JP2013180421A - Laminate and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate in which two protection layers in films including gas-barrier protection layers are laminated, each other, and are firmly bonded without using an adhesive, that does not cause seepage of foreign matters or residual solvent and has excellent gas barrier property.SOLUTION: A laminate 1 is comprised by laminating two gas-barrier protection layers in barrier films 10, 20 that include: thermoplastic resin films 11, 21; thin film layers 12, 22 comprising aluminum oxide or silicon oxide provided on one side surface of the thermoplastic resin film; and the gas-barrier protection layers 13, 23 provided on the thin film layer. The protection layer is comprised of a coating obtained by applying fluorocarbon resin. At least in part of the interface of the opposing protection layers, a bond is formed between an atom in the protection layer and an atom in the other protection layer. The gas-barrier protection layers of both of the barrier films are bonded, each other, without an adhesive.

Description

  The present invention relates to a laminate, and more specifically, two barrier films provided with a thin film layer and a gas barrier protective layer are laminated on a thermoplastic resin film so that the gas barrier protective layers face each other. The present invention relates to a laminate and a manufacturing method thereof.

  A package in which a film or the like is processed into a bag shape is used. In such a package, a multifunctional film in which various materials are laminated is used as a film to be used in order to develop a desired function depending on the contents to be filled. For example, in order to prevent deterioration of the contents due to ultraviolet rays, etc., a film having an ultraviolet absorption function is used, or in order to prevent the contents from being altered by oxygen, a gas-impermeable film or oxygen absorption is used. A film having a function is used.

  In particular, in the packaging field, a gas barrier film is used as a packaging material for foods and drinks, pharmaceuticals, electronic members, and the like in the preservation of contents, maintenance of packaging form, quality assurance, and the like. In the display field, gas barrier laminates that prevent permeation of oxygen and water vapor are used in order to suppress deterioration of display elements that are highly sensitive to oxygen and water vapor. 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. Proposed are films laminated only by vapor deposition or coextrusion (Japanese Patent Laid-Open No. 2003-340956 and Japanese Patent Laid-Open No. 2007-130857), and films laminated by lamination using an adhesive (Japanese Patent Laid-Open No. 2005-161691). Has been.

  Gas barrier films used as packaging materials for electronic members and sealing members for display elements are required to have extremely high gas barrier properties. Therefore, a laminate in which two or more of the above gas barrier films are stacked is used. Things have been done.

  However, when the gas barrier films as described above are bonded and laminated through a laminate resin, the laminate resin component gradually elutes or volatilizes in the package and changes the contents when the package is used. In some cases, especially in the medical field where safety and cleanliness are important, contamination of the contents by the laminate resin may be a problem. Moreover, although the laminated body which laminated | stacked the gas barrier film can prevent suitably permeation | transmission of oxygen and water vapor | steam from the surface, it is from the end surface of a laminated body, ie, the adhesive bond layer which adhere | attached films. Permeation of oxygen and water vapor cannot be prevented.

  By the way, surface modification of a material using radiation or an electron beam has been conventionally performed. For example, Japanese Patent Application Laid-Open No. 2003-119293 (Patent Document 3) proposes that a crosslinked composite fluororesin can be obtained by irradiating the fluororesin with radiation. In Journal of Photopolymer Science and Technology Vol.19, No. 1 (2006), pp123-127 (Non-patent Document 1), a polytetrafluoroethylene film and a polyimide film are laminated and an electron beam ( In the following, it has been proposed to bond each other by irradiating EB. In Material Transactions Vol.50, No.7 (2009), pp1859-1863 (Non-patent Document 2), the surface of the polycarbonate resin is covered with a nylon film, and an electron beam (hereinafter abbreviated as EB) may be applied from above. A technique for adhering a nylon film to a polycarbonate resin surface has been proposed. Furthermore, the Journal of the Japan Institute of Metals, Vol. 72, No. 7 (2008), pp 526-531 (Non-patent Document 3) can be bonded to each other by irradiating EB from a nylon film placed on silicone rubber. Is described.

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

Journal of Photopolymer Science and Technology Vol.19, No. 1 (2006), pp123-127 Material Transactions Vol.50, No. 7 (2009), pp1859-1863 Journal of the Japan Institute of Metals, Vol. 72, No. 7 (2008), pp 526-531

  In the case where the present inventors have laminated a two-layer barrier film provided with a thin film layer and a gas barrier protective layer on a thermoplastic resin film so that the gas barrier protective layers correspond to each other, It was found that by irradiating the barrier film with an electron beam, the films can be firmly bonded to each other without using a laminate resin or the like. And even if it is a laminate that has been bonded to each other with an adhesive, such as a laminate in which a barrier film including a gas barrier protective layer is laminated, an adhesive is used according to electron beam irradiation. Even if it did not, the bond was formed between the atom by the side of one barrier film, and the atom by the side of the other barrier film, and the knowledge that it mutually adhere | attached was acquired. The present invention is based on this finding.

