JP2011062977A - Gas barrier laminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent gas barrier laminated film causing no deterioration of gas barrier property even when subjected to the ordinary processing as a packaging material, suitably used in the packaging field of food, daily articles or pharmaceuticals or the filed of electronic equipment-related members, in particular, for the case of requiring high gas barrier property. <P>SOLUTION: The gas barrier laminated film is formed by sequentially forming an anchor layer, and a gas barrier layer formed of silicon oxide expressed by SiOxCy (x is 1.5-2.0, y is 0-0.5) on at least one face of a base material layer consisting of a plastic film. The anchor layer includes polyvinyl acetal, polyester polyol, an isocyanate compound and a silane coupling agent. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a transparent gas barrier laminate film that is suitably used when high gas barrier properties are required in the fields of packaging of foods, daily necessities, pharmaceuticals, etc., and fields related to electronic devices. .

  Packaging materials used for packaging of food, daily necessities, pharmaceuticals, etc., and packaging materials used for electronic equipment-related materials, etc., to prevent deterioration of the contents and to retain their functions and properties even during packaging In addition, it is necessary to prevent the influence of gases such as oxygen and water vapor that permeate the packaging material, which alters the contents, and it is required to have gas barrier properties that block 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. However, these packaging materials have many disadvantages, such as being unable to see the contents through them, having to be disposed of as non-combustible materials after use, and being unable to use metal detectors to inspect the contents. Had.

  As a packaging material that overcomes these drawbacks, Patent Document 1 discloses that a gas barrier layer is formed by depositing a thin film layer of a transparent inorganic oxide such as silicon oxide, aluminum oxide, or magnesium oxide on a base layer made of a transparent plastic film. In addition, a laminated film obtained by laminating an appropriate gas barrier coating layer thereon is disclosed.

  In recent years, the solar cell market has been 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 durability. 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 durability and high gas barrier properties without using an aluminum foil.

  In addition, developments have 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 on which the sunlight hits with a sheet made of a plastic material. Similarly to the back surface protection sheet, durability and high gas barrier properties are required. As a method for evaluating the durability of these surface protective sheet and back surface protective sheet, an accelerated test can be mentioned. The accelerated test is a method for evaluating the changes in the properties of the front and back protection sheets in a short time when the solar cell module is exposed to high temperatures and high humidity outdoors for a long time. (PCT) is known.

  In recent years, with the development of electronic paper and organic EL, which are expected as next-generation FPDs, in order to achieve flexibility in these FPDs, there is an increasing demand for replacing glass substrates with plastic films. 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 such a plastic film having a high gas barrier property, it is formed by a dry coating method such as a reactive vapor deposition method using electron beam vapor deposition or induction heating vapor deposition, a sputtering method, or a plasma chemical vapor deposition (CVD) method. Inorganic oxide thin films have been studied as those that can be expected to exhibit high gas barrier properties.

  However, even if the dry coating method is used, if a dense film is obtained in order to aim at high gas barrier properties, a high-temperature process is required, or the stress in the film tends to increase due to the denseness. is there. 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.

  Among them, a silicon oxide thin film formed by a plasma chemical vapor deposition method using an organosilane compound has been studied as a barrier layer exhibiting a high gas barrier property, and has been put into 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, but it is described that the water vapor barrier property is slightly inferior, and has a high gas barrier property. Gas barrier properties are insufficient for FPDs such as required electronic paper, LCD, and organic EL.

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

  The laminated film described in Patent Document 1 has a defect that gas barrier properties such as water vapor permeability deteriorate when subjected to normal processing as a packaging material such as printing, laminating, and bag making. It was. Therefore, the object of the present invention is to have a particularly high gas barrier property in which the gas barrier property does not deteriorate even when subjected to normal processing as a packaging material in the field of packaging of foods, daily necessities, pharmaceuticals, etc. and electronic equipment related members. It is to provide a transparent gas barrier laminate film that can be suitably used.

  In particular, it solves the problem of insufficient adhesion and gas barrier properties for FPDs such as the above-described back surface protection sheet and surface protection sheet of solar cell modules, electronic paper, LCD, and organic EL, An object is to provide a transparent gas barrier laminate film excellent in adhesion.

