JP5569129B2 - Packaging bag and enclosed display device including the same - Google Patents

Description

  The present invention is used to suppress deterioration of display elements sensitive to oxygen and water vapor, such as packaging bags made of gas barrier laminates used as packaging materials for foods and drinks, pharmaceuticals and electronic members, and displays. And a sealed display device including the packaging bag.

  The main use of the packaging bag of the present invention is as a packaging bag for sealing, in particular, a packaging bag for sealing display elements such as organic electroluminescence (organic EL) display and electronic paper for displays, foods and drinks, pharmaceuticals and electronics. If it is a use which requires gas barrier properties, such as packaging bags, such as a member, it will not be limited in particular.

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, deterioration of display elements that are sensitive to oxygen and water vapor. 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 obtained by laminating only by vapor deposition or coextrusion (Patent Documents 1 and 2), and others are obtained by laminating by using an adhesive (Patent Document 3).

  A laminate used as a packaging material for electronic members 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 used with an adhesive. It is possible to use a laminated body that is bonded and has an improved gas barrier property. Such a gas barrier laminate can suitably prevent permeation of oxygen and water vapor 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.

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

  Therefore, the present invention can prevent the intrusion of oxygen and water vapor not only from the surface but also from the end face, and has a gas barrier laminate having transparency that can be applied to various packaging applications and display fields. And a sealed display device including the packaging bag.

  As a result of various studies, the present inventors have obtained a first transparent gas barrier film, a first adhesive resin layer laminated on the first transparent gas barrier film, and a laminate on the adhesive resin layer. Second transparent gas barrier film, a second adhesive resin layer laminated on the second transparent gas barrier film, and a heat fusion layer laminated on the second adhesive resin layer And a laminated bag having the heat-fusible layer as the innermost layer, wherein the first and second adhesive resin layers are crosslinked. A layer made of a fluorine-containing resin formed by a fluorine-containing copolymer having a functional group and a curing agent that reacts with the crosslinkable group, and the heat-sealing layer is a layer made of an olefin-based hot melt resin composition A packaging bag characterized by being enclosed in the packaging bag Encapsulated display device comprising 示素Ko were found to achieve the above object.

The present invention is characterized by the following points.
1. A first transparent gas barrier film, a first adhesive resin layer laminated on the first transparent gas barrier film, a second transparent gas barrier film laminated on the adhesive resin layer, A laminate having a second adhesive resin layer laminated on the second transparent gas barrier film and a heat fusion layer laminated on the second adhesive resin layer is formed by the heat fusion. A packaging bag obtained by making a bag so that the layer becomes an innermost layer, wherein the first and second adhesive resin layers are a fluorine-containing copolymer having a crosslinkable group and the A packaging bag, characterized in that it is a layer made of a fluororesin formed by a curing agent that reacts with a crosslinkable group, and the heat fusion layer is a layer made of an olefinic hot melt resin composition.
2. 2. The packaging bag according to 1 above, wherein the fluorine-containing copolymer contains at least a fluoroolefin monomer and a hydroxyl group-containing monomer as monomer components.
3. 3. The packaging bag according to 1 or 2 above, wherein the curing agent is an organic polyisocyanate compound.
4). 4. The packaging bag according to any one of the above 1 to 3, wherein at least one of the first adhesive resin layer and the second adhesive resin layer further contains a silane coupling agent. .
5. At least one of the first transparent gas barrier film and the second transparent gas barrier film is a vapor deposition film having a base material layer and an inorganic oxide vapor deposition layer deposited on the base material layer. The packaging bag according to any one of 1 to 4 above, wherein
6). The vapor deposition film further has a gas barrier coating film provided on the inorganic 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 represents M A gas barrier property obtained by polycondensation by a sol-gel method, containing at least one alkoxide represented by the formula (1) and a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. 6. The packaging bag according to 5 above, which is a film made of a composition.
7). The packaging bag according to any one of the above 1 to 6, wherein the first adhesive resin layer and the second adhesive resin layer each have a thickness of 2 to 6 µm.
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 said any one of 1-7 characterized by the above-mentioned. Packaging bag.
9. 9. The packaging bag according to any one of 1 to 8 above, which is a packaging bag for sealing a display element that prevents deterioration of the display element due to moisture.
10. An encapsulated display device comprising a display element and the packaging bag according to any one of 1 to 9 which encloses the display element.

