JPWO2016017410A1 - Laminated film - Google Patents

Abstract

Even when an inorganic layer and an organic layer are laminated on a plastic film, a laminated film excellent in adhesion and oxygen gas barrier / water vapor barrier properties is provided. A laminated film in which an inorganic layer, a first organic layer, and a second organic layer are provided on at least one surface of a plastic film in this order with or without other layers. The organic layer includes a 1,3,5-triazine derivative having a sulfur-containing group as a substituent in at least one of the 2, 4, and 6 positions, and the second organic layer includes at least one of the 2, 4, and 6 positions. And a 1,3,5-triazine derivative having a group containing oxygen and / or nitrogen as a substituent and / or a condensate thereof.

Description

  The present invention is a laminated film having an inorganic layer and an organic layer and having excellent adhesion and gas barrier properties, and is used not only for packaging foods, pharmaceuticals, industrial products, etc., but also for solar cells, electronic paper, and organic EL elements. The present invention relates to a laminated film that can be widely used in industrial applications such as semiconductor elements.

  Conventionally, as a laminated film having gas barrier properties used for food packaging applications, a thin film of an inorganic oxide such as silicon oxide or aluminum oxide (hereinafter referred to as an inorganic layer) or a metal thin film such as aluminum on the surface of a plastic film. Laminated films were known. However, in industrial applications such as solar cells, electronic paper, organic EL elements, and semiconductor elements, the above-mentioned laminated film has insufficient gas barrier properties, and further needs to improve the gas barrier properties.

  As one means for improving the gas barrier property, a method of laminating an inorganic layer and a thin film containing an organic substance (hereinafter referred to as an organic layer) on a plastic film can be considered.

  The organic layer can be formed by a normal coating method, but a vapor deposition method can also be employed. Vapor deposition methods are broadly divided into physical vapor deposition methods such as vacuum vapor deposition, sputtering, and ion plating, and chemical vapor deposition methods such as PECVD (plasma CVD). Usually, physical vapor deposition is used. Yes.

  When the physical vapor deposition method is used, a certain degree of gas barrier property can be exhibited, and the film thickness can be made uniform even when a substance is deposited on a wider area. In addition, when the physical vapor deposition method is used, an organic material and an inorganic material can be continuously formed into a vacuum to improve production efficiency such as cost reduction and film formation time.

  As a laminated film including an inorganic layer and an organic layer, a laminated film in which an inorganic layer and an organic layer containing melamine are laminated is known (for example, see Patent Documents 1 and 2). Here, a method is proposed in which an inorganic layer is laminated on a plastic film, and an organic layer is deposited on the inorganic layer by a vacuum deposition method. The organic layer is functionalized with a triazine derivative (for example, melamine salt such as melamine, melem, melam, ammelin, ammelide, cyanuric acid, 2-ureidomelamine, melamine cyanurate, or a polymerizable group such as acrylate, epoxy, vinyl ether). Or a mixture of the above triazine derivatives.

  By the way, when using a laminated film for packaging applications, it is necessary not only to have excellent gas barrier properties, but also to have excellent adhesion between the organic layer and the inorganic layer (hereinafter referred to as adhesion). However, although the laminated film produced by the methods described in Patent Documents 1 and 2 has oxygen gas barrier properties, there are problems that water vapor barrier properties are poor and adhesion is weak.

Special table 2007-503529 Special table 2007-508161

  An object of the present invention is to provide a laminated film having an inorganic layer and an organic layer and having excellent adhesion and oxygen gas barrier / water vapor barrier properties.

  The present inventors have provided an organic layer containing a 1,3,5-triazine derivative having a substituent containing sulfur as a substituent at at least one of the 2, 4, 6 positions, and at least one of the 2, 4, 6 positions. Formed an organic layer containing a 1,3,5-triazine derivative having a group containing oxygen and / or a group containing nitrogen as a substituent and / or a condensate thereof, as a result, adhesion, oxygen gas barrier property, water vapor Both barrier properties can be expressed and the present invention has been completed.

  In the laminated film according to the present invention, an inorganic layer, a first organic layer, and a second organic layer are provided on at least one surface of the plastic film in this order with or without other layers interposed therebetween. The first organic layer includes a 1,3,5-triazine derivative having a substituent containing sulfur as a substituent at at least one of the 2, 4, and 6 positions, and the second organic layer includes 2, 4, 6 It includes a 1,3,5-triazine derivative having a group containing oxygen and / or nitrogen at at least one of its positions as a substituent and / or a condensate thereof.

  The 1,3,5-triazine derivative contained in the first organic layer is preferably triazine trithiol or triazine dithiol, and more preferably triazine trithiol.

  1,3,5-triazine derivatives and / or condensates thereof contained in the second organic layer are melamine, melem, melam, ammelin, ammelide, cyanuric acid, 2-ureidomelamine, melamine cyanurate, and polymerizable It is preferably at least one selected from the group consisting of melamine functionalized with a group, more preferably melem.

  The inorganic layer, the first organic layer, and the second organic layer are preferably formed by a vacuum deposition method.

  The laminated film according to the present invention can exhibit both adhesiveness and gas barrier properties. The laminated film according to the present invention can be widely used not only for packaging applications such as foods, pharmaceuticals, and industrial products, but also for industrial applications such as solar cells, electronic paper, organic EL elements, and semiconductor elements.

  In the laminated film according to the present invention, both the first organic layer and the second organic layer contain a triazine derivative having a triazine skeleton, although the substituents are different. Since this triazine skeleton is planar and has a relatively large molecular structure, interaction between these organic layers is likely to occur, and good physical properties are exhibited.

It is the schematic of the vapor deposition apparatus for producing the laminated | multilayer film based on this invention.

  In the laminated film of the present invention, an inorganic layer, a first organic layer, and a second organic layer are provided on at least one surface of the plastic film in this order with or without other layers interposed therebetween. The first organic layer includes a 1,3,5-triazine derivative having a sulfur-containing group as a substituent in at least one of the 2, 4, and 6 positions, and the second organic layer is in the 2, 4, and 6 positions. 1,3,5-triazine derivative having a group containing oxygen and / or nitrogen as a substituent and / or a condensate thereof. Hereinafter, the physical properties and manufacturing method of the laminated film according to the present invention will be described.

[Plastic film]
The plastic film in the present invention is a film made of an organic polymer resin, melt-extruded, stretched in the longitudinal direction and / or width direction, and further heat-set and cooled. As the organic polymer resin, Polyolefins such as polyethylene and polypropylene; Polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene-2,6-naphthalate; Polyamides such as nylon 6, nylon 4, nylon 66, nylon 12 and wholly aromatic polyamides; polyvinyl chloride, Examples thereof include polyvinylidene chloride, polyvinyl alcohol, polyamideimide, polyimide, polyetherimide, polysulfone, polyphenylene sulfide, and polyphenylene oxide. These organic polymer resins may be copolymerized in a small amount with other organic monomers or blended with other organic polymers.

