WO2017221781A1 - Film de polypropylène stratifié - Google Patents

Film de polypropylène stratifié Download PDF

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Publication number
WO2017221781A1
WO2017221781A1 PCT/JP2017/021925 JP2017021925W WO2017221781A1 WO 2017221781 A1 WO2017221781 A1 WO 2017221781A1 JP 2017021925 W JP2017021925 W JP 2017021925W WO 2017221781 A1 WO2017221781 A1 WO 2017221781A1
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film
polypropylene
polypropylene film
laminated
temperature
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PCT/JP2017/021925
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English (en)
Japanese (ja)
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理 木下
山田　浩司
多賀　敦
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東洋紡株式会社
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Application filed by 東洋紡株式会社 filed Critical 東洋紡株式会社
Priority to CN201780038476.6A priority Critical patent/CN109311273A/zh
Priority to MYPI2018002517A priority patent/MY187096A/en
Priority to KR1020237002967A priority patent/KR20230019224A/ko
Priority to JP2018523958A priority patent/JP7451081B2/ja
Priority to KR1020197001732A priority patent/KR102494385B1/ko
Publication of WO2017221781A1 publication Critical patent/WO2017221781A1/fr
Priority to PH12018502649A priority patent/PH12018502649A1/en
Priority to JP2022036338A priority patent/JP7239036B2/ja

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/081—Oxides of aluminium, magnesium or beryllium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/10—Glass or silica
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment

Definitions

  • the present invention relates to a laminated polypropylene film comprising a film using a polypropylene resin and a thin film layer mainly composed of an inorganic compound. More specifically, the present invention relates to a laminated polypropylene film that has excellent gas barrier properties and can be suitably used in various fields that require dimensional stability at high temperatures and high rigidity.
  • a stretched polypropylene film is excellent in flexibility and moisture resistance, so that it has been widely used in a wide range of applications such as packaging of foods and various products, electrical insulation, and surface protection films.
  • oxygen gas barrier properties are often required for film preservation, and conventional laminated films obtained by depositing inorganic compounds on polypropylene films are not sufficient in oxygen gas barrier properties, and oxygen such as polyvinylidene chloride is not sufficient.
  • a solution obtained by applying and drying a solution in which a gas barrier resin is dissolved has been used.
  • there is a limit in reducing the production cost because there is a step of applying and drying a solution in which an oxygen gas barrier resin is dissolved, and the thickness of the oxygen gas barrier resin layer must be about 5 ⁇ m.
  • the present invention has been made against the background of the problems of the prior art. That is, the object of the present invention is mainly a polypropylene film substrate using a polypropylene resin and an inorganic compound, which has a gas barrier property comparable to that of a polypropylene film coated with polyvinylidene chloride, is excellent in workability at low cost. It is providing the laminated polypropylene film provided with the thin film layer used as a component.
  • the laminated polypropylene film of the present invention is a laminated polypropylene film provided with a polypropylene film base material using a polypropylene resin and a thin film layer containing an inorganic compound as a main component.
  • the conventional laminated polypropylene film has a shrinkage rate of 9% or more at 150 ° C. in the vertical direction, and the heat energy of the vapor deposition particles when depositing the inorganic compound on the polypropylene film substrate or the radiant heat from the crucible containing the inorganic compound It is presumed that the polypropylene film base material contracted due to this, and that the change caused the gas barrier property to decrease in the inorganic compound layer itself due to the shrinkage.
  • the haze of the laminated polypropylene film is preferably 6% or less.
  • the heat shrinkage rate in the transverse direction at 150 ° C. of the laminated polypropylene film is 7% or less.
  • a laminate including the laminated polypropylene film and the polyolefin film is preferable.
  • the laminated polypropylene film of the present invention it is possible to have an oxygen gas barrier property comparable to that of a polypropylene film coated with polyvinylidene chloride, and as a result, a thin film can be obtained. Furthermore, the laminated polypropylene film of the present invention can maintain oxygen gas barrier properties and other physical properties even when exposed to an environment of about 150 ° C. as well as oxygen gas barrier properties at room temperature. Oxygen gas barrier properties that were unthinkable for polypropylene films are required, and they can be used even in high-temperature environments, and are preferably applied in a wide range of applications.
  • the laminated polypropylene film of the present invention is used as a base material layer, and a heat seal layer is laminated on the surface layer of the base material layer, so that it can be used in various packaging forms that require heat sealability.
  • the heat-sealing temperature can be set high, and the heat-sealing strength is improved, so that the line speed in bag making processing can be increased, and productivity is increased. Will improve. It can also be used as a base material for extrusion laminate with a large heat load. Furthermore, the amount of deformation of the bag can also be suppressed when high-temperature processing such as retort is performed after bag making.
  • the present invention relates to a laminated polypropylene film excellent in gas barrier properties, dimensional stability at high temperatures, and mechanical properties.
  • the laminated polypropylene film of the present invention is a laminated polypropylene film provided with a polypropylene film base material using a polypropylene resin and a thin film layer mainly composed of an inorganic compound, and the longitudinal heat shrinkage of the laminated polypropylene film at 150 ° C. It is a laminated polypropylene film characterized by having a rate of 7% or less and an oxygen permeability of 150 mL / m 2 / day / MPa or less.
  • the inorganic thin film layer used in the present invention contains an inorganic compound as a main component, and the inorganic compound is preferably an inorganic oxide.
  • the inorganic oxide is preferably at least one of aluminum oxide and silicon oxide or a composite oxide thereof.
  • the “main component” means that the total amount of aluminum oxide, silicon oxide, and a composite oxide of aluminum oxide and silicon oxide exceeds 50% by mass with respect to 100% by mass of the component constituting the thin film layer.
  • it is 70% by mass or more, more preferably 90% by mass or more, and most preferably 100% by mass (components other than aluminum oxide and silicon oxide are not contained as components constituting the thin film layer).
  • aluminum oxide as used herein includes at least one of various aluminum oxides such as AlO, Al 2 O, and Al 2 O 3 , and the content of various aluminum oxides can be adjusted according to the conditions for forming the thin film layer. it can.
  • Silicon oxide is composed of at least one of various silicon oxides such as SiO, SiO 2 and Si 3 O 2 , and the content of various silicon oxides can be adjusted according to the conditions for forming the thin film layer.
  • Aluminum oxide, silicon oxide, and a composite oxide of aluminum oxide and silicon oxide may contain a small amount of other components (up to 3% with respect to all components) within a range in which the characteristics are not impaired.
  • Components other than the “main component” include compounds such as titanium oxide, magnesium oxide, zirconium oxide, cerium oxide, and zinc oxide, and mixtures thereof.
  • the thickness of the inorganic thin film layer is not particularly limited, but is preferably 5 to 500 nm, more preferably 10 to 200 nm, and still more preferably 15 to 50 nm from the viewpoint of gas barrier properties and flexibility. If the thickness of the thin film layer is less than 5 nm, satisfactory gas barrier properties may be difficult to obtain. On the other hand, if it exceeds 500 nm, the corresponding effect of improving gas barrier properties cannot be obtained, and bending resistance and It is disadvantageous in terms of manufacturing cost.
  • the laminated polypropylene film of the present invention is particularly characterized by the laminated film physical properties.
  • the laminated polypropylene film of the present invention exhibits the following film properties.
  • the following physical properties are measured and evaluated by the methods described later in the examples.
  • the laminated polypropylene film of the present invention is a stretched film mainly composed of a polypropylene-based resin, and it is necessary that the heat shrinkage rate in the longitudinal direction at 150 ° C. is 7% or less.
