JP5990945B2 - Gas barrier laminated film - Google Patents

Description

  The present invention relates to a gas barrier laminated film suitable for application when protecting an object from gas.

  The gas barrier film protects the object from moisture, oxygen, carbon dioxide, and other gases in the air and suppresses the deterioration of quality and performance. The use of glass and aluminum foil as an alternative in the electronics field such as backsheets, electronic paper, and organic EL is also being considered.

Currently, the main types of gas barrier films include single films such as ethylene vinyl alcohol copolymer resins, co-extruded multilayer nylon (Ny) films, vinylidene chloride (PVDC) coats and polyvinyl alcohol (PVA) coat wet coat films. . However, even if these types of films have high gas barrier properties, they have a water vapor permeability of about 3 g / m ² / day and are difficult to use as packaging materials and electronic members that require higher gas barrier properties. Therefore, when a higher barrier property is required, a metal foil such as aluminum has to be laminated.

  However, the packaging material using a film in which metal foils are laminated has problems that the contents cannot be seen and the metal detector cannot be used for the contents inspection.

  In order to overcome these problems, for example, Patent Document 1 proposes a transparent gas barrier film in which an inorganic compound such as aluminum oxide, magnesium oxide, or silicon oxide is deposited on a polymer resin substrate. .

  Furthermore, in order to improve the adhesiveness of a vapor deposition layer to the resin base material, many things of the structure which provided the primer layer between the resin base material and the vapor deposition layer are proposed. As the material for these primer layers, acrylic resins are often used. In particular, the reaction mixture of acrylic polyol and isocyanate compound, or a silane coupling agent added thereto, is used as a primer layer for boil sterilization. In addition, a gas barrier film having high boil resistance and retort resistance that does not deteriorate in physical properties and does not generate delamination after retort sterilization (for example, Patent Documents 2 to 4).

Japanese Patent Publication No.63-28017 JP 2004-106443 A JP 2007-69456 A JP 2002-36419 A

  However, these films are generally used for 60-degree C / 90% RH 500 hours as a durability test for display-related members and for 85-degree C / 85% RH 1000 hours as a durability test for solar cell modules (JIS C8917, C8938, It is difficult to maintain adhesion even after a high-temperature and high-humidity test, such as C8990 and C8991), and it is difficult to use for applications that require high durability.

  In order to solve this problem, an object of the present invention is to provide a transparent gas barrier film excellent in durability that maintains adhesion even after a high-temperature and high-humidity test.

The present invention has been made to achieve the above-mentioned problems, and the invention according to claim 1 is a gas barrier laminated film in which a primer layer and a vapor deposition film layer are laminated in order on at least one surface of a resin substrate, The primer layer contains a mixture of a polyol and an isocyanate compound, and the extrapolated glass transition start temperature of the mixture measured in accordance with the provisions of JIS K7121 is an extrapolated glass transition start temperature of the resin substrate + 5 ° C. or more and 30 ° C. It exists in the following ranges, The said vapor deposition film layer contains the silicon oxide at least, It is characterized by the above-mentioned.

  According to a second aspect of the present invention, in the gas barrier laminate film according to the first aspect, the resin base material includes polyethylene terephthalate, and the compensation is measured in accordance with the provision of the mixture of the polyol and the isocyanate compound forming the primer layer. The outer glass transition start temperature is 80 ° C. or higher and 100 ° C. or lower.

  The invention according to claim 3 is the gas barrier laminate film according to claim 1 or 2, wherein the primer layer has a thickness of 30 nm to 200 nm.

The invention according to claim 4 is the gas barrier laminate film according to any one of claims 1 to 3, wherein the primer layer has a hydroxyl value of 130 mgKOH / g or more and 200 mgKOH / g obtained by copolymerizing hydroxyethyl methacrylate and methyl methacrylate. the following acrylic polyol, the general formula _{(O = C = N- (CH} 2) 6 -N = C = O) n ... (1) at the isocyanurate of hexamethylene diisocyanate body represented (where n = 3 to 5 And a mixture thereof.

  A fifth aspect of the present invention is the gas barrier laminate film according to any one of the first to fourth aspects, wherein the vapor deposition film layer is further selected from aluminum, zinc, tin, iron, and manganese. Or it contains the metal oxide, It is characterized by the above-mentioned.