  Preferred polyesters include polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, and the like, and copolymers having these as main components may also be used.

  When a polyester copolymer is used, the main component of the dicarboxylic acid component is preferably an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, phthalic acid, or 2,6-naphthalenedicarboxylic acid, and the other carboxylic acid components are And polyfunctional carboxylic acids such as trimellitic acid and pyromellitic acid; and aliphatic dicarboxylic acids such as adipic acid and sebacic acid. The main component of the glycol component is preferably ethylene glycol or 1,4-butanediol, and the other glycol components include aliphatic glycols such as diethylene glycol, propylene glycol, and neopentyl glycol; p-xylylene glycol and the like. Aromatic glycol; alicyclic glycol such as 1,4-cyclohexanedimethanol; polyethylene glycol having a weight average molecular weight of 150 to 20,000 is used.

  A preferred ratio of the copolymer component in the polyester copolymer is 20% by mass or less. When a copolymerization component exceeds 20 mass%, film strength, transparency, heat resistance, etc. may be inferior. These polyester copolymers may be copolymerized with a small amount of other organic monomers or may be blended with other organic polymers.

  Preferred polyamides include polycaproamide (nylon 6), poly-ε-aminoheptanoic acid (nylon 7), poly-ε-aminononanoic acid (nylon 9), polyundecanamide (nylon 11), polylaurin lactam. (Nylon 12), polyethylene diamine adipamide (nylon 2.6), polytetramethylene adipamide (nylon 4.6), polyhexamethylene adipamide (nylon 6.6), polyhexamethylene sebacamide ( Nylon 6.10), Polyhexamethylene dodecamide (Nylon 6.12), Polyoctamethylene dodecamide (Nylon 8.12), Polyoctamethylene adipamide (Nylon 8.6), Polydecamethylene adipamide ( Nylon 10.6), polydecamethylene sebacamide (nylon 10.10), poly Examples include lidodecamethylene dodecamide (nylon 12 and 12), metaxylylenediamine-6 nylon (MXD6), and a copolymer containing these as main components.

  Polyamide copolymers include caprolactam / laurin lactam copolymer, caprolactam / hexamethylene diammonium adipate copolymer, laurin lactam / hexamethylene diammonium adipate copolymer, hexamethylene diammonium adipate / hexamethylene diammonium sebacate Examples thereof include ethylene diammonium adipate / hexamethylene diammonium adipate copolymer, caprolactam / hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer, and the like.

  It is also effective to blend these polyamides with plasticizers such as aromatic sulfonamides, p-hydroxybenzoic acid and esters, elastomer components with low elastic modulus, and lactams as a film flexibility modifying component. is there.

  Furthermore, known additives such as ultraviolet absorbers, antistatic agents, plasticizers, lubricants, colorants and the like may be added to the organic polymer resin, and the transparency as a film is not particularly limited. However, when transparency is required, one having a light transmittance of 50% or more is preferable.

  In the present invention, as long as the object of the present invention is not impaired, surface treatment such as corona discharge treatment, plasma discharge treatment, flame treatment, surface roughening treatment, etc., on the plastic film before the organic layer or inorganic layer is laminated, Anchor coating treatment, printing, decoration, etc. may be applied.

  The thickness of the plastic film in the present invention is preferably in the range of 3 to 500 μm, and more preferably in the range of 6 to 300 μm.

[Inorganic layer]
The inorganic layer referred to in the present invention is not particularly limited, and examples of the material include metals such as Al, Si, Ti, Zn, Zr, Mg, Sn, Cu, and Fe, and oxides, nitrides, and fluorides of these metals. Specific examples include SiO _x (x = 1.0 to 2.0), alumina, magnesia, zinc sulfide, titania, zirconia, cerium oxide, or a mixture thereof. The inorganic layer may be a single layer or a laminate of two or more layers. The inorganic layer and the organic layer described in detail later may be laminated on only one side of the plastic film or may be laminated on both sides. A commercially available vapor-deposited polyester film such as “Ecosial (registered trademark) VE100” manufactured by Toyobo Co., Ltd., in which a plastic film is vapor-deposited with an inorganic layer, can also be used. A vapor deposited nylon film can also be used.

  The inorganic layer in the present invention is preferably a multi-component inorganic layer containing at least aluminum oxide from the viewpoint of excellent gas barrier properties, and is a binary inorganic layer composed of silicon oxide and aluminum oxide or a two-component inorganic layer composed of magnesium oxide and aluminum oxide. An original inorganic layer is preferred.

The silicon oxide is composed of a mixture of various silicon oxides such as Si, SiO and SiO ₂ , and the aluminum oxide is composed of a mixture of various aluminum oxides such as Al, AlO and Al ₂ O ₃ , Magnesium oxide is a mixture of various magnesium compounds such as Mg and MgO, and the amount of oxygen bound in each oxide varies depending on the respective production conditions.

  When silicon oxide and aluminum oxide are used in combination, the content of aluminum oxide in the inorganic layer is preferably 20 to 99% by mass, and more preferably 20 to 75% by mass.

  When using magnesium oxide and aluminum oxide together, the content of aluminum oxide in the inorganic layer is preferably 20 to 99% by mass, and more preferably 20 to 80% by mass.

  If the content of aluminum oxide is less than 20% by mass, gas barrier properties may not always be sufficient. On the other hand, when the content of aluminum oxide exceeds 99% by mass, the flexibility of the deposited film is lowered, the laminated film is relatively weak against bending and dimensional change, and the combined effect may be reduced.

  The thickness of the inorganic layer is usually preferably 1 to 800 nm, more preferably 5 to 500 nm. If the thickness is less than 1 nm, satisfactory gas barrier properties may be difficult to obtain. On the other hand, even if the thickness exceeds 800 nm, the corresponding gas barrier property improvement effect cannot be obtained, which is disadvantageous in terms of bending resistance and manufacturing cost.

  As a typical production method for forming the inorganic layer, a known method such as a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method, or an ion plating method, a chemical vapor deposition method such as PECVD (plasma CVD), or the like is employed. The The inorganic layer is preferably formed by a vacuum deposition method.

