TWI788532B - gas barrier film - Google Patents

Abstract

A gas barrier film which has a high effect of preventing the permeation of gases such as oxygen or water vapor and which satisfies a certain level of gas barrier properties, has high light transmittance, and can reduce production costs. The gas barrier film has n-layer (n is an integer of 2 or more) gas barrier layer formed of a composition containing a silicon compound, among the aforementioned n-layer gas barrier layers, 1 or more (n-1) or less layers are modified made.

Description

gas barrier film

The present invention relates to a gas barrier thin film which satisfies a certain level of gas barrier properties, has high light transmittance, and can reduce production costs.

In recent years, organic EL elements have attracted attention as light-emitting elements capable of emitting light with high luminance by low-voltage DC driving. However, organic EL elements have a problem that light emission characteristics such as light emission luminance, light emission efficiency, and light emission uniformity tend to decrease with the passage of time. The problem of time-dependent performance degradation typified by organic EL elements is likely to be common to all electronic components and optical components that have attracted attention in recent years. As a cause, it is thought that oxygen, moisture, etc. infiltrate into the inside of an electronic member or an optical member, and cause performance deterioration. Also, as a solution to this cause, several methods have been proposed for sealing electronic components, optical components, etc., which are objects to be sealed, with a gas barrier sealing material having a layered structure.

For example, Patent Document 1 discloses a gas barrier laminate having at least two inorganic layers with gas barrier properties, at least one of which is a silicon oxynitride layer, and the silicon oxynitride layer has A composition gradient region is a composition gradient region in which the presence ratio of oxygen element decreases and the presence ratio of nitrogen element increases as it approaches the substrate side with respect to the thickness direction of the layer. [Prior Art Literature] [Patent Document]

[Patent Document 1] WO2014/157685

[Problem to be Solved by the Invention]

In recent years, gas barrier thin films have been manufactured by laminating two or more gas barrier layers in an attempt to further improve gas barrier properties, but on the other hand, it has also been pointed out that the manufacturing cost increases as the number of steps increases. Therefore, there is a demand for a thin film having gas barrier properties that satisfies a certain level of gas barrier properties and can reduce production costs.

However, in the gas barrier laminate system disclosed in Patent Document 1, among at least two inorganic layers having gas barrier properties, one layer is a silicon oxynitride layer having a specific composition gradient region, although it can obtain Extremely high water vapor barrier properties and excellent bending resistance, but there is still room for improvement when trying to improve light transmission or reduce manufacturing costs.

Therefore, the present invention was made in order to solve the above-mentioned problems, and an object of the present invention is to provide a gas barrier film having a high effect of preventing the permeation of gases such as oxygen or water vapor and having a gas barrier property satisfying a certain level. The light transmittance is high, and the manufacturing cost can be reduced. [Means to solve the problem]

As a result of intensive studies in view of the above-mentioned problems, the present inventors have found that by setting the number of modified layers to 1 or more (n-1) among the gas barrier layers of n layers (n is an integer of 2 or more), In the following, it is possible to obtain a gas barrier thin film which satisfies a certain level of gas barrier properties, has high light transmittance, and can reduce production costs, and thus completed the present invention. That is, the present invention is as follows.

[1]. A gas barrier thin film having n layers (n is an integer greater than 2) of gas barrier layers formed of a composition containing a silicon compound, characterized in that one of the n layers of gas barrier layers Among them, the layer of 1 or more (n-1) or less is modified. [2]. The gas barrier thin film according to the aforementioned [1], wherein, among the n gas barrier layers, one gas barrier layer is modified. [3]. The gas barrier thin film according to the aforementioned [1] or [2], wherein, among the n gas barrier layers, the outermost gas barrier layer is modified. [4]. The gas barrier film according to any one of the aforementioned [1] to [3], which is a gas barrier film comprising a resin layer and laminating the aforementioned n gas barrier layers on the resin layer, And the gas barrier layer closest to the aforementioned resin layer has not been modified. [5]. The gas barrier thin film according to any one of [1] to [4] above, wherein all the n-layer gas barrier layers are layers formed of a composition containing the same type of silicon compound. [6]. The gas barrier thin film according to any one of [1] to [5] above, wherein all the n gas barrier layers are formed of the same composition. [7]. The gas barrier film according to any one of [1] to [6] above, wherein the gas barrier film has a total light transmittance of 89% or more. [8]. The gas barrier film according to any one of [1] to [7] above, wherein the gas barrier film has a water vapor transmission rate of 5×10 ^-3 (g/m ² /day) or less . [Effect of the invention]

According to the present invention, it is possible to provide a gas barrier film which has a high effect of preventing the permeation of gases such as oxygen and water vapor, has a gas barrier property satisfying a certain level, has high light transmittance, and can reduce production costs.

[Best Mode for Carrying Out the Invention]

[Gas barrier film] The gas barrier thin film of the present invention has n layers (n is an integer of 2 or more) of gas barrier layers formed of a composition containing a silicon compound, and among the n layers of gas barrier layers, 1 or more (n-1) or less The gas barrier layer is formed by modification treatment. Here, the "gas barrier property" refers to the property of preventing gas such as oxygen and water vapor from permeating.

The gas barrier thin film of the present invention has n layers (n is an integer of 2 or more) of gas barrier layers, and among the n layers of gas barrier layers, 1 or more (n-1) or less are defined as modified What is necessary is just to comprise the layer of a process, and it does not specifically limit. Furthermore, the n-layer gas barrier layer may be formed by laminating directly on the resin layer, or may be formed by interposing another layer (such as a primer layer) on the resin layer. Also, the n-layer gas barrier layer may be formed by laminating directly on the release sheet, or may be formed by interposing a resin layer on the release sheet.

