WO2022118710A1 - 透明ガスバリアフィルム - Google Patents
透明ガスバリアフィルム Download PDFInfo
- Publication number
- WO2022118710A1 WO2022118710A1 PCT/JP2021/043001 JP2021043001W WO2022118710A1 WO 2022118710 A1 WO2022118710 A1 WO 2022118710A1 JP 2021043001 W JP2021043001 W JP 2021043001W WO 2022118710 A1 WO2022118710 A1 WO 2022118710A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- thickness
- aluminum oxide
- less
- plastic film
- Prior art date
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- 230000004888 barrier function Effects 0.000 title claims abstract description 70
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 64
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 52
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 16
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- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
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Classifications
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- B32B2307/518—Oriented bi-axially
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
- B32B2307/734—Dimensional stability
- B32B2307/736—Shrinkable
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
- B32B2307/737—Dimensions, e.g. volume or area
- B32B2307/7375—Linear, e.g. length, distance or width
- B32B2307/7376—Thickness
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging
Definitions
- the present invention relates to a packaging material that requires airtightness such as foods, pharmaceuticals, and electronic parts having excellent transparency, gas barrier properties, printability, and flexibility. More specifically, the present invention relates to a transparent barrier film having excellent properties as a gas blocking material, in which an aluminum oxide layer is laminated on a plastic film using a polyester resin recycled from a PET bottle.
- a technique of using a packaging material having a gas barrier property low oxygen permeation amount, low water vapor permeation amount
- a technique of a transparent barrier film in which a metal oxide layer is laminated on a plastic film is known.
- the metal oxide silicon oxide, aluminum oxide and the like are often used from the viewpoint of transparency.
- the metal oxide layer is mainly laminated on a plastic film by a vapor deposition method or a CVD method.
- a laminated film having an aluminum oxide layer as a barrier layer which is produced by a reactive vapor deposition method in which aluminum is evaporated and oxygen is introduced, has become the mainstream (see, for example, Patent Document 3).
- the vapor deposition material is aluminum, which is inexpensive, and the evaporation temperature of aluminum is low, so that it is an induced heating type or a resistance heating type. It can be made with a relatively inexpensive device that has a vapor deposition source of. Therefore, it is provided as a packaging material at a lower cost than a transparent barrier film using silicon oxide or silicon oxide and aluminum oxide as a vapor deposition material.
- an acidic content is put in a bag made of a transparent barrier film having an aluminum oxide layer, there is a drawback that the barrier property is lowered and the content is deteriorated.
- the vapor deposition material is expensive, it has been dealt with by using a barrier layer of silicon oxide or by using a layer in which silicon oxide and aluminum oxide are mixed, which is produced by an expensive vapor deposition apparatus using an electron beam vapor deposition source. ..
- an object of the present invention is to provide an inexpensive transparent barrier film having excellent acid resistance in consideration of environmental problems.
- the present invention has the following configuration.
- a transparent gas barrier film having an aluminum oxide layer containing aluminum oxide as a main component on at least one side of the base polyester film the absorption coefficient of the aluminum oxide layer immediately after vapor deposition is less than 0.03 nm -1 , and the vapor deposition film thickness is
- the base material polyester film is 6 nmn or more and 10 nm or less, contains 50% by weight or more of polyester resin recycled from a PET bottle, and is biaxially stretched, and satisfies the following requirements. It is a characteristic transparent gas barrier film.
- the content of the isophthalic acid component with respect to the total dicarboxylic acid component in all the polyester resins constituting the base material polyester film is 0.5 mol% or more and 5.0 mol% or less
- the base material polyester film is formed.
- the ultimate viscosity of the resin is 0.58 dI / g or more and 0.70 dI / g or less.
- the heat shrinkage rate of the base polyester film at 150 ° C in the vertical and horizontal directions is 0.1%% or more and 1.5%.
- the lamination strength is 4.0 N / 15 mm or more and 20.0 N / 15 mm or less (5)
- a transparent gas barrier film characterized by having an absorption coefficient of 0.02 nm -1 or more immediately after vapor deposition.
- a transparent gas barrier film characterized by having an absorption coefficient of 0.002 nm -1 or less in the end.
- Transmittance wavelength characteristics of the substrate plastic film and transparent gas barrier film measured with a spectrophotometer Transmittance wavelength characteristics of the plastic film of the substrate, D65 light source and CIE colorimetric standard observer color matching function
- Thin film deposition schematic diagram Thin film deposition schematic diagram Schematic diagram showing the uniformity inside the extruder of the film forming equipment
- the transparent gas barrier film of the present invention is a plastic film having an aluminum oxide layer containing aluminum oxide as a main component on at least one side of the plastic film, and the absorption coefficient of the aluminum oxide layer immediately after vapor deposition is less than 0.03 nm-1. It is characterized by having a film thickness of 6 nm or more and 10 nm or less.
- the aluminum oxide layer containing aluminum oxide as a main component in the present invention means a layer containing 99% or more of aluminum oxide and containing other components as impurities. Also, aluminum oxide contains not only stoichiometrically perfect oxides, but also aluminum oxide, which is deficient in oxygen.
- the absorption coefficient ⁇ referred to in the present invention can be expressed by Equation 1 when the total light transmittance of the aluminum oxide layer is Tal% and the film thickness of the aluminum oxide layer is tal nm.
- ⁇ -1 / tal ⁇ ln (Tal / 100) ⁇ ⁇ ⁇ Equation (1)
- the total light transmission rate Tal% of the aluminum oxide layer is T0% for the total light transmission rate of the transparent gas barrier film having the aluminum oxide layer, and Tb% for the total light transmission rate of the base plastic film on which the aluminum oxide layer is laminated. When it is done, it can be expressed by the equation (2).
- Tal T0 / Tb ⁇ 100 ⁇ ⁇ ⁇ Equation (2)
- the thickness of the aluminum oxide layer of the present invention is a value obtained by a fluorescent X-ray apparatus as the density of the aluminum oxide thin film is 0.74 times (2.94 g / cm 3 ) the bulk density (3.97 g / cm 3 ). be.
- the reason for setting it to 0.74 times is that it matches well with the actual film thickness obtained by TEM or the like.
- a sample with a known film thickness is measured with a fluorescent X-ray device, and the fluorescence X-ray dose emitted from the sample is determined and a calibration line between the film thickness and the fluorescent X-ray intensity. Need to be created.
- the amount of aluminum adhesion per unit area is identified by inductively coupled plasma emission spectroscopy, and the film thickness is measured by converting it to the film thickness based on the density of the aluminum oxide thin film. Use what was there.
- the total light transmittance referred to in the present invention means the total light transmittance according to JIS K7375.
- a light source such as a fluorescent lamp, a xenon lamp, or a white LED
- the measured value of the amount of light the sample whose total light transmission rate is measured according to JIS K7375 is measured in advance with an optical film thickness meter, and the correlation is taken to treat it as the total light transmission rate.
- FIG. 1 shows a graph in which the light transmittances of the plastic film and the transparent barrier film of the substrate are measured by a spectrophotometer.
- the light transmittance 1 of the plastic film of the substrate and the light transmittance 2 of the transparent barrier film monotonically absorb light at any wavelength, and the D65 light source and CIE color measurement standard observation specified as the light source in JIS K 7375 Considering the wavelength region of the color transmission function of the person, the value converted from the value of the optical film thickness meter can also be treated as the total light transmittance.
- FIG. 2 shows the wavelength range.
- the transparent gas barrier film of the present invention is a plastic film having an aluminum oxide layer containing aluminum oxide as a main component on at least one side of the plastic film, and the absorption coefficient of the aluminum oxide layer immediately after vapor deposition is less than 0.03 nm -1 .
- the method for producing a transparent gas barrier film of the present invention is a method for producing a transparent gas barrier film made of a plastic film having an aluminum oxide layer containing aluminum oxide as a main component on at least one side of the plastic film, immediately after the vapor deposition of the aluminum oxide layer. It has an aluminum oxide layer forming step that adjusts the absorption coefficient to less than 0.03 nm -1 .
- vapor deposition in the present invention means a time point in which the optical thickness is measured for film thickness control or the like immediately after the aluminum oxide layer is vapor-deposited on the plastic film in a vacuum chamber.
- the plastic film vapor-deposited is taken out from the vapor deposition apparatus, and if the total light transmission amount is measured immediately, it coincides with the time when the optical thickness is measured.
- the absorption coefficient immediately after vapor deposition is 0.03 nm -1 or more, even if it is released into the atmosphere to promote oxidation, if a bag is made using this transparent barrier film and an acidic substance is wrapped, the barrier property will deteriorate. Will end up. That is, the barrier film is inferior in acid resistance.
- the absorption coefficient immediately after vapor deposition is preferably less than 0.03 nm -1 . It has a structure in which acid molecules are easily accessible to metal atoms. Alternatively, it is unclear whether the metal oxide atom is in a state where it easily reacts with the acid, but deterioration due to the acid occurs.
- the acid resistance referred to in the present invention means that the aluminum oxide layer, which is a barrier layer, does not lose its barrier property due to a chemical change due to acid when a highly acidic content is put in a package using a transparent barrier film. To tell.
- the absorption coefficient immediately after vapor deposition is preferably 0.02 nm -1 or more.
