WO2017077752A1 - 二軸配向ポリプロピレンフィルム、金属膜積層フィルムおよびフィルムコンデンサ - Google Patents
二軸配向ポリプロピレンフィルム、金属膜積層フィルムおよびフィルムコンデンサ Download PDFInfo
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- WO2017077752A1 WO2017077752A1 PCT/JP2016/073192 JP2016073192W WO2017077752A1 WO 2017077752 A1 WO2017077752 A1 WO 2017077752A1 JP 2016073192 W JP2016073192 W JP 2016073192W WO 2017077752 A1 WO2017077752 A1 WO 2017077752A1
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- Prior art keywords
- film
- biaxially oriented
- oriented polypropylene
- temperature
- polypropylene film
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
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- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/14—Organic dielectrics
- H01G4/18—Organic dielectrics of synthetic material, e.g. derivatives of cellulose
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/33—Thin- or thick-film capacitors (thin- or thick-film circuits; capacitors without a potential-jump or surface barrier specially adapted for integrated circuits, details thereof, multistep manufacturing processes therefor)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
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- B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely thereto
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/10—Polymers of propylene
- B29K2023/12—PP, i.e. polypropylene
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/242—All polymers belonging to those covered by group B32B27/32
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- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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- C—CHEMISTRY; METALLURGY
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Definitions
- the present invention relates to a biaxially oriented polypropylene film, a metal film laminated film, and a film capacitor that, when used as a dielectric for a film capacitor, are excellent in transportability during processing and have excellent withstand voltage characteristics even at high temperatures.
- the present invention relates to a biaxially oriented polypropylene film that is excellent in device processability and high-temperature withstand voltage characteristics and can be suitably used for a dielectric for a film capacitor.
- Biaxially oriented polypropylene films are excellent in transparency, mechanical properties, electrical properties, etc., and are therefore used in various applications such as packaging applications, tape applications, cable wrapping and electrical applications including capacitors.
- capacitors are particularly preferably used for high voltage capacitors because of their excellent withstand voltage characteristics and low loss characteristics, not limited to DC applications and AC applications.
- various types of electrical equipment are being converted to inverters, and accordingly, there is an increasing demand for miniaturization and large capacity of capacitors.
- Patent Documents 2 and 3 do not describe anything about the relationship between the valley formed on the film surface and the dielectric breakdown, and the films of Patent Documents 2 and 3 have the high temperature resistance required for current capacitors. It does not satisfy the voltage characteristics.
- Patent Document 4 Furthermore, in the process of forming a molten polymer into a sheet, a method has been proposed in which the surface shape is controlled by controlling the conditions of the air knife to improve processability and withstand voltage characteristics (see, for example, Patent Document 4).
- Patent Document 4 does not describe the relationship between valleys formed on the film surface and dielectric breakdown, and the film of Patent Document 4 satisfies the high-temperature withstand voltage characteristics required for current capacitors. is not.
- Patent Document 5 There has also been proposed a polyester film for a capacitor that controls the surface roughness of the film and the number of protrusions to achieve both improvement in device workability and insulation resistance (see, for example, Patent Document 5).
- Patent document 5 has the possibility of controlling surface shapes, such as a trough part.
- the surface of the polyester film is formed by containing particles, and even if the film is formed by adding particles to a polypropylene film, a film having excellent high-temperature withstand voltage characteristics cannot be obtained.
- the object of the present invention is to solve the above-mentioned problems. That is, it is a biaxially oriented polypropylene film mainly composed of a polypropylene resin, and provides a biaxially oriented polypropylene film, a metal film laminated film, and a film capacitor that are excellent in device processability and excellent in high-temperature withstand voltage characteristics. It is in.
- the above-described problems are biaxially oriented polypropylene films mainly composed of polypropylene resin, the arithmetic average roughness SRa of at least one surface being 0.03 to 0.10 ⁇ m, and the maximum valley depth SRv of at least one surface being 0. 10 to 0.50 ⁇ m, and at least on one side, a valley side void volume having a depth of 0.05 ⁇ m or more and existing in a visual field area of 1,252 ⁇ 939 ⁇ m by non-contact surface shape measurement is 100 to It can be achieved with a biaxially oriented polypropylene film that is 10,000 ⁇ m 3 .
- the biaxially oriented polypropylene film of the present invention when used as a capacitor dielectric, is excellent in device processability and high-temperature withstand voltage characteristics, and can be suitably used as a capacitor dielectric.
- the biaxially oriented polypropylene film of the present invention comprises a polypropylene resin composition containing a polypropylene resin as a main component.
- the “main component” means that the proportion of the polypropylene resin in the polypropylene resin composition is 80% by mass or more, more preferably 85% by mass or more, still more preferably 90% by mass or more, particularly preferably. Is 95% by mass or more.