  Accordingly, an object of the present invention is a laminate in which two barrier films including a gas barrier protective layer are laminated so that the gas barrier protective layers face each other, and the barrier film is used without using an adhesive. An object of the present invention is to provide a laminate that is firmly bonded to each other, does not exude foreign matter and residual solvent, and has excellent gas barrier properties.

The laminate according to the present invention includes a thermoplastic resin film, a thin film layer made of aluminum oxide or silicon oxide provided on at least one surface of the thermoplastic resin film, and a gas barrier protective layer provided on the thin film layer. A laminated body in which two barrier films are stacked such that the gas barrier protective layers face each other,
The gas barrier protective layer consists of a film obtained by applying a solution containing a fluorine resin,
Bonded between an atom in the gas barrier protective layer of the one barrier film and an atom in the gas barrier protective layer of the other barrier film at at least a part of the interface of the opposing gas barrier protective layer Is formed, and the gas barrier protective layers of both barrier films are bonded to each other without an adhesive.

  Further, as an aspect of the present invention, at least part of the interface of the opposing gas barrier protective layer, the atoms in the gas barrier protective layer of one barrier film and the gas barrier protective layer of the other barrier film It is preferable that a bond is formed between the atom and at least one selected from the group consisting of an oxygen atom, a nitrogen atom and a hydroxyl group.

  Moreover, as an aspect of the present invention, it is preferable that the fluororesin comprises a fluororesin containing a fluorine-containing copolymer having a crosslinkable group and a curing agent that reacts with the crosslinkable group.

  Moreover, as an aspect of the present invention, the thermoplastic resin film is preferably a polyethylene terephthalate film.

Moreover, the manufacturing method as another aspect of the present invention includes a thermoplastic resin film, a thin film layer made of aluminum oxide or silicon oxide provided on at least one surface of the thermoplastic resin film, and provided on the thin film layer. A method of producing a laminate in which a barrier film comprising a gas barrier protective layer is laminated so that the gas barrier protective layers face each other,
Two barrier films comprising a thermoplastic resin film, a thin film layer made of aluminum oxide or silicon oxide provided on at least one surface of the thermoplastic resin film, and a gas barrier protective layer provided on the thin film layer Prepare
Irradiating an electron beam to the gas barrier protective layer surface of the one or both barrier films,
The gas barrier protective layer surface of the one barrier film and the gas barrier protective layer surface of the other barrier film are overlapped to bond the barrier films together.

  Moreover, as an aspect of the present invention, it is preferable to perform electron beam irradiation before and / or after overlapping the barrier films.

  Moreover, as another aspect of the present invention, the bonding is preferably performed by applying pressure, and the bonding is preferably performed by heating.

  According to the present invention, at least part of the interface of the opposing gas barrier protective layer, atoms in the gas barrier protective layer of one barrier film and atoms in the gas barrier protective layer of the other barrier film Since a bond is formed between the two layers, a laminate in which the gas barrier protective layers of the two barrier films are firmly bonded to each other can be obtained even if they are not bonded via an adhesive. As a result, it is possible to realize a laminate that does not exude foreign matter, residual solvent, and the like and has excellent gas barrier properties.

  Since the laminate according to the present invention is obtained by laminating two barrier films without using an adhesive as described above, it is a sealing member that requires extremely high gas barrier properties, particularly an organic electroluminescent display. It can be suitably used as a sealing member for display elements such as luminescence (organic EL) and electronic paper.

It is the schematic sectional drawing which showed one Embodiment of the laminated body of this invention. It is the schematic diagram which showed one Embodiment of the manufacturing method of the laminated body by this invention. It is the schematic schematic diagram which expanded a part of manufacturing process. It is the schematic diagram which showed another embodiment of the manufacturing method of the laminated body by this invention. It is the schematic diagram which showed another embodiment of the manufacturing method of the laminated body by this invention. It is the schematic diagram which showed another embodiment of the manufacturing method of the laminated body by this invention.

  Hereinafter, the laminated body by this invention is demonstrated, referring drawings. As shown in FIG. 1, the laminate 1 according to the present invention has a structure in which a pair of barrier films 10 and 20 are laminated without using an adhesive. The barrier film 10 (20) includes a thermoplastic resin film 11 (21), a thin film layer 12 (22) made of aluminum oxide or silicon oxide provided on at least one surface of the thermoplastic resin film 11 (21), and a thin film It consists of a gas barrier protective layer 13 (23) provided on the layer 12 (22). In the laminate of the present invention, the gas barrier protective layer 13 (23) is opposed to the pair of barrier films 10 and 20. Thus, they are stacked one on top of the other.