- the transparent barrier film in which the aluminum oxide layer is laminated on the plastic film of the substrate is taken out from the vacuum chamber by vapor deposition, and the aluminum oxide layer is exposed to the atmosphere at least 10. It means that the absorption coefficient is 0.002 nm -1 or less when the absorption coefficient is calculated after storing at room temperature of °C to 40 °C for 1 week or more.
- the thickness of the inorganic oxide vapor deposition layer is 6 nm or more and 10 nm or less.
- the method for producing a transparent gas barrier film of the present invention includes an aluminum oxide layer forming step for adjusting the thickness of the aluminum oxide layer to 6 nm or more and 10 nm or less.
- the absorption coefficient finally exceeds 0.002 nm -1
- the light absorption of the thin film exceeds 1% even if the film thickness is 10 nm or less, and coloring becomes a problem. It is also possible to suppress coloring by reducing the film thickness, but barrier properties become a problem at 5 nm.
- the reactive vapor deposition method is suitable as a method for producing a transparent barrier film having an aluminum oxide layer having a film thickness of 10 nm or less and an absorption coefficient immediately after vapor deposition of 0.03 nm -1 or less.
- the reactive vapor deposition method is a method in which metallic aluminum is heated and evaporated, and oxygen is introduced into a vapor deposition tank to react the metallic aluminum with aluminum oxide and deposit it on a plastic film of a substrate.
- a resistance heating method, an induction heating method, and an electron beam heating method can be used as a method for heating and evaporating metallic aluminum.
- a method of controlling the film thickness there is a method of measuring the aluminum oxide layer deposited on the plastic film with a film thickness meter using fluorescent X-rays and adjusting the heating in comparison with the target film thickness.
- a photometer is installed to irradiate light from one side of the plastic film and measure the light transmitted from the other side. Control the amount.
- metallic aluminum is deposited on the plastic film of the substrate.
- An optical film thickness meter that irradiates light from one of the vapor-deposited plastic films and measures the light transmitted from the other to convert it into a film thickness controls the thickness of the deposited metallic aluminum to a constant film thickness. do.
- oxygen is introduced to deposit aluminum oxide.
- an optical film thickness meter is used as a measuring meter of the total light transmittance and the amount of oxygen introduced is controlled so as to reach the target total light transmittance while the evaporation conditions are constant. The latter manufacturing method is preferable because the apparatus is simple.
- a resistance heating method in which an aluminum wire is supplied to a boat-type heating element to evaporate is suitable as an evaporation source. After introducing oxygen, the film thickness cannot be calculated from the total light transmittance.
- aluminum which is an evaporation material
- the evaporation amount will increase if the evaporation slows down and the molten aluminum on the boat increases. It turns out that it has decreased, and when the amount of evaporation increases, the supply of wire cannot catch up, so it does not become excessive above a certain level. It is preferable to determine the vapor deposition rate of aluminum once in this way because it is stable.
- FIGS. 3 and 4 show a schematic diagram of the vapor deposition apparatus.
- Aluminum evaporating from the vapor deposition source (9) is deposited on the coating roll (6) on the plastic film (5) of the substrate.
- a coating window (7) is installed near the coating roll (6) in order to limit the angle of incidence of the aluminum vapor on the substrate and prevent the aluminum vapor from adhering to unnecessary places.
- the oxygen inlet (8) is installed close to the coating roll (6) as shown in FIG. 3 and is installed at a position that does not interfere with the flow of aluminum vapor. It is considered that when the oxygen inlet (8) is brought closer to the evaporation source as shown in FIG. 4, aluminum is oxidized at the evaporation source and the evaporation rate becomes unstable.
- the pressure for vapor deposition is preferably 1 ⁇ 10 ⁇ 2 Pa or less in consideration of increasing the density of aluminum oxide and improving the barrier property.
- the oxygen inlet (8) can be put in the aluminum steam to improve the efficiency, but the efficiency of aluminum or aluminum oxide adhering to the oxygen inlet and depositing on the plastic film of the substrate is lowered. Further, it is not preferable because the amount of evaporation changes when the deposit attached to the oxygen inlet (8) peels off and falls into the evaporation source.
- the amount of air entrainment can be expressed by the equation (3).
- the thickness of the rewound plastic film is t ⁇ m
- the length is 1m
- the diameter of the used paper tube is 2rmm
- the diameter of the rolled plastic film is 2Rmm
- the layer of air caught between the plastic films is expressed by the equation (3).
- tair ⁇ (R 2 -r 2 ) / lt ⁇ ⁇ ⁇ Equation (3)
- the rolled-up roll-shaped plastic film gradually oxidizes the aluminum oxide layer, it is preferable to store it until it stabilizes.
- the storage period should be at room temperature of 10 ° C to 40 ° C for at least one week. It is presumed that the oxidation is promoted when the temperature is raised, but it is not preferable to raise the temperature to 40 ° C. or higher because the physical properties of the film may be affected. Further, if the temperature is 10 ° C. or lower, oxidation is delayed, which is not preferable.
- the gas barrier property of the transparent gas barrier film of the present invention is 1.0 ml / m 2 /, regardless of whether the oxygen permeation amount in an atmosphere of a temperature of 23 ° C. and a relative humidity of 65% RH is 1.0 ml / m 2 / after both untreated and acid resistance evaluation described later. It is preferably day (24hr) / MPa or more and 100 ml / m 2 / day (24hr) / MPa or less. If the gas barrier property exceeds 100 ml / m 2 / day / MPa, it may be difficult to use it in foods, pharmaceuticals, industrial products, etc., which is not very preferable.
- the barrier property in this configuration is 1.0 ml / m 2 / day / MPa, which is the lower limit, and 1.0 ml / m 2 / day / MPa. However, it can be said that it is practically sufficient.
- a more preferable range is 1.0 ml / m 2 / day / MPa or more and 70 ml / m 2 / day / MPa or less, and particularly preferably 1.0 ml / m 2 / day / MPa or more and 30 ml / m 2 / day /. It is in the range of MPa or less.
- the plastic film referred to in the present invention is a film obtained by melt-extruding a polyester resin recycled from a PET bottle and using a biaxial stretching method.
- the biaxial stretching method is not particularly limited, and a tubular method, a simultaneous biaxial stretching method, or the like can be adopted. In particular, the sequential biaxial stretching method is preferable.
- the lower limit of the ultimate viscosity of the resin constituting the plastic film obtained by measuring the plastic film is preferably 0.58 dI / g, more preferably 0.60 dI / g. If it is less than 0.58 dI / g, most of the recycled resins made of PET bottles have an ultimate viscosity of more than 0.68 dI / g, and if the viscosity is lowered when producing a film using it, the thickness unevenness is poor. It is not preferable because it may become. Further, it is not preferable because the plastic film may be colored.
- the upper limit is preferably 0.70 dI / g, more preferably 0.68 dI / g. If it exceeds 0.70 dI / g, it becomes difficult to discharge the resin from the extruder and the productivity may decrease, which is not preferable.
- the lower limit of the thickness of the plastic film is preferably 8 ⁇ m, more preferably 10 ⁇ m, and even more preferably 12 ⁇ m. If it is less than 8 ⁇ m, the strength of the plastic film may be insufficient, which is not preferable.
- the upper limit is preferably 200 ⁇ m, more preferably 50 ⁇ m, and even more preferably 30 ⁇ m. If it exceeds 200 ⁇ m, it may become too thick and difficult to process.
- the lower limit of the heat shrinkage rate of the plastic film after treatment in the vertical direction (sometimes referred to as MD) and the horizontal direction (sometimes referred to as TD) at 150 ° C. for 30 minutes is preferably 0.1%, more preferably. It is 0.3%. If it is less than 0.1%, the effect of improvement is saturated and it may become mechanically brittle, which is not preferable.
- the upper limit is preferably 1.5%, more preferably 1.2%. If it exceeds 1.5%, pitch deviation may occur due to dimensional changes during processing such as printing, which is not preferable. Further, if it exceeds 1.5%, shrinkage in the width direction may occur due to dimensional changes during processing such as printing, which is not preferable.
- the lower limit of the refractive index of the plastic film in the thickness direction is preferably 1.4930, more preferably 1.4940. If it is less than 1.4930, the orientation may not be sufficient and the laminate strength may not be obtained.
- the upper limit is preferably 1.4995, more preferably 1.4980. If it exceeds 1.4995, the orientation of the surface may be distorted and the mechanical properties may be insufficient, which is not preferable.
- the lower limit of the laminating strength is preferably 4.0 N / 15 mm, more preferably 4.5 N / 15 mm, and further preferably 5.0 N / 15 mm. .. If it is less than 4.0N / 15mm, it is not preferable because the laminated part may be easily peeled off when it is made into a bag.
- the upper limit is preferably 20.0 N / 15 mm, more preferably 15.0 N / 15 mm, and even more preferably 10.0 N / 15 mm. If it exceeds 20.0N / 15mm, the plastic film may be substantially destroyed at the time of peeling, which is not preferable.
