JP5921061B2 - Gas barrier film laminate and packaging bag - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a gas barrier laminate for suppressing deterioration of contents sensitive to oxygen and water vapor and used as a packaging material for foods and drinks, pharmaceuticals, and electronic members, and a packaging bag comprising the same.

  The gas barrier film laminate and the packaging bag of the present invention are used as a packaging bag for sealing, particularly a packaging bag for sealing display elements such as organic electroluminescence (organic EL) and electronic paper for display, food, and pharmaceuticals. And other electronic members and the like, and can be used for any application that requires gas barrier properties.

  In recent years, in the packaging field, as a packaging material for foods and drinks, pharmaceuticals, electronic components, etc., in the preservation of contents, maintenance of packaging form, quality assurance, etc., and in the display field, display elements that are sensitive to oxygen and water vapor are deteriorated. In order to suppress this, a packaging bag made of a gas barrier laminate that prevents permeation of oxygen and water vapor is used.

  These gas barrier laminates usually have a structure in which a base material layer, a gas barrier property-imparting layer, and the like are laminated for the purpose of preventing intrusion of oxygen and water vapor from the surface without using an adhesive. Some are laminated only by vapor deposition or co-extrusion (Patent Documents 1 and 2), and others are laminated by using an adhesive (Patent Document 3).

  A laminate used as a packaging material for electronic components or a sealing member for display elements is required to have extremely high gas barrier properties. To satisfy this requirement, two or more gas barrier films are bonded with an adhesive. And there exists a laminated body which improved the gas-barrier property. And such a gas-barrier laminated body can prevent suitably permeation | transmission of oxygen and water vapor | steam from the surface.

  However, it has been found that oxygen and water vapor enter also from the end face, that is, the side face of the gas barrier laminate, and particularly from the adhesive layer that bonds the films to each other, thereby promoting the deterioration of the contents. In the prior art, no measures have been taken from such a viewpoint.

Japanese Patent Laid-Open No. 2003-340956 JP 2007-130857 A JP 2005-161691 A

  The present invention can prevent oxygen and water vapor from entering not only from the surface but also from the end face, and can be applied to various packaging applications and display fields, and has a gas barrier laminate having transparency. And to provide packaging bags.

As a result of earnest research, the present inventors have found that the first transparent gas barrier film, the adhesive resin layer laminated on the first transparent gas barrier film, and the first laminated on the adhesive resin layer. A gas barrier film laminate comprising the transparent gas barrier film according to claim 2, wherein the adhesive resin layer is a cured product formed of an epoxy resin and an epoxy resin curing agent. Found to achieve.

The present invention is characterized by the following points.
1. A laminate having a first transparent gas barrier film, an adhesive resin layer laminated on the first transparent gas barrier film, and a second transparent gas barrier film laminated on the adhesive resin layer A gas barrier film laminate, wherein the adhesive resin layer is a cured product formed of an epoxy resin and an epoxy resin curing agent.
2. At least one of the first transparent gas barrier film and the second transparent gas barrier film is a base material layer, and carbon-containing silicon oxide vapor deposition formed on the base material layer by plasma chemical vapor deposition A gas barrier film laminate comprising a vapor-deposited film having a layer.
3. The vapor deposition film further includes a gas barrier coating film provided on the carbon-containing silicon oxide vapor deposition layer, and the gas barrier coating film has a general formula R ¹ _n M (OR ² ) _m (wherein , R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m is M represents the valence of M.) and is obtained by polycondensation by a sol-gel method, containing at least one alkoxide represented by (2), a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. A gas barrier film laminate, which is a film made of a gas barrier composition.
4). The gas barrier film laminate, wherein the resin layer has a thickness of 2 to 6 μm.
5. The gas barrier film laminate further comprising a heat fusion layer laminated on the second transparent gas barrier film.
6). The gas barrier film laminate, wherein the heat-fusible layer is made of a polyolefin resin.
7). A packaging bag obtained by bag-making the gas barrier film laminate so that the heat-fusible layer becomes the innermost layer.
8). In the measuring method prescribed | regulated to this invention, the water vapor permeability from the end surface of the laminated body which forms a packaging bag is 30 g / m < ² > * day or less, The packaging bag characterized by the above-mentioned.
9. A packaging bag for sealing a display module which prevents deterioration of the display module due to moisture.

  According to the present invention, the two transparent gas barrier films are bonded not only from the surface but also from the end face by adhering with an adhesive resin layer resin layer made of a cured product formed of an epoxy resin and an epoxy resin curing agent. Intrusion of oxygen and water vapor can be prevented, and a gas barrier film laminate having transparency can be obtained.

  Hereinafter, in the present invention, the ability to prevent the entry of oxygen and water vapor from the surface is referred to as surface gas barrier property, and the ability to prevent the entry of oxygen and water vapor from the end face is referred to as end face gas barrier property.

  In the present invention, the adhesive resin layer characterized by comprising an epoxy resin and an epoxy resin curing agent not only prevents the penetration of oxygen and water vapor into the layer, but also the layer and the transparent gas barrier film. Oxygen and water vapor can be prevented from entering the interface. Therefore, by sealing display elements such as organic EL and electronic paper in the packaging bag made of the laminate of the present invention, deterioration of these electronic members due to exposure to oxygen or water vapor can be effectively prevented.

  Further, when a vapor deposition film having a base material layer and a carbon-containing silicon oxide vapor deposition layer formed on the base material layer by plasma chemical vapor deposition is used as the transparent gas barrier film, the base material layer and the An interface suitable for the purpose of the present invention is formed between the vapor deposition layer and the vapor deposition layer and the adhesive resin layer.

Furthermore, on the carbon-containing silicon oxide vapor deposition layer, a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, and M represents a metal atom) N represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M), a polyvinyl alcohol resin and / or Further improving the end face gas barrier property and the surface gas barrier property by providing a gas barrier coating film comprising an ethylene / vinyl alcohol copolymer and further comprising a gas barrier composition obtained by polycondensation by a sol-gel method. Can do.

  In the present invention, a polyolefin resin is used as the heat fusion layer. Since the layer made of this polyolefin resin itself has a good gas barrier property against oxygen and water vapor, it can improve the surface gas barrier property of the laminate and further prevent the end surface gas barrier property from being lowered.

According to the present invention, in the measurement method defined in the present invention, a packaging bag having a high barrier property such that the water vapor permeability from the end surface of the laminate forming the packaging bag is 30 g / m ² · day or less can be obtained.

It is a schematic sectional drawing which shows an example about the layer structure of the gas barrier film laminated body concerning this invention. It is a schematic sectional drawing which shows another example about the layer structure of the gas barrier film laminated body concerning this invention. It is a schematic sectional drawing which shows another example about the layer structure of the gas barrier film laminated body concerning this invention. It is a schematic sectional drawing which shows an example about the usage condition of the packaging bag concerning this invention.

The present invention will be described in more detail below.
<1> Layer Configuration of Laminate Forming Packaging Bag of Present Invention As a laminate forming a packaging bag according to the present invention, for example, as shown in FIG. 1, first and second transparent gas barrier films 1a 1b, the adhesive resin layer 2, and the laminated body which has as a basic structure that it consists of the heat-fusion layer 3 can be mentioned.

  Moreover, as an example of the laminated body which forms the packaging bag concerning this invention, as shown in FIG. 2, the 1st and 2nd transparent gas barrier film is respectively the base material layer 4, the carbon-containing silicon oxide vapor deposition layer 5, and The laminated body which is a vapor deposition film which consists of is mentioned.