For example, when the vacuum deposition method is employed, the deposition raw materials include metals such as aluminum, silicon, titanium, magnesium, zirconium, cerium, and zinc, SiO _x (x = 1.0 to 2.0), alumina, Compounds such as magnesia, zinc sulfide, titania, zirconia and mixtures thereof are used. The vacuum deposition method is a method in which an inorganic substance is heated in a vacuum, and the material contained in the crucible is heated and evaporated to adhere onto the plastic film. In order to make a vacuum, the inside of the vapor deposition apparatus is evacuated and is preferably reduced to 3.0 × 10 ⁻² Pa, and more preferably to 1.0 × 10 ⁻² Pa.

  For heating the inorganic material, resistance heating, high-frequency induction heating, electron beam heating, or the like can be employed. It is also possible to introduce oxygen, nitrogen, hydrogen, argon, carbon dioxide gas, water vapor or the like as the reactive gas, or to employ reactive vapor deposition using means such as ozone addition or ion assist.

  Furthermore, a bias can be applied to the plastic film, or the plastic film can be changed by heating or cooling with a roll, and the roll temperature is preferably -20 to 40 ° C.

  When the inorganic layer in the present invention is a multi-component inorganic layer containing at least silicon oxide and aluminum oxide, the multi-component inorganic layer is treated at a temperature of 40 to 60 ° C. in a steam gas of 1 to 3 kPa for 50 hours or more. It is preferable to do.

  Thin film formation conditions such as vapor deposition material, reaction gas, substrate bias, heating / cooling, and the like can be similarly changed when a sputtering method, an ion plating method, or a CVD method is employed.

[Organic layer]
The organic layer is laminated on the inorganic layer. In the laminated film of the present invention, at least two organic layers (first organic layer and second organic layer) are laminated on the surface of the inorganic layer.
The first organic layer contains a 1,3,5-triazine derivative having as a substituent a group containing sulfur in at least one of the 2, 4, and 6 positions. The second organic layer is a 1,3,5-triazine derivative having a substituent containing oxygen and / or nitrogen in at least one of the 2, 4, 6 positions as a substituent (substitution containing sulfur directly bonded to the triazine ring). Group) and / or a condensate thereof (a dimer or a bicyclic or tricyclic condensate thereof). By combining the first organic layer and the second organic layer with the inorganic layer, adhesion and gas barrier properties are further improved. The organic layer itself may not have gas barrier properties, but it is preferable that the organic layer has gas barrier properties.

[First organic layer]
Examples of the 1,3,5-triazine derivative having a sulfur-containing group as a substituent at at least one of the 2,4,6 positions include 1,3,5-triazine derivatives represented by the following chemical formulas, for example. , Alone or in combination. By including the following 1,3,5-triazine derivative in the organic layer, adhesion and gas barrier properties can be expressed.

The 1,3,5-triazine derivative represented by the above formula has a group containing sulfur at the 2,4,6 positions as a substituent, and the sulfur atom is directly bonded to the carbon atoms at the 2,4,6 positions. . R ¹ , R ² and R ³ in the above formula are, for example, H, CH ₃ , C ₂ H ₅ , C ₄ H ₉ , C ₆ H ₁₃ , C ₈ H ₁₇ , C ₁₀ H ₂₁ , C ₁₂ H _25. , C ₁₈ H ₃₇ , C ₂₀ H ₄₁ , C ₂₂ H ₄₅ , C ₂₄ H ₄₉ , CF ₃ C ₆ H ₄ , C ₄ F ₉ C ₅ H ₄ , C ₆ F ₁₃ C ₅ H ₄ , C ₈ F ₁₇ C ₆ H ₄ , C ₁₀ F ₂₁ C ₆ H ₄ , C ₆ F ₁₁ C ₆ H ₄ , C ₉ F ₁₇ CH ₂ , C ₁₀ F ₂₁ CH ₂ , C ₄ F ₉ CH ₂ , C ₆ F ₁₃ CH _{2 CH 2, C 8 F 17 CH} 2 CH 2, C 10 F 21 CH 2 CH 2, CH 2 = CHCH 2, CH 2 = CH (CH 2) 8, CH 2 = CH (CH 2) 9, C 8 H _{17 CH 2 = C 8 H 16} , C 6 H 11, C 6 H 5 CH 2, C 6 H 5 CH 2 CH 2, CH 2 = CH (CH 2) 4 COOCH 2 CH 2, CH 2 = CH (CH ₂ ) ₈ COOCH ₂ CH ₂ , CH ₂ ═CH (CH ₂ ) ₉ COOCH ₂ CH ₂ , _{C 4 F 9 CH 2 = CHCH} 2, C 6 F 13 CH 2 = CHCH 2, C 8 F 17 CH 2 = CHCH 2, C 10 F 21 CH 2 = CHCH 2, C 4 F 9 CH 2 CH (OH) _{CH 2, C 6 F 13 CH} 2 CH (OH) CH 2, C 8 F 17 CH 2 CH (OH) CH 2, C 10 F 21 CH 2 CH (OH) CH 2, CH 2 = CH (CH 2) ₄ COO (CH ₂ CH ₂ ) ₂ , CH ₂ = CH (CH ₂ ) ₈ COO (CH ₂ CH ₂ ) ₂ , CH ₂ = CH (CH ₂ ) ₉ COO (CH ₂ CH ₂ ) ₂ , C ₄ F ₉ COOCH ₂ CH ₂ , C ₆ F ₁₃ COOCH ₂ CH ₂ , C ₈ F ₁₇ COOCH ₂ CH ₂ , C ₁₀ F ₂₁ COOCH ₂ CH ₂ , and R ^{1 to} R ³ may be the same or different. Absent.

The 1,3,5-triazine derivative represented by the above formula has a sulfur-containing group as a substituent at any two of the 2, 4, 6 positions, and a nitrogen-containing group as any one of the substituents. Have. The sulfur atom of the above substituent is directly bonded to any carbon atom at the 2, 4, 6 position. R ¹ , R ² , R ⁶ , and R ⁷ in the above formula are, for example, R ¹ , R ² , R ¹ , R ² of the 1,3,5-triazine derivative having a substituent containing sulfur at the 2,4,6 positions as described above. It includes the same groups as R ^3. In the above formula, R ¹ , R ² , R ⁶ and R ⁷ may be the same or different.
Examples of the triazine dithiol represented by the above formula include 1,3,5-triazine-2,4-dithiol having a substituent at the 6-position, and 1,3,5-triazine-4,6 having a substituent at the 2-position. -Dithiol is preferred.

The 1,3,5-triazine derivative represented by the above formula has a sulfur-containing group at any one of the 2, 4, and 6 positions as a substituent, and a nitrogen-containing group at any two of the substituents. Have. The sulfur atom of the above substituent is directly bonded to any carbon atom at the 2, 4, 6 position. R ¹ , R ^{4 to} R ⁷ in the above formula are, for example, R ¹ , R ² , R ^{3 of the} 1,3,5-triazine derivative having a substituent containing sulfur at the 2,4,6 positions as described above. The same groups are mentioned. In the above formula, R ¹ and R ^{4 to} R ⁷ may be the same or different.

