JP2010076288A - Gas-barrier laminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas-barrier laminated film which is excellent in water vapor-barrier property and is transparent. <P>SOLUTION: The gas-barrier laminated film is made by successively laminating a gas-barrier layer 2 made of silicon oxide and a coating film layer 3 containing polymerizable acrylic monomer or a mixture of monomer and oligomer on at least one side of a base layer 1 made of transparent plastic film, wherein the gas-barrier layer is made of a silicon oxide represented by SiOxCy (x is 1.5 to 2.0, y is 0.1 to 0.5), a thickness of the gas-barrier layer is 50 nm to 2,000 nm and a thickness of the coating layer is 0.1 μm to 10 μm. <P>COPYRIGHT: (C)2010,JPO&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 to alter 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 through the packaging, having to be disposed of as non-combustible material after use, and being unable to use metal detectors to inspect the packaging. 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, 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 above 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 the 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 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. 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 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, the object of the present invention is to solve the problem of insufficient gas barrier properties for FPDs such as electronic paper, LCD, and organic EL described above, and is a transparent gas barrier laminate film excellent in water vapor barrier properties. Is to provide.

The invention according to claim 1 includes a gas barrier layer made of silicon oxide and a polymerizable acrylic monomer or a mixture of a monomer and an oligomer on at least one surface of a base material layer made of a transparent plastic film. In the gas barrier laminate film formed by sequentially laminating the coating layer,
The gas barrier 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 50 nm or more and 2000 nm or less, The gas barrier laminate film, wherein the coating layer has a thickness of 0.1 μm or more and 10 μm or less.

  According to a second aspect of the present invention, the gas barrier layer is made of silicon oxide represented by SiOxCy (x is 1.6 or more and 1.9 or less, y is 0.1 or more and 0.3 or less), and has a thickness. The gas barrier laminate film according to claim 1, wherein the thickness is from 100 nm to 1000 nm.

  The invention according to claim 3 is the gas barrier laminate film according to claim 1 or 2, wherein the gas barrier layer is formed by a plasma chemical vapor deposition (CVD) method.

  The invention according to claim 4 is the gas barrier laminate film according to any one of claims 1 to 3, wherein the coating layer is formed using a flash vapor deposition method.

  The invention according to claim 5 is characterized in that a curing shrinkage ratio of the polymerizable acrylic monomer or a mixture of the monomer and the oligomer is 0.2% or more and 10% or less. The gas barrier laminate film according to any one of the above.

  According to a sixth aspect of the present invention, the polymerizable acrylic monomer or the mixture of the monomer and the oligomer contains monoacrylate or diacrylate or both, and the monoacrylate or diacrylate or both The gas barrier laminate film according to any one of claims 1 to 5, wherein the content is 50% by weight or more of the polymerizable acrylic monomer or a mixture of the monomer and the oligomer.

  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 an FPD. Furthermore, when the gas barrier laminate film of the present invention uses a flash vapor deposition method when forming a coating layer, the gas barrier layer and the coating layer are continuously laminated on the base material layer in a transparent vapor deposition apparatus. Therefore, the production cost can be reduced.

  Hereinafter, the best mode for carrying out the gas barrier laminate film of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the gas barrier laminate film of the present invention. A gas barrier 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) on the base material layer 1 and has a thickness of 50 nm or more and 2000 nm or less. The layer 2 and the coating layer 3 containing a polymerizable acrylic monomer or a mixture of a monomer and an oligomer and having a thickness of 0.1 μm or more and 10 μm or less are sequentially laminated.

  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, 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 suitability for processing when other layers are laminated, it is practical. 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, practically in the range of 25 μm or more and 200 μm or less in consideration of processing suitability. It is preferable that

  In the gas barrier laminate film of the present invention, the gas barrier layer 2 is formed on the substrate 1 and is made of silicon oxide. The gas barrier layer 2 is 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 50 nm or more and 2000 nm or less.

  The most important point in the gas barrier laminate film of the present invention is that y of the gas barrier layer 2 made of silicon oxide represented by SiOxCy is 0.1 or more and 0.5 or less.

