JP2010173134A - Gas barrier laminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent gas barrier laminated film which can be suitably used in the case where gas barrier property is not deteriorated even if a usual processing is applied as a packaging material, and particularly where high gas barrier property is required in a packaging field such as food, daily commodities, and drug medicines or the field such as electronic apparatus related members. <P>SOLUTION: The gas barrier laminated film is formed by successively laminating on one surface of a base layer 1 a gas barrier layer 2 (thickness Xa), a coated layer 3 (thickness Ya), a gas barrier layer 4 (thickness Xb), and a coated layer 5 (thickness Yb), and the relation among Xa, Xb, Ya, and Yb satisfies 0.002≤XaYa, 0.002≤XbYb, and XaYa+(Xa+Xb)Yb≤0.5 (unit: 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, and the like, 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 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.

  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.

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 the 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.

  Accordingly, the object of the present invention is to have a particularly high gas barrier property in which the gas barrier property is not deteriorated even if the normal processing as a packaging material is performed in the field of packaging such as food, daily necessities, and pharmaceuticals, and electronic equipment-related members. It is to provide a transparent gas barrier laminate film that can be suitably used. In particular, for FPDs such as the above-mentioned electronic paper and organic EL, it solves the problem of insufficient gas barrier properties, and provides a transparent gas barrier laminate film excellent in oxygen barrier properties and water vapor barrier properties. There is.

As means for solving the above-mentioned problems, the invention according to claim 1 is characterized in that a gas barrier layer 2, a coating layer 3, a gas barrier layer 4, and a coating are formed on one surface of a base material layer 1 made of a transparent plastic film. In the gas barrier laminated film in which the layers 5 are sequentially laminated, the gas barrier layer 2 and the gas barrier layer 4 are made of silicon oxide, and the film thickness of the gas barrier layer 2 (thickness Xa) and the film thickness of the gas barrier layer 4 ( The thickness Xb) is 0.005 μm or more and 0.2 μm or less, and the coating layer 3 and the coating layer 5 form an acrylic monomer or a mixture of a monomer and an oligomer that can be polymerized using a flash vapor deposition method. Films are cured by irradiation with ultraviolet rays or electron beams, and the film thickness (thickness Ya) of the coating layer 3 and the film thickness (thickness Yb) of the coating layer 5 are 0.1 μm or less. And at 10μm or less, Xa, Xb, the relationship Ya and Yb, and satisfies the following three formulas, a gas barrier laminate film.
0.002 ≦ XaYa
0.002 ≦ XbYb
XaYa + (Xa + Xb) Yb ≦ 0.5
(The unit of the thickness of Xa, Xb, Ya, Yb in the formula is μm)

  The invention according to claim 2 is that the gas barrier layer 2 and the gas barrier layer 4 laminated on the surface of the base material layer 1 and the coating layer 3 are formed by a plasma chemical vapor deposition (CVD) method. It is characterized by these. It is a gas-barrier laminated film of Claim 1.

  The invention according to claim 3 is the polymerizable acrylic monomer or monomer and oligomer forming the coating layer 3 and the coating layer 5 laminated on the surfaces of the gas barrier layer 2 and the gas barrier layer 4. 3. The gas barrier laminate film according to claim 1, wherein the mixture has a curing shrinkage rate of 0.2% or more and 10% or less.

  According to a fourth aspect of the present invention, the polymerizable acrylic monomer or the mixture of the monomer and the oligomer contains at least one of monoacrylate and diacrylate, and the monoacrylate and diacrylate The gas barrier laminate according to any one of claims 1 to 3, wherein the combined content of acrylates is 50% by weight or more of the polymerizable acrylic monomer or a mixture of monomers and oligomers. It is a film.

  The invention according to claim 5 is characterized in that the surface of the coating layer 5 laminated on the surface of the barrier layer 4 is subjected to plasma treatment. It is a gas barrier laminate film.

  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. Therefore, 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.

It is sectional drawing of an example of the gas barrier laminated film in the Example of this invention.

  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 cross-sectional view of an example of the gas barrier laminate film of the present invention. On one surface of the base material layer 1, a gas barrier layer 2 made of silicon oxide, a coating layer 3 made by curing a polymerizable acrylic monomer or a mixture of a monomer and an oligomer, and a gas barrier layer made of silicon oxide 4 and a coating layer 5 formed by curing a polymerizable acrylic monomer or a mixture of a monomer and an oligomer are sequentially laminated in the thickness direction.