  The 1,3,5-triazine derivative has a sulfur-containing group as a substituent in at least one of the 2,4,6 positions, and the sulfur atom of the sulfur-containing group is any of the 2,4,6 positions. Bonding directly to such carbon atoms is preferred.

The 1,3,5-triazine derivative is a triazine dithiol having a sulfur-containing group as a substituent at any two of the 2,4,6 positions, or a group containing sulfur at all of the 2,4,6 positions. Is a triazine trithiol (thiocyanuric acid) in which all of R ¹ , R ² , and R ³ are H, and more preferably triazine trithiol.

[Second organic layer]
The second organic layer for improving the gas barrier property includes a triazine derivative having a group containing oxygen and / or nitrogen as a substituent at at least one of the 2,4,6 positions of the 1,3,5-triazine derivative. It is out. Further, a dimer of this triazine derivative or a bicyclic or tricyclic condensate is used alone or at least one of the 2,4,6 positions of the 1,3,5-triazine derivative as oxygen and / or nitrogen. As a mixture with a triazine derivative having a group containing as a substituent. When such an organic layer is used, gas barrier properties are improved when combined with an inorganic layer. The 1,3,5-triazine derivatives and their condensates used in the second organic layer of the present invention are represented by the following 18 formulas.

The 1,3,5-triazine derivative represented by the above formula has a nitrogen-containing group as a substituent at any one of the 2, 4, and 6 positions, and the nitrogen atom of the substituent is 2, 4, 6 Directly attached to any carbon atom in the position. R ¹ and R ² in the above formula are, for example, the same groups as R ¹ , R ² and R ^{3 of the} 1,3,5-triazine derivative having a substituent containing sulfur at the 2,4,6 positions as described above. Can be mentioned. In the above formula, R ¹ and R ² may be the same or different.

The 1,3,5-triazine derivative represented by the above formula has a nitrogen-containing group as a substituent at any two of the 2, 4, and 6 positions, and the nitrogen atom of the substituent is 2, 4, 6 Directly attached to any carbon atom in the position. R ¹ , R ² , R ³ , and R ⁴ in the above formula are, for example, R ¹ , R ² , R ¹ , R ² of the 1,3,5-triazine derivative having a substituent containing sulfur at the 2,4,6 positions as described above. It includes the same groups as R ^3. In the above formula, R ¹ , R ² , R ³ and R ⁴ may be the same or different.

The 1,3,5-triazine derivative represented by the above formula has a group containing nitrogen at the 2,4,6 position as a substituent, and the nitrogen atom of the above substituent is a carbon atom at the 2,4,6 position. Directly coupled. R ^{1 to} R ⁶ in the above formula are, for example, the same groups as R ¹ , R ² , and R ^{3 of the} 1,3,5-triazine derivative having a substituent containing sulfur at the 2,4,6 positions. Can be mentioned. In the above formula, R ^{1 to} R ⁶ may be the same or different.

The 1,3,5-triazine derivative represented by the above formula has a group containing oxygen at any one of the 2, 4, 6 positions as a substituent, and the oxygen atom of the substituent has 2, 4, 6 Directly attached to any carbon atom in the position. R ¹ in the above formula includes, for example, the same groups as R ¹ , R ² and R ^{3 of the} 1,3,5-triazine derivative having a substituent containing sulfur at the 2,4,6 positions.

The 1,3,5-triazine derivative represented by the above formula has a group containing oxygen at any two of the 2, 4, 6 positions as a substituent, and the oxygen atom of the substituent is 2, 4, 6 It is directly bonded to any two carbon atoms. R ¹ and R ³ in the above formula are, for example, the same groups as R ¹ , R ² and R ^{3 of the} 1,3,5-triazine derivative having a substituent containing sulfur at the 2,4,6 positions as described above. Can be mentioned. In the above formula, R ¹ and R ³ may be the same or different.

The 1,3,5-triazine derivative represented by the above formula has a group containing oxygen at the 2,4,6 position as a substituent, and the oxygen atom of the above substituent is a carbon atom at the 2,4,6 position. Directly coupled. R ¹ , R ³ , R ⁵ in the above formula are, for example, R ¹ , R ² , R ^{3 of the} 1,3,5-triazine derivative having a substituent containing sulfur at the 2,4,6 positions as described above. The same groups are mentioned. In the above formula, R ¹ , R ³ and R ⁵ may be the same or different.

The 1,3,5-triazine derivative represented by the above formula has as a substituent a group containing one each of oxygen and nitrogen at any two of the 2, 4 and 6 positions. The atom is directly bonded to any carbon atom in the 2, 4, 6 position. R ^1, R ^2, R ³ in the above formulas, for example, the R ^1, R ^2, R ³ of 1,3,5-triazine derivatives having a substituent containing a sulfur 2,4,6-position described above The same groups are mentioned. In the above formula, R ¹ , R ² and R ³ may be the same or different.

The 1,3,5-triazine derivative represented by the above formula has two substituents containing oxygen and one substituent containing nitrogen at any of the 2, 4 and 6 positions. The nitrogen atom is directly bonded to the carbon atoms at the 2, 4, and 6 positions. R ¹ , R ² , R ³ , R ⁵ in the above formula are, for example, R ¹ , R ² , R ¹ , R ² , It includes the same groups as R ^3. In the above formula, R ¹ , R ² , R ³ and R ⁵ may be the same or different.

The 1,3,5-triazine derivative represented by the above formula has one substituent containing oxygen at any of the 2, 4 and 6 positions and two substituents containing nitrogen. The nitrogen atom is directly bonded to the carbon atoms at the 2, 4, and 6 positions. R ^{1 to} R ⁵ in the above formula are, for example, the same groups as R ¹ , R ² and R ^{3 of the} 1,3,5-triazine derivative having a substituent containing sulfur at the 2,4,6 positions as described above. Can be mentioned. In the above formula, R ^{1 to} R ⁵ may be the same or different.

[Dimer]
In the second organic layer of the present invention, a 1,3,5-triazine derivative having as a substituent a group containing oxygen and / or nitrogen at at least one of the 2,4,6 positions shown in the above formulas Of the dimer may be contained.

[Condensate]
In the second organic layer of the present invention, a 1,3,5-triazine derivative having as a substituent a group containing oxygen and / or nitrogen at at least one of the 2,4,6 positions shown in the above formulas (See the following formulas).

