WO2024225155A1 - ポリプロピレンフィルム - Google Patents

ポリプロピレンフィルム Download PDF

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WO2024225155A1
WO2024225155A1 PCT/JP2024/015373 JP2024015373W WO2024225155A1 WO 2024225155 A1 WO2024225155 A1 WO 2024225155A1 JP 2024015373 W JP2024015373 W JP 2024015373W WO 2024225155 A1 WO2024225155 A1 WO 2024225155A1
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polypropylene film
film
polypropylene
less
film according
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PCT/JP2024/015373
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English (en)
French (fr)
Japanese (ja)
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遼 下川床
一馬 岡田
正寿 大倉
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東レ株式会社
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Priority to JP2024523863A priority Critical patent/JP7691031B2/ja
Publication of WO2024225155A1 publication Critical patent/WO2024225155A1/ja
Priority to JP2025007480A priority patent/JP2025065159A/ja

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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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • the present invention relates to a polypropylene film that combines low shrinkage and high rigidity at high temperatures and has excellent heat resistance.
  • Polypropylene film has excellent transparency and electrical properties, and is therefore used in a variety of applications, including packaging, tape, cable wrapping, and electrical applications such as capacitors.
  • polypropylene film also has excellent mechanical properties and releasability, making it particularly suitable for use as a release film or process film for a variety of components, including plastic products, building materials, and optical components.
  • Release films are used as supports for coatings and melt-forming films, and as spacers during press molding.
  • the properties required for release films are set appropriately depending on the application, but heat resistance is becoming particularly important because temperatures during heating processes and press molding are rising year by year as materials become more highly functional and productivity improves.
  • PET polyethylene terephthalate
  • conventional polypropylene films have high releasability, they begin to significantly shrink at around 120-130°C, and begin to melt at around 160°C, which is close to their melting point, causing a significant decrease in film rigidity, which can cause problems with compromising the quality of mating parts made of thermoplastic resin compositions or thermosetting resin compositions that require drying or molding at high temperatures. For this reason, it has been very difficult to use polypropylene films as release films at high temperatures above 150°C, especially above 160°C.
  • Important properties of the heat resistance of polypropylene film include heat shrinkage properties and rigidity at high temperatures.
  • heat shrinkage properties i.e. to reduce heat shrinkage stress
  • a method is generally used in which the molecular weight of the polypropylene raw material is reduced and the orientation and residual strain caused by stretching are relaxed or heat fixed.
  • this method tends to reduce the rigidity of the polypropylene film because the structure that contributes to mechanical strength, such as elastic modulus, is reduced.
  • a method is used to increase the molecular weight of the polypropylene raw material, increase the molecular orientation and the tension of the amorphous part by low-temperature stretching or high-magnification stretching, and increase the elastic modulus from the room temperature state.
  • this method tends to increase the structure that is easily relaxed at high temperatures, so the heat shrinkage stress tends to increase.
  • Patent Document 1 describes an example of lowering the heat shrinkage rate by lowering the molecular weight of the polypropylene raw material.
  • Patent Document 2 describes an example of lowering the heat shrinkage rate by increasing the heat treatment temperature in the relaxation treatment to relax the molecular orientation.
  • Patent Document 3 describes an example of increasing the film rigidity at high temperatures by multi-stage stretching in the width direction, including low-temperature stretching at 150°C or less.
  • Patent Documents 1 and 2 have the problem that the polypropylene film obtained has low rigidity and low stretching stability at high temperatures.
  • the method described in Patent Document 3 has the problem that the polypropylene film obtained has high heat shrinkage stress at high temperatures, and it is difficult to achieve both heat shrinkage properties and rigidity at high temperatures. In other words, the polypropylene films obtained by these methods are difficult to use as release films in high-temperature environments.
  • the object of the present invention is to solve the above problems.
  • the polypropylene film of the present invention has the following configuration: That is, the polypropylene film of the present invention is a polypropylene film that satisfies the following formulas 1 and 2, where the main orientation axis direction is the A direction, the direction perpendicular to the main orientation is the B direction, the 160°C storage moduli in the A direction and the B direction in dynamic viscoelasticity measurement are E'A (GPa) and E'B (GPa), respectively, and the 160°C shrinkage stresses in the A direction and the B direction in TMA measurement are P A (MPa) and P B (MPa), respectively.
  • Formula 1 0.30 ⁇ E′ A +E′ B ⁇ 2.00
  • Formula 2 -1.0 ⁇ P A +P B ⁇ 5.0
  • the present invention makes it possible to provide a polypropylene film that can be suitably used as a release film even in high-temperature environments where conventional polypropylene films were not usable as release films.
  • FIG. 4 is a schematic diagram illustrating a pressurizing method used in evaluating heat resistance characteristics.
  • the polypropylene film of the present invention satisfies the following formulas 1 and 2, where the main orientation axis direction is the A direction, the direction perpendicular to the main orientation is the B direction, the 160° C. storage moduli in the A direction and the B direction in dynamic viscoelasticity measurement are E' A (GPa) and E' B (GPa), respectively, and the 160° C. shrinkage stresses in the A direction and the B direction in TMA measurement are P A (MPa) and P B (MPa), respectively.
  • the polypropylene film of the present invention will be described in detail below.
  • Formula 1 0.30 ⁇ E′ A +E′ B ⁇ 2.00 Equation 2: -1.0 ⁇ P A +P B ⁇ 5.0.
  • the polypropylene film of the present invention satisfies 0.30 ⁇ E′ A +E′ B ⁇ 2.00 , where the main orientation axis direction is the A direction, the direction perpendicular to the main orientation is the B direction, and the 160° C. storage moduli in the A direction and B direction in dynamic viscoelasticity measurement are E′ A (GPa) and E′ B (GPa), respectively.
  • the lower limit of E′ A +E′ B is preferably 0.40, more preferably 0.50, even more preferably 0.60, and particularly preferably 0.70.
  • E′ A +E′ B is less than 0.30, when the polypropylene film is attached to a counter member and treated in a molding press or a heating oven at high temperatures, the polypropylene film cannot withstand the heat and is compressed or elongated, inducing excessive sinking or sticking to the counter member. Therefore, there is a concern that the counter member may be damaged or deformed when the polypropylene film is peeled off from the counter member.
  • the upper limit of E'A + E'B is 2.00 in view of the thermal properties of polypropylene, and is preferably 1.50 in view of compatibility with the heat shrinkage stress.