  A sixth aspect of the present invention is the gas barrier laminate film according to any one of the first to fifth aspects, wherein the surface of the deposited film layer contains a water-soluble polymer and alkoxysilane or a hydrolysis product thereof. A gas barrier coating layer, which is a dry film of a thin film made of a coating solution, is provided.

  According to the present invention, a primer layer composed of a mixture of a polyol and an isocyanate compound having an extrapolated glass transition start temperature of a resin base material + 5 ° C. to 30 ° C. Combined with the contained vapor deposition film layer, it retains adhesion even after high-temperature and high-humidity tests, such as 60 ° C / 90% RH for 500 hours and 85 ° C / 85% RH for 1000 hours. A transparent gas barrier film having the following can be provided.

It is sectional drawing which shows one structural example of the gas barrier laminated film which concerns on embodiment of this invention. It is sectional drawing which shows the other structural example of the gas barrier laminated film which concerns on embodiment of this invention. It is sectional drawing which shows an example of the double-sided laminated structure of the gas barrier laminated film which concerns on embodiment of this invention.

  Embodiments of the present invention will be described below with reference to the drawings.

Hereinafter, embodiments of the gas barrier laminate film of the present invention will be described with reference to the drawings.
As shown in FIG. 1, a gas barrier laminated film 10 according to an embodiment of the present invention includes a resin base material 11, a primer layer 12, and a vapor deposition film layer 13, and the primer layer 12 and vapor deposition are formed on one side of the resin base material 11. The film layer 13 is sequentially stacked. The gas barrier laminate film according to the embodiment of the present invention may have a configuration in which the primer layer 12 and the vapor deposition film layer 13 are sequentially laminated on both surfaces of the resin base material 11 in order to achieve higher water vapor barrier properties.

  Examples of the resin substrate 11 include polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin films such as polyethylene and polypropylene, polyether sulfone (PES), polystyrene film, polyamide film, and polyvinyl chloride. Examples include films, polycarbonate films, polyacrylonitrile films, polyimide films, and biodegradable plastic films such as polylactic acid. The thickness of the resin base material 11 is not particularly limited, but is practically about 6 μm to 200 μm, preferably 12 μm to 125 μm, and more preferably 12 μm to 25 μm.

  In addition, in order to improve the adhesion on the surface on which other layers of the resin base material 11 are laminated, chemical treatment such as physical treatment such as corona treatment, plasma treatment, flame treatment, or chemical treatment with acid or alkali is performed. Processing may be performed.

  The primer layer 12 is provided on the resin base material 11, enhances the adhesion between the resin base material 11 and the vapor deposition film layer 13, performs various sterilization treatments such as boil sterilization and retort sterilization, and peeling of the vapor deposition layer by long-term outdoor installation. It is provided to prevent the occurrence.

  By forming the primer layer 12 using a mixture of a polyol and an isocyanate compound, the adhesion between the resin substrate 11 and the vapor deposition film layer 13 can be enhanced.

  A polyol is a general term for compounds having a plurality of hydroxyl groups in the molecule, and reacts with an isocyanate group of an isocyanate compound. The main polyol is a polyether polyol having an ether bond in the main chain, a polyester polyol having an ester bond in the main chain, a polymer compound obtained by polymerizing a (meth) acrylic acid derivative monomer, or a (meth) acrylic acid derivative. Acrylic polyol, which is a polymer compound obtained by copolymerizing a monomer and another monomer, can be used.

  The polyether polyol mainly includes polyoxyalkylene polyol obtained by addition polymerization of alkylene oxide with polyhydric alcohol or polyamine as an initiator, and polyoxytetramethylene glycol obtained by cationic polymerization of tetrahydrofuran.

  Polyester polyols include polycaprolactone polyols obtained by ring-opening polymerization of a lodging polymerized polyester polyol mainly obtained from dibasic acids and glycols and ε-caprolactone. Examples of the dibasic acid used in the hotel polymerization polyester polyol include adipic acid, terephthalic acid, and isophthalic acid. Examples of glycols include ethylene glycol, neopentyl glycol, and 3-methyl-1,5-pentadiol. Is mentioned.