The gas barrier protective layer 13 (23) corresponding to the adhesive interface of the laminate according to the present invention is made of a film obtained by applying a solution containing a fluororesin. In the present invention, at least part of the adhesion interface, bonding is performed between atoms in the gas barrier protective layer 13 of one barrier film 10 and atoms in the gas barrier protective layer 23 of the other barrier film 20. Is formed, the barrier films are firmly bonded to each other. Since the fluorine-based resin as the gas barrier protective layer usually has a very small surface tension, and since there are no functional groups involved in hydrogen bonding such as hydroxyl groups on the surface of the fluorine resin or polyolefin resin,
Normally, the two cannot be bonded together without using an adhesive. In the present invention, as will be described later, the surface of either or both of the gas barrier protective layers 13 (23) of both barrier films 10 (20) is irradiated with an electron beam to generate radicals. 2, a bond is formed between atoms in the gas barrier protective layer 13 and atoms of atoms in the gas barrier protective layer 23, or in the gas barrier protective layer 13 of one barrier film 10. And an atom in the gas barrier protective layer 23 of the other barrier film 20 are bonded via an oxygen atom, a nitrogen atom, or a hydroxyl group, without using an adhesive, The barrier film 10 and the barrier film 20 can be firmly bonded. The generation of radicals by electron beam irradiation is confirmed by identifying the free radical species existing in the film after electron beam irradiation using an electron spin resonance apparatus (hereinafter also referred to as ESR). be able to.

  In addition, since the laminate in which the pair of barrier films 10 and 20 are bonded together by electron beam irradiation is bonded between the atoms of the gas barrier protective layers of both barrier films described above, an adhesive is used. Even if it is not used at all, a laminate that does not peel off can be obtained.

  Hereinafter, the barrier film constituting the laminate according to the present invention will be described.

  As shown in FIG. 1, the barrier film 10 (20) is a thin film layer made of aluminum oxide or silicon oxide provided on at least one surface of the thermoplastic resin film 11 (21) or the thermoplastic resin film 11 (21). 12 (22) and a gas barrier protective layer 13 (23) provided on the thin film layer 12 (22). Although the barrier film 10 (20) is not shown, the thin film layer 12 (22) and the gas barrier protective layer 13 (23) are not only on one surface of the thermoplastic resin film 11 (21) but on both surfaces. It may be provided.

  In the barrier film 10 (20) used in the laminate according to the present invention, the thin film layer 12 (22) and the gas barrier protective film 13 (23) are, for example, a chemical bond, a hydrogen bond, a hydrolytic bond, Alternatively, a coordination bond or the like is formed, and the adhesion between the thin film layer 12 (22) and the gas barrier protective layer 13 (23) is improved, and the synergistic effect of the two layers exhibits a better gas barrier effect. It is possible.

  As the thermoplastic resin film, any plastic film that can support a thin film layer made of aluminum oxide or silicon oxide can be used. For example, polyolefin resin such as polyethylene, polypropylene, polybutene, ( (Meth) acrylic resin, polyvinyl chloride resin, polystyrene resin, polyvinylidene chloride resin, saponified ethylene-vinyl acetate copolymer, polyvinyl alcohol, polycarbonate resin, fluorine resin, polyvinyl acetate resin, acetal Polyester resin such as polyethylene resin, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyamide resin such as nylon 6 and nylon 66, etc. You It is possible. Among these, polyethylene terephthalate (PET) is preferable, and transparent one is more preferable.

  The thermoplastic resin film may be uniaxially or biaxially stretched, and the thickness is preferably about 10 to 200 μm, particularly about 10 to 100 μm. If necessary, the surface may be coated with an anchor coating agent or the like to be subjected to a surface smoothing treatment or the like.

The thin film layer is a thin film of aluminum oxide represented by a general formula: AlO _x (wherein x represents a number of 0.5 to 1.5), or a general formula: SiO _x (where, x Represents a number of 0 to 2), and is formed on the surface of a thermoplastic resin film. As the aluminum oxide thin film represented by the above general formula, an aluminum oxide thin film in which the value of x increases in the depth direction from the film surface toward the inner surface can also be used. In the above, as the value of x, basically, x = 0.5 or more can be used. However, when x = less than 1.0, it is easy to be colored, and transparency, microwave oven Since it is inferior in suitability, it is preferable to use x = 1.0 or more. As the upper limit, those up to x = 1.5 in which aluminum and oxygen are completely oxidized can be used.

