JP6547241B2 - Gas barrier laminated film - Google Patents

Description

  The present invention is a transparent gas barrier laminate suitably used when particularly high gas barrier properties are required in the fields of packaging of food products, daily necessities, pharmaceutical products etc., solar battery related members, electronic equipment related members etc. It is about a film.

Packaging materials used for packaging of food products, daily necessities, medicines, etc. suppress the deterioration of the contents and can retain their functions and properties even during packaging, so oxygen, water vapor, etc. which permeate the packaging material, etc. It is necessary to prevent the influence of the gas that degrades the contents, and it is required to have a gas barrier property that blocks these gases.
As a packaging material having normal gas barrier properties, a vinylidene chloride resin film or a film coated with a vinylidene chloride resin, which is relatively excellent in gas barrier properties, etc. has often been used, but these packaging materials have high gas barrier properties. Can not be used for packaging where Therefore, when high gas barrier properties are required, a packaging material in which a metal foil such as aluminum is laminated as a gas barrier layer has to be used. The packaging material which laminated metal foils, such as aluminum, hardly has the influence of temperature or humidity, and has high gas barrier property. However, such packaging materials have many drawbacks, such as the inability to see through the container to confirm the contents, to dispose of them as non-combustibles after use, to use a metal detector for inspection of the contents, etc. Had.

As a packaging material that overcomes these drawbacks, Patent Document 1 discloses that a vapor deposited thin film layer of an inorganic oxide such as transparent silicon oxide, aluminum oxide, or magnesium oxide is used as a gas barrier layer in a substrate layer made of a transparent plastic film. There is disclosed a laminated film formed by laminating an appropriate gas barrier coating layer thereon.
On the other hand, in recent years, the solar cell market has been rapidly expanding while the concern for the global warming problem has been increasing. As a structure of a solar cell, a single solar cell element is not used as it is, but in general, several to several tens of elements are connected in series and in parallel to protect the elements for a long time Is done and unitized. The unit incorporated in this package is called a solar cell module, and generally covers the surface exposed to sunlight with glass, fills the gaps with a filler made of thermoplastic plastic, and is made of heat resistant, weather resistant plastic material etc. It has a sheet protected configuration.

Since these solar cell modules are used outdoors, sufficient durability and weather resistance are required in the materials used and their configurations. In particular, the back protective sheet is required to have high gas barrier properties as well as weather resistance. This is because the filler in the unit peels off due to moisture permeation, causing corrosion of the wiring and adversely affecting the output of the module itself.
Conventionally, as this back surface protection sheet for solar cells, a laminated structure in which an aluminum foil is sandwiched from both sides by a white fluorine-based film has been often used. However, since this fluorine-based film has a weak mechanical strength, there is a disadvantage that the solar cell element and the aluminum foil short-circuit to adversely affect the cell performance, and the price is high. It is one obstacle. In order to ameliorate these problems, there is an increasing demand for a gas barrier film having weather resistance and high gas barrier properties without using an aluminum foil.

In addition, development is also underway to make this solar cell module flexible, and in order to achieve this, it is also necessary to replace the glass substrate on the surface that receives sunlight with a sheet made of a plastic material or the like. Similar to the back surface protective sheet, weather resistance and high gas barrier properties are required.
Also, in recent years, with the development of electronic paper, organic EL, etc. expected as the next-generation flat panel display (FPD), there is a demand to replace the glass substrate with a plastic film in order to achieve flexibility of these FPDs. It is rising. The glass substrate has a gas barrier property required to suppress deterioration of the internal element due to oxygen and water vapor from the environment. However, the above-mentioned gas barrier film for packaging materials has not reached its barrier level, and in electronic paper, organic EL, etc. to which a plastic film can be applied, a gas barrier of 100 to 10,000 times the barrier film for food packaging materials. It is also said that sex is necessary.

In order to realize a plastic film having such high gas barrier properties, dry coating methods such as reactive deposition method using electron beam deposition or induction heating deposition, sputtering method, plasma CVD method (chemical vapor deposition method), etc. The inorganic oxide thin film formed into a film is considered as what can anticipate the expression of high gas barrier property.
Among them, a silicon oxide thin film formed by plasma CVD using an organosilane compound is considered as a barrier layer exhibiting high gas barrier properties, and is put to practical use in the food packaging field. Patent Document 2 reports that adhesion and transparency are improved by controlling the carbon concentration and the composition of the silicon oxide thin film.

Japanese Patent Application Laid-Open No. 7-164591 Unexamined-Japanese-Patent No. 11-322981

However, the laminated film described in Patent Document 1 does not require gas barrier properties such as oxygen permeability and water vapor permeability when performing ordinary processing as a packaging material, such as printing, laminating, bag-making, etc. The
In addition, even if the above dry coating method is used to obtain a plastic film having high gas barrier properties, a high temperature process is required or fineness is required to obtain a dense film to achieve high gas barrier properties. Therefore, the stress in the film tends to increase. Therefore, it is difficult to obtain a dense film in the usable temperature range of the plastic film, or a problem such as adhesion failure or cracking occurs because the difference in thermal expansion coefficient between the plastic film and the inorganic oxide thin film is large. And the expression of high gas barrier properties is not easy.

