JP2014168932A - Gas barrier laminate film - Google Patents

Abstract

[PROBLEMS] In the field of packaging of foods, daily necessities, pharmaceuticals, etc., and in fields such as solar cell-related members and electronic device-related members, the gas barrier properties are not deteriorated even when subjected to normal processing, and particularly high gas barrier properties are required. The present invention provides a transparent gas barrier laminate film that can be suitably used in the case of
A first gas barrier layer 2 made of an inorganic oxide, an intermediate layer 3 and a second gas barrier layer 4 made of an inorganic oxide are sequentially formed on one surface of a base material layer 1 made of a transparent plastic film. In the laminated gas barrier film, the intermediate layer 3 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), and The thickness is 20 nm or more and 500 nm or less.
[Selection] Figure 1

Description

  The present invention is a transparent gas barrier laminate that is suitably used when high gas barrier properties are required in the fields of packaging of foods, daily necessities, pharmaceuticals, etc., and fields such as solar cell related members and electronic device related members. Related to film.

  Packaging materials used for packaging of food, daily necessities, pharmaceuticals, etc., suppress the alteration of the contents, so that the functions and properties can be maintained even during packaging, oxygen, water vapor, etc. that permeate the packaging material, It is necessary to prevent the influence of the gas that alters the contents, and it is required to have a gas barrier property that blocks these gases.

  As packaging materials having ordinary gas barrier properties, vinylidene chloride resin films or films coated with vinylidene chloride resins that are relatively excellent in gas barrier properties have been often used. However, these packaging materials have high gas barrier properties. Cannot be used for packaging that requires Therefore, when a high gas barrier property is required, a packaging material in which a metal foil such as aluminum is laminated as a gas barrier layer has to be used. A packaging material in which a metal foil such as aluminum is laminated has almost no influence of temperature and humidity and has a high gas barrier property.

But with these packaging materials,
(1) The contents cannot be confirmed through seeing through it.
(2) It must be disposed of as non-combustible material after use.
(3) A metal detector cannot be used for inspection of the contents.
Had many drawbacks.

  As a packaging material that overcomes these disadvantages, conventionally, a vapor-deposited thin film layer of inorganic oxide such as silicon oxide, aluminum oxide, and magnesium oxide is used as a gas barrier layer on a base layer made of a transparent plastic film. A laminated film formed by laminating an appropriate gas barrier coating layer is known (for example, see Patent Document 1).

  On the other hand, in recent years, the solar cell market is rapidly expanding with increasing interest in global warming issues. As a solar cell structure, a single solar cell element is not used as it is, and generally several to several tens of elements are wired in series and in parallel, and packaged to protect the element for a long period of time. Is done and unitized. The unit built in this package is called a solar cell module. Generally, the surface that is exposed to sunlight is covered with glass, the gap is filled with a filler made of thermoplastic, and the back is made of a heat-resistant, weather-resistant plastic material, etc. The structure is protected by a sheet.

  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 is peeled off due to the permeation of moisture and the wiring is corroded, which adversely affects the module output itself.

  Conventionally, as this back surface protection sheet for solar cells, a laminated structure in which an aluminum foil is sandwiched from both sides with a white fluorine-based film has been often used. However, this fluorine-based film has a weak mechanical strength, so that the solar cell element and the aluminum foil are short-circuited to adversely affect the battery performance. Further, since the price is high, it is necessary to reduce the price of the solar cell module. There are two obstacles. In order to improve these problems, there is an increasing demand for a gas barrier film having both weather resistance and high gas barrier properties without using an aluminum foil.

  Also, development has been made to make this solar cell module flexible, and in order to achieve this, it is necessary to replace the glass substrate on the surface where the sunlight hits with a sheet made of a plastic material, etc. Similarly to the back protective sheet, weather resistance and high gas barrier properties are required.

  In recent years, with the development of electronic paper and organic EL, which are expected to be the next generation FPD (Flat Panel Display), there is a demand to replace the glass substrate with a plastic film in order to achieve flexibility in these FPDs. It is growing. The glass substrate has a gas barrier property required to suppress deterioration of internal elements due to oxygen and water vapor derived from the environment. However, the above-mentioned gas barrier film for packaging materials does not reach the barrier level, and in electronic paper, organic EL, etc. to which a plastic film can be applied, the gas barrier is 100 to 10,000 times that of a food packaging material barrier film. It is said that sex is necessary.