  As will be described later, one of the roles of the coating layer 3 is to improve the gas barrier property that the internal stress due to curing shrinkage at the time of forming the coating layer 3 is manifested by tightening the gas barrier layer 2. If the gas barrier layer 2 cannot withstand, the adhesion of the gas barrier layer 2 will be reduced. Therefore, the gas barrier layer 2 made of silicon oxide contains a carbon component, and the gas barrier layer 2 has a film quality that is flexible enough to relieve the internal stress. In order to alleviate internal stress due to the carbon content as described above, it is preferable to set y to 0.1 or more in SiOxCy indicating the composition ratio of the gas barrier layer 2.

  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 2 too much, and it is preferable to set y to 0.5 or less. When higher transparency is required, y is set to 0.3 or less. It is preferable. Further, in the gas barrier laminate film of the present invention, there is no problem even if y is a different value in the gas barrier layer 2. For example, in the depth direction of the gas barrier layer 2, this y is increased or decreased in the opposite direction. You can also do it.

  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.

  Further, in the gas barrier laminate film of the present invention, there is no problem even if x is a different value in the gas barrier layer 2. For example, x is increased or decreased in the depth direction of the gas barrier layer 2. You can also do it.

  In the gas barrier laminate film of the present invention, the thickness of the gas barrier layer 2 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) is 50 nm or more and 2000 nm or less, More preferably, it is 100 nm or more and 1000 nm or less. When the film thickness is less than 50 nm, the function as a gas barrier material cannot be sufficiently achieved. On the other hand, when the film thickness exceeds 2000 nm, it is difficult to maintain flexibility in the gas barrier layer 2, and bending is difficult. This is because if the external stress such as tension or tension is applied, the gas barrier layer 2 may be cracked.

  In the gas barrier laminate film of the present invention, the method for forming the gas barrier layer 2 is not particularly limited, but the gas barrier layer 2 made of silicon oxide is formed on the surface of the base material layer 1 in a vacuum, In order to develop a high gas barrier property and to make the y value of the gas barrier layer 2 represented by SiOxCy 0.1 or more and 0.5 or less as described later, plasma chemical vapor deposition (CVD) method is currently used. Preferably, it can form into a film on the single side | surface or both surfaces of the base material layer which consists of the said 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 2 made of silicon oxide 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 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. Among these silane compounds, considering that the film formation pressure and the vapor pressure, and the y value of the surface portion of the gas barrier layer 2 represented by SiOxCy is 0.1 or more and 0.5 or less, as will be described later, TEOS, TMOS, TMS, HMDSO, tetramethylsilane and the like are preferable.

  In the film formation by the plasma CVD method, the silane compound is 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 is laminated on the base material layer 1. Can do. In the plasma CVD method, the film quality of the gas barrier layer 2 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 2 can be increased and decreased relatively easily. For example, changing the silane compound and the gas type, mixing ratio of the silane compound and oxygen gas, increase / decrease in applied power, and the like are effective techniques.

  The coating layer 3 in the gas barrier laminate film of the present invention is formed on the gas barrier layer 2 and contains a polymerizable acrylic monomer or a mixture of a monomer and an oligomer. Thereby, as will be described later, the coating layer 3 exhibits a function of improving the gas barrier property.

  The role of the coating layer 3 in the gas barrier laminate film of the present invention is to protect the gas barrier layer 2 having excellent gas barrier properties when it is subjected to normal processing such as printing, laminating, bag making, A protective function when an external stress such as a tensile force is applied, and a gas barrier property improving function that is manifested by tightening the gas barrier layer by an internal stress due to curing shrinkage when the coating layer 3 is formed.

  The thickness of the coating layer 3 is preferably 0.1 μm or more and 10 μm or less. If the film thickness is less than 0.1 μm, it is difficult to form a uniform coating layer and a sufficient protective function cannot be exhibited, and internal stress due to curing shrinkage at the time of forming the coating layer 3 only slightly occurs. Since the gas barrier layer cannot be sufficiently tightened, the function of improving the gas barrier property cannot be expected so much. Further, if the film thickness exceeds 10 μm, curing by electron beam irradiation or UV irradiation at the time of forming the coating layer 3 becomes difficult, and internal stress due to curing shrinkage works excessively, and the adhesion of the gas barrier layer 2 may be lowered. Becomes higher.