  • the main orientation axis direction (A direction) in the polypropylene film of the present invention refers to the direction that shows the highest storage modulus at 30°C when dynamic viscoelasticity measurement is performed in each direction that forms an angle of 0°, 15°, 30°, 45°, 60°, 75°, 90°, 105°, 120°, 135°, 150°, and 165° with respect to the longitudinal direction in the film plane, where the longitudinal direction is set to 0°.
  • the longitudinal direction refers to the direction in which the film runs during the production process (corresponding to the winding direction in the case of a film roll), and the direction perpendicular to this in the film plane is called the width direction.
  • the main orientation perpendicular direction (B direction) in the polypropylene film of the present invention means a direction perpendicular to the main orientation axis direction in the film plane.
  • the details of the method for measuring the storage modulus by dynamic viscoelasticity measurement including E'A and E'B will be described later.
  • the polypropylene film of the present invention satisfies -1.0 ⁇ P A +P B ⁇ 5.0, where the 160° C. shrinkage stresses in the A and B directions in the TMA measurement are P A (MPa) and P B (MPa), respectively.
  • the upper limit of P A +P B is preferably 4.0, more preferably 3.5, even more preferably 3.0, particularly preferably 2.0, and most preferably 1.0. If P A +P B exceeds 5.0, the polypropylene film will undergo thermal shrinkage when the mating member is layered or attached and treated in a molding press or heating oven at high temperature.
  • the lower limit of P A +P B is -1.0 from the viewpoint of the film formability of the film, and 0.0 is preferable in consideration of compatibility with the rigidity of the film at high temperatures. The method for measuring the 160° C. shrinkage stress in the TMA measurement will be described later in detail.
  • a method can be used in which the raw material composition of the polypropylene film is set in the range described later, and the film-forming conditions are set in the range described later.
  • the raw material composition of the polypropylene film is set in the range described later, and the film-forming conditions are set in the range described later.
  • it is effective to use a polypropylene composition having a high melting point, a fast crystallization rate, and an appropriate range of angular frequency ⁇ (details described later) showing relaxation characteristics as a raw material.
  • ( PA + PB )/( E'A + E'B ) is preferably 0.001 or more and 7.500 or less.
  • ( PA + PB )/( E'A + E'B ) is an index showing the balance between the elastic modulus and heat shrinkage stress at high temperatures, which have traditionally been in a trade-off relationship, and by having this in the above range, it is possible to reduce compression and elongation deformation in a high-temperature environment.
  • the upper limit of ( PA + PB )/( E'A + E'B ) is more preferably 5.000, even more preferably 2.000, and particularly preferably 1.000.
  • the elastic modulus becomes relatively higher than the heat shrinkage stress, and when a mating member is attached in a molding press or a heating oven at high temperature, the heat shrinkage of the polypropylene film is suppressed, and deterioration in the quality of the mating member to which the film is attached can be reduced.
  • the lower limit of (P A +P B )/(E' A +E' B ) is preferably 0.001, more preferably 0.0100, and even more preferably 0.500.
  • the polypropylene film of the present invention preferably has a shrinkage start temperature in both directions A and B measured by TMA measurement of 140°C or higher and 170°C or lower (hereinafter, “shrinkage start temperature in TMA measurement” may be referred to as “TMA shrinkage stress start temperature”).
  • the lower limit of the TMA shrinkage stress start temperature in both directions A and B is more preferably 145°C, and even more preferably 150°C.
  • TMA shrinkage stress start temperature 140°C or higher in both directions A and B, it becomes easier to keep the heat shrinkage rate of the polypropylene film low in all directions, even in high-temperature regions where it is difficult to use conventional polypropylene films, and as a result, dimensional stability is improved.
  • the upper limit of the TMA shrinkage stress start temperature is substantially 170°C. The method for measuring the TMA shrinkage stress start temperature will be described in detail later.
  • the TMA shrinkage stress onset temperature in the above range it is effective to set the raw material composition of the polypropylene film in the range described below and the film-making conditions in the range described below.
  • a polypropylene resin or composition whose lower limit of the angular frequency ⁇ (details described below), which indicates the relaxation characteristics, is 15 rad/s or more (preferably 19 rad/s or more).
  • ⁇ the angular frequency
  • the polypropylene film of the present invention preferably has a heat of fusion ratio H of 175°C to 200°C to the total heat of fusion in the first run of DSC measurement at a heating rate of 20°C/min of 10% ⁇ H ⁇ 50% (hereinafter, "heat of fusion ratio H of 175°C to 200°C in the first run of DSC measurement at a heating rate of 20°C/min" may be referred to as "heat of fusion ratio H").
  • This heat of fusion ratio H is an index showing the content ratio of crystals that melt at 175°C or higher, the presence of which is extremely low in conventional polypropylene films, and a high heat of fusion ratio H means that the polypropylene film has excellent heat resistance.
  • the lower limit of the heat of fusion ratio H is more preferably 15%, even more preferably 20%, and particularly preferably 25%.
  • the heat of fusion ratio H of a polypropylene film is 10% or more, many crystals remain unmelted even in high-temperature environments of 160°C or more, which conventional polypropylene films cannot withstand, making it easier to achieve high heat resistance.
  • the upper limit of the heat of fusion ratio H is preferably substantially 50%, and 40% is more preferable when considering compatibility with other properties. The method for measuring the heat of fusion ratio H will be described in detail later.
  • the melting heat ratio H in the above range it is effective to set the raw material composition of the film in the range described later and the film-making conditions in the range described later.
  • the polypropylene film of the present invention preferably has a root-mean-square slope Sdq of 0.005 or more and 1.000 or less on at least one side (hereinafter, "root-mean-square slope Sdq" may be referred to as "Sdq").
  • root-mean-square slope Sdq may be referred to as "Sdq”
  • at least one side means one side or both sides.
  • Sdq is one of the surface parameters that indicates the slope of the uneven structure of the film surface, and shows a high value when the surface contains a steep uneven structure.
  • the lower limit of Sdq is preferably 0.005, more preferably 0.007, and even more preferably 0.015.
  • the upper limit of Sdq is not particularly limited, but is substantially 1.000, preferably 0.100, from the viewpoint of film formability of the film. If Sdq is 0.005 or more, the polypropylene film will have a steep uneven structure on the surface, and when used as a release film, the films are less likely to adhere to each other, and the fusion resistance at high temperatures is likely to be improved. Sdq can be measured using a known non-contact surface/layer cross-sectional shape measurement system (e.g., the "VertScan" (registered trademark) series from Ryoka Systems Co., Ltd.), the details of which will be described later.