  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 3 to 200 μm, particularly in the range of 6 to 30 μm.

  In the gas barrier laminate film of the present invention, the method for forming the gas barrier layer 2 and the gas barrier layer 4 is not particularly limited, but the gas barrier layer 2 and the gas barrier made of silicon oxide are formed on the surfaces of the base material layer 1 and the coating layer 3. In order to form the layer 4 in a vacuum and exhibit a high gas barrier property, the plasma CVD method 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 2 and the gas barrier layer 4 made of silicon oxide, which are 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 an inert gas is added to the raw materials. A film can also be formed. 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 on the surface of the substrate layer 1 and It can be laminated on the surface of the coating layer 3. In the plasma CVD method, the film quality of the gas barrier layer 2 and the gas barrier layer 4 made of silicon oxide can be changed by various methods. For example, the silane compound and the gas species can be changed, and the silane compound and oxygen gas can be changed. The mixing ratio, increase / decrease in applied power, etc. can be considered.

  Further, as a method for forming the gas barrier layer 2 and the gas barrier layer 4 other than the plasma CVD method, a vacuum vapor deposition method is preferable. As with the plasma CVD method, the gas barrier layer 2 and the gas barrier layer 4 are formed on one side or both sides of the substrate layer made of the plastic film. Can do. 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. In order to improve the adhesion between the base material layer 1 and the coating layer 3, a plasma assist method, an ion beam assist method, or the like can be used. Further, in order to increase the transparency of the deposited thin film layer, reactive deposition may be performed by blowing oxygen gas or the like.

  In the gas barrier laminate film of the present invention, the gas barrier layer 2 and the gas barrier layer 4 laminated on the surface of the base material layer 1 and the surface of the coating layer 3 are transparent and alter the contents of oxygen, water vapor and other contained materials. It has excellent gas barrier properties that block gas. The thickness Xa [μm] of the gas barrier layer 2 and the thickness Xb [μm] of the gas barrier layer 4 are each 0.005 μm or more and 0.2 μm or less, more preferably 0.005 μm or more and 0.1 μm or less. Here, if the film thickness is less than 0.005 μm, a uniform vapor-deposited thin film layer may not be obtained, and the function as a gas barrier material cannot be sufficiently achieved. On the other hand, if the film thickness exceeds 0.2 μm, it is difficult to maintain flexibility in the deposited thin film layer, and if an external stress such as bending or pulling is applied, the deposited thin film layer may be cracked.

  Further, in the present invention, the gas barrier layer 2 and the gas barrier obtained by laminating an acrylic monomer or a mixture of a monomer and an oligomer, which can be polymerized by the flash vapor deposition method, on one surface of the base material layer 1 as an uncured flash vapor deposition coating layer. The gas barrier layer 2 and the coating layer 3 made of silicon oxide can be laminated on the layer 4 and cured by irradiating ultraviolet rays or an electron beam in vacuum in a vacuum vapor deposition apparatus. Since the gas barrier layer 4 and the coating layer 5 made of silicon oxide can be successively 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 flash-deposited coating layer is vaporized by dropping a polymerizable acrylic monomer or a mixture of monomer and oligomer from a nozzle inserted in a high-temperature evaporation source in a vacuum deposition apparatus. Vapor deposition), the gas barrier layer 2 and the gas barrier layer 4 can be continuously laminated.

  When the uncured flash-deposited coating layer is cured by irradiation 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 flash vapor deposition coating layer is cured by irradiation with an electron beam, the balance between the thickness of the flash vapor deposition 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 flash vapor deposition coating layer is charged, and as a result, the gas barrier properties of the gas barrier layer 2 and the gas barrier layer 4 may be impaired by the peeling discharge.

  The role of the coating layer 3 and the coating layer 5 in the gas barrier laminate film of the present invention is that the gas barrier layer 2 and the gas barrier layer 4 having excellent gas barrier properties are subjected to usual processing such as printing, laminating, bag making and the like. Protective function in the case of, and a protective function when external stress such as bending or pulling is applied, and further, gas barrier properties that are manifested by tightening the gas barrier layer by internal stress due to curing shrinkage when the coating layer 3 and the coating layer 5 are formed It is an improvement function.