As a layer structure which the gas barrier thin film of this invention has, the aspect shown below is mentioned, for example. ・Resin layer/n-layer gas barrier layer ・Resin layer/primer layer/n-layer gas barrier layer ・Resin layer/n-layer gas barrier layer/adhesive layer/1st release sheet ・2nd release sheet/n-layer gas barrier layer/adhesive layer/1st release sheet ・2nd release sheet/resin layer/n-layer gas barrier layer/adhesive layer/1st release sheet In the aforementioned aspect of the layer constitution, the first release sheet and the second release sheet may be the same or different. The state of the aforementioned layer constitution represents the state before using the gas barrier film as a sealing material. When a gas barrier film is used as a sealing material, generally, the first release sheet is peeled and removed, and the surface of the exposed adhesive layer is bonded to the surface of the object to be sealed to obtain a sealed body. In addition, after the surface of the adhesive layer of the sealing material is bonded to the surface of the object to be sealed, generally, the second release sheet is peeled and removed, and the n-layer gas barrier layer or resin layer is exposed, thereby producing the following: The layer composition represented. ・n-layer gas barrier layer/adhesive layer ・Resin layer/n-layer gas barrier layer/adhesive layer Also, when there is no resin layer or when the resin layer does not sufficiently function as a support for the gas barrier film, the second release sheet functions as a support for the gas barrier film until it is peeled off and removed.

In the gas barrier film of the present invention, the water vapor transmission rate is preferably not more than 5×10 ^-1 (g/m ² /day), more preferably not more than 5×10 ^-2 (g/m ² /day), More preferably, it is 5×10 ^-3 (g/m ² /day) or less. In the present invention, by setting the water vapor transmission rate within the above range, a gas barrier film having a high effect of preventing permeation of gases such as oxygen and water vapor and satisfying a certain level of gas barrier properties can be obtained. Here, the so-called "water vapor transmission rate" refers to the value measured by using a water vapor transmission rate measuring device in a high-temperature and high-humidity environment at 40°C and a relative humidity of 90%. However, the more specific measurement method is based on the implementation described below. example method.

In addition, the total light transmittance of the gas barrier film of the present invention is preferably at least 89%, more preferably at least 89.5%, and more preferably at least 90%. By setting the total light transmittance of the gas barrier thin film within the above range, a gas barrier thin film with excellent light transmittance can be obtained, so it can be used particularly advantageously for sealing optical members such as organic EL elements. The use of materials. Here, the "total light transmittance" refers to the ratio of the light that is incident on the gas barrier film to the light that will pass through the gas barrier film. It is a value measured using a haze meter in accordance with JIS K7361-1. The specific measurement method is based on the method of the examples described later. The higher the total light transmittance, the higher the light transmittance can be evaluated.

[Gas barrier layer] The number of laminated gas barrier layers in the present invention is set to be n layers (n is an integer of 2 or more), that is, 2 or more layers. When the number of laminated gas barrier layers is set to be 2 or more, the gas barrier properties of the gas barrier layers can be further improved simply by increasing the number of layers shielding gases such as oxygen or water vapor. Therefore, specifically setting the number of laminated gas barrier layers to two or more layers can be performed in accordance with the level required for the object to be sealed when the object to be sealed is sealed with a gas barrier film as a sealing material. Decide. For example, when the object to be sealed is an optical member such as an organic EL element, the number of laminated gas barrier layers is preferably 2 to 6 layers, more preferably 2 to 4 layers, and more preferably 2 to 3 layers. layer. By setting the lamination number of the gas barrier layer within the above range, it is possible to further improve the gas barrier properties, so it is particularly advantageous for use as a sealing material for sealing optical members such as organic EL elements.

In the present invention, the number of gas barrier layers to be modified is set to be 1 or more (n-1) or less among the gas barrier layers of n layers (n is an integer of 2 or more). Hitherto, in a gas barrier film formed by laminating n gas barrier layers, it has been semi-common sense to try to improve the gas barrier properties by modifying all n gas barrier layers. However, if the entire gas barrier layer is modified, the ratio of light passing through the gas barrier film tends to decrease among the light incident on the gas barrier film at this time, that is, the total light transmittance will decrease. And the light transmittance tends to deteriorate. When the gas barrier layer is modified, in general, the surface layer of the gas barrier layer on the modified side is modified to become denser, while the inside of the gas barrier layer is not modified and becomes denser. The original density state. Therefore, even in the so-called reformed gas barrier layer, there are areas where the surface layer is densified and areas where the original density state is present inside. Between the regions with different characteristics, the refractive index is also different, and a difference in the refractive index occurs, and reflection of light occurs at the boundary between the different regions. The frequency causing light reflection increases with the increase in the number of modified gas barrier layers. Therefore, if the entire gas barrier layer is modified, the frequencies causing reflection of light are many, so the total light transmittance decreases and the light transmittance tends to deteriorate. In order to improve the gas barrier properties, the present inventors conducted studies from various angles, such as increasing the thickness of the gas barrier layer and increasing the number of gas barrier layers. The insights obtained therein are as follows: when the total thickness of the gas barrier layer is set to be the same, when comparing the gas barrier layer formed by a single layer with the gas barrier layer formed by multiple layers, the gas barrier layer formed by multiple layers is Even if a part of the gas barrier layer is not modified, the gas barrier property is high. The reason for this is considered to be that in the step of forming the gas barrier layer, defects such as unavoidable scratches and pinholes are generated on the surface of the gas barrier layer, which causes the gas barrier properties to decrease. In the present invention, by having two or more gas barrier layers, even when defects such as scratches or pinholes are generated on the surface of the gas barrier layer in the step of forming the gas barrier layer, the gas in the rear layer and subsequent layers The step of forming the barrier layer is also a step of blocking the defects, and as a result, the reduction of the gas barrier properties can be prevented. Also, in the present invention, by having two or more gas barrier layers, on the contrary, even in the case where defects such as scratches or pinholes are generated on the surface of the gas barrier layer in the step of forming the subsequent gas barrier layer In this case, at least one gas barrier layer itself present in the front layer also functions to block the defects, and as a result, the reduction of the gas barrier properties can be prevented.