  In addition, in order for the coating layer 3 to exhibit a gas barrier property improving function and not deteriorate the adhesion, it is necessary to consider the balance between the thickness of the coating layer 3 and the thickness of the gas barrier layer 2 made of silicon oxide. That is, as described above, one of the roles of the coating layer 3 is to improve the gas barrier property by tightening the gas barrier layer by internal stress due to curing shrinkage at the time of forming the coating layer 3. As the thickness of the layer 3 increases, the gas barrier layer 2 works more greatly. Also, the resistance of the gas barrier layer 2 to the internal stress decreases as the thickness of the gas barrier layer 2 increases. Even if it acts on the layer 2, as the thickness of the gas barrier layer 2 increases, the gas barrier layer 2 cannot withstand internal stress, and the adhesion tends to decrease.

  The method for forming the covering layer 3 of the present invention is not limited to dry coating, and may be wet coating, but an uncured acrylic monomer or a mixture of monomers and oligomers that can be polymerized by flash vapor deposition. A gas barrier layer 2 made of silicon oxide is laminated on the gas barrier layer 2 as a coating layer, cured by irradiation with ultraviolet rays or an electron beam, and continuously on the base material layer 1 in a vacuum in a vacuum evaporation apparatus. Since the coating layer 3 can be laminated and the production cost can be reduced efficiently, it is desirable to use the flash vapor deposition method at the present time.

  The uncured coating layer is vaporized by dropping a polymerizable acrylic monomer or a mixture of monomers and oligomers from a nozzle inserted into a high-temperature evaporation source in a vacuum deposition apparatus (flash deposition). The gas barrier layer 2 can be continuously laminated.

  When the uncured coating layer is cured by irradiating with ultraviolet rays, a photopolymerization initiator is mixed with a polymerizable acrylic monomer or a mixture of a monomer and an oligomer. Specific examples of the photopolymerization initiator include benzoin ethers, benzophenones, xanthones, and acetophenone derivatives. These photopolymerization initiators are mixed in a proportion of 0.01 to 10% by weight, preferably 0.1 to 5% by weight.

  When the uncured coating layer is cured by irradiation with an electron beam, the balance between the thickness of the coating layer, the energy condition of the electron beam, the processing speed, and the charge removal becomes important. This is because if excessive electron beam energy is supplied, the coating layer is charged, and as a result, the gas barrier property of the gas barrier layer 2 may be impaired by peeling discharge.

  The curing shrinkage of the polymerizable acrylic monomer or mixture of monomer and oligomer forming the coating layer 3 of the present invention is preferably 0.2% or more and 10% or less, more preferably 5% or more and 10%. % Or less.

Here, the curing shrinkage percentage is a value set by calculating the change (%) in density before and after curing according to the following formula.
Curing shrinkage rate = (density after curing−density before curing) / density after curing × 100

  If the cure shrinkage rate is less than 0.2%, the gas barrier layer 2 cannot be sufficiently tightened due to the slight internal stress caused by the cure shrinkage when the coating layer 3 is formed, and therefore the gas barrier property improving function cannot be expected. . On the other hand, if the cure shrinkage rate exceeds 10%, the internal stress due to cure shrinkage during the formation of the coating layer 3 will act excessively, and the possibility that the adhesion of the gas barrier layer 2 will be reduced.

  In the gas barrier laminate film of the present invention, a polymerizable acrylic monomer or a mixture of a monomer and an oligomer, which is a raw material of the coating layer 3, contains at least one of monoacrylate and diacrylate, The total content of acrylate and diacrylate is preferably 50% by weight or more. That is, if the combined content of acrylates having a trifunctional or higher acryloyl group exceeds 50% by weight, it is difficult to suppress the curing shrinkage at the time of forming the coating layer 3 to 10% or less, and the internal stress due to the curing shrinkage is excessive. This is because there is a high possibility that the adhesion of the gas barrier layer 2 is lowered. However, since an acrylate having a tri- or higher functional acryloyl group has an effect of improving the degree of cross-linking, it is preferably used in a small amount when forming a strong coating layer. About% by weight is desirable.

  As these acrylates, polyester monomers, polyether acrylates, acrylic acrylates, urethane acrylates, epoxy acrylates, silicone acrylates, polyacetal acrylates, polybutadiene acrylates, melamine acrylates and other highly polymerizable acrylic monomers or oligomers are appropriately selected. Can be used.

  There are various types of monoacrylates, diacrylates and triacrylates, which are not particularly limited. However, when the flash vapor deposition method is used, the adhesiveness with the gas barrier layer 2 is good and the uncured coating layer is efficiently cured. It is preferable to select a material that can be formed with excellent hygiene.