- polypropylene resin a homopolymer of propylene can be mainly used, but a copolymer component of propylene and other unsaturated hydrocarbons may be used as long as the object of the present invention is not impaired.
- a homopolymer may be blended with a copolymer of propylene and another unsaturated hydrocarbon.
- Examples of the monomer component constituting such a copolymer component include, for example, ethylene, propylene (in the case of a copolymerized blend), 1-butene, 1-pentene, 3-methylpentene-1, 3-methylbutene- 1,1-hexene, 4-methylpentene-1,5-ethylhexene-1,1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1- Examples include eicosene, vinylcyclohexene, styrene, allylbenzene, cyclopentene, norbornene, and 5-methyl-2-norbornene.
- the copolymerization amount of other unsaturated hydrocarbons or the blend amount of the copolymer is less than 1 mol% of the above-mentioned other unsaturated hydrocarbons in the propylene resin. It is preferable to do this.
- the cold xylene soluble part (hereinafter referred to as CXS) of the polypropylene resin constituting the biaxially oriented polypropylene film of the present invention is preferably 4% by mass or less.
- CXS refers to a polypropylene component dissolved in xylene when the film is completely dissolved in xylene at 135 ° C. and then precipitated at 20 ° C., and has low stereoregularity and low molecular weight. This is considered to correspond to a component that is difficult to crystallize.
- the CXS of the polypropylene resin is more preferably 3% by mass or less, further preferably 2% by mass or less, and particularly preferably 1% by mass or less.
- the high-temperature withstand voltage characteristics and dimensional stability of the biaxially oriented polypropylene film may be inferior.
- there are a method for increasing the catalytic activity in obtaining the polypropylene resin a method for washing the obtained polypropylene resin with a solvent or the propylene monomer itself, and the like.
- the mesopentad fraction (mmmm) of the polypropylene resin constituting the biaxially oriented polypropylene film of the present invention is preferably in the range of 0.950 to 0.990, more preferably 0.960 to 0.990. 0.970 to 0.990 is more preferable, and 0.970 to 0.985 is particularly preferable.
- the mesopentad fraction is an index indicating the stereoregularity of the crystalline phase of polypropylene measured by a nuclear magnetic resonance method (so-called NMR method). The higher the numerical value, the higher the crystallinity and the melting point, and the higher the temperature. It is preferable because it is excellent in withstand voltage characteristics even under.
- the mesopentad fraction of the polypropylene resin When the mesopentad fraction of the polypropylene resin is less than 0.950, the high-temperature withstand voltage characteristics and dimensional stability may be inferior. On the other hand, when the mesopentad fraction of the polypropylene resin exceeds 0.990, the biaxially oriented polypropylene film cannot be obtained stably due to inferior film forming property, or the crystallinity becomes too high and the high-temperature withstand voltage characteristics deteriorate. Sometimes.
- a method of washing the polypropylene resin powder obtained with a solvent such as n-heptane, selection of a catalyst and / or promoter, and a polypropylene resin composition A method of appropriately selecting components is preferably employed.
- melt flow rate (hereinafter referred to as MFR) of the polypropylene resin constituting the biaxially oriented polypropylene film of the present invention is measured in accordance with the condition M (230 ° C., 2.16 kg) of JIS K 7210 (1995) Is preferably 0.5 to 10 g / 10 minutes, more preferably 1 to 8 g / 10 minutes, further preferably 1.5 to 5 g / 10 minutes, and 2 to 5 g / 10 minutes. And particularly preferred.
- MFR of the polypropylene resin is less than 0.5 g / 10 minutes, the biaxially oriented polypropylene film may not be obtained stably due to poor film forming properties.
- the MFR of the polypropylene resin exceeds 10 g / 10 minutes, the high-temperature withstand voltage characteristics may be inferior.
- a method of controlling the average molecular weight or molecular weight distribution of the polypropylene resin is preferably employed.
- the biaxially oriented polypropylene film of the present invention has an arithmetic average roughness SRa of at least one side of 0.03 to 0.10 ⁇ m from the viewpoint of device processability.
- the arithmetic average roughness SRa is more preferably 0.03 to 0.08 ⁇ m, further preferably 0.04 to 0.07 ⁇ m, and particularly preferably 0.04 to 0.06 ⁇ m.
- the arithmetic average roughness SRa is less than 0.03 ⁇ m, the slipping property is deteriorated, and in the film conveyance process during film formation and processing, conveyance wrinkles are likely to occur, and the roll shape of the film roll is deteriorated. It may break.