  The thickness Ya of the coating layer 3 and the thickness Yb of the coating layer 5 are 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 the internal stress due to curing shrinkage when the coating layer 3 and the coating layer 5 are formed is slight. As a result, the coating layer 3 cannot sufficiently tighten the gas barrier layer 2, and the coating layer 5 cannot sufficiently tighten the gas barrier layer 4, so that the gas barrier property improving function cannot be expected so much. On the other hand, if the film thickness exceeds 20 μm, curing by electron beam irradiation or UV irradiation at the time of forming the coating layer 3 and the coating layer 5 becomes difficult, and internal stress due to curing shrinkage works excessively, and the gas barrier layer 2 and the gas barrier layer 4 There is a high possibility that the adhesiveness will decrease.

  In addition, in order for the coating layer 3 and the coating layer 5 to exhibit the above-described gas barrier property-improving function and not deteriorate the adhesion, the thickness of the coating layer 3 and the coating layer 5 and the gas barrier made of silicon oxide are used. It is also necessary to consider the balance between the thickness of the layer 2 and the gas barrier layer 4. That is, as described above, one of the roles of the coating layer 3 and the coating layer 5 is to improve the gas barrier property by tightening the gas barrier layer due to internal stress caused by curing shrinkage during the formation of the coating layer 3 and the coating layer 5. However, the internal stress acts on the gas barrier layer 2 and the gas barrier layer 4 as the thickness of the coating layer 3 and the coating layer 5 increases, and the resistance of the gas barrier layer 2 and the gas barrier layer 4 to the internal stress is the gas barrier. As the thickness of the layer 2 and the gas barrier layer 4 increases, the thickness decreases. For example, even if the same internal stress acts on the gas barrier layer 2 and the gas barrier layer 4, the thickness of the gas barrier layer 2 and the gas barrier layer 4 increases. Along with this, it cannot withstand internal stress, and the adhesion tends to decrease.

  The coating layer 3 and the coating layer 5 can be formed by curing an uncured flash vapor deposition coating layer by irradiating ultraviolet rays or electron beams. At this time, the base material layer 1 made of a plastic film is used. Tends to be softened by irradiation heat, and when the internal stress due to the above-described curing shrinkage is applied thereto, the adhesiveness is lowered. That is, when the gas barrier layer 2, the coating layer 3, the gas barrier layer 4, and the coating layer 5 are laminated on one surface of the base material layer 1 as in the present invention, ultraviolet light or Since it is necessary to cure the coating layer 3 and the coating layer 5 by irradiating the electron beam twice, internal stress is generated due to the softening of the base material layer 1 by the irradiation heat and the curing shrinkage due to the above-described decrease in adhesion. It occurs twice, and there is a higher possibility of lowering the adhesion than when the gas barrier layer 2 and the coating layer 3 are laminated on the base material layer 1, for example, a coating with the same thickness as the gas barrier layer. In the case of laminating only the gas barrier layer 2 and the coating layer 3 on one surface of the base material layer 1, and in the case of laminating the gas barrier layer 4 and the coating layer 5, the latter case However, the adhesion decreases.

  That is, in order to produce a gas barrier laminate film with good adhesion, an inversely proportional relationship is established between the upper limit value of the thickness of the gas barrier layer and the upper limit value of the thickness of the coating layer. First, when only the gas barrier layer 2 and the coating layer 3 are laminated on one surface of the base material layer 1, internal stress due to curing shrinkage when forming the coating layer 3 does not act on the gas barrier layer 4, but only on the gas barrier layer 2. Therefore, an inversely proportional relationship is established between the upper limit value of the thickness Xa [μm] of the gas barrier layer 2 and the upper limit value of the thickness Ya [μm] of the coating layer 3, and the thicknesses Xa and Ya are inequalities XaYa ≦ α1. (Positive number) must be satisfied. In addition, when the gas barrier layer 4 and the coating layer 5 are laminated after the gas barrier layer 2 and the coating layer 3 are laminated on one surface of the base material layer 1, internal stress due to curing shrinkage when the coating layer 5 is formed. Acts on both the gas barrier layer 2 and the gas barrier layer 4, and therefore, the upper limit value of the thickness Xa [μm] of the gas barrier layer 2 and the thickness Xb [μm] of the gas barrier layer 4 and the thickness Yb of the coating layer 5 Therefore, the thicknesses Xa, Xb, and Yb must satisfy the inequality (Xa + Xb) Yb ≦ α2 (positive number).