  According to the present invention, two transparent gas barrier films are bonded not only from the surface, but also by using a fluorine-based resin having a high barrier property against oxygen and water vapor and having excellent heat resistance and adhesiveness. In addition, it is possible to prevent gas and water vapor from entering from the end face and to obtain a gas barrier laminate having transparency. Hereinafter, in the present invention, the ability to prevent the entry of oxygen and water vapor from the surface is called surface gas barrier property, and the ability to prevent the entry of oxygen and water vapor from the end face is called end face gas barrier property.

  In the present invention, the adhesive resin layer made of a fluorine-based resin not only prevents the penetration of oxygen and water vapor into the layer, but also allows oxygen and water vapor to enter the interface between the layer and the transparent gas barrier film. Can be prevented. 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 significantly prevented.

  Moreover, when a vapor deposition film having a base material layer and an inorganic oxide vapor deposition layer deposited on the base material layer is used as the transparent gas barrier film, the base material layer, the vapor deposition layer, and the vapor deposition layer are bonded. An interface suitable for the purpose of the present invention is formed between the conductive resin layer.

Furthermore, the inorganic oxide vapor deposition layer, the general formula _{^{R 1 n M (OR 2)}} m ( where in the formula, R ^1, R ² represents an organic group having 1 to 8 carbon atoms, M 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 ethylene. By providing a gas barrier coating film comprising a vinyl alcohol copolymer and further comprising a gas barrier composition obtained by polycondensation by a sol-gel method, end face gas barrier properties and surface gas barrier properties can be further improved. .

  Moreover, in this invention, an olefin type hot-melt resin composition is used as a resin composition which forms a heat-fusion layer. The olefin-based hot melt resin composition has a good barrier property against oxygen and water vapor, and can achieve a strong sealing strength with a thin layer thickness. Suppressed well.

It is a schematic sectional drawing which shows an example about the layer structure of the laminated body which forms the packaging bag concerning this invention. It is a schematic sectional drawing which shows another example about the layer structure of the laminated body which forms the packaging bag concerning this invention. It is a schematic sectional drawing which shows another example about the layer structure of the laminated body which forms the packaging bag concerning this invention. It is a schematic sectional drawing which shows an example about the layer structure of the enclosure display device concerning this invention.

The above-described present invention will be described in more detail below.
<1> Layer structure of laminate forming the packaging bag of the present invention As the laminate forming the packaging bag according to the present invention, for example, as shown in Fig. 1, first and second transparent gas barrier films ( A laminate having the basic structure of 1a, 1b), the first and second adhesive resin layers (2a, 2b), and the heat fusion layer (3) can be given.

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

  Furthermore, as an example of the laminated body which forms the packaging bag concerning this invention, as shown in FIG. 3, a 1st and 2nd transparent gas barrier film is a base material layer (4), an inorganic oxide vapor deposition layer ( 5) and a laminate that is a vapor-deposited film composed of a gas barrier coating film (6).

<2> Adhesive Resin Layer The adhesive resin layer constituting the laminate forming the packaging bag according to the present invention includes a fluorine-containing copolymer having a crosslinkable group and a curing agent that reacts with the crosslinkable group. It consists of the formed fluororesin. The adhesive resin layer 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.

Fluorine-containing copolymer The fluorine-containing copolymer used in the present invention is a polymer soluble in a general-purpose organic solvent, and can be copolymerized with the fluoroolefin monomer (A) and the fluoroolefin monomer. The crosslinkable group-containing monomer (B) is used as a monomer component.

Examples of the fluoroolefin monomer (A) include tetrafluoroethylene, trifluoroethylene, hexafluoropropylene and the like. Since high adhesive strength can be obtained, trifluoroethylene represented by Formula 1: CF ₂ = CFX (where X is a fluorine atom, a chlorine atom, a hydrogen atom or a trifluoromethyl group) is preferable. More preferably, it is chlorotrifluoroethylene in which X in the formula is a chlorine atom.