  In order to realize a plastic film having such a high gas barrier property, dry coating methods such as reactive vapor deposition using electron beam vapor deposition and induction heating vapor deposition, sputtering, and plasma CVD (chemical vapor deposition) are used. The formed inorganic oxide thin film has been studied as one that can be expected to exhibit high gas barrier properties.

  Among them, a silicon oxide thin film formed by a plasma CVD method using an organosilane compound has been studied as a barrier layer exhibiting high gas barrier properties, and has been put into practical use in the food packaging field. Conventionally, a transparent barrier film that improves adhesion and transparency by controlling the carbon concentration and the composition of the silicon oxide thin film has been considered (see, for example, Patent Document 2).

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

  However, the laminated film described in Patent Document 1 has deteriorated gas barrier properties such as oxygen permeability and water vapor permeability when subjected to normal processing as a packaging material such as printing, laminating, and bag making. It had the disadvantage that it would end up. Moreover, even if the dry coating method is used to obtain a plastic film having a high gas barrier property, a high-temperature process is necessary or dense if an attempt is made to obtain a dense film in order to aim at a high gas barrier property. For this reason, the stress in the film tends to increase. For this reason, it is difficult to obtain a dense film within the usable temperature range of the plastic film, or problems such as poor adhesion and cracking due to the large difference in thermal expansion coefficient between the plastic film and the inorganic oxide thin film. And high gas barrier properties are not easily developed. In addition, the transparent barrier film described in Patent Document 2 is described as being slightly inferior in water vapor barrier properties, and is not gas barrier properties for FPDs such as electronic paper and organic EL that require high gas barrier properties. It is enough.

  Therefore, the object of the present invention is to provide a particularly high gas barrier property, in which the gas barrier property is not deteriorated even when subjected to ordinary processing in the field of packaging of food, daily necessities, pharmaceuticals, etc., and in the field of solar cell related members and electronic device related members. It is an object of the present invention to provide a transparent gas barrier laminate film that can be suitably used when the is required. In particular, the object of the present invention is to solve the problem of insufficient gas barrier properties for FPDs such as the back surface protection sheet and surface protection sheet of the solar cell module described above, electronic paper and organic EL, and the oxygen barrier. An object of the present invention is to provide a transparent gas barrier laminate film having excellent properties and water vapor barrier properties.

  As a means for solving the above-mentioned problems, the invention according to claim 1 includes a first gas barrier layer made of an inorganic oxide, an intermediate layer, on one surface of a base material layer made of a transparent plastic film, In the gas barrier laminate film formed by sequentially laminating the second gas barrier layer made of an inorganic oxide, the intermediate layer is made of SiOxCy (x is 1.5 or more and 2.0 or less, y is 0.1 or more and 0.5 or less. And a thickness of 20 nm or more and 500 nm or less.

  The invention according to claim 2 is that an intermediate layer laminated between the first gas barrier layer and the second gas barrier layer is formed by a plasma CVD method (chemical vapor deposition method). The gas barrier laminate film according to claim 1, wherein the gas barrier laminate film is a film.

  The invention described in claim 3 is characterized in that the first gas barrier layer and the second gas barrier layer are any one of silicon oxide, aluminum oxide, titanium oxide, and magnesium oxide. Or it is a gas barrier laminated film of 2.

In the invention according to claim 4, the gas barrier laminate film has a water vapor transmission rate (X) in a 40 ° C. and 90% RH environment of 0.1 g / m ² · day or less,
The water vapor permeability (Y) of the gas barrier laminate film under an environment of 85 ° C. and 85% RH is 1.0 g / m ² · day or less,
The relationship between X and Y is expressed by the following formula: Y / X ≦ 10
The gas barrier laminate film according to any one of claims 1 to 3, wherein the gas barrier laminate film is satisfied.

  According to the present invention, in the packaging field of foods, daily necessities, pharmaceuticals, etc., gas barrier properties are not deteriorated even if normal processing as a packaging material is performed, and the contents can be confirmed by seeing through the packaging material. Moreover, the transparent gas barrier laminated film which can be used suitably when especially high gas barrier property is required for solar cell modules and FPD can be provided.