- the arithmetic average roughness SRa exceeds 0.10 ⁇ m, the film is likely to meander in the film transport process during film formation and processing, and the roll shape of the film roll may be deteriorated. If the arithmetic average roughness SRa at least on one side satisfies the above range, the slippage between the transport roll contacting the surface and the surface becomes good, and the workability is improved. In particular, when the arithmetic average roughness SRa satisfies the above range on both sides, both sides of the film are excellent in slipperiness with the conveyance roll, resulting in excellent workability regardless of the roll arrangement of the apparatus in the film conveyance process. preferable. In order to control the arithmetic average roughness SRa within the above range, the above-described polypropylene resin is used, and a casting process during film formation may be set as a specific condition as described later.
- the biaxially oriented polypropylene film of the present invention has a maximum valley depth SRv of at least one side of 0.10 to 0.50 ⁇ m from the viewpoint of high-temperature withstand voltage characteristics.
- the maximum valley depth SRv is more preferably 0.10 to 0.40 ⁇ m, further preferably 0.10 to 0.30 ⁇ m, and particularly preferably 0.10 to 0.20 ⁇ m.
- the maximum valley depth SRv exceeds 0.50 ⁇ m, dielectric breakdown is likely to occur, and the high-temperature withstand voltage characteristics may deteriorate.
- the maximum valley depth SRv Is substantially the lower limit of 0.10 ⁇ m.
- the withstand voltage characteristics are good.
- the valley portion that tends to cause dielectric breakdown as a whole is small. Therefore, it is more preferable in terms of withstand voltage characteristics.
- the above-described polypropylene resin is used, and a casting process during film formation may be set as a specific condition as described later.
- the biaxially oriented polypropylene film of the present invention is a valley having a depth of 0.05 ⁇ m or more that exists in a visual field area of 1,252 ⁇ 939 ⁇ m by non-contact surface shape measurement on at least one side from the viewpoint of high-temperature withstand voltage characteristics.
- the side void volume is 100 to 10,000 ⁇ m 3 .
- Valley void volume is more preferably if 100 ⁇ 8,000 ⁇ m 3, more preferably when the 100 ⁇ 6,000 ⁇ m 3, particularly preferable if 100 ⁇ 5,000 .mu.m 3.
- the valley side void volume exceeds 10,000 ⁇ m 3 , dielectric breakdown is likely to occur, and the high-temperature withstand voltage characteristics may be deteriorated.
- the valley side void volume is 100 ⁇ m 3 is substantially the lower limit.
- the withstand voltage characteristics are good, but particularly when the valley side void volume satisfies the above range on both sides, the valley portion that tends to break down as a whole becomes small. More preferable in terms of withstand voltage characteristics.
- the above-described polypropylene resin may be used, and the casting process during film formation may be a specific condition as described later.
- the biaxially oriented polypropylene film of the present invention preferably has a maximum peak height SRp of at least one side of 0.30 to 1.0 ⁇ m from the viewpoint of device processability.
- the maximum peak height SRp is more preferably 0.50 to 0.95 ⁇ m, further preferably 0.55 to 0.90 ⁇ m, and particularly preferably 0.60 to 0.85 ⁇ m.
- the maximum peak height SRp is less than 0.30 ⁇ m, the slipping property is deteriorated, and conveyance wrinkles are easily generated in the film conveyance process during film formation and processing, and the roll shape of the film roll is deteriorated or the film is broken in some cases. May end up.
- the film roll may buckle when the film is wound into a roll shape, and the winding shape may be deteriorated.
- the high temperature withstand voltage characteristics may deteriorate.
- the maximum peak height SRp on one side satisfies the above range, the slipping property between the transport roll contacting the surface and the surface becomes good, and the workability is improved.
- both sides of the film are excellent in slipperiness with the transport roll, so that it is excellent in workability regardless of the roll arrangement of the apparatus in the film transport process, and more preferable.
- the above-described polypropylene resin is used, and a casting process during film formation may be set as a specific condition as described later.
- the ratio SRp / SRv of the maximum valley depth SRv and the maximum peak height SRp of at least one surface is 2.0 or more from the viewpoint of compatibility between device processability and high temperature withstand voltage characteristics. Is preferred.
- SRp / SRv is more preferably 2.5 or more, further preferably 3.5 or more, and particularly preferably 4.0 or more.
- SRp / SRv is less than 2.0, it means that the peak portion is low or the valley portion is deep, and it may be difficult to achieve both device processability and high-temperature withstand voltage characteristics.
- the withstand voltage characteristic tends to be good, but particularly when SRp / SRv satisfies the above range on both sides, it becomes easy to achieve both element workability and high temperature withstand voltage characteristics. Especially, since it becomes a result excellent also in workability irrespective of the roll arrangement
- the above-described polypropylene resin is used, and the casting process at the time of film formation may be a specific condition as described later.
- the biaxially oriented polypropylene film of the present invention preferably has a film thickness t of 1.0 to 10 ⁇ m.