As the crosslinkable group-containing monomer (B) copolymerizable with the fluoroolefin monomer, a monomer having a hydroxyl group, an epoxy group, a carboxyl group, an amide group, an amino group or a hydrolyzable silyl group as the crosslinkable group. The body is mentioned. Specifically, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether , Hydroxyl group-containing monomers such as 2-hydroxyethyl allyl ether and 4-hydroxybutyl allyl ether, epoxy group-containing monomers such as glycidyl vinyl ether and glycidyl (meth) acrylate, carboxyl groups such as acrylic acid and methacrylic acid Monomers, amide group-containing monomers such as (meth) acrylamide and N-methylolacrylamide, and amino groups such as aminoalkyl vinyl ether and aminoalkyl allyl ether Hydrolyzable silyl group-containing monomers such as monomers, trimethoxyvinylsilane, triethoxyvinylsilane, γ-methacryloxypropyltrimethoxysilane, etc. can be mentioned, but they can be easily processed by the gravure coating method and can be cured appropriately. Since the speed is obtained, a hydroxyl group-containing monomer, in particular, formula 2: CH ₂ = CHR ¹ [wherein R ¹ is —OR ² to —CH ₂ OR ² (where R ² is an alkyl group having a hydroxyl group) It is particularly preferable to use a hydroxyl group-containing monomer represented by

In addition to the fluoroolefin monomer and the crosslinkable group-containing monomer, the fluorine-containing copolymer used in the present invention further improves coating properties and coating properties (hardness, flexibility, etc.) as necessary. Therefore, a monomer copolymerizable with the above two types of monomers can be copolymerized and contained. As such a monomer, β-methyl-substituted α-olefin monomer represented by the formula 3: CH ₂ = CR (CH ₃ ) [wherein R is an alkyl group having 1 to 8 carbon atoms] Compound (C), Formula 4: CHR ³ = CHOR ³ (CH ₃ ), wherein R ³ is an alkyl group having 1 to 8 carbon atoms, Formula 5: A vinyl ether monomer (E) represented by CH ₂ ═CHR ³ , wherein R ³ is —OR ⁴ to —CH ₂ OR ⁴ (where R ⁴ is an alkyl group having a carboxyl group), and And other monomer (F) which does not have a crosslinkable functional group and can be copolymerized with the monomers of the above formulas 1 to 5.

In the present invention, a copolymer containing all of the monomers (A) to (F) is particularly preferable because the coating property is stabilized.
The fluorine-containing copolymer used in the present invention contains a fluoroolefin monomer (A) and a crosslinkable group-containing monomer (B) copolymerizable with the fluoroolefin monomer as essential components. Accordingly, at least one monomer selected from the monomers (C), (D), (E), and (F) is added, and a known method such as emulsion polymerization, solution polymerization, or suspension polymerization is performed. It can be obtained by copolymerization.

  The number average molecular weight of the fluorine-containing copolymer of the present invention is 1,000 to 500,000, preferably 3000 to 100,000 as a value in terms of polystyrene measured by gel permeation chromatography (GPC). When the number average molecular weight is less than 1000, the barrier property against water vapor and oxygen may be lowered. Moreover, when larger than 500,000, it may be inferior to coating property.

  The composition ratio between the fluoroolefin monomer (A) in the fluorine-containing copolymer of the present invention and the crosslinkable group-containing monomer (B) copolymerizable with the fluoroolefin monomer is in terms of mole. , (A) :( B) is preferably 1: 1 to 10: 1, particularly preferably 2: 1 to 5: 1. If the ratio of the monomer (A) is too low, the barrier property against water vapor and oxygen may be lowered, and if it is too high, the coatability may be inferior.

  The total amount of the monomers (C), (D), (E), and (F) is not particularly limited as long as the effects of the present invention are not impaired. It is preferable that it is 5-30 mol% with respect to quantity, and it is further more preferable that it is 10-25 mol%. The composition ratio between the monomers (C), (D), (E) and (F) can be appropriately set according to the application.

  A compounding agent known to those skilled in the art may be added to the fluorine-containing copolymer used in the present invention, if necessary.

Curing Agent As the curing agent used in the present invention, a compound that reacts with the above-described crosslinkable group to form a crosslink can be used. The curing agent for the hydroxyl group-containing monomer is a compound having an isocyanate group or a carboxyl group, and an organic polyisocyanate compound having an isocyanate group is preferable because a suitable curing reaction rate can be obtained.

  Examples of the organic polyisocyanate compound include 2,4-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine methyl ester diisocyanate, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate. , N-pentane-1,4-diisocyanate, and trimers thereof, adducts and burettes thereof, or polymers having two or more isocyanate groups, and further blocked. Examples include isocyanates. Preferably, it is a trimer of isophorone diisocyanate or hexamethylene diisocyanate. This is because the compatibility with the fluorine-containing copolymer is good, the curing rate is appropriate, and the laminate strength is high. Moreover, the compound which has a hydroxyl group, a carboxyl group, an amide group, an amino group, or an isocyanate group can be used for the hardening | curing agent with respect to an epoxy group containing monomer.