In addition, the transparent barrier film described in Patent Document 2 is not required to have high water vapor barrier properties, and was not assumed for FPDs such as electronic paper and organic EL that require high gas barrier properties.
Therefore, the object of the present invention is to secure the gas barrier property sufficiently and to be excellent in oxygen barrier property and water vapor barrier property as a back surface protection sheet and a surface protection sheet of a solar cell module, and for FPD such as electronic paper and organic EL. An object of the present invention is to provide a transparent gas barrier laminate film.

  In order to solve the above problems, the gas barrier laminate film according to one aspect of the present invention comprises a transparent primer layer and a transparent first gas barrier layer on one surface of a substrate layer made of a transparent plastic film. A transparent intermediate layer and a transparent second gas barrier layer are laminated in this order. Each of the primer layer and the intermediate layer is made of silicon oxide represented by SiOxCy. x is 1.5 or more and 2.0 or less. y is 0.1 or more and 0.5 or less. The thickness of the primer layer is 5 nm or more and 50 nm or less. The arithmetic mean roughness of the surface of the primer layer is 2 nm or less. The thickness of the intermediate layer is 20 nm or more and 200 nm or less. Each of the first gas barrier layer and the second gas barrier layer is made of an inorganic oxide. The thickness of the first gas barrier layer and the second gas barrier layer is 3 nm or more and 30 nm or less.

For example, the intermediate layer is formed between the first gas barrier layer and the second gas barrier layer by plasma CVD (chemical vapor deposition). The primer layer is formed between the base material layer and the first gas barrier layer by plasma CVD. Each of the first gas barrier layer and the second gas barrier layer is made of any of silicon oxide, aluminum oxide, titanium oxide or magnesium oxide.
Further, the water vapor transmission rate X of the gas barrier laminate film under a 40 ° C. 90% RH environment is 0.1 g / m ² · day or less. The water vapor transmission rate Y under the environment of 85 ° C. and 85% RH of the gas barrier laminate film is 1.0 g / m ² · day or less. The relationship between X and Y satisfies the equation Y / X ≦ 10.

  The gas barrier laminate film according to one aspect of the present invention sufficiently secures the gas barrier property and transparency, and is excellent in oxygen barrier property and water vapor barrier property, so the back surface protection sheet or surface protection sheet of the solar cell module For FPDs such as paper and organic EL, it can be suitably used particularly when high gas barrier properties and transparency are required.

It is sectional drawing of an example of the gas-barrier laminated film which concerns on one Embodiment of this invention.

Embodiment
Hereinafter, an embodiment of the present invention will be described with reference to the attached drawings.
As shown in FIG. 1, in the gas barrier laminate film according to the present embodiment, the primer layer 2, the first gas barrier layer 3, the intermediate layer 4, and the second layer are formed on one surface of the base material layer 1. The gas barrier layer 5 is sequentially laminated in the thickness direction, and the primer layer 2 and the intermediate layer 4 are made of silicon oxide represented by SiOxCy. Here, x is 1.5 or more and 2.0 or less. Moreover, y is 0.1 or more and 0.5 or less.

  In the gas barrier laminate film according to the present embodiment, the base material layer 1 is made of a transparent plastic film. Examples of transparent plastic films 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, polyvinyl chloride Films, polycarbonate films, polyacrylonitrile films, polyimide films, biodegradable plastic films such as polylactic acid, and the like are considered.

  These transparent plastic films may be either stretched or unstretched, but those having excellent mechanical strength and dimensional stability are preferred. In particular, in view of heat resistance, dimensional stability, etc., biaxially stretched polyethylene terephthalate is preferably used. The transparent plastic film may also contain additives such as an antistatic agent, an ultraviolet light inhibitor, a plasticizer, and a lubricant. Furthermore, in the case of a transparent plastic film, the surface on which the other layer is laminated may be subjected to corona treatment, low temperature plasma treatment, ion bombardment treatment, chemical treatment, solvent treatment, etc. in order to improve adhesion. .

  The thickness of the base material layer 1 made of these transparent plastic films is not particularly limited, but considering the suitability as a packaging material and the processability in laminating other layers, it is practically practical. Is preferably in the range of 6 μm to 100 μm, and more preferably in the range of 9 μm to 25 μm. In addition, the thickness of the base material layer 1 is not particularly limited even when it is used as a surface protection sheet or back surface protection sheet of a solar cell, and further, in an electronic paper, an organic EL, etc. In consideration of the processing suitability and the like in the post-process of the gas barrier laminate film according to the present invention, practically it is desirable to be in the range of 12 μm to 200 μm, particularly in the range of 12 μm to 125 μm.

