between the gas barrier layer and the ion barrier layer is an ion block surface .

According to the present invention, it is possible to obtain a manufacturing method of the resolver rear film having a high barrier performance and ion elution prevention performance.

It is explanatory drawing which shows an example of the barrier film which concerns on this invention. It is explanatory drawing which shows an example of the barrier film which concerns on this invention. It is sectional drawing which shows an example of the liquid crystal display panel which sealed the liquid crystal display element using the barrier film. Example 1 (1), Reference Example 2 (2), Example 3 (3), Example 4 (4), Comparative Example 1 (5), Comparative Example 2 (6), and Comparative Example 3 (7) ) Is an explanatory view showing Comparative Example 4 (8).

  Hereinafter, preferred embodiments for carrying out the present invention will be described with reference to the drawings. However, although various technically preferable limitations for implementing the present invention are given to the embodiments described below, the scope of the invention is not limited to the following embodiments and illustrated examples.

The barrier film (10, 11) according to the present invention includes at least one gas barrier layer 2 and at least one ion barrier layer 3 on a substrate 1 such as a resin film.
The gas barrier layer 2 is a layer formed by modifying a coating film containing polysilazane by irradiating the coating film formed by applying and drying a coating liquid containing polysilazane with vacuum ultraviolet light.
The ion barrier layer 3 is a layer formed by modifying a coating film containing polysiloxane by irradiating the coating film formed by applying and drying a coating solution containing polysiloxane with vacuum ultraviolet light. is there.
The gas barrier layer 2 and the ion barrier layer 3 are provided adjacent to each other.

As a result of intensive studies by the present inventors, high gas barrier properties and high ion barrier properties (ion elution) can be achieved by applying a modification treatment to irradiate vacuum ultraviolet rays having a wavelength of 100 nm to 200 nm as a modification method for each coating film. It has been found that both prevention properties can be achieved.
In particular, the high gas barrier property of the polysilazane modified layer (gas barrier layer 2) is manifested by laminating two different modified layers of the gas barrier layer 2 and the ion barrier layer 3, and the high gas barrier property. Was found to be stable for a long time.
The polysiloxane modified layer (ion barrier layer 3) has voids at the atomic level (several nm to several tens of nm size), which is a structural feature thereof, and the polysilazane modified layer (gas barrier layer 2). It was found that a high ion barrier property of the polysiloxane modified layer (ion barrier layer 3) is expressed by being adjacent to each other.
Furthermore, the interface between the polysilazane modified layer (gas barrier layer 2) and the polysiloxane modified layer (ion barrier layer 3) functions as an ion block surface, so that various substrates including soda glass (1) And ions that are considered to diffuse from a functional layer such as a photocured layer are prevented from passing through the interface and eluting from the barrier film. For example, ions are present on the liquid crystal element side sealed by the barrier film. It was found that the elution was effectively suppressed.
In the present application, “gas barrier property” means that the water vapor permeability (60 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by a method according to JIS K 7129-1992 is 1 × 10 ⁻² g / (m ² · 24 h) or less, and oxygen permeability measured by a method according to JIS K 7126-1987 is 1 × 10 ⁻² ml / m ² · 24 h · atm or less. That means.

Moreover, you may provide the smooth layer 4 and an anchor coat layer in the base-material surface as an intermediate | middle layer for improving the smoothness of the base material 1, and the adhesiveness of the gas barrier layer 2 with respect to the base material 1. FIG.
Moreover, in order to prevent the base material 1 from being scratched or soiled, a so-called bleed-out layer is suppressed so that when the base material 1 is heated, low molecular weight components such as monomers and oligomers are deposited from the inside to the surface. For this purpose, a bleed-out prevention layer 5 may be provided on the surface of the substrate.

Specifically, the barrier film 10 according to the present invention includes, for example, as shown in FIG. 1, a base material 1, and a gas barrier layer 2 and an ion barrier layer that are sequentially laminated on one surface of the base material 1. 3 is provided.
Moreover, the barrier film 11 according to the present invention is laminated on the base material 1, the smooth layer 4 formed on one surface of the base material 1, and the smooth layer 4, for example, as shown in FIG. A gas barrier layer 2 and an ion barrier layer 3 are provided, and a bleed-out prevention layer 5 is provided on the other surface of the substrate 1.

  Hereinafter, the structure of the barrier films 10 and 11 of the present invention will be described in detail.

(Base material)
The base material constituting the barrier film of the present invention and serving as a support for the barrier film is preferably a flexible and foldable film base material. The substrate is not particularly limited as long as it can hold a gas barrier layer or an ion barrier layer.

Examples of the resin base material applicable to the base material of the barrier film include acrylic acid ester, methacrylic acid ester, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, Polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), polystyrene (PS), nylon (Ny), aromatic polyamide, polyetheretherketone, polysulfone, polyethersulfone (PES), polyimide (PI), Resin films such as polyamideimide (PAI) and polyetherimide, heat-resistant transparent film based on silsesquioxane having an organic-inorganic hybrid structure (product name: Sila-DEC, manufactured by Chisso Corporation), Can the mentioned resin film formed by laminating a resin obtained by the two or more layers.
In terms of cost and availability, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyethersulfone (PES), and the like are preferably used. Further, in terms of optical transparency, heat resistance, and adhesion to constituent layers such as a gas barrier layer, a heat resistant transparent film having a basic skeleton of silsesquioxane having an organic-inorganic hybrid structure can be preferably used.

Moreover, the heat resistant base material in this invention refers to the base material whose continuous use temperature is 150 degreeC or more among the base materials which consist of above-described resin.
Examples of the heat-resistant substrate include resin films such as polyethylene naphthalate (PEN), polyethersulfone (PES), polyimide (PI), and polyamideimide (PAI). Examples thereof include a cycloolefin polymer film (for example, ZEONOR manufactured by ZEON Co., Ltd., F film manufactured by Gunze Co., Ltd.), cellulose nanofiber film, glass cloth, and the like. In addition, the glass substrate containing thin glass is also included in the meaning of a heat-resistant substrate. When using a glass substrate as the substrate of the barrier film, it is not necessary to form a gas barrier layer, but when using soda glass as the glass, by forming an ion barrier layer mainly composed of an inorganic skeleton, It is preferable to impart the effect of the ion barrier layer alone.
The gas barrier layer and the ion barrier layer in the present invention are both layers mainly composed of inorganic components and have high heat resistance. Therefore, by combining with the heat resistant substrate as described above, It is possible to pass through a high-temperature treatment process such as a drive circuit formation process such as a TFT or a color filter formation process. However, since the process temperature in the drive circuit formation step and the color filter formation step varies depending on the manufacturing method, it is preferable to select a substrate that can withstand the process temperature as appropriate.

The thickness of this base material is preferably about 5 to 500 μm, more preferably 25 to 250 μm.
Moreover, it is preferable that the base material which functions as a support body of a barrier film has a light transmittance and is transparent. Since the base material is transparent and the constituent layer formed on the base material is also transparent, it becomes possible to make a transparent barrier film, so that it becomes possible to make a transparent substrate such as an organic EL element. It is.

The base material using the above-described resin or the like may be an unstretched film or a stretched film.
Specifically, the base material made of the above-described resin material can be manufactured by a conventionally known general method. For example, an unstretched substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. In addition, the unstretched substrate is uniaxially stretched, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular-type simultaneous biaxial stretching, and other known methods, such as the substrate flow (vertical axis) direction, or A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the base material, but is preferably 2 to 10 times in each of the vertical axis direction and the horizontal axis direction.

(Gas barrier layer)
The gas barrier layer of the present invention can be formed by a technique in which at least one silicon compound layer (polysilazane layer) having a polysilazane skeleton is provided on at least one surface of a base material, and the polysilazane layer is subjected to a modification treatment. A particularly preferable treatment as this modification treatment is a treatment of irradiating vacuum ultraviolet light having a wavelength of 100 nm to 200 nm. By irradiating the polysilazane layer with vacuum ultraviolet light, a gas barrier layer containing silicon oxide, silicon oxynitride or the like is formed. Can be formed.