If the improvement of the gas barrier properties is only pursued, it is sufficient to modify all the n-layer gas barrier layers, but on the other hand, the total light transmittance will decrease and the light transmittance tends to deteriorate. Therefore, in the present invention, by setting the number of gas barrier layers to be modified to 1 or more (n-1), the gas to be modified can be determined in consideration of the balance between gas barrier properties and light transmittance. The number of barrier layers. For example, if the object to be sealed is an optical member such as an organic EL element, the number of laminated gas barrier layers is preferably 2 to 6 layers. For this, the range of the number of gas barrier layers to be reformed is preferably , as shown below.

When there are two gas barrier layers, the number of modifying treatments is preferably one layer. If there are three gas barrier layers, the number of modifying treatments is preferably 1 to 2 layers, and more preferably 1 layer. If there are four gas barrier layers, the number of modifying treatments is preferably 1-3 layers, more preferably 1-2 layers, and more preferably 1 layer. When there are five gas barrier layers, the number of modifying treatments is preferably 1 to 4 layers, more preferably 1 to 3 layers, more preferably 1 to 2 layers, and even more preferably 1 layer. If the gas barrier layer is 6 layers, the number of modification treatment is preferably 1-5 layers, more preferably 1-4 layers, more preferably 1-3 layers, more preferably 1-2 layers , and more preferably 1 layer.

In the present invention, the number of gas barrier layers to be modified is at least 1 (n-1), preferably 1 layer among n or more gas barrier layers (n is an integer of 2 or more). Accordingly, it is possible to minimize the "boundary between the modified region and the unmodified region" which is the cause of the decrease in light transmittance in the gas barrier layer. Moreover, since the balance of a gas barrier property and a light transmittance is excellent, it can be used especially advantageously as a sealing material which seals the optical member, such as an organic EL element. Furthermore, compared with the case where all n layers are subjected to modification treatment, since the number of steps of modification treatment can be reduced, the manufacturing cost can also be reduced.

In the present invention, the position of the modified gas barrier layer is not particularly limited, but the outermost gas barrier layer is preferably modified. Although the mechanism of the improvement of the gas barrier properties according to the present invention is unclear, if defects such as scratches or pinholes are generated on the surface of the outermost gas barrier layer, if the degree of the defects is deep, it will Generally speaking, the vicinity of the surface of the gas barrier layer reaching the front layer can be a cause of a decrease in gas barrier properties. However, when the position of the gas barrier layer to be reformed is set as the outermost gas barrier layer, the step of performing reforming treatment on the outermost gas barrier layer also has the function of converting the gas in the previous layer through this defect. As a result of the step of performing the reforming treatment near the surface of the barrier layer, the reduction of the gas barrier properties can be effectively prevented, and therefore it is considered that the gas barrier properties are improved. From such a viewpoint, it is preferable that the outermost gas barrier layer is directly laminated on the previous gas barrier layer. Also, the so-called "outermost layer" here refers to the meaning of the gas barrier layer formed last among all the gas barrier layers, and does not refer to the side of the outermost gas barrier layer that is far away from the gas barrier layer of the previous layer. The above does not form the meaning of any layer. For example, an adhesive layer described later may be laminated on the surface of the outermost gas barrier layer.

On the other hand, the position of the unmodified gas barrier layer in the present invention is not particularly limited, and if the gas barrier film has a resin layer, it is more preferable that the gas barrier layer closest to the resin layer is unmodified. good. That is, in the present invention, at least one of the two or more gas barrier layers is an unreformed gas barrier layer, but the position of the at least one unreformed gas barrier layer is determined by The gas barrier layer closest to the resin layer is preferred. The mechanism of the improvement of the gas barrier properties brought about by the present invention is unclear, but if the gas barrier layer after the gas barrier layer closest to the resin layer has scratches or scratches on the surface of the modified material In the case of defects such as pinholes, at least one gas barrier layer in the front layer itself also has the function of blocking the defect, and the step of modifying the gas barrier layer after the rear layer is also The step of modifying the vicinity of the surface of the gas barrier layer of the front layer through this defect is also included, and as a result, the reduction of the gas barrier property can be effectively prevented, and the gas barrier property is considered to be improved due to this. From such a viewpoint, it is preferable that the gas barrier layer to be modified is directly laminated on the previous gas barrier layer.

The n-layer gas barrier layers may all have the same thickness or may have different thicknesses. The thickness of the gas barrier layer 1 is preferably from 50 to 500 nm, more preferably from 50 to 400 nm, more preferably from 50 to 300 nm. By setting the thickness of the first gas barrier layer within the above range, a gas barrier film having a high effect of preventing permeation of gases such as oxygen and water vapor and satisfying a certain level of gas barrier properties can be obtained.

The total thickness of the laminate in which n layers of gas barrier layers are laminated is preferably from 50 to 2000 μm, more preferably from 50 to 1000 μm, more preferably from 50 to 500 μm. By setting the total thickness of the laminate of the gas barrier layer laminated with the above-mentioned n layers within the above range, the gas barrier property can be exhibited suitably, and the balance between the gas barrier property and the light transmittance is excellent, so it is particularly advantageous. It is used as a sealing material for sealing optical components such as organic EL elements.

(composition for gas barrier layer) Each n-layer gas barrier layer in the present invention is a layer formed of a composition for a gas barrier layer containing a silicon compound. Accordingly, a gas barrier thin film having a high effect of preventing permeation of gases such as oxygen and water vapor and satisfying a certain level of gas barrier properties can be obtained.