It is sectional drawing which shows an example of the gas barrier laminated film which concerns on embodiment of this invention.

Hereinafter, embodiments of the gas barrier laminate film of the present invention will be described with reference to the drawings.
FIG. 1 is a cross-sectional view showing an example of a gas barrier laminate film 10 of the present invention. The gas barrier laminated film 10 has a thickness of the first gas barrier layer 2 made of an inorganic oxide, the intermediate layer 3 and the second gas barrier layer 4 made of an inorganic oxide on one surface of the base material layer 1. The intermediate layer 3 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).

  In the gas barrier laminate film of the present invention, 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 films, polyamide films, and polyvinyl chloride. Films, polycarbonate films, polyacrylonitrile films, polyimide films, biodegradable plastic films such as polylactic acid, and the like are used.

  These transparent plastic films may be either stretched or unstretched, but those having excellent mechanical strength and dimensional stability are preferred. In particular, polyethylene terephthalate stretched in the biaxial direction is preferably used from the viewpoints of heat resistance and dimensional stability. Moreover, the transparent plastic film may contain additives such as an antistatic agent, an ultraviolet ray preventing agent, a plasticizer, and a lubricant. Further, in the transparent plastic film, the surface on the side where other layers are 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. However, considering the suitability as a packaging material and the suitability for processing when other layers are laminated, it is practical. Is preferably in the range of 6 μm to 100 μm, particularly in the range of 9 μm to 25 μm. Moreover, the thickness of the base material layer 1 is not particularly limited when used in a surface protection sheet or a back surface protection sheet of a solar cell, or even in electronic paper or an organic EL. Considering the processing suitability in the subsequent process of the gas barrier laminated film, it is practically 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 of the present invention, the smoothness of the surface of the base material layer 1 on which the first gas barrier layer 2 is laminated is one of the important characteristics for developing high gas barrier properties. This is because the smoother the surface of the base material layer 1, the denser the gas barrier layer can be formed from the vicinity of the surface, and a uniform film thickness can be easily obtained. It is considered that the arithmetic average roughness Ra showing the smoothness is 5 nm or less as a necessary condition for developing a high gas barrier property.

  In the gas barrier laminate film of the present invention, the first gas barrier layer 2 and the second gas barrier layer 4 are made of an inorganic oxide, and the formation method is not particularly limited, but the first gas barrier layer 1 is made of an inorganic oxide. In order for the gas barrier layer 2 and the second gas barrier layer 4 to exhibit high gas barrier properties, vacuum film formation capable of forming a gas barrier layer in a vacuum is suitable, and in particular, when laminating at a higher speed, Vacuum deposition is the best.

  In the current vacuum vapor deposition method, the electron source heating method, the resistance heating method, the induction heating method, or the like is preferable as the heating means for the evaporation source material in the vacuum vapor deposition apparatus. Moreover, in order to improve the adhesiveness with the base material layer 1, a plasma assist method, an ion beam assist method, etc. can also be used. Further, in order to improve transparency, reactive vapor deposition may be performed by blowing oxygen gas or the like.

  Further, as a method other than the vacuum vapor deposition method, the deposition rate for forming the gas barrier layer is not as fast as the vacuum vapor deposition method, but the plasma CVD method is preferable as a method that easily exhibits higher gas barrier properties. As the plasma generator, a low-temperature plasma generator such as direct current (DC) plasma, low-frequency plasma, high-frequency plasma, pulse wave plasma, tripolar plasma, or microwave plasma is used.

  In the gas barrier laminate film of the present invention, the composition of the first gas barrier layer 2 and the second gas barrier layer 4 is particularly limited as long as it is an inorganic oxide that is transparent and exhibits gas barrier properties. However, at present, 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 thicknesses of the first gas barrier layer 2 and the second gas barrier layer 4 are 5 nm or more and 200 nm or less. In general, since the gas barrier property can be improved by increasing the thickness of the gas barrier layer, in a gas barrier layered film that requires a higher gas barrier property, increasing the film thickness is one method for improving the gas barrier property. Sometimes used. However, an internal stress is generated in the formed gas barrier layer, and this internal stress increases as the thickness of the gas barrier layer increases, and cracks that deteriorate the gas barrier properties are likely to occur. Further, increasing the film thickness makes it difficult to maintain the flexibility of the gas barrier layer, and if an external stress such as bending or pulling is applied, the gas barrier layer may be cracked. For these reasons, it is necessary to provide an upper limit for increasing the film thickness for improving the gas barrier properties. Depending on the gas barrier layer forming method and the film composition, the first gas barrier layer 2 and the second gas barrier layer 4 are required. The film thickness is desirably 200 nm or less. As for the lower limit of the film thickness, if the film thickness is less than 5 nm, a uniform thin film may not be obtained, and the film cannot sufficiently function as a gas barrier material. It is desirable to be.