- the film thickness t is more preferably 1.2 to 7 ⁇ m, further preferably 1.5 to 5 ⁇ m, and particularly preferably 1.5 to 3 ⁇ m.
- the film thickness t is less than 1.0 ⁇ m, the mechanical strength and high-temperature withstand voltage characteristics may be inferior, or film breakage may occur during film formation and processing.
- the film thickness t exceeds 10 ⁇ m, the capacity per volume may be small when used as a capacitor dielectric.
- it can be appropriately set by adjusting the discharge amount of the resin or adjusting the draft ratio when forming the sheet.
- the longitudinal stretching step and the lateral stretching step during film formation are specified conditions as described later. This makes it possible to form a film stably.
- the ratio SRv / t between the film thickness t and the maximum valley depth SRv of at least one side is preferably 0.30 or less.
- SRv / t is more preferably 0.15 or less, further preferably 0.10 or less, and particularly preferably 0.080 or less.
- SRv / t exceeds 0.30, the ratio of troughs per film thickness is large, and the high-temperature withstand voltage characteristics may deteriorate.
- the withstand voltage characteristic tends to be good, but particularly when SRv / t satisfies the above range on both sides, the valley portion that tends to cause dielectric breakdown on both sides of the film becomes shallow. More preferable in terms of withstand voltage characteristics.
- the biaxially oriented polypropylene film of the present invention preferably has a glossiness of 120 to 150% on both sides.
- the glossiness is more preferably 123 to 145% on both sides, further preferably 125 to 140%, and particularly preferably 128 to 138%.
- the glossiness of at least one surface is less than 120%, the density of light scattering on the film surface increases. That is, it means that there are many irregularities on the film surface, and the high-temperature withstand voltage characteristics may be reduced due to the irregularities.
- the film surface has less unevenness, so it is inferior in slipperiness and easily causes wrinkles in the film transport process during film formation and processing, and deteriorates the roll shape of the film roll. In some cases, the film may break.
- it can be achieved by using the above-mentioned polypropylene resin and setting the casting process at the time of film formation as a specific condition as described later. .
- the biaxially oriented polypropylene film of the present invention may contain a branched polypropylene for the purpose of improving the film forming property or controlling the film surface shape.
- the branched polypropylene satisfies the relational expression that the melt tension (MS) and the melt flow rate (MFR) measured at 230 ° C. are log (MS)> ⁇ 0.56 log (MFR) +0.74.
- a branched polypropylene is preferred.
- To obtain a branched polypropylene satisfying the relational expression that the melt tension (MS) and the melt flow rate (MFR) measured at 230 ° C. are log (MS)> ⁇ 0.56 log (MFR) +0.74.
- a method or a method described in Japanese Patent No. 2869606 is preferably used. Specific examples include “Profax (trademark) PF-814” manufactured by LyondellBasel, and “Daploy HMS-PP” (WB130HMS, WB135HMS, etc.) manufactured by Borealis.
- resins obtained by the electron beam crosslinking method are exemplified. It is preferably used because the gel component in the resin is small.
- the branched polypropylene referred to here is a polypropylene having 5 or less internal trisubstituted olefins per 10,000 carbon atoms, and the presence of these internal trisubstituted olefins is the proton in the 1 H-NMR spectrum. It can be confirmed by the ratio.
- the branched polypropylene can act as an ⁇ crystal nucleating agent, and can form a rough surface by a crystal form as long as the amount is within a certain range.
- a biaxially oriented polypropylene film that can control the size of the spherulite of the polypropylene produced in the cooling process of the melt-extruded resin sheet to be small, suppress the generation of insulation defects produced in the stretching process, and has excellent high-temperature withstand voltage characteristics. Obtainable.
- the content is preferably 0.05 to 3% by mass, more preferably 0.1 to 2% by mass, It is more preferable that the amount is ⁇ 1.5% by mass, and it is particularly preferable that the amount is 0.5 to 1% by mass.
- the content of the branched polypropylene is less than 0.05% by mass, the above effect may not be obtained.
- the content of the branched polypropylene exceeds 3% by mass, the stereoregularity as a biaxially oriented polypropylene film is lowered, and the high-temperature withstand voltage characteristics may be lowered.
- various additives such as a crystal nucleating agent, an antioxidant, a heat stabilizer, an antistatic agent, and an antiblocking agent are used as long as the object of the present invention is not impaired. It is also preferable to include an agent, a filler, a viscosity modifier, an anti-coloring agent and the like.
- the type and content of the antioxidant are important from the viewpoint of long-term heat resistance. That is, the antioxidant is a phenolic compound having steric hindrance, and at least one of them is preferably a high molecular weight type having a molecular weight of 500 or more.