  Moreover, the compound which has a hydroxyl group, an amino group, an isocyanate group, or an epoxy group can be used for the hardening | curing agent with respect to a carboxyl group-containing monomer. Moreover, the compound which has an epoxy group can be used for the hardening | curing agent with respect to an amide group containing monomer. Moreover, the compound which has a carboxyl group, an epoxy group, or an isocyanate group can be used for the hardening | curing agent with respect to an amino group containing monomer. Moreover, the compound which has an amino group or an isocyanate group can be used for the hardening | curing agent with respect to a hydrolysable silyl group containing monomer.

  Examples of the compound having a hydroxyl group include 1,4-bis-2'-hydroxyethoxybenzene and bishydroxyethyl terephthalate. Examples of the compound having a carboxyl group include aliphatic dibasic acids such as fumaric acid, succinic acid, adipic acid, and azelaic acid, and acid anhydrides such as phthalic anhydride. Examples of the compound having an epoxy group include terephthalic acid diglycidyl ester and p-hydroxybenzoic acid diglycidyl ester.

Silane Coupling Agent In the present invention, the adhesive resin layer may contain a silane coupling agent in addition to the fluororesin, in order to further increase the adhesive strength and the barrier property against oxygen and water vapor.
As the silane coupling agent, a known organic reactive group-containing organoalkoxysilane can be used.

  In the present invention, an organoalkoxysilane having an epoxy group is particularly suitable. For example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane or the like can be used. These silane coupling agents may be used alone or in combination of two or more.

  As a compounding quantity of a silane coupling agent, it can set suitably in the range by which the effect of this invention is not impaired, For example, it is preferable in it being 0.05-10 mass% with respect to a fluorine resin, More preferably, it is 0.1-5 mass%. If the amount is less than 0.05% by mass, a sufficient effect cannot be obtained. If the amount is more than 10% by mass, the reaction rate may be slow, which may not be preferable.

Method for Preparing Adhesive Resin Layer A method for preparing the adhesive resin layer used in the present invention will be described using a fluorine-containing copolymer containing a hydroxyl group as an example. The fluorine-containing copolymer containing a hydroxyl group and the curing agent are dissolved in a solvent in which one or two or more of acetates, ketones, ethers, aromatic hydrocarbons and the like are mixed. Here, the curing agent is a group that reacts with the crosslinkable group in the curing agent, such as an isocyanate group or a carboxyl group, with respect to 1 equivalent of the crosslinkable group in the fluorine-containing copolymer, such as a hydroxyl group (—OH group). Is added in an amount of 0.1 to 5.0 equivalents, preferably 0.5 to 1.5 equivalents. Coating and drying the solution containing the fluorine-containing copolymer and the curing agent on the first transparent gas barrier film using a known coating method such as roll coating, gravure coating, or bar coating. Thus, the first adhesive resin layer is formed, and similarly, the second adhesive resin layer is formed by applying and drying on the second gas barrier film.

  The thicknesses of the first adhesive resin layer and the second adhesive resin layer are 2 to 6 μm, more preferably 3 to 5 μm, respectively. 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.

<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 sealing display elements. 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 60 ° C. and 90% RH in accordance with 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-deposited film As the transparent gas barrier film used in the present invention, for example, a vapor-deposited film having a substrate layer and an inorganic oxide vapor-deposited layer deposited on the substrate layer is particularly preferably used.
The deposited film not only exhibits excellent surface gas barrier properties and transparency, but also has high adhesion between the base material layer and the inorganic oxide deposited layer, and oxygen and water vapor are less likely to enter the interface between the layers. Therefore, it shows a good end face gas barrier property.

As the base layer of the base layer deposited film, it has excellent chemical or physical strength, can withstand the conditions for forming the inorganic oxide deposited layer, etc., and keeps it well without impairing the properties of the inorganic oxide deposited layer. Plastic films that can be obtained 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 this invention is 12-400 micrometers, More preferably, it is 50-200 micrometers.

  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 carried out as a method for improving the adhesion between the plastic film and the inorganic oxide vapor deposition layer. As a method for improving the adhesion, for example, the surface of the plastic film is used. In addition, a primer coating agent layer, an undercoat layer, a vapor deposition anchor coating agent layer, or the like can be arbitrarily formed in advance.