  • the longitudinal direction is a film flow direction (also referred to as a length direction or a longitudinal direction)
  • the lateral direction is a direction perpendicular to the film flow direction (a lateral direction or a width direction).
  • the 150 ° C. heat shrinkage in the longitudinal direction is 9% or more.
  • the upper limit of the 150 ° C. heat shrinkage in the longitudinal direction of the laminated polypropylene film of the present invention is preferably 6%, more preferably 5%, and even more preferably 4%.
  • the gas barrier property is better.
  • the film using the propylene polymer shrinks due to the thermal energy of the inorganic compound molecules used for the vapor deposition material or the radiant heat from the crucible containing the inorganic compound. It is presumed that when the degree of shrinkage of such a polypropylene film substrate is small at the time of forming the inorganic thin film layer, it is difficult for gas to pass through. As a reason, if the shrinkage of the polypropylene film substrate occurs during the formation of the inorganic thin film layer, it is considered that the inorganic thin film layer is broken due to the protrusion of the substrate surface or the like, and it is difficult to form a dense inorganic thin film layer.
  • the lower limit of the 150 ° C. heat shrinkage in the longitudinal direction is preferably 0.2%, more preferably 0.3%, still more preferably 0.5%, and particularly preferably 0.7%. Most preferably, it is 1.0%.
  • the upper limit of the 150 ° C. heat shrinkage in the transverse direction of the laminated polypropylene film of the present invention is preferably 7%, more preferably 6%, still more preferably 5%, and particularly preferably 4%. .
  • the lower limit of the 150 ° C. heat shrinkage in the transverse direction is preferably 0.2%, more preferably 0.3%, still more preferably 0.5%, and particularly preferably 0.7%. Most preferably, it is 1.0%. If the lower limit of the 150 ° C. thermal shrinkage in the lateral direction is within the above range, realistic manufacturing may be facilitated in terms of cost and thickness unevenness may be reduced.
  • the upper limit of the oxygen permeability of the laminated polypropylene film at a temperature of 23 ° C. and a relative humidity of 65% needs to be 150 mL / m 2 / day / MPa or less. More preferably, it is 130 mL / m 2 / day / MPa or less, still more preferably 120 mL / m 2 / day / MPa or less, still more preferably 100 mL / m 2 / day / MPa or less, and particularly preferably It is 90 mL / m 2 / day / MPa or less.
  • the lower limit of the oxygen permeability of the laminated polypropylene film at a temperature of 23 ° C. and a humidity of 65% is not particularly limited, but is preferably 0.1 mL / m 2 / day / MPa or more. From the viewpoint of production, 0.1 mL / m 2 / day / MPa is considered the lower limit.
  • the upper limit of the haze of the laminated polypropylene film of the present invention is preferably 6%, more preferably 5%, still more preferably 4.5%, still more preferably 4%, and particularly preferably 3%. .5%.
  • the upper limit of the haze is within the above range, it may be easy to use in applications where transparency is required.
  • the inorganic thin film layer is preferably transparent.
  • the lower limit of the haze of the laminated polypropylene film of the present invention is, as a practical value, preferably 0.1%, more preferably 0.2%, still more preferably 0.3%, and particularly preferably 0. 4%.
  • the polypropylene film substrate used for the laminated polypropylene film of the present invention is particularly characterized in film properties.
  • the stretched polypropylene film of the present invention exhibits the following film properties.
  • the following physical properties be the value measured and evaluated by the method mentioned later in an Example, for example.
  • the polypropylene film substrate used in the present invention is a stretched film mainly composed of a polypropylene resin, and the upper limit of the heat shrinkage in the longitudinal direction at 150 ° C. is preferably 10%, more preferably 9 %, More preferably 7%, and particularly preferably 5%.
  • the 150 ° C. heat shrinkage in the longitudinal direction is 11% or more.
  • the polypropylene film substrate used in the present invention is a stretched film mainly composed of a polypropylene resin, and preferably has a heat shrinkage rate of 15% or less in the transverse direction at 150 ° C., more preferably 9 %, More preferably 7%, and particularly preferably 7%.
  • the 150 ° C. heat shrinkage in the lateral direction is 16% or more.
  • the heat shrinkage rate of the polypropylene film substrate is set to 10% or less
  • the heat shrinkage rate in the transverse direction at 150 ° C. of the laminated polypropylene film of the present invention can be set to 7% or less.
  • the longitudinal direction is the film flow direction (also referred to as the length direction)
  • the horizontal direction is the direction perpendicular to the film flow direction (also referred to as the width direction).
  • the lower limit of the 150 ° C. heat shrinkage in the machine direction and the transverse direction of the polypropylene film substrate used in the present invention is preferably 0.2%, more preferably 0.3%, and even more preferably 0.5. %, Particularly preferably 0.7%, and most preferably 1.0%.
  • the 150 ° C. heat shrinkage ratio is in the above range, realistic manufacturing may be facilitated in terms of cost or the like, and thickness unevenness may be reduced. If the heat shrinkage at 150 ° C.
  • annealing treatment is up to about 1.5%, for example, it is possible to increase the low molecular weight component of polypropylene in the film substrate, by adjusting the stretching conditions and heat setting conditions of the film, In order to reduce it to 1.5% or less, it is preferable to perform an annealing treatment offline.
  • the lower limit of the haze of the polypropylene film substrate used in the present invention is, as a practical value, preferably 0.1%, more preferably 0.2%, still more preferably 0.3%, particularly preferably. Is 0.4%.
  • the upper limit of haze is preferably 6%, more preferably 5%, still more preferably 4.5%, particularly preferably 4%, and most preferably 3.5%. If the haze is in the above range, it may be easy to use in applications where transparency is required. For example, when the stretching temperature and the heat setting temperature are too high, the haze tends to be deteriorated when the cooling roll (CR) temperature is high and the stretching rate of the stretched raw sheet is slow, or when the low molecular weight is too large. By adjusting, it can control within the said range.
  • the minimum of the thickness of the polypropylene film base material used for this invention is 3 micrometers, Preferably it is 4 micrometers, More preferably, it is 8 micrometers.
  • the lower limit of the thickness of the film is less than 3 ⁇ m, the laminated polypropylene film tends to curl and the gas barrier property tends to decrease.
  • the upper limit is preferably 300 ⁇ m, more preferably 250 ⁇ m, still more preferably 200 ⁇ m, further preferably 150 ⁇ m, particularly preferably 100 ⁇ m, and most preferably 50 ⁇ m. is there.
  • the lower limit of the impact resistance (23 ° C.) of the polypropylene film substrate used in the present invention is preferably 0.6 J, more preferably 0.7 J. When the impact resistance is within the above range, the film has sufficient toughness and does not break during handling.
  • the upper limit of impact resistance is preferably 2 J, more preferably 1.8 J, even more preferably 1.6 J, and particularly preferably 1.5 J from the practical viewpoint.
  • the impact resistance can be controlled within the above range by adjusting these factors according to the application.
  • the lower limit of the Young's modulus (23 ° C.) in the longitudinal direction is preferably 2 GPa, more preferably 2.1 GPa, and even more preferably 2. 2 GPa, particularly preferably 2.3 GPa, and most preferably 2.4 GPa.
  • the upper limit of the Young's modulus in the longitudinal direction is preferably 4 GPa, more preferably 3.7 GPa, still more preferably 3.5 GPa, particularly preferably 3.4 GPa, and most preferably 3.3 GPa. .
  • the lower limit of the Young's modulus (23 ° C.) in the transverse direction is preferably 3.8 GPa, more preferably 4 GPa, and even more preferably 4 .1 GPa, particularly preferably 4.2 GPa.