  Acrylic polyol has a hydroxyl group at the terminal among polymer compounds obtained by copolymerizing (meth) acrylic acid derivative monomers or (meth) acrylic acid derivative monomers and other monomers by radical polymerization. Examples of the (meth) acrylic acid derivative monomer having a hydroxyl group at the terminal include hydroxyethyl (meth) acrylate and hydroxybutyl (meth) acrylate.

  Monomers that can be copolymerized with a (meth) acrylic acid derivative monomer having a hydroxyl group at the terminal include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, and the like. Monomer having an alkyl group at the terminal, (meth) acrylic acid derivative monomer having a carboxyl group at the terminal such as (meth) acrylic acid, aromatic ring or cyclic structure at the terminal such as benzyl (meth) acrylate or cyclohexyl (meth) acrylate There are (meth) acrylic acid derivative monomers having: Other than (meth) acrylic acid derivative monomers, there are styrene monomers, cyclohexylmaleimide monomers, phenylmaleimide monomers, and the like.

  The molecular weight of the polyol is not particularly specified, but specifically, it is 3000 or more and 200000 or less, preferably 5000 or more and 100000 or less, and more preferably 5000 or more and 40000 or less.

  An isocyanate compound has two or more isocyanate groups in the molecule. For example, monomeric isocyanates include aromatic isocyanates such as tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), bisisocyanate methylcyclohexane (H6XDI), isophorone diisocyanate (IPDI), and dicyclohexylmethane diisocyanate. Examples thereof include aliphatic isocyanates such as (H12MDI), aromatic aliphatic isocyanates such as xylene diisocyanate (XDI) and tetramethylxylylene diisocyanate (TMXDI). Also, polymers or derivatives of these monomeric isocyanates can be used. For example, there are a tripentameric nurate type, an adduct type reacted with 1,1,1-trimethylolpropane, a biuret type reacted with biuret, and the like.

  The isocyanate compound may be arbitrarily selected from the above-mentioned isocyanate compounds, polymers or derivatives thereof, and may be used alone or in combination of two or more.

  Moreover, in addition to the said polyol and isocyanate type compound, an additive can also be added according to a use. For example, there are a catalyst that accelerates the curing reaction, a light stabilizer such as an ultraviolet absorber (UVA) and a hindered amine light stabilizer (HALS), an antioxidant, an antistatic agent, a plasticizer, and a silane coupling agent.

  At this time, the extrapolated glass transition start temperature measured in accordance with JIS K7121 of the reaction mixture of the polyol and isocyanate compound (and additive) forming the primer layer 12 is the extrapolated glass transition start temperature of the resin base material 11. When a polyol and an isocyanate compound are selected so as to be in the range of + 5 ° C. or more and 30 ° C. or less, it is a general 60 ° C./90% RH for 500 hours as a durability test for display-related members and a general durability test for a solar cell module. A gas barrier laminate that maintains the adhesion between the resin substrate 11 and the deposited film layer 13 even after a high-temperature and high-humidity test such as 85 ° C./85% RH 1000 hours (JIS C8917, C8938, C8990, C8991). Become a film. The extrapolated glass transition start temperature of the reaction mixture of polyol and isocyanate compound is lower than the extrapolated glass transition start temperature of the resin base material + 5 ° C., or the extrapolated glass transition start temperature of the resin base material + 30 ° C. If it is too high, the primer layer 12 cannot follow the movement of the resin base material 11 that softens under high temperature and high humidity, and the adhesion cannot be maintained.

  When the resin substrate 11 is PET, the extrapolated glass transition start temperature measured according to JIS K7121 of the mixture of polyol and isocyanate compound (and additive) forming the primer layer 12 is 80 ° C. or higher and 100 ° C. It is desirable to select a polyol, an isocyanate compound, and an additive so that the following is satisfied, and the temperature is preferably 85 ° C. or higher and 95 ° C. or lower. When the extrapolated glass transition start temperature is lower than 80 ° C., the primer layer 12 is softened under high temperature and high humidity, and adhesion with PET (extrapolated glass transition start temperature of about 70 ° C.) as the resin base material 11 is achieved. If the temperature is higher than 100 ° C., the film quality of the primer layer 12 is too hard, so that the primer layer 12 cannot follow the movement of the PET under high temperature and high humidity, and the adhesion cannot be maintained.