The condensate of the triazine derivative represented by the above formula has a nitrogen-containing group as a substituent at any one of the 2, 5, and 8 positions, and the nitrogen atom of the above substituent has any of the 2, 5, and 8 positions. It is directly bonded to the carbon atom. R ¹ and R ² in the above formula are, for example, the same groups as R ¹ , R ² and R ^{3 of the} 1,3,5-triazine derivative having a substituent containing sulfur at the 2,4,6 positions as described above. Can be mentioned. In the above formula, R ¹ and R ² may be the same or different.

The condensate of the triazine derivative represented by the above formula has a nitrogen-containing group as a substituent at any two of the 2, 5, and 8 positions, and the nitrogen atom of the above substituent has any of the 2, 5, and 8 positions. It is directly bonded to the carbon atom. In the above formula, R ^{1 to} R ⁴ are, for example, the same groups as R ¹ , R ² and R ^{3 of the} 1,3,5-triazine derivative having a substituent containing sulfur at the 2,4,6 positions. Can be mentioned. In the above formula, R ^{1 to} R ⁴ may be the same or different.

The condensate of the triazine derivative represented by the above formula has a nitrogen-containing group at the 2, 5 and 8 positions as a substituent, and the nitrogen atom of the above substituent is directly bonded to the carbon atoms at the 2, 5 and 8 positions. ing. R ^{1 to} R ⁶ in the above formula are, for example, the same groups as R ¹ , R ² , and R ^{3 of the} 1,3,5-triazine derivative having a substituent containing sulfur at the 2,4,6 positions. Can be mentioned. In the above formula, R ^{1 to} R ⁶ may be the same or different. A compound in which R ^{1 to} R ⁶ are all H is referred to as melem (2,5,8-triamino-1,6-diazonia-3,4,7,9,9b-pentaaza-9bH-phenalene).

The condensate of the triazine derivative represented by the above formula has an oxygen-containing group as a substituent at any one of the 2, 5, and 8 positions, and the oxygen atom of the substituent has any of the 2, 5, and 8 positions. It is directly bonded to the carbon atom. R ¹ in the above formula includes, for example, the same groups as R ¹ , R ² and R ^{3 of the} 1,3,5-triazine derivative having a substituent containing sulfur at the 2,4,6 positions.

The condensate of the triazine derivative represented by the above formula has an oxygen-containing group as a substituent at any two of the 2, 5, and 8 positions, and the oxygen atom of the substituent has any of the 2, 5, and 8 positions. Directly bonded to two carbon atoms. R ¹ and R ³ in the above formula are, for example, the same groups as R ¹ , R ² and R ^{3 of the} 1,3,5-triazine derivative having a substituent containing sulfur at the 2,4,6 positions as described above. Can be mentioned. In the above formula, R ¹ and R ³ may be the same or different.

The condensate of the triazine derivative represented by the above formula has a group containing oxygen at the 2, 5, and 8 positions as a substituent, and the oxygen atom of the substituent is directly bonded to the carbon atoms at the 2, 5, and 8 positions. ing. R ¹ , R ³ , R ⁵ in the above formula are, for example, R ¹ , R ² , R ^{3 of the} 1,3,5-triazine derivative having a substituent containing sulfur at the 2,4,6 positions as described above. The same groups are mentioned. In the above formula, R ¹ , R ³ and R ⁵ may be the same or different.

The condensate of the triazine derivative represented by the above formula has one substituent containing oxygen and one substituent containing nitrogen at any of the 2, 5 and 8 positions, and the oxygen and nitrogen atoms of the substituent are It is directly bonded to any of the carbon atoms at the 2, 5 and 8 positions. R ^{1 to} R ³ in the above formula are, for example, the same groups as R ¹ , R ² and R ^{3 of the} 1,3,5-triazine derivative having a substituent containing sulfur at the 2,4,6 positions as described above. Can be mentioned. In the above formula, R ^{1 to} R ³ may be the same or different.

The condensate of the triazine derivative represented by the above formula has two substituents containing oxygen at one of the 2, 5 and 8 positions and one substituent containing nitrogen, and the oxygen and nitrogen atoms of the substituents are , Bonded directly to the 2, 5 and 8 carbon atoms. R ¹ , R ² , R ³ , R ⁵ in the above formula are, for example, R ¹ , R ² , R ¹ , R ² , It includes the same groups as R ^3. In the above formula, R ¹ , R ² , R ³ and R ⁵ may be the same or different.

The condensate of the triazine derivative represented by the above formula has one substituent containing oxygen and two substituents containing nitrogen at any of the 2, 5, and 8 positions, and the oxygen and nitrogen atoms of the substituent are , Bonded directly to the 2, 5 and 8 carbon atoms. R ^{1 to} R ⁵ in the above formula are, for example, the same groups as R ¹ , R ² and R ^{3 of the} 1,3,5-triazine derivative having a substituent containing sulfur at the 2,4,6 positions as described above. Can be mentioned. In the above formula, R ^{1 to} R ⁵ may be the same or different.

  The triazine derivatives having a substituent containing oxygen and / or nitrogen and the condensates thereof are functionalized with melamine, melem, melam, ammelin, ammelide, cyanuric acid, 2-ureidomelamine, melamine cyanurate and a polymerizable group. One or more selected from the group consisting of melamine. Melamine functionalized with a polymerizable group refers to melamine in which a polymerizable group is introduced into a compound by reacting acrylate, epoxy, vinyl ether or the like. By including a triazine derivative having a substituent containing oxygen and / or nitrogen and / or a condensate thereof in the organic layer, gas barrier properties can be exhibited. As the triazine derivative having a substituent containing oxygen and / or nitrogen and / or a condensate thereof, the above-mentioned melem is preferable.

  As the triazine derivative having a substituent containing oxygen and / or nitrogen, a dimer, a bicyclic or a tricyclic condensate, or a mixture thereof can be used.

  The sulfur-containing triazine derivative used in the first organic layer has poor water resistance and solvent resistance. In some cases, the adhesiveness to the adhesive is rather difficult to decrease due to poor solvent resistance, but it has been found that there is a problem that the water vapor barrier property is poor only with the sulfur-containing triazine derivative layer. . In order to improve this, the present inventors have made various studies, and as a result of trial and error, it has been found that an oxygen and / or nitrogen-containing triazine derivative or a condensate thereof may be used.

  The organic layer is a composite of the above two types of materials, but is a layer (first organic layer) composed only of a sulfur-containing 1,3,5-triazine derivative from the surface of the inorganic thin film to the middle. A structure composed of a layer (second organic layer) composed only of oxygen and / or nitrogen-containing triazine derivatives and / or their condensates is preferable.