Furthermore, as an example of the laminated body which forms the packaging bag concerning this invention, as shown in FIG. 3, the 1st and 2nd transparent gas barrier film is respectively the base material layer 4, the carbon containing silicon oxide vapor deposition layer 5, and The laminated body which is a vapor deposition film which consists of the gas-barrier coating film 6 is mentioned.
In addition, the transparent gas barrier film of the present invention may be a single layer or a multilayer of two or more layers, and can be appropriately set as necessary.

<2> Adhesive Resin Layer The gas barrier film laminate of the present invention includes a first transparent gas barrier film, an adhesive resin layer laminated on the first transparent gas barrier film, and the adhesive resin layer. A laminate having a second transparent gas barrier film laminated thereon, wherein the adhesive resin layer is made of a cured product formed of an epoxy resin and an epoxy resin curing agent.
The resin layer of the present invention bonds the first transparent gas barrier film and the second transparent gas barrier film with an excellent adhesive force, and also excellently bonds the second transparent gas barrier film and the heat fusion layer. It adheres by force and further plays a role of preventing permeation of oxygen and water vapor from the end face into the laminate.

Epoxy Resin The epoxy resin in the present invention may be a saturated or unsaturated aliphatic compound, alicyclic compound, aromatic compound, or heterocyclic compound, but in order to exhibit high gas barrier properties, it is aromatic. An epoxy resin containing a ring in the molecule is preferred.

  Specifically, an epoxy resin having a glycidylamine moiety derived from diaminodiphenylmethane, an epoxy resin having a glycidylamine moiety derived from metaxylylenediamine, and a glycidyl derived from 1,3-bis (aminomethyl) cyclohexane Epoxy resin having amine moiety, glycidylamine moiety derived from paraaminophenol and / or epoxy resin having glycidyl ether moiety, epoxy resin having glycidyl ether moiety derived from bisphenol A, glycidyl ether moiety derived from bisphenol F Epoxy resin having a glycidyl ether moiety derived from phenol novolac, an epoxy resin having a glycidyl ether moiety derived from resorcinol Such as carboxymethyl resin.

  Among them, an epoxy resin having a glycidylamine moiety derived from metaxylylenediamine, an epoxy resin having a glycidylamine moiety derived from 1,3-bis (aminomethyl) cyclohexane, and a glycidyl ether moiety derived from bisphenol F An epoxy resin having a glycidyl ether moiety derived from resorcinol and an epoxy resin having the same are preferable.

  Moreover, it is more preferable to use an epoxy resin having a glycidyl ether moiety derived from bisphenol F or an epoxy resin having a glycidyl amine moiety derived from metaxylylenediamine as a main component, and derived from metaxylylenediamine It is particularly preferable to use an epoxy resin having a glycidylamine moiety as a main component.

  Moreover, in order to improve various performances, such as a softness | flexibility and heat-and-moisture resistance, said epoxy resin can also be mixed and used.

  The epoxy resin of the present invention is obtained by reaction of various alcohols, phenols and amines with epihalohydrin. For example, an epoxy resin having a glycidylamine moiety derived from metaxylylenediamine can be obtained by adding epichlorohydrin to metaxylylenediamine.

  The glycidylamine moiety comprises a mono-, di-, tri- and / or tetra-glycidylamine moiety that can replace the four hydrogen atoms of the diamine in xylylenediamine. The ratio of mono-, di-, tri- and / or tetra-glycidylamine moieties can be varied by changing the reaction ratio of metaxylylenediamine to epichlorohydrin. For example, an epoxy resin mainly having a tetraglycidylamine moiety can be obtained by addition reaction of about 4 times mole of epichlorohydrin to metaxylylenediamine.

  The epoxy resin is an excess of epihalohydrin with respect to various alcohols, phenols and amines in the presence of an alkali such as sodium hydroxide, 20 to 140 ° C., preferably 50 to 120 ° C. in the case of alcohols and phenols, amine In the case of a kind, it is synthesized by reacting at a temperature of 20 to 70 ° C. and separating the produced alkali halide. The number average molecular weight of the produced epoxy resin varies depending on the molar ratio of epihalohydrin to various alcohols, phenols and amines, but is about 80 to 4000, preferably about 200 to 1000, preferably about 200 to 500. It is more preferable.

The epoxy resins of the present invention, in particular, and those content of 30 mass% or more of the skeletal structure shown in (1) below, a phenylene skeleton in the epoxy resin curing agent (-C ₆ H ₄ -) In which the skeletal structure represented by formula (2) is contained in an amount of 40% by mass or more in a cured reaction product of a composition mainly composed of an epoxy resin and an epoxy resin curing agent. Is desirable.

Epoxy resin curing agent The epoxy resin curing agent of the present invention may be any of an aliphatic compound, an alicyclic compound, an aromatic compound, or a heterocyclic compound, and is a polyamine, phenol, acid anhydride, or carboxylic acid. An epoxy resin curing agent that can be generally used can be used.

  Polyamines include aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine, aliphatic amines having aromatic rings such as metaxylylenediamine and paraxylylenediamine, 1,3-bis (aminomethyl) Examples thereof include alicyclic amines such as cyclohexane, isophorone diamine and norbolden diamine, and aromatic amines such as diaminodiphenylmethane and metaphenylene diamine.

Further, it is possible to form an oligomer by forming an amide group site by reaction with an epoxy resin or a monoglycidyl compound made from these polyamines, an addition reaction product with epichlorohydrin, or a reaction with these polyamines. A reaction product with a polyfunctional compound having one acyl group, a polyfunctional compound having at least one acyl group capable of forming an amide group site by reaction with these polyamines to form an oligomer; A reaction product with a divalent carboxylic acid and / or a derivative thereof can be used.
Examples of phenols include multi-substituent monomers such as catechol, resorcinol and hydroquinone, and resole type phenol resins.

  Acid anhydrides or carboxylic acids include aliphatic acid anhydrides such as dodecenyl succinic anhydride and polyadipic anhydride, and alicyclic acid anhydrides such as (methyl) tetrahydrophthalic anhydride and (methyl) hexahydrophthalic anhydride. Aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and carboxylic acids thereof can be used. In consideration of the expression of high gas barrier properties, an epoxy resin curing agent containing an aromatic moiety in the molecule is preferable.

  Specifically, metaxylylenediamine or paraxylylenediamine, a modified reaction product with an epoxy resin or a monoglycidyl compound made from these, an addition reaction product with epichlorohydrin, and an amide group site by reaction with these polyamines A reaction product with a polyfunctional compound having at least one acyl group capable of forming an oligomer and forming at least one acyl group capable of forming an amide group site by reaction with these polyamines to form an oligomer It is preferable to use a reaction product of a polyfunctional compound having a group and a monovalent carboxylic acid and / or a derivative thereof.

The epoxy resin curing agent of the present invention is particularly a reaction product of the following (A) and (B) or a reaction product of (A), (B) and (C).
(A) polyamine (B) a polyfunctional compound having at least one acyl group capable of forming an amide group site by reaction with polyamine and forming an oligomer (C) a monovalent carboxylic acid having 1 to 8 carbon atoms and / Or a derivative thereof.
Most preferably, the (A) polyamine is metaxylylenediamine or paraxylylenediamine.

  In the present invention, the reaction ratio in the reaction for synthesizing the epoxy resin curing agent is preferably such that the molar ratio of the polyfunctional compound to the polyamine component is 0.3 to 0.95. When the ratio is less than 0.3, a sufficient amount of amide groups are not generated in the epoxy resin curing agent, and a high level of gas barrier properties is not exhibited. Moreover, in the range higher than 0.95, the amount of amino groups that react with the epoxy resin is reduced, the performance of the cured product is lowered, and the workability is also lowered because the viscosity is further increased.

