JP2016112798A - Gas barrier laminate and manufacturing method of gas barrier laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier laminate capable of achieving strong adhesiveness between an organic layer and an inorganic layer applicable to an electronic device, etc. requiring high reliability or durability, and capable of avoiding separation between the organic layer and the inorganic layer during a production process.SOLUTION: A manufacturing method is provided for a gas barrier laminate having an organic layer and an inorganic layer on a film base material 11 serving as a support medium. The manufacturing method of a gas barrier laminate includes: the step of applying a plasma treatment onto a surface of an inorganic layer after forming the inorganic layer on the film base material; and the step of forming a primer layer containing silicon atoms on the surface of the inorganic layer with the plasma treatment applied.SELECTED DRAWING: Figure 1

Description

  The present invention relates to the field of packaging foods such as dried foods, confectionery, bread, delicacy, foods that dislike moisture and oxygen, disposable body warmers, tablets, powdered drugs or poultices, patches, etc., and electronic devices such as liquid crystal display elements such as FPDs. The present invention relates to a gas barrier laminate used in the device field. Furthermore, in detail, by improving the adhesion between the inorganic layer and the organic layer by producing by a specific production method, the inorganic layer and the organic layer are preferably not peeled off even in a cleaning process in the electronic device field. The present invention relates to a usable gas barrier laminate.

  In the packaging materials used for packaging foods and pharmaceuticals, the ingress of gas that alters water vapor, oxygen, and other contents in order to prevent the contents from being altered or spoiled and retain their functions and properties. The property (gas barrier property) which interrupts is necessary.

  Therefore, a barrier layer has been formed on the base film by sputtering, vapor deposition, wet coating, printing, or the like. Further, as the gas barrier layer, a metal foil made of a metal such as aluminum, a metal vapor deposition film, a resin film such as polyvinyl alcohol, an ethylene-vinyl alcohol copolymer, or polyvinylidene chloride is used (for example, Patent Documents 1 to 3). 5).

  However, the metal vapor-deposited film is excellent in gas barrier properties, but is opaque, so the contents cannot be confirmed, and since it is inferior in stretchability, there is a problem that cracks occur and the gas barrier properties are lowered. .

  In addition, a gas barrier layer made of a resin film of non-chlorinated polyvinyl alcohol or ethylene-vinyl alcohol copolymer exhibits a high gas barrier property in a low-humidity atmosphere, but has a drawback that the gas barrier property greatly decreases as the humidity increases. It was.

  On the other hand, although the gas barrier layer made of a polyvinylidene chloride resin film exhibits good gas barrier properties that are not dependent on humidity, the generation of harmful substances such as dioxins has been cited as a problem in the disposal process.

  As a packaging material that overcomes these drawbacks, Patent Document 6 discloses an inorganic organic laminate in which an inorganic oxide such as silicon oxide and aluminum oxide is formed on a transparent film substrate by vapor deposition, and a gas barrier layer and an organic layer are further formed. A film is disclosed.

  In recent years, in the field of electronic devices such as liquid crystal display elements and organic EL elements, replacement of heavy and fragile glass substrates with light and hard to break plastic films has been progressing. However, since a plastic film has a water vapor barrier property inferior to that of glass, when a plastic film is used for a substrate of an electronic device, there is a problem that a display element deteriorates and a display defect occurs.

  For this reason, transparent inorganic / organic laminated films having gas barrier properties are used, and they are now widely used in addition to packaging foods and pharmaceuticals. However, a gas barrier film in which an inorganic layer and an organic layer are laminated has a problem that the adhesion between the inorganic layer and the organic layer is poor, and peeling of the inorganic layer and the organic layer occurs in the panel manufacturing process, resulting in a decrease in barrier performance. It was.

JP 2001-287294 A JP 11-165369 A JP-A-6-93133 JP-A-9-150484 Japanese Patent No. 3764109 Japanese Patent Laid-Open No. 7-164591

  In view of the above problems, the present invention provides a gas barrier laminate that maintains strong adhesion between an inorganic layer and an organic layer and can be applied to electronic devices and the like that are required to have high reliability and durability.

As a means for solving the above problems, the invention according to claim 1 is a gas barrier laminate including an inorganic layer and an organic layer in this order on a film base material which is a support.
The inorganic layer contains one or both of aluminum oxide and silicon oxide,
On the surface of the inorganic layer, a modified layer is formed by plasma treatment,
A gas barrier laminate, wherein a primer layer containing any one or both of molecules that can be represented by the following general formula 1 or 2 is formed between the modified layer and the organic layer Is the body.
General formula 1: Silane monomer represented by R—Si (OR ′) ₃ or a hydrolyzate thereof General formula 2: One or more metal alkoxides represented by M (OR ′) n or a hydrolyzate thereof, silane Coupling agent or a hydrolyzate thereof, or a mixture thereof, wherein R is a functional group selected from an alkyl group, a (meth) acryloyl group, a vinyl group, an amino group, an epoxy group, and an isocyanate group, and R ′ is an alkyl group M is a metal ion and n is the valence of the ion.