  In the gas barrier laminate film according to the present embodiment, the role of the primer layer 2 is to obtain stable high adhesion between the base material layer 1 and the first gas barrier layer 3, and the first gas barrier layer 3. And improving the gas barrier properties of the second gas barrier layer 5. And especially the smoothness of the surface of primer layer 2 which laminates the 1st gas barrier layer 3 is one of the important characteristics for expressing high gas barrier property. This is because as the surface of the primer layer 2 is smoother, a more precise gas barrier layer can be formed from the vicinity of the surface, and a uniform film thickness can be easily obtained. Generally, it is considered that the arithmetic mean roughness Ra indicating the smoothness of the surface is 5 nm or less as a necessary condition for expressing high gas barrier properties. However, in the gas barrier laminate film according to the present embodiment, as described later, the thickness of each of the first gas barrier layer 3 and the second gas barrier layer 5 is reduced to 3 nm or more and 30 nm or less in consideration of productivity. It is a feature that Therefore, more surface smoothness is required than the arithmetic mean roughness of 5 nm or less described above. Specifically, in the gas barrier laminate film according to the present embodiment, the arithmetic average roughness Ra needs to be 2 nm or less.

  In the gas barrier laminate film according to the present embodiment, the primer layer 2 is made of silicon oxide represented by SiOxCy. Here, x is 1.5 or more and 2.0 or less. Moreover, y is 0.1 or more and 0.5 or less. By controlling the content of the contained carbon component, it is possible to express both the adhesion as the primer layer 2 and the smoothness of the surface. That is, the softness | flexibility as the primer layer 2 runs short as said y value which shows content of a carbon component is less than 0.1, and adhesiveness falls. When the y value exceeds 0.5, the flexibility as the primer layer 2 is high, but a dense film can not be obtained, and the surface smoothness is reduced. Therefore, the y value needs to be 0.1 or more and 0.5 or less, and controlling this y value is one of the important points in the gas barrier laminate film according to the present embodiment.

  In the gas barrier laminate film according to the present embodiment, the method for forming the primer layer 2 is not particularly limited, but as described above, the y value of the primer layer 2 represented by SiOxCy is 0.1 or more and 0.1 or more. At the present time, the plasma CVD method (chemical vapor deposition method) is preferable in order to set it to 5 or less. Further, as a plasma generation device, a low temperature plasma generation device such as direct current (DC) plasma, low frequency plasma, high frequency plasma, pulse wave plasma, triode structure plasma, microwave plasma and the like can be considered.

  The thickness of the primer layer 2 is 5 nm or more and 50 nm or less. Here, if the film thickness is less than 5 nm, it is difficult to obtain surface smoothness which is a role as the primer layer 2 formed between the base material layer 1 and the first gas barrier layer 3. On the other hand, when the film thickness exceeds 50 nm, it is difficult to maintain flexibility (flexibility) in the primer layer, and when an external stress such as bending or tension is applied, a crack may occur in the deposited thin film layer.

  The primer layer 2 made of silicon oxide laminated by plasma CVD can be formed into a film by using a silane compound having carbon in the molecule and oxygen gas as a raw material, and an inert gas is added to the raw material to form a film. You can also. Examples of silane compounds having carbon in the molecule include tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), tetramethylsilane (TMS), hexamethyldisiloxane (HMDSO), tetramethyldisiloxane, methyltrimethoxy Relatively low molecular weight silane compounds such as silanes are contemplated. One or more (at least one) of these silane compounds may be selected. Among these silane compounds, TEOS, TMOS, TMS, HMDSO and the like are particularly preferable in consideration of the film forming pressure and the vapor pressure.

  In the film formation by the plasma CVD method, a silane compound is vaporized and mixed with oxygen gas is introduced between the electrodes, power is applied by a low-temperature plasma generator to convert it into plasma, and it is laminated on the surface of the substrate layer 1 be able to. Further, in the plasma CVD method, it is possible to change the film quality of the primer layer 2 made of silicon oxide by various methods. For example, change of silane compound or gas type, mixing ratio of silane compound and oxygen gas, increase / decrease of applied electric power, etc. can be considered.

  In the gas barrier laminate film according to the present embodiment, each of the first gas barrier layer 3 and the second gas barrier layer 5 is made of an inorganic oxide, and the formation method thereof is not particularly limited. In order for the first gas barrier layer 3 and the second gas barrier layer 5 made of the above to exhibit high gas barrier properties, vacuum film formation capable of forming the gas barrier layer in vacuum is suitable. Among them, the vacuum evaporation method is the best when laminating at a higher speed.

  In the vacuum evaporation method at present, as a heating means of the evaporation source material in the vacuum evaporation apparatus, an electron beam heating method, a resistance heating method, an induction heating method or the like is preferable. Further, in order to improve the adhesion to the primer layer 2, it is also possible to use a plasma assist method, an ion beam assist method or the like. Furthermore, in order to improve transparency, you may blow in oxygen gas etc. and reactive vapor deposition may be performed.