  • the upper limit of the Young's modulus in the lateral direction is preferably 8 GPa, more preferably 7.5 GPa, still more preferably 7 GPa, and particularly preferably 6.5 GPa.
  • the Young's modulus in the machine direction and the transverse direction can be increased, for example, by increasing the draw ratio in each direction, and when stretching in the machine direction after stretching in the machine direction, set the machine draw ratio to a lower value.
  • the Young's modulus in the transverse direction can be increased by setting the transverse draw ratio high.
  • the lower limit of the uniformity of the thickness of the polypropylene film substrate used in the present invention is preferably 0%, more preferably 0.1%, still more preferably 0.5%, and particularly preferably 1%. is there.
  • the upper limit of the thickness uniformity is preferably 20%, more preferably 17%, still more preferably 15%, particularly preferably 12%, and most preferably 10%. When the thickness uniformity is within the above range, defects are unlikely to occur during post-processing such as coating and printing, and it is easy to use for applications that require precision.
  • the lower limit of the density of the polypropylene film substrate used in the present invention is preferably 0.910 g / cm 3 , more preferably 0.911 g / cm 3 , still more preferably 0.912 g / cm 3 , particularly Preferably it is 0.913 g / cm 3 .
  • the upper limit of the film density is preferably 0.930 g / cm 3 , more preferably 0.928 g / cm 3 , still more preferably 0.926 g / cm 3 , and particularly preferably 0.925 g / cm 3 . is there. If the film density exceeds the upper limit, production may be difficult in practice.
  • the film density can be increased by increasing the stretching ratio and stretching temperature, increasing the heat setting temperature, and further performing offline annealing.
  • the lower limit of the longitudinal refractive index (Nx) of the polypropylene film substrate used in the present invention is preferably 1.502, more preferably 1.503, and even more preferably 1.504.
  • the upper limit of Nx is preferably 1.520, more preferably 1.517, and even more preferably 1.515.
  • the lower limit of the lateral refractive index (Ny) of the polypropylene film substrate used in the present invention is preferably 1.523, and more preferably 1.525.
  • the upper limit of Ny is preferably 1.535, and more preferably 1.532.
  • the lower limit of the refractive index (Nz) in the thickness direction of the polypropylene film substrate used in the present invention is preferably 1.480, more preferably 1.490, and even more preferably 1.500.
  • the upper limit of Nz is preferably 1.510, more preferably 1.507, and even more preferably 1.505.
  • the lower limit of the plane orientation coefficient of the polypropylene film used for the substrate of the present invention is preferably 0.0125, more preferably 0.0126, still more preferably 0.0127, and particularly preferably 0.0128. It is.
  • the upper limit of the plane orientation coefficient is preferably 0.0155, more preferably 0.0150, even more preferably 0.0148, and particularly preferably 0.0145 as a practical value.
  • the plane orientation coefficient can be set within the range by adjusting the draw ratio. When the plane orientation coefficient is in this range, the thickness unevenness of the film tends to be good.
  • a polypropylene film substrate generally has a crystal orientation, and its direction and degree have a great influence on film properties.
  • the degree of crystal orientation varies depending on the molecular structure of the polypropylene used and the process and conditions in film production.
  • the orientation direction of the stretched polypropylene film can be determined by measuring the azimuth angle dependency of the scattering peak derived from the crystal by making X-rays incident perpendicular to the film surface by wide-angle X-ray diffraction method. it can.
  • the stretched polypropylene film typically has a monoclinic ⁇ -type crystal structure.
  • the ⁇ -type crystal has a strong orientation mainly in one axis when the azimuth angle dependence of the scattering intensity of 110 planes (plane spacing: 6.65 ⁇ ) is measured by wide-angle X-ray diffraction. That is, when the scattering intensity derived from the 110 plane of the ⁇ -type crystal is plotted against the azimuth angle, the strongest peak is observed in the direction perpendicular to the orientation of the molecular axis.
  • the degree of orientation is defined by the half width of the maximum peak.
  • FIG. 1 shows the full width at half maximum of the main peak (maximum peak, azimuth angles 180 ° and 360 °) on the azimuth angle dependency of the 110 plane.
  • the half width of the maximum peak when plotting the scattering intensity of the 110 plane measured by the wide angle X-ray scattering method against the azimuth is 30 degrees or less.
  • the upper limit of the full width at half maximum is more preferably 29 degrees and even more preferably 28 degrees.
  • the lower limit of the FWHM of the azimuth angle dependence of the scattering intensity derived from the 110 plane is preferably 5 degrees, more preferably 7 degrees, and even more preferably 8 degrees. If the full width at half maximum of the 110 plane is smaller than the above range, impact resistance may be lowered and orientation cracks may occur.
  • the half width defined above is preferably measured using X-rays with high parallelism, and radiant light is preferably used.
  • X-ray generation source used for wide-angle X-ray diffraction measurement, a general apparatus such as a tube type or a rotary type used in a laboratory may be used, but a high-intensity light source capable of emitting high-intensity synchrotron radiation. Is preferably used. With synchrotron radiation, X-rays do not spread easily and the brightness is high, so measurements can be performed with high accuracy and in a short time.
  • Examples of facilities that can emit high-luminance synchrotron radiation with high parallelism include, for example, large-scale synchrotron radiation facilities such as SPring-8, which are owned by the Frontier Soft Matter Development-Academia Federation (FSBL), for example. It is preferable to measure the half width of the present invention using the beam line BL03XU.
  • FSBL Frontier Soft Matter Development-Academia Federation
  • the polypropylene film substrate used in the present invention preferably has a large long period size.
  • a crystalline polymer has a regular laminated structure (periodic structure) composed of repeating crystals and amorphous.
  • the size of the repeating unit composed of a crystal and an amorphous is called a long period size.
  • the long period size can be obtained from the scattering peak angle derived from the long period structure in the main orientation direction measured by the small angle X-ray scattering method.
  • the long-period scattering peak by the small-angle X-ray scattering measurement of the polypropylene film used for the substrate of the present invention is preferably clearly observed in the main orientation direction.
  • the main orientation direction indicates a direction in which scattering due to the long period of the polymer crystal is more strongly observed in the two-dimensional X-ray scattering pattern.
  • the main orientation direction In the case of uniaxial stretching, the main orientation direction often coincides with the stretching direction.
  • the main orientation direction in the transverse stretching direction In the case of sequential biaxial stretching of longitudinal stretching and transverse stretching, depending on the respective stretching ratios, the main orientation direction in the transverse stretching direction. Often match. It is shown that a long-period structure with high ordering is formed as the long-period peak attributed to the polymer crystal is clearly observed.
  • the long period size obtained from the long period scattering peak is preferably 40 nm or more.
  • the lower limit of the long period size is more preferably 41 nm, and still more preferably 43 nm.
  • the upper limit of the long period size is preferably 100 nm, more preferably 90 nm, and further preferably 80 nm.
  • the X-ray generation source used for the small-angle X-ray scattering measurement is not particularly limited, and a general apparatus such as a tube type or a rotary type used in a laboratory can be used. It is preferable to use a high-intensity light source capable of irradiating radiation with high luminance, similar to the X-ray generation source used in the above.
  • a high-intensity light source capable of irradiating radiation with high luminance, similar to the X-ray generation source used in the above.
  • X-ray scattering derived from the long period structure is in a smaller angle region.
  • the beam diameter can be reduced to several hundred microns or less, and It is preferable to measure an ultra-small angle region under a long camera length using synchrotron radiation having high luminance.
  • the camera length is preferably 7 m or longer.