  Therefore, in order to improve the adhesion in the gas barrier laminate film of the present invention, the internal stress due to curing shrinkage must be taken into account both when the coating layer 3 and the coating layer 5 are formed. It is necessary to satisfy XaYa + (Xa + Xb) Yb ≦ α1 + α2 = α (positive number) that combines the inequalities. The value of α is defined by the method for forming the gas barrier layer 2 and the gas barrier layer 4 made of silicon oxide, the kind of polymerizable acrylic monomer or monomer / oligomer mixture, and the curing conditions for the uncured flash vapor deposition coating layer. Although α varies by 0.5 or less, the adhesion of the gas barrier laminate film is generally good. Therefore, the thicknesses Xa, Xb, Ya and Yb preferably satisfy the inequality XaYa + (Xa + Xb) ≦ 0.5.

  Furthermore, as described above, the internal stress due to curing shrinkage during the formation of the coating layer 3 increases as the thickness of the coating layer 3 increases, and the resistance of the gas barrier layer 2 increases as the thickness of the gas barrier layer 2 increases. Get smaller. That is, the above-described thickness Xa [μm] of the gas barrier layer 2 is (0.005 ≦ Xa ≦ 0.2), and the thickness Ya [μm] (0.1 ≦ Ya ≦ 20) of the coating layer 3 is As the thickness Xa of the gas barrier layer 2 is increased, and the thickness Ya of the coating layer 3 is further increased, the effect of the gas barrier property improving function that is manifested by tightening the gas barrier layer 2 is increased. However, in other words, when the thickness Xa of the gas barrier layer 2 is thin, the thickness Ya of the coating layer 3 is thick, and when the thickness Ya of the coating layer 3 is thin, the thickness Xa of the gas barrier layer 2 is thick. Otherwise, the above-mentioned gas barrier property improving function will not be sufficiently developed. That is, in order to fully exhibit the gas barrier property improving function, an inversely proportional relationship is established between the lower limit value of the thickness Xa of the gas barrier layer 2 made of silicon oxide and the lower limit value of the thickness Ya of the coating layer 3. The thicknesses Xa and Ya must satisfy the inequality XaYa ≧ β1 (positive number).

  Furthermore, in the same manner as the relationship between the gas barrier layer 2 and the coating layer 3 described above, the internal stress due to curing shrinkage when forming the coating layer 5 increases as the thickness of the coating layer 5 increases, and the resistance of the gas barrier layer 4 increases. The force decreases as the thickness of the gas barrier layer 4 increases. That is, the above-described thickness Xb [μm] of the gas barrier layer 4 is (0.005 ≦ Xb ≦ 0.2) and the thickness Yb [μm] (0.1 ≦ Ya ≦ 20) of the coating layer 5 is As the thickness Xa of the gas barrier layer 4 increases, the thickness Ya of the coating layer 5 further increases, and the effect of the gas barrier property improving function that is manifested by tightening the gas barrier layer 4 increases. However, in other words, when the thickness Xb of the gas barrier layer 4 is thin, the thickness Yb of the coating layer 5 is thick, and when the thickness Yb of the coating layer 5 is thin, the thickness Xb of the gas barrier layer 4 is thick. Otherwise, the above-mentioned gas barrier property improving function will not be sufficiently developed. That is, in order to fully exhibit the gas barrier property improving function, an inversely proportional relationship is established between the lower limit value of the thickness Xb of the gas barrier layer 4 made of silicon oxide and the lower limit value of the thickness Yb of the coating layer 5. The thicknesses Xb and Yb must satisfy the inequality XbYb ≧ β2 (positive number).

  Furthermore, the values of β1 and β2 are determined by the method for forming the gas barrier layer 2 and the gas barrier layer 4 made of silicon oxide, the kind of polymerizable acrylic monomer or monomer / oligomer mixture, and the uncured flash vapor deposition coating layer. However, β1 and β2 are 0.002 or more, and the gas barrier property-improving function works sufficiently. Therefore, it is preferable that the thicknesses Xa and Ya satisfy the inequality XaYa ≧ 0.002, and the thicknesses Xb and Yb also satisfy the inequality XbYb ≧ 0.002.