  • a known non-contact surface/layer cross-sectional shape measurement system e.g., the "VertScan" (registered trademark) series from Ryoka Systems Co., Ltd.
  • the polypropylene film of the present invention preferably has a melting point Tm 2 obtained in the second run of DSC measurement at a temperature rise rate of 20° C./min of 164.0° C. or more and 170.0° C. or less (hereinafter, the "melting point Tm 2 obtained in the second run of DSC measurement at a temperature rise rate of 20° C./min" may be referred to as "Tm 2 ").
  • the lower limit of the melting point Tm 2 is more preferably 165.0° C., and even more preferably 166.0° C.
  • the upper limit of the melting point Tm 2 is 170.0° C. in consideration of the characteristics of polypropylene. The details of the measurement method of Tm 2 will be described later.
  • the melting point Tm2 is an index showing the melting point of the raw material of the entire polypropylene film, and if it is within the above range, film formation under higher temperature conditions is possible. Therefore, it is easy to improve the heat shrinkage characteristics, and it is also advantageous in terms of the formation of high melting point crystals, and as a result, it is easy to improve the heat resistance of the polypropylene film.
  • it is effective to set the raw material composition of the polypropylene film to the range described later, in particular, to use a raw material with a high melting point, to minimize the amount of mixtures other than the high melting point raw material, and to increase the proportion of the X layer described later.
  • the angular frequency ⁇ is an index showing the relaxation characteristics of the polymer in the polypropylene film, and the lower the value, the lower the relaxation characteristics, and the higher the value, the higher the relaxation characteristics.
  • the lower limit of the angular frequency ⁇ is more preferably 15 rad/s, and even more preferably 20 rad/s.
  • the upper limit of the angular frequency ⁇ is more preferably 60 rad/s, even more preferably 50 rad/s, and particularly preferably 40 rad/s.
  • the polypropylene film has appropriate relaxation characteristics, and is excellent in achieving both a high crystalline melting point and amorphous relaxation during film formation, and is likely to exhibit excellent heat resistance.
  • the angular frequency ⁇ can be measured using a rotational rheometer, and the measurement method will be described in detail later.
  • the angular frequency ⁇ in the above range, it is effective to set the raw material composition of the polypropylene film within the range described below and to set the film-making conditions within the range described below. In particular, it is effective to use a resin whose angular frequency ⁇ falls within the range described below and to reduce the amount of branched polypropylene added, which is a factor that deteriorates the relaxation characteristics.
  • the thickness of the polypropylene film of the present invention is adjusted appropriately depending on the application and is not particularly limited, but is preferably 0.5 ⁇ m or more and 100 ⁇ m or less from the viewpoint of handleability. To make the most of such characteristics, the thickness of the polypropylene film is more preferably 1 ⁇ m or more and 40 ⁇ m or less, even more preferably 1 ⁇ m or more and 30 ⁇ m or less, and particularly preferably 6 ⁇ m or more and 30 ⁇ m or less.
  • the thickness of the polypropylene film can be adjusted by the screw rotation speed of the extruder, the width of the unstretched sheet, the film-forming speed, the stretching ratio, etc., within a range that does not deteriorate other physical properties. The thickness of the polypropylene film can be measured using a known micro thickness meter, the details of which will be described later.
  • the proportion of components with a logarithmic molecular weight Log(M) of 5.0 or less is preferably 39.0 mass% or less, more preferably 37.0 mass% or less, even more preferably 36.0 mass% or less, and particularly preferably less than 35.0 mass%.
  • the lower limit of the proportion of components with a logarithmic molecular weight Log(M) of 5.0 or less is preferably 30.0 mass% or more, and more preferably 33.0 mass% or more.
  • the proportion of components with a logarithmic molecular weight Log(M) of 6.0 or more is preferably 10.0 mass% or less, more preferably 8.0 mass% or less, and even more preferably 6.0 mass% or less.
  • the lower limit of the proportion of components with a logarithmic molecular weight Log(M) of 6.0 or more is preferably 3.0 mass% or more, and more preferably 4.0 mass% or more.
  • the polypropylene film of the present invention has appropriate relaxation characteristics, and is excellent in both crystalline high melting point and amorphous relaxation during film formation, and is likely to exhibit excellent heat resistance.
  • it is effective to set the raw material composition of the polypropylene film to the range described below and the film formation conditions to the range described below.
  • a polypropylene resin or polypropylene resin composition with an angular frequency ⁇ of 15 rad/s to 70 rad/s as a raw material, and to adjust the kneading temperature during pre-mixing and film formation to appropriately control the molecular weight.
  • the X layer occupies 90% to 100% of the entire polypropylene film based on thickness.
  • the lower limit of the proportion of the X layer in the polypropylene film of the present invention is preferably 90% based on thickness, more preferably 92%, even more preferably 95%, and particularly preferably 98%.
  • the thickness basis means that the ratio is calculated with the entire thickness of the polypropylene film being 100%.
  • the polypropylene film of the present invention preferably contains the above-mentioned X layer at an appropriate thickness ratio, but the layer structure may be a single layer or a laminated structure having multiple layers such as two-type three-layer or three-type three-layer.
  • Polypropylene composition X is a resin composition that contains 95% to 100% by mass of polypropylene resin when the entire composition is taken as 100% by mass, has a melting point of 166.0°C to 170.0°C, a half crystallization time of 5 seconds to 200 seconds, and an angular frequency ⁇ of 10 rad/s to 70 rad/s (described later).
  • the composition is considered to be polypropylene composition X if the total amount of these exceeds 95% by mass and the melting point, half crystallization time, and angular frequency ⁇ are within the above ranges.
  • Polypropylene resin refers to a resin that contains more than 50 mol% to 100 mol% of propylene units when the total structural units constituting the molecular chain of the resin are taken as 100 mol%.
  • the melting point of polypropylene composition X is 166.0°C or higher and 170.0°C or lower.
  • the lower limit of the melting point of polypropylene composition X is preferably 166.5°C, more preferably 167.0°C, and even more preferably 167.5°C.
  • the melting point of polypropylene composition X is 166.0°C or higher, high melting point crystals are likely to form when the film is formed at high temperatures, improving heat resistance such as film rigidity in the high temperature range.
  • the melting point of polypropylene composition X can be measured by DSC, the details of which will be described later.
  • polypropylene composition X has a half crystallization time, which indicates the crystallization rate obtained by DSC isothermal crystallization measurement described below, of 5 seconds or more and 200 seconds or less.