Inorganic Oxide Deposition Layer An inorganic oxide deposition layer suitable for the present invention is described below from the viewpoints of tight adhesion to the substrate layer and the adhesive resin layer, transparency, and surface and end face gas barrier properties. A vapor deposition layer made of an inorganic oxide can be applied.
The material for forming the inorganic oxide 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 In addition, oxides such as titanium oxide, boron oxide, hafnium oxide, and barium oxide are preferable, and aluminum oxide, silicon oxide, silicon oxynitride, and silicon oxide carbide are particularly preferable in terms of gas barrier properties and production efficiency. .

As a method for forming the inorganic oxide vapor deposition layer, vacuum deposition, reactive vapor deposition, ion beam assisted vapor deposition, sputtering, ion plating, plasma CVD, thermal CVD, and other vacuum film formation methods can be used. Can be mentioned.
Moreover, the inorganic oxide vapor deposition layer may consist of a single layer formed by a single vapor deposition step, or may have a multilayer structure formed by repeating the vapor deposition step 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 inorganic 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, by further providing a gas barrier coating film as described below on the inorganic oxide vapor deposition layer, not only a more excellent surface gas barrier property can be obtained, but also the above-mentioned adhesiveness. The tight adhesion with the resin layer is enhanced, and a 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 And n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents an atomic valence of M).

  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 formed gas barrier coating film is increased, and its weather resistance and the like are also deteriorated.

  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 = 1000), Kuraray Poval LM-20SO manufactured by the same company (degree of saponification = 40%, degree of polymerization = 2000), GOHSENOL NM-14 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (degree of saponification = 99%, polymerization) Degree = 1400) and Gohsenol NH-18 (degree of saponification = 98-99%, 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 inorganic oxide vapor-deposited layer, at 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. It 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 an organic solvent, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, etc. can be used, for example.

  Further, regarding the gas barrier composition, the polyvinyl alcohol 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 inorganic 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. Is done.

  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 inorganic oxide deposition layer, close adhesion between the inorganic oxide deposition layer and the gas barrier coating film, etc. Will be good.

  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 inorganic 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. In addition, a better surface gas barrier property can be exhibited by a synergistic effect.

  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 inorganic 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 as described above and preferably forming the gas barrier coating film to be the outermost layer.

<4> Heat-fusion layer The heat-fusion layer constituting the laminate forming the packaging bag of the present invention is a layer made of an olefinic 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.

  In the present invention, the heat-sealing layer made of the olefin-based hot melt resin composition is laminated on the second transparent gas barrier film via the second adhesive resin layer. By laminating the heat-sealable layer via the above-mentioned adhesive resin layer made of fluororesin, the heat-seal layer is maintained while maintaining a high end face gas barrier property even though the total thickness of the laminate is increased. The adhesion strength between the layer and the second gas barrier film can be increased.

  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.

  For the purpose of the present invention, an α-olefin copolymer is preferably used as the olefin resin. The α-olefin copolymer is a copolymer composed of two or more monomers of α-olefins, and can be a copolymer containing other copolymerizable monomers as necessary. . Those skilled in the art can arbitrarily set characteristics such as copolymerization ratio, viscosity, intramolecular branching, and molecular weight distribution.

  The α-olefin includes 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 composed of 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 as a mixture 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. can be used.

  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 heat fusion 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.

<5> Bonding In the present invention, on the first transparent gas barrier film, a solution containing a fluorine-containing copolymer and a curing agent is applied and dried to form a first adhesive resin layer, A second transparent gas barrier film is laminated on the adhesive resin layer, and again a solution containing a fluorine-containing copolymer and a curing agent is applied thereon and dried to form a second adhesive resin layer. In addition, a heat-bonding layer is further laminated thereon to obtain a laminate that forms the packaging bag of the present invention.

Here, when the first transparent gas barrier film is the above-described vapor deposition film, the gas barrier coating film is provided so that the inorganic oxide vapor deposition layer is in contact with the first adhesive resin layer. The gas barrier coating film is preferably bonded so as to be in contact with the first adhesive resin layer, and the base material layer is the surface layer of the laminate, which is preferable from the viewpoint of the handleability of the laminate.
The adhesive resin layer of the present invention firmly adheres to the inorganic oxide vapor deposition layer or the gas barrier coating film, and prevents the entry of oxygen and water vapor into 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 the film is bonded via an adhesive resin, even if the thickness of the laminate is increased by bonding using the adhesive resin layer made of the fluororesin of the present invention, a high end surface 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.