  • the polypropylene resin used for the polypropylene film substrate of the present invention is not particularly limited.
  • a propylene homopolymer, a copolymer of ethylene and / or an ⁇ -olefin having 4 or more carbon atoms, and a mixture thereof. Can be used.
  • a propylene homopolymer substantially free of a comonomer is preferable.
  • the comonomer amount is preferably 0.5 mol% or less.
  • the upper limit of the comonomer amount is preferably 0.3 mol%, more preferably 0.1 mol%.
  • the polypropylene resin constituting the film is more preferably a propylene homopolymer obtained only from a propylene monomer, and even a propylene homopolymer does not contain a heterogeneous bond such as a head-to-head bond. preferable.
  • the lower limit of the mesopentad fraction measured by 13C-NMR, which is an index of the stereoregularity of the polypropylene resin constituting the film, is preferably 96%.
  • the lower limit of the mesopentad fraction is preferably 96.5%, more preferably 97%.
  • the upper limit of the mesopentad fraction is preferably 99.8%, more preferably 99.6%, still more preferably 99.5%. In the above range, realistic production may be easy.
  • the lower limit of the meso average chain length of the polypropylene resin constituting the film is preferably 100, more preferably 120, and still more preferably 130. When it is in the above range, the crystallinity may be improved, and the thermal shrinkage rate at a high temperature may be small.
  • the upper limit of the meso average chain length is preferably 5000 from a practical aspect.
  • the lower limit of the xylene-soluble content of the polypropylene resin constituting the film is preferably 0.1% by mass from a practical aspect.
  • the upper limit of the xylene-soluble content is preferably 7% by mass, more preferably 6% by mass, and further preferably 5% by mass. When it is in the above range, the crystallinity may be improved, and the thermal shrinkage at high temperatures may be reduced.
  • the lower limit of the melt flow rate (MFR) (230 ° C., 2.16 kgf) of the polypropylene resin is 0.5 g / 10 minutes.
  • the lower limit of the MFR is preferably 1.0 g / 10 minutes, more preferably 1.3 g / 10 minutes, still more preferably 1.5 g / 10 minutes, still more preferably 2.0 g / 10 minutes. Yes, particularly preferably 4.0 g / 10 min, and preferably 6.0 g / 10 min.
  • the mechanical load is small, and extrusion and stretching may be easy.
  • the upper limit of MFR is 20 g / 10 minutes, preferably 17 g / 10 minutes, more preferably 16 g / 10 minutes, and further preferably 15 g / 10 minutes.
  • stretching may be easy, thickness unevenness may be reduced, and the stretching temperature and heat setting temperature may be easily increased, resulting in a lower thermal shrinkage rate.
  • the lower limit of the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of the polypropylene resin constituting the film is preferably 20000, more preferably 22000, still more preferably 24000, Particularly preferred is 26000, and most preferred is 27000.
  • Mn number average molecular weight measured by gel permeation chromatography
  • the effects of the present application such as a low heat shrinkage rate of the polypropylene film substrate at a high temperature, which is an effect of a low molecular weight material of polypropylene resin, may be easily obtained, or may be easily stretched.
  • the lower limit of the mass average molecular weight (Mw) measured by GPC of the polypropylene resin constituting the film is preferably 180,000, more preferably 200000, still more preferably 230000, and further preferably 240000, Particularly preferred is 250,000, and most preferred is 270000.
  • Mw mass average molecular weight measured by GPC of the polypropylene resin constituting the film.
  • the polypropylene resin used in the present invention preferably has the following characteristics. That is, when the gel permeation chromatography (GPC) integration curve of the polypropylene resin constituting the film is measured, the lower limit of the amount of the component having a molecular weight of 100,000 or less is preferably 35% by mass, more preferably 38% by mass. More preferably, it is 40% by mass, particularly preferably 41% by mass, and most preferably 42% by mass. Within the above range, the effects of the present application such as a low heat shrinkage rate at a high temperature, which is an effect of a low molecular weight substance, may be easily obtained, and stretching may be facilitated.
  • GPC gel permeation chromatography
  • the upper limit of the amount of a component having a molecular weight of 100,000 or less in the GPC integration curve is preferably 65% by mass, more preferably 60% by mass, still more preferably 58% by mass, and particularly preferably 56% by mass. Most preferably, it is 55 mass%.
  • stretching may be easy, thickness unevenness may be reduced, and the stretching temperature and heat setting temperature may be easily increased, resulting in a low thermal shrinkage rate.
  • the lower limit of the mass average molecular weight (Mw) / number average molecular weight (Mn), which is an index of the molecular weight distribution, is preferably 4, more preferably 4.5, More preferably, it is 5, particularly preferably 5.5, and most preferably 6.
  • the upper limit of Mw / Mn is preferably 30, more preferably 25, still more preferably 22, particularly preferably 21, and most preferably 20. When Mw / Mn is in the above range, realistic production is easy.
  • the molecular weight distribution of polypropylene is such that components with different molecular weights are polymerized in a series of plants in multiple stages, components with different molecular weights are blended offline in a kneader, or catalysts with different performances are blended for polymerization. Or by using a catalyst capable of realizing a desired molecular weight distribution.
  • the polypropylene-based resin is obtained by polymerizing propylene as a raw material using a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. Among these, in order to eliminate heterogeneous bonds, it is preferable to use a catalyst capable of polymerization with high stereoregularity among Ziegler-Natta catalysts.
  • a known method may be employed as a polymerization method of propylene.
  • a method of polymerizing in an inert solvent such as hexane, heptane, toluene, xylene
  • a method of polymerizing in a liquid monomer a gas monomer
  • examples thereof include a method of adding a catalyst and polymerizing in a gas phase state, or a method of polymerizing by combining these.
  • an additive and another resin to the polypropylene film base material used for this invention as needed.
  • the additive include an antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, a nucleating agent, an adhesive, an antifogging agent, a flame retardant, an antiblocking agent, and an inorganic or organic filler.
  • other resins include polypropylene resins other than the polypropylene resins used in the present invention, random copolymers that are copolymers of propylene and ethylene and / or ⁇ -olefins having 4 or more carbon atoms, and various elastomers. It is done.
  • the polypropylene film used for the substrate of the present invention may be a uniaxially stretched film in the longitudinal direction (longitudinal direction) or the transverse direction (width direction), but is preferably a biaxially stretched film.
  • biaxial stretching sequential biaxial stretching or simultaneous biaxial stretching may be used.
  • a method for producing a longitudinally-laterally stretched sequential biaxially stretched film which is the most preferred example, will be described below.
  • a polypropylene resin is heated and melted with a single or twin screw extruder and extruded onto a chill roll to obtain an unstretched sheet.
  • the melt extrusion conditions are such that the resin temperature is 200 to 280 ° C.
  • the sheet is extruded from a T-die and cooled and solidified with a cooling roll having a temperature of 10 to 100 ° C.
  • the film is stretched 3 to 8 times, preferably 3 to 7 times in the length (longitudinal) direction with a stretching roll of 120 to 165 ° C., and then 155 ° C.
  • a roll sample can be obtained by subjecting the polypropylene film thus obtained to a corona discharge treatment on at least one surface, if necessary, and then winding it with a winder.
  • the lower limit of the stretching ratio in the machine direction is preferably 3 times, more preferably 3.5 times. If the stretching ratio in the longitudinal direction is less than the above, film thickness unevenness may occur.
  • the upper limit of the draw ratio in the machine direction is preferably 8 times, more preferably 7 times. If the draw ratio in the machine direction exceeds the above, it may be difficult to carry out the transverse drawing to be performed subsequently.