  • the upper limit of the half crystallization time of polypropylene resin X is preferably 100 seconds, more preferably 50 seconds, and even more preferably 30 seconds. If the half crystallization time is within the above range, recrystallization is likely to occur even during film formation, and high melting point crystals are likely to be formed.
  • polypropylene composition X In order to bring the half crystallization time of polypropylene composition X into the above range, it is effective to appropriately adjust the stereoregularity and molecular weight distribution of the polypropylene resin constituting polypropylene composition X, or to add a branched polypropylene that exhibits a crystal nucleating agent effect.
  • the angular frequency ⁇ is the angular frequency at which the storage viscoelastic modulus G' and loss viscoelastic modulus G'' of molten polypropylene match, and is an index of the relaxation characteristics of polypropylene.
  • the lower limit of the angular frequency ⁇ of polypropylene composition X is preferably 15 rad/s, more preferably 20 rad/s.
  • the upper limit of the angular frequency ⁇ is preferably 60 rad/s, more preferably 50 rad/s or less, and even more preferably 40 rad/s.
  • the angular frequency ⁇ is within the above range, it is easy to achieve both high crystal melting point and amorphous relaxation of polypropylene composition X, and it is possible to further improve the heat resistance of the resulting polypropylene film.
  • polypropylene composition X In order to set the angular frequency ⁇ of polypropylene composition X within the above range, it is effective to adjust the molecular weight distribution of the polypropylene resin constituting polypropylene composition X to an appropriate range, adjust the molecular weight distribution of the polypropylene resin under the pre-mixing conditions, and adjust the amount of branched polypropylene resin added. These methods can be combined as appropriate.
  • Polypropylene composition X may be composed of homopolypropylene resin alone, but other resin components may be mixed in by pre-kneading or the like within the range that does not deteriorate the properties as described below.
  • the amount added is preferably 1.2 mass% or less, more preferably 1.0 mass% or less, and even more preferably 0.5 mass% or less, with the total resin of polypropylene composition X being 100 mass%.
  • homopolypropylene resin refers to polypropylene resin in which the amount of propylene units is 99.9 mol% or more and 100 mol% or less, when the total structural units constituting the molecular chain of the resin are 100 mol%.
  • polypropylene composition X examples include, for example, polyolefin resin (a resin that is not a polypropylene resin and contains 50 mol% to 100 mol% of olefin units when the total constituent units constituting the molecular chain of the resin are taken as 100 mol%) and polymer particles such as acrylic that are not completely compatible with polypropylene.
  • polyolefin resin a resin that is not a polypropylene resin and contains 50 mol% to 100 mol% of olefin units when the total constituent units constituting the molecular chain of the resin are taken as 100 mol%
  • polymer particles such as acrylic that are not completely compatible with polypropylene.
  • polypropylene composition X that constitutes the outermost layer (the polypropylene film itself in the case of a single-layer polypropylene film)
  • polypropylene composition X that constitutes the outermost layer
  • the polypropylene resin used in polypropylene composition X can be preferably selected from those that satisfy the conditions of polypropylene composition X described above, and commercially available ones include, for example, polypropylene resins F-704NP and F133A manufactured by Prime Polymer Co., Ltd., polypropylene resin HC310BF manufactured by Borealis, and polypropylene resin FY6H manufactured by Japan Polypropylene Corporation.
  • polypropylene composition X examples include, for example, "Daploy” (trademark) WB130HMS, WB135HMS, and WB140HMS manufactured by Borealis, and "WAYMAX” (registered trademark) MFX8, MFX6, and MFX3 manufactured by Japan Polypropylene Corporation.
  • the entire resin, including polypropylene composition X, used in the polypropylene film of the present invention may contain various additives, such as crystal nucleating agents, antioxidants, heat stabilizers, slipping agents, antistatic agents, antiblocking agents, fillers, viscosity modifiers, and color inhibitors, within the scope of the present invention.
  • antioxidants are sterically hindered phenol-based, and at least one of them is preferably a high molecular weight type with a molecular weight of 500 or more.
  • BHT 2,6-di-t-butyl-p-cresol
  • BHT molecular weight 220.4
  • 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene e.g., BASF's "Irganox” (registered trademark) 1330: molecular weight 775.2
  • tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane e.g., BASF's "Irganox" (registered trademark) 1010: molecular weight 1177.7), etc., either alone or in combination.
  • phosphorus-based antioxidants may easily bleed out onto the surface of the polypropylene film. Such bleeding out may induce various problems. For example, when a resin film is formed on the surface of a polypropylene film, curing treatment of the uncured or semi-cured resin film may inhibit curing. In addition, when an electrolyte membrane or metal membrane is formed on the surface of a polypropylene film, the properties of the electrolyte membrane and the quality of the metal layer may be deteriorated.
  • the content of the phosphorus-based antioxidant in the polypropylene film is preferably 0.01 parts by mass or less, more preferably 0.005 parts by mass or less, and even more preferably 0.001 parts by mass or less, relative to 100 parts by mass of the total polypropylene resin. From the above viewpoint, it is preferable that the phosphorus-based antioxidant is not contained in the polypropylene film, and the content of the phosphorus-based antioxidant is at a lower limit of 0.000 parts by mass.
  • phosphorus-based antioxidants examples include tris(2,4-di-t-butylphenyl)phosphite (e.g., BASF's "Irgafos" (registered trademark) 168: molecular weight 647).
  • the total content of these antioxidants is preferably in the range of 0.03 to 1.0 parts by mass per 100 parts by mass of the total polypropylene resin. If there is too little antioxidant, the polymer may deteriorate during the extrusion process, causing the film to become discolored, or the long-term heat resistance may be poor. If there is too much antioxidant, the antioxidants may bleed out, causing a decrease in transparency.
  • a more preferred content is 0.05 to 0.9 parts by mass, and particularly preferably 0.1 to 0.8 parts by mass.
  • a crystal nucleating agent can be added to the polypropylene raw material (including polypropylene composition X) used in the polypropylene film of the present invention, within the scope of the object of the present invention.
  • ⁇ crystal nucleating agents dibenzylidene sorbitols, sodium benzoate, etc.
  • ⁇ crystal nucleating agents potassium 1,2-hydroxystearic acid, magnesium benzoate
  • amide-based compounds such as N,N'-dicyclohexyl-2,6-naphthalenedicarboxamide, quinacridone-based compounds, etc.
  • the amount added is usually 0.5 parts by mass or less, preferably 0.1 parts by mass or less, and more preferably 0.05 parts by mass or less, when the entire raw material is 100 parts by mass.