  As a factor in which the gas barrier layer formed by modifying the polysilazane layer exhibits high gas barrier performance, the present inventors have proposed that the three to five cyclic structures contained in the polysilazane are a dense structure of silicon oxide or silicon oxynitride. It is thought that the main factor is to have an interatomic distance advantageous for forming the layer, and the modification process of vacuum ultraviolet light irradiation is involved in the existing short-range order, and the layer structure can be ordered with less energy. For example, it is assumed that processes such as dissolution, rearrangement, and crystallization at 1000 ° C. or higher are unnecessary. Moreover, in the process of irradiating with vacuum ultraviolet light, the breakage of chemical bonds such as Si-OH by the vacuum ultraviolet light and the oxidation by ozone generated in the irradiation space occur at the same time. It is presumed that an efficient modification is also a preferable factor by the modification treatment using the oxidation treatment together.

In the present invention, the polysilazane layer serving as a gas barrier layer provided on the base material or an intermediate layer (for example, a smooth layer) formed on the base material is coated with a coating liquid containing polysilazane to form a coating film containing polysilazane. Can be formed.
Any appropriate method can be adopted as a coating method of the coating liquid containing polysilazane. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.

The thickness of the coating film can be appropriately set according to the purpose. For example, the coating thickness can be set so that the thickness after drying is preferably about 1 nm to 100 μm, more preferably about 10 nm to 10 μm, and most preferably about 10 nm to 1 μm.
In addition, in order to form a coating film stably before application | coating, it is also possible to surface-treat the application surface of a base material. Examples of the surface treatment method include conventionally known treatment methods such as flame treatment, corona discharge treatment, glow discharge treatment, oxygen plasma treatment, UV ozone treatment, and excimer light treatment. It is preferable to perform the treatment so that the contact angle between the coating surface of the substrate and the coating solution is 10 ° to 30 ° by such surface treatment. When the contact angle is greater than 30 °, it may be difficult to form a uniform coating film or the adhesion strength of the gas barrier layer may be reduced. When the contact angle is smaller than 10 °, the surface of the base material may be deteriorated or damaged, and the adhesion strength of the gas barrier layer may be lowered.

The “polysilazane” used in the present invention is a polymer having a silicon-nitrogen bond, and includes SiO ₂ , Si ₃ N ₄ and both intermediate solid solutions SiO _x N _{y made of} Si—N, Si—H, N—H, or the like. Such as a ceramic precursor inorganic polymer.
Further, the polysilazane is preferably a compound that is ceramicized at a relatively low temperature and modified to silica so as to be applied so as not to impair the properties of the substrate. For example, the following general formula described in JP-A-8-112879 A compound having a main skeleton composed of the unit represented by (1) is preferred.

In the general formula (1), R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group. Represent.
In the present invention, perhydropolysilazane in which all of R ₁ , R _2, and R ₃ are hydrogen atoms is particularly preferred from the viewpoint of the denseness of the resulting water vapor barrier layer.
In addition, the organopolysilazane in which a part of the hydrogen atom bonded to Si is substituted with an alkyl group or the like has an alkyl group such as a methyl group, thereby improving adhesion with a base material as a base and being hard. The ceramic film made of brittle polysilazane can be provided with toughness, and even when the film thickness (average film thickness) is made thicker, the occurrence of cracks can be suppressed. Accordingly, perhydropolysilazane and organopolysilazane may be appropriately selected 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. Its 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. These are marketed in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as a polysilazane-containing coating solution.

  As another example of polysilazane which becomes ceramic at low temperature, a silicon alkoxide-added polysilazane obtained by reacting a silicon alkoxide with a polysilazane having a main skeleton composed of a unit represented by the general formula (1) (for example, Japanese Patent Laid-Open No. Hei. No. 5-238827), glycidol-added polysilazane obtained by reacting glycidol (for example, see JP-A-6-122852), and alcohol-added polysilazane obtained by reacting alcohol (for example, JP-A-6-240208). Gazette), metal carboxylate-added polysilazanes obtained by reacting metal carboxylates (for example, see JP-A-6-299118), and acetylacetonate complexes obtained by reacting metal-containing acetylacetonate complexes Additional polysilazanes (for example, See JP -306329), a metal fine metal particles added polysilazane obtained by adding (e.g., JP-see JP 7-196986), and the like.

  As the organic solvent for preparing the first coating solution containing polysilazane, it is not preferable to use an alcohol or water-containing one having a characteristic that easily reacts with polysilazane. Therefore, specifically, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, ethers such as aliphatic ethers and alicyclic ethers can be used. . 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 polysilazane and the evaporation rate of the organic solvent, and a plurality of organic solvents may be mixed.

  The polysilazane concentration in the polysilazane-containing coating solution varies depending on the film thickness of the target polysilazane coating film and the pot life of the coating solution, but is preferably about 0.2 to 35% by mass.

In the present invention, the composition containing polysilazane is not particularly limited as long as it contains perhydropolysilazane. As the material other than perhydropolysilazane in the composition, any material may be used as long as it has compatibility with perhydropolysilazane and its solvent.
Further, the composition may contain a catalyst such as amine or metal added to promote the oxidation reaction at about 0.1 to 10% by mass relative to perhydropolysilazane. 5-5 mass% containing is preferable at the point of application | coating property and shortening of reaction.
The content of perhydropolysilazane excluding the solvent and additives in the composition is preferably 80% by mass or more from the viewpoint of barrier properties, and 100% by mass, that is, consisting of only perhydropolysilazane, It is most preferable in that a dense film having a high barrier property can be formed.
Examples of materials that can be obtained as perhydropolysilazane in the present invention include Aquamica NN120, NN110, NAX120, NAX110, NL120A, NL110A, NL150A, NP110, and NP140 manufactured by AZ Electronic Materials.

(Ion barrier layer)
The ion barrier layer of the present invention is formed by a method in which at least one silicon compound layer (polysiloxane layer) having a polysiloxane skeleton is provided on at least one surface of a base material, and the polysiloxane layer is subjected to a modification treatment. Can do. A particularly preferable treatment as this modification treatment is a treatment of irradiating vacuum ultraviolet light having a wavelength of 100 nm to 200 nm. By irradiating the polysiloxane layer with vacuum ultraviolet light, a silicon oxide compound having an organic group derived from polysiloxane is obtained. In addition, an ion barrier layer mainly containing an inorganic skeleton can be formed.

The polysiloxane material is, for example, a polymer having a silicon-oxygen bond such as (—SiR ₁ R ₂ —O—SiR ₃ R ₄ —O—SiR ₅ R ₆ —). The polysiloxane material may contain a functional group containing carbon (C _n H _{2n + 1} ) in its skeleton, but if the number of carbons is too large, the void size at the atomic level after modification becomes too large, and the ion trap effect Is unfavorable because it may decrease and the rigidity of the gas barrier layer may decrease. For this reason, carbon number n of the functional group contained in the inorganic skeleton is preferably 0 to 5, more preferably 1 to 3. Specific examples include hydrogenated silsesquioxane (HSQ) and methylated silsesquioxane (MSQ).

In the present invention, the molecular weight of the polysiloxane used in the ion barrier layer mainly composed of an inorganic skeleton is preferably 1000 to 10,000, more preferably 3000 to 6000.
When the molecular weight is less than 1000, defects such as cracks are likely to occur when a film is formed by the method of the present invention. On the other hand, when the molecular weight is larger than 10,000, gelation is likely to proceed, and it becomes difficult to store the material, and the pot life at the time of production is shortened.
In addition, the formation of a three-dimensional crosslinked structure using a polysiloxane material can be generally realized by applying a heat treatment at 200 ° C. or higher. For example, an ion is formed on a resin substrate having low heat resistance. It is difficult to form a barrier layer. As a result of intensive studies by the present inventor, a coating film of polysiloxane material is formed on a resin base material, and solvent removal and initial curing reaction (pre-curing treatment) are performed by heat treatment at a temperature lower than the heat resistant temperature of the resin base material. After performing, a structure having an ion trap ability according to the object of the present invention without damaging the resin base material by irradiating high energy rays, for example, vacuum ultraviolet light having a wavelength of 200 nm or less (post-curing treatment) It is possible to manufacture an ion barrier layer.