  • the lower limit of the stretching temperature in the machine direction is preferably 120 ° C, more preferably 125 ° C, and even more preferably 130 ° C. When the stretching temperature in the longitudinal direction is less than the above, the mechanical load may be increased, the thickness unevenness may be increased, or the film may be roughened.
  • the upper limit of the stretching temperature in the machine direction is preferably 165 ° C, more preferably 160 ° C, still more preferably 155 ° C, and particularly preferably 150 ° C.
  • a higher stretching temperature is preferable for lowering the thermal shrinkage, but it may adhere to the roll and cannot be stretched, or surface roughness may occur.
  • the lower limit of the horizontal draw ratio is preferably 4 times, more preferably 5 times, and even more preferably 6 times. When the horizontal draw ratio is less than the above, thickness unevenness may occur.
  • the upper limit of the transverse draw ratio is preferably 20 times, more preferably 17 times, still more preferably 15 times, and particularly preferably 12 times. When the horizontal draw ratio exceeds the above, the heat shrinkage rate may be increased or the film may be broken during stretching.
  • the preheating temperature in the transverse stretching is preferably set 5 to 15 ° C. higher than the stretching temperature in order to quickly raise the film temperature in the vicinity of the stretching temperature.
  • the transverse stretching is preferably performed at a temperature 3 to 5 ° C. higher than that of a conventional stretched polypropylene film.
  • the lower limit of the TD stretching temperature is preferably 155 ° C, more preferably 157 ° C, and even more preferably 158 ° C.
  • the upper limit of the transverse stretching temperature is preferably 175 ° C, more preferably 170 ° C, and further preferably 168 ° C. In order to lower the heat shrinkage rate, it is preferable that the transverse stretching temperature is higher. However, if the above is exceeded, the low molecular weight component is melted and recrystallized to reduce the orientation, as well as surface roughness and whitening of the film. There are things to do.
  • the stretched film is usually heat-set.
  • heat setting can be performed at a temperature 3 to 10 ° C. higher than that of a conventional stretched polypropylene film.
  • the lower limit of the heat setting temperature is preferably 165 ° C, more preferably 166 ° C.
  • the upper limit of the heat setting temperature is preferably 175 ° C, more preferably 173 ° C. If the heat setting temperature exceeds the above, the low molecular weight component may melt and recrystallize, resulting in surface roughness and whitening of the film.
  • the lower limit of relaxation is preferably 1%, more preferably 2%, and even more preferably 3%. If the relaxation is less than the above, the heat shrinkage rate may be high.
  • the upper limit of relaxation is preferably 10%, more preferably 8%. When the relaxation is more than the above, thickness unevenness may increase.
  • the film manufactured in the above process can be once rolled up and then annealed offline.
  • the lower limit of the offline annealing temperature is preferably 160 ° C., more preferably 162 ° C., and further preferably 163 ° C. If the offline annealing temperature is lower than the above, the effect of annealing may not be obtained.
  • the upper limit of the offline annealing temperature is preferably 175 ° C, more preferably 174 ° C, and further preferably 173 ° C. When the off-line annealing temperature exceeds the above, transparency may be reduced or thickness unevenness may be increased.
  • the lower limit of the offline annealing time is preferably 0.1 minutes, more preferably 0.5 minutes, and even more preferably 1 minute. If the offline annealing time is less than the above, the annealing effect may not be obtained.
  • the upper limit of the offline annealing time is preferably 30 minutes, more preferably 25 minutes, and further preferably 20 minutes. When the offline annealing time exceeds the above, productivity may be reduced. If the heat shrinkage at 150 ° C. is up to about 1.5%, for example, it is possible to increase the low molecular weight component, and adjust the stretching conditions and heat setting conditions. It is preferable to perform an annealing treatment offline.
  • the stretching temperature and the heat setting temperature are too high, the haze tends to be deteriorated when the cooling roll (CR) temperature is high and the stretching rate of the stretched raw sheet is slow, or when the low molecular weight is too large.
  • the cooling roll (CR) temperature is high and the stretching rate of the stretched raw sheet is slow, or when the low molecular weight is too large.
  • the stretched polypropylene film obtained in this way is usually formed into a film having a width of about 2000 to 12000 mm and a length of about 1000 to 50000 m, and wound into a roll. Furthermore, it is slit according to each application and used as a slit roll having a width of 300 to 2000 mm and a length of about 500 to 5000 m.
  • a known production method such as a PVD method (physical vapor deposition method) such as a vacuum vapor deposition method, a sputtering method or an ion plating method, or a CVD method (chemical vapor deposition method) is appropriately used.
  • Vapor deposition is preferable, and vacuum vapor deposition is more preferable.
  • a heating method includes resistance heating, high frequency induction heating, electron beam heating, etc. Can be used.
  • the reactive gas oxygen, nitrogen, water vapor or the like may be introduced, or reactive vapor deposition using means such as ozone addition or ion assist may be used.
  • the production conditions may be changed as long as the object of the present invention is not impaired, such as applying a bias to the film substrate, increasing the temperature of the film substrate, or decreasing the temperature of the film substrate.
  • a coating layer may be provided between the polypropylene film substrate and the inorganic thin film layer, or a coating layer may be provided on the inorganic thin film layer.
  • the laminated polypropylene film of the present invention has excellent characteristics as described above which are not present in the past. When used as a packaging film, it can be used as an alternative to polyvinylidene chloride-coated polypropylene film because of its excellent gas barrier properties, and because it is more rigid, it can be thinned, further reducing costs, Weight can be reduced.
  • the laminated polypropylene film of the present invention has high heat resistance, it can be processed at a high temperature during coating and printing, and it is possible to use a coating agent, an ink, a laminating adhesive, or the like, which has been difficult to use conventionally, or production. it can.
  • the laminated polypropylene film of the present invention is not limited to packaging, and can also be used as an insulating film such as a capacitor or a motor, or as a base film for a solar cell backsheet.
  • laminate manufacturing method Chemical or cosmetic products such as foods and drinks, pharmaceuticals, detergents, shampoos, oils, toothpastes, adhesives, adhesives, etc., using the laminate comprising the heat-sealing polyolefin resin layer provided on the laminated polypropylene film of the present invention
  • a packaging container excellent in filling and packaging suitability, storage suitability, and the like of various other articles can be produced.
  • the polyolefin resin layer having heat sealability a resin film or sheet that can be melted by heat and fused to each other can be used.
  • low density polyethylene low density polyethylene, medium density polyethylene, High density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid
  • Polyolefin resin such as copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyethylene or polypropylene, acrylic acid, methacrylic acid, maleic acid, maleic anhydride
  • Unsaturated cals such as fumaric acid, itaconic acid Modified acid-modified polyolefin resin in phosphate, polyvinyl acetate resins, poly (meth) acrylic resins, polyvinyl chloride resins, other various resin films or sheets - may be used and.
  • a typical one is a film or sheet made of linear (linear) low density polyethylene or polypropylene.
  • the upper limit of oxygen permeability at a laminate laminate temperature of 23 ° C. and a relative humidity of 65% is preferably 50 mL / m 2 / day / MPa, more preferably 30 mL / m 2 / day / MPa, It is preferably 20 mL / m 2 / day / MPa, particularly preferably 15 mL / m 2 / day / MPa.
  • the upper limit of the oxygen permeability is 50 mL / m 2 / day / MPa, the preservability of a substance or food deteriorated by oxygen is excellent.