  • the polypropylene film of the present invention is preferably a biaxially stretched film.
  • the biaxial stretching method any of the inflation simultaneous biaxial stretching method, the stenter simultaneous biaxial stretching method, and the stenter sequential biaxial stretching method may be used, but among these, it is preferable to employ the stenter sequential biaxial stretching method in terms of controlling the film formation stability, thickness uniformity, and the rigidity and dimensional stability of the film.
  • homopolypropylene resin 99.8:0.2 (mass ratio)
  • acrylic particles 99.8:0.2 (mass ratio)
  • pellets of polypropylene composition X obtained by the above-mentioned procedure are fed to single-screw extruders for the base layer (A layer) and the surface layer (B layer), respectively, and melt extruded at 200 to 290°C, more preferably 240 to 280°C, and even more preferably 260 to 280°C.
  • the layers are laminated in a multi-manifold type composite T-die in a layer structure of surface layer (B layer)/base layer (A layer)/surface layer (B layer), and discharged onto a casting drum and cooled and solidified to obtain a laminated unstretched sheet having a layer structure of surface layer (B layer)/base layer (A layer)/surface layer (B layer).
  • the ratio of A layer is preferably 90% or more and 100% or less in thickness conversion, with the lower limit being more preferably 92%, even more preferably 95%, and particularly preferably 98%.
  • the surface temperature of the casting drum is preferably 20 to 80°C, more preferably 25 to 60°C, and even more preferably 30 to 60°C.
  • the casting temperature is within the above range, the formation of ⁇ -crystals, which have a low melting point among crystals, can be suppressed, and the proportion of high melting point crystals in the film is likely to increase.
  • any method such as electrostatic application method, adhesion method using the surface tension of water, air knife method, press roll method, and underwater casting method may be used, but the air knife method is preferred because it is easy to control the surface roughness.
  • the air temperature of the air knife is preferably 20 to 100°C, and the blowing air speed is preferably 130 to 150 m/s.
  • the position of the air knife in order to prevent vibration of the laminated unstretched sheet, it is also preferable to appropriately adjust the position of the air knife so that air flows downstream of the film production.
  • the obtained laminated unstretched sheet is introduced into the longitudinal stretching process (stretching in the longitudinal direction).
  • the laminated unstretched sheet is preheated by a metal roll heated to 150°C to 160°C, preferably 152°C to 158°C, more preferably 154°C to 158°C before stretching. If the preheating temperature is within the above range, the laminated unstretched sheet will proceed to the longitudinal stretching process in a softened state, and stretching is possible in the longitudinal stretching process without applying more stress than necessary, which makes it easier to reduce thermal shrinkage stress.
  • the unstretched laminated sheet may be heated by contacting it with multiple metal rolls kept at 50°C to 145°C as a preliminary preheating.
  • the film is stretched between rolls with a difference in peripheral speed at 4.0 to 8.0 times in the longitudinal direction to obtain a uniaxially stretched film.
  • the stretching ratio is preferably 4.0 to 7.0 times, more preferably 4.3 to 6.0 times.
  • the stretching temperature is greater than 150°C and less than 160°C, preferably 152°C to 158°C, more preferably 154°C to 158°C.
  • the stretching temperature is within the above range, it is possible to pull out molecular chains from the softened crystals while suppressing the remaining of excessive strain, and together with the subsequent relaxation process, the crystals are promoted to have a high melting point. Therefore, the heat resistance of the resulting polypropylene film, as indicated by the storage modulus obtained by dynamic viscoelasticity measurement, is likely to be improved.
  • the longitudinal uniaxially stretched film is brought into contact with a metal roll having a peripheral speed difference and maintained at 140 to 160°C, and relaxed in the longitudinal direction at a relaxation rate of more than 0% and not more than 10%, and then cooled to room temperature.
  • the relaxation temperature is preferably 145 to 160°C, more preferably 150 to 160, and even more preferably 154 to 160°C.
  • the relaxation temperature is preferably the stretching temperature -10°C or more and the stretching temperature +5°C or less, more preferably the stretching temperature -5°C or more and the stretching temperature +5°C or less, and even more preferably the stretching temperature -5°C or more and the stretching temperature or less.
  • the relaxation temperature is within the above range, it is possible to promote the rearrangement of the molecular chains drawn out from the crystals by the longitudinal stretching, and form crystals with a thicker lamellar thickness and a higher melting point.
  • the relaxation rate in the longitudinal stretching process is preferably 0.1 to 10%, more preferably 1.0 to 10%, even more preferably 3.0 to 10%, and particularly preferably 5.0 to 10%.
  • the longitudinally uniaxially stretched film is introduced into a tenter, both ends in the width direction are held by clips, and after preheating, it is transversely stretched 7.0 to 13 times, preferably 9.6 to 13 times, in the width direction (transverse stretching process).
  • the resulting polypropylene film has improved resistance to high-temperature crimping.
  • the temperature in the preheating process before stretching is preferably 170°C or higher and 190°C or lower, more preferably 173°C or higher and 185°C or lower, even more preferably 175°C or higher and 185°C or lower, and particularly preferably 177°C or higher and 185°C or lower.
  • the preheating temperature is within the above range, the crystals formed in the longitudinal stretching process can be softened before proceeding to the transverse stretching process, and stretching is possible without applying more stress than necessary in the transverse stretching process, making it easier to reduce heat shrinkage stress.
  • the stretching temperature in the transverse stretching step after the preheating step is preferably above 170°C and below 180°C, more preferably between 173°C and 180°C, and even more preferably between 175°C and 180°C. If the transverse stretching temperature is within the above range, it is possible to pull out molecular chains from the crystals softened by preheating while suppressing the remaining of excessive strain. Therefore, together with the subsequent relaxation step, the crystals are promoted to have a high melting point, and the heat resistance indicated by the storage modulus obtained by dynamic viscoelasticity measurement of the polypropylene film is likely to improve.
  • the sheet is relaxed in the transverse direction with a Relax rate of preferably 10% to 20%, more preferably 11% to 18%, and even more preferably 12% to 15% while being held with moderate tension in the transverse direction by clips.
  • the Relax rate after transverse stretching is within the above range, which makes it easier to relieve tension in the molecular chains. Therefore, in addition to promoting amorphous relaxation and reducing shrinkage stress, the mobility of the molecular chains is in a moderate range, and rearrangement of the molecular chains is also easily promoted.