- ⁇ Level means that there is no minute peeling of the adhesive on the surface after peeling
- ⁇ level means that the total peeling area is 10% or less
- ⁇ level means that there is no minute peeling. It is more than 10% of the area. It is preferably ⁇ , and more preferably ⁇ . In case of ⁇ , the appearance of the laminated part after peeling is poor and the commercial value is lowered, which is not preferable. If the laminate strength is less than 40 N / 15 mm, it does not satisfy the basic characteristics of the present invention, and therefore, even if it is at the 0 level, it is an unfavorable plastic film.
- a recycled polyester resin made of a PET bottle containing an isophthalic acid component As a raw material for the plastic film, it is preferable to use a recycled polyester resin made of a PET bottle containing an isophthalic acid component as an acid component. Crystallinity is controlled in the polyester used for PET bottles in order to improve the appearance of the bottle, and as a result, polyester containing 10 mol% or less of an isophthalic acid component may be used. .. In order to utilize the recycled resin, a material containing an isophthalic acid component may be used.
- the lower limit of the amount of the terephthalic acid component in the total dicarboxylic acid component constituting the polyester resin contained in the plastic film is preferably 95.0 mol%, more preferably 96.0 mol%, still more preferably 96.5 mol%. , Particularly preferably 97.0 mol%. If it is less than 95.0 mol%, the crystallinity is lowered, so that the heat shrinkage rate may be high, which is not so preferable.
- the upper limit of the amount of the terephthalic acid component of the polyester resin contained in the plastic film is preferably 99.5 mol%, more preferably 99.0 mol%.
- the lower limit of the amount of the isophthalic acid component in the total dicarboxylic acid component constituting the polyester resin contained in the plastic film is preferably 0.5 mol%, more preferably 0.7 mol%, still more preferably 0.9 mol%. , Particularly preferably 1.0 mol%. Since some recycled polyester resins made of PET bottles contain a large amount of isophthalic acid component, the fact that the isophthalic acid component constituting the polyester resin in the film is less than 0.5 mol% means that the polyester film having a high proportion of recycled resin has a high proportion of recycled resin. As a result, it becomes difficult to manufacture, which is not very preferable.
- the upper limit of the amount of the isophthalic acid component in the total dicarboxylic acid component constituting the polyester resin contained in the plastic film is preferably 5.0 mol%, more preferably 4.0 mol%, still more preferably 3.5 mol%. , Particularly preferably 3.0 mol%. If it exceeds 5.0 mol%, the crystallinity decreases, so that the heat shrinkage rate may increase, which is not very preferable. Further, setting the content of the isophthalic acid component within the above range facilitates the production of a plastic film having excellent laminating strength, shrinkage rate, and uneven thickness, which is preferable.
- the upper limit of the ultimate viscosity of the recycled resin made of PET bottles is preferably 0.90 dI / g, more preferably 0.80 dI / g, still more preferably 0.77 dI / g, and particularly preferably 0.75 dI / g. .. If it exceeds 0.90 dI / g, it may be difficult to discharge the resin from the extruder and the productivity may decrease, which is not very preferable.
- the lower limit of the content of the polyester resin recycled from the PET bottle with respect to the plastic film is preferably 50% by weight, more preferably 65% by weight, and further preferably 75% by weight. If it is less than 50% by weight, the content of the recycled resin is poor and it is not very preferable in terms of contributing to environmental protection.
- the upper limit of the content of the polyester resin recycled from the PET bottle is preferably 95% by weight, more preferably 90% by weight, and further preferably 85% by weight. If it exceeds 95% by weight, it may not be possible to sufficiently add lubricants and additives such as inorganic particles in order to improve the function of the plastic film, which is not very preferable. It should be noted that polyester resin recycled from PET bottles can also be used as a masterbatch (high-concentration-containing resin) used when a lubricant such as inorganic particles or an additive is added to improve the function of the plastic film.
- the lubricant type in addition to inorganic lubricants such as silica, calcium carbonate and alumina, organic lubricants are preferable, and silica and calcium carbonate are more preferable. With these, transparency and slipperiness can be exhibited.
- the lower limit of the lubricant content in the plastic film is preferably 0.01% by weight, more preferably 0.015% by weight, and even more preferably 0.02% by weight. If it is less than 0.01% by weight, the slipperiness may decrease.
- the upper limit is preferably 1% by weight, more preferably 0.2% by weight, and even more preferably 0.1% by weight. If it exceeds 1% by weight, the transparency may decrease, which is not preferable.
- the manufacturing method of the plastic film used for the laminated film of the present invention is not particularly limited, but for example, the following manufacturing method is recommended. It is important to set the temperature for melting and extruding the resin in the extruder.
- the basic idea is that (1) the polyester resin used for PET bottles contains an isophthalic acid component, so while suppressing deterioration by extruding at the lowest possible temperature, (2) extreme viscosity and fine high crystals. In order to melt the sex portion sufficiently and evenly, it is necessary to have a portion that melts at a high temperature or high pressure. The content of the isophthalic acid component lowers the stereoregularity of the polyester, which leads to a lower melting point.
- the melt viscosity is significantly reduced or deteriorated due to heat, the mechanical strength is lowered, and the deteriorated foreign matter is increased. Further, simply lowering the extrusion temperature does not allow sufficient melt-kneading, which may cause problems such as increased thickness unevenness and foreign matter such as fish eyes.
- the recommended manufacturing methods include, for example, using two extruders in tandem, increasing the pressure in the filter section, and using a screw with strong shearing force as part of the screw configuration. Can be mentioned. The following is an example of temperature control using one extruder.
- FIG. 5 shows an aspect of the inside of the extruder of the film forming equipment in the present invention.
- the compression unit 14 is a region where the space between the screw 10 and the barrel 11 becomes narrower.
- the set temperature of the supply unit 13 and the measuring unit 15 is set as low as possible, and the set temperature of the compression unit 14 is increased. It is preferable that the compression section 14 having a high shear is sufficiently melt-kneaded, and the supply section 13 and the measuring section 15 are devised to prevent thermal deterioration.
- the lower limit of the set temperature of the resin melted portion in the extruder (excluding the maximum set temperature of the compressed portion of the screw in the extruder) is preferably 270 ° C, and the upper limit is preferably 290 ° C. Extrusion is difficult below 270 ° C, and deterioration of the resin may occur above 290 ° C, which is not very preferable.
- the lower limit of the maximum set temperature of the compressed part of the screw in the extruder is preferably 295 ° C. Polyester resin used for PET bottles often contains crystals having a high melting point (260 ° C to 290 ° C) from the viewpoint of transparency. In addition, additives, crystallization nucleating agents, and the like are added, and the fine melting behavior in the resin material is different.
- the upper limit of the maximum set temperature of the compressed part of the screw in the extruder is preferably 310 ° C. If the temperature exceeds 310 ° C, deterioration of the resin may occur, which is not very preferable.
- the lower limit of the time for the resin to pass through the region of the highest set temperature of the compressed portion of the screw in the extruder is preferably 10 seconds, more preferably 15 seconds. If it is less than 10 seconds, the polyester resin used for the PET bottle cannot be sufficiently melted, which is not very preferable.
- the upper limit is preferably 60 seconds, more preferably 50 seconds. If it exceeds 60 seconds, deterioration of the resin tends to occur, which is not very preferable.
- the resin melted in this way is extruded into a sheet on a cooling roll and then biaxially stretched.
- a simultaneous biaxial stretching method may be used, but a sequential biaxial stretching method is particularly preferable. These make it easy to meet the productivity and the quality required for the present invention.
- the method of stretching the film is not particularly limited, but the following points are important.
- the magnification and temperature of longitudinal (MD) stretching and transverse (TD) stretching are important. If the MD stretching ratio and temperature are not appropriate, the stretching force may not be applied evenly, the orientation of the molecules may be insufficient, the thickness unevenness may increase, and the mechanical properties may be insufficient.
- the film may be broken or an extreme increase in thickness unevenness may occur in the next TD stretching step.
- the stretch ratio and temperature are not appropriate, the stretch may not be evenly performed, the vertical and horizontal orientation balance may be poor, and the mechanical properties may be insufficient.
- the process proceeds to the next heat fixing process with large thickness unevenness or insufficient molecular chain orientation, it cannot be alleviated evenly, further increase in thickness unevenness, and insufficient mechanical properties.
- MD stretching it is recommended to adjust the temperature as described below to perform stepwise stretching
- TD stretching it is recommended to stretch at an appropriate temperature so that the orientation balance does not become extremely poor.
- a roll stretching method and an IR heating method are preferable.
- the lower limit of the MD stretching temperature is preferably 100 ° C, more preferably 110 ° C, and even more preferably 120 ° C. If the temperature is lower than 100 ° C, even if a polyester resin with an ultimate viscosity of 0.64 dI / g or more is stretched and molecularly oriented in the vertical direction, the plastic film may break in the next transverse stretching step or the thickness may be extremely poor. Is not preferable because of the occurrence of.
- the upper limit is preferably 140 ° C, more preferably 135 ° C, and even more preferably 130 ° C. If the temperature exceeds 140 ° C, the orientation of the molecular chain becomes insufficient and the mechanical properties may become insufficient, which is not very preferable.
- the lower limit of the MD stretch ratio is preferably 2.5 times, more preferably 3.5 times, and even more preferably 4 times. If it is less than 2.5 times, even if a polyester resin having an ultimate viscosity of 0.64 dI / g or more is stretched and molecularly oriented in the vertical direction, the film may be broken or an extreme thickness defect may occur in the next transverse stretching step. This is not very desirable.