In the present invention, the polysiloxane layer serving as an ion barrier layer provided on the base material or an intermediate layer (for example, a smooth layer) formed on the base material is coated with a coating liquid containing polysiloxane and contains polysiloxane. It can be formed as a coating film.
Any appropriate method can be adopted as a coating method of the coating liquid containing polysiloxane. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.
The thickness of the coating film can be appropriately set according to the purpose. For example, the coating thickness can be set so that the thickness after drying is preferably about 1 nm to 100 μm, more preferably about 10 nm to 10 μm, and most preferably about 10 nm to 1 μm.
In addition, similarly to the polysilazane-containing coating film, in order to stabilize the coating film, it is possible to surface-treat the coated surface of the substrate by a conventionally known method prior to coating.

<Thickness of gas barrier layer and ion barrier layer>
The thickness of the gas barrier layer in the present invention is preferably 1 nm to 100 nm, more preferably 10 nm to 50 nm, per layer. When the thickness is 1 nm or less, the barrier performance is not sufficient, and when the thickness is more than 100 nm, the barrier layer, which is a dense metal oxide film, easily cracks. As an example of a method for the gas barrier layer to achieve both improvement in gas barrier properties and prevention of cracks, there is a method of subdividing the layer with a constant total film thickness. If the gas barrier layer is subdivided and multiple gas barrier layers are formed, the residual stress during metal oxide film formation can be reduced, and when the gas barrier layer and the adjacent layers of the gas barrier layer are highly modified However, the occurrence of cracks can be suppressed. Further, by sequentially stacking the gas barrier layers, it becomes possible to shift the position of the defect, and the gas barrier performance is further improved by the detour effect.
The thickness of the ion barrier layer is preferably 100 nm to 10 μm, more preferably 300 nm to 4 μm. If it is thinner than 100 nm, the ion trap effect is small, and the functions as a protective layer and an underlayer are not sufficient. If it is thicker than 10 μm, cracks are likely to occur, and flexibility and curl balance may be deteriorated.

<Combined effect by laminating polysilazane modified layer and polysiloxane modified layer>
As described above, when the gas barrier layer is formed from the polysilazane coating and the ion barrier layer mainly composed of the inorganic skeleton is formed from the polysiloxane coating, after coating / modifying one layer, the other layer By applying / modifying and laminating the gas barrier layer and the ion barrier layer, the interface between the two layers can be clearly formed, and this interface region can function as an ion block surface.
In addition, each of the gas barrier layer and the ion barrier layer includes voids at an atomic level, and at least a part of the voids of the ion barrier layer is larger in size than the voids of the gas barrier layer. Can exhibit higher ion trapping properties. Furthermore, since the interface between the gas barrier layer and the ion barrier layer is a boundary where the void size at the atomic level is switched, an effect of increasing the ion trapping property and ion blocking property of the interface can be expected.
Moreover, in order to relieve the film-forming stress of a gas barrier layer and to express higher gas barrier property, it is effective to provide an ion barrier layer as a base of a polysilazane coating film. In addition, when the ion barrier layer is the base of the gas barrier layer, the ions that diffuse into the gas barrier layer are reduced as much as possible due to the ion trapping effect of the ion barrier layer itself and the ion blocking effect at the interface with the gas barrier layer. It is also possible to suppress the deterioration of the barrier properties of the gas barrier layer due to the diffusion ions.
Moreover, the ion barrier layer can be made to function as a protective layer of the gas barrier layer by providing the ion barrier layer so as to relieve the external force applied to the gas barrier layer so as to cover the gas barrier layer. In this case, it can be easily imagined that the ion barrier layer prevents the gas barrier layer from being damaged and maintains the gas barrier performance. However, a small amount of ionic substances diffusing from the gas barrier layer are separated from the ion barrier layer and the gas. It is possible to trap at the interface with the barrier layer.
When laminating the gas barrier layer and the ion barrier layer in this way, the arrangement configuration of the upper and lower sides thereof is changed so that the gas barrier layer is provided so as to cover the ion barrier layer, and the ion barrier layer is a gas barrier layer. And a layer structure suitable for the gas barrier function and a layer structure suitable for the ion barrier function.
In order to further enhance the stacking effect of the gas barrier layer and the ion barrier layer, a three-layer structure may be used. For example, the gas barrier layer may be provided between the paired ion barrier layers. Moreover, the ion barrier layer may be provided in an arrangement sandwiched between the gas barrier layers forming a pair. Further, the gas barrier layer and the ion barrier layer may be laminated in four or more layers. For example, a unit in which the gas barrier layer covers the ion barrier layer may be laminated, or a unit in which the ion barrier layer covers the gas barrier layer. A laminated structure such as a laminated structure may be used.

[Reforming treatment]
<Modification treatment by UV irradiation>
The modification treatment applied to the polysilazane layer containing polysilazane and the polysiloxane layer containing polysiloxane is performed by irradiating ultraviolet rays in an appropriate oxidizing gas atmosphere and a low humidity environment.
By irradiating a silicon compound layer such as a polysilazane layer or a polysiloxane layer with ultraviolet rays, an active film or ozone is generated and an oxidation reaction proceeds, whereby an inorganic film having a desired composition can be obtained.
Since this active oxygen and ozone are very reactive, the silicon compound in the coating film is directly oxidized without going through silanol, so that the silicon oxide film or silicon oxynitride film with higher density and fewer defects Is formed.
The reforming treatment in the present invention is more preferably performed in combination with heat treatment.
Moreover, ozone may be produced from oxygen by a known method such as a discharge method at a portion different from the ultraviolet irradiation for the shortage of reactive ozone and introduced into the ultraviolet irradiation site.
Although the wavelength of the ultraviolet rays irradiated at this time is not particularly limited, the wavelength of the ultraviolet rays is preferably from 100 to 450 nm, and more preferably from about 100 to 300 nm.

As a light source that outputs ultraviolet rays, a low-pressure mercury lamp, a deuterium lamp, a xenon excimer lamp, a metal halide lamp, an excimer laser, or the like can be used. The output of the light source ^{400W~30kW, 100mW / cm 2 ~100kW /} cm 2 as illuminance, preferably 10~5000mJ / cm ² as irradiation energy, 100 to 2000 mJ / cm ² is more preferable. Moreover, the illuminance at the time of ultraviolet irradiation is preferably 1 mW / cm ^{2 to} 10 W / cm ² .
Among these, as the wavelength, vacuum ultraviolet light of 100 to 200 nm is most preferable, and the oxidation reaction can be advanced at a lower temperature and in a shorter time. As a light source, a rare gas excimer lamp such as a xenon excimer lamp is most preferably used.
For example, polysilazane in a coating film formed from a composition containing perhydropolysilazane is converted to a high-density silicon oxide film, that is, a high-density silica film, by irradiating ultraviolet rays in an oxidizing gas atmosphere. However, the film thickness and density of the silica film can be controlled by the intensity of ultraviolet light, irradiation time, and wavelength (light energy density), and the type of light source is properly selected to obtain the desired film structure. Is possible. In addition to continuous irradiation, multiple irradiations may be performed, and pulse irradiation in which the multiple irradiations are performed in a short time may be used.
In addition, heating the coating film simultaneously with ultraviolet irradiation is also preferably used to accelerate the reaction (also referred to as oxidation reaction, conversion treatment, or modification treatment). The heating method is such that the substrate is brought into contact with a heating element such as a heat block, the coating film is heated by heat conduction, the atmosphere is heated by an external heater such as a resistance wire, and infrared light such as an IR heater is applied. Although the method used etc. are mentioned, it does not specifically limit. What is necessary is just to select suitably the method which can maintain the smoothness of a coating film, when performing heat processing.
As temperature to heat, the range of 50-200 degreeC is preferable, More preferably, it is the range of 80-150 degreeC, As the heating time, the range of 1 second-10 hours is preferable, More preferably, it is 10 seconds-1 hour Heating in a range.