- 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
- Irganox® 1330 manufactured by BASF: molecular weight 775.2 1,3,5-trimethyl-2,4,6-tris (3,5-di- -T-butyl-4-hydroxybenzyl) benzene
- the total content of these antioxidants is preferably 0.03 to 1.0% by mass, more preferably 0.1 to 0.9% by mass, based on the total amount of the polypropylene resin composition, It is more preferably from 0.8 to 0.8% by mass, particularly preferably from 0.15 to 0.6% by mass.
- the antioxidant content in the polypropylene resin composition is less than 0.03% by mass, the antioxidant effect is hardly obtained and the long-term heat resistance may be poor.
- the antioxidant content in the polypropylene resin composition exceeds 1.0% by mass, the high-temperature withstand voltage characteristics may deteriorate.
- the biaxially oriented polypropylene film of the present invention preferably has an ash content of 50 ppm (mass basis, hereinafter the same) or less, more preferably 40 ppm or less, further preferably 30 ppm or less, and particularly preferably 20 ppm or less. .
- the ash content exceeds 50 ppm, the high-temperature withstand voltage characteristics of the biaxially oriented polypropylene film may deteriorate.
- a method of sufficiently washing the flow path of the polymer with the polypropylene resin can be preferably employed. Also, as will be described later, it is important not to contain a lubricant. When inorganic particles are included, it is detected as ash content of the biaxially oriented polypropylene film, and the high-temperature withstand voltage characteristics may deteriorate as described above. Also, when organic particles are included, the ash content is generally not sufficiently suppressed, and it is difficult to control the ash content within the above-described range even as a biaxially oriented polypropylene film.
- the biaxially oriented polypropylene film of the present invention preferably has a total content of inorganic and / or organic particles of 1% by mass or less.
- the total content of inorganic and / or organic particles is more preferably 0.8% by mass or less, further preferably 0.5% by mass or less, and particularly preferably not contained.
- a smooth and low slippery film may be given slipperiness by adding a slippery agent composed of inorganic and / or organic particles to form protrusions on the surface of the film. When used as a dielectric, this easy-to-lubricant may become a foreign substance and reduce the high-temperature withstand voltage characteristics.
- crystals formed in a polypropylene cast sheet are deformed by a subsequent stretching process as described later, and the film surface It is sufficient to form irregularities on the surface.
- the biaxially oriented polypropylene film of the present invention preferably has a surface wetting tension of at least one side of 37 to 50 mN / m, more preferably 38 to 49 mN / m, and further preferably 39 to 48 mN / m.
- a range of 40 to 47 mN / m is particularly preferable.
- the surface wetting tension is less than 37 mN / m, adhesion to the metal may be insufficient during metal deposition.
- the surface wetting tension exceeds 50 mN / m, the high-temperature withstand voltage characteristics may deteriorate.
- a polypropylene film usually has a low surface energy and a surface wetting tension of about 30 mN / m.
- a method of performing surface treatment after biaxial stretching is preferably employed during film formation. Specifically, corona discharge treatment, plasma treatment, glow treatment, flame treatment, and the like can be employed.
- the biaxially oriented polypropylene film of the present invention is preferably obtained by preparing a sheet mainly composed of the above-described polypropylene resin and biaxially stretching.
- the biaxial stretching method can be obtained by any of the inflation simultaneous biaxial stretching method, the tenter simultaneous biaxial stretching method, and the tenter sequential biaxial stretching method, but from the viewpoint of film formation stability and thickness uniformity, It is preferable to employ an axial stretching method.
- it is preferable that the film is stretched in the longitudinal direction (direction in which the film flows during film formation) and then stretched in the width direction (direction orthogonal to the longitudinal direction on the film plane).
- a functional layer may be laminated on at least one side for the purpose of imparting various effects.
- the laminated structure may be a two-layered structure, a three-layered structure, or a larger number of stacked layers.
- a lamination method for example, a feed block method or a multi-manifold method by co-extrusion or a method of laminating polypropylene films by lamination may be used.
- the propylene resin composition containing the preferred polypropylene resin described above is supplied to a uniaxial melt extruder, and melt extrusion is performed at 200 to 260 ° C.
- melt extrusion is performed at 200 to 260 ° C.
- the shear rate at the T die is 100 to 1,000 sec ⁇ 1 from the viewpoint of suppressing the deterioration of the polymer. It is more preferably 150 to 800 sec ⁇ 1 , further preferably 200 to 700 sec ⁇ 1 , particularly preferably 300 to 600 sec ⁇ 1 .
- the shear rate at the T-die is expressed by equation (1).
- shear rate at the T-die is less than 100 sec ⁇ 1 , shear is not sufficient and the crystal arrangement in the cast sheet is insufficient, so that uniform stretching becomes difficult in the subsequent stretching step, and the crystallinity is uniform. An axially oriented polypropylene film may not be obtained.