In addition, in the present invention, it is preferable that all the n-layer gas barrier layers are formed of the same composition. Accordingly, the interlayer adhesion between the n-layer gas barrier layers can be improved. In addition, the difference in refractive index between each of the n-layer gas barrier layers can be reduced, thereby improving the light transmittance of the gas barrier thin film.

In one aspect of the gas barrier layer of the present invention, in the composition for the gas barrier layer used, the content of the silicon compound relative to the total amount (100% by mass) of the active ingredients of the aforementioned composition for the gas barrier layer is It is preferably 70 to 100%, more preferably 80 to 100% by mass, more preferably 90 to 100% by mass. In addition, the "active ingredient of the composition for a gas barrier layer" here means the component which remove|eliminates the solvent contained in the composition for a gas barrier layer. Hereinafter, each component suitable as a material for forming a gas barrier layer and contained in the composition for a gas barrier layer will be described.

(silicon compound) The composition for the gas barrier layer exhibits a high effect of preventing permeation of gases such as oxygen and water vapor and satisfies a certain level of gas barrier properties by containing a silicon compound. Here, the "silicon compound" is not particularly limited as long as it is a compound containing a silicon atom, and may be an organic compound or an inorganic compound, and may be a high-molecular compound or a low-molecular compound.

Examples of silicon compounds include polymer silicon compounds such as polyorganosiloxane compounds, polysilazane compounds, polysilane compounds, and polycarbosilane compounds; particles of silicon oxide, silicon nitride, and silicon oxynitride; and the like. Among them, polymer silicon compounds such as polysilazane compounds, polysilane compounds, and polycarbosilane compounds are preferable, among which polysilazane compounds are preferable. From the standpoint of reducing the refractive index difference between the n-layer gas barrier layers and improving the light transmittance of the gas barrier film, the compositions of the n-layer gas barrier layers in the present invention are Preferably, all of them contain the same type of silicon compound. For example, when one of the n-layer gas barrier layers is formed of a composition containing a polysilazane compound, all the other layers are also formed of a composition containing a polysilazane compound. better.

Here, the so-called "polysilazane compound" refers to a polymer having repeating units including -Si-N-bond (silazane bond) in the molecule, and specifically refers to a polymer having the following formula 1: A polymer of repeating units. Furthermore, the polysilazane compound represented by Formula 1 may also be a modified polysilazane.

In Formula 1, n represents a repeating unit and represents an integer of 1 or more. In addition, Rx, Ry, and Rz independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted Aryl group, unsubstituted or substituted alkylsilyl group.

Examples of the polysilazane compound represented by formula 1 include: an organopolysilazane compound having a carbon atom-containing group in which at least one group among Rx, Ry, and Rz is a hydrogen atom; An inorganic polysilazane compound in which all Rz are hydrogen atoms. Among these, inorganic polysilazane compounds are preferable, and specifically, perhydropolysilazane is preferable from the viewpoint that the effect of exhibiting a gas barrier property satisfying a certain level is high.

(solvent) When forming the gas barrier layer by coating, from the viewpoint of easily adjusting the composition for the gas barrier layer to a property suitable for coating, it is more preferable to form a solution in which the composition for the gas barrier layer is added to a solvent. good. The solvent is not particularly limited as long as it can dissolve or disperse the aforementioned silicon compound, and examples include aliphatic hydrocarbon solvents such as n-hexane and n-heptane; aromatic solvents such as toluene and xylene; Hydrocarbon-based solvents; halogenated hydrocarbon-based solvents such as dichloromethane, ethylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, etc.; methanol, ethanol, propanol, butanol, propylene glycol Alcohol-based solvents such as monomethyl ether; ketone-based solvents such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, and cyclohexanone; ester-based solvents such as ethyl acetate and butyl acetate; Cellosolve-based solvents such as cellosolve; ether-based solvents such as 1,3-dioxolane, etc. Among them, aromatic hydrocarbon-based solvents and alcohol-based solvents are preferable as the solvent system.

The amount of the solvent used in preparing the composition for a gas barrier layer is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, more preferably 10% by mass, based on the concentration of the active ingredient in the composition for a gas barrier layer. ~30% by mass can be used. In addition, the "active ingredient of the composition for a gas barrier layer" here means the component which remove|eliminates the solvent contained in the composition for a gas barrier layer.

(other ingredients) In addition to the silicon compound and the solvent, the composition system for the gas barrier layer may further contain other components within the range not impairing the effect of the present invention. Examples of other components include UV curable resins, curing agents, antiaging agents, light stabilizers, flame retardants and the like.

Examples of methods for modifying the gas barrier layer include: ion implantation for modifying by implanting ions; plasma treatment for modifying by exposure to plasma; ultraviolet irradiation for modifying by irradiating ultraviolet rays processing etc. Among them, the surface of the gas barrier layer can be efficiently modified without making the surface of the gas barrier layer rough, and the gas barrier layer with excellent gas barrier properties can be formed. The treatment is preferably ion implantation.

Ions used in the ion implantation process are preferably ions of rare gases such as argon, helium, neon, krypton, and xenon, among which argon is more preferable. The method of implanting ions is not particularly limited, but the method of implanting ions in plasma (ions of plasma-generated gas) is preferable because ion implantation treatment can be easily performed.

Furthermore, as a method of reforming the gas barrier layer, ultraviolet irradiation treatment for reforming by irradiating ultraviolet rays can also be used. The ultraviolet rays used in the ultraviolet irradiation treatment include, for example, vacuum ultraviolet rays. As the ultraviolet irradiation treatment for reforming by irradiating vacuum ultraviolet light, for example, methods described in JP-A-2017-095758 and the like can be employed.