  The amide group site introduced by the reaction has a high cohesive force, and the presence of the amide group site in a high proportion in the epoxy resin curing agent results in higher gas barrier properties and better flexibility for the flexible polymer film. Adhesive strength is obtained. Furthermore, in order to improve various performances such as flexibility, impact resistance, and heat-and-moisture resistance, the above various epoxy resin curing agents can be mixed and used at an appropriate ratio.

  In the present invention, the blending ratio of the epoxy resin and the epoxy resin curing agent that forms the gas barrier layer is such that the ratio of the number of active hydrogens in the epoxy resin curing agent to the number of epoxy groups in the epoxy resin is 0.5 to 5.0, preferably Is in the range of 0.8 to 3.0.

  In order to improve various performances such as gas barrier properties of the gas barrier laminate film of the present invention, inorganic fillers such as silica, alumina, mica, talc, aluminum flakes and glass flakes may be added to the epoxy resin composition. . In consideration of the transparency of the film, it is preferable that such an inorganic filler has a flat plate shape. When adding these, it is the range of 0.01 mass%-10.0 mass% on the basis of the total mass of a hardening reaction material.

  Moreover, in order to improve the adhesiveness with respect to various film materials, the epoxy resin composition may contain a tackifier such as a xylene resin, a terpene resin, a phenol resin, or a rosin resin. Is preferably in the range of 0.01% by mass to 5.0% by mass based on the total mass of the adhesive composition.

  Furthermore, in order to improve the adhesion of the gas barrier layer formed in the present invention to the plastic film material, a coupling agent such as a silane coupling agent or a titanium coupling agent may be added to the epoxy resin composition. good. When adding these, the range of 0.01 mass%-5.0 mass% is preferable on the basis of the total mass of an adhesive composition.

Formation method of adhesive resin layer Although it does not specifically limit as a formation method of an adhesive resin layer, The method by printing, coating, etc. is mentioned.

  The thickness of the adhesive resin layer is 2 to 6 μm, more preferably 3 to 5 μm. In order to ensure the laminate strength, 2 μm or more is necessary, but in order to minimize the moisture permeation from the end face, the thickness of the adhesive resin layer should be as thin as possible, and the layer thickness should be 6 μm. If it exceeds, the end face gas barrier property required as a sealing member such as a display element may not be maintained. And it can select suitably in the range which does not impair the adhesiveness and adhesiveness with respect to a barrier film surface in consideration of the state, shape, etc. of the barrier film surface which touches a resin layer.

<3> Transparent gas barrier film As the transparent gas barrier film constituting the laminate forming the packaging bag of the present invention, various transparent gas barrier films can be used depending on the application, but for display element sealing. In order to use it as a packaging bag, it is preferable to use a transparent film having a water vapor permeability from the surface of 0.1 g / m ² · day or less.

  In the present invention, the water vapor permeability from the surface is a value measured using AQUATRAN manufactured by MOCON in an environment of a temperature of 60 ° C. and a humidity of 90% (RH) according to ASTM F1249-90. . Further, in the present invention, the transparent means that it has a necessary transparency depending on the use, and includes colorless or colored and transparent, particularly as a packaging bag for sealing such as a display element of a display. When using, high transparency is requested | required, for example, the average light transmittance in visible light region 380 nm-780 nm says the case where it is 80% or more. In addition, the measurement of light transmittance uses the value measured in room temperature and air | atmosphere using the ultraviolet visible spectrophotometer (For example, Shimadzu Corporation UV-3100PC).

Vapor Deposition Film As the transparent gas barrier film used in the present invention, for example, a vapor deposition film having a base layer and a carbon-containing silicon oxide vapor deposition layer formed on the base layer is particularly preferably used.
The deposited film not only exhibits excellent surface gas barrier properties and transparency, but also has high close adhesion between the base material layer and the carbon-containing silicon oxide deposited layer, and oxygen and water vapor are relatively infiltrated into the interface between the layers. Since it is difficult to do, good end face gas barrier properties are exhibited.

As the base material layer of the base material layer deposition film, it has excellent chemical or physical strength, withstands the conditions for forming the carbon-containing silicon oxide deposition layer, etc., and without impairing the characteristics of these carbon-containing silicon oxide deposition layers. A plastic film that can be retained can be used.

Examples of such plastic films include polyolefin films such as polypropylene and polyethylene, polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyamide films, polycarbonate films, cyclic olefin copolymer films, cyclic olefin polymer films, liquid crystal polymer films, Polyimide film, TAC film and other various resin films or sheets can be used.

In particular, when used as a packaging bag for sealing, such as a display element of a display, from the viewpoint of transparency and heat resistance, it is preferable to use a film made of a cyclic olefin copolymer, among the films made of the above plastic material. .
The layer thickness of the base material layer of the present invention is 2 to 400 μm, more preferably 10 to 200 μm.

  The plastic film may be subjected to, for example, corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, or other pretreatment. Can be applied arbitrarily. The surface pretreatment is performed as a method for improving the adhesion between the plastic film and the carbon-containing silicon oxide vapor deposition layer. As a method for improving the adhesion, for example, a plastic film A primer coating agent layer, an undercoat layer, a vapor deposition anchor coating agent layer, or the like can be arbitrarily formed on the surface in advance.

Carbon-containing silicon oxide vapor deposition layer The vapor deposition layer suitable for the present invention is a plasma chemistry described below from the viewpoints of tight adhesion to the substrate layer and the adhesive resin layer, transparency, and surface and edge gas barrier properties. A carbon-containing silicon oxide vapor deposition layer formed by a vapor deposition method can be applied.

  The material for forming the vapor deposition layer may be any material having transparency and gas barrier properties such as oxygen and water vapor. For example, aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, zirconium oxide, titanium oxide Boron oxide, hafnium oxide, barium oxide, and the like, and carbon-containing silicon oxide formed by plasma chemical vapor deposition is particularly preferable from the viewpoint of gas barrier properties and production efficiency.

  As a method for forming the carbon-containing silicon oxide vapor deposition layer of the present invention, a vacuum film formation method such as a vacuum vapor deposition method, a reactive vapor deposition method, an ion beam assisted vapor deposition method, a sputtering method, an ion plating method, a plasma CVD method, a thermal CVD method, etc. It is mentioned to do in.

  Moreover, the carbon-containing silicon oxide vapor deposition layer may consist of a single layer formed by one vapor deposition process, or may have a multilayer structure formed by repeating the vapor deposition process a plurality of times. In the case of a multilayer structure, each layer may be made of the same material or different materials, and may be formed by the same forming method or by different forming methods. Good. For example, a vapor deposition film made of silicon oxide may be formed on the base material layer by chemical vapor deposition, and then a vapor deposition film made of aluminum oxide may be formed by physical vapor deposition.

The layer thickness of the carbon-containing silicon oxide vapor deposition layer can be appropriately set within the range of 5 to 100 nm, more preferably 10 to 50 nm, as the thickness of the entire layer. If it exceeds 100 nm, the flexibility will be reduced, and the deposited layer may be cracked by external forces such as bending and pulling after film formation, transparency may be reduced, and the stress of the material itself will increase. Coloring is not preferable. On the other hand, if the thickness exceeds 100 nm, productivity is remarkably lowered, and further, protrusions tend to be formed due to abnormal grain growth, which is not preferable.
On the other hand, when the thickness of the inorganic compound layer is less than 5 nm, the transparency is good, but it is difficult to obtain a uniform layer and it is difficult to sufficiently perform the gas barrier function.

Gas barrier coating film In the present invention, a gas barrier coating film may be provided on the carbon-containing silicon oxide vapor deposition layer.
By providing a gas barrier coating film on the carbon-containing silicon oxide vapor-deposited layer, not only a more excellent surface gas barrier property can be obtained, but also the tight adhesion with the adhesive resin layer is increased, and an even higher end face gas barrier property. Is obtained.