  • the heat setting temperature at this time is preferably 168°C to 190°C, more preferably more than 170°C to 190°C, even more preferably 173°C to 185°C, and particularly preferably 175°C to 185°C, and is preferably higher than the stretching temperature of the immediately preceding stretching process, and more preferably 2°C higher than the stretching temperature of the immediately preceding stretching process. If the relaxation temperature is within the above range, it will promote the rearrangement of molecular chains pulled out of the crystals by lateral stretching, making it possible to form crystals with a thicker lamellar thickness and a higher melting point.
  • the polypropylene film of the present invention includes a Relax step in the longitudinal stretching step and the transverse stretching step, and the total area Relax rate (%) calculated from the stretch ratios and Relax rates in the longitudinal stretching step and the transverse stretching step is preferably 10.0% to 30.0%, more preferably 13.0% to 25.0%, and even more preferably 15.0% to 20.0%.
  • the total area Relax rate (%) is calculated by the following formula, and when it is within the above range, amorphous relaxation is likely to proceed, and the shrinkage stress of the entire polypropylene film is likely to be reduced.
  • Total area relaxation rate (%) [1-(1-longitudinal stretching process relaxation rate/100) ⁇ (1-transverse stretching process relaxation rate/100)] ⁇ 100.
  • the film is cooled at 80-130°C and then led to the outside of the tenter, where the clips on the film ends are released, and the film edges are slit in the winder process, and the film product roll is wound up.
  • the polypropylene film of the present invention obtained in the above manner can be used for various applications such as packaging films, surface protection films, processing films, battery films, sanitary products, agricultural products, construction products, and medical products. Since it has particularly excellent heat resistance, it can be preferably used as processing films that require high-temperature processing such as drying coating materials and molding thermosetting resins, release films, base films for current collectors in secondary batteries, and packaging films for retort pouches, and is particularly preferably used as release films for use in high-temperature regions.
  • a release film refers to a film that has the function of being attached to an object such as a molded body or film to protect the object from scratches, contamination, etc. during processing or transportation, and can be easily peeled off and discarded when it is time to use it as a final product.
  • a process film refers to a film used in the manufacturing process of an object such as a molded body or film, and examples of such films include those that are attached to an object during the manufacturing process to protect it from scratches, contamination, etc., and those that function as a support when it is difficult to form a film because the object itself is thin or fragile.
  • the polypropylene film of the present invention has excellent heat resistance and releasability, and can therefore be preferably used when forming a laminate with a metal film by subjecting the polypropylene film to deposition processing or sputtering processing.
  • one embodiment of the laminate of the present invention is one in which a metal film or an electrolyte membrane is in contact with at least one surface of the polypropylene film.
  • PET polyethylene terephthalate
  • the laminate of the present invention preferably contains a metal belonging to Group 1 or 2 of the periodic table, since it is possible to obtain a laminate suitably even in cases where it is difficult to use PET films due to the presence of a small amount of moisture.
  • the metals belonging to Group 1 or 2 refer to lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, and radium.
  • the metal film may contain one or more of these metal components, and in the latter case, the combination of components is arbitrary.
  • the moisture in the film evaporates as outgassing, and the effects are particularly noticeable under high vacuum conditions such as in metal deposition processes.
  • the degree of vacuum in the system deteriorates, and the quality of the metal film formed by deposition and the yield of the deposition process may decrease.
  • the polypropylene film of the present invention which has a lower moisture content than PET film, can be suitably used in applications where a metal film is formed, and the laminate of the present invention can maintain good metal film quality.
  • electrolyte membranes used in fuel cells, semi-solid batteries, all-solid batteries, etc. are usually manufactured in an environment where temperature and humidity are strictly controlled.
  • sulfide-type electrolyte membranes react with moisture to generate hydrogen sulfide, so the process film used in their manufacture is also required to have an extremely low moisture content.
  • the polypropylene film of the present invention is preferably used as a process film in the manufacture of such electrolyte membranes.
  • a preferred embodiment of the laminate of the present invention includes one in which an electrolyte membrane is in contact with at least one side of a polypropylene film, and it is particularly preferred that the electrolyte membrane is for a fuel cell, a semi-solid battery, or an all-solid battery.
  • the upper limit of the moisture content of the polypropylene film of the present invention is preferably 2000 ppm, more preferably 1000 ppm, even more preferably 500 ppm, particularly preferably 200 ppm, and most preferably 100 ppm.
  • the lower limit of the moisture content is not particularly limited, but is essentially 1 ppm.
  • the moisture content of the polypropylene film can be measured by the Karl Fischer method, the details of which will be described later.
  • the total components of the polypropylene film of the present invention are taken as 100% by mass, and the lower limit of the content of polyolefin resins such as polypropylene resins is preferably 90% by mass, more preferably 95% by mass, and even more preferably 97% by mass.
  • the upper limit of the content of these resins is substantially 100% by mass.
  • the content of the antioxidant is preferably 0.03 to 1.0 parts by mass, more preferably 0.05 to 0.9 parts by mass, and even more preferably 0.1 to 0.8 parts by mass, relative to 100 parts by mass of the total polypropylene resin of the polypropylene film of the present invention.
  • the phosphorus-based antioxidant that bleeds out to the surface may deteriorate the properties and quality of the metal film formed on the surface, it is preferable to control the content.
  • the content of the phosphorus-based antioxidant is preferably 0.01 parts by mass or less, more preferably 0.005 parts by mass ppm or less, and even more preferably 0.001 parts by mass.
  • the lower limit of the content of the phosphorus-based antioxidant there is no particular restriction on the lower limit of the content of the phosphorus-based antioxidant, and it is theoretically 0.000 parts by mass (same as not containing the phosphorus-based antioxidant).
  • the content of the antioxidant including the phosphorus-based antioxidant is the same even when the film formed on the surface is not a metal film.
  • the total content of additives other than antioxidants is preferably 0 to 0.05 parts by mass or less.
  • the antioxidants preferably used in the polypropylene film of the present invention are sterically hindered phenols, and at least one of them is preferably a high molecular weight type having a molecular weight of 500 or more.
  • Specific examples include various types, but it is preferable to use 2,6-di-t-butyl-p-cresol (BHT: molecular weight 220.4) in combination with 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene (e.g., BASF's "Irganox" (registered trademark) 1330: molecular weight 775.2) or tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane (e.g., BASF's "Irganox" (registered trademark) 1010: molecular weight 1177.7), etc.
  • BHT 2,6-di
  • the polypropylene film of the present invention has an extremely low moisture content and generates very little outgassing, and is smoother and easier to handle than existing olefin-based films, making it suitable for use in forming transparent conductive films that require stricter vacuum conditions or high quality.