  • the lower limit of the oxygen permeability of the laminated polypropylene film at a temperature of 23 ° C. and a humidity of 65% is not particularly limited, but is preferably 0.1 mL / m 2 / day / MPa. From the viewpoint of production, 0.1 mL / m 2 / day / MPa is considered the lower limit.
  • the lower limit of the laminate strength in the longitudinal direction of the laminate is preferably 1.1 N / 15 mm, more preferably 1.2 N / 15 mm, and still more preferably 1.2 N / 15 mm.
  • the upper limit of the laminate strength in the longitudinal direction is not particularly limited, but is preferably 3.0 N / 15 mm. Further, from the viewpoint of manufacturing, 3.0 N / 15 mm is considered the upper limit.
  • the measuring method of the physical property in an Example is as follows.
  • the mesopentad fraction ([mmmm]%) and meso average chain length were measured using 13C-NMR as follows.
  • the mesopentad fraction was calculated according to the method described in “Zambelli et al., Macromolecules, Vol. 6, 925 (1973)”.
  • the meso-average chain length was calculated according to the method described in “Polymer Sequence Distribution”, Chapter 2 (1977) (Academic Press, New York) by JC Randall.
  • the 13C-NMR measurement was performed at 110 ° C. by using “AVANCE 500” manufactured by BRUKER, and dissolving 200 mg of a sample in an 8: 2 (volume ratio) mixture of o-dichlorobenzene and heavy benzene at 135 ° C.
  • Xylene solubles (unit: mass%) 1 g of a polypropylene sample is dissolved in 200 ml of boiling xylene, allowed to cool, then recrystallized in a constant temperature water bath at 20 ° C. for 1 hour, and the ratio of the mass dissolved in the filtrate to the original sample amount is determined as the xylene solubles ( Mass%).
  • MFR Melt flow rate
  • the number average molecular weight (Mn), the mass average molecular weight (Mw), and the Z + 1 average molecular weight (Mz + 1) are determined by the molecular number (Ni) of the molecular weight (Mi) at each elution position of the GPC curve obtained through the molecular weight calibration curve. It is defined by the following formula.
  • the obtained two-dimensional image was subjected to air scattering correction in consideration of dark current (dark noise) and transmittance.
  • the camera length was measured using cerium oxide (CeO 2 ) and Fit 2D (European Synchrotron Radiation Facility software [http://www.esrf.eu/computing/scientific/FIT2D/]) (110) The azimuth profile of was calculated.
  • Air scattering correction was performed on the obtained scattered image in consideration of dark current and transmittance in the same manner as the WAXS measurement, and collagen calibrated separately with silver behenate was used for accurate camera length measurement.
  • a profile in the width direction of the sample was calculated using the Fit2d software described above, and plotted with the scattering vector q (nm-1) on the horizontal axis and the common logarithm of intensity I (q) on the vertical axis.
  • the calculation range of the profile was ⁇ 5 degrees from the width direction.
  • DSC Differential scanning calorimetry
  • Thermal shrinkage (unit:%) It measured by the following method based on JISZ1712: 2009.
  • the film substrate and the laminated film were each 20 mm wide and 200 mm long, each cut into 5 pieces in the vertical and horizontal directions, suspended in a hot air oven at 150 ° C. and heated for 15 minutes.
  • the length at the marked lines at intervals of about 50 mm after heating was measured, and the ratio (percentage) of the contracted length to the original length was defined as the thermal contraction rate.
  • Young's modulus (unit: GPa) In accordance with JIS K 7127: 1999, the Young's modulus in the longitudinal direction and the transverse direction of the film substrate and the laminated film was measured at 23 ° C.
  • the film base material and the laminated film are each 15 mm wide and 200 mm long, and are each cut into 5 pieces each in the longitudinal direction and the transverse direction, and 200 mm / min.
  • the tensile strength at the time of the tensile test was measured at a tensile speed.
  • Thickness uniformity (thickness unevenness) (unit:%)
  • a square sample having a length of 1 m was cut out from the wound film roll, and 100 samples for measurement were prepared by dividing the sample into 10 equal parts in the vertical and horizontal directions. The thickness was measured with a contact-type film thickness meter at the approximate center of the measurement sample. The average value A of the obtained 100 points of data was obtained, the difference (absolute value) B between the minimum value and the maximum value was obtained, and the value calculated using the formula of (B / A) ⁇ 100 was used as the thickness variation of the film. It was.
  • Refractive index (Nx, Ny, Nz) Using an Abbe refractometer (manufactured by Atago Co., Ltd.), the film substrate was measured at 23 ° C., humidity 65%, the measurement solution was benzyl alcohol, and the measurement wavelength was 589 nm (sodium D line). The refractive indexes along the vertical and horizontal directions were Nx and Ny, respectively, and the refractive index in the thickness direction was Nz.
  • each film whose adhesion amount was determined was analyzed with an X-ray fluorescence analyzer (ZSX100e, manufactured by Rigaku Corporation, conditions of an excitation X-ray tube: 50 kv, 70 mA), thereby fluorescent X-rays of aluminum oxide and silicon oxide of each sample.
  • the strength was determined.
  • a calibration curve was created by obtaining the relationship between the fluorescent X-ray intensity and the adhesion amount obtained by ICP. Since the adhesion amount obtained by ICP is basically mass, it was converted as follows in order to make it a film thickness composition. The film thickness was calculated on the assumption that the density of the inorganic oxide thin film was 80% of the bulk density, and that the volume was maintained even when aluminum oxide and silicon oxide were mixed.
  • the content ratio wa (mass%) in the aluminum oxide film and the content ws (mass%) in the silicon oxide film are the adhesion amount per unit area of aluminum oxide Ma (g / cm 2 ), When the adhesion amount per unit area is Ms (g / cm 2 ), the following formulas (1) and (2) are obtained, respectively.
  • the adhesion amount per unit area of aluminum oxide is Ma (g / cm 2 )
  • the bulk density thereof is ⁇ a (3.97 g / cm 3 )
  • the adhesion amount of silicon oxide per unit area is Ms (g / g cm 2 )
  • the bulk density is ⁇ s (2.65 g / cm 3 )
  • the film thickness t (nm) is obtained by the following formula (3).
  • Oxygen permeability (mL / m 2 / day / MPa) Using an oxygen permeability measuring device (OX-TRAN 2/21 manufactured by MOCON), the polypropylene film substrate, the laminated polypropylene film, and the laminated laminate were measured under the conditions of a temperature of 23 ° C. and a relative humidity of 65%. The surface opposite to the inorganic thin film layer was set to the humidity control side.
  • Water vapor transmission rate (g / m 2 ⁇ day) The amount of water vapor transmission was measured using a water vapor transmission rate measuring device (PERMATRAN-W3 / 33 manufactured by MOCON) under the conditions of a temperature of 37.8 ° C. and a relative humidity of 90% according to the following procedure. The produced laminate laminate was measured. The surface opposite to the inorganic thin film layer was set to the high humidity side.
  • PERMATRAN-W3 / 33 manufactured by MOCON
  • Laminate strength The laminate strength was measured by the following procedure. 1) Preparation of laminated laminate with sealant film Using a continuous dry laminating machine, the following was performed. The corona surface of the laminated polypropylene films obtained in Examples and Comparative Examples was gravure coated with an adhesive so that the coating amount when dried was 3.0 g / m 2 , then led to a drying zone and dried at 80 ° C. for 5 seconds. did. Subsequently, it was bonded to a sealant film between rolls provided on the downstream side (roll pressure 0.2 MP, roll temperature: 60 ° C.). The obtained laminate laminate was aged at 40 ° C. for 3 days in a wound state.