That is, in order for the coating layer 3 and the coating layer 5 to exhibit the above-described function of improving the gas barrier property and not deteriorate the adhesion, the thickness Xa [μm] of the gas barrier layer 2 made of silicon oxide and the gas barrier The thickness Xb [μm] of the layer 4 (0.005 ≦ Xa (or Xb) ≦ 0.2), the thickness Ya [μm] of the coating layer 3 and the thickness Yb [μm] of the coating layer 5 (0 0.1 ≦ Ya (or Yb) ≦ 20) preferably satisfies the following three inequalities.
0.002 ≦ XaYa
0.002 ≦ XbYb
XaYa + (Xa + Xb) Yb ≦ 0.5
The unit of Xa, Xb, Ya, Yb in the formula is μm.

  In the gas barrier laminate film of the present invention, the coating layer 3 and the coating layer 5 are formed by curing a polymerizable acrylic monomer or a mixture of a monomer and an oligomer on the surfaces of the gas barrier layer 2 and the gas barrier layer 4. can do. The forming method is not limited to dry coating, and may be wet coating.

The shrinkage ratio when the polymerizable acrylic monomer or the mixture of the monomer and the oligomer is cured is preferably 0.2% or more and 10% or less, and more preferably 5% or more and 10% or less. It is. 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 = (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 and the gas barrier layer 4 cannot be sufficiently tightened because the internal stress due to the cure shrinkage during the formation of the coating layer 3 and the coating layer 5 is slightly generated. The gas barrier property improving function cannot be expected. Further, if the cure shrinkage rate exceeds 10%, internal stress due to cure shrinkage during the formation of the coating layer 3 and the coating layer 5 is excessively acted, and the possibility of lowering the adhesion between the gas barrier layer 2 and the gas barrier layer 4 is increased. .

  In the gas barrier laminate film of the present invention, the polymerizable acrylic monomer or the mixture of the monomer and the oligomer, which is a raw material for the coating layer 3 and the coating layer 5, contains at least one of monoacrylate and diacrylate. And it is preferable that the content rate which combined the said monoacrylate and diacrylate is 50 weight% or more. That is, if the combined content of acrylates having a tri- or higher functional acryloyl group exceeds 50% by weight, it is difficult to suppress the curing shrinkage at the time of forming the coating layer 3 and the coating layer 5 to 10% or less. This is because the internal stress works excessively and the possibility that the adhesion between the gas barrier layer 2 and the gas barrier layer 4 is lowered is increased. 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, but have good adhesion to the gas barrier layer, and can efficiently form an uncured flash vapor deposition coating layer. It is preferable to select an excellent one. 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).

  The viscosity of the polymerizable acrylic monomer or the mixture of this monomer and oligomer is desirably 200 mPa · s / 25 ° C. or less, more preferably 100 mPa · s / 25 ° C. or less. 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 flash vapor deposition coating layer is continuously laminated on the surfaces of the gas barrier layer 4 and the gas barrier layer 4, if the viscosity is too high, it is dropped at a constant rate little by little from a nozzle inserted in a high temperature evaporation source. This is because it becomes difficult.

  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.

  In the gas barrier laminate film of the present invention, it is desirable to subject the surface of the coating layer 5 to plasma treatment. This is to improve the adhesion between the coating layer 5 and the other film layer or printing layer when the other film layer or printing layer is laminated on the coating layer 5 of the gas barrier laminate film.

  When the coating layer 5 is subjected to plasma treatment, a DC power source or an RF power source is used to generate plasma continuously and stably, so that an uncured component of a polymerizable acrylic monomer or a mixture of a monomer and an oligomer is obtained. In order to remove efficiently, it is desirable to use a mixed gas for plasma treatment containing a normal gas such as hydrogen, oxygen, nitrogen, carbon dioxide and at least one inert gas such as helium or argon. .