<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 heat-fusible layers facing each other, Further, for example, side seal type, two-side seal type, three-side seal type, four-side seal type, envelope-attached seal type, joint-attached seal type (pillow seal type), pleated seal type, flat bottom seal type, It can be manufactured as a packaging bag of various forms by heat-sealing by a heat-seal form such as a square-bottom 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 a packaging bag for sealing, such as a display element in 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 enclosed 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).
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, which is mounted on a winding roll of a wind-up vacuum deposition apparatus, and then conveyed at a line speed of 600 mm / min. Using a sputtering apparatus, argon gas 500 sccm is introduced, plasma treatment is performed at an output of 20 kW, a plasma treatment surface with an inert gas is formed on one surface of the base film, and then the plasma treatment surface is formed on the plasma treatment surface. A vapor deposition layer made of aluminum oxide having a thickness of 10 nm was formed under the following vapor deposition conditions by vacuum deposition using an electron beam (EB) heating method while supplying oxygen gas using aluminum as a vapor deposition source.

(Deposition conditions)
Degree of vacuum in the deposition chamber: 2 × 10 ⁻⁴ mbar
Degree of vacuum in the take-up chamber: 2 × 10 ^-2 mbar
Electron beam power: 25kw
Film transport speed: 600 m / min
Thereafter, using another magnetron sputtering apparatus, oxygen gas 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 aluminum oxide vapor 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 hydrolyzed solution 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. Heat treatment was performed to form a first gas barrier coating film having a thickness of 0.4 g / m ² (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 aluminum oxide vapor 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 was introduced, plasma treatment was performed at an output of 3 kW, and the plasma treatment surface by oxygen gas was applied to the surface of the aluminum oxide vapor deposition layer. 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 a solution having the following composition is applied to the gas barrier coating film surface with a gravure roll coat A first adhesive resin layer (layer thickness: 4 μm) was formed by applying and drying using a method.

(composition)
・ 100 parts by mass of fluoroolefin-hydroxyl group-containing vinyl ether copolymer (solid content 60%, manufactured by Daikin Industries, Ltd., Zeffle GK550)
-Hexamethylene diisocyanate trimer 60 parts by mass (solid content 70%) (amount equivalent to 1.1 equivalent to 1 equivalent of hydroxyl group of fluoroolefin-hydroxyl group-containing vinyl ether copolymer)
・ 160 parts by mass of ethyl acetate ・ 0.5 parts by mass of silane coupling agent (glycidoxypropyltrimethoxysilane)

(6) Next, the gas barrier coating film surface of the second transparent gas barrier film produced in the above (4) is opposed to the first adhesive resin layer, dry laminated, and cured at 80 ° C. for 72 hours. Promoted.

(7) Next, on one surface of the laminate obtained in (6) above, a second adhesive resin layer (layer thickness: 4 μm) is formed in the same manner as in (5) above using a gravure roll coating method. Formed.

(8) Next, on the second adhesive resin layer obtained in the above (7), a film (thickness 20 μm, manufactured by Toa Gosei Co., Ltd., Aron Melt HMP) made of an olefin-based hot melt resin composition is dry laminated. Then, a heat-sealing layer was formed, and the curing reaction was promoted at 80 ° C. for 72 hours to produce a laminate (total thickness 52 μm) according to the present invention.

(9) Next, the heat-sealing layers of the laminate obtained in the above (8) 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 according to the present invention was produced 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 deposited layer of silicon oxide having a thickness of 10 nm was formed on the corona-treated surface of the film.

(Deposition conditions)
Reaction gas mixing ratio: Hexamethyldisiloxane: Oxygen gas: Helium = 1.2: 5.0: 2.5 (unit: slm)
Ultimate pressure: 5.0 × 10 ^-5 mbar
Film ^- forming pressure: 7.0 × 10 ⁻² mbar
Line speed: 300m / min
Power: 35kW

(2) Next, the biaxially stretched polyethylene terephthalate film on which a 10 nm-thick silicon oxide vapor deposition layer was formed as described above was used, and this was mounted on a take-up roll of a wind-up type vacuum vapor deposition apparatus. 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 is introduced at 500 sccm, 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. An aluminum oxide vapor deposition film having a thickness of 10 nm was formed according to the vapor deposition conditions of

(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. A plasma-treated surface was formed in which the surface tension of the deposited surface of the aluminum oxide was improved by 54 dyne / cm or more.