Moreover, as a thin film of silicon oxide represented by the above general formula, the value of x is preferably 1.3 to 1.9. The silicon oxide thin film may be mainly composed of silicon oxide, and may further contain at least one kind of compound composed of one kind of carbon, hydrogen, silicon, or oxygen, or two or more kinds of elements by a chemical bond or the like. For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, or the like, the raw material organosilicon compound or a derivative thereof is further added. It may be contained by a chemical bond or the like. For example, hydrocarbons having a CH 3 site, hydrosilica such as SiH ₃ silyl, SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol can be used. As content which said compound contains in the vapor deposition film | membrane of a silicon oxide, it is 0.1-50 mass%, Preferably it is 5-20 mass%. Moreover, when a silicon oxide thin film contains the said compound, it is preferable that content of a compound is reducing toward the depth direction from the surface of the vapor deposition film | membrane of a silicon oxide. As a result, the impact resistance and the like are enhanced by the above compound on the surface of the silicon oxide vapor deposition film, and on the other hand, since the content of the above compound is small at the interface with the base film, the vapor deposition of the base film and the silicon oxide is performed. The tight adhesion with the film becomes strong.

  The film thickness of the thin film layer is preferably selected and formed arbitrarily within a range of, for example, about 10 to 3000 mm, particularly about 60 to 1000 mm. The thin film layer may be crystalline or non-crystalline.

  In the present invention, when the total light transmittance of the thermoplastic resin film constituting the barrier film is 100%, aluminum oxide or silicon oxide is deposited so that the total light transmittance after deposition is less than 90%. It is particularly preferable to deposit aluminum oxide or silicon oxide so that the total light transmittance after deposition is 85% or more and less than 90% when the total light transmittance of the base film is 100%. . When the total light transmittance after vapor deposition is 90% or more after vapor deposition, although the transparency is sufficient, the gas barrier property, particularly the gas barrier property against water vapor, may not be sufficiently high. Moreover, when the total light transmittance after vapor deposition is less than 85%, although the gas barrier property is excellent, the final transparency may not reach the total light transmittance of the thermoplastic resin film.

  Next, a method for forming a thin film layer on a thermoplastic resin film will be described. As a method for forming the thin film layer, for example, a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum deposition method, a sputtering method, or an ion plating method, a plasma chemical vapor deposition method, a thermochemistry, or the like. A chemical vapor deposition method (Chemical Vapor Deposition method, CVD method) such as a vapor deposition method or a photochemical vapor deposition method can be given. In addition, when manufacturing the film which consists of a transparent laminated body used for the packaging material, a vacuum vapor deposition method is mainly used and a plasma chemical vapor deposition method is also used partially.

In addition, for example, a composite film composed of two or more vapor-deposited films of different kinds of inorganic oxides can be formed by using both physical vapor deposition and chemical vapor deposition. In the case of forming an aluminum oxide thin film in which the value of x increases in the depth direction from the film surface to the inner surface, the aluminum oxide thin film is disclosed in Japanese Patent Application Laid-Open No. 10-226011 by the present applicant. It can be manufactured by the method. The degree of vacuum deposition chamber, before ^introduction of oxygen 10 ^-2 to 10 -8 mbar approximately, in ^particular, is preferably about 10 ^-3 to 10 -7 mbar, in the post-oxygen ^{introduction,} 10 -1 to 10 ^{- About 6} mbar, especially about 10 ⁻² to 10 ⁻⁵ mbar is preferable. The amount of oxygen introduced varies depending on the size of the vapor deposition machine. For the oxygen to be introduced, an inert gas such as argon gas, helium gas, nitrogen gas or the like may be used as a carrier gas within a range where there is no problem. As a conveyance speed of the thermoplastic resin film used as a base material, about 10-800 m / min, especially about 50-600 m / min are preferable. Moreover, the silicon oxide thin film layer in which the content of the compound as described above decreases from the surface of the deposited silicon oxide film in the depth direction is described in Japanese Patent Application Laid-Open No. 2008-143097 by the applicant. It can be formed by such a method.

  In the present invention, the surface of the thin film layer formed as described above may be subjected to oxygen plasma treatment. The amount of oxygen introduced for the oxygen plasma treatment varies depending on the size of the vapor deposition apparatus and the like, but is usually about 50 sccm to 2000 sccm, and particularly preferably about 300 sccm to 800 sccm. Here, sccm means the average amount of oxygen introduced (cc) per minute in the standard state (STP: 0 ° C., 1 atm). For the oxygen to be introduced, an inert gas such as argon gas, helium gas, nitrogen gas or the like may be used as a carrier gas within a range where there is no problem. As described above, the method for forming a thin film layer made of aluminum oxide or silicon oxide on the thermoplastic resin film and the method for subjecting the surface of the thin film layer made of aluminum oxide or silicon oxide to oxygen plasma treatment as required have been described. It is an example and this invention is not limited to what was obtained by these methods.