  The gas barrier laminate film of the present invention has an uncured flash vapor deposition comprising a gas barrier layer 2 composed of at least silicon oxide and a polymerizable acrylic monomer or a mixture of a monomer and an oligomer on one surface of a substrate layer 1. An uncured flash comprising a coating layer 3 formed by irradiating the coating layer with ultraviolet rays or an electron beam, a gas barrier layer 4 made of silicon oxide, and a polymerizable acrylic monomer or a mixture of a monomer and an oligomer. What is necessary is just to have laminated | stacked the coating layer 5 formed by sequentially irradiating an ultraviolet-ray or an electron beam, and the vapor deposition coating layer, and may have taken the more complicated laminated structure. For example, a laminate of the gas barrier layer and the coating layer may be laminated on the laminate of the gas barrier layer 2, the coating layer 3, the gas barrier layer 4, and the coating layer 5. Further, the gas barrier layer 2 and the coating layer 3 may be sequentially stacked on the other surface of the base material layer 1 where the gas barrier layer 2, the coating layer 3, the gas barrier layer 4 and the coating layer 5 are not stacked. . Furthermore, a printing layer may be laminated on the surface of the coating layer 5. 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 or a heat seal layer may be laminated via an adhesive. Moreover, the gas barrier laminate film of the present invention is used as an intermediate layer, 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 formed on the other side of the film via an adhesive. A stacked structure 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, 2, and 3, as shown in FIG. 1, the gas barrier layer 2, the coating layer 3, the gas barrier layer 4, and the coating layer 5 are sequentially laminated on one surface of the base material layer 1. A gas barrier laminate film was prepared.

<Example 1>
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 take-up vacuum deposition apparatus. A mixed gas of 5 sccm of hexamethyldisiloxane (HMDSO) / 100 sccm of oxygen was introduced between the electrodes, and plasma was formed by applying a high frequency of 13.56 MHz at 0.5 kW, with a thickness of 0.02 μm on one surface of the base material layer 1 A gas barrier layer 2 made of silicon oxide was laminated. Continuously, 60/30/10 (% by weight) of 2-hydroxy-3-phenoxypropyl acrylate, propoxylated neopentyl glycol diacrylate, and ethoxylated trimethylolpropane triacrylate on the gas barrier layer 2 by flash evaporation. An uncured flash vapor-deposited coating layer having a thickness of 1 μm and a mixture of the above (curing shrinkage: 6.3%) was laminated. The flash-deposited coating layer was irradiated with an electron beam and cured to form a coating layer 3. Next, a mixed gas of 5 sccm of hexamethyldisiloxane (HMDSO) / 100 sccm of oxygen was introduced between the electrodes, and a high frequency of 13.56 MHz was applied to form 0.5 kW to generate plasma, and a thickness of 0. A gas barrier layer 4 made of 02 μm silicon oxide was laminated. Continuously, 60/30/10 (% by weight) of 2-hydroxy-3-phenoxypropyl acrylate, propoxylated neopentyl glycol diacrylate and ethoxylated trimethylolpropane triacrylate on the gas barrier layer 4 by flash vapor deposition. An uncured flash vapor-deposited coating layer having a thickness of 1 μm and a mixture of the above (curing shrinkage: 6.3%) was laminated. The flash-deposited coating layer was irradiated with an electron beam and cured to form a coating layer 5. Thus, the gas barrier laminate film of Example 1 was produced.

<Example 2>
In the gas barrier laminate film of Example 1, the thicknesses of the gas barrier layer 2 and the gas barrier layer 4 made of silicon oxide laminated on the surface of the base material layer 1 and the surface of the coating layer 3 were both 0.1 μm. Other conditions were the same as in Example 1. Thus, a gas barrier laminate film of Example 2 was produced.

<Example 3>
In the gas barrier laminate film of Example 1, the thicknesses of the gas barrier layer 2 and the gas barrier layer 4 made of silicon oxide laminated on the surface of the base material layer 1 and the surface of the coating layer 3 were both 0.01 μm. Other conditions were the same as in Example 1. Thus, the gas barrier laminate film of Example 3 was produced.

<Example 4>
In the same manner as in Example 1, the gas barrier layer 2, the coating layer 3, the gas barrier layer 4, and the coating layer 5 were sequentially laminated on the surface of the base material layer 1, and then 1/1 mixing of nitrogen and argon was performed using a DC power source. The gas was turned into plasma, and the surface of the coating layer 5 was subjected to plasma treatment. Thus, a gas barrier laminate film of Example 4 was produced.