- the shear rate at the T-die exceeds 1,000 sec ⁇ 1 , excessive shearing may occur and polymer degradation may occur.
- Shear rate (sec ⁇ 1 ) 6Q / ⁇ Wt 2 (1)
- Q Flow rate (kg / sec) ⁇ : specific gravity (kg / cm 3 )
- W T die groove width (cm)
- t T-die groove gap (cm)
- the flow rate of the polypropylene resin composition, the groove width of the T die, and the groove gap are appropriately adjusted so that the shear rate of the T die is in the above-described range.
- the flow rate of the polypropylene resin composition is preferably in the range of 150 to 500 kg / hr from the viewpoint of extrusion stability.
- the groove width of the T die is preferably in the range of 500 to 1,000 mm from the viewpoint of productivity.
- the groove gap of the T die is preferably in the range of 0.8 to 2 mm from the viewpoint of internal pressure in the extrusion system and casting accuracy.
- the cast drum may be continuously arranged from the viewpoint of controlling the arithmetic average roughness SRa, the maximum valley depth SRv, the valley side void volume, the maximum peak height SRp, and the glossiness to an appropriate range.
- the surface temperature of CD1 and CD2 is preferably 25 to 50 ° C., more preferably 25 to 45 ° C., 30 It is more preferable that the temperature is ⁇ 45 ° C., and particularly preferable that the temperature is 30 to 40 ° C.
- the surface temperature of CD3 and CD4 is preferably 50 to 100 ° C., more preferably 60 to 98 ° C., further preferably 70 to 96 ° C., and particularly preferably 80 to 95 ° C.
- the temperatures of CD3 and CD4 are increased, the values of SRa, SRv, valley side void volume, and SRp change to higher values, and the glossiness changes to lower values.
- the surface temperature of CD3 and CD4 is less than 50 ° C., almost no ⁇ crystals are formed in the cast sheet, so that unevenness does not occur on the film surface even after the subsequent stretching step, which is a problem in terms of device workability. Sometimes.
- the surface temperature of CD3 and CD4 exceeds 100 ° C., a large number of ⁇ crystals are formed in the cast sheet, and large unevenness is generated on the film surface in the subsequent stretching process, so that the high-temperature withstand voltage characteristics may deteriorate. is there.
- the surface temperature of the fifth and subsequent cast drums is preferably the same as that of CD4, but it is unlikely that various physical properties will change even if these temperatures are changed.
- the present invention is not limited to this.
- the time for the molten sheet discharged from the T-die to land on the cast drum and be in close contact with the drum is 0.3 to 0.8 seconds for each of CD1 and CD2 from the viewpoint of limiting the formation of ⁇ crystals. It is preferably 0.3 to 0.7 seconds, more preferably 0.4 to 0.7 seconds or more, and particularly preferably 0.4 to 0.6 seconds.
- the time for which each cast drum and the molten sheet are in close contact is less than 0.3 seconds, a large number of ⁇ crystals are formed in the cast sheet, resulting in large irregularities in the subsequent stretching process, resulting in high temperature withstand voltage characteristics. May decrease.
- the time for which the respective cast drums and the molten sheet are in close contact exceeds 0.8 seconds, since ⁇ crystals are hardly formed in the cast sheet, unevenness occurs on the film surface even after the subsequent stretching step. However, it may be a problem from the viewpoint of device processability. It is preferable that the time for which the CD3 and CD4 are in close contact with the molten sheet is 0.3 seconds or more. When the time for which each cast drum and the molten sheet are in close contact is less than 0.3 seconds, the molten sheet cannot be solidified, or a large number of ⁇ crystals are formed in the cast sheet. As a result, the high-temperature withstand voltage characteristics may deteriorate.
- the reason for using four or more cast drums is to suppress the formation of ⁇ crystals on one side of the sheet with CD1 set at a low temperature, and then suppress the formation of ⁇ crystals on the other side with CD2 set at a low temperature.
- CD4 controlled to the above range can then promote ⁇ crystal generation on the other side. That is, by using a plurality of CDs and making the heat application conditions on the front and back of the film equal, the crystal forms on both sides of the sheet can be made similar.
- the crystal form on one side of the cast sheet is often different from the crystal form on the other side, and it is difficult to control to the preferred form of the present invention.
- the cast sheet of each cast drum is It is preferred that the surfaces contact alternately. For example, if the surface of the cast sheet that contacts CD1 is the A surface and the other surface is the B surface, CD1 is the A surface, CD2 is the B surface, CD3 is the A surface, CD4 is the B surface, etc.
- the cast sheet is preferably in contact with the cast drum.
- the air knife method is preferable.