  In order to solve the above-mentioned problem, the invention according to claim 1 is characterized in that an anchor layer and SiOxCy (x is 1.5 or more and 2.0 or less, y is 0 or more and 0 or more) on at least one side of a base material layer made of a plastic film. In the gas barrier laminated film in which the gas barrier layer made of silicon oxide represented by the following formula is sequentially formed, the anchor layer contains at least a polyvinyl acetal, a polyester polyol, an isocyanate compound, and a silane coupling agent. This is a gas barrier laminate film.

  The invention according to claim 2 is the gas barrier laminate film according to claim 1, wherein the anchor layer has a thickness of 10 nm to 1000 nm.

  The invention according to claim 3 is characterized in that the silane coupling agent is contained in the anchor layer in an amount of 0.01 wt% to 20 wt%. It is a film.

  Moreover, as invention which concerns on Claim 4, the glass transition point of the said polyvinyl acetal is 50 to 130 degreeC, It is a gas barrier laminated film in any one of Claim 1 to 3 characterized by the above-mentioned. .

  Moreover, as invention which concerns on Claim 5, the glass transition point of the said polyester polyol is 50 to 130 degreeC, It is a gas barrier laminated film in any one of Claim 1 to 4 characterized by the above-mentioned. .

  The invention according to claim 6 is characterized in that the isocyanate compound is one or more isocyanate compounds selected from TDI, MDI, XDI, and HDI. The gas barrier laminate film according to any one of the above.

  The invention according to claim 7 is the gas barrier laminate film according to any one of claims 1 to 6, wherein the gas barrier layer is formed by a plasma chemical vapor deposition method.

  The invention according to claim 8 is the gas barrier laminate film according to any one of claims 1 to 7, wherein the thickness of the gas barrier layer is 10 nm or more and 1000 nm or less.

  The invention according to claim 9 is characterized in that the blending ratio of the polyvinyl acetal and the polyester polyol is in the range of 99/1 to 10/90 in terms of weight ratio. The gas barrier laminate film according to any one of the above.

  According to the present invention, the gas barrier properties are not deteriorated even if normal processing as a packaging material is performed in the field of packaging of foods, daily necessities, pharmaceuticals, etc., and fields related to electronic devices, and the packaging material is seen through. Thus, it is possible to provide a transparent gas barrier laminate film that can be suitably used when a particularly high gas barrier property is required for solar cells and FPDs.

It is a schematic sectional drawing which shows an example of the gas barrier laminated film of this invention.

  Hereinafter, the form for implementing the gas-barrier laminated film of this invention is demonstrated along drawing. FIG. 1 is a schematic cross-sectional view showing an example of the gas barrier laminate film of the present invention.

  From the silicon oxide represented by the anchor layer (2) and SiOxCy (x is 1.5 or more and 2.0 or less, y is 0 or more and 0.5 or less) on the base material layer (1). The gas barrier layer (3) is sequentially laminated.

  In the gas barrier laminate film of the present invention, the substrate 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. A film, a polycarbonate film, a polyacrylonitrile film, a polyimide film, a biodegradable plastic film such as polylactic acid, or the like is used.

  These transparent plastic films may be either stretched or unstretched, but those having excellent mechanical strength and dimensional stability are preferred. In particular, from the standpoint of heat resistance and dimensional stability, polyethylene terephthalate stretched biaxially is preferably used as the packaging material, and LCDs, organic EL, etc. that require higher heat resistance and dimensional stability. For FPD, polyethylene naphthalate, polyether sulfone, polycarbonate and the like are preferably used.

  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 workability when other layers are laminated, it is practical. Specifically, it is preferably in the range of 3 μm or more and 200 μm or less, particularly in the range of 6 μm or more and 30 μm or less. For FPDs such as electronic paper and organic EL, in consideration of processing suitability, it is practically 25 μm or more and 200 μm or less. It is preferable that it is the range of these.

  The anchor layer (2) in the gas barrier laminate film of the present invention is formed on the base material layer (1), and the base material (1) made of a plastic film and the gas barrier layer (3) made of silicon oxide. The function which improves adhesion and improves gas barrier property is exhibited.

  As the main component of the anchor layer (2), a combination of polyvinyl acetal, a polyester polyol, an isocyanate compound, and a silane coupling agent is particularly preferable.

  A silane coupling agent is a functional group in which an organic functional group present at one end of a silane coupling agent interacts in a composite composed of a polyol and an isocyanate compound, or reacts with a hydroxyl group of a polyol or an isocyanate group of an isocyanate compound. By using a silane coupling agent having a group, a stronger anchor layer (2) is formed, and the silanol group formed by hydrolysis of the alkoxy group at the other end and the surface functional group of the gas barrier layer (3) are strong. By the interaction, high adhesion with the gas barrier layer (3) can be expressed.