In the present invention, the gas barrier coating film is a film obtained by applying and drying a gas barrier composition obtained by polycondensation of an alkoxide and a water-soluble polymer by a sol-gel method.
The alkoxide used in the gas barrier composition has a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, and M is a metal An atom is represented, n represents an integer greater than or equal to 0, m represents an integer greater than or equal to 1, n + m represents the valence of M.) At least 1 type or more alkoxide represented by this can be mentioned. .

As the water-soluble polymer, either a polyvinyl alcohol resin or an ethylene / vinyl alcohol copolymer or both can be preferably used.
In the present invention, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , silicon, zirconium, titanium, aluminum or the like can be used as the metal atom M. Moreover, in this invention, the alkoxide of a single or 2 or more types of different metal atoms can be mixed and used in the same solution.

In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ¹ include, for example, a methyl group, an ethyl group, an n-propyl group, i Examples include -propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group and other alkyl groups.
In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ² include, for example, a methyl group, an ethyl group, an n-propyl group, i -Propyl group, n-butyl group, sec-butyl group and the like.
In the present invention, these alkyl groups may be the same or different in the same molecule.

In the present invention, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , for example, an alkoxysilane in which M is Si can be used. As the alkoxysilane, for example, tetramethoxy Examples thereof include silane Si (OCH ₃ ) ₄ , tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane Si (OC ₃ H ₇ ) ₄ , tetrabutoxysilane Si (OC ₄ H ₉ ) _{4 and the} like.

  Moreover, in this invention, it is preferable that content of a polyvinyl alcohol-type resin and / or an ethylene vinyl alcohol copolymer is the range of 5-500 mass parts with respect to 100 mass parts of total amounts of said alkoxide. In the above, if it exceeds 500 parts by mass, the brittleness of the gas barrier coating film to be formed becomes large, and its weather resistance and the like are also unfavorable.

  In the present invention, as the polyvinyl alcohol-based resin, generally obtained by saponifying polyvinyl acetate can be used. Specific examples of the polyvinyl alcohol resin include PVA110 (degree of saponification = 98 to 99%, degree of polymerization = 1100), PVA117 (degree of saponification = 98 to 99%, degree of polymerization = 1700), PVA124 (made by Kuraray Co., Ltd.) Degree of saponification = 98-99%, degree of polymerization = 2400), PVA135H (degree of saponification = 99.7% or more, degree of polymerization = 3500), RS-110 (degree of saponification = 99%) manufactured by the same company , Degree of polymerization = 1,000), Kuraray Poval LM-20SO (degree of saponification = 40%, degree of polymerization = 2,000) manufactured by the same company, Gohsenol NM-14 (degree of saponification = 99%, degree of polymerization = 1,400) and gohsenol NH-18 (degree of saponification = 98 to 99%, degree of polymerization = 1700) and the like can be used.

  In the present invention, as the ethylene-vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer should be used. Can do.

  Such saponification products include partial saponification products in which several tens mol% of acetic acid groups remain to complete saponification products in which only several mol% of acetic acid groups remain or no acetic acid groups remain. The Although not particularly limited, it is desirable to use a saponification degree of 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of gas barrier properties.

  The content of repeating units derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%. Is preferably used. Specific examples of the ethylene / vinyl alcohol copolymer include Kuraray Co., Ltd., Eval EP-F101 (ethylene content: 32 mol%), Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908 (ethylene content: 29 mol%). ) Etc. can be used.

  In the present invention, a silane coupling agent or the like can also be added to prepare a gas barrier composition for forming a gas barrier coating film according to the present invention. Suitable silane coupling agents include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2- Amino group-containing silane coupling agents such as aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 2 -Epoxy group-containing silanes such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane Coupling agent, 3-mercaptopro Examples include mercapto group-containing silane coupling agents such as rumethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, and isocyanate group-containing silane coupling agents such as 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropyltrimethoxysilane. .

  The gas barrier composition used in the present invention can be prepared by hydrolyzing and polycondensing an alkoxide and a water-soluble polymer by a sol-gel method in the presence of an acid, water and an organic solvent.

  The gas barrier coating film is formed by applying the gas barrier composition on the carbon-containing silicon oxide vapor-deposited layer, and having a temperature of 20 ° C. to 200 ° C., preferably 140 ° C. or higher, and below the melting point of the plastic film constituting the base material layer. Can be formed by heat treatment for 10 seconds to 10 minutes.

  Moreover, as an acid used in preparation of said gas-barrier composition, organic acids, such as mineral acids, such as a sulfuric acid, hydrochloric acid, nitric acid, and an acetic acid, tartaric acid, etc. can be used, for example. Furthermore, as the organic solvent, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, or the like can be used.

  Further, regarding the gas barrier composition, the polyvinyl alcohol-based resin and / or the ethylene / vinyl alcohol copolymer is preferably in a state of being dissolved in a coating solution containing the alkoxide, the silane coupling agent, or the like. Therefore, the type of the organic solvent is appropriately selected. In the present invention, as the ethylene / vinyl alcohol copolymer solubilized in a solvent, for example, those commercially available as Soarnol (manufactured by Nippon Synthetic Chemical Co., Ltd.) can be used.

  When the above gas barrier composition is applied on the carbon-containing silicon oxide vapor deposition layer and heated to remove the solvent and the alcohol produced by the polycondensation reaction, the polycondensation reaction is completed, and a transparent gas barrier coating film is formed. It is formed.

  Furthermore, since the hydroxyl group generated by hydrolysis and the silanol group derived from the silane coupling agent are bonded to the hydroxyl group on the surface of the carbon-containing silicon oxide deposition layer, the carbon-containing silicon oxide deposition layer and the gas barrier coating film are closely bonded. Good properties and the like.

  By being formed as described above, the gas barrier coating film of the present invention includes a linear polymer having crystallinity and has a structure in which a large number of minute crystals are embedded in an amorphous portion. . Such a crystal structure is the same as that of a crystalline organic polymer (for example, vinylidene chloride or polyvinyl alcohol), and a polar group (OH group) is partially present in the molecule, and the cohesive energy of the molecule is high. Good surface gas barrier properties.

  In the present invention, the carbon-containing silicon oxide vapor deposition layer and the gas barrier coating film form, for example, a chemical bond, a hydrogen bond, or a coordinate bond by hydrolysis / co-condensation, and the adhesion between these two layers is improved. By improving and synergistic effect, a better surface gas barrier effect can be exhibited.

  In the present invention, the gas barrier composition may be applied by one or more times by a coating means such as a roll coat such as a gravure roll coater, a spray coat, dipping, a brush, a bar coat, or an applicator. With this coating, a gas barrier coating film having a dry film thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm can be formed.

  In the present invention, in order to obtain a higher surface gas barrier property, after providing the gas barrier coating film, the carbon-containing silicon oxide vapor deposition layer and the gas barrier coating film are alternately or once in this order. A transparent gas barrier film may be formed by repeatedly laminating further, and preferably forming the gas barrier coating film as the outermost layer.

<4> Heat-fusion layer The heat-fusion layer constituting the laminate of the present invention may be a layer made of an olefin-based heat-fusion resin composition (olefin-based hot melt resin composition), or It may be a layer made of a heat-fusible film (sealant film).

Olefin-based heat fusion resin composition (olefin-based hot melt resin composition)
In the present invention, the hot melt resin composition means a resin composition containing a base polymer and a tackifier and having heat melting property and adhesiveness, and the base polymer is an olefin resin, in particular. It is called an olefin-based hot melt resin composition.
The heat-sealing layer composed of the hot melt resin composition can be directly laminated on the transparent gas barrier film. Thereby, since the layer thickness can be set thin, the gas permeability from the end face can be kept low.