<Example 5>
In the gas barrier laminated film of Example 1, the gas barrier layer 2 and the gas barrier layer 4 laminated on the surface of the base material layer 1 and the surface of the coating layer 3 were evaporated by silicon beam by an electron beam heating method, and both had a thickness of 0. The gas barrier layer was 03 μm. Other conditions were the same as in Example 1. Thus, a gas barrier laminate film of Example 5 was produced.

<Comparative Example 1>
In the gas barrier laminate film of Example 1, only the gas barrier layer 2 and the gas barrier layer 4 made of silicon oxide were laminated on one surface of the base material layer 1, and the coating layer 3 and the coating layer 5 were 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 thicknesses of the gas barrier layer 2 and the gas barrier layer 4 made of silicon oxide were both 0.1 μm, and the thicknesses of the coating layer 3 and the coating layer 5 were both 5 μm. 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, the thicknesses of the gas barrier layer 2 and the gas barrier layer 4 made of silicon oxide were both 0.01 μm, and the thicknesses of the coating layer 3 and the coating layer 5 were 0.1 μm. 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 laminated film of Example 5, the thicknesses of the gas barrier layer 2 and the gas barrier layer 4 made of silicon oxide were both 0.1 μm, and the thicknesses of the coating layer 3 and the coating layer 5 were both 5 μm. Other conditions were the same as in Example 5. Thus, a gas barrier laminate film of Comparative Example 4 was produced.

  Hereinafter, the gas barrier laminate film of each of the single films of Examples 1, 2, 3, 4, 5 and Comparative Examples 1, 2, 3, 4 prepared as described above is referred to as a single film.

  Next, on the surface of the coating layer 5 of each of the single films of Examples 1, 2, 3, 4, 5 and Comparative Examples 2, 3, 4 and the surface of the gas barrier layer 4 of the single film of Comparative Example 1, A 1.2 μm printed layer was laminated. Hereinafter, these are called printing films.

  Next, the thickness of the printed layer of each of the printed films of Examples 1, 2, 3, 4, 5 and Comparative Examples 1, 2, 3, 4 is 50 μm thick via a 5 g / m 2 polyurethane adhesive. A polypropylene heat seal layer was laminated. Hereinafter, these are called laminated films.

<Comparison evaluation>
1. Oxygen Permeability Oxygen permeability meter (MOCON OX-TRAN 2 manufactured by Modern Control Co., Ltd.) was used for the single films, printed films and laminated films of Examples 1, 2, 3, 4, 5 and Comparative Examples 1, 2, 3, 4. / 21), the oxygen permeability (cc / m 2 · 24 h · MPa) in an atmosphere of 30 ° C.-70% RH was measured.
2. Water Vapor Permeability For the single films of Examples 1, 2, 3, 4, 5 and Comparative Examples 1, 2, 3, 4, 40 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 · 24 h) in an atmosphere at −90% RH was measured.
3. Laminate Strength For test pieces slit to 15 mm width from the laminated films of Examples 1, 2, 3, 4, 5 and Comparative Examples 1, 2, 3, 4, laminate strength (N / 15 mm).
These measurement results are shown in Table 1.

  As can be seen from Table 1, the gas barrier laminate films (single film, print film and laminate film) of Example 1, Example 2, Example 3, Example 4 and Example 5 have low oxygen permeability and water vapor permeability. Combined with high laminate strength. In particular, the oxygen barrier property and water vapor barrier property of Example 2 and the laminated film of Example 4 had high laminate strength. On the other hand, the printed film and laminated film made of the gas barrier laminated film of Comparative Example 1 in which the coating layer is not laminated are compared with the gas barrier laminated films of Example 1, Example 2, Example 3 and Example 4. The oxygen permeability was high and the gas barrier property was poor.

  Further, the gas barrier layer 2 and the gas barrier layer 4 are formed by a plasma CVD method, the thickness Xa [μm] of the gas barrier layer 2, the thickness Xb [μm] of the gas barrier layer 4, the thickness Ya [μm] of the coating layer 3; The gas barrier laminate film of Comparative Example 2 in which the thickness Yb [μm] of the coating layer 5 is XaYa + (Xa + Xb) Yb> 0.5 is the gas barrier property of Example 1, Example 2, Example 3 and Example 4. Compared with the laminated film, the gas barrier property is almost the same level, but the laminated film has a significantly inferior laminate strength.