  As for the film formation method, continuous film formation by a winding method utilizing the characteristics of the base material layer 1 made of plastic is possible. Therefore, a winding type vacuum evaporation film forming apparatus or a winding type plasma CVD is used. It is preferable to use a film forming apparatus.

  As described above, film thickness may be used as one of the techniques for improving the barrier property of the gas barrier layer. However, as the film thickness of the gas barrier layer is increased, the generation of cracks due to excessive internal stress, On the other hand, due to the occurrence of cracks due to lack of flexibility, it tends to cause a decrease in gas barrier properties. Therefore, in order to prevent these, it is necessary to form a highly flexible intermediate layer serving as a buffer layer between the first gas barrier layer 2 and the second gas barrier layer 4, and as this intermediate layer, In consideration of flexibility, an organic thin film layer is often used rather than an inorganic thin film layer. However, the organic thin film layer has a drastic decrease in gas barrier properties at high temperatures as compared with inorganic materials, and is not suitable for applications requiring high gas barrier properties even in high temperature environments such as solar cells, electronic paper, and organic EL. .

  Therefore, in the gas barrier laminate film of the present invention, the intermediate layer 3 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) and contained. By controlling the content of the carbon component to be performed, it becomes possible to express both flexibility and gas barrier properties as an intermediate layer. That is, if the y value indicating the carbon component content is less than 0.1, the flexibility as the intermediate layer is insufficient, and if the y value exceeds 0.5, the flexibility as the intermediate layer is high. However, since a dense film cannot be obtained, 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 an important point in the gas barrier laminate film of the present invention.

In the gas barrier laminate film of the present invention, as described above, it is one of the important points of the present invention that the intermediate layer 3 is inorganic so that a high gas barrier property can be expressed even in a high temperature environment. And as an effect of developing a high gas barrier in a high temperature region using an inorganic intermediate layer, the gas barrier laminate film used mainly for evaluation for packaging materials is used in a 40 ° C. and 90% RH (relative humidity) environment. The water vapor transmission rate (X) is 0.1 g / m ² · day or less, and the water vapor transmission rate (Y) in an 85 ° C. and 85% RH environment of a gas barrier laminate film used mainly for evaluation for solar cells. 1.0 g / m ² · day or less, and the relationship between X and Y preferably satisfies the expression “Y / X ≦ 10”.

  In the gas barrier laminate film of the present invention, the method for forming the intermediate layer 3 is not particularly limited. As described above, the y value of the intermediate layer 3 represented by SiOxCy is 0.1 or more and 0.5 or less. In order to achieve this, the plasma CVD method is currently preferred. As the plasma generator, a low-temperature plasma generator such as direct current (DC) plasma, low-frequency plasma, high-frequency plasma, pulse wave plasma, tripolar plasma, or microwave plasma is used.

  The thickness of the intermediate layer 3 is 20 nm or more and 500 nm or less. Here, if the film thickness is less than 20 nm, the function as the buffer layer described above, which is the role of the intermediate layer 3 formed between the first gas barrier layer 2 and the second gas barrier layer 4, is sufficient. Can't fulfill. On the other hand, if the film thickness exceeds 500 nm, it is difficult to maintain flexibility in the intermediate layer 3, and if an external stress such as bending or pulling is applied, the deposited thin film layer may be cracked.

  The intermediate layer 3 made of silicon oxide, which is laminated by the plasma CVD method, can be formed using a silane compound having carbon in the molecule and oxygen gas as raw materials, and is formed by adding an inert gas to the raw materials. You can also. Examples of the silane compound having carbon in the molecule include tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), tetramethylsilane (TMS), hexamethyldisiloxane (HMDSO), and tetramethyldisiloxane. A relatively low molecular weight silane compound such as methyltrimethoxysilane may be selected, and one or more of these silane compounds may be selected. Among these silane compounds, TEOS, TMOS, TMS, HMDSO, tetramethylsilane and the like are preferable in view of the film forming pressure and the vapor pressure.