[resin layer] When the gas barrier film of the present invention has a resin layer, it has n layers (n is an integer of 2 or more) of gas barrier layers. The n-layer gas barrier layer may be formed by laminating directly on the resin layer, or may be formed by interposing another layer (for example, a primer layer) on the resin layer. In the gas barrier film, the resin layer may have a function as a support for supporting the gas barrier layer (substrate film), or may not function as a support.

The thickness of the resin layer is not particularly limited, and can be appropriately determined according to the purpose of use of the gas barrier film. The thickness of the resin layer is preferably 0.5-500 μm, more preferably 1-100 μm, more preferably 20-80 μm. In another embodiment of the present invention, the thickness of the resin layer is preferably 1-40 μm, more preferably 2-30 μm, more preferably 3-20 μm, and more preferably 3-15 μm. Accordingly, the gas barrier film can be used with a thinner thickness than the thickness of a generally used base film. As a result, the total thickness of the entire gas barrier film can be reduced. Therefore, the gas barrier film of the present invention can also be suitably used as a sealing material for a sealing object (for example, a display element, etc.) that requires a thin member. Such a thinner resin layer has a lower specific gravity to function as a support for a gas barrier film than a normal base film, but the presence of the resin layer generally makes it suitable. While extremely suppressing damage or deterioration of the gas barrier layer formed with an ultra-thin film, handling of the gas barrier thin film can be facilitated compared to the state of the gas barrier layer alone. In addition, when the resin layer has a layer configuration of the second release sheet as described above, the second release sheet can be efficiently and appropriately peeled and removed.

Examples of the material constituting the resin layer include polyimide, polyamide, polyamide imide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polyamide Resins such as ash, polyether sulfide, polyphenylene sulfide, acrylic resins, cycloolefin-based polymers, aromatic-based polymers, etc.; paper such as cellophane, coated paper, high-quality paper; lamination of the aforementioned on such paper Resin laminated paper, etc.

Among them, in terms of excellent transparency, polyester, polyamide, polysulfone, polyethersulfide, polyphenylene sulfide, and cycloolefin-based polymers are preferred, and polyester is particularly preferred. . As polyester, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, etc. are mentioned, for example. The resin layer system may be formed by adding a curable component or a polymerization initiator used in the primer layer described later to the above-mentioned resin.

[primer layer] (primer layer) The gas barrier film of the present invention can improve the interlayer adhesion between the resin layer, especially the base film, and the n-layer gas barrier layer by having the primer layer.

The thickness of the primer layer is preferably 0.01-50 μm, more preferably 0.1-30 μm, more preferably 0.3-20 μm, and more preferably 0.5-10 μm. By setting the thickness of the primer layer within the above range, it becomes easy to properly improve the interlayer adhesion between the resin layer, especially the base film, and the n-layer gas barrier layer.

The primer layer is preferably formed, for example, from a composition for a primer layer containing a curable component (A) and a filler (B). Hereinafter, each component suitable as a primer layer forming material and included in the primer layer composition will be described.

＜Hardening component (A)＞ The primer layer composition can be made into a primer layer excellent in solvent resistance by containing the curable component (A). Here, the so-called "hardening component (A)" refers to: (i) a component capable of causing a controllable curing reaction, such as an epoxy resin or the like that is cured by heating; Saturated bonds to form a hardened product by polymerization, or (iii) a cross-linking reaction between polymers produced by polymerization to form a hardened product.

Among the above (i) to (iii), as (ii) a component having a polymerizable unsaturated bond and forming a hardened product by polymerization reaction (hereinafter also referred to as "polymerizable component (B1)"), for example, : A monofunctional monomer or polymer having one polymerizable unsaturated bond, a bifunctional or more polyfunctional monomer or polymer having two or more polymerizable unsaturated bonds. Furthermore, examples of polymers having polymerizable unsaturated bonds include urethane (meth)acrylate oligomers, acrylic polymers having (meth) Acryl-based polymers. As the polymerizable component (B1), a bifunctional or higher polyfunctional monomer or polymer is preferable, and especially a difunctional or higher polyfunctional monomer is preferable. Hereinafter, the polymerizable component (B1) will be described in detail by taking a bifunctional or higher polyfunctional monomer as an example. As a bifunctional or more polyfunctional type monomer, the di- to hexafunctional (meth)acrylic acid derivative is mentioned, for example. As a bifunctional (meth)acrylic acid derivative, the compound represented by following formula 2 is mentioned.

In Formula 2, ^R1 represents a hydrogen atom or an alkyl group having 1 to 6 carbons, and ^R2 represents a divalent organic group. Examples of the divalent organic group represented by R ² include groups represented by the following formula 3.

In Formula 3, s represents an integer from 1 to 20, t represents an integer from 1 to 30, u and v represent an integer from 1 to 30 independently, and "-" at both ends represent a bond.

Specific examples of bifunctional (meth)acrylate acid derivatives represented by formulas 2 and 3 include tricyclodecane dimethanol di(meth)acrylate, polyethylene glycol di(meth)acrylate ) acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, 1,10-decanediol di(meth) Acrylate, 1,6-hexanediol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl] terpene, etc.

Trifunctional (meth)acrylic acid derivatives include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate , Propylene oxide modified trimethylolpropane tri(meth)acrylate, ginseng (acryloxy) isocyanurate, etc. Pentaerythritol tetra(meth)acrylate etc. are mentioned as a tetrafunctional (meth)acrylic acid derivative. Examples of the pentafunctional (meth)acrylic acid derivative include propionic acid-modified dipentaerythritol penta(meth)acrylate. Examples of the hexafunctional (meth)acrylic acid derivative include dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like.

Among the aforementioned 2-6 functional (meth)acrylic acid derivatives, 6-functional (meth)acrylic acid derivatives are preferred, among which dipentaerythritol hexa(meth)acrylate is preferred, especially Dipentaerythritol hexaacrylate is preferred.