The primer layer 12, and a hydroxyethyl methacrylate and methyl methacrylate copolymerized with a hydroxyl value 130 mgKOH / g or more and 200 mg KOH / g or less of acrylic polyol, the general formula _{(O = C = N- (CH} 2) 6 -N = C = O) n: It is desirable to use a mixture with a nurate of hexamethylene diisocyanate represented by (1) (where n = 3 to 5).

  The hydroxyl value is an index of the amount of hydroxyl group in the polyol, and indicates the number of mg of potassium hydroxide necessary for acetylating the hydroxyl group in 1 g of polyol.

  When the hydroxyl value of the above mixture is smaller than 130 mgKOH / g, the extrapolation glass transition start temperature becomes too high, and when it exceeds 200 mgKOH / g, the extrapolation glass transition start temperature becomes too low. There is a problem that the adhesiveness with the resin base material 11 cannot be maintained under high humidity. A complex of a hexamethylene diisocyanate nurate represented by the general formula (1) and the acrylic polyol can form a primer layer 12 having good adhesion to the resin substrate 11.

  The primer layer 12 is formed by applying a solution composed of a mixture of the above polyol and the above isocyanate compound and a solvent onto the resin substrate 11 and reacting and curing it. The solvent used may be any solvent that dissolves the polyol and the isocyanate compound. Examples thereof include methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, dioxolane, tetrahydrofuran, cyclohexanone, and acetone. One type or a combination of two or more types can be used.

  As a method for forming the primer layer 12, a normal coating method can be used. For example, known methods such as dipping, roll coating, gravure coating, reverse coating, air knife coating, comma coating, die coating, screen printing, spray coating, and gravure offset method can be used. As the drying method, one or a combination of two or more methods of applying heat such as hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, and UV irradiation can be used.

  The film thickness of the primer layer 12 is desirably 30 nm or more and 200 nm or less, and preferably 100 nm or more and 200 nm or less. If the thickness is thinner than this, the adhesion between the resin base material 11 and the vapor deposition film layer 13 becomes insufficient, and if it is thicker than 300 nm, the influence of internal stress becomes large, and the vapor deposition film layer 13 is not laminated neatly, There is a problem that the expression of sex becomes insufficient.

  The vapor deposition film layer 13 is provided on the primer layer 12 and is provided in order to give gas barrier properties to the entire film. The vapor deposition film layer 13 contains at least silicon oxide. Moreover, when higher barrier property is required, it is preferable that the vapor deposition film layer 13 contains either the metal selected from aluminum, zinc, tin, iron, manganese, or its metal oxide.

  As the material of the vapor deposition film layer 13, a vapor deposition material containing metal silicon and silicon dioxide is used. By depositing a deposition material containing metal silicon and silicon dioxide, high gas barrier properties can be imparted to the entire film. Further, a vapor deposition material in which any one metal selected from aluminum, zinc, tin, iron, and manganese or a metal oxide thereof is mixed with metal silicon and silicon dioxide is vapor-deposited, whereby a vapor deposition film layer 13 having a high film density is formed. Is formed, exhibits high water vapor barrier properties, and has an extrapolated glass transition start temperature of the resin substrate 11 formed by a mixture of a polyol and an isocyanate compound + 5 ° C. or more and 30 or less. Due to the synergistic effect with the primer layer 12, a gas barrier film having both high gas barrier properties and high durability is obtained.

  Metal silicon and silicon dioxide are desirably mixed so that the element ratio O / Si is 1 or more and 1.8 or less, and preferably 1.2 or more and 1.7 or less. In addition, any metal selected from aluminum, zinc, tin, iron, and manganese, or a metal oxide thereof, is desirably mixed in an amount of 1 wt% to 50 wt% with respect to the mixed material of metal silicon and silicon dioxide. Preferably, it is 1 to 40% by weight, more preferably 5 to 30% by weight.

As a method for forming the vapor deposition film layer 13, a known method such as a vacuum vapor deposition method, a sputtering method, or a plasma vapor deposition method may be used as appropriate, but a vacuum vapor deposition method is desirable. Further, in order to increase the transparency of the vapor deposition film layer 13, when vapor deposition material is vapor deposited, reactive vapor deposition may be performed in which vapor deposition is performed by reacting with evaporated particles and oxygen gas introduced into the atmosphere. By performing reactive vapor deposition with oxygen gas or argon gas, the metal component in the vapor deposition material is oxidized, and the transparency of the vapor deposition film layer 13 can be improved. When introducing the gas, it is desirable that the pressure in the film forming chamber be 2 × 10 ⁻¹ Pa or less. If the pressure in the film forming chamber becomes higher than 2 × 10 ⁻¹ Pa, the vapor deposition film layer 13 is not neatly laminated, and the water vapor barrier property is lowered.