  Further, as a method other than the vacuum deposition method, although the deposition rate for forming the gas barrier layer is not as fast as the vacuum deposition method, the plasma CVD method is preferable as a method which easily exhibits higher gas barrier properties. In addition, as an example of the plasma generator, a low temperature plasma generator such as direct current (DC) plasma, low frequency plasma, high frequency plasma, pulse wave plasma, triode structure plasma, microwave plasma, etc. is used.

  In the gas barrier laminate film according to the present embodiment, each of the first gas barrier layer 3 and the second gas barrier layer 5 is transparent, and the composition is particularly limited as long as it is an inorganic oxide that exhibits gas barrier properties. It is not a thing. At this time, it is desirable to use any composition of silicon oxide, aluminum oxide, titanium oxide, and magnesium oxide as an inorganic oxide that can achieve both transparency and high gas barrier properties against oxygen, water vapor, and the like.

  The thickness of each of the first gas barrier layer 3 and the second gas barrier layer 5 is 3 nm or more and 30 nm or less. In general, the gas barrier properties can be improved by thickening the film thickness of the gas barrier layer, so in the case of a gas barrier laminate film requiring higher gas barrier properties, thickening is one method for improving the gas barrier properties. May be used. However, in consideration of productivity, it is ideal that the film thickness of the gas barrier layer be as thin as possible. In addition, internal stress is generated in the formed gas barrier layer, and the internal stress becomes larger as the film thickness of the gas barrier layer becomes thicker, and a crack which reduces the gas barrier property is easily generated. Furthermore, by increasing the film thickness, it becomes difficult to maintain the flexibility of the gas barrier layer, and when external stress such as bending or pulling is applied, the gas barrier layer may be cracked. From these reasons, the upper limit of the film thickness of each of the first gas barrier layer 3 and the second gas barrier layer 5 is preferably 30 nm or less, although it depends on the method of forming the gas barrier layer and the film composition. With respect to the lower limit of the film thickness, when the film thickness is less than 3 nm, a uniform thin film may not be obtained, and the film can not sufficiently function as a gas barrier material. It is desirable to have.

Further, as a film forming method, continuous film formation by a coiling method is possible by utilizing the characteristics of the base material layer 1 made of plastic, so a coiling type vacuum deposition film forming apparatus or plasma coil CVD filming by coiling method is possible. It is preferred to use a membrane device.
As described above, film thickness formation may be used as one of the methods for improving the barrier properties of the gas barrier layer, but as the film thickness of the gas barrier layer is increased, cracking due to excessive internal stress, or On the contrary, the occurrence of cracks due to the lack of flexibility, etc. tends to cause the deterioration of the gas barrier properties. Therefore, in order to prevent these, it is necessary to form an intermediate layer 4 with high flexibility acting as a buffer layer between the first gas barrier layer 3 and the second gas barrier layer 5. In general, organic thin film layers are generally used rather than inorganic ones in consideration of flexibility. However, the thin film layer of the organic type is significantly inferior to the inorganic type in the gas barrier property in the high temperature region, and is not suitable for applications requiring high gas barrier property even under high temperature environment such as solar cell, electronic paper, organic EL . Therefore, it is one of the important points in the gas barrier laminate film according to the present embodiment that the intermediate layer 4 is made inorganic so that high gas barrier properties can be expressed even under a high temperature environment.

  In the gas barrier laminate film according to the present embodiment, the intermediate layer 4 is made of silicon oxide represented by SiOxCy. Here, x is 1.5 or more and 2.0 or less. Moreover, y is 0.1 or more and 0.5 or less. By controlling the content of the contained carbon component, it becomes possible to express both flexibility and gas barrier property as the intermediate layer 4. That is, when the y value indicating the content of the carbon component is less than 0.1, the flexibility as the intermediate layer is insufficient. When the y value exceeds 0.5, the flexibility as the intermediate layer 4 is high, but a dense film can not be obtained, and the gas barrier properties are lowered. Therefore, the y value needs to be 0.1 or more and 0.5 or less, and controlling this y value is one of the important points in the gas barrier laminate film according to the present embodiment.

And, as an effect of expressing high gas barrier properties in a high temperature region by using the inorganic intermediate layer 4, water vapor permeation in an environment of 40 ° C. 90% RH of a gas barrier laminate film mainly used as an evaluation for packaging materials Degree (X) is 0.1 g / m ² · day or less, and the water vapor transmission rate (Y) of the gas barrier laminate film under 85 ° C 85% RH environment, which is mainly used as an evaluation for solar cells, is 1 It is desirable that the ratio is not more than 0 g / m ² · day, and the relationship between X and Y satisfies the formula of Y / X ≦ 10. For example, although the water vapor transmission rate of the barrier film is high in a high temperature region used in an environmental test of a solar cell, a display, etc., the gas barrier layer according to the present embodiment has a gas barrier layer as a configuration to suppress this even a little. Not only that, the primer layer and the intermediate layer are formed of an inorganic film. As an effect, based on the water vapor transmission rate (X) under the general test conditions (40 ° C. 90% RH) of the conventional packaging barrier film, under the test conditions (85 ° C. 85% RH) for solar cell evaluation It is desirable that the water vapor permeability (Y) of the above be 10 times or less (Y / X ≦ 10).