- the upper limit is preferably 5 times, more preferably 4.8 times, and even more preferably 4.5 times. If it exceeds 5 times, the effect of improving mechanical strength and thickness unevenness may be saturated, which is not so significant.
- the MD stretching method may be the above-mentioned one-step stretching, but it is more preferable to divide the stretching into two or more steps. By dividing into two or more stages, it becomes possible to satisfactorily stretch a polyester resin made of a recycled resin having a high ultimate viscosity and containing isophthalic acid, and the thickness unevenness, the laminating strength, the mechanical properties and the like become good.
- the lower limit of the MD stretching temperature in the first stage is preferably 110 ° C, more preferably 115 ° C. If the temperature is lower than 110 ° C., heat will be insufficient, sufficient longitudinal stretching will not be possible, and flatness will be poor, which is not preferable.
- the upper limit of the MD stretching temperature in the first stage is preferably 125 ° C, more preferably 120 ° C. If the temperature exceeds 125 ° C, the orientation of the molecular chain becomes insufficient and the mechanical properties may deteriorate, which is not preferable.
- the lower limit of the MD stretch ratio in the first stage is preferably 1.1 times, more preferably 1.3 times. If it is 1.1 times or more, the polyester resin having an ultimate viscosity of 0.64 dI / g or more can be sufficiently longitudinally stretched to increase the productivity by performing the weak stretching in the first stage.
- the upper limit of the MD stretch ratio in the first stage is preferably 2 times, more preferably 1.6 times. If it exceeds 2 times, the orientation of the molecular chains in the vertical direction becomes too high, which may make it difficult to stretch the second and subsequent stages and may result in a film having poor thickness unevenness, which is not very preferable.
- the lower limit of the MD stretching temperature of the second stage (or the final stage) is preferably 10 ° C, more preferably 115 ° C.
- the upper limit is preferably 130 ° C, more preferably 125 ° C. If the temperature exceeds 130 ° C., crystallization is promoted, lateral stretching may become difficult, and thickness unevenness may increase, which is not very preferable.
- the lower limit of the MD stretch ratio of the second stage (or the final stage) is preferably 2.1 times, more preferably 2.5 times. If it is less than 2.1 times, even if a polyester resin having an ultimate viscosity of 0.64 dI / g or more is stretched and molecularly oriented in the vertical direction, the plastic film may be broken or extremely poor in thickness in the next transverse stretching step. It may occur and is not very desirable.
- the upper limit is preferably 3.5 times, more preferably 3.1 times. If it exceeds 3.5 times, the vertical orientation becomes too high, and it may not be possible to stretch the second and subsequent steps, or the plastic film may have a large uneven thickness, which is not very preferable.
- the lower limit of the TD stretching temperature is preferably 110 ° C, more preferably 120 ° C, and even more preferably 125 ° C. If the temperature is lower than 110 ° C., the stretching stress in the lateral direction becomes high, the plastic film may be broken, and the thickness unevenness may become extremely large, which is not very preferable.
- the upper limit is preferably 150 ° C, more preferably 145 ° C, and even more preferably 140 ° C. If the temperature exceeds 150 ° C., the orientation of the molecular chain does not increase and the mechanical properties may deteriorate, which is not very preferable.
- the lower limit of the lateral (TD) draw ratio is preferably 3.5 times, more preferably 3.9 times. If it is less than 3.5 times, the molecular orientation may be weak and the mechanical strength may be insufficient, which is not very preferable. Further, the orientation of the molecular chains in the vertical direction is large, and the balance between the vertical and horizontal directions becomes poor, so that the thickness unevenness becomes large, which is not very preferable.
- the upper limit is preferably 5.5 times, more preferably 4.5 times. If it exceeds 5.5 times, it may break, which is not very preferable.
- a polyester film containing a recycled resin made of a PET bottle containing isophthalic acid has lower crystallinity than a normal polyethylene terephthalate film containing no isophthalic acid, is easily melted to a very small size, and has mechanical strength. low. Therefore, if the film is exposed to a high temperature under abrupt tension after the end of stretching, or if it is cooled under abrupt tension after the end of high-temperature heat fixing, the tension balance in the width direction is unavoidable due to the temperature difference in the width direction of the film.
- the method is not limited to this method, for example, a method of controlling the film tension according to the speed of hot air in the tenter and the temperature of each zone, and a heat treatment at a relatively low temperature in which the furnace length is sufficient after the stretching is completed. And a method of relaxing with a heating roll after the heat fixing is completed.
- the method by controlling the temperature of the tenter is shown below.
- the lower limit of the temperature of heat fixation 1 is preferably 160 ° C, more preferably 170 ° C. If the temperature is lower than 160 ° C., the heat shrinkage rate will eventually increase, which may cause misalignment or shrinkage during processing, which is not very preferable.
- the upper limit is preferably 215 ° C, more preferably 210 ° C. If the temperature exceeds 215 ° C, a high temperature is suddenly applied to the plastic film, which may increase the thickness unevenness or break, which is not preferable.
- the lower limit of the time for heat fixing 1 is preferably 0.5 seconds, more preferably 2 seconds. If it is less than 0.5 seconds, the temperature of the plastic film may not rise sufficiently.
- the upper limit is preferably 10 seconds, more preferably 8 seconds. If it exceeds 10 seconds, productivity may decrease, which is not very preferable.
- the lower limit of the temperature of the heat fixing 2 is preferably 220 ° C, more preferably 227 ° C. If the temperature is lower than 220 ° C., the heat shrinkage rate becomes large, which may cause deviation or shrinkage during processing, which is not very preferable.
- the upper limit is preferably 240 ° C, more preferably 237 ° C. If the temperature exceeds 240 ° C., the film may melt, and even if it does not melt, it may become brittle, which is not very preferable.
- the lower limit of the time for heat fixing 2 is preferably 0.5 seconds, more preferably 3 seconds. If it is less than 0.5 seconds, it may easily break during heat fixing, which is not very preferable.
- the upper limit is preferably 10 seconds, more preferably 8 seconds. If it exceeds 10 seconds, slack may occur and uneven thickness may occur, which is not very preferable.
- the lower limit of the temperature when the heat fixing 3 is provided is preferably 205 ° C, more preferably 220 ° C. If the temperature is lower than 205 ° C., the heat shrinkage rate becomes large, which may cause deviation or shrinkage during processing, which is not very preferable.
- the upper limit is preferably 240 ° C, more preferably 237 ° C. If the temperature exceeds 240 ° C., the film will melt, and even if it does not melt, it may become brittle, which is not very preferable.
- the lower limit of the time when the heat fixing 3 is provided is preferably 0.5 seconds, more preferably 3 seconds. If it is less than 0.5 seconds, it may easily break during heat fixing, which is not very preferable.
- the upper limit is preferably 10 seconds, more preferably 8 seconds. If it exceeds 10 seconds, slack may occur and uneven thickness may occur, which is not very preferable.
- TD relaxation can be performed at any location where heat is fixed.
- the lower limit is preferably 0.5%, more preferably 3%. If it is less than 0.5%, the heat shrinkage rate in the lateral direction becomes particularly large, which may cause deviation or shrinkage during processing, which is not very preferable.
- the upper limit is preferably 10%, more preferably 8%. If it exceeds 10%, slack may occur and uneven thickness may occur, which is not very preferable.
- the lower limit of the slow cooling temperature after TD heat fixing is preferably 90 ° C, more preferably 100 ° C. If the temperature is lower than 90 ° C., since the plastic film contains isophthalic acid, the thickness unevenness may increase or breakage may occur due to shrinkage due to a sudden temperature change, which is not very preferable.
- the upper limit of the slow cooling temperature is preferably 150 ° C, more preferably 140 ° C. If the temperature exceeds 150 ° C, a sufficient cooling effect may not be obtained, which is not very preferable.
- the lower limit of the slow cooling time after heat fixing is preferably 2 seconds, more preferably 4 seconds. If it is less than 2 seconds, a sufficient slow cooling effect may not be obtained, which is not very preferable.
- the upper limit is preferably 20 seconds, more preferably 15 seconds. If it exceeds 20 seconds, it tends to be disadvantageous in terms of productivity, which is not very preferable.
- the transparent barrier film of the present invention may be provided with various layers provided by a known gas barrier film, if necessary.
- a transparent barrier film provided with an inorganic thin film layer is used as a packaging material, it is preferable to form a heat-sealing resin layer called a sealant.
- the heat-sealing resin layer is usually provided on the inorganic thin film layer, but may be provided on the outside of the plastic film (opposite the surface of the inorganic thin film layer).
- the heat-sealing resin layer is usually formed by an extrusion laminating method or a dry laminating method.
- the thermoplastic polymer that forms the heat-sealable resin layer may be any polymer that can sufficiently exhibit sealant adhesiveness, and is a polyethylene resin such as HDPE, LDPE, LLDPE, a polypropylene resin, or an ethylene monoacetate vinyl copolymer. , Ethethylene-a-olefin random copolymer, ionomer resin and the like can be used.
- the transparent gas barrier film provided with the inorganic thin film layer includes at least one printing layer or other plastic film and / or paper between the inorganic thin film layer or the plastic film and the heat-sealing resin layer or the outside thereof. It may be laminated.