<Modification treatment by irradiation with vacuum ultraviolet rays (VUV light)>
Of the light irradiation treatment and ultraviolet irradiation treatment, vacuum ultraviolet light (VUV light) treatment is particularly preferable.
With this vacuum ultraviolet light irradiation, molecular bonds of polysilazane and polysiloxane are broken, and even a small amount of oxygen in the coating film or atmosphere can be efficiently converted into ozone or active oxygen. Surface ceramization (silica modification) is promoted, and the resulting ceramic film becomes denser. The vacuum ultraviolet light irradiation is effective at any time point after the coating film is formed.
Specifically, vacuum ultraviolet light of 100 to 200 nm is used as the vacuum ultraviolet light in the present invention. The irradiation intensity and / or irradiation time of vacuum ultraviolet light can be set as appropriate. As the vacuum ultraviolet light irradiation apparatus, a commercially available lamp (for example, manufactured by USHIO INC.) Can be used.

Vacuum ultraviolet light irradiation can be applied to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be coated.
For example, in the case of batch processing, the base material provided with the coating film is accommodated in a vacuum ultraviolet ray firing furnace equipped with a vacuum ultraviolet light generation source, and the surface is ceramicized by processing in the vacuum ultraviolet ray firing furnace. be able to. The vacuum ultraviolet ray baking furnace itself is generally known, and, for example, a product manufactured by USHIO INC. Can be used.
Moreover, when the base material provided with the coating film is in the form of a long film, it is irradiated with vacuum ultraviolet light continuously in the drying zone equipped with the vacuum ultraviolet ray generation source as described above while being conveyed. The surface can be ceramicized.
Since vacuum ultraviolet light is larger than the interatomic bonding force of most substances, it can be preferably used because the bonding of atoms can be cut directly by the action of only photons called photon processes. By using this action, the reforming process can be efficiently performed at a low temperature without requiring hydrolysis.

A rare gas excimer lamp is preferably used as the vacuum ultraviolet light source necessary for the treatment in the present invention.
Since noble gas atoms such as Xe, Kr, Ar, Ne, and the like are chemically bonded and do not form molecules, they are called inert gases. However, rare gas atoms (excited atoms) that have gained energy by discharge or the like can be combined with other atoms to form molecules. When the rare gas is xenon,
e + Xe → Xe ^*
Xe ^* + 2Xe → Xe ₂ ^* + Xe
Xe ₂ ^* → Xe + Xe + hν (172 nm)
Thus, when the excited excimer molecule Xe ₂ ^* transitions to the ground state, excimer light of 172 nm is emitted. A feature of the excimer lamp is that the radiation is concentrated on one wavelength, and since only the necessary light is not emitted, the efficiency is high. Further, since no extra light is emitted, the temperature of the object can be kept low. Furthermore, since no time is required for starting and restarting, instantaneous lighting and blinking are possible.
In order to obtain excimer light emission, a method using dielectric barrier discharge is known. Dielectric barrier discharge refers to lightning generated in a gas space by arranging a gas space between both electrodes via a dielectric (transparent quartz in the case of an excimer lamp) and applying a high frequency high voltage of several tens of kHz to the electrode. It is a similar very thin discharge called micro discharge. When the micro discharge streamer reaches the tube wall (dielectric), the electric charge accumulates on the dielectric surface, and the micro discharge disappears. The dielectric barrier discharge is a discharge in which the micro discharge spreads over the entire tube wall and is repeatedly generated and extinguished. For this reason, flickering of light that can be seen with the naked eye occurs. Moreover, since a very high temperature streamer reaches a pipe wall directly locally, there is a possibility that deterioration of the pipe wall may be accelerated.

As a method for efficiently obtaining excimer light emission, electrodeless electric field discharge can be used in addition to dielectric barrier discharge. Electrodeless field discharge by capacitive coupling is also called RF discharge. The lamp, the electrode, and the arrangement thereof may be basically the same as those of the dielectric barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz. Since the electrodeless field discharge can provide a spatially and temporally uniform discharge in this way, a long-life lamp without flickering can be obtained.
In the case of dielectric barrier discharge, since micro discharge occurs only between the electrodes, the outer electrode covers the entire outer surface and transmits light to extract light to the outside in order to discharge in the entire discharge space. Must be something to do. For this reason, an electrode in which a fine metal wire is formed in a net shape is used. Since this electrode uses as thin a line as possible so as not to block light, it is easily damaged by ozone generated by vacuum ultraviolet light in an oxygen atmosphere. In order to prevent this, it is necessary to create an atmosphere of an inert gas such as nitrogen around the lamp, that is, the inside of the irradiation apparatus, and provide a synthetic quartz window to extract the irradiation light. Synthetic quartz windows are not only expensive consumables, but also cause light loss.

Since the double cylindrical lamp used for excimer light emission has an outer diameter of about 25 mm, the difference in the distance to the irradiation surface cannot be ignored between the position directly below the lamp shaft and the side surface of the lamp, resulting in a large difference in illuminance. Therefore, even if the lamps are closely arranged, a uniform illuminance distribution cannot be obtained. If the irradiation device is provided with a synthetic quartz window, the distance in the oxygen atmosphere can be made uniform, and a uniform illuminance distribution can be obtained.
When electrodeless field discharge is used, it is not necessary to make the external electrodes mesh. The glow discharge spreads over the entire discharge space simply by providing an external electrode on a part of the outer surface of the lamp. As the external electrode, an electrode that also serves as a light reflector made of an aluminum block is usually used on the back of the lamp. However, since the outer diameter of the lamp is as large as in the case of the dielectric barrier discharge, synthetic quartz is required to obtain a uniform illuminance distribution.
The biggest feature of the capillary excimer lamp is its simple structure. The quartz tube is closed at both ends, and only gas for excimer light emission is sealed inside. The outer diameter of the tube of the thin tube lamp is about 6 to 12 mm, and if it is too thick, a high voltage is required for starting.
As for the form of discharge, either dielectric barrier discharge or electrodeless field discharge can be used. The electrode may have a flat surface in contact with the lamp, but if the shape is matched to the curved surface of the lamp, the lamp can be firmly fixed, and the discharge is more stable when the electrode is in close contact with the lamp. If the curved surface is mirrored with aluminum, it becomes a light reflector.

The Xe excimer lamp is excellent in luminous efficiency because it emits ultraviolet light having a short wavelength of 172 nm at a single wavelength. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen. In addition, it is known that the energy of light having a short wavelength of 172 nm for dissociating the bonds of organic substances has high ability. The silicon compound layer (polysilazane layer, polysiloxane layer) can be modified in a short time by the high energy of such active oxygen, ozone and ultraviolet radiation. Therefore, the Xe excimer lamp has a higher throughput than a low-pressure mercury lamp that emits light with a wavelength of 185 nm or 254 nm and plasma cleaning, and can reduce the process time and the equipment area associated with the high throughput, and can also be reduced by heat. It enables irradiation to organic materials and plastic substrates that are easily damaged.
Since the excimer lamp has high light generation efficiency, it can be lit with low power. In addition, since light with a long wavelength that causes a temperature increase due to light is not emitted and energy is irradiated with a short wavelength in the ultraviolet region, the surface temperature of the irradiation object can be suppressed from increasing.