  In the gas barrier laminate film according to the present embodiment, the method for forming the intermediate layer 4 is not particularly limited, but as described above, the y value of the intermediate layer 4 represented by SiOxCy is 0.1 or more and 0.1 or more. At the present time, the plasma CVD method is preferable in order to make it 5 or less. Further, as a plasma generation device, a low temperature plasma generation device such as direct current (DC) plasma, low frequency plasma, high frequency plasma, pulse wave plasma, triode structure plasma, microwave plasma and the like can be considered.

  The thickness of the intermediate layer 4 is 20 nm or more and 200 nm or less. Here, if the film thickness is less than 20 nm, the role as the intermediate layer 4 formed between the first gas barrier layer 3 and the second gas barrier layer 5 (function as the above-mentioned buffer layer) is sufficiently It can not be done. On the other hand, when the film thickness exceeds 200 nm, the productivity is deteriorated. Furthermore, it is difficult to maintain flexibility in the intermediate layer 4, and when an external stress such as bending or tension is applied, a crack may occur in the deposited thin film layer.

  The intermediate layer 4 made of silicon oxide laminated by plasma CVD can be formed into a film by using a silane compound having carbon in the molecule and oxygen gas as a raw material, and an inert gas is added to the raw material to form a film. You can also. Examples of silane compounds having carbon in the molecule include tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), tetramethylsilane (TMS), hexamethyldisiloxane (HMDSO), tetramethyldisiloxane, methyltrimethoxy Relatively low molecular weight silane compounds such as silanes are contemplated. One or more (at least one) of these silane compounds may be selected. Among these silane compounds, TEOS, TMOS, TMS, HMDSO and the like are particularly preferable in consideration of the film forming pressure and the vapor pressure.

  In the film formation by the plasma CVD method, a silane compound is vaporized and mixed with oxygen gas is introduced between the electrodes, power is applied by the low-temperature plasma generator to convert it into plasma, and the surface of the first gas barrier layer 3 is formed. It can be stacked. Further, in the plasma CVD method, it is possible to change the film quality of the intermediate layer 4 made of silicon oxide by various methods. For example, change of silane compound or gas type, mixing ratio of silane compound and oxygen gas, increase / decrease of applied electric power, etc. can be considered.

  Moreover, as a formation method of the intermediate | middle layer 4 other than plasma CVD method, a vacuum evaporation method is preferable. In the vacuum evaporation method at present, as a heating means of the evaporation source material in the vacuum evaporation apparatus, an electron beam heating method, a resistance heating method, an induction heating method or the like is preferable. Moreover, in order to improve the adhesion to the first gas barrier layer 3, it is also possible to use a plasma assist method, an ion beam assist method, or the like. Furthermore, in order to increase the transparency of the intermediate layer 4, reactive vapor deposition may be performed by blowing oxygen gas or the like.

  In addition, the gas barrier laminate film according to the present embodiment can be laminated with other films and used in the fields of packaging of food, daily necessities, medicines and the like, solar battery related members, electronic equipment related members and the like. For example, in the packaging field, the gas barrier laminate film according to the present embodiment may be used as the outermost layer, and an intermediate film layer, a heat seal layer or the like may be laminated via an adhesive. In addition, the gas barrier laminate film according to the present embodiment is used in the middle, and an outer film layer or the like is laminated on one surface side via an adhesive, and a heat seal layer or the like on the other surface via an adhesive. May be stacked.

Examples of the intermediate film layer or the outer film layer include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyolefin films such as polyethylene and polypropylene, polyamide films, polycarbonate films, polyacrylonitrile films, polyimide films, etc. Transparent film layers are conceivable.
Examples of heat seal layers include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer Synthetic resins such as united and these metal cross-linked products are used.

  The thickness of the intermediate film layer, the outer film layer, and the heat seal layer may be determined depending on the purpose, but is generally in the range of 15 μm to 200 μm. As an example of the adhesive, a one-component curing type or a two-component curing type polyurethane adhesive can be considered. In order to laminate these layers through an adhesive, a dry lamination method or the like can be used. In addition, as another lamination method of the heat seal layer, it is also possible to use a method of melting and extruding a synthetic resin of the heat seal layer (extrusion lamination).

  Hereinafter, the gas barrier laminate film according to the present embodiment will be described in detail by way of Examples and Comparative Examples to be compared, but the present invention is not actually limited to the following examples. In the following Examples 1, 2, 3, 4 and 5, as shown in FIG. 1, the primer layer 2, the first gas barrier layer 3, and the intermediate layer are formed on one surface of the base material layer 1. A gas barrier laminate film was produced in which 4 and the second gas barrier layer 5 were sequentially laminated.