  Furthermore, the gas barrier layer 2 and the gas barrier layer 4 are formed by plasma CVD, and the thickness Xa [μm] of the gas barrier layer 2, the thickness Xb [μm] of the gas barrier layer 4, and the thickness Ya [μm] of the coating layer 3 are formed. The gas barrier laminate film of Comparative Example 3 in which the thickness Yb [μm] of the coating layer 5 is XaYa <0.002 and XbYb <0.002 is the same as Example 1, Example 2, Example 3 and Example. Compared with the gas barrier laminate film 4, the laminate film has a laminate strength equal to or higher than that, but the oxygen permeability and water vapor permeability of the single film, the oxygen permeability of the printed film and laminate film are high, and the gas barrier property is high. It was extremely inferior.

  Furthermore, the gas barrier layer 2 is formed by an electron beam heating method, the thickness Xa [μm] of the gas barrier layer 2, the thickness Xb [μm] of the gas barrier layer 4, the thickness Ya [μm] of the coating layer 3, and the coating layer Compared with the gas barrier laminate film of Example 5, the gas barrier laminate film of Comparative Example 4 in which the thickness Yb [μm] of No. 5 is XaYa + (Xa + Xb) Yb> 0.5 is almost the same level as the gas barrier laminate film of Example 5. However, the laminate strength of the laminated film was extremely inferior.

  The gas barrier laminate film of the present invention is suitably used in the fields of packaging of foods, daily necessities, pharmaceuticals, etc., and fields such as electronic equipment-related members when particularly high gas barrier properties are required.

DESCRIPTION OF SYMBOLS 1 ... Base material layer 2 ... Gas barrier layer 3 ... Coating layer 4 ... Gas barrier layer 5 ... Coating layer

Claims (5)

In the gas barrier laminate film in which the gas barrier layer 2, the coating layer 3, the gas barrier layer 4, and the coating layer 5 are sequentially laminated on one surface of the base material layer 1 made of a transparent plastic film,
The gas barrier layer 2 and the gas barrier layer 4 are made of silicon oxide,
The film thickness (thickness Xa) of the gas barrier layer 2 and the film thickness (thickness Xb) of the gas barrier layer 4 are 0.005 μm or more and 0.2 μm or less,
The coating layer 3 and the coating layer 5 are formed by forming a polymerizable acrylic monomer or a mixture of a monomer and an oligomer using a flash vapor deposition method, and curing by irradiating with ultraviolet rays or electron beams.
The film thickness (thickness Ya) of the coating layer 3 and the film thickness (thickness Yb) of the coating layer 5 are 0.1 μm or more and 10 μm or less,
A gas barrier laminate film, wherein the relationship among Xa, Xb, Ya and Yb satisfies the following three formulas:
0.002 ≦ XaYa
0.002 ≦ XbYb
XaYa + (Xa + Xb) Yb ≦ 0.5
(The unit of the thickness of Xa, Xb, Ya, Yb in the formula is μm)   The gas barrier layer 2 and the gas barrier layer 4 laminated on the surface of the base material layer 1 and the coating layer 3 are formed by a plasma chemical vapor deposition (CVD) method. Gas barrier laminate film.   Curing shrinkage rate of the polymerizable acrylic monomer or mixture of monomer and oligomer forming the coating layer 3 and the coating layer 5 laminated on the surfaces of the gas barrier layer 2 and the gas barrier layer 4 is 0. The gas barrier laminate film according to claim 1, wherein the gas barrier laminate film is 2% or more and 10% or less.   The polymerizable acrylic monomer or the mixture of monomer and oligomer contains at least one of monoacrylate and diacrylate, and the combined content of the monoacrylate and diacrylate allows the polymerization. The gas barrier laminate film according to any one of claims 1 to 3, wherein the gas barrier laminate film is 50% by weight or more of a novel acrylic monomer or a mixture of a monomer and an oligomer.   The gas barrier laminate film according to any one of claims 1 to 4, wherein the surface of the coating layer 5 laminated on the surface of the barrier layer 4 is subjected to plasma treatment.

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