The invention according to claim 2 is a method for producing a gas barrier laminate comprising an inorganic layer and an organic layer on a film base material to be a support,
A step of performing plasma treatment on the surface of the inorganic layer after forming the inorganic layer on the film substrate;
And a step of forming a primer layer containing silicon atoms on the surface of the plasma-treated inorganic layer. A method for producing a gas barrier laminate, comprising:

  The invention described in claim 3 is the method for producing a gas barrier laminate according to claim 2, wherein the gas used in the plasma treatment is nitrogen gas or argon gas.

  According to the present invention, strong adhesion between an inorganic layer and an organic layer is achieved, and it can be applied to applications such as electronic devices that require high reliability and durability. It is possible to provide a gas barrier laminate that does not cause peeling between the organic layers.

It is a schematic sectional drawing which shows an example of the gas-barrier laminated body of this invention.

  FIG. 1 is a schematic cross-sectional view showing an example of a gas barrier laminate 10 of the present invention. An inorganic layer 12 is formed on the film substrate 11, and the surface of the inorganic layer 12 is subjected to plasma treatment to form the modified layer 13, and further subjected to primer treatment to form the primer layer 14 and then the organic layer 15 Is applied to form the gas barrier laminate 10.

  The inorganic layer 12 is usually a thin film layer made of a metal compound, and in the present invention, any one of aluminum oxide, silicon oxide, or a mixture thereof is used from the viewpoint of performance. As the method for forming the inorganic layer 12, any method can be used as long as it can form a target thin film having gas barrier properties. For example, there are physical vapor deposition methods (PVD methods) such as vapor deposition, sputtering, and ion plating methods, various chemical vapor deposition methods (CVD methods), and liquid phase growth methods such as plating and sol-gel methods. .

  Although it does not specifically limit regarding the thickness of the inorganic layer 12, It is desirable in the range of 20-500 nm from a viewpoint of the performance of gas-barrier property and the internal stress which also affects the adhesive force of the inorganic layer 12 and the film base material 11. .

  The plasma treatment may be performed under atmospheric pressure or under reduced pressure, but the adhesion can be improved by using nitrogen gas or argon gas as the treatment gas.

The primer layer 14 is a compound containing a silicon atom, and preferably contains a compound represented by the following general formula.
Silane monomer represented by general formula: R—Si (OR ′) ₃ or a hydrolyzate thereof General formula: one or more metal alkoxides represented by M (OR ′) n or a hydrolyzate thereof, silane coupling Wherein R is a functional group selected from an alkyl group, a (meth) acryloyl group, a vinyl group, an amino group, an epoxy group, and an isocyanate group, and R ′ is an alkyl group, etc. Yes, M is a metal ion, and n is the valence of the ion.

By using the above two types, it is possible to form a hydrogen bond with a metal surface having M (OR ′) n or a hydroxyl group by hydrolysis of R—Si (OR ′) ₃ , thereby improving adhesion and barrier properties. it can.

  The thickness of the primer layer 14 in the present invention is not particularly limited as long as it is a thickness that allows a continuous thin film to be formed on the surface of the inorganic layer 12.

  Examples of the organic material that can be used as the organic layer 15 include a material that forms a polymer by polymerization. Specific examples include acrylates and methacrylates that initiate polymerization with UV (ultraviolet light), EB (electron beam), or the like.

  Examples of the method for forming the organic layer 15 include a normal solution coating method. Specific examples include a roll coating method, a die coating method, a spin coating method, and a dip coating method.

  In UV polymerization, by adding a polymerization initiator to a monomer made of an organic material, the monomer can start polymerization. Examples of the polymerization initiator include Irgacure (registered trademark) series (for example, Irgacure 184) commercially available from Ciba Specialty Chemicals. In EB polymerization, a polymerization initiator is unnecessary.

Radical species formed in the organic layer 15 by UV irradiation or EB irradiation are deactivated by oxygen in the air, and are therefore irradiated in a space substituted with an inert gas such as nitrogen gas. Irradiation energy required for the polymerization varies depending on the material, film thickness, initiator, and the like of the organic layer 15 and cannot be generally stated. However, it is preferable that the irradiation energy is 90% or higher as the monomer polymerization rate.

  The film thickness of the organic layer 15 is not particularly limited, but if it is thinner than 200 nm, it becomes difficult to ensure barrier properties and obtain uniformity of the film thickness. descend. Therefore, the film thickness of the organic layer 15 is preferably 200 nm to 2000 nm.

  A plastic film is used as the film substrate 11. The plastic film used is not particularly limited in material, thickness, etc. as long as it is a film that can hold a laminate of inorganic and organic layers without deformation.