  Next, the gas barrier protective layer provided on the thin film layer formed as described above will be described. The gas barrier protective layer is formed by applying a solution containing a fluorine-based resin on the above-described thin film layer.

  The fluororesin includes a fluorine-containing copolymer having crosslinkability and a curing agent that reacts with the crosslinkable group. The fluorine-containing copolymer is a polymer soluble in a general-purpose organic solvent, and includes a fluoroolefin monomer (A) and a crosslinkable group-containing monomer copolymerizable with the fluoroolefin monomer ( And B) as monomer components.

  Examples of the fluoroolefin monomer (A) include tetrafluoroethylene, trifluoroethylene, hexafluoropropylene and the like.

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 is used. A monomer 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 speed is obtained, a hydroxyl group-containing monomer, in particular:
CH ₂ = CHR ¹
It is particularly preferable to use a hydroxyl group-containing monomer represented by the formula (wherein R ¹ represents —OR ² or —CH ₂ OR ² (where R ² represents an alkyl group having a hydroxyl group)).

In addition to the fluoroolefin monomer and the crosslinkable group-containing monomer, the fluorine-containing copolymer that constitutes the gas barrier protective layer may further have coating properties and coating properties (such as hardness and flexibility). In order to improve the above, a monomer copolymerizable with the above two types of monomers can be copolymerized and contained. Such monomers include the following formula:
CH ₂ = CR (CH ₃ )
Β-methyl-substituted α-olefin monomer (C) represented by the formula (wherein R is an alkyl group having 1 to 8 carbon atoms):
CHR ³ = CHOR ³ (CH ₃ )
A vinyl ether monomer (D) represented by the formula (wherein R ³ is an alkyl group having 1 to 8 carbon atoms):
CH ₂ = CHR ³
(Wherein R ³ is —OR ⁴ or —CH ₂ OR ⁴ (where R ⁴ is an alkyl group having a carboxyl group)), and a crosslinkable functional group And other monomers (F) that can be copolymerized with the fluoroolefin monomers (A) to (E) represented by the above formula.

  In the present invention, a copolymer containing all of the above-mentioned fluoroolefin monomers (A) to (F) is particularly preferred because the coating property is stabilized.

  The fluorine-containing copolymer contains a fluoroolefin monomer (A) and a crosslinkable group-containing monomer (B) copolymerizable with the fluoroolefin monomer as essential components. ), (D), (E) and (F) at least one monomer selected from the monomers is added and copolymerized by a known method such as emulsion polymerization, solution polymerization or suspension polymerization. Can be obtained. In addition, you may add the compounding agent known to those skilled in the art to the fluorine-containing copolymer used in this invention as needed.

  The composition ratio between the fluoroolefin monomer (A) in the fluorine-containing copolymer and the crosslinkable group-containing monomer (B) copolymerizable with the fluoroolefin monomer is (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 fluoroolefin monomers (C) to (F) is not particularly limited as long as the effect of the present invention is not impaired. For example, the total amount of the fluoroolefin monomers is , 5 to 30 mol% is preferable, and 10 to 25 mol% is more preferable. The composition ratio between the fluoroolefin monomers (C) to (F) can be appropriately set according to the application.

  The curing agent that reacts with the crosslinkable group of the above-mentioned fluorine-containing copolymer 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 is 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 hydrolyzable 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.

  The gas barrier protective layer may further contain a silane coupling agent in addition to the above-described fluorine-based resin. As the silane coupling agent, a known organic reactive group-containing organoalkoxysilane can be used. In particular, an organoalkoxysilane having an epoxy group is suitable. For example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, 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 which does not impair the effect of this invention.

  Next, a method for forming a gas barrier protective layer on the above-described thin film layer 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, for example, in a solvent in which one 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. By applying and drying a solution in which the fluorine-containing copolymer and the curing agent are dissolved on a thin film layer using a known coating method such as a roll coating method, a gravure coating method, or a bar coating method, the gas barrier property is protected. Form a layer.

  The thickness of the gas barrier protective layer may be in the range of about 0.01 to 100 μm after drying. However, if the thickness is 50 μm or more, cracks are likely to occur in the film, so 0.01 to 50 μm. preferable. The thickness of the gas barrier protective layer can be appropriately adjusted according to the amount of the solution applied.

<Method for producing laminate>
Next, a method for producing the laminate as described above will be described with reference to the drawings. First, two barrier films 10 (20) described above are prepared (FIG. 2 (1)), and one or both of the two films are irradiated with an electron beam (FIG. 2 (2). )). As a result, as shown in FIG. 2 (3), the mutual barrier films are bonded only to the portion irradiated with the electron beam.