  In the film formation by the plasma CVD method, the silane compound vaporized and mixed with oxygen gas is introduced between the electrodes, and the plasma is formed by applying electric power with a low-temperature plasma generator and the surface of the first gas barrier layer 2. Can be laminated on top. In the plasma CVD method, the film quality of the intermediate layer 3 made of silicon oxide can be changed by various methods. For example, the silane compound and the gas species can be changed, the mixing ratio of the silane compound and the oxygen gas, and the application Increase or decrease in power can be considered.

  Further, as a method for forming the intermediate layer 3 other than the plasma CVD method, a vacuum vapor deposition method is preferable. In the current vacuum vapor deposition method, the electron source heating method, the resistance heating method, the induction heating method, or the like is preferable as the heating means for the evaporation source material in the vacuum vapor deposition apparatus. Further, in order to improve the adhesion to the first gas barrier layer 2, a plasma assist method, an ion beam assist method, or the like can be used. Furthermore, in order to increase the transparency of the intermediate layer, reactive vapor deposition may be performed by blowing oxygen gas or the like.

  In addition, the gas barrier laminate film of the present invention can be laminated with other films and used in the fields of packaging of food, daily necessities, pharmaceuticals, etc., solar cell related members, electronic equipment related members and the like. For example, in the packaging field, the gas barrier laminate film of the present invention 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 of the present invention is used in the middle, an outer film layer or the like is laminated on one side of the film via an adhesive, and a heat seal layer or the like is laminated on the other side of the film via an adhesive. You may make it the structure which carried out.

  A transparent film layer is used as the intermediate film layer or the outer film layer. Examples of such transparent film layers include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyolefin films such as polyethylene and polypropylene, polyamide films, polycarbonate films, polyacrylonitrile films, and polyimide films. It is done. Examples of the heat seal layer include polyethylene, polypropylene, ethylene vinyl acetate copolymer, ethylene / methacrylic acid copolymer, ethylene / methacrylic acid ester copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester. Synthetic resins such as copolymers and cross-linked products of these metals are used. The thicknesses of the intermediate film layer, the outer film layer, and the heat seal layer are determined according to the purpose, but are generally in the range of 15 μm to 200 μm. As the adhesive, a one-component curable type or two-component curable polyurethane adhesive or the like is used. In order to laminate these layers through an adhesive, a dry laminating method or the like can be used. In addition, as another method for laminating the heat seal layer, a method (extrusion lamination) in which the synthetic resin of the heat seal layer is hot melt extruded can be used.

  EXAMPLES Hereinafter, although an Example and a comparative example further demonstrate this invention, this invention is not restrict | limited to the following example. In the following Examples 1, 2, 3, and 4, as shown in FIG. 1, the first gas barrier layer 2, the intermediate layer 3, and the second gas barrier are formed on one surface of the base material layer 1. A gas barrier laminate film in which the layers 4 were sequentially laminated was produced.

  A biaxially stretched polyethylene terephthalate (PET) film having a thickness of 25 μm was prepared as the base material layer 1 and placed in a vacuum film forming apparatus. Metal aluminum was evaporated by an electron beam heating method, oxygen gas was introduced therein, and a first gas barrier layer 2 made of aluminum oxide having a thickness of 20 nm was laminated on the surface of the base material layer 1.

  Next, in the same 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 by 0.5 kW to form plasma. An intermediate layer 3 made of silicon oxide represented by SiOxCy having a thickness of 300 nm was laminated on the surface of the gas barrier layer 2. At this time, the x value was 1.8 and the y value was 0.3.

  Next, in the same manner as in the lamination of the first gas barrier layer 2 in the vacuum film forming apparatus, metal aluminum is evaporated by an electron beam heating method, oxygen gas is introduced therein, and the intermediate layer 3 is A second gas barrier layer 4 made of aluminum oxide having a thickness of 20 nm was laminated on the surface of the substrate. Thus, the gas barrier laminate film of Example 1 was produced.