  • the adhesive was obtained by mixing 17.9% by mass of a main agent (manufactured by Toyo Morton, TM329), 17.9% by mass of a curing agent (CAT8B, manufactured by Toyo Morton) and 64.2% by mass of ethyl acetate.
  • An ether adhesive was used, and a non-stretched polypropylene film (Pyrene (registered trademark) CTP1128, thickness 30 ⁇ m) manufactured by Toyobo Co., Ltd. was used as the sealant film.
  • the laminate laminate obtained above was cut into a strip shape (length 200 mm, width 15 mm) having a long side in the longitudinal direction of a biaxially oriented polypropylene film, and a tensile tester (Tensilon, Orientec Co., Ltd.).
  • the peel strength (N / 15 mm) at the time of T-peeling at a tensile speed of 200 mm / min in an environment of 23 ° C. was measured. The measurement was performed three times, and the average value was taken as the laminate strength.
  • NOVATEC registered trademark
  • Table 1 shows the characteristics of the polypropylene constituting the film
  • Table 2 shows the film forming conditions.
  • the physical properties of the obtained film are as shown in Table 3.
  • the heat shrinkage rate was low and the Young's modulus was high.
  • the chart obtained by the differential scanning calorimetry (DSC) of this film is shown in FIG.
  • As a deposition source particulate Al 2 O 3 (purity 99.5%) and SiO 2 (purity 99.9%) having a size of about 3 to 5 mm are used, and the above-mentioned stretched polypropylene film is deposited by electron beam deposition. Al 2 O 3 and SiO 2 were vapor-deposited at the same time to form an Al 2 O 3 —SiO 2 thin film layer.
  • a circular crucible having a diameter of 40 mm was divided into two by a carbon plate, and granular Al 2 O 3 and granular SiO 2 were respectively added without mixing.
  • single electron gun as a heat source, heating by irradiation of electron beams in time division each of Al2O3 and SiO2, and heated and vaporized in the polypropylene film surface by evaporating a mixture of a Al 2 O 3 and SiO 2 It was.
  • the emission current of the electron gun was 205 mA
  • the acceleration voltage was 6 kV
  • the aluminum oxide charged in the crucible was equivalent to 160 mA ⁇ 6 kV
  • the silicon oxide was equivalent to 45 mA ⁇ 6 kV.
  • the vacuum pressure during vapor deposition was 1.1 ⁇ 10 ⁇ 4 Pa
  • the temperature of the roll supporting the film was 23 ° C.
  • the thickness of the thin film layer was vapor-deposited so as to be 20 nm using a quartz vibrator type film thickness meter by changing the film forming speed to obtain a laminated polypropylene film.
  • the obtained film physical properties are shown in Table 3.
  • the thickness of the obtained film was 20 ⁇ m.
  • Table 1 shows the structure of the polypropylene constituting the film, and Table 2 shows the film forming conditions.
  • the physical properties of the obtained film were as shown in Table 3.
  • an inorganic thin film layer was deposited on the stretched polypropylene film.
  • the obtained film physical properties are shown in Table 3.
  • PP-3 A pellet of a mixture of 96.5% propylene polymer
  • this pellet As a polypropylene resin, it carried out similarly to Example 1, and obtained the extending
  • the thickness of the obtained film was 20 ⁇ m.
  • Table 1 shows the structure of the polypropylene constituting the film, and Table 2 shows the film forming conditions.
  • the physical properties of the obtained film were as shown in Table 3.
  • an inorganic thin film layer was deposited on the stretched polypropylene film.
  • the obtained film physical properties are shown in Table 3.
  • Example 4 A stretched polypropylene film used for the substrate of the present invention was obtained in the same manner as in Example 3 except that the film was stretched 5.5 times in the length direction and 12 times in the transverse direction. The thickness of the obtained film was 20 ⁇ m.
  • Table 1 shows the characteristics of the polypropylene constituting the film, and Table 2 shows the film forming conditions. The physical properties of the obtained film were as shown in Table 3.
  • an inorganic thin film layer was deposited on the stretched polypropylene film.
  • the obtained film physical properties are shown in Table 3.
  • Example 5 The stretched polypropylene film produced in Example 1 was sandwiched between clips at both ends in the film width direction in a tenter and subjected to heat treatment at 170 ° C. for 5 minutes to obtain a stretched polypropylene film of the present invention.
  • the thickness of the obtained film was 20 ⁇ m.
  • Table 1 shows the characteristics of the polypropylene constituting the film, and Table 2 shows the film forming conditions.
  • the physical properties of the obtained film were as shown in Table 3.
  • an inorganic thin film layer was deposited on the stretched polypropylene film.
  • the obtained film physical properties are shown in Table 3.
  • PP-4 a stretched polypropylene film used for the substrate of the present invention was obtained in the same manner as in Example 1.
  • the thickness of the obtained film was 20 ⁇ m.
  • Table 1 shows the structure of the polypropylene constituting the film, and Table 2 shows the film forming conditions.
  • the physical properties of the obtained film were as shown in Table 3.
  • an inorganic thin film layer was deposited on the stretched polypropylene film.
  • the obtained film physical properties are shown in Table 3.
  • Example 7 A laminated film (B layer / A layer / B layer) in which the B layer is laminated on both sides of the A layer.
  • the polypropylene homopolymer PP-4 shown in Table 1 is used for the A layer, and the The polypropylene homopolymer PP-8 shown in No. 1 was mixed with 0.15% by mass of silica as an antiblocking agent. Lamination strength can be improved by laminating the B layer. Using a 60 mm extruder for layer A and a 65 mm extruder for layer B, after extruding into a sheet form from a T die at 250 ° C, cooling and solidifying with a chill roll at 30 ° C, stretching 4.5 times in the longitudinal direction at 135 ° C did.
  • Table 1 shows the characteristics of the polypropylene constituting the film, and Table 2 shows the film forming conditions.
  • Table 4 shows the physical properties of the obtained film. In the same manner as in Example 1, an inorganic thin film layer was deposited on the stretched polypropylene film. Table 4 shows the obtained film physical properties.
  • Comparative Example 2 A stretched polypropylene film was obtained in the same manner as in Comparative Example 1 except that the preheating temperature in transverse stretching was 171 ° C, the transverse stretching temperature was 160 ° C, and the heat treatment temperature after transverse stretching was 165 ° C. The thickness of the obtained film was 20 ⁇ m.
  • Table 1 shows the characteristics of the polypropylene constituting the film, and Table 2 shows the film forming conditions.
  • Table 4 shows the physical properties of the obtained film. In the same manner as in Example 1, an inorganic thin film layer was deposited on the stretched polypropylene film. Table 4 shows the obtained film physical properties.
  • Example 5 A stretched polypropylene film is obtained in the same manner as in Example 1, except that the longitudinal stretching temperature is 125 ° C., the preheating temperature in transverse stretching is 168 ° C., the transverse stretching temperature is 155 ° C., and the heat treatment temperature after transverse stretching is 163 ° C. It was. The thickness of the obtained film was 20 ⁇ m.
  • Table 1 shows the characteristics of the polypropylene constituting the film, and Table 2 shows the film forming conditions.
  • Table 4 shows the physical properties of the obtained film. In the same manner as in Example 1, an inorganic thin film layer was deposited on the stretched polypropylene film. Table 4 shows the obtained film physical properties.
  • the laminated polypropylene film of the present invention can be widely used for packaging applications, industrial applications, etc., but it is particularly excellent in gas barrier properties, so that it can be thinned and can be reduced in cost and weight.
  • the laminated polypropylene film of the present invention has high heat resistance, it can be processed at a high temperature during coating and printing, and it is possible to use a coating agent, an ink, a laminating adhesive, etc., which has been difficult to use conventionally and production efficiency. Can do.