Moreover, if the irradiation intensity of vacuum ultraviolet light is high, the probability that the photon and the chemical bond in the silicon compound (polysilazane, polysiloxane) collide increases, and the modification reaction can be shortened. Further, since the number of photons penetrating to the inside increases, the modified film thickness can be increased and / or the film quality can be improved (densification). However, if the irradiation time is too long, the flatness may be deteriorated or the material other than the silicon compound in the coating film may be damaged. In general, the progress of the reaction is considered by the integrated amount of light expressed by the product of the irradiation intensity and the irradiation time, but this material, which has the same composition as in silicon oxide but takes various structural forms, The absolute value may be important.
Therefore, in this invention, it is preferable to perform the modification | reformation process which gives the maximum irradiation intensity | strength of 100-200 mW / cm < ² > at least once in a vacuum ultraviolet light irradiation process. If it is less than this strength, the reforming efficiency deteriorates abruptly, and processing takes time. On the other hand, if the irradiation intensity is higher than this, damage to the lamp and other members of the lamp unit will increase, and the deterioration of the lamp itself will be accelerated.

The irradiation time of the vacuum ultraviolet light can be arbitrarily set, but the irradiation time in the high illuminance process is preferably 0.1 second to 3 minutes. More preferably, it is 0.5 second to 1 minute.
The oxygen concentration at the time of vacuum ultraviolet light irradiation is preferably 500 to 10,000 ppm (1%). More preferably, it is 1000-5000 ppm. If the oxygen concentration is higher than the above concentration range, the reforming efficiency is lowered. In addition, when the oxygen concentration is lower than the above-mentioned concentration range, the replacement time with the atmosphere becomes longer, and at the same time, when continuous production such as roll-to-roll is performed, the air entrained in the vacuum ultraviolet irradiation chamber by web conveyance The amount (including oxygen) increases, and the oxygen concentration cannot be adjusted unless a large flow rate of gas is passed.
In the coating film containing a silicon compound (polysilazane, polysiloxane), oxygen and a small amount of water are mixed at the time of coating. Further, other than the coating film, adsorbed oxygen or adsorbed water is present on the thin glass or resin layer. It has been found that there is a sufficient oxygen source for supplying oxygen required for the reforming reaction without intentionally introducing oxygen into the irradiation chamber.
Further, the vacuum ultraviolet light of 172 nm is absorbed by oxygen, and the amount of light of 172 nm reaching the film surface is decreased, so that the efficiency of the processing by vacuum ultraviolet light may be lowered. That is, at the time of vacuum ultraviolet light irradiation, it is preferable to perform the modification treatment in a state where the vacuum ultraviolet light efficiently reaches the coating film in a state where the oxygen concentration is as low as possible.
It is preferable to supply a dry inert gas as the gas other than oxygen at the time of irradiation with vacuum ultraviolet light, and it is particularly preferable to use 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 irradiation chamber and changing the flow rate ratio.

(Other component layers)
Next, constituent layers other than the gas barrier layer and the ion barrier layer used in the barrier film of the present invention will be described.

<Smooth layer>
The barrier film of the present invention may further have a smooth layer between the substrate and the gas barrier layer (or ion barrier layer). The smooth layer is provided in order to flatten the surface of the substrate on which the protrusions and the like exist, for example, a rough surface such as a transparent resin film, and to fill the irregularities and pinholes. Such a smooth layer is basically formed by photocuring a photopolymerizable monomer.

  Examples of the photopolymerizable monomer forming the smooth layer include a photopolymerizable monomer composition containing an acrylate compound having a radical reactive unsaturated compound, and a photopolymerizable monomer containing an acrylate compound and a mercapto compound having a thiol group. Examples thereof include a photopolymerizable monomer composition in which a polyfunctional acrylate monomer such as a composition, epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, and glycerol methacrylate is dissolved. It is also possible to use any mixture of photopolymerizable monomer compositions as described above, and a composition 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, or 2 or more types of mixture.

  The photopolymerizable monomer composition contains a photopolymerization initiator. As photopolymerization initiators, benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino-acetophenone, 4,4-dichlorobenzophenone, 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, benzoin methyl Ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (p-azidobenzylidene ) 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) oxime, mihi -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 tetrabrominated, tribromophenyl sulfone, benzoin peroxide, A combination of a photoreducing substance such as eosin or methylene blue and a reducing agent such as ascorbic acid or triethanolamine can be used. These photopolymerization initiators can be used alone or in combination of two or more.

The method for forming the smooth layer is not particularly limited, but the above-described light is applied by a wet coating method such as a spin coating method, a spray coating method, a blade coating method, a bar coating method, a dip method, or a dry coating method such as a vapor deposition method. It is preferable to form by applying the polymerizable monomer composition and forming a dried coating film, and then irradiating with ultraviolet rays. In addition, as a method of irradiating ultraviolet rays, ultraviolet rays having a wavelength region of 100 to 400 nm, 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 can be used. The irradiation energy is preferably 0.1 to 100 J / cm ² .

  Moreover, in formation of a smooth layer, additives, such as antioxidant, a ultraviolet absorber, a plasticizer, can be added to the above-mentioned photopolymerizable monomer composition as needed. In addition, regardless of the position where the smooth layer is laminated, in any smooth layer, an appropriate resin or additive may be used for improving the film formability and preventing the generation of pinholes in the film.

  Solvents used for the coating solution containing the photopolymerizable monomer composition include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol, terpenes such as α- or β-terpineol, and acetone. , Ketones such as methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve , Carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, di Glycol ethers such as propylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol 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 and other acetates, diethylene glycol dialkyl ether, dipropylene glycol Dialkyl ether, 3-ethoxypro Ethyl propionic acid, methyl benzoate, N, N- dimethylacetamide, N, may be mentioned N- dimethylformamide.

The smoothness of the smooth layer is a value expressed by the surface roughness specified by JIS B 0601 (2001), and the maximum cross-sectional height Rt (p) is preferably 10 nm or more and 30 nm or less. If the value is smaller than this range, the coating liquid containing the photopolymerizable monomer composition is applied, and the coating means comes into contact with the smooth layer surface by a coating method such as a wire bar or a wireless bar. In addition, applicability may be impaired. Moreover, when larger than this range, it may become difficult to smooth the unevenness | corrugation of the coating film formed by apply | coating a coating liquid.
The surface roughness is calculated from an uneven sectional curve continuously measured with a detector having a stylus having a minimum tip radius using an AFM (atomic force microscope), and the measurement direction is determined by the stylus having a minimum tip radius. It is the roughness related to the amplitude of fine irregularities measured many times in a section of several tens of μm.

  One preferred embodiment of the smooth layer is a reactive silica particle in which a polymerizable group having photopolymerization reactivity with the resin is introduced into the resin constituting the smooth layer (hereinafter simply referred to as “reactive silica particle”). There is something that includes). For example, examples of the polymerizable group (photosensitive group) having photopolymerization include polymerizable unsaturated groups represented by (meth) acryloyloxy groups. Further, the photopolymerizable monomer composition is a compound capable of photopolymerization reaction with a photosensitive group having photopolymerization reactivity introduced on the surface of the reactive silica particles, for example, an unsaturated organic compound having a polymerizable unsaturated group. It may contain a compound. In addition, as the photopolymerizable monomer composition, a solid content adjusted by appropriately mixing a general-purpose diluent solvent with such reactive silica particles and unsaturated organic compounds having a polymerizable unsaturated group should be used. Can do.

Here, the average particle diameter of the reactive silica particles is preferably 0.001 to 0.1 μm. The method for measuring the average particle diameter is not particularly limited, but it is preferable to use a dynamic light scattering method or a laser scattering method from the viewpoint of measurement accuracy and simplicity. By making the average particle size in such a range, by using in combination with a matting agent composed of inorganic particles having an average particle size of 1 to 10 μm, which will be described later, optical properties satisfying a good balance between anti-glare properties and resolution. It becomes easy to form a smooth layer having hard coat properties. From the viewpoint of making it easier to obtain such an effect, it is more preferable to use an average particle diameter of 0.001 to 0.01 μm.
The smooth layer used in the present invention preferably contains 20% or more and 60% or less of the inorganic particles as described above as a mass ratio. By adding 20% or more, adhesion with the gas barrier layer or the ion barrier layer is improved. If it is 60% or less, the film will not be bent or cracked when heat-treated, and the optical properties such as the transparency and refractive index of the barrier film will not be affected. .