  Specific examples of the monoacrylate include 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-succinic acid, methoxy-polyethylene glycol acrylate, and phenoxy-polyethylene glycol acrylate. Examples of the diacrylate include triethylene glycol diacrylate, tripropylene glycol diacrylate, propoxylated neopentyl glycol diacrylate, and 1,9-nonanediol diacrylate. Examples of the triacrylate include trimethylolpropane triacrylate and ethoxylated trimethylolpropane triacrylate. These ratios are desirably set to, for example, monoacrylate / diacrylate / triacrylate = 60/30/10 (% by weight).

  When the flash vapor deposition method is used, the viscosity of the polymerizable acrylic monomer or the mixture of the monomer and the oligomer is 200 mPa · s / 25 ° C. or less, more preferably 100 mPa · s / 25 ° C. or less. desirable. This is a gas barrier layer in which a polymerizable acrylic monomer or a mixture of a monomer and an oligomer is dropped from a nozzle inserted into a high-temperature evaporation source in a vacuum deposition apparatus and vaporized instantaneously. When the uncured coating layer is continuously laminated on the surface of No. 2, if the viscosity is too high, it is difficult to drop at a constant rate little by little from a nozzle inserted into a high-temperature evaporation source. It is.

  Since the gas barrier laminate film of the present invention is used as a packaging material in the fields of packaging such as foods, daily necessities, and pharmaceuticals and electronic equipment-related members, a polymerizable acrylic monomer or a mixture of monomers and oligomers is The PII (Primary Irritation Index) is preferably 2.0 or less. In addition, PII shows the degree of skin disorder of chemicals, and the smaller the value, the lower the irritation.

  The gas barrier laminate film of the present invention 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) on the base layer 1 and has a thickness of 50 nm. A gas barrier layer 2 having a thickness of 2000 nm or less and a coating layer 3 containing a polymerizable acrylic monomer or a mixture of a monomer and an oligomer and having a thickness of 0.1 μm or more and 10 μm or less are sequentially laminated. What is necessary is just to have a more complicated laminated structure. For example, the gas barrier layer 2 and the coating layer 3 may be sequentially laminated on the surfaces on both sides of the base material layer 1. Further, a laminate of the gas barrier layer 2 and the coating layer 3 may be laminated on the laminate of the gas barrier layer 2 and the coating layer 3. Furthermore, a printing layer may be laminated on the surface of the coating layer 3. In this case, a printing layer having a thickness of 0.1 to 2.0 μm can be laminated without any particular limitation by a known printing method or coating method using a conventional printing ink conventionally used.

  The gas barrier laminate film of the present invention can be laminated with other films and used as a packaging material in the fields of packaging such as foods, daily necessities, and pharmaceuticals, and electronic device related members. For example, 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 on the inner surface (coating layer 3) side with an adhesive. Further, the gas barrier laminate film of the present invention is used as an intermediate layer, and an outer film layer and the like are laminated on the outer surface (base material layer 1) side through an adhesive, and the adhesive on the inner surface (coating layer 3) side. A structure in which a heat seal layer or the like is laminated via a gap may be used.

  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.

  Although the thickness of an intermediate | middle film layer, an outer film layer, and a heat seal layer is decided according to the objective, generally it is the range of 15-200 micrometers. 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 and 2, as shown in FIG. 1, a gas barrier laminated film in which a gas barrier layer 2 and a coating layer 3 were sequentially laminated on a base material layer 1 was produced.

<Example 1>
A polyethylene naphthalate (PEN) film having a thickness of 100 μm was prepared as the base material layer 1 and placed in a vacuum deposition apparatus. Using a plasma CVD method, a mixed gas of hexamethyldisiloxane (HMDSO) / oxygen = 10/100 sccm is introduced between the electrodes, electric power is applied to 0.5 kW to form plasma, and SiOxCy (x = The gas barrier layer 2 having a thickness of 200 nm represented by 1.65, y = 0.16) was laminated to form the gas barrier layer 2 made of silicon oxide. Subsequently, 60/30/10 (% by weight) of 2-hydroxy-3-phenoxypropyl acrylate, propoxylated neopentyl glycol diacrylate, and ethoxylated trimethylolpropane triacrylate was formed on the gas barrier layer 2 by flash vapor deposition. An uncured coating layer made of a mixture (curing shrinkage: 6.3%) was laminated, and then cured by irradiation with an electron beam to form a coating layer 3 having a thickness of 3 μm. Thus, the gas barrier laminate film of Example 1 was produced.