  In the present invention, it is preferable to press the superimposed films 10 and 20 using a roller 6 or the like as shown in FIG. 3 immediately after irradiating the barrier film with an electron beam. Since the surfaces of the films 10 and 20 are uneven at the micro level as shown in FIG. 3, even if the films are overlapped, they are not completely adhered to each other, and the contact area at the contact interface between the films is small. In this invention, since the contact area in the adhesive surface of both films increases by pressing the films 10 and 20 with the roller 6 etc. immediately after irradiating an electron beam, adhesiveness improves.

  When the laminated body 1 is pressed after the barrier films 10 and 20 are overlapped, it is preferable to press both the films 10 and 20 while heating. By pressing while heating, the flexibility of the films 10 and 20 is improved, and the contact area at the interface (adhesion surface) of the films 10 and 20 can be further increased, so that the adhesion is further improved. The heating temperature may be any temperature at which the film can be thermally deformed, although it depends on the type of film to be used. For example, the heating can be performed at a temperature higher than the glass transition temperature of the resin constituting the film. For example, when a barrier film having polyethylene terephthalate as a base material is overlaid, the heating temperature is 80 to 180 ° C, preferably 130 to 160 ° C. If the heating temperature is too high, the generated radicals are deactivated, and a strong bond cannot be realized. The pressing force (contact pressure) may be increased, and the heating temperature can be lowered by increasing the contact pressure.

  In order to press the laminated body 1 on which the barrier films 10 and 20 are overlapped, the heat roller 6 or the like can be suitably used as described above. Further, as shown in FIG. 3, the support roller 7 may be placed at a position facing the heat roller 6 so that the superposed film can be pressed between the heat roller 6 and the support roller 7. . In this way, by placing the support roller 7 at a position facing the heat roller 6, the contact between the laminated body (10, 20) and the heat roller 6 is brought close to the line contact, and the heat roller 6 is laminated by heat. Deformation occurring in the body (10, 20) can be minimized.

  FIG. 4 is a schematic view showing another embodiment of the manufacturing method according to the present invention. In the process of laminating and bonding the barrier films 10 and 20, the respective films 10 and 20 are guided to the electron beam irradiation position 3 by the guide roller, and both the films 10 and 20 are irradiated with the electron beam 4 and then the heat roller 6. The process of pressing each other's films 10 and 20 is performed continuously. Each film 10, 20 may be supplied in roll form.

  When irradiating each film with the electron beam 4 from the electron beam irradiation apparatus 3, it is preferable to irradiate the electron beam 4 from the film side with a smaller thickness. Since the electron beam has the property that its transmission power increases as the acceleration voltage increases, depending on the thickness of the film, the electron beam may reach the other film when irradiated with the electron beam from one of the film sides. May not arrive. In that case, the electron beam can reach the deep part of the other film by increasing the acceleration voltage of the electron beam, but unnecessary irradiation is performed on the film itself as the electron beam energy increases. It will deteriorate. Therefore, when a thick film and a thin film are laminated and bonded, it is preferable to irradiate an electron beam from the thin film side without increasing the electron beam energy so much. For example, when the thickness of the barrier film 10 is 25 μm or less and the thickness of the barrier film 20 is 50 μm or more, the electron beam is irradiated from the barrier film 10 side. By adopting such an electron beam irradiation method, deterioration of the film can be minimized.

  In the case where both the barrier films 10 and 20 to be superimposed are thick, as shown in FIG. 4, the barrier films 10 and 20 are separately provided at positions facing the electron beam irradiation device 3 so that the electron beams can be irradiated from both film sides. The electron beam irradiation device 3 ′ may be provided. According to this aspect, since the irradiation energy of an electron beam can be adjusted according to the thickness of a film, both films can be adhere | attached, without deteriorating a film.

  FIG. 5 is a schematic view showing another embodiment of the manufacturing method according to the present invention. In this embodiment, the electron beam irradiation is performed before the barrier films 10 and 20 are overlapped. First, before the supplied pair of barrier films 10 and 20 are superposed, the electron beam irradiation device 3 (3 ′) irradiates the film 10 (20) with the electron beam 4 (4 ′). . In the embodiment shown in FIG. 4, the films 10 and 20 are overlapped so that the surfaces opposite to the electron beam irradiation side of the films 10 and 20 face each other, whereas in the embodiment shown in FIG. 5, The difference is that the films 10 and 20 are overlapped so that the surfaces of the films 10 and 20 on the electron beam irradiation side face each other. Thus, by superimposing the other film 20 on the surface of the film 10 irradiated with the electron beam, the irradiation energy of the electron beam can be made smaller regardless of the thickness of the film. As a result, the film Degradation due to electron beam irradiation can be further reduced.