- water-based and solvent-based resin-containing printing inks can be preferably used as the printing ink forming the printing layer.
- the resin used for the printing ink include an acrylic resin, a urethane resin, a polyester resin, a vinyl chloride resin, a vinyl acetate copolymer resin, and a mixture thereof.
- Known printing inks include antistatic agents, light blocking agents, UV absorbers, plasticizers, lubricants, fillers, colorants, stabilizers, lubricants, defoamers, cross-linking agents, blocking agents, antioxidants and the like. Additives may be included.
- the printing method for providing the print layer is not particularly limited, and known printing methods such as an offset printing method, a gravure printing method, and a screen printing method can be used.
- known drying methods such as hot air drying, hot roll drying, and infrared drying can be used.
- the other plastic base material or paper base material paper, polyester resin, polyamide resin, biodegradable resin and the like are preferably used from the viewpoint of obtaining sufficient rigidity and strength of the laminated body. Further, in order to obtain a laminated body having excellent mechanical strength, a stretched film such as a biaxially stretched polyester film or a biaxially stretched nylon film is preferable.
- a nylon film is used between the inorganic thin film layer and the heat-sealing resin layer in order to improve mechanical properties such as pinhole property and piercing strength. It is preferable to stack them.
- nylon 6 nylon 66, metaxylene adipamide and the like are usually used.
- the thickness of the nylon film is usually 10 to 30 ⁇ m, preferably 15 to 25 ⁇ m. If the nylon film is thinner than 10 ⁇ m, the strength may be insufficient, while if it exceeds 30 ⁇ m, it may be stiff and unsuitable for processing.
- a biaxially stretched film having a stretching ratio in each of the vertical and horizontal directions of usually 2 times or more, preferably about 2.5 to 4 times is preferable.
- the transparent barrier film of the present invention also includes an embodiment having each of the above-mentioned layers other than the inorganic thin film layer.
- a transparent barrier film was produced using a thin-film deposition apparatus having a boat-type resistance-heated vapor-film deposition source (9) arranged in the schematic diagram shown in FIG. 6 and having a roll-to-roll type film traveling system.
- Aluminum wire is sent to the boat made of BN composite.
- the oxygen inlet (8) is installed in the coating window (7).
- the coating roll (6) was set at -5 ° C.
- the plastic film (5) of the substrate is unwound from the unwinding roll (16), treated with a planar type plasma source (17), and guided to the coating roll (6).
- the plasma source (17) was set to an input power of 10 kw, and an argon gas of 400 sccm and an oxygen gas of 100 sccm were passed to generate plasma.
- the plastic film (5) of the substrate is guided to the coating window position by the coating roll (6) and vapor deposition is performed.
- the vapor-deposited plastic film is moved to an optical film thickness meter (18) to measure the total light transmittance. After the measurement, the film is wound on a take-up roll (19).
- the evaluation method is shown below.
- (1) Total light transmittance The total light transmittance during vapor deposition can be converted to the value of the optical film thickness meter using a sample measured by a turbidity meter (Nippon Denshoku Industries Co., Ltd. NDH5000) according to JIS K 7375. It was obtained by converting the value of the film thickness meter. The sample taken out after vapor deposition was measured with a turbidity meter.
- Oxygen permeability The oxygen permeability (OTR) was measured using an oxygen permeability measuring device (OXTRAN-2 / 20 manufactured by MOCON, USA) in accordance with JIS K7126-2 under the measurement conditions of temperature 23 ° C and humidity 65% RH.
- WVTR Water vapor permeability
- the water vapor transmission rate (WVTR) was measured according to the JIS K7129 B method using a water vapor permeability measuring device (PERMATRAN-W3 / 31 manufactured by MOCON, USA) at a temperature of 40 ° C and a humidity of 90% RH.
- a laminated film is prepared by dry-laminating a linear low density polyethylene film (LLDEP: L4102 40 ⁇ m manufactured by Toyobo Co., Ltd.) on the acid-resistant transparent barrier film.
- LDEP linear low density polyethylene film
- an adhesive made by mixing TM569 and CAT-10L manufactured by Toyo Morton Co., Ltd. was used. Cut out two laminated films into A5 size (148 mm x 210 mm), stack the L4012 sides and seal the three sides to make a bag. The seal width is 10 mm.
- Vinegar Mizukan Grain Vinegar Co., Ltd.
- diluted to 50% with water is packed in a bag with 100 ml and sealed. Place this bag in a room at 40 ° C and store it for a week. After 1 week, the contents are taken out, washed with water and dried, and then the oxygen permeability is measured. Acid resistance is evaluated by oxygen permeability.
- the refractive index (Nz) in the thickness direction was determined using the Abbe refractometer NAR-1T (manufactured by Atago Co., Ltd.) in accordance with JIS K7142.
- the light source was a sodium D line, a test piece having a refractive index of 1.74 was used, and methylene iodide was used as an intermediate solution.
- Laminating strength of plastic film A urethane-based adhesive (TM569, CAT10L, ethyl acetate, manufactured by Toyo Morton Co., Ltd., 33.6) is used to combine a formed plastic film and a polyethylene film with a thickness of 40 ⁇ m (“L4102” manufactured by Toyo Spinning Co., Ltd.). : 4.0: 62.4 (weight ratio)) is used to attach the inorganic thin film layer of the base film to the opposite side of the laminating surface by the dry laminating method, and aged at 40 ° C for 4 days to evaluate the laminating strength. A laminate was obtained.
- TM569, CAT10L, ethyl acetate, manufactured by Toyo Morton Co., Ltd., 33.6 is used to combine a formed plastic film and a polyethylene film with a thickness of 40 ⁇ m (“L4102” manufactured by Toyo Spinning Co., Ltd.). : 4.0: 62.4 (weight ratio)) is used to
- the bonding conditions were such that the line speed was 20 m / min, the dryer temperature was 80 ° C., and the coating amount after drying was 3 g / m 2 .
- the laminate was cut out to a width of 15 mm and a length of 200 mm to make a test piece, and the base was used under the conditions of a temperature of 23 ° C and a relative humidity of 65% using "Tencilon UMT-II-500 type" manufactured by Toyo Baldwin.
- the peel strength (N / 15 mm) at the joint surface between the opposite side surface of the laminated surface of the inorganic thin film layer of the material film and the polyolefin resin layer was measured.
- the tensile speed was 20 cm / min and the peeling angle was 180 degrees.
- the film thickness of the aluminum oxide layer was determined by a fluorescent X-ray apparatus (Supermini200 manufactured by Rigaku Co., Ltd.). The calibration curve was prepared by identifying the amount of aluminum adhered to the sample prepared in advance by inductively coupled plasma emission spectroscopy, determining the film thickness, and determining the fluorescent X-ray intensity of the sample.
- Example 1 Adjustment of polyester resin recycled from PET bottles After washing away foreign substances such as remaining beverages from PET bottles for beverages, the flakes obtained by crushing are melted with an extruder, and filters are sequentially applied to finer ones with a spread size. After changing, the finer foreign matter was filtered out twice, and the third time was filtered through the filter having the smallest opening size of 50 ⁇ m to obtain a recycled polyester raw material.
- polyester B has an average particle diameter of 1.5 ⁇ m.
- the melt extruded from the T-die was brought into close contact with a cooling roll to form an unstretched sheet, which was subsequently heated to 118 ° C and stretched 1.41 times in the vertical direction on a roll with a peripheral speed difference (MD1). It was stretched 2.92 times (MD2) in the vertical direction on a roll heated to 128 ° C. with a difference in peripheral speed.
- MD1 peripheral speed difference
- MD2 peripheral speed difference
- the vertically stretched sheet was guided to a tenter, preheated at 121 ° C, and then transversely stretched 4.3 times at 131 ° C.
- TS 1 no relaxation
- TS2 relax 5%
- 222 ° C 2.5 seconds without relaxation.
- the plastic film contains 80% of polyester A recycled from PET bottles.
- the content of the isophthalic acid component in the total polyester resin constituting the plastic film is 2.4 mol% with respect to the total dicarboxylic acid component.
- the ultimate viscosity of the constituent resin is 0.64 dl / g.
- the 150 ° C heat shrinkage of the plastic film is 0.8% in the vertical direction and 0.5% in the horizontal direction.
- the thickness unevenness of the plastic film in the vertical direction is 7.6%, and the thickness unevenness in the horizontal direction is 6.4%.
- the laminating strength when the polyethylene film was laminated was 6.1 N / 15 mm, and the appearance of the peeled surface was also at the level of ⁇ .
- the total light transmittance of the plastic film is 84%.
- This plastic film was set in the vapor deposition apparatus. First, aluminum was vapor-deposited with the goal of total light transmittance of 18% without oxygen. After the total light transmittance became stable, oxygen was introduced to control the total light transmittance to 64%. The amount of introduced oxygen was 12509 sccm. The pressure in the vapor deposition chamber after oxygen introduction was 1.4 ⁇ 10 -3 Pa. Table 1 shows the conditions of Example 1. This transparent barrier film was rewound at a speed of 333 m / min using a slitter. From the diameter of the rolled plastic film, it was estimated that the amount of air entrained was included in the thickness of about 0.4 ⁇ m between the plastic films.