<Example 2>
In the gas barrier laminate film of Example 1, the thickness of the gas barrier layer 2 made of silicon oxide represented by SiOxCy (x = 1.65, y = 0.16) was set to 500 nm. Furthermore, the thickness of the coating layer 3 on the gas barrier layer 2 was 1 μm. Other conditions were the same as in Example 1. Thus, a gas barrier laminate film of Example 2 was produced.

<Comparative Example 1>
In the gas barrier laminate film of Example 1, only the gas barrier layer 2 made of silicon oxide represented by SiOxCy (x = 1.65, y = 0.16) was formed on the base material layer 1 in the same manner as in Example 1. The film layer 3 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, x of the gas barrier layer 2 made of silicon oxide represented by SiOxCy was set to 1.70 and y was set to 0.05. Other conditions were the same as in Example 1. Thus, a gas barrier laminate film of Comparative Example 2 was produced.

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

Next, the surface of the coating layer 3 of each of the single films of Examples 1 and 2 and Comparative Example 2 and the surface of the gas barrier layer 2 of the single film of Comparative Example 1 are passed through a polyurethane adhesive of 5 g / m ^2. A 50 μm thick polypropylene heat seal layer was laminated. Hereinafter, these are called laminated films.

<Comparison evaluation>
1. Water Vapor Permeability For single films of Examples 1 and 2 and Comparative Examples 1 and 2, water vapor in a 40 ° C.-90% RH atmosphere was measured with a water vapor permeability meter (MOCON PERMATRAN-W 3/31) manufactured by Modern Control. The transmittance (g / m ² · 24 h) was measured.

2. Laminate Strength The test pieces slit to 15 mm width from the laminated films of Examples 1 and 2 and Comparative Examples 1 and 2 were measured for laminate strength (N / 15 mm) with an ordinary Tensilon universal testing machine.
These measurement results are shown in Table 1.

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

  On the other hand, the gas barrier layered film of Comparative Example 2 in which the gas barrier layer 2 represented by SiOxCy does not satisfy y ≧ 0.1 has almost the same gas barrier property as the gas barrier layered films of Example 1 and Example 2. Although it was a level, the laminate strength of the laminated film was remarkably inferior.

  In addition, the gas barrier laminated film of Comparative Example 1 in which no coating layer was laminated had higher water vapor and poor gas barrier properties than the gas barrier laminated films of Example 1 and Example 2.

  The gas barrier laminate film of the present invention is suitable for the field of packaging of foods, daily necessities, pharmaceuticals, etc., the field of electronic equipment-related members, etc., and also when a particularly high gas barrier property is required as a plastic substrate for FPD. Used.

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

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material layer, 2 ... Gas barrier layer, 3 ... Coating layer.

Claims (6)

A gas barrier layer made of silicon oxide and a coating layer containing a polymerizable acrylic monomer or a mixture of a monomer and an oligomer are sequentially laminated on at least one surface of a base material layer made of a transparent plastic film. In the gas barrier laminate film,
The gas barrier 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 50 nm or more and 2000 nm or less, A gas barrier laminate film, wherein the thickness of the coating layer is 0.1 μm or more and 10 μm or less.   The gas barrier layer is made of silicon oxide represented by SiOxCy (x is 1.6 or more and 1.9 or less, y is 0.1 or more and 0.3 or less), and has a thickness of 100 nm or more and 1000 nm or less. The gas barrier laminate film according to claim 1.   The gas barrier layered film according to claim 1 or 2, wherein the gas barrier layer is formed by a plasma chemical vapor deposition (CVD) method.   The gas barrier laminate film according to any one of claims 1 to 3, wherein the coating layer is formed using a flash vapor deposition method.   The gas-barrier laminate according to any one of claims 1 to 4, wherein a curing shrinkage ratio of the polymerizable acrylic monomer or a mixture of the monomer and the oligomer is 0.2% or more and 10% or less. the film.   The polymerizable acrylic monomer or mixture of monomer and oligomer contains monoacrylate or diacrylate or both, and the content of the monoacrylate or diacrylate or both is the polymerizable acrylic type. The gas barrier laminate film according to any one of claims 1 to 5, which is 50% by weight or more of a monomer or a mixture of a monomer and an oligomer.

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