  The base polymer imparts cohesive force by imparting bulk physical properties to the hot-melt resin composition, and is tough and has a strong property against tensile strength and compressive stress. An olefin-based hot melt resin composition containing an olefin-based resin as a base polymer is preferable because it is excellent in suppressing the intrusion of oxygen and water vapor from the end face.

  As the olefin resin of the present invention, an α-olefin copolymer is preferably used. The α-olefin copolymer is a copolymer composed of two or more kinds of α-olefins, and may be a copolymer containing other copolymerizable monomers if necessary. . Those skilled in the art can arbitrarily set characteristics such as copolymerization ratio, viscosity, intramolecular branching, and molecular weight distribution. α-olefins include ethylene, propylene, pentene-1, 4-methylpentene-1, butene-1, hexene-1, octene-1, decene-1, and dodecene-1. Of these, propylene, ethylene, pentene-1, 4-methylpentene-1, decene-1, and hexene-1 are preferred because of their high density and excellent suppression of water vapor penetration. Particularly preferred is a copolymer comprising propylene, ethylene and butene-1, particularly a copolymer of ethylene and another α-olefin, that is, an ethylene / α-olefin copolymer.

  Commercially available α-olefin copolymers suitably used in the present invention include “Bureon” (manufactured by Mitsui Petrochemical Co., Ltd.), “Nack Flex” (manufactured by Nihon Unicar), “Shell Polybutylene” (Shell Chemical). ), “Tuffmer” (manufactured by Mitsui Petrochemical Co., Ltd.), “Excellen VL” (manufactured by Sumitomo Chemical Co., Ltd.) and the like. These α-olefin copolymers may be used in combination of two or more.

  A tackifier is used in order to adjust the adhesiveness of a hot-melt resin composition. As the tackifier used in the present invention, saturated petroleum resins such as aliphatic hydrocarbons, cycloaliphatic hydrocarbons, hydrogenated petroleum resins and the like are preferable. Specifically, for example, C9 to C10 fractions such as resins obtained by copolymerizing C5 fractions containing pentenes, isoprene, piperine, 1,3-pentadiene, indene, vinyltoluene, α-methylstyrene and the like. And a resin obtained by polymerizing a cyclic monomer such as dicyclopentadiene. Examples of commercially available tackifiers suitably used in the present invention include “FTR-600” (manufactured by Mitsui Petrochemical Industries), “Arcon” (manufactured by Arakawa Chemical Industries), “Quinton” (Nippon Zeon Corporation) ), “Escollets” (manufactured by Tonex), etc.

  In the olefin-based hot melt resin composition of the present invention, the ratio of base polymer: tackifier is 70:30 to 95: 5, preferably 75:25 to 90:10. When the ratio of the base polymer is small, the handleability and the adhesive strength are lowered. On the other hand, when the ratio of the base polymer is large, the adhesive strength is also lowered.

  It does not specifically limit as a preparation method and the coating method of an olefin type hot-melt resin composition, A conventionally well-known method is employable. As a specific preparation method, it can be carried out by kneading each component by an operation usually performed using an apparatus having heating, stirring, kneading functions and the like. And the method and apparatus which apply | coat the obtained hot-melt resin composition to a coating layer are conventionally well-known, such as spray coating, nozzle coating, dip coating, roll coating, gravure coating, rolling coating, brush coating, etc. A coating method and a coating apparatus can be used. Such a coating method and a coating apparatus can be appropriately selected in consideration of the viscosity and viscosity of the olefinic hot melt resin composition according to the present invention. Moreover, it is good also as a heat-fusion layer by adhere | attaching the film which consists of an olefin type hot-melt resin composition by hot press.

  The layer thickness of the hot melt resin composition forming the heat-sealing layer is preferably 20 to 50 μm. When it is thicker than 50 μm, the amount of oxygen and water vapor penetrating from the end face of the heat-fusible layer increases. On the other hand, if it is thinner than 20 μm, the heat seal strength is lowered, which causes a leak.

 In the present invention, the olefin-based heat-sealing resin composition (olefin-based hot-melt resin composition) is provided on the second weather-resistant coating layer, and in that case, it is laminated via an appropriate adhesive resin layer. I decided to.

Heat-sealable film (sealant film)
The heat-sealable film (sealant film) of the present invention is non-adhesive at room temperature, but after being melted by heat, it is overlapped with the heat-sealable layer that is also melted by heat, and is pressure-bonded and cooled. By adhering to each other. Here, normal temperature refers to a temperature state in the range of 5 ° C. to 35 ° C. based on JIS Z 8703. Non-adhesive means a material that cannot be measured by a 180-degree peeling test measured according to JIS Z 0237.

  The heat-fusible film (sealant film) constituting the laminate forming the packaging bag of the present invention is preferably made of a polyolefin resin.

  Polyolefin resins include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, ethylene-butene copolymer and other polyethylene resins, homopolypropylene, ethylene-propylene copolymer, ethylene-propylene- Polypropylene resins such as butene copolymers are used alone or as a mixture of two or more, as a resin composition containing an optional additive in some cases. When the polyolefin resin contains an optional additive and is used as a resin composition, the composition is a tackifier such as an aliphatic hydrocarbon, a cyclic aliphatic hydrocarbon, a hydrogenated petroleum resin, or the like. Does not contain saturated petroleum resin.

  The film made of polyolefin resin may be a single layer film made of polyolefin resin or a coextruded film having a layer made of polyolefin resin as the outermost layer. In order to maintain excellent end face gas barrier properties, a single-layer film made of a polyolefin resin or a coextruded film in which all layers are layers made of a polyolefin resin is preferable.

  In the present invention, the heat-fusible film (sealant film) is laminated on the second transparent gas barrier film. In addition, when the film which consists of polyolefin resin is a coextrusion film, it laminates | stacks so that the layer which consists of polyolefin resin may become an outermost layer.

  Since the polyolefin-based resin exhibits waterproofness, it is possible to improve the surface gas barrier property of the laminate and to prevent the end-face gas barrier property from being lowered by bonding the heat-sealing layer made of the polyolefin-based resin.

  The film thickness of the heat-fusible film (sealant film) forming the heat-sealing layer is preferably 15 to 50 μm. When it is thicker than 50 μm, the amount of oxygen and water vapor penetrating from the end face of the heat-fusible layer increases. On the other hand, if it is thinner than 15 μm, the heat seal strength is lowered, which causes leakage.

<5> Bonding In the present invention, the gas barrier coating film surfaces of the first transparent gas barrier film and the second transparent gas barrier film are dry-laminated with the adhesive resin layer, and are cured and laminated. Further, a gas barrier film laminate in which the heat-sealing layer is laminated on one surface thereof to form the packaging bag of the present invention can be obtained.

  Here, when the first transparent gas barrier film is the above-described vapor-deposited film, the gas-barrier coating film is provided so that the carbon-containing silicon oxide vapor-deposited layer is in contact with the pressure-sensitive adhesive layer. It is preferable from the viewpoint of the handleability of the laminate that the adhesive coating film is bonded so as to be in contact with the pressure-sensitive adhesive layer and the base material layer is the surface layer of the laminate.

  The adhesive resin layer of the present invention strongly adheres to the carbon-containing silicon oxide vapor deposition layer or the gas barrier coating film, and prevents oxygen and water vapor from entering the bonded boundary surface, thereby further improving the end face gas barrier property.

  Moreover, as one aspect of the present invention, one or more additional layers may be laminated on the surface of the first transparent gas barrier film opposite to the surface facing the second transparent gas barrier film. As a further layer, when a film such as a transparent gas barrier film is bonded via an adhesive resin, a high end face is obtained even if the thickness of the laminate is increased by bonding using the pressure-sensitive adhesive layer of the present invention. Gas barrier properties can be maintained.