  The film thickness of the entire organic layer is preferably 1 nm or more. The upper limit of the thickness of the organic layer is preferably 500 nm, more preferably 400 nm.

  The upper limit of the film thickness of the first organic layer is preferably 25 nm, more preferably 10 nm. Moreover, it is preferable that the upper limit of the film thickness of a 2nd organic layer is 500 nm, More preferably, it is 400 nm.

  As a method for laminating the organic layer on the inorganic layer, it is preferable to use a vapor deposition method instead of using an organic polymer resin as a binder resin. When the vapor deposition method is used, the organic polymer resin that may impair the gas barrier property in the organic layer can be reduced, so that the excellent gas barrier property of the organic layer can be sufficiently exhibited.

  When laminating the first organic layer and the second organic layer, it is better not to use a binder resin and to contain 100% by mass of the triazine derivative. This is because a higher order structure such as a crystal structure between the two organic layers is easily maintained.

  As a vapor deposition method, a known method, for example, a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method, or an ion plating method, a chemical vapor deposition method such as PECVD (plasma CVD), or the like is employed. The organic layer is preferably formed by a vacuum deposition method.

The vacuum deposition method is a method in which an organic substance is heated in a vacuum, and a material contained in a crucible is heated and evaporated to be deposited on a plastic film or an inorganic layer. In order to make a vacuum, the inside of the vapor deposition apparatus is evacuated and is preferably reduced to 3.0 × 10 ⁻² Pa, more preferably to 1.0 × 10 ⁻² Pa, more preferably 1.0 It is most preferable to carry out at a high vacuum of ^10-4 Pa or less.

  Resistance heating, high frequency induction heating, electron beam heating, or the like can be employed for heating the organic matter. When vapor-depositing the sulfur-containing 1,3,5-triazine derivative for forming the first organic layer on the surface of the inorganic layer, it is preferably performed at 200 to 400 ° C, and preferably at 250 to 350 ° C. Is more preferable. On the other hand, when vapor-depositing a triazine derivative having a group containing oxygen and / or nitrogen for forming the second organic layer as a substituent, it is preferably performed at 200 to 500 ° C., preferably at 250 to 450 ° C. Is more preferable. Moreover, it is also possible to introduce oxygen, nitrogen, hydrogen, argon, carbon dioxide gas, water vapor or the like as a reactive gas, or to employ reactive vapor deposition using a stage such as ozone addition or ion assist. Furthermore, thin film formation conditions can be arbitrarily changed, such as applying a bias to the plastic film, heating or cooling the plastic film, and the like.

[Physical properties of laminated film]
Oxygen permeability is preferably not more than 25 ml / m ² DMPA, more preferably not more than 17 ml / m ² DMPA, more preferably not more than 15 ml / m ² DMPA, even more preferably 10 ml / m ² DMPA It is as follows.

The water vapor permeability is preferably 1 g / m ² d or less, more preferably 0.7 g / m ² d or less, still more preferably 0.6 g / m ² d or less, and even more preferably 0. 0.5 g / m ² d or less.

  The laminate strength is preferably 0.4 N / 15 mm or more, more preferably 1.0 N / 15 mm or more, still more preferably 1.3 N / 15 mm or more, and even more preferably 2.0 N / 15 mm or more. .

  Methods for measuring oxygen permeability, water vapor permeability, and laminate strength will be described later.

[Other layers]
In addition to the plastic film, the inorganic layer, the first organic layer, and the second organic layer, the laminated film of the present invention can be provided with various layers provided in a known laminated film, if necessary.

  For example, when using a laminated film provided with an inorganic layer and an organic layer as a packaging material, it is preferable to form a heat-sealable resin layer called a sealant. The heat-sealable resin layer is usually formed by an extrusion lamination method or a dry lamination method. The thermoplastic polymer for forming the heat-sealable resin layer is not particularly limited as long as the sealant adhesiveness can be sufficiently exhibited, such as polyethylene resins such as HDPE, LDPE, and LLDPE, polypropylene resin, and ethylene-vinyl acetate. A polymer, an ethylene-α-olefin random copolymer, an ionomer resin, or the like can be used.

  Furthermore, the laminated film of the present invention includes a printed layer or other plastic substrate and / or paper between any two adjacent layers of a plastic film, an inorganic layer, or an organic layer or on the outer side of the outermost layer. At least one layer of the base material may be laminated.

  The printing ink for forming the printing layer may be an aqueous resin-containing printing ink or a solvent-based resin-containing printing ink. Examples of the resin used in the printing ink include acrylic resins, urethane resins, polyester resins, vinyl chloride resins, vinyl acetate copolymer resins, and mixtures thereof. For printing inks, known antistatic agents, light blocking agents, ultraviolet absorbers, plasticizers, lubricants, fillers, colorants, stabilizers, lubricants, antifoaming agents, crosslinking agents, antiblocking agents, antioxidants, etc. These additives may be included. The printing method for providing the printing layer is not particularly limited, and a known printing method such as an offset printing method, a gravure printing method, a screen printing method, or the like can be used. For drying the solvent after printing, known drying methods such as hot air drying, hot roll drying and infrared drying can be used.

  On the other hand, as other plastic substrates and paper substrates, paper, polyester resin, polyamide resin, biodegradable resin, and the like are preferably used from the viewpoint of obtaining sufficient rigidity and strength of the laminate. Moreover, when setting it as the film excellent in mechanical strength, stretched films, such as a biaxially stretched polyester film and a biaxially stretched nylon film, are preferable.

  This application claims the benefit of priority based on Japanese Patent Application No. 2014-158176 filed on Aug. 1, 2014. The entire contents of the specification of Japanese Patent Application No. 2014-158176 filed on August 1, 2014 are incorporated herein by reference.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples, and may be appropriately modified and implemented within a range that can meet the purpose described above and below. All of which are within the scope of the present invention.

  The evaluation methods and physical property measurement methods for the test materials obtained in the examples and comparative examples are as follows.

(1) Oxygen permeability evaluation method For the test material, an oxygen permeability measuring device ("OX-TRAN 2/21" manufactured by MOCON Co., Ltd.) was used in accordance with the electrolytic sensor method (B method: isobaric method) of JIS-K7126-2. )), And the oxygen permeability in a normal state was measured in an atmosphere of a temperature of 23 ° C. and a humidity of 65% RH. The oxygen permeability was measured in the direction in which oxygen permeates from the organic layer side to the plastic film side.