  The film thickness of the vapor deposition film layer 13 is preferably 0.005 μm or more and 0.3 μm or less, and more preferably 0.03 μm or more and 0.05 μm or less. When 0.005 μm is small, sufficient barrier property is not exhibited, and when it exceeds 0.3 μm, it is brittle and cracks are likely to occur, resulting in a problem that barrier property is not exhibited.

  A gas barrier laminated film of the present invention is formed on a vapor-deposited film layer 13 of the gas barrier laminated film 10 of FIG. 1 and a water-soluble polymer and alkoxysilane or a hydrolysis product thereof, like a gas barrier laminated film 20 shown in FIG. A gas barrier coating layer 21 which is a dry film of a thin film made of a coating solution containing s may be provided.

  The gas barrier coating layer 21 is provided to protect the hard and fragile deposited film layer 13 and prevent the occurrence of cracks due to rubbing or bending, and from a component containing a water-soluble polymer and alkoxysilane or a hydrolysis product thereof. Become. It is formed by applying a coating liquid containing a water-soluble polymer and alkoxysilane or a hydrolysis product thereof onto the deposited film layer 13 and drying it.

  As a method for forming the gas barrier coating layer 21, a normal coating method can be used similarly to the primer layer 12. For example, known methods such as dipping method, roll coating, gravure coating, reverse coating, air knife coating, comma coating, die coating, screen printing method, spray coating, and gravure offset method can be used. As the drying method, one or a combination of two or more methods of applying heat such as hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, and UV irradiation can be used.

  As the water-soluble polymer, polyvinyl alcohol resin (PVA), ethylene-vinyl alcohol copolymer resin (EVOH), polyvinyl pyrrolidone resin (PVP), etc. can be used, and these may be used alone or in combination.

  As the alkoxysilane, tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, methyltriethoxysilane, methyltrimethoxysilane, or the like can be used. Examples of the hydrolysis product of alkoxysilane include those prepared by dissolving alkoxysilane in an alcohol such as methanol, adding an aqueous solution of an acid such as hydrochloric acid to the solution, and causing a hydrolysis reaction.

  Moreover, in order to improve adhesiveness with the vapor deposition film layer 13, you may add a silane coupling agent. Examples of the silane coupling agent include those having an epoxy group such as 3-glycidoxypropyltrimethoxysilane, those having an amino group such as 3-aminopropyltrimethoxysilane, and mercapto groups such as 3-mercaptopropyltrimethoxysilane. And those having an isocyanate group such as 3-isocyanatopropyltriethoxysilane. These silane coupling agents can be used alone or in combination of two or more.

  The gas barrier laminate film of the present invention is more practical by providing a laminate resin layer 32 via an adhesive layer 31 on both sides of the gas barrier laminate film 20 of FIG. 2, like the gas barrier laminate film 30 shown in FIG. 3. High laminated film can be provided. The laminate resin layer 32 is used for an adhesive portion when a bag-shaped package or the like is formed by laminating a heat sealable sealant film. For example, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer and their Resins such as metal cross-linked products are used. The thickness is determined according to the purpose, but is generally in the range of 15 μm to 200 μm. Note that the laminate resin layer 32 may be provided only on one side of the gas barrier laminated film 20 of FIG. 2 via the adhesive layer 31.

  In addition, by laminating polyethylene terephthalate film or polyethylene naphthalate film on one or both sides of the gas barrier laminate film of the present invention, sealing materials such as transparent conductive sheets used in liquid crystal display elements, solar cells, electromagnetic wave shields, and touch panels Can also be used.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example and a comparative example, this invention is not limited to this form.

(Examples 1-11, Comparative Examples 1-13)
Production and evaluation of the gas barrier laminated film and measurement of the extrapolated glass transition start temperature of the mixture forming the primer layer were performed according to the following method.