  In the gas barrier laminated film of Example 1, the first gas barrier layer 2 laminated on the surface of the base material layer 1 is evaporated into silicon oxide by an electron beam heating method to form a gas barrier layer made of silicon oxide having a thickness of 20 nm. did. Further, the second gas barrier layer 4 laminated on the surface of the intermediate layer 3 was vaporized by the same electron beam heating method to form a gas barrier layer made of silicon oxide having a thickness of 20 nm. Other conditions were the same as in Example 1. Thus, a gas barrier laminate film of Example 2 was produced.

  In the gas barrier laminated film of Example 1, the first gas barrier layer 2 laminated on the surface of the base material layer 1 was vaporized by an electron beam heating method to form a gas barrier layer made of silicon oxide having a thickness of 20 nm. . Other conditions were the same as in Example 1. Thus, the gas barrier laminate film of Example 3 was produced.

  In the gas barrier laminate film of Example 1, the thickness of the intermediate layer 3 made of silicon oxide represented by SiOxCy was set to 50 nm. At this time, similarly to Example 1, the x value was 1.8 and the y value was 0.3. Other conditions were the same as in Example 1. Thus, a gas barrier laminate film of Example 4 was produced.

Comparative Example 1

  In the gas barrier laminate film of Example 1, as the intermediate layer 3 to be laminated on the surface of the first gas barrier layer 2, the solutions (A) to (C) prepared by the following method were A / B / C = 100 / A coating solution mixed at a ratio of 20/10 (weight ratio of solid content) is applied onto the surface of the first gas barrier layer 2 by a bar coater, dried at 120 ° C. for 1 minute, and an organic intermediate having a thickness of 300 nm. Layer 3 was formed. Other conditions were the same as in Example 1. Thus, a gas barrier laminate film of Comparative Example 1 was produced.

≪Solution for intermediate layer≫
(A): 17.9 g of tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ , hereinafter referred to as TEOS) and 72.1 g of hydrochloric acid (0.1N) are added to 10 g of methanol, followed by stirring for 30 minutes and hydrolysis. Hydrolysis solution having a solid content of 5% (weight ratio in terms of SiO ₂ ) (B): 5% (weight ratio) of polyvinyl alcohol, water / methanol = 95/5 (weight ratio) aqueous solution (C): 1, 3 , 5-tris (3-trimethoxysilylpropyl) isocyanurate, water / IPA = 1/1 solution, solid content 5% (weight ratio R ² Si (OH) ₃ conversion)

Comparative Example 2

  In the gas barrier laminate film of Example 1, when laminating the intermediate layer 3, a mixed gas of 5 sccm of hexamethyldisiloxane (HMDSO) / 100 sccm of oxygen was introduced between the electrodes in the vacuum film forming apparatus, and the 13.56 MHz An intermediate layer 3 made of silicon oxide represented by SiOxCy having a thickness of 300 nm was stacked on the surface of the first gas barrier layer 2 by applying a high frequency of 0.5 kW to form plasma. At this time, the x value was 1.9 and the y value was 0.05. Other conditions were the same as in Example 1. Thus, a gas barrier laminate film of Comparative Example 2 was produced.

Comparative Example 3

  In the gas barrier laminate film of Example 1, when the intermediate layer 3 was laminated, a mixed gas of 5 sccm of hexamethyldisiloxane (HMDSO) / 10 sccm of oxygen was introduced between the electrodes in a vacuum film forming apparatus. An intermediate layer 3 made of silicon oxide represented by SiOxCy having a thickness of 300 nm was stacked on the surface of the first gas barrier layer 2 by applying a high frequency of 0.5 kW to form plasma. At this time, the x value was 1.5 and the y value was 0.8. Other conditions were the same as in Example 1. Thus, a gas barrier laminate film of Comparative Example 3 was produced.

Comparative Example 4

  In the gas barrier laminate film of Example 1, the second gas barrier layer 4 was laminated directly on the surface of the first gas barrier layer 2 without laminating the intermediate layer 3. Other conditions were 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 2, the second gas barrier layer 4 was laminated directly on the surface of the first gas barrier layer 2 without laminating the intermediate layer 3. Other conditions were the same as in Example 2. Thus, a gas barrier laminate film of Comparative Example 5 was produced.