The molecular weight of the curable component (A) is generally less than 3000, preferably 200-2000, and more preferably 200-1000.

＜Filler (B)＞ The composition for the primer layer can improve the interlayer adhesion between the resin layer and the n-layer gas barrier layer by containing the filler (B). Any of inorganic fillers and organic fillers may be used as "filler (B)", but inorganic fillers are preferred from the viewpoint of high effect of interlayer adhesion.

As the inorganic filler, for example: silicate such as clay, talc, mica, kaolin, zeolite, calcium silicate, montane, bentonite; substances; hydroxides of aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, etc.; carbonates of calcium carbonate, magnesium carbonate, dolomite, dawsonite, etc.; sulfates of calcium sulfate, barium sulfate, calcium sulfite, etc. salt or sulfite etc. Among them, oxides are preferred, and among them, silicon dioxide is preferred.

The particle size of the filler (B) is preferably 3-100 nm, more preferably 3-60 nm, more preferably 5-30 nm. By setting the particle size of the primer layer within the above range, the interlayer adhesion between the resin layer and the n-layer gas barrier layer can be improved.

The inorganic filler can also be used in a dried powder form, but it is preferable to use a colloidal solution dispersed in an organic solvent from the viewpoint of dispersion stability.

(solvent) As the organic solvent (dispersion medium) for dispersing the filler (B), for example: aromatic hydrocarbon-based solvents such as toluene and xylene; alcohol-based solvents such as methanol, ethanol, propanol, butanol, and propylene glycol monomethyl ether; Solvents; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone, isophorone, cyclohexanone, etc.; ester-based solvents such as ethyl acetate and butyl acetate; 1, Ether-based solvents such as 3-dioxolane, etc. Among these, ketone-based solvents are preferred, among which methyl ethyl ketone and methyl isobutyl ketone are preferred.

The amount of the organic solvent (dispersion medium) used to disperse the filler (B) is preferably 5 to 80 mass %, more preferably 10 to 70 mass %, and more preferably 20 mass %, based on the solid content concentration of the filler (B). ~60% by mass can be used.

(polymerization initiator) When the composition for a primer layer contains a polymerizable component (B1), it is preferable that a polymerization initiator is contained in the composition for a primer layer. As a polymerization initiator, a thermal polymerization initiator and a photopolymerization initiator are mentioned, for example. Among them, photopolymerization initiators are preferred as polymerization initiators, specifically, alkylphenone-based photopolymerization initiators, phosphorous-based photopolymerization initiators, oxime ester-based photopolymerization initiators, etc. Initiator, benzophenone-based photopolymerization initiator, thioxanthone-based photopolymerization initiator, and aromatic ketone-based photopolymerization initiator are preferred, wherein the aromatic ketone-based photopolymerization initiator is And better. As an aromatic ketone type photoinitiator, 1-hydroxycyclohexyl phenyl ketone etc. are mentioned, for example.

The content of the polymerization initiator contained in the primer layer composition is preferably 0.2 to 6.2 parts by mass, more preferably 0.2 to 5.2 parts by mass, relative to 100 parts by mass of the curable component (A), More preferably, it is 0.2 to 4.2 parts by mass.

(other ingredients) In addition to the curable component (A), filler (B), polymerization initiator, and solvent, the composition for the primer layer may further contain other components within the range that does not impair the effect of the present invention. As other components, plasticizers, antioxidants, ultraviolet absorbers, etc. are mentioned, for example.

[adhesive layer] The gas barrier thin film of the present invention may be one in which at least 1 (n-1) of the n-layer (n is an integer of 2 or more) gas barrier layers constitutes a layer to be modified, and It is not particularly limited, and an adhesive layer may be laminated on the surface of the outermost gas barrier layer or the surface of the resin layer opposite to the side in contact with the gas barrier layer. The gas barrier film of the present invention has an adhesive layer, and the surface of the adhesive layer is bonded to the surface of the object to be sealed to obtain a sealed body.

The adhesive layer included in the gas barrier film of the present invention is not particularly limited, and conventionally known ones can be used as long as the effects of the present invention are not impaired. As a material which forms an adhesive bond layer, the composition for adhesive bond layers containing a polyolefin resin and a thermosetting resin is mentioned, for example.

The thickness of the adhesive layer is preferably 0.5-100 μm, more preferably 1-60 μm, more preferably 3-40 μm. By making the thickness of the said adhesive layer into the said range, when using the gas barrier film of this invention as a sealing material, it can use suitably.

[peel off flakes] As the release sheet, the first release sheet, and the second release sheet that can be used in the gas barrier film and the sealing body of the present invention, a release sheet that has been subjected to a double-sided release treatment, or a release sheet that has been subjected to a single-side release treatment, etc., can be used. Examples thereof include a release sheet in which a release agent is applied to a base material for the release sheet.

As the base material for the release sheet, for example: papers such as high-quality paper, cellophane, kraft paper; polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate Polyester resin films such as resins, plastic films such as olefin resin films such as polypropylene resins and polyethylene resins, etc.

Examples of the release agent include rubber-based elastomers such as silicone-based resins, olefin-based resins, isoprene-based resins, and butadiene-based resins, long-chain alkyl-based resins, alkyd-based resins, fluorine-based resins, etc. Department of resin, etc.

The thickness of the peeling sheet is not particularly limited, and is preferably 10-200 μm, more preferably 25-170 μm, and more preferably 35-80 μm.