<Production of gas barrier laminated film>
(1) Preparation process of primer layer solution Hydroxyethyl methacrylate (HEMA), Hydroxyethyl acrylate (HEA), Hydroxybutyl acrylate (HBA), Methyl methacrylate (MMA), Methyl acrylate (MA), Ethyl methacrylate (EMA), n -Butyl methacrylate (nBMA), t-butyl methacrylate (tBMA), cyclohexyl methacrylate (CHMA), benzyl methacrylate (BzMA), methacrylic acid (MAA), 3-methacryloxytrimethoxysilane (KBM-503), styrene (St) methyl ethyl ketone solution having a solid fraction concentration of 5% acrylic polyols obtained by copolymerizing a monomer (weight average molecular weight 1 × 10 ⁴⁾ and isocyanate with a solid fraction concentration of 5% Methyl ethyl ketone solution of preparative compounds, and additives were mixed according to a predetermined blending ratio. As isocyanate compounds, HDI nurate is Sumidur N3300 (Suika Bayer Urethane), TDI adduct is Coronate L (Nippon Polyurethane), XDI adduct is Takenate D-110N (Mitsui Chemicals), IPDI adduct is Takenate D-140N (Mitsui Chemicals) )It was used. As additives, hindered amine light stabilizer (HALS) was Tinuvin 292 (Ciba Japan), and silane coupling agent was 3-isocyanatopropyltriethoxysilane KBE-9007 (Shin-Etsu Silicone). The components of the polyol, the hydroxyl value, the type of isocyanate compound, the weight blending ratio, and the additive content are shown in Table 1.

(2) Primer layer solution coating process A 12 μm thick biaxially stretched PET film (Toray film processing, P60) with a corona treatment on one side is used for the resin substrate, and a gravure coating machine is used on the corona treatment surface. The primer layer solution was applied, and a primer layer having a thickness of 0.20 μm after drying was laminated.

(3) Lamination process of vapor deposition film layer Material (A) in which metal silicon powder and silicon dioxide powder are mixed so that element ratio O / Si is 1.5, and element ratio O / Si is 1.5. A vapor deposition material (B) in which a metal silicon powder and a silicon dioxide powder are mixed with 20 wt% of a metal tin powder is prepared, and a thickness of 0.05 μm is formed on the primer layer using a vacuum vapor deposition machine. The target gas barrier laminated film was produced by laminating the deposited film layers.

(4) Preparation Step of Gas Barrier Coating Layer Solution A solution obtained by hydrolyzing tetraethoxysilane with 0.02 mol / L hydrochloric acid was added to a 5% aqueous solution of PVA having a saponification degree of 99% and a polymerization degree of 2400 with SiO ₂ / PVA = 60. It was added at a ratio of / 40 to obtain a gas barrier coating layer solution.
(5) Coating process of gas barrier coating layer solution Gas barrier coating layer having a thickness of 0.40 μm after coating and drying the gas barrier coating layer solution on the inorganic oxide vapor deposition layer using a gravure coater. Were laminated.

(6) Laminating resin layer laminating step on gas barrier laminate film Hydrolysis resistant PET having a thickness of 50 μm on both surfaces of the gas barrier laminate film on which the gas barrier coating layer is laminated via a 5 g / m ² polyurethane adhesive. (Toray film processing, X10S) was laminated by a dry laminating method.

<Evaluation of gas barrier laminated film>
(1) Measurement of water vapor permeability About the gas barrier laminated film of resin base material / primer layer / deposition film layer structure of Examples 1-11 and Comparative Examples 1-13, a water vapor permeability meter (MOCON PERMATRAN- W 3/31), water vapor permeability (g / m ² / day) in a 40 ° C.-90% RH atmosphere was measured.

(2) Implementation of high-temperature and high-humidity test The gas barrier laminate film subjected to dry lamination was placed in an environment of 85 ° C./85% RH for 3000 hours.

(3) Measurement of adhesion strength For samples before and after the high-temperature and high-humidity test, a test piece cut to a width of 10 mm from a gas barrier laminated film subjected to dry lamination was tested using a Tensilon type universal testing machine and a test method of JIS K6854 The laminate strength (N / 10 mm width) was measured by performing a T-time peel test and a 180 degree peel test, and those having strengths of 1 N / 10 mm width or more in both peel tests were accepted. .