  • the polypropylene film of the present invention is also suitable for insulating films such as capacitors and motors, back sheets for solar cells, and base films for transparent conductive films such as ITO.

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Abstract

L'invention fournit un film de polypropylène stratifié qui possède des propriétés de barrière au gaz comparables à celles d'un film à base de polypropylène revêtu d'un polychlorure de vinylidène. Plus précisément, l'invention concerne un film de polypropylène stratifié qui est équipé d'un matériau de base de film de polypropylène mettant en œuvre une résine à base de polypropylène, et d'une couche de film mince ayant pour composant principal un composé inorganique, et qui est caractéristique en ce que son retrait par refroidissement dans une direction longitudinale à 150°C est inférieur ou égal à 7%, et sa perméabilité à l'oxygène est inférieure ou égale à １５０ｍＬ／ｍ２／ｄａｙ／ＭＰａ.
PCT/JP2017/021925 2016-06-23 2017-06-14 Film de polypropylène stratifié WO2017221781A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
CN201780038476.6A CN109311273A (zh) 2016-06-23 2017-06-14 层叠聚丙烯薄膜
MYPI2018002517A MY187096A (en) 2016-06-23 2017-06-14 Laminated polypropylene film
KR1020237002967A KR20230019224A (ko) 2016-06-23 2017-06-14 적층 폴리프로필렌 필름
JP2018523958A JP7451081B2 (ja) 2016-06-23 2017-06-14 積層ポリプロピレンフィルム
KR1020197001732A KR102494385B1 (ko) 2016-06-23 2017-06-14 적층 폴리프로필렌 필름
PH12018502649A PH12018502649A1 (en) 2016-06-23 2018-12-14 Laminated polypropylene film
JP2022036338A JP7239036B2 (ja) 2016-06-23 2022-03-09 積層ポリプロピレンフィルム

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* Cited by examiner, † Cited by third party
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WO2020137791A1 (fr) * 2018-12-28 2020-07-02 東洋紡株式会社 Film de polypropylène à orientation biaxiale
WO2020137790A1 (fr) * 2018-12-28 2020-07-02 東洋紡株式会社 Film de polypropylène à orientation biaxiale
WO2020137794A1 (fr) * 2018-12-28 2020-07-02 東洋紡株式会社 Film de polypropylène à orientation biaxiale
WO2020137793A1 (fr) * 2018-12-28 2020-07-02 東洋紡株式会社 Film de polypropylène à orientation biaxiale
CN112175220A (zh) * 2020-09-03 2021-01-05 广东以色列理工学院 耐高温的改性聚丙烯薄膜及其制备方法和应用
WO2021070671A1 (fr) * 2019-10-10 2021-04-15 東レ株式会社 Film de polyoléfine
WO2021193508A1 (fr) * 2020-03-24 2021-09-30 東洋紡株式会社 Film de polypropylène à orientation biaxiale
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JPWO2022019192A1 (fr) * 2020-07-21 2022-01-27
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000233478A (ja) * 1998-12-18 2000-08-29 Tokuyama Corp 積層フィルム
JP2004168040A (ja) * 2002-10-31 2004-06-17 Toray Ind Inc 金属蒸着二軸延伸ポリプロピレンフィルム
JP2008132614A (ja) * 2006-11-27 2008-06-12 Daicel Chem Ind Ltd ポリプロピレン系積層フィルムおよびガスバリア性フィルム
JP2014205344A (ja) * 2013-03-18 2014-10-30 東レ株式会社 積層多孔性フィルムおよび蓄電デバイス
WO2015012324A1 (fr) * 2013-07-23 2015-01-29 東洋紡株式会社 Film de polypropylène étiré

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3953597B2 (ja) 1997-10-07 2007-08-08 大日本印刷株式会社 透明バリア性フィルム、それを使用した積層体および包装用容器
JP2000355068A (ja) 1999-06-15 2000-12-26 Dainippon Printing Co Ltd ハム・ソ−セ−ジ包装用積層体
JP2001225424A (ja) * 2000-02-16 2001-08-21 Dainippon Printing Co Ltd 透明バリア性フィルムおよびそれを使用した積層体
JP2003205573A (ja) 2002-01-16 2003-07-22 Dainippon Printing Co Ltd バリア性フィルムおよびそれを使用した積層材
JP4032764B2 (ja) * 2002-02-12 2008-01-16 東洋紡績株式会社 易剥離性ポリプロピレン系フィルム
JP2005096275A (ja) * 2003-09-25 2005-04-14 Dainippon Printing Co Ltd バリア性フィルム
CN101535040A (zh) * 2006-11-16 2009-09-16 三菱树脂株式会社 阻气膜叠层体
JP5073378B2 (ja) 2007-06-26 2012-11-14 大日本印刷株式会社 透明バリア性ポリプロピレンフィルムの製造法
JP5213522B2 (ja) * 2008-05-16 2013-06-19 三菱樹脂株式会社 有機デバイス用ガスバリア性積層フィルム
TWI616335B (zh) * 2013-03-29 2018-03-01 Toppan Printing Co Ltd 阻氣性積層體及阻氣性積層體之製造方法
TWI622609B (zh) * 2013-07-23 2018-05-01 東洋紡股份有限公司 含空洞聚丙烯膜
JP6443334B2 (ja) * 2013-07-23 2018-12-26 東洋紡株式会社 ヒートシール性ポリプロピレン積層延伸フィルム
JP6425564B2 (ja) 2014-01-31 2018-11-21 ユニチカ株式会社 ポリプロピレン樹脂押出しラミネート用アンカーコート剤、包装材料およびその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000233478A (ja) * 1998-12-18 2000-08-29 Tokuyama Corp 積層フィルム
JP2004168040A (ja) * 2002-10-31 2004-06-17 Toray Ind Inc 金属蒸着二軸延伸ポリプロピレンフィルム
JP2008132614A (ja) * 2006-11-27 2008-06-12 Daicel Chem Ind Ltd ポリプロピレン系積層フィルムおよびガスバリア性フィルム
JP2014205344A (ja) * 2013-03-18 2014-10-30 東レ株式会社 積層多孔性フィルムおよび蓄電デバイス
WO2015012324A1 (fr) * 2013-07-23 2015-01-29 東洋紡株式会社 Film de polypropylène étiré

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EP3904052A4 (fr) * 2018-12-28 2022-09-28 Toyobo Co., Ltd. Film de polypropylène à orientation biaxiale
WO2020137790A1 (fr) * 2018-12-28 2020-07-02 東洋紡株式会社 Film de polypropylène à orientation biaxiale
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JPWO2020137790A1 (ja) * 2018-12-28 2021-11-11 東洋紡株式会社 二軸配向ポリプロピレンフィルム
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JP7107383B2 (ja) 2019-10-10 2022-07-27 東レ株式会社 ポリオレフィンフィルム
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JP7166317B2 (ja) 2020-09-03 2022-11-07 広東以色列理工学院 耐高温の変性ポリプロピレンフィルム、その製造方法及び使用
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KR102494385B1 (ko) 2023-02-02
PH12018502649A1 (en) 2019-10-14
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TW201815586A (zh) 2018-05-01
JP7239036B2 (ja) 2023-03-14
JP7451081B2 (ja) 2024-03-18
MY187096A (en) 2021-08-31
JP2022088433A (ja) 2022-06-14
KR20190020763A (ko) 2019-03-04
CN109311273A (zh) 2019-02-05
KR20230019224A (ko) 2023-02-07

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