  • a preferred embodiment of the laminate of the present invention is one in which a transparent conductive film is in contact with at least one side of the polypropylene film of the present invention.
  • the transparent conductive film here refers to a thin film formed from a material that is conductive and transmits visible light, and specific examples include indium-tin oxide (ITO), zinc oxide (ZnO), and palladium film.
  • the current collector of the present invention is made of the polypropylene film of the present invention.
  • the polypropylene film of the present invention is preferably used as a current collector because of its excellent heat resistance.
  • the current collector is a foil-like laminate used for the electrodes of storage batteries such as lithium ion batteries.
  • metal foil is used as the current collector, but a laminate in which a metal film is laminated on a resin film as a base material is also used for the purpose of improving safety and reducing weight. This metal film is laminated by processing such as vapor deposition, sputtering, plating, and electroless plating.
  • the film as the base material of the current collector is required to have a small thickness, but as the film becomes thinner, its stiffness decreases, and the handling properties during processing are greatly reduced.
  • high heat such as radiant heat is applied during processing, and tension is also applied in the transport direction, so the film is required to have good handling properties.
  • the polypropylene film of the present invention can be made thin and has good handling properties, so it is preferably used as a current collector.
  • the storage battery of the present invention uses the polypropylene film of the present invention.
  • the polypropylene film of the present invention has excellent heat resistance and is therefore preferably used as a current collector, and is generally used in storage batteries in which the current collector is used as an electrode.
  • a storage battery is a device that stores electrical energy and converts it back to electrical energy when needed. Specific examples include lead acid batteries, nickel-metal hydride batteries, lithium ion batteries, NAS batteries, and redox flow batteries.
  • Film Thickness Measured using a micro thickness meter (manufactured by Anritsu Corporation). The film was sampled in an area of 10 cm square, and measurements were taken at any five points to calculate the average value.
  • E'A + E'B storage modulus
  • EA '+ EB ' was calculated by adding up the obtained EA ' and EB '.
  • the measuring device and conditions are as follows: ⁇ Measurement equipment and conditions> Apparatus: EXSTAR DMS6100 (Seiko Instruments Inc.) Geometry: tension; Chuck distance: 20mm Frequency: 10Hz Distortion: 0.1 to 0.2% - Temperature range: -100 to 200°C Heating rate: 5°C/min. Measurement atmosphere: nitrogen.
  • the heat was calculated from the area surrounded by the linear baseline and the melting curve at 175 ° C. or higher, and this was converted to a value per sample mass to obtain the heat of fusion at 175 ° C. or higher (J / g).
  • the maximum peak temperature in the temperature range of 30°C to 180°C was taken as the melting point of the raw material for the melting curve observed when the temperature was lowered from 260°C to 30°C at 20°C/min.
  • the polypropylene film was also measured in the same manner, and the maximum peak temperature in the temperature range of 30°C to 180°C was taken as the Tm 2 (°C) of the polypropylene film.
  • Crystallization half time Using a differential scanning calorimeter (EXSTAR DSC6220 manufactured by Seiko Instruments), 3 mg of polypropylene film was heated from 25°C to 250°C at 20°C/min in a nitrogen atmosphere and held for 5 minutes. The temperature was then lowered from 250°C to 130°C at 20°C/min and held at 130°C for 30 minutes. The time when the sample temperature reached 130°C was defined as 0 seconds, and the elapsed time from the first peak to the endothermic curve obtained during isothermal holding at 130°C was defined as the crystallization half time (seconds).
  • EXSTAR DSC6220 manufactured by Seiko Instruments
  • Angular frequency ⁇ Measurements were performed by mounting a 25 mm diameter cone plate on a rotational rheometer (MCR302 manufactured by Anton Paar Japan). The raw material was left to stand on a plate heated to 200 ° C for 10 minutes under a nitrogen atmosphere.
  • the sample was a polypropylene film, it was melted in a press machine heated to 200 ° C beforehand and cooled to form a sheet, and then left to stand on the plate in the same manner as the raw material. After confirming that the sample was melted on the plate, the gap between the upper and lower plates was narrowed to the measurement setting value (0.25 mm) and left to stand for 5 minutes until it stabilized at 200 ° C under a nitrogen atmosphere.
  • the cardboard was rated as passed when no folds or wrinkles were observed, and was rated as failed when at least either folds or wrinkles were observed, and was evaluated according to the following criteria. (Fusing resistance) If the polypropylene films or PET films outside the pressure surface after the pressure treatment were not fused to each other, they were deemed to have passed, and if they were fused even partially, they were deemed to have failed. The evaluation was based on the following criteria (if they were fused, the fused parts were cut out and then peeled off from the cardboard, and the above evaluation was performed).
  • ⁇ Evaluation criteria (common to crimping resistance, dimensional stability, and fusion resistance)> The resistance to compression, dimensional stability, and resistance to fusion were evaluated according to the following criteria. If each characteristic was A to C, the sample was deemed to have heat resistance. A: Passed at 160°C, 165°C, and 170°C. B: Passed at 160°C and 165°C, but failed at 170°C. C: Passed at 160°C, but failed at 165°C. D: Failed at 160°C.
  • Moisture Content A polypropylene film or PET film sample was left for 4 hours or more in a room conditioned at 23° C. and a relative humidity of 20%, and then immersed for 24 hours in distilled water at 23° C. Thereafter, moisture on the surface of the sample was wiped off, and the moisture in the sample was dried and evaporated at a temperature of 150° C. using a trace moisture meter (manufactured by Mitsubishi Chemical Corporation, CA-20 model), and the moisture amount was quantified by the Karl Fischer method to calculate the moisture content.
  • Polypropylene resin, etc. The raw materials and their properties used in the polypropylene films of the Examples and Comparative Examples are shown in Tables 1 to 3 below. These property values are values evaluated in the form of resin pellets. Eight types of polypropylene raw materials (PP1 to PP8) were prepared. All of PP1 to PP8 contain 1000 ppm to 5000 ppm of "Irganox” (registered trademark) 1010 manufactured by BASF as an antioxidant, and only PP8 further contains 3000 ppm of "Irgafos" (registered trademark) 168 manufactured by BASF.
  • Seven types of polypropylene resin pellets (PP9 to PP15) were prepared by pre-kneading with the composition in Table 3 (kneading was performed by dry blending, feeding into a twin-screw extruder, kneading at 260 ° C., and cooling).