In the present invention, a polymerizable unsaturated group-modified hydrolyzable silane is chemically bonded to a silica particle by generating a silyloxy group by a hydrolysis reaction of a hydrolyzable silyl group. Can be used as reactive silica particles.
Examples of the hydrolyzable silyl group include a carboxylylate silyl group such as an alkoxylyl group and an acetoxysilyl group, a halogenated silyl group such as a chlorosilyl group, an aminosilyl group, an oxime silyl group, and a hydridosilyl group.
Examples of the polymerizable unsaturated group include acryloyloxy group, methacryloyloxy group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, malate group, and acrylamide group.

  The thickness of the smooth layer in the present invention is preferably 1 to 10 μm, more preferably 2 to 7 μm. By making it 1 μm or more, it becomes easy to make the smoothness as a film having a smooth layer sufficiently, and by making it 10 μm or less, it becomes easy to adjust the balance of optical properties of the film, and the smooth layer is made of a transparent polymer. When the film is provided only on one surface of the film, curling of the barrier film can be easily suppressed.

As an additive used for the smooth layer, a matting agent, a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator used for forming the ionizing radiation resin, or the like 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 preferably 2 parts by mass or more, more preferably 4 parts by mass or more, and still more preferably 6 parts per 100 parts by mass of the solid content of the hard coating agent (resin constituting the smooth layer). It is desirable that they are mixed in a proportion of not less than 20 parts by mass, preferably not more than 20 parts by mass, more preferably not more than 18 parts by mass, and still more preferably not more than 16 parts by mass.
Thermoplastic resins include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, and methylcellulose, polyvinyl acetate and copolymers thereof, polyvinyl chloride and copolymers thereof, polyvinylidene chloride and copolymers thereof. Vinyl resins such as polymers, polyacetal resins such as polyvinyl formal and polyvinyl butyral, polyacrylic acid resins and copolymers thereof, acrylic resins such as polymethacrylic acid resins and copolymers thereof, polystyrene resins, polyamide resins, Examples thereof include linear polyester resins and polycarbonate 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 silicone resin etc. are mentioned.
Moreover, as ionizing radiation curable resin, it hardens | cures by irradiating ionizing radiation (an ultraviolet ray or an electron beam) to the ionizing radiation hardening coating material which mixed 1 type (s) or 2 or more types, such as a photopolymerizable prepolymer or a photopolymerizable monomer. You can use what you want. 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.

<Bleed-out prevention layer>
The barrier film of the present invention may further have a bleed-out preventing layer. The bleed-out prevention layer is a phenomenon in which, when a substrate (film) having a smooth layer is heated, unreacted oligomers etc. migrate from the substrate (film) to the surface and contaminate the contact surface. For the purpose of suppression, it is preferably provided on the surface opposite to the surface of the substrate having the smooth layer. The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.

  In addition, when a coating such as a polysilazane layer or a polysiloxane layer is modified to form a metal oxide (or nitride or oxynitride), it is accompanied by large film shrinkage, so that lateral deformation is suppressed and cracking is prevented. It is preferable to do. For this purpose, it is conceivable to provide a so-called hard coat layer having a high surface hardness or elastic modulus, but the bleed-out prevention layer can also serve as the hard coat layer. Therefore, when forming a metal oxide (or nitride or oxynitride) thin film in the present invention, the bleed-out prevention layer preferably has a surface hardness of 2H or more and an elastic modulus of 15 GPa or more. In order to measure the mechanical properties of such a thin film, for example, nanoindentation measurement is preferably used.

  The unsaturated organic compound having a polymerizable unsaturated group for forming a bleed-out preventing layer is a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule, or 1 in the molecule. Examples thereof include monounsaturated organic compounds having a single polymerizable unsaturated group. These may be used alone or in combination of two or more.

  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, ditrimethylolprop Tetra (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate.

  Moreover, as a unit price unsaturated organic compound, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, 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-e Xoxyethoxy) 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. .

  In addition, the bleed-out prevention layer may contain a matting agent, a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator, and the like as additives. As the matting agent, thermoplastic resin, thermosetting resin, ionizing radiation curable resin, and photopolymerization initiator, the same additives as those for the smoothing layer described above can be used.

As described above, the bleed-out prevention layer is prepared by blending a hard coat agent, a matting agent, and other components as necessary, and applying a coating solution prepared by a diluting solvent appropriately used on the film surface by a conventionally known coating method. Then, it can form by irradiating with ionizing radiation and making it harden | cure.
In addition, as a method of irradiating ionizing radiation, 100-400 nm emitted from 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, preferably irradiating ultraviolet rays in a wavelength region of 200-400 nm, 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. As irradiation amount, 0.1-100 J / cm < ² > is preferable.
The thickness of the bleed-out prevention layer in the present invention is preferably 1 to 10 μm, more 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 the optical properties of the film and to make it easy to suppress the curling of the barrier film. become able to.

<Adhesive protective film>
The barrier film of the present invention may further have an adhesive protective film on the outermost layer.
When the barrier film includes the adhesive protective film, the barrier film surface can be protected from damage and can be easily installed on an object (for example, an electronic device such as a liquid crystal display element) to be sealed with the barrier film.
The adhesive protective film is not particularly limited as long as it can be applied to a barrier film, and conventionally known ones can be used. For example, acrylic resin, urethane resin, epoxy resin, polyester resin, melamine resin, phenol resin, polyamide resin, ketone What was formed with resin, vinyl resin, hydrocarbon resin, etc. can be used.

(Liquid crystal display panel as electronic equipment)
The barrier film 10 (11) according to the present invention can be used as a sealing film for sealing electronic devices such as solar cells, liquid crystal display elements, and organic EL elements.
FIG. 3 shows an example of a liquid crystal display panel (liquid crystal display) which is an electronic device using the barrier film 10 (11) as a sealing film.
As shown in FIG. 3, the liquid crystal display panel 20 is configured such that, for example, a liquid crystal display element 9 having a configuration in which a liquid crystal 8 is sandwiched between a transparent electrode 6 such as ITO and a polyimide alignment film 7 is sandwiched between a pair of barrier films 10. The peripheral side of the liquid crystal display element 9 (transparent electrode 6, polyimide alignment film 7, liquid crystal 8) is sealed with a sealing material 9a.
A transparent electrode 6 is disposed on the surface of the barrier film 10 on which the ion barrier layer 3 (or the gas barrier layer 2) is formed, so that the liquid crystal display element 9 is sealed.
Thus, if the liquid crystal display panel 20 is formed by sealing the liquid crystal display element 9 with the barrier film 10 of the present invention, impurity ions diffusing from the base material 1 are not eluted into the liquid crystal, Further, deterioration of the liquid crystal display element can be prevented from gas such as water vapor.

  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.

Example 1
<< Production of support substrate >>
A support base material formed by forming a bleed-out prevention layer and a smooth layer on a resin base material (resin film) serving as the base material of the barrier film was prepared.
<Base material>
A polyethylene terephthalate (PET) film (A4300, manufactured by Toyobo Co., Ltd.) having a thickness of 125 μm and subjected to easy adhesion processing on both sides was used as a substrate.
<Formation of bleed-out prevention layer>
On one side of the base material, UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation was applied with a wire bar so that the film thickness after drying was 4 μm, and then dried at 80 ° C. for 3 minutes. The bleed-out prevention layer was formed by performing treatment and curing treatment by irradiation with light having an irradiation energy amount of 1.0 J / cm ² using a high-pressure mercury lamp in an air atmosphere. In addition, all the bleed-out prevention layers of an Example and a comparative example were made common.
<Formation of smooth layer>
Subsequently, a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation was applied to the opposite surface of the substrate with a wire bar so that the film thickness after drying was 4 μm, and then 3 at 80 ° C. A smoothing layer was formed by performing a drying treatment for 1 minute and a curing treatment by light irradiation with an irradiation energy amount of 1.0 J / cm ² using a high-pressure mercury lamp in an air atmosphere. The maximum cross-sectional height Rt (p) of this smooth layer was 16 nm. In addition, all the smooth layers of an Example and a comparative example were made common.
Thus, a bleed-out prevention layer and a smooth layer were formed on the base material, and a support base material that was a PET film with a double-sided hard coat was prepared.