  The gas barrier laminate 10 of the present invention is an electronic device (liquid crystal display element, organic EL, solar cell, etc.) whose performance is deteriorated by chemical components (oxygen, water vapor, etc.) in the air in addition to ordinary food packaging materials. Can also be used.

<Example>
Examples of the present invention will be described below.
An aluminum oxide layer having a thickness of 300 nm was formed on a polyethylene naphthalate film (PEN film) as a film substrate using an EB vapor deposition apparatus at room temperature. Nitrogen plasma treatment was performed in an EB vapor deposition apparatus at the time of winding up the film substrate after completion of the vapor deposition. Nitrogen plasma treatment conditions are: high frequency plasma power density: 3.0 W / cm ² (13.56 MHz), nitrogen gas pressure: 0.3 mmHg, nitrogen gas flow rate 100 sccm (however, the volume of the nitrogen plasma treatment chamber is 1 m ³ ). did.
Next, a hydrolyzed solution of tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ) and 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate are mixed with a water / IPA = 1/1 solution. The resulting solution was applied by a spray method and dried at room temperature for 15 minutes to form a primer layer.

On the aluminum oxide layer, which is an inorganic layer subjected to nitrogen plasma treatment, an acrylate monomer solution containing a photopolymerization initiator (45 parts of acrylate monomer, 5 parts of photopolymerization initiator, 50 g of methyl ethyl ketone) is applied using a wire bar. did. An organic layer having a polymerization degree of 94% was formed by UV irradiation under a low oxygen concentration by a nitrogen substitution method.
Next, adhesion evaluation at the time of manufacturing these devices was performed as performance evaluation.
<Comparative Examples 1-5>

  As a comparative example, except for nitrogen plasma and primer treatment, the same method as in the example was performed, and the part was as follows. In Comparative Example 1, no treatment is performed. In Comparative Example 2, only corona treatment in the atmosphere is performed. In Comparative Example 3, only primer treatment is performed. In Comparative Example 4, only nitrogen plasma treatment is performed. In Comparative Example 5, primer treatment and corona treatment are performed. The sample was prepared and the same adhesion evaluation as in the example was performed.

<Evaluation results>
Table 1 shows the results of Examples and Comparative Examples. “○ = good”, “△, × = bad” as the evaluation criteria for adhesion evaluation and barrier performance, and “△> ×” (where △ is better than ×) even when judged as “bad” It was.
As is clear from Table 1, in Example 1, the nitrogen plasma treatment and the primer treatment were performed, and no peeling was observed in the adhesion evaluation that was a problem during device fabrication.

  In Comparative Examples 1 and 2, peeling was observed between the inorganic layer and the organic layer due to insufficient adhesion during device fabrication, and the barrier performance was greatly reduced.

In Comparative Examples 3 to 5, peeling was suppressed as compared with the case where no pretreatment such as nitrogen plasma treatment was performed, but there was no sufficient barrier performance.

  The gas barrier laminate of the present invention has high adhesion between the organic layer and the inorganic layer and is excellent in water vapor barrier properties. For this reason, if it is used not only as a normal packaging material but also as a film substrate of an electronic device or the like whose adhesion is a problem at the time of processing, it is effective because performance deterioration caused by peeling or the like can be suppressed. The roll-to-roll type plasma treatment is effective because it can ensure a uniform treatment and film formation even when used for a long time.

DESCRIPTION OF SYMBOLS 10 ... Gas barrier laminated body 11 ... Film base material 12 ... Inorganic layer 13 ... Modified layer 14 ... Primer layer 15 ... Organic layer

Claims (3)

In a gas barrier laminate comprising an inorganic layer and an organic layer in this order on a film base material to be a support,
The inorganic layer contains one or both of aluminum oxide and silicon oxide,
On the surface of the inorganic layer, a modified layer is formed by plasma treatment,
A gas barrier laminate, wherein a primer layer containing any one or both of molecules that can be represented by the following general formula 1 or 2 is formed between the modified layer and the organic layer body.
General formula 1: Silane monomer represented by R—Si (OR ′) ₃ or a hydrolyzate thereof General formula 2: One or more metal alkoxides represented by M (OR ′) n or a hydrolyzate thereof, silane Coupling agent or a hydrolyzate thereof, or a mixture thereof, wherein R is a functional group selected from an alkyl group, a (meth) acryloyl group, a vinyl group, an amino group, an epoxy group, and an isocyanate group, and R ′ is an alkyl group M is a metal ion and n is the valence of the ion. A method for producing a gas barrier laminate comprising an inorganic layer and an organic layer on a film substrate to be a support,
A step of performing plasma treatment on the surface of the inorganic layer after forming the inorganic layer on the film substrate;
And a step of forming a primer layer containing silicon atoms on the surface of the plasma-treated inorganic layer. A method for producing a gas barrier laminate, comprising:   The gas barrier laminate according to claim 2, wherein the gas used in the plasma treatment is nitrogen gas or argon gas.

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