- the air temperature of the air knife is preferably 25 to 50 ° C. from the viewpoint of controlling the arithmetic average roughness SRa, the maximum valley depth SRv, the valley side void volume, the maximum mountain height SRp, and the glossiness to an appropriate range. 25 to 45 ° C is more preferable, 30 to 45 ° C is further preferable, and 30 to 40 ° C is particularly preferable.
- the values of SRa, SRv, valley side void volume, and SRp change to higher values, and the glossiness changes to lower values.
- the air knife temperature is less than 25 ° C., almost no ⁇ crystals are formed in the cast sheet, so that unevenness does not occur on the film surface even after the subsequent stretching step, which may be a problem in terms of device workability.
- the air knife temperature exceeds 50 ° C., a large number of ⁇ crystals are formed in the cast sheet, and large unevenness is generated in the subsequent stretching process, so that the high-temperature withstand voltage characteristics may be deteriorated.
- the atmospheric temperature for forming the cast sheet can control the arithmetic average roughness SRa, the maximum valley depth SRv, the valley side void volume, the maximum peak height SRp, and the glossiness to an appropriate range, and can obtain a uniform surface shape. It is preferable to adjust the temperature.
- the atmospheric temperature for forming the cast sheet is preferably 25 to 50 ° C., more preferably 25 to 45 ° C., further preferably 30 to 45 ° C., and particularly preferably 30 to 40 ° C. When the atmospheric temperature for forming the cast sheet is increased, the values of SRa, SRv, valley side void volume, and SRp change to higher values, and the glossiness changes to lower values.
- the atmospheric temperature for forming the cast sheet is less than 25 ° C., since ⁇ crystals are hardly formed in the cast sheet, unevenness does not occur on the film surface even after the subsequent stretching step, and this is a problem in terms of device workability. May be.
- the atmospheric temperature for forming the cast sheet exceeds 50 ° C., a large number of ⁇ crystals are formed in the cast sheet, and large unevenness is generated in the subsequent stretching process, so that the high-temperature withstand voltage characteristics may be deteriorated.
- the obtained cast sheet is biaxially stretched to be biaxially oriented.
- the temperature at which the cast sheet is stretched in the longitudinal direction is controlled.
- a temperature control method a method using a temperature-controlled rotating roll, a method using a hot air oven, or the like can be adopted.
- the film temperature for stretching in the longitudinal direction is preferably 100 to 150 ° C., more preferably 110 to 145 ° C., still more preferably 120 to 145 ° C., and particularly preferably 130 from the viewpoints of uniform stretching and stable film formation. ⁇ 145 ° C.
- the stretching ratio is preferably 4 to 6.5 times from the viewpoint of uniform stretching and stable film formation, more preferably 4.5 to 6 times, still more preferably 5 to 6 times, and particularly preferably 5.5 to 6 times.
- the higher the draw ratio the more uniform the surface shape of the film and the better the high-temperature withstand voltage characteristics.
- the film is stretched more than 6.5 times, the film breaks easily in the longitudinal stretching process or in the next transverse stretching process. It may become.
- the stretching speed in the longitudinal direction is preferably 1,000,000 to 3,500,000% / min from the viewpoint of uniform stretching and stable film formation, and 1,000,000 to 3,000,000% / min. Is more preferable, 1,500,000 to 3,000,000% / min is further preferable, and 2,000,000 to 3,000,000% / min is particularly preferable.
- the stretching speed in the longitudinal direction is less than 1,000,000% / min, a uniform film surface shape cannot be obtained, and the high-temperature withstand voltage characteristics may deteriorate.
- the stretching speed in the longitudinal direction exceeds 3,500,000% / min, film breakage may occur during film formation.
- a method of calculating the stretching speed in the longitudinal direction is represented by the formula (2).
- the neck-down ratio (film width after stretching / film width before stretching ⁇ 100) is preferably 90 to 99%.
- the film end is held by a tenter type stretching machine and introduced. From the viewpoint of uniform stretching and stable film formation, it is preferably heated to 140 to 165 ° C., more preferably 142 to 163 ° C., further preferably 144 to 160 ° C., particularly preferably 145 to 155 ° C.
- the film is stretched up to 15 times, more preferably 9 to 14 times, still more preferably 10 to 13 times, particularly preferably 10 to 12 times.
- the transverse stretching speed at this time is preferably 15,000 to 45,000% / minute from the viewpoint of uniform stretching and stable film formation, and more preferably 18,000 to 40,000% / minute. It is preferably 20,000 to 35,000% / min, more preferably 25,000 to 30,000% / min.