<Barrier film 1>
On the smooth layer of the above-mentioned support substrate, after applying and drying a polysiloxane hard coat material Glasca HPC7003 manufactured by JSR so as to have a dry film thickness of 900 nm, Xe excimer light irradiation was performed under the following conditions to form an inorganic skeleton. A main ion barrier layer (polysiloxane layer) was formed. In addition, 3 wt% of an amine catalyst was added as a curing agent with respect to the solid content of Glasca HPC7003.
(Excimer light irradiation conditions)
Irradiation device: MIRH-M-1-200H manufactured by MDI Excimer
Substrate temperature: 100 ° C
Integrated light quantity: ² J / cm ²
Maximum illuminance: 100 mW / cm ²

Further, a polysilazane solution containing 1 wt% of an amine catalyst (a solution in which NAX120 and NN120 are mixed at a ratio of 1: 4) is applied on the ion barrier layer and dried at 80 ° C. for 2 minutes, and then a polysilazane coating having a dry film thickness of 150 nm is applied. A film was formed. A gas barrier layer (polysilazane layer) containing silicon oxide was formed by irradiating the polysilazane coating film with Xe excimer light under the following conditions for modification.
(Excimer light irradiation conditions)
Irradiation device: MIRH-M-1-200H manufactured by MDI Excimer
Substrate temperature: 100 ° C
Integrated light quantity: 3 J / cm ²
Maximum illuminance: 100 mW / cm ²

  Thus, the barrier film 1 (refer FIG. 4 (1)) which laminated | stacked the ion barrier layer (polysiloxane layer) and the gas barrier layer (polysilazane layer) in order on the support base material was produced.

<Barrier film 2>
A polysilazane solution containing 1 wt% of an amine catalyst (a solution in which NAX120 and NN120 are mixed at a ratio of 1: 4) is applied on the smooth layer of the above-mentioned supporting substrate and dried at 80 ° C. for 2 minutes, and the dry film thickness is 150 nm. A polysilazane coating film was formed. A gas barrier layer (polysilazane layer) containing silicon oxide was formed by irradiating the polysilazane coating film with Xe excimer light under the following conditions for modification.
(Excimer light irradiation conditions)
Irradiation device: MIRH-M-1-200H manufactured by MDI Excimer
Substrate temperature: 100 ° C
Integrated light quantity: 3 J / cm ²
Maximum illuminance: 100 mW / cm ²

Furthermore, on the gas barrier layer, a polysiloxane hard coat material Glassca HPC7003 manufactured by JSR Co. was applied and dried so as to have a dry film thickness of 900 nm, and then irradiated with Xe excimer light under the following conditions to mainly comprise an inorganic skeleton. An ion barrier layer (polysiloxane layer) was formed. In addition, 3 wt% of an amine catalyst was added as a curing agent with respect to the solid content of Glasca HPC7003.
(Excimer light irradiation conditions)
Irradiation device: MIRH-M-1-200H manufactured by MDI Excimer
Substrate temperature: 100 ° C
Integrated light quantity: ² J / cm ²
Maximum illuminance: 100 mW / cm ²

  Thus, the barrier film 2 (refer FIG. 4 (2)) which laminated | stacked the gas barrier layer (polysilazane layer) and the ion barrier layer (polysiloxane layer) in order on the support base material was produced.

<Barrier film 3>
On the gas barrier layer of the barrier film 1, after applying and drying a polysiloxane hard coat material Glassca HPC7003 manufactured by JSR so as to have a dry film thickness of 900 nm, Xe excimer light irradiation is performed under the following conditions to mainly form an inorganic skeleton. An ion barrier layer (polysiloxane layer) was formed. In addition, 3 wt% of an amine catalyst was added as a curing agent with respect to the solid content of Glasca HPC7003.
(Excimer light irradiation conditions)
Irradiation device: MIRH-M-1-200H manufactured by MDI Excimer
Substrate temperature: 100 ° C
Integrated light quantity: ² J / cm ²
Maximum illuminance: 100 mW / cm ²

  In this way, a barrier film 3 in which an ion barrier layer (polysiloxane layer), a gas barrier layer (polysilazane layer), and an ion barrier layer (polysiloxane layer) are sequentially laminated on a supporting substrate (see FIG. 4 (3)). Was made.

<Barrier film 4>
A gas barrier layer and an ion barrier layer were further laminated in this order on the ion barrier layer of the barrier film 2 in the same manner as the barrier film 2.
As described above, a barrier film 4 in which a gas barrier layer (polysilazane layer), an ion barrier layer (polysiloxane layer), a gas barrier layer (polysilazane layer), and an ion barrier layer (polysiloxane layer) are sequentially laminated on a supporting substrate. (See FIG. 4 (4)).

<Barrier film 5>
In the barrier film 2, the ion barrier layer was not formed, but only the gas barrier layer (polysilazane layer) was formed on the supporting base material, thereby preparing the barrier film 5 (see FIG. 4 (5)).

<Barrier film 6>
In the barrier film 1, the gas barrier layer was not formed, but only the ion barrier layer (polysiloxane layer) was formed on the supporting base material, thereby preparing the barrier film 6 (see FIG. 4 (6)).

<Barrier film 7>
The polysilazane solution for forming the gas barrier layer of the barrier film 2 is changed to the following solution, and a gas barrier layer (TEOS sol-gel barrier layer) is formed by the sol-gel method, and the barrier film 7 (see FIG. 4 (7)) Was made.
In addition, in the sol-gel method, since the film thickness equivalent to the coating film by a polysilazane solution was not obtained by one application | coating, application | coating-drying was repeated 3 times.
(Preparation of coating solution for sol-gel SiO ₂ film)
A sol solution was prepared by mixing and stirring 1 mol of tetraethoxysilane (TEOS), 4 mol of ion-exchanged water, 4 mol of ethanol as an organic solvent, and 0.4 mol of hydrochloric acid as a catalyst. This sol solution was aged at room temperature for 3 days to obtain a silica sol coating solution.
(Formation of SiO ₂ film)
The silica sol coating solution was applied three times and dried at 80 ° C. for 5 minutes so that the dry film thickness was 150 nm, and then fired at 120 ° C. for 1 hr to form a gas barrier for the SiO ₂ thin film on the support substrate. A layer (TEOS sol-gel barrier layer) was formed.

<Barrier film 8>
The polysilazane solution for forming the gas barrier layer of the barrier film 1 is changed to the above-mentioned silica sol coating solution, and a gas barrier layer (TEOS sol-gel barrier layer) is formed by a sol-gel method to form a barrier film 8 (FIG. 4 (8)). Reference) was made.

(Evaluation of barrier film)
Sample No. of the barrier film produced as described above. Examples 1 to 8 (No. 1 ; Examples (present invention), No. 2; Reference Examples, Nos. 3 to 4; Examples (present invention), Nos. 5 to 8; Comparative Examples) as barrier films Performance evaluation was performed.
The performance evaluation of the barrier film was performed on the evaluation items of gas barrier properties and ion elution properties.