  When many transparent gas barrier films are bonded to obtain a high surface gas barrier property, the end surface gas barrier property is generally lowered instead of improving the surface gas barrier property.

However, in order to be suitably used as a packaging bag for sealing display elements, the packaging bag needs to exhibit both excellent surface gas barrier properties and end surface gas barrier properties. Especially for the end face gas barrier property, as a measured value of the water vapor permeability from the end face based on the method described below, the water vapor permeability from the end face of the laminate forming the packaging bag is 30 g / m ² · day or less. Preferably, it is required to show a low value of 15 g / m ² · day or less, and more preferably 10 g / m ² · day or less. According to the present invention, this requirement can be achieved.

Post-treatment The gas barrier film laminate of the present invention can further improve the barrier properties by treating the uncured product by irradiating an electron beam as a post-treatment after lamination (lamination).

  Here, the acceleration voltage of the electron beam can be appropriately selected according to the resin to be used and the thickness of the layer, but it is preferable to cure the uncured resin layer at an acceleration voltage of about 70 to 300 kV. In electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when using a base material that deteriorates due to the electron beam as the base material, the transmission depth of the electron beam and the thickness of the resin layer are substantially equal. By selecting the accelerating voltage so as to be equal to each other, it is possible to suppress the irradiation of the electron beam to the base material, and to minimize the deterioration of the base material due to the excessive electron beam.

The irradiation dose is preferably such that the crosslink density of the resin layer is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).
Further, the electron beam source is not particularly limited. For example, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type Can be used.

<6> Manufacture and use of packaging bag The packaging bag of the present invention is obtained by folding the above-mentioned laminated body in two or by preparing two laminated bodies, with the surfaces of the sealant films facing each other, and further Peripheral end, for example, side seal type, two-side seal type, three-side seal type, four-side seal type, envelope-attached seal type, palm-attached seal type (pillow seal type), pleated seal type, flat bottom seal type, square bottom It can be manufactured as a packaging bag of various forms by heat-sealing with a heat-sealing form such as a seal-type or a gusset-type.

In the above, as a heat sealing method, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used.
Although the packaging bag of this invention can be used as various packaging materials, it can be conveniently used especially as sealing packaging bags, such as a display element of a display.

  When manufacturing a sealed display device by sealing a display element in the packaging bag of the present invention, the display element to be sealed includes an organic EL display element, an electrophoretic display element, a liquid crystal display element, a light emitting diode display element, and the like. For example, but not limited to. Furthermore, as a display element enclosed in the packaging bag of this invention, what was described in special table 2004-526210 grade | etc., Can be applied, for example.

As one aspect of the encapsulated display device obtained by enclosing the display element in the packaging bag of the present invention, the display element includes a pair of substrates (7a, 7b) and the pair of substrates as shown in FIG. A display element having a pair of electrodes (8a, 8b) disposed between substrates and a light emitter (9) disposed between the pair of electrodes. It is enclosed with the packaging bag of the present invention consisting of 10b).
The barrier film laminate of the present invention is obtained by laminating a barrier film having a high water vapor barrier property and further imparting performance capable of withstanding use in a high temperature and high humidity environment.

  Therefore, according to the barrier film laminate of the present invention, it has excellent water vapor barrier properties and can prevent deterioration and alteration of the contents due to water vapor, so that it can be used for food and drink, pharmaceuticals, electronic parts, chemicals, daily necessities. It can be suitably used as a packaging material for various articles such as. Further, it can be suitably used as a protective material for electrophoretic ink of electronic paper that is easily affected by moisture.

Furthermore, the barrier film laminate of the present invention can be applied to a solar cell backsheet, a display substrate such as a liquid crystal display and an organic EL display. When the display element is exposed to water vapor, its performance deteriorates, and troubles such as not emitting light may occur. According to the barrier film laminate of the present invention, for example, the display element can be protected from water vapor by applying to the outside of the glass substrate instead of the two glass substrates of the display.
Next, the present invention will be specifically described with reference to examples.

[Example 1]
(1) A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used as a base film, and this is mounted on a feeding roll of a plasma chemical vapor deposition apparatus. A carbon-containing silicon oxide vapor deposition layer having a thickness of 10 nm was formed on the corona-treated surface of the film.

(Deposition conditions)
Mixing ratio of mixed gas reaction gas composition for vapor deposition
Hexamethyldisiloxane: Oxygen gas: Helium
= 1: 10: 10 (unit: slm)
Degree of vacuum: 6Pa
Cooling / electrode drum supply power: 22Kw
Line speed: 100m / min

  Thereafter, using another magnetron sputtering apparatus, oxygen gas of 1000 sccm was introduced, plasma treatment was performed at an output of 5 kW, and the plasma treatment surface by oxygen gas was applied to the surface of the silicon oxide deposition layer. Was formed and wound up.

(2) On the other hand, according to the composition shown in Table 1 below, the composition a. Composition prepared in advance in EVOH solution in which EVOH (ethylene copolymerization ratio 29%) was dissolved in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzate composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum and ion-exchanged water, and stirred, and further prepared in advance c. A liquid mixture consisting of an aqueous polyvinyl alcohol solution, a silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent gas barrier composition.

Next, using the gas barrier composition produced above on the plasma-treated surface with oxygen gas formed in (1) above, this is coated by the gravure roll coating method, and then at 100 ° C. for 30 seconds. A heat treatment was performed to form a first gas barrier coating film having a thickness of 0.4 g / m ² (0.4 μ) (in a dry operation state).

(3) Next, the base film on which the first gas barrier coating film is formed as described above is used, and this is again mounted on the unwinding roll of the take-up vacuum deposition apparatus, and the first gas barrier coating film is formed. A plasma-treated surface with an inert gas was formed on this surface, and then a 10 nm-thick silicon oxide deposition layer was formed on the plasma-treated surface under the same conditions as in (1) above.

  Thereafter, using another magnetron sputtering apparatus, oxygen gas 500 sccm is introduced, plasma treatment is performed at an output of 3 kW, and the surface of the silicon oxide vapor deposition layer is subjected to a plasma treatment surface using oxygen gas. Was formed and wound up.

(4) Using the gas barrier composition produced in (2) above on the plasma-treated surface with oxygen gas formed in (3) above, this is coated by gravure roll coating, and then at 100 ° C. Heat treatment was carried out for 30 seconds to form a second gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state), thereby producing first and second transparent gas barrier films.

(5) The first transparent gas barrier film produced in (4) above is mounted on the first delivery roll of a dry laminating machine, and the gas barrier coating film surface is coated with an epoxy resin adhesive MAXIVE M-M-by Mitsubishi Gas Chemical. A solution prepared by adding 3 times equivalent of epoxy resin curing agent C-93T to 1 time equivalent of 100 is applied using a gravure roll coating method and dried to form an adhesive resin layer (
A layer thickness of 4 μm) was formed.

(6) Next, the gas barrier coating film surface of the second transparent gas barrier film produced in the above (5) is opposed to the adhesive resin layer and dry-laminated to accelerate the curing reaction at 40 ° C. for 72 hours. The laminate according to the present invention was manufactured.

(7) Next, on one surface of the laminate obtained in (6) above, an olefin-based hot melt resin composition (Aronmelt HMP, manufactured by Toagosei Co., Ltd.) melted at 230 ° C. is extruded, A heat-bonding layer having a layer thickness of 30 μm was formed to produce a laminate (total thickness of 64 μm) forming the packaging bag according to the present invention.

(8) Next, the heat-sealing layers of the laminate obtained in the above (6) are faced to each other and heat sealed (temperature 120 ° C., time 1 second, pressure 0.1 MPa, seal width 3 mm). A packaging bag of the present invention was manufactured as a seal bag.