(Manufacturing method of gas barrier thin film) The method for producing the gas barrier thin film in the present invention is not particularly limited, and examples thereof include the methods shown below. First, the primer layer composition is coated on the surface of the substrate film (resin layer) to form a coating film, and the coating film is dried under specified conditions to form a primer layer on the surface of the substrate film. The composition for the gas barrier layer is coated on the primer layer to form a coating film, and the coating film is dried under predetermined conditions to form the first gas barrier layer on the primer layer. Then, a composition for a gas barrier layer is applied on the first gas barrier layer to form a coating film, and the coating film is dried under predetermined conditions to form a second layer on the first gas barrier layer. The gas barrier layer is modified by plasma ion implantation on the surface of the second gas barrier layer, so that a gas barrier layer (unmodified) with base film/primer layer/first layer can be produced )/gas barrier layer (modified) layer of the second layer gas barrier thin film.

Examples of coating methods for the aforementioned compositions include solution methods, such as die coating, spin coating, bar coating, dipping, roll coating, gravure coating, and blade coating. Cloth method, air knife coating method, roller blade coating method, screen printing method, spray coating method, gravure offset printing method, doctor blade coating method, etc.

[seal body] The sealing system of the present invention uses the gas barrier film of the present invention as a sealing material to seal the object to be sealed. According to the present invention, it is possible to obtain a gas barrier film that has a high effect of preventing permeation of gases such as oxygen and water vapor, satisfies a certain level of gas barrier properties, has high light transmittance, and can reduce production costs. The object to be sealed includes at least one selected from the group consisting of organic EL elements, organic EL display elements, inorganic EL elements, inorganic EL display elements, electronic paper elements, liquid crystal display elements, and solar cell elements.

(How to make the sealing body) The method for producing the sealing body of the present invention is not particularly limited. For example, if the gas barrier film of the present invention as a sealing material is in the following state, the peeling sheet is first peeled and removed, and the exposed adhesive layer is removed. The surface of the sealant is bonded to the surface of the object to be sealed, and then bonded under the desired conditions to obtain a sealed body. ・Base film/primer layer/1st gas barrier layer/2nd gas barrier layer/adhesive layer/peeling sheet In addition, when the gas barrier film of the present invention as a sealing material is in the form shown below, first, the second release sheet is peeled and removed, and the surface of the exposed adhesive layer is bonded to the surface of the object to be sealed. , according to the desired conditions to make it follow, so as to obtain a sealed body. ・2nd release sheet/resin layer/1st gas barrier layer/2nd gas barrier layer/adhesive layer/1st release sheet Generally, the second release sheet is peeled and removed after the surface on which the adhesive layer is formed and the object to be sealed are separated. According to such a method of producing a sealing body, even when the resin layer does not have a sufficient function as a support for the gas barrier film (that is, when the thickness of the resin layer is very thin), the second peeling process is performed. Since the second peeling sheet functions as a support for the gas barrier film until the sheet is peeled and removed, cracking or deformation of the resin layer can be prevented, and the handleability is excellent. [Example]

The following examples are given to illustrate the present invention in more detail. However, the present invention is not limited by the following examples. Also, "parts" and "%" described below are "quality standards" unless otherwise specified.

(Example 1) [Production of gas barrier film] (1) Formation steps of the primer layer Dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., "A-DPH") as the hardening component (A) and filler (B) Organosilica Sol (Organosilica Sol) (manufactured by Nissan Chemical Industry Co., Ltd., "MIBK-AC-2140Z"), and 1-hydroxycyclohexyl phenyl ketone (BASF Co. manufactured, "Irgacure 184") by 1 part by mass (relative to 100 parts by mass of the curable component (A)) to prepare a primer layer composition. Here, the aforementioned "MIBK-AC-2140Z" is a colloid solution prepared by adjusting the concentration of acryl-modified silica with a particle diameter of 10-15 nm to a 40% solution using methyl isobutyl ketone.

As a base film, the primer prepared above was coated on the surface of a polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., "PET50A-4300", thickness 50 μm) by the bar coating method. The layer composition is used to form a coating film. After heating and drying the coating film at 70° C. for 1 minute, UV light irradiation was performed using UV light rays (high-pressure mercury lamp, line speed: 20 m/min, cumulative light intensity: 100 mJ/cm ² , peak intensity: 1.466 W, number of passes: 2 second), a primer layer with a thickness of 1 μm was formed on the aforementioned substrate film.

(2) Formation steps of the gas barrier layer ＜Level 1＞ Next, an inorganic polysilazane-based coating agent, which is a composition for a gas barrier layer, is coated on the primer layer formed above by a solution-based spin coating method to form a coating film. . Here, the aforementioned "inorganic polysilazane-based coating agent" was prepared by adjusting the concentration of "AQUAMICA NL110-20 (main component: perhydropolysilazane)" manufactured by Merck Performance Materials to 20% xylene. A coating agent made of mass %. Furthermore, the obtained coating film was dried by heating at 120° C. for 2 minutes to form a “first gas barrier layer” containing an inorganic polysilazane compound with a thickness of 200 nm on the aforementioned primer layer. .

＜Level 2＞ Next, on the gas barrier layer of the first layer formed above, by the same operation as the step of forming the gas barrier layer of the first layer mentioned above, a layer containing an inorganic polysilazane compound with a thickness of 200 nm was formed. "The gas barrier layer of the second layer".

Furthermore, using a plasma ion implantation apparatus (RF power supply: "RF56000" manufactured by JEOL Ltd., high-voltage pulse power supply: "PV-3-HSHV-0835" manufactured by Kurita Seisakusho Co., Ltd.), the aforementioned The surface of the formed second gas barrier layer is subjected to modification treatment by plasma ion implantation to produce a gas barrier layer (unmodified) with base film/primer layer/first layer/second layer "Gas barrier thin film of Example 1" composed of two layers of gas barrier layers (modified). <Plasma ion implantation conditions> ・Plasma generation gas: Argon ・Gas flow rate: 100sccm ・Duty ratio: 0.5% ・Applied voltage: -6kV ・RF power supply: frequency 13.56MHz, external power 1000W ・Chamber internal pressure: 0.2Pa ・Pulse width: 5μsec ・Processing time (ion implantation time): 200 seconds

(comparative example 1) In the formation step of the gas barrier layer in Example 1, except that the first layer of the gas barrier layer was formed on the primer layer with a thickness of 200 nm, the same operation as in Example 1 was used to form the first layer of the gas barrier layer. The gas barrier thin film of Comparative Example 1 was produced in the same manner as in Example 1, except that the surface was modified by plasma ion implantation and the second gas barrier layer was not formed.