<Measurement of extrapolated glass transition start temperature>
The extrapolation glass transition temperature was measured by thermal flow rate differential scanning calorimetry (DSC).

(1) Production of DSC measurement sample The resin base material was obtained by stacking a plurality of cut pieces of about 3 mm square and used as a measurement sample. The measurement sample of the mixture forming the primer layer is a solution in which a methyl ethyl ketone solution of a polyol adjusted to a solid content concentration of 20% and a methyl ethyl ketone solution of an isocyanate compound adjusted to a solid content concentration of 20% are mixed in a proportion according to Table 1. Was put in a polypropylene container having a bottom area of about 16 cm ⁻¹ and dried in an oven set at 100 ° C. for 60 minutes. Next, a measurement sample was placed overnight at 60 ° C.

(2) Measurement of extrapolated glass transition start temperature DSC was measured according to JIS K7121 to determine the extrapolated glass transition point.

<Evaluation results of gas barrier laminated film>
The evaluation results are shown in Table 2. The extrapolated glass transition start temperature of PET used as the resin substrate was 72 ° C. In Examples 1 to 11, the extrapolated glass transition start temperature of the mixture forming the primer layer is 82 to 96 ° C, the extrapolated glass transition start temperature of the resin base material is in the range of 5 ° C to 30 ° C, and 80 ° C. or higher and 100 ° C. or lower. Moreover, the high temperature high of 85 degreeC / 85% RH 3000 hours which is severer test conditions than 85 degreeC / 85% RH 1000 hours (JIS C8917, C8938, C8990, C8991) common as an endurance test of a solar cell module. Even after the moisture test, the adhesion was maintained and the durability was good. Moreover, water vapor | steam barrier property was able to be improved by using metal tin for vapor deposition material. (Example 6)
On the other hand, in the case of a primer layer having an extrapolated glass transition start temperature of less than 80 ° C. and a primer layer greater than 100 ° C., the adhesion could not be maintained after the high temperature and high humidity test, resulting in insufficient durability. (Comparative Examples 1 to 13)

  The gas barrier film laminate of the present invention is expected to be suitably used particularly in the fields of packaging such as foods, daily necessities, and pharmaceuticals, and fields related to electronic equipment, particularly when high durability is required.

  DESCRIPTION OF SYMBOLS 10, 20, 30 ... Gas barrier laminated film, 11 ... Resin base material, 12 ... Primer layer, 13 ... Deposition film layer, 21 ... Gas barrier coating layer, 31 ... Adhesive layer, 32 ... Laminate resin layer.

Claims (6)

A gas barrier laminated film in which a primer layer and a vapor deposition film layer are laminated in order on at least one surface of a resin substrate,
The primer layer includes a mixture of a polyol and an isocyanate compound, and an extrapolated glass transition start temperature of the mixture measured according to JIS K7121 is an extrapolated glass transition start temperature of the resin base material + 5 ° C. or higher. A gas barrier laminated film, wherein the vapor-deposited film layer contains at least a silicon oxide in a range of not higher than ° C.   The resin base material includes polyethylene terephthalate, and an extrapolated glass transition start temperature measured according to the above-mentioned provision of the mixture of polyol and isocyanate compound forming the primer layer is 80 ° C. or higher and 100 ° C. or lower. The gas barrier laminate film according to claim 1.   The gas barrier laminate film according to claim 1 or 2, wherein the primer layer has a thickness of 30 nm or more and 200 nm or less. The primer layer comprises an acrylic polyol having a hydroxyl value of 130 mgKOH / g or more and 200 mgKOH / g or less obtained by copolymerizing hydroxyethyl methacrylate and methyl methacrylate;
General formula (O = C═N— (CH ₂ ) ₆ —N═C═O) _n Including a mixture with a hexamethylene diisocyanate nurate (where n = 3 to 5) represented by (1) The gas barrier laminate film according to any one of claims 1 to 3, wherein   The vapor-deposited film layer further contains any metal selected from aluminum, zinc, tin, iron, and manganese, or a metal oxide thereof. The gas barrier laminate film described in 1.   A gas barrier coating layer, which is a dry film of a thin film made of a coating solution containing a water-soluble polymer and alkoxysilane or a hydrolysis product thereof, is provided on the surface of the vapor deposition film layer. Item 6. The gas barrier laminated film according to any one of Items 1 to 5.

Images