Example 1
A biaxially stretched polyethylene terephthalate (PET) film having a thickness of 25 μm and an arithmetic mean roughness Ra of one surface of 8 nm is prepared as the base material layer 1 and placed in a vacuum film-forming apparatus. A mixed gas of siloxane (HMDSO) 5 sccm / oxygen 50 sccm is introduced between the electrodes, and a high frequency of 13.56 MHz is applied by applying 0.5 kW for plasma conversion, and one surface of the substrate layer 1 having an arithmetic average roughness Ra of 8 nm On top of this, a primer layer 2 made of silicon oxide represented by SiOxCy with a thickness of 20 nm was laminated. At this time, the x value is 1.8 and the y value is 0.3. At this time, Ra of the surface of the primer layer 2 is 1.2.

Next, in the same vacuum film forming apparatus, metal aluminum is evaporated by an electron beam heating method, oxygen gas is introduced there, and the first 20 nm thick aluminum oxide is formed on the surface of the primer layer 2. The gas barrier layer 3 of
Next, similarly, in the vacuum film forming apparatus, a mixed gas of 5 sccm of hexamethyldisiloxane (HMDSO) / 50 sccm of oxygen is introduced between the electrodes, and a high frequency of 13.56 MHz is applied for 0.5 kW to generate plasma. On the surface of the gas barrier layer 3, an intermediate layer 4 made of silicon oxide represented by SiOxCy having a thickness of 100 nm was laminated. At this time, the x value is 1.8 and the y value is 0.3.
Next, similarly to the lamination of the first gas barrier layer 3 in the same vacuum film forming apparatus, metal aluminum is evaporated by an electron beam heating method, oxygen gas is introduced there, and the surface of the intermediate layer 4 is formed. A second gas barrier layer 5 made of aluminum oxide and having a thickness of 20 nm was laminated thereon.
Thus, the gas barrier laminate film of Example 1 was produced.

(Example 2)
In the gas-laminated laminated film of Example 1, the first gas barrier layer 3 laminated on the surface of the primer layer 2 was made into a gas barrier layer of silicon oxide having a thickness of 20 nm by evaporating silicon oxide by an electron beam heating method. . Furthermore, the second gas barrier layer 5 laminated on the surface of the intermediate layer 4 was similarly vaporized of silicon oxide by the electron beam heating method to form a gas barrier layer of silicon oxide having a thickness of 20 nm. The other conditions are the same as in Example 1. Thus, the gas barrier laminate film of Example 2 was produced.
(Example 3)
In the gas-laminated laminated film of Example 1, the first gas barrier layer 3 laminated on the surface of the primer layer 2 was evaporated into silicon oxide by an electron beam heating method to form a gas barrier layer made of silicon oxide with a thickness of 20 nm. The other conditions are the same as in Example 1. Thus, the gas barrier laminate film of Example 3 was produced.

(Example 4)
In the gas-via multilayer film of Example 1, the thickness of the intermediate layer 4 made of silicon oxide represented by SiOxCy was 30 nm. At this time, as in the first embodiment, the x value is 1.8 and the y value is 0.3. The other conditions are the same as in Example 1. Thus, the gas barrier laminate film of Example 4 was produced.
(Example 5)
In the gas barrier laminate film of Example 1, the thickness of the primer layer 2 made of silicon oxide represented by SiOxCy was 15 nm. At this time, as in the first embodiment, the x value is 1.8 and the y value is 0.3. At this time, the arithmetic average roughness Ra of the surface of the primer layer 2 is 1.8 nm. The other conditions are the same as in Example 1. Thus, the gas barrier laminate film of Example 5 was produced.

(Comparative example 1)
In the gas barrier laminate film of Example 1, as the intermediate layer 4 to be laminated on the surface of the first gas barrier layer 3, solutions (A) to (C) prepared by the following method were prepared: A / B / C = 100 / A coating solution mixed at a ratio of 20/10 (solid weight ratio) is applied on the surface of the gas barrier layer 3 by a bar coater, dried at 120 ° C. for 1 minute, and an organic intermediate layer 4 having a thickness of 100 nm. It formed. The other conditions are the same as in Example 1. Thus, a gas barrier laminate film of Comparative Example 1 was produced.