  Also in the embodiment shown in FIG. 5, a pair of electron beam irradiation devices 3 and 3 ′ are provided, and similarly to the embodiment shown in FIG. 4 'may be irradiated. By these combinations, the deterioration of the film can be further reduced and the adhesive strength can be improved.

  FIG. 6 is a schematic view showing an embodiment of another manufacturing method according to the present invention. In this embodiment, the barrier films 10 and 20 are overlapped and pressed by the heat roller 6 and then irradiated with an electron beam. First, the pair of supplied films 10 and 20 are led to a guide roller and overlapped. Subsequently, both the films 10 and 20 are pressed by the heat roller 6 and the support roller 7, and heating is performed by the heat roller 6. Thereafter, the electron beam irradiation device 3 irradiates the surfaces of the films 10 and 20 with the electron beam 4 so that the films 10 and 20 are continuously bonded. In the embodiment shown in FIG. 6, a pair of electron beam irradiation devices 3 and 3 ′ are provided, and the electron beams 4 and 4 are respectively applied to both films 10 and 20 in the same manner as the embodiment shown in FIGS. 4 'may be irradiated. By these combinations, the deterioration of the film can be further reduced and the adhesive strength can be improved.

  The irradiation energy of the electron beam needs to be appropriately adjusted according to the film thickness and the like as described above. In the present invention, the electron beam is irradiated in an irradiation energy range of about 20 to 750 kV, preferably 25 to 400 kV, and more preferably about 30 to 300 kV. However, the irradiation energy is preferably lower, and 40 to 200 kV. Can do. Thus, by setting it as low irradiation energy, not only deterioration of a film can be suppressed, but since radical generation | occurrence | production of a film surface occurs more efficiently, stronger bond can be implement | achieved. Further, the electron beam irradiation is performed in the range of absorbed dose of 5 to 2000 kGy, preferably 10 to 1000 kGy.

  As such an electron beam irradiation apparatus, conventionally known ones can be used. For example, a curtain type electron irradiation apparatus (LB1023, manufactured by I. Electron Beam Co., Ltd.) or a line irradiation type low energy electron beam irradiation apparatus (EB-ENGINE). , Manufactured by Hamamatsu Photonics Co., Ltd.) can be preferably used.

  When irradiating with an electron beam, the oxygen concentration is preferably 100 ppm or less. This is because irradiation with an electron beam in the presence of oxygen generates ozone, which may adversely affect the apparatus and the environment. In order to reduce the oxygen concentration to 100 ppm or less, the film may be irradiated with an electron beam in a vacuum or in an inert gas atmosphere such as nitrogen or argon. For example, by filling the electron beam irradiation apparatus with nitrogen, A concentration of 100 ppm or less can be achieved.

  The laminate obtained by laminating the barrier films obtained by the above-described adhesion method can realize an adhesive strength equal to or higher than that obtained by using a conventional laminate resin. In addition, since no laminate resin or the like is used, foreign matter or residual solvent does not bleed out even when the laminate is used, and the gas barrier property is excellent.

Example 1
<Preparation of film>
A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used, and a silicon oxide thin film was formed on one surface of the film so as to have a film thickness of 20 nm using a vapor deposition apparatus under the following conditions.
Deposition conditions:
Degree of vacuum in the deposition chamber (after introducing oxygen): 2 × 10 ⁻⁴ mbar
Vacuum degree in the winding chamber: 5 × 10 ⁻³ mbar
Electron beam power: 25kW

Next, a fluororesin solution having the following composition was prepared as a gas barrier protective layer-forming coating solution.
Composition I:
・ Hydroxyl-containing tetrafluoroethylene copolymer (solid content 60%, Zeffle GK550, manufactured by Daikin Industries, Ltd.) 100 mass parts ・ Hexamethylene diisocyanate trimer (solid content 70%) 70 mass parts ・ Ethyl acetate 800 mass parts

  The coating liquid was coated on the silicon oxide thin film by a gravure roll coating method to form a gas barrier protective layer having a thickness of 0.2 μm (in the dry operation state), thereby obtaining a barrier film.

<Production of laminate>
Two samples obtained by cutting the barrier film obtained as described above into a size of 150 mm × 75 mm were prepared, and an electron beam irradiation device (line irradiation type low energy electron beam irradiation device EB-ENGINE, Hamamatsu Photonics Co., Ltd.). On the sample stage). At this time, in order to provide a portion where the sample is not irradiated with the electron beam, masking is performed on one end portion of both samples of about 5 to 10 mm.