  In general, silane coupling agents having any organic functional group can be used, such as ethyl methoxysilane, vinyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, glycidoxypropyltrimethoxysilane, γ-methacryloxypropyl. One or more silane coupling agents such as methyl methoxymethoxy silane or hydrolysates thereof can be used.

  Furthermore, it is particularly preferred that the organic functional group of the silane coupling agent reacts with the hydroxyl group of the polyol or the isocyanate group of the isocyanate compound. For example, those having an isocyanate group such as γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, those having an amino group such as γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, Those with epoxy groups, such as γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, any of these may be used, and two or more types are mixed May be.

  If the addition amount of the silane coupling agent is too small, the high adhesion effect cannot be exhibited, and if it is too much, the gas barrier property may be deteriorated. It is preferably 20% by weight or less, more practically 10% by weight or less.

  The polyvinyl acetal is a polymer compound obtained by acetalization by condensing a hydroxyl group and an aldehyde group of polyvinyl alcohol or a saponified product of an ester portion thereof. The main skeleton is composed of an acetal group, an acetyl group, and a hydroxyl group, and reacts with an isocyanate group of an isocyanate compound described later to generate a urethane bond, which is excellent in film forming properties as an anchor layer. Especially, what consists of co-condensation of polyvinyl alcohol, acetaldehyde, and butyraldehyde is used preferably.

  Considering the reactivity with an isocyanate compound described later, the hydroxyl value of polyvinyl acetal is preferably between 5 and 200 KOHmg / g.

  Polyester polyol is terephthalic acid, isophthalic acid, phthalic acid, methylphthalic acid, trimellitic acid, pyromellitic acid, azelaic acid, adipic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid Acid materials such as acid, hexahydrophthalic acid, dodecanedioic acid, oleic acid, linoleic acid, stearic acid, caproic acid, myristic acid and their reactive derivatives; ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, neopentyl glycol, bishydroxyethyl terephthalate, trimethylolmethane, trimethylolpropane, glycerin, A polyester resin obtained from a alcoholic material such as nantaerythritol by a well-known production method has two or more hydroxyl groups at the inner end, and reacts with an isocyanate group of an isocyanate compound described later to generate a urethane bond. Yes, and excellent in film forming properties as an anchor layer.

  Considering the reactivity with the isocyanate compound described later, the hydroxyl value of the polyester polyol is preferably between 5 and 200 KOHmg / g.

  The glass transition point of polyvinyl acetal and polyester polyol is preferably 50 ° C. or higher and 130 ° C. or lower.

  When the glass transition point of polyvinyl acetal and polyester polyol is 50 ° C. or less, the anchor layer is soft, the anchor layer is thermally damaged, and cracks are generated in the gas barrier layer.

  Further, when the glass transition point is 130 ° C. or higher, the anchor layer becomes too hard, and when a force applied from the outside reaches a certain limit value, a micro crack (crack) is first generated, leading to brittle fracture. The brittle fracture is a fracture that occurs when the toughness and ductility are greatly reduced.

  The blending ratio of polyvinyl acetal and polyester polyol is preferably in the range of 99/1 to 10/90 in terms of weight ratio. More preferably, it is in the range of 90/10 to 50-50. A known method can be used as the mixing method, and is not particularly limited.

  The isocyanate compound is added to increase the adhesion with the base material layer (1) and the gas barrier layer (3) by a urethane bond formed by reacting with the polyvinyl acetal and the polyester polyol. Acts as a crosslinking or curing agent. In general, TDI (tolylene diisocyanate), MDI (diphenylmethane diisocyanate), XDI (xylylene diisocyanate), HDI (hexamethylene diisocyanate), and adducts and nurates thereof can be used. Such a urethane polymer may be used. Any of these may be used, or two or more of them may be mixed.

  If the amount of the isocyanate compound added is too small, the anchor layer (2) may be poorly cured, and if it is too large, a white flower phenomenon due to unreacted isocyanate groups may occur. Therefore, the amount of isocyanate compound added is preferably 50 equivalents or less of the isocyanate group derived from the isocyanate compound relative to the hydroxyl group derived from polyvinyl acetal and polyester polyol, and in particular, the isocyanate group and the hydroxyl group are equivalent. It is more preferable to add. A known method can be used as the addition method, and is not particularly limited.