[Solution for interlayer]
(A): 17.9 g of tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ , hereinafter referred to as TEOS) and 72.1 g of hydrochloric acid (0.1 N) are added to 10 g of methanol, and the mixture is stirred for 30 minutes for hydrolysis Hydrolyzed solution (B) of solid content 5% (weight ratio SiO ₂ equivalent): 5% (weight ratio) of polyvinyl alcohol, water / methanol = 95/5 (weight ratio) aqueous solution (C): 1, 3 Water / IPA = 1/1 solution, solid content 5% (weight ratio R ² Si (OH) ₃ equivalent) of 5-tris (3-trimethoxysilylpropyl) isocyanurate

(Comparative example 2)
In the gas barrier laminate film of Example 1, when laminating the intermediate layer 4, a mixed gas of 5 sccm of hexamethyldisiloxane (HMDSO) / 100 sccm of oxygen is introduced between the electrodes in the vacuum film forming apparatus, and 13.56 MHz A high frequency of 0.5 kW was applied for plasma conversion, and an intermediate layer 4 made of silicon oxide represented by SiOxCy with a thickness of 100 nm was laminated on the surface of the first gas barrier layer 3. At this time, the x value is 1.9 and the y value is 0.05. The other conditions are the same as in Example 1. Thus, a gas barrier laminate film of Comparative Example 2 was produced.

(Comparative example 3)
In laminating the intermediate layer 4 in the gas barrier laminate film of Example 1, a mixed gas of 5 sccm of hexamethyldisiloxane (HMDSO) / 10 sccm of oxygen is introduced between the electrodes in the vacuum film forming apparatus, and 13.56 MHz A high frequency of 0.5 kW was applied for plasma conversion, and an intermediate layer 4 made of silicon oxide represented by SiOxCy with a thickness of 100 nm was laminated on the surface of the first gas barrier layer 3. At this time, the x value is 1.5 and the y value is 0.8. The other conditions are the same as in Example 1. Thus, the gas barrier laminate film of Comparative Example 3 was produced.

(Comparative example 4)
In laminating the primer layer 2 in the gas barrier laminate film of Example 1, a mixed gas of 5 sccm of hexamethyldisiloxane (HMDSO) / 10 sccm of oxygen is introduced between the electrodes in the vacuum film forming apparatus, and 13.56 MHz A high frequency of 0.5 kW was applied for plasma conversion, and a primer layer 2 made of silicon oxide represented by SiOxCy with a thickness of 30 nm was laminated on the surface of the base material layer 1. At this time, the x value is 1.5 and the y value is 0.8. The other conditions are the same as in Example 1. Thus, a gas barrier laminate film of Comparative Example 4 was produced.

(Comparative example 5)
In the gas barrier laminate film of Example 1, the second gas barrier layer 5 was laminated directly on the surface of the first gas barrier layer 3 without laminating the intermediate layer 4. The other conditions are the same as in Example 1. Thus, a gas barrier laminate film of Comparative Example 5 was produced.
(Comparative example 6)
In the gas barrier laminate film of Example 2, the second gas barrier layer 5 was laminated directly on the surface of the first gas barrier layer 3 without laminating the intermediate layer 4. The other conditions are the same as in Example 2. Thus, a gas barrier laminate film of Comparative Example 6 was produced.

(Comparative example 7)
In the gas barrier laminate film of Example 1, without laminating the primer layer 2, the first gas barrier layer 3 is directly coated on one of the surfaces having an arithmetic mean roughness Ra of 8 nm on the surface of the base material layer 1. Stacked. The other conditions are the same as in Example 1. Thus, a gas barrier laminate film of Comparative Example 7 was produced.

[Comparative evaluation]
(1) Water vapor permeability in an environment of 40 ° C. and 90% RH For the gas barrier laminate films of Examples 1, 2, 3, 4, 5 and Comparative Examples 1, 2, 3, 4, 5, 6, 7, modern modern The water vapor transmission rate (g / m ² · day) in a 40 ° C. 90% RH environment was measured by a water vapor transmission rate meter (MOCON PERMATRAN-W 3/31) manufactured by Control Company. Moreover, the measured value of the water vapor transmission rate measured in this 40 degreeC90% RH environment was made into X. FIG.

(2) Water Vapor Permeability in an 85 ° C. 85% RH Environment The modern gas barrier laminate films of Examples 1, 2, 3, 4, 5 and Comparative Examples 1, 2, 3, 4, 5, 6, 7 The high-temperature test system TH-85 made by Hitachi High-Technologies Corporation was installed in a control-made water vapor transmission rate meter (MOCON PERMATRAN-W 3/31), and the water vapor transmission rate under 85 ° C 85% RH environment ( g / m ² · day) was measured. Moreover, the measured value of the water vapor transmission rate measured in this 85 degreeC 85% RH environment was made into Y. FIG.
The measurement results are shown in Table 1. Also, in order to show the degree to which the gas barrier property is lowered in the high temperature region, the value of Y / X obtained by dividing Y by X is also shown in Table 1. The larger the value, the lower the gas barrier property in the high temperature region.