- Table 2 shows the OTR and WVTR obtained by measuring the laminated film in which LLDEP is laminated on the transparent barrier film. Table 2 shows the results of the acid resistance test.
- the content of the isophthalic acid component in the total polyester resin constituting the plastic film is 1.8 mol% with respect to the total dicarboxylic acid component.
- the ultimate viscosity of the constituent resin is 0.63 dl / g.
- the 150 ° C heat shrinkage of the plastic film is 0.9% in the vertical direction and 0.5% in the horizontal direction.
- the thickness unevenness of the plastic film in the vertical direction is 7.9%, and the thickness unevenness in the horizontal direction is 6.4%.
- the laminating strength when the polyethylene film was laminated was 6.2N / 15mm, and the appearance of the peeled surface was also at the level of ⁇ .
- the total light transmittance of the plastic film is 83%.
- Example 3 In Example 1, a sample was prepared by the same method as in Example 1 except that the vapor deposition was carried out under the conditions shown in Table 1. The results of evaluating Example 2 are shown in Table 2.
- the content of the isophthalic acid component in the total polyester resin constituting the plastic film is 2.4 mol% with respect to the total dicarboxylic acid component.
- the ultimate viscosity of the constituent resin is 0.64 dl / g.
- the 150 ° C heat shrinkage of the plastic film is 0.8% in the vertical direction and 0.5% in the horizontal direction.
- the thickness unevenness of the plastic film in the vertical direction is 7.6%, and the thickness unevenness in the horizontal direction is 6.4%.
- the laminating strength when the polyethylene film was laminated was 6.1 N / 15 mm, and the appearance of the peeled surface was also at the level of ⁇ .
- the total light transmittance of the plastic film is 84%.
- Comparative Example 1 A sample was prepared by the same method as in Example 1 except that the vapor deposition was carried out under the conditions shown in Table 1.
- Table 2 shows the results of evaluating the sample of Comparative Example 1.
- the content of the isophthalic acid component in the total polyester resin constituting the plastic film is 2.4 mol% with respect to the total dicarboxylic acid component.
- the ultimate viscosity of the constituent resin is 0.64 dl / g.
- the 150 ° C heat shrinkage of the plastic film is 0.8% in the vertical direction and 0.5% in the horizontal direction.
- the thickness unevenness of the plastic film in the vertical direction is 7.6%, and the thickness unevenness in the horizontal direction is 6.4%.
- the laminating strength when the polyethylene film was laminated was 6.1 N / 15 mm, and the appearance of the peeled surface was also at the level of ⁇ .
- the total light transmittance of the plastic film is 84%.
- Comparative Example 1 as compared with Examples 1 to 3, the absorption coefficient immediately after vapor deposition was higher than 0.03 nm-1, so that the OTR value after the acid resistance test was high, and the barrier property was impaired.
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Abstract
Description
金属酸化物としては透明の観点より酸化珪素、酸化アルミニウムなどのが多く利用されている。金属酸化物層は蒸着法、あるいはCVD法によりプラスチックフィルムに積層されるのが主流である。
中でも、アルミニウムを蒸発させ酸素を導入する反応性蒸着法などにより作成する酸化アルミニウム層をバリア層とする積層フィルムが主流となっている(例えば、特許文献3参照。)。
そこで、蒸着材料が高価ではあるが酸化珪素のバリア層を使ったり、電子ビーム蒸着源を使う高価な蒸着装置で作成する酸化珪素と酸化アルミニウムとを混合した層を使ったりして対処されてきた。
基材ポリエステルフィルムの少なくとも片面に酸化アルミニウムを主成分とする酸化アルミニウム層を有する透明ガスバリアフィルムにおいて、前記酸化アルミニウム層の蒸着直後の吸収係数が0.03nm-1未満であり、かつ蒸着膜厚が6nmn以上、10nm以下であり、前記基材ポリエステルフィルムが、ペットボトルからリサイクルされたポリエステル樹脂を50重量%以上含有し、二軸延伸されてなるポリエステルフィルムであり、以下の要件を満足することを特徴とする透明ガスバリアフィルムである。
(1)基材ポリエステルフィルムを構成する全ポリエステル樹脂中の全ジカルボン酸成分に対するイソフタル酸成分の含有率が0.5モル%以上5.0モル%以下
(2)基材ポリエステルフィルムを構成している樹脂の極限粘度が0.58dI/g以上、0.70dI/g以下
(3)基材ポリエステルフィルムの縦方向及び横方向の150℃熱収縮率が0.1%%以上、1.5%以下
(4)基材ポリエステルフィルムの酸化アルミニウム層積層面の反対側にポリオレフィンフィルムをラミネートした場合に、ラミネート強度が4.0N/15mm以上、20.0N/15mm以下
(5)縦方向および横方向のフィルム1m長を各々5mm毎に測定した各厚みTn(n=l~200) (単位:μm)200点を測定し、この時の最大厚みをTmax,最小厚みをTmin,平均厚みをTaveとするときの下記の式で求める厚みムラが、縦方向および横方向の各々で16%以下
厚みムラ={(Tmax-Tmin)/Tave}×100(%)
本発明の透明ガスバリアフィルムは、プラスチックフィルムの少なくとも片面に酸化アルミニウムを主成分とする酸化アルミニウム層を有するプラスチックフィルムにおいて、前記酸化アルミニウ層の蒸着直後の吸収係数が0.03nm-1未満であり、かつ膜厚が6nm以上10nm以下であることを特徴とするものである。
α=-1/tal・ln(Tal/100)・・・式(1)
酸化アルミニウム層の全光線透過率Tal%は、酸化アルミニウム層を持つ透明ガスバリアフィルムの全光線透過率をT0 %とし、酸化アルミニウム層を積層する基材のプラスチックフィルムの全光線透過率をTb %としたときに式(2)で表すことができる。
Tal=T0/Tb×100 ・・・式(2)
蛍光X線装置により膜厚を求めるためには、あらかじめ既知の膜厚のサンプルを蛍光X線装置で測定し、サンプルから出てくる蛍光X線量をもとめ膜厚と蛍光X線強度との検量線を作成しておく必要がある。
本発明の透明ガスバリアフィルムの製造方法は、プラスチックフィルムの少なくとも片面に酸化アルミニウムを主成分とする酸化アルミニウム層を有するプラスチックフィルムからなる透明ガスバリアフィルムを製造する場合において、前記酸化アルミニウム層の蒸着直後の吸収係数を0.03nm-1未満に調整する酸化アルミニウム層形成工程を有する。
本発明で言う蒸着直後とは真空槽内でプラスチックフィルムに酸化アルミニウム層を蒸着した直後に膜厚制御等のために、光学的厚みを測定している時点をいう。