  In the gas barrier laminate film of the present invention, the anchor layer (2) is prepared by mixing a polyvinyl acetal, a polyester polyol, an isocyanate compound, and a silane coupling agent in an arbitrary mixing ratio, and the mixed solution is used as a base layer ( It is formed by coating 1). The mixed solution may be diluted to an arbitrary concentration by adding a solvent.

  The anchor layer (2) is formed on one surface or both surfaces of the base material layer (1) using a known coating method such as a dipping method, a roll coating method, a gravure coating method, a reverse coating method, an air knife coating method, or a comma coating method. It can be obtained by coating, then removing the solvent, and drying and curing the coating film.

  The film thickness of the anchor layer (2) is preferably 10 nm or more and 1000 nm or less. If the film thickness is less than 10 nm, it is difficult to form a uniform film, and the adhesion may be lowered. On the other hand, if it exceeds 1000 nm, it is difficult to maintain flexibility in the anchor layer, cracks may occur, and gas barrier properties may be deteriorated, which is not preferable. Practically, it is preferably 20 nm or more and 500 nm or less.

  In the gas barrier laminate film of the present invention, the gas barrier layer (3) is formed on the anchor layer (2) and is made of silicon oxide. Further, the gas barrier layer (3) is represented by SiOxCy (x is 1.5 or more and 2.0 or less, y is a number of 0 or more and 0.5 or less) and has a thickness of 10 nm or more and 1000 nm or less. is there.

  However, since the gas barrier layer made of silicon oxide decreases in transparency as the carbon component increases, plastic materials for packaging materials such as food and daily necessities, and FPDs such as electronic paper and organic EL that require transparency are required. In the material, it is necessary not to increase the carbon component of the gas barrier layer (3) too much, and it is preferable to set y to 0.5 or less, and when higher transparency is required, y is set to 0.3 or less. It is preferable to make it.

  Moreover, in the gas barrier laminate film of the present invention, y may be a different value in the gas barrier layer (3), for example, in the depth direction of the gas barrier layer (3), Conversely, it can be made smaller.

  Further, regarding the oxygen component of the gas barrier layer represented by SiOxCy, there is a general tendency that transparency is improved by bringing x close to 2, and conversely, by reducing x from 2, gas barrier Tend to improve.

  That is, when x is too large, both of transparency and gas aria properties are adversely affected. Therefore, x is preferably 2.0 or less, and more highly transparent and high gas barrier properties can be achieved at the same time. Therefore, it is preferably 1.9 or less.

  Also, if x is less than 1.5, the transparency is significantly lowered, and is not suitable for packaging materials such as foods and daily necessities, and plastic substrates for FPD such as electronic paper and organic EL, which require transparency. For this reason, x is preferably 1.5 or more, and x is preferably 1.6 or more when higher transparency is required.

  Therefore, the practical range of x indicating the composition ratio of the oxygen component is 1.5 or more and 2.0 or less. Within such a range of x, both high transparency and high gas barrier properties are achieved. In order to achieve this, x is preferably 1.6 or more and 1.9 or less.

  In the gas barrier laminate film of the present invention, x may have a different value in the gas barrier layer (3). For example, in the depth direction of the gas barrier layer 2, x may be increased or vice versa. It can also be made smaller.

  In the gas barrier laminate film of the present invention, the thickness of the gas barrier layer (3) represented by SiOxCy (x is 1.5 or more and 2.0 or less, y is 0 or more and 0.5 or less), It is 10 nm or more and 1000 nm or less. If the film thickness is less than 10 nm, the function as a gas barrier material cannot be sufficiently achieved. On the other hand, if the film thickness exceeds 1000 nm, it is difficult to maintain flexibility in the gas barrier layer (3). This is because if an external stress such as bending or pulling is applied, the gas barrier layer (3) may be cracked.

  In the gas barrier laminate film of the present invention, the method for forming the gas barrier layer (3) is not particularly limited, but the gas barrier layer (3) made of silicon oxide is formed in a vacuum on the surface of the anchor layer (2). In order to exhibit a high gas barrier property by forming a film, plasma chemical vapor deposition is preferred at present, and the film can be formed on one or both sides of the base material layer made of the plastic film.