As can be seen from Table 1, in the gas via laminate films of Example 1, Example 2, Example 3, Example 4 and Example 5, the water vapor transmission rate is 40 ° C. 90% RH and 85 ° C. 85% RH. It was low and had high gas barrier properties.
On the other hand, the gas barrier laminate film of Comparative Example 1 using the organic intermediate layer 4 was compared with the gas barrier laminate films of Example 1, Example 2, Example 3, Example 4 and Example 5, Although the water vapor transmission rate (X) at 40 ° C. 90 RH was at the same level, the water vapor transmission rate (Y) at 85 ° C. 85% RH is high, and Y / X showing the degree to which the gas barrier properties decrease in high temperature region The value of 10 was 10 or more, and it was confirmed that the gas barrier property was greatly reduced in the high temperature range.

  Furthermore, the gas barrier laminate film of Comparative Example 2 in which the y value of the intermediate layer 4 made of silicon oxide represented by SiOxCy is smaller than 0.1 and the comparative example 3 in which the value of y value is larger than 0.5 Water vapor transmission rate (X) at 40 ° C. 90 RH and water vapor transmission rate at 85 ° C. 85% RH as compared with the gas barrier laminate films of Example 1, Example 2, Example 3, Example 4 and Example 5 Both (Y) were high and the gas barrier properties were inferior.

  Furthermore, the gas barrier laminate film of Comparative Example 4 in which the value of the y value of the primer layer 2 made of silicon oxide represented by SiOxCy is larger than 0.5 is Example 1, Example 2, Example 3, Implementation Both the water vapor transmission rate (X) at 40 ° C. and 90 RH and the water vapor transmission rate (Y) at 85 ° C. and 85% RH were both higher than the gas barrier laminate films of Example 4 and Example 5, and the gas barrier properties were inferior. .

Furthermore, the gas barrier laminate films of Comparative Example 5 and Comparative Example 6 in which the intermediate layer 4 was not formed were the same as the gas barrier laminate films of Example 1, Example 2, Example 3, Example 4 and Example 5 In comparison, the water vapor transmission rate (X) at 40 ° C. and 90 RH and the water vapor transmission rate (Y) at 85 ° C. and 85% RH were both high, and the gas barrier properties were inferior.
Furthermore, the gas barrier laminate film of Comparative Example 7 in which the primer layer 2 is not formed is compared with the gas barrier laminate films of Example 1, Example 2, Example 3, Example 4 and Example 5, Both the water vapor transmission rate (X) at 40 ° C. and 90 RH and the water vapor transmission rate (Y) at 85 ° C. and 85% RH were high, and the gas barrier properties were inferior.

The gas barrier laminate film according to the present embodiment is suitably used when particularly high gas barrier properties are required in the fields of packaging of food, daily necessities, medicines, etc., solar battery related members, electronic equipment related members, etc. Be
As mentioned above, although the embodiment of the present invention has been described in detail, the present invention is not limited to the above embodiment in fact, and the present invention is included in the present invention even if there are changes within the scope of the present invention.

DESCRIPTION OF SYMBOLS 1 ... Base material layer 2 ... Primer layer 3 ... 1st gas barrier layer 4 ... Intermediate layer 5 ... 2nd gas barrier layer

Claims (7)

A transparent primer layer, a transparent first gas barrier layer, a transparent intermediate layer, and a transparent second gas barrier layer are laminated in this order on one surface of a substrate layer made of a transparent plastic film. Has been
Each of the primer layer and the intermediate layer is made of silicon oxide represented by SiOxCy, x is 1.5 or more and 2.0 or less, and y is 0.1 or more and 0.5 or less,
The primer layer has a thickness of 5 nm to 50 nm, and an arithmetic average roughness of the surface of 2 nm or less.
The intermediate layer has a thickness of 20 nm to 200 nm,
Wherein each of the first gas barrier layer and the second gas barrier layer, an inorganic oxide state, and are the 3nm or 30nm or less thick,
The base layer, a gas barrier laminate film which arithmetic average roughness of the surface is characterized by 8nm der Rukoto. The intermediate layer is characterized by being formed between the second gas barrier layer and the first gas barrier layer by plasma CVD method, gas barrier laminate film according to claim 1.   The gas barrier laminate film according to claim 1 or 2, wherein the primer layer is formed between the base material layer and the first gas barrier layer by a plasma CVD method.   4. The device according to claim 1, wherein each of the first gas barrier layer and the second gas barrier layer is made of any of silicon oxide, aluminum oxide, titanium oxide, or magnesium oxide. The gas barrier laminate film as described in Item. The water vapor transmission rate X under an environment of 40 ° C. and 90% RH is 0.1 g / m ² · day or less,
The water vapor transmission rate Y under an environment of 85 ° C. and 85% RH is 1.0 g / m ² · day or less,
The gas barrier laminate film according to any one of claims 1 to 4, wherein the relationship between X and Y satisfies the formula of Y / X ≦ 10. The gas barrier laminate film according to any one of claims 1 to 5, wherein at least one of the first gas barrier layer and the second gas barrier layer is made of titanium oxide. The gas barrier laminate film according to any one of claims 1 to 5, wherein each of the first gas barrier layer and the second gas barrier layer is made of titanium oxide.

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