<Comparison evaluation>
[Water vapor permeability in an environment of 1.40 ° C. and 90% RH]
About the gas-barrier laminated film of Examples 1, 2, 3, 4 and Comparative Examples 1, 2, 3, 4, 5, 40 ° C. using a water vapor permeability meter (MOCON PERMATRAN-W 3/31) manufactured by Modern Control Co., Ltd. The water vapor transmission rate (g / m ² · day) in a 90% RH environment was measured. Moreover, the measured value of the water vapor permeability measured in this 40 ° C. and 90% RH environment was defined as X.

[Water vapor permeability under an environment of 2.85 ° C. and 85% RH]
About the gas-barrier laminated films of Examples 1, 2, 3, 4 and Comparative Examples 1, 2, 3, 4, 5 to Hitachi Modern Control's water vapor permeability meter (MOCON PERMATRAN-W 3/31), Hitachi A high temperature test system TH-85 type manufactured by High Technologies was installed, and the water vapor transmission rate (g / m ² · day) in an environment of 85 ° C. and 85% RH was measured. Moreover, the measured value of the water vapor transmission rate measured in this 40 degreeC 90% RH environment was set to Y.

  These measurement results are shown in Table 1. Table 1 also shows the Y / X value obtained by dividing Y by X in order to show the degree of decrease in gas barrier properties in the high temperature region. Note that the larger this value, the lower the gas barrier property in the high temperature region.

  As can be seen from Table 1, the gas barrier laminate films of Example 1, Example 2, Example 3 and Example 4 have both low and high water vapor permeability at 40 ° C. 90% RH and 85 ° C. 85% RH. It had gas barrier properties.

  On the other hand, the gas barrier laminate film of Comparative Example 1 using the organic intermediate layer 3 is 40 ° C. and 90 RH compared to the gas barrier laminate films of Example 1, Example 2, Example 3 and Example 4. Although the water vapor transmission rate (X) was at the same level, the water vapor transmission rate (Y) at 85 ° C. and 85% RH was increased, and the Y / X value indicating the degree of decrease in gas barrier properties at a high temperature region was 10 As described above, it was confirmed that the gas barrier property was greatly lowered in the high temperature region.

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

  Furthermore, the gas barrier laminate films of Comparative Example 4 and Comparative Example 5 in which the intermediate layer 3 is not formed are compared with the gas barrier laminate films of Example 1, Example 2, Example 3 and Example 4, Both the water vapor permeability (X) at 40 ° C. and 90 RH and the water vapor permeability (Y) at 85 ° C. and 85% RH were both high, and the gas barrier properties were poor.

  Note that the present invention is not limited to the above-described embodiment as it is, and can be embodied by modifying constituent elements without departing from the scope of the invention in the implementation stage.

  The gas barrier laminate film of the present invention is suitably used in the field of packaging of foods, daily necessities, pharmaceuticals, etc., and in the field of solar cell related members and electronic equipment related members, where particularly high gas barrier properties are required.

  DESCRIPTION OF SYMBOLS 1 ... Base material layer, 2 ... Gas barrier layer, 3 ... Intermediate | middle layer, 4 ... Gas barrier layer, 10 ... Gas barrier property laminated | multilayer film.

Claims (4)

A gas barrier laminate film in which a first gas barrier layer made of an inorganic oxide, an intermediate layer, and a second gas barrier layer made of an inorganic oxide are sequentially laminated on one surface of a base material layer made of a transparent plastic film. In
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), and has a thickness of 20 nm or more and 500 nm or less. Characteristic gas barrier laminate film.   The gas barrier property according to claim 1, wherein an intermediate layer laminated between the first gas barrier layer and the second gas barrier layer is formed by a plasma CVD method (chemical vapor deposition method). Laminated film.   The gas barrier laminate film according to claim 1 or 2, wherein the first gas barrier layer and the second gas barrier layer are any one of silicon oxide, aluminum oxide, titanium oxide, and magnesium oxide. The water vapor transmission rate (X) of the gas barrier laminate film at 40 ° C. and 90% RH is 0.1 g / m ² · day or less,
The water vapor permeability (Y) of the gas barrier laminate film under an environment of 85 ° C. and 85% RH is 1.0 g / m ² · day or less,
The relationship between X and Y is expressed by the following formula: Y / X ≦ 10
The gas barrier laminate film according to any one of claims 1 to 3, wherein:

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