  Further, it is possible to perform continuous vapor deposition by taking up the characteristics of the plastic substrate, and it is preferable to use a wind-up vacuum deposition apparatus. 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 gas barrier layer (3) made of silicon oxide, which is laminated by the plasma chemical vapor deposition 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. A membrane can also be formed. Examples of silane compounds having carbon in the molecule include tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), tetramethylsilane (TMS), hexamethyldisiloxane (HMDSO), tetramethyldisiloxane, and methyltrimethoxysilane. A relatively low molecular weight silane compound may be selected, and one or more of these silane compounds may be selected.

  In the film formation by the plasma chemical vapor deposition method, the silane compound vaporized and mixed with oxygen gas is introduced between the electrodes, and the plasma is formed by applying power with a low temperature plasma generator, and is laminated on the anchor layer (2). can do. In the plasma chemical vapor deposition method, the film quality of the gas barrier layer (3) made of silicon oxide can be changed by various methods, and the composition ratio of the oxygen component and the carbon component of the gas barrier layer (3) can be increased or decreased. For example, changing the silane compound and the gas type, mixing ratio of the silane compound and oxygen gas, and increasing / decreasing applied power are effective techniques.

  The gas barrier laminate film of the present invention comprises an anchor layer (2) mainly composed of polyvinyl acetal, polyester polyol, isocyanate compound and silane coupling agent on a base layer (1), and SiOxCy (x is 1.5). 2.0 or less, y represents a number of 0 or more and 0.5 or less.) And a gas barrier layer (3) made of silicon oxide represented by It may be taken. For example, the anchor layer (2) and the gas barrier layer (3) may be sequentially laminated on the surfaces on both sides of the base material layer (1).

  EXAMPLES Hereinafter, although an Example and a comparative example further demonstrate this invention, this invention is not restrict | limited to the following example.

(Preparation of anchor mixture)
(Mixed liquid A)
In a diluting solvent, polyvinyl butyral (molecular weight 800, Tg 70 ° C.) and adipic acid-based polyester polyol (molecular weight 1500, Tg 100 ° C.) are mixed at a weight ratio of 7/3 and stirred. Hexamethylene diisocyanate (HDI) is added so that the isocyanate groups of the isocyanate compound are equivalent to the hydroxyl groups of polyvinyl butyral and polyester polyol. A solution obtained by adding γ-isocyanatopropyltriethoxysilane to 0.5 wt% with respect to the total solid content and diluting to an arbitrary concentration is defined as (mixed solution A).

(Mixed liquid B)
In (mixture A), γ-isocyanatopropyltriethoxysilane was added so as to be 5% by weight based on the total solid content, and the mixture prepared in the same manner as (mixture A) (mixture B) ).

(Mixed liquid C)
In (mixture A), γ-isocyanatopropyltriethoxysilane is not added, and the mixture prepared in the same manner as in (mixture A) is referred to as (mixture C).

Example 1
As the base material layer 1, a polyethylene terephthalate (PET) film having a thickness of 100 μm is prepared, and the one side of the film is coated with (mixed liquid A) by a gravure coating method, dried and cured, and an anchor layer having a thickness of 80 nm (2) Formed. Subsequently, using a plasma chemical vapor deposition method, a mixed gas of hexamethyldisiloxane (HMDSO) / oxygen = 10/100 sccm is introduced between the electrodes, and a plasma is formed by applying electric power of 0.5 kW, on the anchor layer (2). A gas barrier layer (3) having a thickness of 100 nm represented by SiOxCy (x = 1.8, y = 0.05) was laminated. Thus, a gas barrier laminate film of Example 1 was produced.

(Example 2)
In the gas barrier laminate film of (Example 1), the anchor layer (2) was formed using (mixed liquid B). Other conditions were the same as in (Example 1), and a gas barrier laminate film of (Example 2) was produced.

(Example 3)
In the gas barrier laminate film of (Example 1), polyethylene naphthalate (PEN) having a thickness of 100 μm is prepared as the base material layer (1), and the anchor layer (2) and the gas barrier layer are prepared in the same manner as in (Example 1). (3) was laminated to produce a gas barrier laminate film of (Example 3).

(Comparative Example 1)
In the gas barrier laminate film of (Example 1), from the silicon oxide represented by SiOxCy (x = 1.8, y = 0.05) on the base material layer (1) in the same manner as (Example 1). Only the gas barrier layer (3) to be formed was laminated, and the anchor layer (2) was not laminated. Thus, a gas barrier laminate film of (Comparative Example 1) was produced.