(2) Evaluation method of water vapor transmission rate About the test material, according to the infrared sensor method of JIS-K7129-2008, using a water vapor transmission measuring device ("PERMA-TRAN 2/21" manufactured by MOCON), the temperature Under an atmosphere of 40 ° C. and humidity 90% RH, the water vapor permeability in a normal state was measured. In addition, the water vapor permeability was measured in a direction in which water vapor permeates from the organic layer side to the plastic film side.

(3) Preparation of laminate laminate for evaluation On the test material, urethane-based two-component curable adhesive ("Takelac (registered trademark) A525S", "Takenate (registered trademark) A50" manufactured by Mitsui Chemicals, Inc.) and ethyl acetate (Made by Nacalai Tesque) at a ratio of 13.5: 1: 8.2 (mass ratio) was applied using a wire bar # 5 to a film thickness of about 4 μm, and then applied to an oven at 60 ° C. For 30 seconds to evaporate the solvent. Thereafter, an unstretched polypropylene film (“Pyrene (registered trademark) film P1146” manufactured by Toyobo Co., Ltd.) having a film thickness of 70 μm is pasted together by dry laminating method and seasoned at 40 ° C. for 3 days to obtain a laminate for evaluation. A gas barrier laminate (hereinafter sometimes referred to as “laminate laminate”) was obtained.

(4) Laminate Strength Evaluation Method The laminate laminate produced in (3) above was cut into a width of 15 mm and a length of 200 mm to form a test piece, and a Tensilon universal material testing machine under the conditions of a temperature of 23 ° C. and a relative humidity of 65%. The laminate strength was measured using “Tensilon UMT-II-500 type” manufactured by Toyo Baldwin. The laminate strength was the maximum strength when peeling was performed at a peeling angle of 90 degrees in a normal state with a tensile speed of 200 mm / min.

  FIG. 1 is a schematic view of a vapor deposition apparatus for producing the laminated film of the present invention, but is not limited to this apparatus.

  In FIG. 1, 1 is a film having an inorganic layer fed from a substrate (film), specifically, a take-up roll. Reference numeral 2 denotes a roll for supporting the film 1, and the film 1 travels along the rolls 3 and 3 '. Or you may fix the sheet | seat film of a specific magnitude | size to a metal fitting. The crucible 4 is for holding the sulfur-containing triazine derivative 5, and the sulfur-containing triazine derivative vaporized by heating is deposited on the inorganic layer provided in the film. Next, from the crucible 4 ′, oxygen and / or nitrogen-containing triazine derivative 5 ′ is deposited on the layer (first organic layer) of the sulfur-containing triazine derivative 5 to form a second organic layer.

The apparatus of FIG. 1 is housed in a vacuum chamber (not shown) capable of producing a vacuum of 1.0 × 10 ⁻⁵ Pa. At this time, it is also possible to prepare a laminated film according to the present invention using a film having an inorganic layer deposited on the film and using a film that does not have an inorganic layer. Can be made.

Example 1
First, a polyester film (“EcoSear (registered trademark) VE100” manufactured by Toyobo Co., Ltd., film thickness 12 μm; indicated as VE100 in the table) on which ceramic (alumina / silica = 40/60; mass ratio) has been deposited is shown in FIG. 5 g of triazine trithiol (manufactured by Tokyo Chemical Industry Co., Ltd.) was filled in the crucible 4. Further, 15 g of melem (Delamine) was filled in the adjacent crucible 4 '. In addition, the polyester film which gave vapor deposition of ceramic (alumina / silica) can be manufactured by the method of Unexamined-Japanese-Patent No. 2013-014126, for example.

Next, the inside of the vapor deposition apparatus was evacuated and reduced to 5.0 × 10 ⁻⁵ Pa, and then heated at 180 ° C. for 60 minutes to remove moisture and impurities. Thereafter, the crucible 4 containing triazine trithiol was heated to 250 ° C. and deposited on the surface of the polyester film on which the ceramic was deposited to a thickness of 10 nm. Next, the melem side crucible 4 ′ was heated to 450 ° C., and the melem was deposited on the surface on which the ceramic / triazine trithiol was deposited to a thickness of 50 nm. Table 1 shows the physical property evaluation results of the obtained laminated film.

(Example 2)
A 12 μm polyethylene terephthalate film (“E5100” manufactured by Toyobo Co., Ltd.) was used as the plastic film. These composite inorganic compound thin films were formed on the surface of the PET film by vapor deposition using aluminum oxide and magnesium oxide as raw materials for vapor deposition. Specifically, using a single electron gun, aluminum oxide and magnesium oxide are irradiated with an electron beam in a time-sharing manner and heated to evaporate these deposition materials and deposit an inorganic compound thin film. It was. The film thickness and composition of the inorganic compound thin film composed of aluminum oxide and magnesium oxide were adjusted by adjusting the output of the electron beam and the irradiation time for each vapor deposition raw material. Basically, the film feed rate was 95 m / min, the emission current of the electron gun was 1.2 A, and the irradiation time of the electron beam was time-divided at a ratio of magnesium oxide 2 to aluminum oxide 13. The pressure during the vapor deposition of the inorganic compound thin film was 2.5 × 10 ⁻¹ Pa or less. The thickness of the obtained inorganic compound thin film was 13 nm.

In Example 1, instead of “Ecosiale (registered trademark) VE100”, the above-mentioned vapor-deposited film (shown as PET / MgO / Al ₂ O _{3 in} Table 1) was used, and the film thickness of triazine trithiol was 5 nm. A laminated film was obtained in the same manner as in Example 1 except that the film thickness was changed to 200 nm. Table 1 shows the physical property evaluation results of the obtained laminated film.

(Example 3)
In Example 2, a laminated film was obtained in the same manner as in Example 2 except that the film thickness of melem was changed to 100 nm. Table 1 shows the physical property evaluation results of the obtained laminated film.

Example 4
In Example 2, a laminated film was obtained in the same manner as in Example 2 except that the film thickness of melem was changed to 75 nm. Table 1 shows the physical property evaluation results of the obtained laminated film.

(Example 5)
In Example 2, a laminated film was obtained in the same manner as in Example 2 except that the film thickness of melem was changed to 50 nm. Table 1 shows the physical property evaluation results of the obtained laminated film.

(Example 6)
In Example 2, a laminated film was obtained in the same manner as in Example 2 except that the film thickness of triazine trithiol was changed to 1 nm and the film thickness of melem was changed to 53 nm. Table 1 shows the physical property evaluation results of the obtained laminated film.

(Example 7)
In Example 2, a laminated film was obtained in the same manner as in Example 2 except that the film thickness of triazine trithiol was changed to 2 nm and the film thickness of melem was changed to 70 nm. Table 1 shows the physical property evaluation results of the obtained laminated film.