(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, it heat-processed for 30 second at 100 degreeC, the gas barrier coating film of thickness 0.4g / m < ² > (dry operation state) was formed, and the 1st and 2nd transparent gas barrier film was manufactured.

(4) The first transparent gas barrier film produced in the above (3) is mounted on the first delivery roll of the dry laminating machine, and the gas barrier coating film surface is applied in the same manner as in Example 1 (5). A first adhesive resin layer (layer thickness: 4 μm) was formed.

(5) Next, the gas barrier coating film surface of the second transparent gas barrier film produced in the above (3) is dry laminated so as to face the first adhesive resin layer, and a curing reaction is carried out at 80 ° C. for 72 hours. Promoted.

(6) Next, a second adhesive resin layer (layer thickness: 4 μm) is formed on one surface of the laminate obtained in (5) in the same manner as in (4) above using a gravure roll coating method. Formed.

(7) Next, on the second adhesive resin layer obtained in (6) above, a film (thickness 30 μm, manufactured by Kurashiki Boseki Co., Ltd., Cranbetter M4) made of an olefin-based hot melt resin composition was dry laminated. Thus, a heat-sealing layer was formed, and the curing reaction was promoted at 80 ° C. for 72 hours to produce a laminate (total thickness 62 μm) according to the present invention.

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

[Example 3]
(1) In the same manner as in (1) and (2) of Example 2, on a biaxially stretched polyethylene terephthalate film (thickness 12 μm), a silicon oxide deposition layer (thickness 10 nm) and an aluminum oxide deposition layer ( (Thickness 10 nm) were provided in order, and a plasma-treated surface was formed on the surface of the aluminum oxide vapor-deposited layer to obtain first and second transparent gas barrier films.

(2) Next, the first transparent gas barrier film produced in the above (1) is mounted on the first delivery roll of the dry laminating machine, and the plasma treatment surface thereof is the same as in Example 1 (5). A first adhesive resin layer (layer thickness: 4 μm) was formed.

(3) Next, the plasma treatment surface of the second transparent gas barrier film produced in the above (1) was dry laminated so as to face the adhesive resin layer, and the curing reaction was promoted at 80 ° C. for 72 hours.

(4) Next, a second adhesive resin layer (layer thickness: 4 μm) is applied to one surface of the laminate obtained in (3) above using the gravure roll coating method in the same manner as in (2) above. Formed.

(5) Next, on the second adhesive resin layer obtained in the above (4), a film (thickness 50 μm, manufactured by Toa Gosei Co., Ltd., Aron Melt HMP) made of an olefin-based hot melt resin composition is dry laminated. Then, a heat-sealing layer was formed, and the curing reaction was promoted at 80 ° C. for 72 hours to produce a laminate (total thickness 82 μm) according to the present invention.

(6) Next, the heat-sealing layers of the laminate obtained in the above (5) 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 according to the present invention was produced as a seal bag.

[Example 4]
(1) The first transparent gas barrier film produced in the same manner as in Example 1 (1) to (4) is mounted on the first delivery roll of a dry laminating machine, and the gas barrier coating film surface is provided with the following The solution having the composition was applied using a gravure roll coating method and dried to form a first adhesive resin layer (layer thickness: 4 μm).

(composition)
・ 100 parts by mass of fluoroolefin-amide group-containing (meth) acrylamide copolymer (solid content 70%, manufactured by Asahi Glass, Lumiflon)
-Epoxy curing agent 60 parts by mass (solid content 75%, manufactured by Mitsubishi Chemical, JER, 1.1 equivalent to 1 equivalent of amide group (-NH ₂ group))
-200 parts by mass of ethyl acetate-0.5 parts by mass of silane coupling agent (glycidoxypropyltrimethoxysilane)

(2) Next, the gas barrier coating film surface of the second transparent gas barrier film produced in the same manner as in Examples 1 (1) to (4) was dry laminated so as to face the first adhesive resin layer. The curing reaction was accelerated at 80 ° C. for 72 hours.

(3) Next, a second adhesive resin layer (layer thickness: 4 μm) is formed on one surface of the laminate obtained in (2) above using the gravure roll coating method in the same manner as in (1) above. Formed.