(Evaluation of gas barrier properties)
The gas barrier property was evaluated based on the water vapor transmission rate.
In evaluating the gas barrier property (water vapor transmission rate), the following apparatuses and materials were used.
<Device used>
Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
<Evaluation materials>
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
<Manufacture of water vapor barrier property evaluation cell>
Using a vacuum vapor deposition device (JEOL-made vacuum vapor deposition device JEE-400), on each barrier film sample's barrier layer (gas barrier layer, ion barrier layer) surface, metal calcium is applied in an area of 1 cm × 1 cm using a mask. Evaporated. Thereafter, the mask was removed in a vacuum state, and aluminum was deposited on the entire surface of one side of the sheet. After sealing with aluminum, the vacuum state is released, and it is immediately transferred to a dry nitrogen gas atmosphere, and a quartz glass having a thickness of 0.2 mm is provided on the aluminum vapor deposition surface via a sealing UV curable resin (manufactured by Nagase ChemteX). Were bonded together, and the resin was cured and adhered, followed by main sealing, thereby producing a water vapor barrier property evaluation cell.
Then, using a constant temperature and humidity oven, the obtained evaluation cell was stored under high temperature and high humidity of 60 ° C. and 90% RH, and based on the method described in JP-A-2005-283561, the corrosion amount of metallic calcium The amount of moisture permeated into the cell was calculated.
In addition, in order to confirm that there is no permeation of water vapor from other than the barrier film surface, a cell using a sample in which metallic calcium is vapor-deposited on a quartz glass plate having a thickness of 0.2 mm instead of the barrier film sample as a comparative sample. Similarly, it was stored under high temperature and high humidity at 60 ° C. and 90% RH, and it was confirmed that corrosion of metallic calcium did not occur even after 1000 hours.
The average WVTR (water vapor permeability) was calculated from the time (100% corrosion time) in which all calcium was corroded by the method described above, and the gas barrier properties were evaluated according to the following criteria. In practice, a level of Δ or higher is necessary. The evaluation results are shown in Table 1.
○: WVTR is less than 1 × 10 ⁻³ Δ: WVTR is 1 × 10 ⁻³ or more and less than 1 × 10 ⁻² ×: WVTR is 1 × 10 ⁻² or more

(Evaluation of ion dissolution)
Ion elution was evaluated by the following method.
<Production of simple cell for evaluation>
A pixel electrode (transparent electrode) made of ITO was formed on the barrier layer (gas barrier layer, ion barrier layer) surface of each barrier film sample, and a vertical polyimide alignment film was formed on the electrode. In this manner, a pair of films (two samples each) on which a pixel electrode and a vertical polyimide alignment film were formed was prepared.
A pair of films prepared in this manner are opposed to each other so that the alignment films face each other, and are aligned using spacer beads while keeping the distance between both films constant, and the periphery is sealed with a sealant so as to leave an opening for liquid crystal injection. Stopped. Next, a VA liquid crystal MLC-6610 (manufactured by Merck & Co., Inc.) was injected between the alignment portions from the openings, and the openings were sealed to prepare a simple liquid crystal cell.
The obtained simple liquid crystal cell was put into a constant temperature and humidity chamber at 60 ° C. for 500 hours, and then a current-voltage Lissajous waveform of the liquid crystal cell was measured using a liquid crystal cell ion density measuring device (manufactured by Toyo Technica Co., Ltd.). From the waveform, the density of ions eluted in the liquid crystal disposed between the films was evaluated. At this time, the height of the director peak of the liquid crystal was compared with the height of the peak due to the eluted ions, and the ion elution was evaluated as follows. The evaluation results are shown in Table 1.
○: Almost no influence on liquid crystal drive △: Can be used but may affect the drive of liquid crystal ×: Influence on drive of liquid crystal

As is clear from the evaluation results shown in Table 1, a barrier film (sample Nos. 1 to 4) having a structure in which a gas barrier layer (polysilazane layer) and an ion barrier layer (polysiloxane layer) are laminated is a gas barrier. It can be seen that this is a barrier film having both gas barrier performance and ion elution prevention performance.
For example, in the case of a barrier film having an ion barrier layer on the outermost layer, impurity ions that have passed through the gas barrier layer are blocked (trapped) at the interface between the gas barrier layer and the ion barrier layer and at the ion barrier layer. While exhibiting high ion barrier properties (ion elution prevention properties), the ion barrier layer also functions as a protective film for the gas barrier layer. In addition, if the barrier film has a gas barrier layer on the outermost layer, impurity ions from the substrate side are blocked (trapped) at the ion barrier layer or interface, so the gas barrier layer is not deteriorated by impurity ions. High gas barrier properties can be maintained.
Furthermore, the gas barrier layer (polysilazane layer) and ion barrier layer (polysiloxane layer) of these barrier films can be formed by a coating process, and since the production efficiency is high, a lightweight and flexible barrier film is manufactured at low cost. It becomes possible.

(Example 2)
The base material used in Example 1 is changed from a PET film to a polyethersulfone (PES) film, and a support base material using the PES film as a base material is the same layer as barrier films 1 to 5 in Example 1. Barrier films 11 to 15 having a configuration were prepared.
These barrier films 11 to 15 were subjected to the following treatment as a simulated LCD production process, and then evaluated for gas barrier properties and ion elution properties in the same manner as in Example 1. The evaluation results are shown in Table 2.

《Simulated LCD element manufacturing process》
<Washing process>
After ultrasonic cleaning with ultrapure water, ultrasonic cleaning is performed with a 5-fold diluted solution of weak alkaline detergent (Clean Through: Asahi Kasei), followed by ultrasonic cleaning with ultrapure water and ultrapure water. Washed with running water.
<Drying process>
After removing water droplets with dry nitrogen air, heat drying was performed in air at 100 ° C. for 30 minutes.
<Main drying and drive circuit or color filter manufacturing process>
The treatment was performed at 180 ° C. under reduced pressure (about 10 ⁻³ Torr) for 1 hour.

As is clear from the evaluation results shown in Table 2, the barrier film (sample Nos. 11 to 14) having a structure in which a gas barrier layer (polysilazane layer) and an ion barrier layer (polysiloxane layer) are laminated is a gas barrier. Therefore, the deterioration due to the LCD device fabrication process is extremely small. It can be seen that the process resistance is high.
That is, it can be seen that the barrier film according to the present invention has good gas barrier performance and ion elution prevention performance excellent in durability.

  As described above, the barrier film according to the present invention has high gas barrier performance and ion elution prevention performance, and can be said to be an excellent barrier film for sealing electronic devices.

  The application of the present invention is not limited to the above-described embodiment, and can be appropriately changed without departing from the spirit of the present invention.

DESCRIPTION OF SYMBOLS 1 Base material 2 Gas barrier layer 3 Ion barrier layer 4 Smooth layer 5 Bleed-out prevention layer 9 Liquid crystal display element (electronic device)
10 Water vapor barrier film 11 Water vapor barrier film 20 Liquid crystal display panel (electronic equipment)

Claims (3)

A method for producing a barrier film comprising a gas barrier layer and an ion barrier layer mainly composed of an inorganic skeleton on a substrate,
After forming a coating film containing polysilazane, forming the gas barrier layer by modifying the coating film by applying vacuum ultraviolet light; and
Forming a coating film containing polysiloxane, and then forming the ion barrier layer by modifying the coating film by irradiating it with vacuum ultraviolet light.
Providing the gas barrier layer in an arrangement covering the ion barrier layer;
A method for producing a barrier film, wherein an interface between the gas barrier layer and the ion barrier layer is an ion block surface. A method for producing a barrier film comprising a gas barrier layer and an ion barrier layer mainly composed of an inorganic skeleton on a substrate,
After forming a coating film containing polysilazane, forming the gas barrier layer by modifying the coating film by applying vacuum ultraviolet light; and
Forming a coating film containing polysiloxane, and then forming the ion barrier layer by modifying the coating film by irradiating it with vacuum ultraviolet light.
The gas barrier layer is provided in an arrangement sandwiched between the paired ion barrier layers ,
Method of manufacturing features and to Luba rear film to the surface of the ion barrier layer and the gas barrier layer and the ion blocking surface. A method for producing a barrier film comprising a gas barrier layer and an ion barrier layer mainly composed of an inorganic skeleton on a substrate,
After forming a coating film containing polysilazane, forming the gas barrier layer by modifying the coating film by applying vacuum ultraviolet light; and
Forming a coating film containing polysiloxane, and then forming the ion barrier layer by modifying the coating film by irradiating it with vacuum ultraviolet light.
The ion barrier layer is provided in an arrangement sandwiched between the gas barrier layers forming a pair ,
Method of manufacturing features and to Luba rear film to the surface of the ion barrier layer and the gas barrier layer and the ion blocking surface.

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