(Example 8)
In Example 2, a laminated film was obtained in the same manner as in Example 2 except that the film thickness of triazine trithiol was changed to 3 nm and the film thickness of melem was changed to 81 nm. Table 1 shows the physical property evaluation results of the obtained laminated film.

Example 9
In Example 2, a laminated film was obtained in the same manner as in Example 2 except that the film thickness of triazine trithiol was changed to 4 nm and the film thickness of melem was changed to 150 nm. Table 1 shows the physical property evaluation results of the obtained laminated film.

(Example 10)
In Example 2, a laminated film was obtained in the same manner as in Example 2 except that the film thickness of triazine trithiol was changed to 5 nm and the film thickness of melem was changed to 151 nm. Table 1 shows the physical property evaluation results of the obtained laminated film.

(Comparative Example 1)
In Example 1, the deposition raw material was changed to only melamine (manufactured by Wako Pure Chemical Industries, Ltd.), heated to 250 ° C., and melamine was deposited on the surface of the polyester film (VE100) on which the ceramic was deposited, A laminated film was obtained in the same manner as in Example 1 except that the film thickness of the organic layer was changed to 118 nm. Table 1 shows the physical property evaluation results of the obtained laminated film.

(Comparative Example 2)
In Example 1, the deposition raw material was changed to only melamine (manufactured by Wako Pure Chemical Industries, Ltd.), heated to 250 ° C., and melamine was deposited on the surface of the polyester film (VE100) on which the ceramic was deposited, A laminated film was obtained in the same manner as in Example 1 except that the thickness of the organic layer was changed to 59 nm. Table 1 shows the physical property evaluation results of the obtained laminated film.

(Comparative Example 3)
In Example 1, a polyethylene terephthalate film (“Cosmo Shine (registered trademark) A4100” manufactured by Toyobo Co., Ltd., film thickness 50 μm; indicated as PET A4100 in the table) was used instead of triazine trithiol. -Amino-1,3,5-triazine-4,6-dithiol (manufactured by Alfa Aesars, part number B20510), the amount thereof was adjusted to change the film thickness of the first organic layer to 109 nm, and the above PET A laminated film was obtained in the same manner as in Example 1 except that the film was laminated on the surface of A4100 and the second organic layer was not laminated. Table 1 shows the physical property evaluation results of the obtained laminated film.

(Comparative Example 4)
Example 1 Example 1 except that the PET A4100 was used, the amount of triazine trithiol was adjusted to change the thickness of the first organic layer to 100 nm, and the second organic layer was not laminated. In the same manner, a laminated film was obtained. Table 1 shows the physical property evaluation results of the obtained laminated film.

(Comparative Example 5)
In Example 1, the deposition raw material was changed to only 2-amino-1,3,5-triazine-4,6-dithiol, heated to 250 ° C., and 2-amino-1,3,5-triazine-4. , 6-dithiol is deposited on the surface of the polyester film ("VE100") on which the ceramic is deposited, the thickness of the first organic layer is changed to 200 nm, and the second organic layer is not laminated. A laminated film was obtained in the same manner as in Example 1 except that. Table 1 shows the physical property evaluation results of the obtained laminated film.

(Comparative Example 6)
In Example 1, the vapor deposition raw material was changed to only triazine trithiol, heated to 250 ° C., and triazine trithiol was vapor-deposited on the surface of the polyester film (“VE100”) on which the ceramic was vapor-deposited. A laminated film was obtained in the same manner as in Example 1 except that the thickness of the layer was changed to 200 nm and the second organic layer was not laminated. Table 1 shows the physical property evaluation results of the obtained laminated film.

(Comparative Example 7)
In Example 1, the above PET A4100 was used, the amount of melem was adjusted, the film thickness of the organic layer was changed to 100 nm, and the inorganic layer and the first organic layer were not formed. Thus, a laminated film was obtained. Table 1 shows the physical property evaluation results of the obtained laminated film.

(Comparative Example 8)
In Example 2, the vapor deposition material was changed to melem, the amount of melem was adjusted, the thickness of the organic layer was changed to 37 nm, and the inorganic layer and the first organic layer were not formed. A laminated film was obtained in the same manner. Table 1 shows the physical property evaluation results of the obtained laminated film.

(Comparative Example 9)
Evaluation was performed in a state where neither the first organic layer nor the second organic layer was provided on the polyester film used in Example 1 (the “VE100”). The physical property evaluation results are shown in Table 1.

(Comparative Example 10)
Evaluation was performed in a state where neither the first organic layer nor the second organic layer was provided on the PET / MgO / Al ₂ O ₃ used in Example 2. The physical property evaluation results are shown in Table 1.

(Comparative Example 11)
Evaluation was performed in a state where neither the first organic layer nor the second organic layer was provided in PET A4100 used in Comparative Example 3. The physical property evaluation results are shown in Table 1.

  The laminated film according to the present invention was able to exhibit both adhesion and gas barrier properties even when an inorganic layer and an organic layer were laminated on a plastic film. Therefore, the laminated film according to the present invention can be widely used not only for packaging applications such as foods, pharmaceuticals, and industrial products, but also for industrial applications such as solar cells, electronic paper, organic EL elements, and semiconductor elements.

1 Film 2 Roll 3, 3 'Roll 4, 4' Crucible 5 Sulfur-containing triazine derivative 5 'Oxygen and / or nitrogen-containing triazine derivative

Claims (6)

  A laminated film in which an inorganic layer, a first organic layer, and a second organic layer are provided on at least one surface of a plastic film in this order with or without other layers. The organic layer includes a 1,3,5-triazine derivative having a sulfur-containing group as a substituent in at least one of the 2, 4, and 6 positions, and the second organic layer includes at least one of the 2, 4, and 6 positions. 1. A laminated film comprising a 1,3,5-triazine derivative having a group containing oxygen and / or nitrogen as a substituent and / or a condensate thereof.   The laminated film according to claim 1, wherein the 1,3,5-triazine derivative contained in the first organic layer is triazine trithiol or triazine dithiol.   The laminated film according to claim 1 or 2, wherein the 1,3,5-triazine derivative contained in the first organic layer is triazine trithiol.   1,3,5-triazine derivatives and / or condensates thereof contained in the second organic layer are melamine, melem, melam, ammelin, ammelide, cyanuric acid, 2-ureidomelamine, melamine cyanurate, and polymerizable The laminated film according to any one of claims 1 to 3, which is at least one selected from the group consisting of melamine functionalized with a group.   The laminated film according to claim 4, wherein the condensate of the triazine derivative contained in the second organic layer is melem.   The laminated film according to any one of claims 1 to 5, wherein the inorganic layer, the first organic layer, and the second organic layer are formed by a vacuum deposition method.