  • Homopolypropylene resin 1 (PP1): manufactured by Prime Polymer Homopolypropylene resin 2 (PP2): manufactured by Prime Polymer Homopolypropylene resin 3 (PP3): manufactured by Prime Polymer Branched chain polypropylene resin 4 (PP4): manufactured by Borealis Homopolypropylene resin 5 (PP5): manufactured by Prime Polymer Homopolypropylene resin 6 (PP6): manufactured by Sumitomo Chemical Homopolypropylene resin 7 (PP7): manufactured by Japan Polypropylene Homopolypropylene resin 8 (PP8): manufactured by Prime Polymer
  • Acrylic particles 1 (particles 1): Acrylic beads "Eposter” (registered trademark) MA1002 manufactured by Nippon Shokubai Co., Ltd.
  • Polypropylene resin 9 (PP9): Mixed polypropylene resin pellets obtained by mixing PP1 and PP4 in the mass ratio shown in Table 3
  • Polypropylene resin 10 (PP10): Mixed polypropylene resin pellets obtained by mixing PP2 and PP4 in the mass ratio shown in Table 3
  • Polypropylene resin 11 (PP11): Mixed polypropylene resin pellets obtained by mixing PP3 and PP8 in the mass ratio shown in Table 3
  • Polypropylene resin 12 (PP12): Mixed polypropylene resin pellets obtained by mixing PP5 and particles 1 in the mass ratio shown in Table 3
  • Polypropylene resin 13 (PP13): Mixed polypropylene resin pellets obtained by mixing PP3 and PP4 in the mass ratio shown in Table 3
  • Polypropylene resin 14 (PP14): Mixed polypropylene resin pellets obtained by mixing PP5 and PP4 in the mass ratio shown in Table 3
  • Polypropylene resin 15 (PP15): Mixed polypropylene resin pellets obtained by mixing
  • Example 1 Polypropylene resin 9 was supplied to a single-screw extruder for the base layer (A layer), and polypropylene resin 15 was supplied to a single-screw extruder for the surface layer (B layer).
  • the resin mixture for each layer was melt-extruded at 260°C, and after removing foreign matter with a 20 ⁇ m cut sintered filter, the layers were laminated in a feed block type B/A/B composite T die so that the thickness ratio of the surface layer (B layer)/base layer (A layer)/surface layer (B layer) was 1/28/1, and the resulting molten laminate was molded into a sheet shape with a T die.
  • the molten sheet-like material was discharged from the T die onto a casting drum whose surface temperature was controlled at 30°C, and compressed air at 25°C was sprayed with an air knife at an air speed of 140m/s to adhere the molten sheet-like material to the casting drum, thereby obtaining an unstretched sheet.
  • the unstretched sheet was then preheated to 156°C by a ceramic roll, stretched between rolls at 156°C with a peripheral speed difference at a ratio of 4.3 times in the longitudinal direction, and then relaxed by 5.6% in the longitudinal direction with rolls at 155°C with a peripheral speed difference to obtain a uniaxially stretched film.
  • the uniaxially stretched film was then introduced into a tenter-type stretching machine with both ends in the width direction held by clips, preheated at 180°C for 10 seconds, stretched 9.8 times in the width direction at 176°C, and heat-set at 178°C while providing 13% relaxation in the width direction. After that, it was cooled at 100°C and introduced to the outside of the tenter-type stretching machine, the clips at both ends in the width direction were released, and it was wound around a core to obtain a polypropylene film with a thickness of 30 ⁇ m.
  • Table 4 The physical properties and evaluation results of the obtained polypropylene film are shown in Table 4.
  • Examples 2 to 5, Comparative Examples 1 to 5 A polypropylene film was obtained in the same manner as in Example 1, except that the raw material composition of each layer and the film-forming conditions were as shown in Table 4. At this time, the thickness was adjusted by adjusting the discharge amount during extrusion and the speed of the casting drum. The physical properties and evaluation results of the obtained polypropylene film are shown in Table 4. In Examples 2 to 4 and Comparative Examples 1 and 3 to 5, which have a single-layer structure, the same resin or resin composition was charged into two single-screw extruders.
  • the polypropylene films of Examples 2-4 and Comparative Examples 1, 3-5 are single-layer polypropylene films produced by feeding the same resin or resin composition into two single-screw extruders, so the resin type in the table only shows Layer A. Also, in Comparative Examples 1 and 3, the Sdq values were the same on both sides, so there was no distinction between the high and low sides, but the values for both sides are shown in the table. Note that only Example 1, Comparative Examples 3, and 6 were evaluated for moisture content and yield during metal film production.
  • the polypropylene film of the present invention can be used for various purposes such as packaging films, release films, processing films, sanitary products, agricultural products, construction products, medical products, current collectors, and storage batteries.
  • it can be preferably used as a release film or processing film for use at high temperatures where conventional polypropylene films are difficult to use.

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  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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JP2014051658A (ja) * 2012-08-09 2014-03-20 Toyobo Co Ltd ポリプロピレンフィルム
WO2020137791A1 (ja) * 2018-12-28 2020-07-02 東洋紡株式会社 二軸配向ポリプロピレンフィルム
WO2022210693A1 (ja) * 2021-03-31 2022-10-06 東レ株式会社 ポリプロピレンフィルム
WO2023008400A1 (ja) * 2021-07-28 2023-02-02 東レ株式会社 積層体、包装材、及び梱包体
WO2024058078A1 (ja) * 2022-09-16 2024-03-21 王子ホールディングス株式会社 二軸延伸ポリプロピレンフィルム、金属化フィルム、及び、コンデンサ

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CN117120523A (zh) * 2021-03-30 2023-11-24 住友化学株式会社 膜、膜的制造方法以及丙烯系聚合物组合物

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Publication number Priority date Publication date Assignee Title
JP2014051658A (ja) * 2012-08-09 2014-03-20 Toyobo Co Ltd ポリプロピレンフィルム
WO2020137791A1 (ja) * 2018-12-28 2020-07-02 東洋紡株式会社 二軸配向ポリプロピレンフィルム
WO2022210693A1 (ja) * 2021-03-31 2022-10-06 東レ株式会社 ポリプロピレンフィルム
WO2023008400A1 (ja) * 2021-07-28 2023-02-02 東レ株式会社 積層体、包装材、及び梱包体
WO2024058078A1 (ja) * 2022-09-16 2024-03-21 王子ホールディングス株式会社 二軸延伸ポリプロピレンフィルム、金属化フィルム、及び、コンデンサ

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