(Comparative Example 2)
In the gas barrier laminate film of (Example 1), the anchor layer (2) was formed using (mixed liquid C). Other than that was carried out similarly to (Example 1), and produced the gas barrier laminated film of (Comparative Example 2).

(Comparative Example 3)
In the gas barrier laminate film of (Example 3), the anchor layer (2) was formed using (mixed liquid C). Other than that was carried out similarly to (Example 3), and produced the gas-barrier laminated film of (Comparative Example 3).

  Hereinafter, the gas barrier laminate films of (Example 1), (Example 2), (Comparative Example 1), and (Comparative Example 2) produced as described above are referred to as single films.

Next, a PET film having a thickness of 50 μm was laminated on the surface of the gas barrier layer (3) of each single film by a dry laminating method through a polyurethane adhesive of 5 g / m ² . These are hereinafter referred to as laminated films.

(Comparison evaluation)
"Water vapor permeability"
About the single films of (Example 1), (Example 2) and (Comparative Example 1), (Comparative Example 2), the water vapor permeability meter (MOCON PERMATRAN-W 3/31) manufactured by Modern Control Co., Ltd. was used. The water vapor transmission rate (g / m ² / day) under a -90% RH atmosphere was measured.

“Lamination strength”
About the test piece slit to 15 mm width from the laminated film of (Example 1), (Example 2), (Comparative Example 1), and (Comparative Example 2), the laminate strength (N / 15 mm) was measured with a Tensilon type universal testing machine. Was measured.

  Further, a pressure cooker test (PCT) of the laminated film was performed (stored at 105 ° C. under 100% RH for 96 hours), and the laminate strength after PCT was measured. The measurement results are shown in (Table 1).

  As can be seen from (Table 1), the gas barrier laminate films (single films) of (Example 1), (Example 2), and (Example 3) have a low water vapor permeability, particularly (Example 3). The water vapor barrier property of was high. Furthermore, the laminated films of (Example 1), (Example 2), and (Example 3) have high laminate strength.

  On the other hand, the gas barrier laminate film in which the anchor layer is not laminated (Comparative Example 1) is inferior in water vapor permeability and laminate strength as compared with the gas barrier laminate film in (Example 1).

  The gas barrier laminated film of Comparative Example 2 and Comparative Example 3 that does not contain a silane coupling agent in the anchor layer is a single layer film of water vapor as compared with the gas barrier laminated film of Example 1. Although the transmittance was at the same level, the laminate strength of the laminated film stored for 96 hours at 105 ° C. and 100% RH was remarkably inferior.

1 Base material layer 2 Anchor layer 3 Gas barrier layer

Claims (9)

  From at least one surface of a base material layer made of a plastic film, an anchor layer and silicon oxide represented by SiOxCy (x is 1.5 or more and 2.0 or less, y is 0 or more and 0.5 or less). In the gas barrier laminate film in which the gas barrier layers are sequentially formed, the anchor layer contains at least a polyvinyl acetal, a polyester polyol, an isocyanate compound, and a silane coupling agent.   The gas barrier laminate film according to claim 1, wherein the anchor layer has a thickness of 10 nm or more and 1000 nm or less.   The gas barrier laminate film according to claim 1 or 2, wherein the silane coupling agent is contained in the anchor layer in an amount of 0.01 wt% to 20 wt%.   4. The gas barrier laminate film according to claim 1, wherein a glass transition point of the polyvinyl acetal is 50 ° C. or higher and 130 ° C. or lower. 5.   5. The gas barrier laminate film according to claim 1, wherein the polyester polyol has a glass transition point of 50 ° C. or higher and 130 ° C. or lower.   The gas barrier laminate film according to any one of claims 1 to 5, wherein the isocyanate compound is one or more isocyanate compounds selected from TDI, MDI, XDI, and HDI.   The gas barrier layered film according to any one of claims 1 to 6, wherein the gas barrier layer is formed by a plasma chemical vapor deposition method.   The thickness of the said gas barrier layer is 10 nm or more and 1000 nm or less, The gas barrier laminated film in any one of Claim 1 to 7 characterized by the above-mentioned.   The gas barrier laminate film according to any one of claims 1 to 8, wherein a blending ratio of the polyvinyl acetal and the polyester polyol is in a range of 99/1 to 10/90 in terms of weight ratio.

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