[Example 2]
(1) A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used as a base film, and this is mounted on a feeding roll of a plasma chemical vapor deposition apparatus. A carbon-containing silicon oxide vapor deposition layer having a thickness of 10 nm was formed on the corona-treated surface of the film.

(Deposition conditions)
Mixing ratio of mixed gas reaction gas composition for vapor deposition
Hexamethyldisiloxane: Oxygen gas: Helium
= 1: 10: 10 (unit: slm)
Degree of vacuum: 6Pa
Cooling / electrode drum supply power: 22Kw
Line speed: 100m / min

(2) Next, the biaxially stretched polyethylene terephthalate film on which the deposited layer of silicon oxide having a thickness of 10 nm was formed as described above was mounted on the feed roll of a wind-up type vacuum deposition apparatus, and then this And a magnetron sputtering device is used on the surface of the 10 nm thick silicon oxide vapor-deposited layer of the biaxially stretched polyethylene terephthalate film, the line speed is 600 m / min, argon gas 500 sccm is introduced, and the output is 20 kW. Plasma treatment is performed to form a plasma treatment surface, and then the following vacuum deposition method using an electron beam (EB) heating method is performed while supplying oxygen gas to the plasma treatment surface using aluminum as an evaporation source. Under the above deposition conditions, a 10 nm-thick aluminum oxide deposited film was formed.

(Deposition conditions)
Degree of vacuum in the deposition chamber; 2 × 10 ⁻⁴ mbar
Degree of vacuum in the winding chamber; 2 × 10 ⁻² mbar
Electron beam power: 25 kW
Film transport speed: 600 m / min

Next, immediately after forming the 10 nm-thick aluminum oxide vapor deposition film as described above, a glow discharge plasma generator is used on the aluminum oxide vapor deposition film surface, and the power is 9 kw, oxygen gas (O ₂ ): argon gas. (Ar) = 7.0: 2.5 (unit: slm) is used, oxygen / argon mixed gas plasma treatment is performed at a mixed gas pressure of 6.0 × 10 ⁻² mbar and a processing speed of 600 m / min. The surface tension of the deposited film surface of aluminum oxide was 54 dy
A plasma-treated surface improved by ne / cm or more was formed.

(3) On the other hand, a colorless and transparent gas barrier composition was obtained in the same manner as in Example 1 (2), and this was coated on the plasma-treated surface formed in (2) above by a gravure roll coating method. Subsequently, a heat treatment is performed at 100 ° C. for 30 seconds to form a gas barrier coating film having a thickness of 0.4 g / m ² (0.4 μ) (in a dry operation state), and the first and second transparent gas barrier films. Manufactured.

(4) The first transparent gas barrier film produced in (3) above is mounted on the first delivery roll of a dry laminating machine, and the gas barrier coating film surface is coated with an epoxy resin adhesive MAXIVE M-M-by Mitsubishi Gas Chemical. A solution prepared by adding 3 times equivalent of epoxy resin curing agent C-93T to 100 times equivalent of 100 is applied using a gravure roll coating method and dried to form an adhesive resin layer (layer thickness 4 μm). Formed.

(5) Next, the gas barrier coating film surface of the second transparent gas barrier film produced in the above (4) is opposed to the adhesive resin layer and dry-laminated to accelerate the curing reaction at 40 ° C. for 72 hours. The laminate according to the present invention was manufactured.

(6) Next, on one surface of the laminate obtained in (5) above, an olefin-based hot melt resin composition (Aronmelt HMP, manufactured by Toagosei Co., Ltd.) melted at 230 ° C. is extruded, A heat-bonding layer having a layer thickness of 30 μm was formed to produce a laminate (total thickness of 64 μm) forming the packaging bag according to the present invention.

(7) Next, the heat-sealing layers of the laminate obtained in the above (6) are faced to each other and heat sealed (temperature 120 ° C., time 1 second, pressure 0.1 MPa, seal width 3 mm). A packaging bag of the present invention was manufactured as a seal bag.

[Example 3]
(1) The first transparent gas barrier film produced in Example 1 (4) is mounted on the first delivery roll of a dry laminating machine, and the gas barrier coating film surface is coated with Mitsui Chemicals' epoxy resin adhesive Takelac A980. A solution prepared by adding 1 equivalent equivalent of epoxy resin curing agent Takenate A19 to 10 equivalents was applied using a gravure roll coating method and dried to form an adhesive resin layer (layer thickness 4 μm). .

(2) Next, the gas barrier coating film surface of the second transparent gas barrier film produced in the above (1) is opposed to the adhesive resin layer and dry-laminated to accelerate the curing reaction at 40 ° C. for 72 hours. The laminate according to the present invention was manufactured.

(3) Next, on one surface of the laminate obtained in (2) above, an olefin-based hot melt resin composition (Aronmelt HMP, manufactured by Toagosei Co., Ltd.) melted at 230 ° C. is extruded, A heat-bonding layer having a layer thickness of 30 μm was formed to produce a laminate (total thickness of 64 μm) forming the packaging bag according to the present invention.

(4) Next, the heat fusion layers of the laminate obtained in the above (3) are faced to each other and heat sealed (temperature 120 ° C., time 1 second, pressure 0.1 MPa, seal width 3 mm). A packaging bag of the present invention was manufactured as a seal bag.

[Example 4]
(1) The first transparent gas barrier film produced in Example 2 (3) is mounted on the first delivery roll of a dry laminating machine, and the gas barrier coating film surface is coated with Mitsui Chemicals' epoxy resin adhesive Takelac A980. A solution prepared by adding 1 equivalent equivalent of epoxy resin curing agent Takenate A19 to 10 equivalents was applied using a gravure roll coating method and dried to form an adhesive resin layer (layer thickness 4 μm). .

(2) Next, the gas barrier coating film surface of the second transparent gas barrier film produced in the above (1) is opposed to the adhesive resin layer and dry-laminated to accelerate the curing reaction at 40 ° C. for 72 hours. The laminate according to the present invention was manufactured.

(3) Next, on one surface of the laminate obtained in (2) above, an olefin-based hot melt resin composition (Aronmelt HMP, manufactured by Toagosei Co., Ltd.) melted at 230 ° C. is extruded, A heat-bonding layer having a layer thickness of 30 μm was formed to produce a laminate (total thickness of 64 μm) forming the packaging bag according to the present invention.

(4) Next, the heat fusion layers of the laminate obtained in the above (1) are faced to each other and heat sealed (temperature 120 ° C., time 1 second, pressure 0.1 MPa, seal width 3 mm). A packaging bag of the present invention was manufactured as a seal bag.

[Comparative Example 1]
(1) The first transparent gas barrier film produced in Example 1 (4) is mounted on the first delivery roll of a dry laminating machine, and a two-component curable polyurethane adhesive ( A solution made of Mitsui Chemicals, main ingredient Takelac A-515 / curing agent Takenate A-50) was applied using a gravure roll coating method and dried to form an adhesive resin layer (layer thickness 4 μm).

(2) Next, the gas barrier coating film surface of the second transparent gas barrier film produced in Example 1 (4) was opposed to the adhesive resin layer, dry-laminated, and cured at 40 ° C. for 72 hours. Promoted.

(3) Next, on one surface of the laminate obtained in (2) above, an olefin-based hot melt resin composition (Aronmelt HMP, manufactured by Toagosei Co., Ltd.) melted at 230 ° C. is extruded, A heat-sealing layer having a layer thickness of 30 μm was formed to produce a laminate (total thickness 58 μm) according to the present invention.