蒸着した酸化アルミニウム層は酸素に触れると更に酸化が進み、全光線透過率が変化する。
蒸着終了後、蒸着装置より蒸着したプラスチックフィルムを取り出し、すぐに全光線透過量を測定すれば、光学的厚みを測定している時点と一致する。
酸の分子が金属原子に近づきやすい構造をとっている。あるいは酸化金属原子が酸と反応しやすい状態にあるのか不明であるが酸による劣化が起こってしまう。
なお、本発明で言う耐酸性とは、透明バリアフィルムを使った包装体に酸性が強い内容物を入れたときにバリア層である酸化アルミニウム層が酸による化学変化でバリア性を喪失しないことを言う。
蒸着中に酸素と多く反応することで酸化アルミニウム層の密度が低下するのではないかと推定されるが定かではない。
反応性蒸着法とは金属アルミニウムを加熱して蒸発させ、酸素を蒸着槽に導入することで金属アルミニウムを酸化アルミニウムに反応させて基板のプラスチックフィルムに堆積させる方法である。金属アルミニウムを加熱蒸発させる方法としては、抵抗加熱法、誘導加熱法、電子ビーム加熱法が使用可能である。
酸素導入口(8)は図3で示す通りにコーティングロール(6)に近接して設置し、アルミニウム蒸気の流れを邪魔しない位置に設置することが好ましい。
図4のように酸素導入口(8)を蒸発源に近づけると蒸発源でアルミニウムが酸化し蒸発速度を不安定にすると考えられる。図4で示すようにアルミニウム蒸気の流れより離れた位置で酸素を導入すると酸素がアルミニウム原子と遭遇する確率が減り有効に酸素が使われない。消費されない酸素は真空蒸着槽内の圧力を上昇させてしまう。圧力が高い状況で蒸着を行うと形成した膜の密度が下がる傾向にある。
従って、蒸着を行う圧力としては、酸化アルミニウムの密度が上がりバリア性が良くなることを考え1×10-2Pa以下が好ましい。
空気の巻き込み量は式(3)で表すことができる。 巻き返したプラスチックフィルムの厚みをtμm、長さを1m、また使用した紙管の直径を2rmmとし、巻き取ったロール状のプラスチックフィルムの直径を2Rmmとしたとき、プラスチックフィルム間に巻き込んだ空気の層の厚みtair μmは式(3)で表すことができる。
tair=π(R2-r2)/l-t ・・・式(3)
温度を上げると酸化は促進されると推定されるが、40℃以上に上げるとフィルムの物性等に影響が出る可能性があるので好ましくない。また、10℃以下にすると酸化が遅くなるので好ましくない。
厚みムラ={(Tmax-Tmin)/Tave}×100(%)・・・式(4)
プラスチックフィルム中の滑剤含有率の下限は好ましくは0.01重量%であり、より好ましくは0.015重量%であり、さらに好ましくは0.02重量%である。0.01重量%未満であると滑り性が低下することがある。上限は好ましくは1重量%であり、より好ましくは0.2重量%であり、さらに好ましくは0.1重量%である。1重量%を超えると透明性が低下することがあり、あまり好ましくない。
押出機内のスクリューの圧縮部の最高の設定温度の下限は好ましくは295℃である。ペットボトルに使用されるポリエステル樹脂は、透明性の点から高融点の結晶(260℃~290℃)が存在していることが多い。また、添加剤や結晶化核剤などが添加されており、樹脂材料内の微細な溶融挙動にバラッキがみられる。295℃未満であるとそれらを十分に溶融させることが困難となり、あまり好ましくない。押出機内のスクリューの圧縮部の最高の設定温度の上限は好ましくは310℃である。310℃を超えると樹脂の劣化が起こる場合があり、あまり好ましくない。
例えば、無機薄膜層を備えた透明バリアフィルムを包装材料として用いる場合には、シーラントと呼ばれるヒートシール性樹脂層を形成することが好ましい。ヒートシール性樹脂層は通常、無機薄膜層上に設けられるが、プラスチックフィルムの外側(無機薄膜層のある面の反対面)に設けることもある。ヒートシール性樹脂層の形成は、通常押出しラミネート法あるいはドライラミネート法によりなされる。ヒートシール性樹脂層を形成する熱可塑性 重合体としては、シーラント接着性が十分に発現できるものであればよく、HDPE、LDPE、LLDPEなどのポリエチレン樹脂類、ポリプロピレン樹脂、エチレン一酢酸ビニル共重合体、エチレン―a―オレフィンランダム共重合体、アイオノマー樹脂等を使用できる。
図6記載の概略図で示したボートタイプの抵抗加熱蒸着源(9)を並べた蒸着源を持ち、ロール ツウ ロールタイプフィルム走行系を持つ蒸着装置を使い透明バリアフィルムを作成した。
BNコンポジット製のボートにはアルミニウムワイヤーが送りこまれる機構になっている。
酸素導入口(8)はコーティングウインドー(7)に設置してある。
コーティングロール(6)は-5℃に設定した。
プラズマ源(17)は投入電力10kwに設定しアルゴンガス400sccm、酸素ガス100sccmを流してプラズマを発生させた。
蒸着したプラスチックフィルムは光学式膜厚計(18)に移動し全光線透過率を測定する。測定した後フィルムは巻取りロール(19)に巻き取られる。
(1) 全光線透過率
蒸着中の全光線透過率はJIS K 7375 に準じ濁度計(日本電色工業株式会社 NDH5000)により測定したサンプルを使い光学式膜厚計の値を換算できるようにして膜厚計の値を換算して得た。
また、蒸着後取り出したサンプルは濁度計で測定を行った。
酸素透過率(OTR)はJIS K7126-2に準じ酸素透過度測定装置(米MOCON社製 OXTRAN-2/20)を用い、温度23℃、湿度65%RHの測定条件で測定した。
水蒸気透過率(WVTR)はJIS K7129 B法に準じ水蒸気透過度測定装置(米MOCON社製 PERMATRAN-W3/31)を用い温度40℃、湿度90%RHの測定条件で測定した。
作成した透明バリアフィルムにリニアローデンシティポリエチレンフィルム(LLDEP:東洋紡株式会社製 L4102 40μm )をドライラミネートした積層フィルム作成する。ドライラミネートには東洋モートン株式会社製 TM569とCAT-10Lとを混合した接着剤を使用した。
積層フィルムをA5サイズ(148mm×210mm)に2枚切り出し、L4012側を重ねて3方をシールし、袋を作成する。シール幅は10mm。
食酢(株式会社Mizukan 穀物酢)を水で50%に薄めたものを袋に100ml詰めシールする。この袋を40℃の部屋に置き1週間保管する。
1週間後内容物を取り出し、水洗して乾燥した後、酸素透過率を測定する。
酸素透過率により耐酸性を評価する。
クロロホルムD(ユーリソップ社製)とトリフルオロ酢酸D1(ユーリソップ社製)を10:1(体積比)で混合した溶媒に、原料ポリエステル樹脂又はポリエステルフィルムを溶解させて、試料溶液を調製した。その後、調製した試料溶液をNMR装置(Varian社製核磁気共鳴分析計:GEMINI-200)を用いて、温度23℃、積算回数64回の測定条件で試料溶液のプロトンのNMRを測定した。NMR測定では、所定のプロトンのピーク強度を算出して、酸成分100モル%中のテレフタル酸成分およびイソフタル酸成分の含有率(モル%)を算出した。
試料を130℃で一昼夜真空乾燥後、粉砕又は切断し、その80mgを精秤して、フェノール/テトラクロロエタン=60/40(体積比)の混合溶液に80℃で30分間、加熱溶解した。80℃で加熱溶解の後、常温まで冷却し、メスフラスコ内で前記割合で調製した混合溶媒を足して20mlにした後、30℃で測定した(単位:dI/g)。極限粘度の測定にはオストワルド粘度計を用いた。
PEACOCKダイアルゲージ(尾崎製作所製)を用いて、縦および横方向のフィルム1m長を5mm毎に測定した厚みTn(n=l~200) μmを200点測定し、その平均値を基材フィルムの厚みとした。
幅10mmにサンプリングして、室温(27℃)にて200mmの間隔に標線をマークして、標線の間隔を測定(L0)した後、そのプラスチックフィルムを紙の間に挟み、150℃の温度に制御した熱風オーブンに入れ30分処理した後取り出し、標線の間隔を測定(L)して、次式から熱収縮率を求めた。縦方向と横方向の双方向についてそれぞれ試料を採取して実施する。
熱収縮率(%)={(L0-L)/L0}×100
JIS K7142に準拠して、アッベ屈折計NAR-1T(株式会社アタゴ製)を用いて、厚み方向の屈折率(Nz)を求めた。光源は、ナトリウムD線とし、屈折率1.74のテストピースを使用し、中間液としてヨウ化メチレンを使用した。
製膜したプラスチックフィルムと厚さ40μmのポリエチレンフィルム(東洋紡績株式会社製「L4102」)をウレタン系の接着剤(東洋モートン社製、TM569、CAT10L、酢酸エチルを33.6:4.0:62.4(重量比))を用いてドライラミネート法により基材フィルムの無機薄膜層を積層する面の反対側に貼り合わせ、40℃にて4日間エージングを施すことにより、ラミネート強度評価用積層体を得た。尚、貼り合わせ条件は、ライン速度20m/min、ドライヤー温度80℃、乾燥後の塗布量3g/m2となるように実施した。積層体を、幅15mm、長さ200mmに切り出して試験片とし、東洋ボールドウイン社製の「テンシロンUMT-II-500型」を用いて、温度23℃、相対湿度65%の条件下で、基材フィルムの無機薄膜層積層面の反対側面とポリオレフィン樹脂層との接合面での剥離強度(N/15mm)を測定した。なお、引張速度は20cm/分、剥離角度は180度とした。
(10)の剥離処理後のシートにネオカルミン液で50℃、30分間の処理を施し、ピンク色に染色されなかった部分の面積比率を求めることでプラスチックフィルムのラミネートはく離後の 外観評価を行った。〇レベルとは、はく離後の面の接着剤の抜けが無いこと、△レベルとは、接着剤の抜けが全はく離面積の10%以下であること、×レベルは10%を超えることである。
PEACOCKダイアルゲージ(尾崎製作所製)を用いて、縦および横方向のフィルム1m長を5mm毎に測定した厚みTn(n=1~200)(μm)を200点測定し、この時の最大厚みをTmax,最小厚みをTmin, 平均厚みをTaveとして、下記の式(4)より求めた。
厚みムラ={(Tmax-Tmin)/Tave}×100(%)・・・式(4)
酸化アルミニウム層の膜厚は、蛍光X線装置(株式会社リガク製 Supermini200)によって求めた。検量線はあらかじめ準備したサンプルを誘導結合プラズマ発光分光法によりアルミニウム付着量を同定して膜厚をもとめ、そのサンプルの蛍光X線強度を求めて作成した。
ペットボトルからリサイクルされたポリエステル樹脂の調整
飲料用ペットボトルから残りの飲料などの異物を洗い流した後、粉砕して得たフレークを押出機で溶融し、順次目開きサイズの細かなものにフィルタを変えて2回更に細かな異物を濾別し、3回目に50μmの最も小さな目開きサイズのフィルタで濾別して、ポリエステル再生原料を得た。得られた樹脂の構成は、テレフタル酸/イソフタル酸//エチレングリコール=97.0/3.0//100(モル%)で、樹脂の極限粘度は0.70d1/gであった。これをポリエステルAとする。