Next, after purging with nitrogen gas so that the oxygen concentration in the chamber of the electron irradiation apparatus becomes 100 ppm or less, the surface of the sample (gas barrier protective layer surface) was irradiated with an electron beam under the following electron beam irradiation conditions.
Voltage: 40 kV
Absorbed dose: 200kGy
In-device oxygen concentration: 100 ppm or less

  After irradiating the electron beam, the sample was taken out from the apparatus and immediately laminated so that the electron beam irradiation surface sides of both films were opposed to each other, and both films were bonded by a thermal laminating method to obtain a laminate.

Examples 2 and 3
In Example 1, a laminate was obtained in the same manner as in Example 1 except that the electron beam irradiation conditions were changed as shown in Table 1 below.

Comparative Example 1
A laminate was obtained in the same manner as in Example 1 except that electron irradiation was not performed. However, in the obtained laminate, the barrier films were not adhered to each other.

Comparative Example 2
The barrier films used in Example 1 are bonded to each other with a two-component curable aromatic ester adhesive (Takelac A-3, manufactured by Mitsui Chemicals, Inc.) so that the gas barrier protective layer faces each other. As a result, a laminate was obtained.

<Evaluation of adhesive strength of laminate>
The obtained laminate was cut into a strip shape with a width of 15 mm, and a 90 ° peel test was performed at a rate of 50 mm / min using a tensile tester (Tensilon Universal Material Tester RTC-1310A, manufactured by ORIENTEC). went. As described above, in the laminate of Comparative Example 1, the barrier films were not bonded to each other, and the adhesive strength of the laminate could not be measured. The evaluation results were as shown in Table 1 below.

  Moreover, the laminated body of Examples 1-3 was stored in water, and the adhesive strength of the laminated body was measured like the above after that. The evaluation results were as shown in Table 1 below.

  As is clear from the evaluation results in Table 1, the laminates of Examples 1 to 3 maintained adhesiveness even after storage in water. Although indirectly, at least part of the interface of the opposing gas barrier protective layer, the atoms in the gas barrier protective layer of the one barrier film and the gas barrier protective layer of the other barrier film It can be inferred that a bond is formed between the atoms, and has an adhesive strength comparable to that of a conventional laminate laminated with an adhesive.

DESCRIPTION OF SYMBOLS 1 Laminated body 10 1st barrier film 20 20 2nd barrier film 11, 21 Thermoplastic resin film 12, 22 Thin film layer 13, 23 Gas barrier protective layer 3, 3 'Electron beam irradiation apparatus 4, 4' Electron beam 5 Film substrate contact interface 6 Heat roller 7 Support roller

Claims (8)

A barrier film comprising a thermoplastic resin film, a thin film layer made of aluminum oxide or silicon oxide provided on at least one surface of the thermoplastic resin film, and a gas barrier protective layer provided on the thin film layer, A laminated body in which two gas barrier protective layers are stacked so that they face each other,
The gas barrier protective layer consists of a film obtained by applying a solution containing a fluorine resin,
Bonded between an atom in the gas barrier protective layer of the one barrier film and an atom in the gas barrier protective layer of the other barrier film at at least a part of the interface of the opposing gas barrier protective layer Is formed, and the gas barrier protective layers of both barrier films are bonded to each other without using an adhesive.   At least part of the interface of the opposing gas barrier protective layer, oxygen atoms between atoms in the gas barrier protective layer of one barrier film and atoms in the gas barrier protective layer of the other barrier film The laminate according to claim 1, wherein a bond is formed through at least one selected from the group consisting of oxygen atom and hydroxyl group.   The laminate according to claim 1 or 2, wherein the fluororesin comprises a fluororesin comprising a fluorine-containing copolymer having a crosslinkable group and a curing agent that reacts with the crosslinkable group.   The laminate according to any one of claims 1 to 3, wherein the thermoplastic resin film is a polyethylene terephthalate film. A barrier film comprising a thermoplastic resin film, a thin film layer made of aluminum oxide or silicon oxide provided on at least one surface of the thermoplastic resin film, and a gas barrier protective layer provided on the thin film layer, A method for producing a laminate in which two gas barrier protective layers are stacked so as to face each other,
Two barrier films comprising a thermoplastic resin film, a thin film layer made of aluminum oxide or silicon oxide provided on at least one surface of the thermoplastic resin film, and a gas barrier protective layer provided on the thin film layer Prepare
Irradiating an electron beam to the gas barrier protective layer surface of the one or both barrier films,
A method comprising superposing a gas barrier protective layer surface of the one barrier film and a gas barrier protective layer surface of the other barrier film, and bonding the barrier films together.   The method according to claim 5, wherein the electron beam irradiation is performed before and / or after the barrier films are overlapped.   The method according to claim 5 or 6, wherein the adhesion is performed under pressure.   The method according to claim 5, wherein the adhesion is performed by heating.

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