(4) Next, on the obtained second adhesive resin layer, a film made of an olefinic hot melt resin composition (thickness 30 μm, manufactured by Kurashiki Boseki Co., Ltd., Clanbetter M4) is dry-laminated to form a heat-sealing layer. And the curing reaction was promoted at 80 ° C. for 72 hours to produce a laminate (total thickness 62 μm) according to the present invention.

(5) Next, the heat fusion layers of the laminate obtained in the above (4) 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 according to the present invention was produced as a seal bag.

[Comparative Example 1]
Except for forming an adhesive resin layer (4 μm) using a two-component curable polyurethane adhesive (manufactured by Mitsui Chemicals, main ingredient Takelac A-515 / curing agent Takenate A-50), the same procedure as in Example 1 was performed. A packaging bag was produced.

[Comparative Example 2]
Except that the adhesive resin layer (4 μm) was formed by using a two-component curable polyurethane adhesive (manufactured by Mitsui Chemicals, main ingredient Takelac A-515 / curing agent Takenate A-50), the same procedure as in Example 2 was performed. A packaging bag was produced.

[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 are measured using a color luminance meter BM-5AS manufactured by Topcon Technohouse Co., Ltd. in an environment of 60 ° C. and 90% RH. 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 manufactured above is left still in an environment of 60 ° C. and 90% RH, and the weight increase of calcium chloride after 24 hours is measured.

(3) On the other hand, according to ASTM F1249-90, using AQUATRAN manufactured by MOCON in an environment of 60 ° C. and 90% RH, the following is per 24 hours per stack of 0.01 m ² as follows: The amount of water vapor transmission in the surface direction 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 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 devices using the packaging bags of Examples 1 to 4 had a contrast ratio of 30 or more even after 200 hours, and almost no deterioration was observed. On the other hand, in the sealed display device using the packaging bags of Comparative Examples 1 and 2, the contrast ratio significantly decreased after 200 hours.
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 adhesive resin layer made of a fluorine-based resin prevents the permeation of water vapor from the end surface, the water vapor permeability from the end surface is suppressed to an extremely low value.

1a, 1b. Transparent gas barrier films 2a, 2b. 2. Adhesive resin layer 3. Thermal fusion layer Base material layer 5. 5. Inorganic oxide vapor deposition layer Gas barrier coating films 7a, 7b. Substrates 8a, 8b. Electrode 9. Light emitters 10a, 10b. Laminated body

Claims (8)

A first transparent gas barrier film, a first adhesive resin layer laminated on the first transparent gas barrier film, a second transparent gas barrier film laminated on the adhesive resin layer, A laminate having a second adhesive resin layer laminated on the second transparent gas barrier film and a heat fusion layer laminated on the second adhesive resin layer is formed by the heat fusion. A packaging bag obtained by making a bag so that the layer becomes the innermost layer,
The first and second adhesive resin layers are layers composed of a fluorine-containing resin formed by a fluorine-containing copolymer having a crosslinkable group and a curing agent that reacts with the crosslinkable group ;
The heat-sealing layer is a layer made of an olefinic hot-melt resin composition ;
The first and second transparent gas barrier films are vapor deposition films having a base material layer and an inorganic oxide vapor deposition layer deposited on the base material layer, or on the inorganic oxide vapor deposition layer. Furthermore, it is a film having a gas barrier coating film,
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 represents a valence of M), a polyvinyl alcohol-based resin and / or ethylene. A packaging bag comprising a film made of a gas barrier composition containing a vinyl alcohol copolymer and further obtained by polycondensation by a sol-gel method .   The packaging bag according to claim 1, wherein the fluorine-containing copolymer contains at least a fluoroolefin monomer and a hydroxyl group-containing monomer as monomer components.   The packaging bag according to claim 1, wherein the curing agent is an organic polyisocyanate compound.   4. The method according to claim 1, wherein at least one of the first adhesive resin layer and the second adhesive resin layer further contains a silane coupling agent. 5. Packaging bags. 5. The packaging bag according to claim 1, wherein each of the first adhesive resin layer and the second adhesive resin layer has a thickness of 2 to 6 μm. 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 any one of Claims 1-5 characterized by the above-mentioned. Packaging bag as described in. The packaging bag according to any one of claims 1 to 6 , which is a packaging bag for sealing a display element that prevents deterioration of the display element due to moisture. An encapsulated display device comprising: a display element; and the packaging bag according to any one of claims 1 to 7 , which encloses the display element.

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