(4) Next, the heat fusion layers of the laminate obtained in the above (3) are faced to each other and heat sealed (temperature 120 ° C., time 1 second, pressure 0.1 MPa, seal width 3 mm). A packaging bag of the present invention was manufactured as a seal bag.

[Comparative Example 2]
1) The first transparent gas barrier film produced in Example 2 (3) was mounted on the first delivery roll of a dry laminating machine, and a two-component curable polyurethane adhesive (Mitsui) was applied to the gas barrier coating film surface. A solution made of Chemical, main ingredient Takelac A-515 / curing agent Takenate A-50) was applied using a gravure roll coating method and dried to form an adhesive resin layer (layer thickness 4 μm).

(2) Next, the gas barrier coating film surface of the second transparent gas barrier film produced in Example 2 (3) was opposed to the adhesive resin layer, dry-laminated, and cured at 40 ° C. for 72 hours. Promoted.

(3) Next, on one surface of the laminate obtained in (2) above, an olefin-based hot melt resin composition (Aronmelt HMP, manufactured by Toagosei Co., Ltd.) melted at 230 ° C. is extruded, A heat-sealing layer having a layer thickness of 30 μm was formed to produce a laminate (total thickness 58 μm) according to the present invention.

(4) Next, the heat fusion layers of the laminate obtained in the above (3) are faced to each other and heat sealed (temperature 120 ° C., time 1 second, pressure 0.1 MPa, seal width 3 mm). A packaging bag of the present invention was manufactured as a seal bag.

[Evaluation of gas barrier properties]
(1) A flexible printed circuit board (thickness 100 μm) with an aluminum electrode on a polyimide film, and an electronic ink sheet (thickness 100 μm) with an ITO transparent electrode on a polyethylene terephthalate film and uniformly coated with microcapsules Prepared. The electrophoretic display element was manufactured by superimposing the surface of the flexible printed board on which the aluminum electrode was applied and the surface of the electronic ink sheet on which the microcapsules were applied. In this display element, the black pigment piece (negatively charged) and the white pigment piece (positively charged) in the microcapsule move according to the voltage applied to the aluminum electrode, so that a black and white image can be formed. It is configured.

(2) The display element is inserted into the packaging bags of Examples 1 to 4 and Comparative Examples 1 to 2, and the remaining side is sealed with a hot press (110 ° C., 5 seconds, 0.1 MPa) for evaluation. An encapsulated display device was created.

(3) The encapsulated display device is connected to the driving device, and the brightness at the time of white display and the brightness at the time of black display in the environment of temperature 60 ° C. and humidity 90% (RH) is a color luminance meter BM manufactured by Topcon Technohouse Co., Ltd. -5AS was used for measurement, and the contrast ratio (= brightness when displaying white / brightness when displaying black) was calculated.
When oxygen and water vapor enter the inside from the surface and end face of the packaging bag, the movement of the white pigment and the black pigment in the microcapsule is prevented, and the contrast ratio is lowered.
The results are shown in Table 2.

[Measurement method of water vapor permeability from end face of laminate]
(1) Laminate two laminates so that the surfaces of the heat-sealing layer face each other, heat-seal three sides, put 10 g of calcium chloride, heat-seal the other side, A packaging bag having a size of 100 mm × 100 mm and a seal width of 3 mm is manufactured.

(2) The packaging bag produced above is allowed to stand in an environment of a temperature of 60 ° C. and a humidity of 90% (RH), and the mass increase of calcium chloride after 24 hours is measured.

(3) On the other hand, in accordance with ASTM F1249-90, using an AQUATRAN manufactured by MOCON under an environment of a temperature of 60 ° C. and a humidity of 90% (RH), the laminate is obtained as follows. The water vapor transmission rate in the surface direction per 01 m ² is measured.

(4) Obtained by subtracting twice the measured value of (3) (water vapor permeation in the surface direction per 0.01 m ² ) from the measured value of (2) above (water vapor permeability of the packaging bag). The obtained value is divided by the area of the end face of the packaging bag, and the value obtained thereby is taken as the water vapor permeability from the end face of the laminate.
Water vapor transmission rate from end face = {(water vapor transmission rate of evaluation bag) −2 × (water vapor transmission rate in surface direction per 0.01 m ² )} / (area of end surface of evaluation bag)

[Evaluation of end face gas barrier properties]
Based on said method, the water vapor permeability from an end surface was measured about each laminated body which forms the packaging bag manufactured in Examples 1-4 and Comparative Examples 1-2.
The results are shown in Table 3.

[Evaluation results]
The sealed display device using the packaging bags of Examples 1 to 4 had a contrast ratio of 20 or more after 200 hours, but the sealed display device using the packaging bags of Comparative Examples 1 to 2 had a contrast after 200 hours. The ratio has dropped significantly.
Moreover, although the laminated body which forms the packaging bag of Examples 1-4 and Comparative Examples 1-2 showed the substantially equal value about the water vapor transmission amount of the surface direction, the water vapor transmission amount of a packaging bag is an Example. The packaging bags of 1-4 showed a smaller value than the packaging bags of Comparative Examples 1-2.
In the packaging bags of Examples 1 to 4, since the cured epoxy resin layer prevented the permeation of water vapor from the end face, the water vapor permeability from the end face was suppressed to an extremely low value.

1a, 1b. 1. Transparent gas barrier film 2. Adhesive resin layer 3. Thermal fusion layer Base material layer 5. 5. Carbon-containing silicon oxide vapor deposition layer Gas barrier coating films 7a, 7b. Substrates 8a, 8b. Electrode 9. Light emitters 10a, 10b. Laminate

Claims (7)

A laminate comprising a first transparent gas barrier film, an adhesive resin layer laminated on the first transparent gas barrier film, and a second transparent gas barrier film laminated on the adhesive resin layer. And
The adhesive resin layer is a cured product formed by an epoxy resin and an epoxy resin curing agent,
The blend ratio of the epoxy resin and the epoxy resin curing agent is such that the ratio of the number of active hydrogens in the epoxy resin curing agent to the number of epoxy groups in the epoxy resin is in the range of 0.1 to 3.0 ,
At least one of the first transparent gas barrier film and the second transparent gas barrier film is a base material layer, and a carbon-containing silicon oxide vapor deposition layer formed on the base material layer by a plasma chemical vapor deposition method. The other is a vapor deposition film having a base material layer and a carbon-containing silicon oxide vapor deposition layer formed on the base material layer by plasma chemical vapor deposition,
Wherein both the one and the other deposited film, further comprising a gas barrier coating film provided on the carbon-containing silicon oxide deposited layer, a gas barrier coating film of the general formula _{^{R 1 n M (OR 2)}} m ( In the formula, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, and m represents an integer of 1 or more. , N + m represents the valence of M.) and contains at least one alkoxide represented by the formula (1), a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and further polycondensation by a sol-gel method. A gas barrier film laminate, which is a film made of a gas barrier composition obtained as described above.   The gas barrier film laminate according to claim 1, wherein the adhesive resin layer has a thickness of 2 to 6 μm.   The gas barrier film laminate according to claim 1 or 2, further comprising a heat fusion layer laminated on the second transparent gas barrier film.   The gas barrier film laminate according to claim 3, wherein the heat-fusible layer is made of a polyolefin-based resin. Packaging bag gas barrier film laminate according to claim 3 or 4, thermal adhesive layer is characterized by being Seibukuro so that the innermost layer. In the measuring method prescribed | regulated to this invention, the water vapor permeability from the end surface of the laminated body which forms a packaging bag is 30 g / m < ² > * day or less, The packaging bag of Claim 5 characterized by the above-mentioned.   The packaging bag according to claim 5 or 6, wherein the packaging bag is a display module sealing packaging bag that prevents deterioration of the display module due to moisture.

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