ポリエステルBとしてテレフタル酸//エチレングリコール=100//100(モル%)からなる極限粘度0.62d1/gのポリエチレンテレフタレート樹脂を、ポリエステルCとして、ポリエステルBに平均粒子径1.5μmの不定形シリカを0.3%含有するマスターバッチとしてものを作製した。各原料は、33Paの減圧下、125℃で8時間乾燥した。それらをポリエステルA/B/C=80/10/10(重量比)となるよう混合したものを、一軸押出機に投入した。押出機から、メルトライン、フィルタおよびT-ダイまでは樹脂の温度が280℃となるように温度設定した。ただし、押出機のスクリューの圧縮部の開始点から45秒間は樹脂の温度が305℃となるように設定し、その後は再び、280℃となるようにした。
プラスチックフィルムを構成する全ポリエステル樹脂中の全ジカルボン酸成分に対するイソフタル酸成分の含有率は2.4モル%である。また、構成する樹脂の極限粘度は0.64dl/gである。
プラスチックフィルムの150℃熱収縮率は縦方向が0.8%であり横方向が0.5%である。
縦方向のプラスチックフィルムの厚み斑は7.6%であり、横方向の厚み斑は6.4%である。
ポリエチレンフィルムをラミネートした時のラミネート強度は6.1N/15mmであり、剥離面の外観も〇の水準であった。
プラスチックフィルムの全光線透過率は84%である。
この透明バリアフィルムをスリッターを使い333m/minの速度で巻き返した。巻き返したロール状のプラスチックフィルムの径から空気の巻き込み量はプラスチックフィルム間におよそ0.4μm厚み含まれると推定した。
巻き返した透明バリアフィルムを23℃の部屋に3週間保管した後、濁度計で全光線透過率を測定し吸収係数を算出した。表2に結果を示す。また、透明バリアフィルムにLLDEPを張り合わせた積層フィルムを測定したOTR、WVTRを表2に示す。さらに耐酸テストを行った結果を表2に示す。
実施例1において、ポリエステルA/B/C=60/30/10(重量比)となるよう混合した他は、実施例1と同じ方法でサンプルを作成した。実施例2を評価した結果を表2に示す。プラスチックフィルムを構成する全ポリエステル樹脂中の全ジカルボン酸成分に対するイソフタル酸成分の含有率は1.8モル%である。また、構成する樹脂の極限粘度は0.63dl/gである。
プラスチックフィルムの150℃熱収縮率は縦方向が0.9%であり横方向が0.5%である。
縦方向のプラスチックフィルムの厚み斑は7.9%であり、横方向の厚み斑は6.4%である。
ポリエチレンフィルムをラミネートした時のラミネート強度は6.2N/15mmであり、剥離面の外観も〇の水準であった。
プラスチックフィルムの全光線透過率は83%である。
実施例1において、表1に示す条件で蒸着を実施した他は、実施例1と同じ方法でサンプルを作成した。実施例2を評価した結果を表2に示す。プラスチックフィルムを構成する全ポリエステル樹脂中の全ジカルボン酸成分に対するイソフタル酸成分の含有率は2.4モル%である。また、構成する樹脂の極限粘度は0.64dl/gである。
プラスチックフィルムの150℃熱収縮率は縦方向が0.8%であり横方向が0.5%である。
縦方向のプラスチックフィルムの厚み斑は7.6%であり、横方向の厚み斑は6.4%である。
ポリエチレンフィルムをラミネートした時のラミネート強度は6.1N/15mmであり、剥離面の外観も〇の水準であった。
プラスチックフィルムの全光線透過率は84%である。
表1に示す条件で蒸着を実施した他は、実施例1と同じ方法でサンプルを作成した。
比較例1のサンプルを評価した結果を表2に示す。プラスチックフィルムを構成する全ポリエステル樹脂中の全ジカルボン酸成分に対するイソフタル酸成分の含有率は2.4モル%である。また、構成する樹脂の極限粘度は0.64dl/gである。
プラスチックフィルムの150℃熱収縮率は縦方向が0.8%であり横方向が0.5%である。
縦方向のプラスチックフィルムの厚み斑は7.6%であり、横方向の厚み斑は6.4%である。
ポリエチレンフィルムをラミネートした時のラミネート強度は6.1N/15mmであり、剥離面の外観も〇の水準であった。
プラスチックフィルムの全光線透過率は84%である。
2:酸化アルミニウム層を積層した透明ガスバリアフィルムの透過率波長特性
3:D65光源の分光パワー波長特性
4:y等色関数
5:プラスチックフィルム
6:コーティングロール
7:コーティングウインドー
8:酸素導入口
9:蒸着源(抵抗加熱ボート)
10:スクリュー
11:フライト
12:バレル
13:供給部
14:圧縮部
15:計量部
16:巻出しロール
17:プラズマ源
18:光学式膜厚計
19:巻取りロール
Claims (3)
- 基材ポリエステルフィルムの少なくとも片面に酸化アルミニウムを主成分とする酸化アルミニウム層を有する透明ガスバリアフィルムにおいて、前記酸化アルミニウム層の蒸着直後の吸収係数が0.03nm-1未満であり、かつ蒸着膜厚が6nmn以上、10nm以下であり、前記基材ポリエステルフィルムが、ペットボトルからリサイクルされたポリエステル樹脂を50重量%以上含有し、二軸延伸されてなるポリエステルフィルムであり、以下の要件を満足することを特徴とする透明ガスバリアフィルム。
(1)基材ポリエステルフィルムを構成する全ポリエステル樹脂中の全ジカルボン酸成分に対するイソフタル酸成分の含有率が0.5モル%以上5.0モル%以下
(2)基材ポリエステルフィルムを構成している樹脂の極限粘度が0.58dI/g以上、0.70dI/g以下
(3)基材ポリエステルフィルムの縦方向及び横方向の150℃熱収縮率が0.1%%以上、1.5%以下
(4)基材ポリエステルフィルムの酸化アルミニウム層積層面の反対側にポリオレフィンフィルムをラミネートした場合に、ラミネート強度が4.0N/15mm以上、20.0N/15mm以下
(5)縦方向および横方向のフィルム1m長を各々5mm毎に測定した各厚みTn(n=l~200) (単位:μm)200点を測定し、この時の最大厚みをTmax,最小厚みをTmin,平均厚みをTaveとするときの下記の式で求める厚みムラが、縦方向および横方向の各々で16%以下
厚みムラ={(Tmax-Tmin)/Tave}×100(%) - 蒸着直後の吸収係数が0.02nm-1以上であることを特徴とする、請求項1に記載の透明ガスバリアフィルム
- 吸収係数が最終的に0.002nm-1以下であることを特徴とする、請求項1又は2に記載の透明ガスバリアフィルム。
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WO2019031263A1 (ja) * | 2017-08-10 | 2019-02-14 | 東洋紡株式会社 | ガスバリア性積層体 |
WO2020241621A1 (ja) * | 2019-05-31 | 2020-12-03 | 東洋紡株式会社 | 透明ガスガリアフィルム及びその製造方法 |
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2021
- 2021-11-24 EP EP21900465.2A patent/EP4257351A1/en active Pending
- 2021-11-24 CA CA3201217A patent/CA3201217A1/en active Pending
- 2021-11-24 WO PCT/JP2021/043001 patent/WO2022118710A1/ja active Application Filing
- 2021-11-24 KR KR1020237015930A patent/KR20230109137A/ko unknown
- 2021-11-24 JP JP2022566861A patent/JPWO2022118710A1/ja active Pending
- 2021-11-24 US US18/255,050 patent/US20240017529A1/en active Pending
- 2021-11-24 CN CN202180080966.9A patent/CN116600999A/zh active Pending
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JP2638797B2 (ja) | 1987-03-13 | 1997-08-06 | 東レ株式会社 | 透明ガスバリアフイルムの製造方法 |
JP2929609B2 (ja) | 1989-06-20 | 1999-08-03 | 東洋紡績株式会社 | 透明ガスバリアフイルムおよびその製法 |
JP2000025183A (ja) * | 1998-07-08 | 2000-01-25 | Dainippon Printing Co Ltd | 酸化アルミニウム蒸着フィルム |
JP2005178100A (ja) * | 2003-12-18 | 2005-07-07 | Toray Advanced Film Co Ltd | 蒸着フイルム及びその製造方法 |
WO2014050844A1 (ja) | 2012-09-27 | 2014-04-03 | 東洋紡株式会社 | ポリエステルフィルム |
WO2015146496A1 (ja) | 2014-03-26 | 2015-10-01 | 東洋紡株式会社 | 積層フィルム |
JP2017177343A (ja) * | 2016-03-28 | 2017-10-05 | 東レフィルム加工株式会社 | 積層フィルムおよびその製造方法 |
WO2019031263A1 (ja) * | 2017-08-10 | 2019-02-14 | 東洋紡株式会社 | ガスバリア性積層体 |
WO2020241621A1 (ja) * | 2019-05-31 | 2020-12-03 | 東洋紡株式会社 | 透明ガスガリアフィルム及びその製造方法 |
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TW202231490A (zh) | 2022-08-16 |
JPWO2022118710A1 (ja) | 2022-06-09 |
CN116600999A (zh) | 2023-08-15 |
EP4257351A1 (en) | 2023-10-11 |
US20240017529A1 (en) | 2024-01-18 |
CA3201217A1 (en) | 2022-06-09 |
KR20230109137A (ko) | 2023-07-19 |
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