(comparative example 2) In the step of forming the gas barrier layer in Example 1, except that the first layer of the gas barrier layer was formed on the primer layer with a thickness of 400 nm, the same operation as in Example 1 was carried out on the surface of the first layer of the gas barrier layer. The gas barrier thin film of Comparative Example 2 was produced in the same manner as in Example 1, except that the modification treatment by plasma ion implantation was applied and the second gas barrier layer was not formed.

(comparative example 3) In the formation step of the gas barrier layer in Example 1, except that the surface of the first layer of the gas barrier layer was modified by plasma ion implantation in the same operation as in Example 1, the rest were the same as in Example 1. 1 The gas barrier thin film of Comparative Example 3 was produced in the same manner.

For the gas barrier films produced in the aforementioned Example 1 and Comparative Examples 1 to 3, according to the methods shown below, (1) evaluation of gas barrier properties, (2) evaluation of light transmittance, and The results are summarized in Table 1.

[Evaluation method] (1) Evaluation of gas barrier properties The gas barrier films produced in the aforementioned Example 1 and Comparative Examples 1 to 3 were used as test samples for measuring the water vapor transmission rate. The water vapor transmission rate (g/m ² /day) of the measurement sample in a high-temperature and high-humidity environment of 40°C and a relative humidity of 90% was measured using a water vapor transmission rate measuring device (manufactured by MOCON Corporation, "AQUATRAN") . Furthermore, the detection lower limit of the water vapor transmission rate measuring device is 5×10 ^-4 (g/m ² /day). From the results of the water vapor transmission rate (g/m ² /day) measured in this way, the gas barrier property was evaluated according to the criteria shown below. A: The water vapor transmission rate is 5×10 ^-3 (g/m ² /day) or less B: The water vapor transmission rate exceeds 5×10 ^-3 (g/m ² /day)

(2) Evaluation of light transmission Each of the gas barrier films produced in the aforementioned Example 1 and Comparative Examples 1 to 3 was used as a sample for measuring the total light transmittance. The total light transmittance (%) was measured using a haze meter (manufactured by Nippon Denshoku Industries, Ltd., "HAZE METER NDH5000") in accordance with JIS K7361-1.

(compilation of results) Based on the evaluation results shown in Table 1, the following can be known. In the manufacture of the gas barrier thin film of Comparative Example 1, although the gas barrier thin film of Comparative Example 1 can obtain the same level of light transmittance as that of Example 1 because the gas barrier layer of the second layer is not formed, it can be It is known that the gas barrier property is inferior to that of Example 1. In the production of the gas barrier thin film of Comparative Example 2, although the total thickness of the gas barrier layer was set to be the same as that of Example 1, the gas barrier thin film of Comparative Example 2 was not formed because the second gas barrier layer was not formed. Although light transmittance was obtained, it was found that the gas barrier property was inferior to that of Example 1. In the production of the gas barrier thin film of Comparative Example 3, since the first layer and the second layer are both modified layers, although the gas barrier thin film of Comparative Example 3 can obtain a certain level of gas barrier properties, but It can be seen that the light transmittance is worse than that of Example 1.

In contrast, in the production of the gas barrier thin film of Example 1, the number of laminated gas barrier layers was set to 2 or more, and the number of gas barrier layers to be modified was set to 1 or more. (n-1) or less, so the gas barrier thin film of Example 1 has gas barrier properties satisfying a certain level, high light transmittance, and excellent balance between gas barrier properties and light transmittance. In Comparative Example 1 in which both the first layer and the second layer are reformed layers, it can be seen that the number of steps for performing reforming treatment can be reduced, and the manufacturing cost can also be reduced. [Industrial Utilization]

The gas barrier film of the present invention has a high effect of preventing the permeation of gases such as oxygen and water vapor, has a certain level of gas barrier properties, has high light transmittance, and can reduce production costs. Therefore, it can be suitably used in a wide range of fields such as various electronic devices, electronic components, and optical components. For example, it can be used in organic EL elements, organic EL display elements, inorganic EL elements, inorganic EL display elements, electronic paper elements, Liquid crystal display components, solar cell components, etc.

Claims (6)

A gas barrier thin film having n layers (n is an integer of 2 or more) of gas barrier layers formed of a composition containing a silicon compound, characterized in that, among the n layers of gas barrier layers, 1 or more The layers below (n-1) are reformed, the thickness of the gas barrier layer as a whole is 400 nm or more, the gas barrier film has a resin layer, and the n gas barrier layers are laminated on the resin layer, In addition, the gas barrier layer closest to the resin layer is not modified, and the total light transmittance of the gas barrier film is above 90%. The gas barrier thin film according to claim 1, wherein, among the n gas barrier layers, one gas barrier layer is modified. The gas barrier thin film according to claim 1 or 2, wherein, among the aforementioned n-layer gas barrier layers, the outermost gas barrier layer is modified. The gas barrier film according to claim 1 or 2, wherein all the n-layer gas barrier layers are layers formed of a composition containing the same type of silicon compound. The gas barrier thin film according to claim 1 or 2, wherein all the n-layer gas barrier layers are layers formed of the same composition. The gas barrier film according to claim 1 or 2, wherein the gas barrier film has a water vapor transmission rate of 5×10 ^-3 (g/m ² /day) or less.