- the heat treatment may be performed as it is in the tenter without changing the heat treatment temperature, but from the viewpoint of high-temperature withstand voltage characteristics, the heat treatment temperature is preferably 147 to 167 ° C., more preferably 150 to 165 ° C., The temperature is more preferably 152 to 163 ° C, and particularly preferably 155 to 160 ° C. Further, the heat treatment may be performed while relaxing in the longitudinal direction and / or the width direction of the film, and in particular, the relaxation rate in the width direction is 5 to 15%, more preferably 8 to 13%, still more preferably 9 to 12%. Particularly preferably, it is 10 to 12% from the viewpoint of thermal dimensional stability in the width direction.
- a metal film laminated film can be obtained by performing corona discharge treatment in or in a mixed gas thereof.
- the biaxially oriented polypropylene film of the present invention is preferably used as a dielectric for a capacitor, but is not limited to the type of capacitor. Specifically, from the viewpoint of electrode configuration, either a foil-wound capacitor or a metal-deposited film capacitor may be used, and it is also preferable for an oil-immersion type capacitor containing insulating oil or a dry-type capacitor not using insulating oil at all. Used. Further, from the viewpoint of shape, it may be a winding type or a laminated type. In view of the characteristics of the biaxially oriented polypropylene film of the present invention, it is particularly preferably used as a metal vapor deposition film capacitor.
- a metal film laminated film by providing a metal film on at least one surface of the biaxially oriented polypropylene film.
- the method is not particularly limited, for example, a method in which aluminum is vapor-deposited on at least one surface of the film to provide a metal film such as an aluminum vapor-deposited film that serves as an internal electrode of the film capacitor is preferably used.
- other metal components such as nickel, copper, gold, silver, chromium, and zinc can be deposited simultaneously or sequentially with aluminum.
- a protective layer can be provided on the deposited film with oil or the like.
- the thickness of the metal film of the metal film laminated film is preferably 20 to 100 nm from the viewpoint of the electrical characteristics and self-heeling property of the film capacitor.
- the surface resistance value of the metal film is preferably 1 to 20 ⁇ / ⁇ . The surface resistance value can be controlled by the type of metal used and the film thickness.
- the metal film laminated film can be subjected to aging treatment at a specific temperature or heat treatment after forming a metal film as necessary.
- a coating such as polyphenylene oxide can be applied to at least one surface of the metal film laminated film for insulation or other purposes.
- the film capacitor can be obtained by laminating or winding the metal film laminated film thus obtained by various methods. Although the preferable manufacturing method of a winding type capacitor is demonstrated below, it is not necessarily limited to this.
- aluminum is vacuum-deposited on one side of the biaxially oriented polypropylene film of the present invention.
- aluminum is vapor-deposited in the stripe form which runs in the longitudinal direction of a film.
- a margin portion where aluminum is not vapor deposited.
- a tape-shaped take-up reel having a margin on one side is prepared by inserting a blade into the center of each vapor deposition section on the surface and the center of each margin section.
- Two tape-shaped take-up reels with margins on the left or right are wound on the left margin and one on the right margin, overlapping each other so that the vapor deposition part protrudes from the margin part in the width direction. Get the body.
- the core material is removed from the wound body and pressed, and the metallicon is thermally sprayed on both end sides to form external electrodes, and then a lead wire is welded to the metallicon to obtain a wound film capacitor.
- the film capacitors are used for various purposes such as for vehicles, home appliances (TVs, refrigerators, etc.), general noise prevention, automobiles (hybrid cars, power windows, wipers, etc.), and power supplies. Capacitors can also be suitably used for these applications.
- Measurement direction Film width direction Width direction feed rate: 0.1 mm / second Measurement range (width direction ⁇ length direction): 1.0 mm ⁇ 0.249 mm Reference plane of height dimension: LOWER (lower side) Width direction sampling interval: 2 ⁇ m Sampling interval in the length direction: 10 ⁇ m Number of samplings in the length direction: 25 Cutoff: 0.25 mm / second Magnification in the width direction: 200 times Magnification in the length direction: 20,000 times Waviness, roughness Cut: None Measuring method Use a special sample holder for film measurement.
- the sample holder is a detachable metal plate with a circular hole in the center. The sample is sandwiched between the sample holders, and the film is fixed to the four sides of the sample holder. Measurements were made on the film.
- Measurement conditions CCD camera: SONY HR-57 1/2 Objective lens: 10X Lens tube: 0.5X BODY Wavelength filter: 530 white Measurement mode: Wave Field size: 640 ⁇ 480 Scan range: start 5 ⁇ m, stop -0.5 ⁇ m B.
- Measuring method Use a special sample holder for film measurement.
- the sample holder is a detachable metal plate with a circular hole in the center. The sample is sandwiched between the sample holders, and the film is fixed to the four sides of the sample holder. Measurements were made on the film. Subsequently, the obtained data was subjected to surface correction by quartic polynomial approximation to remove the waviness component, and then complete interpolation was performed as an interpolation process.
- the image data obtained as described above was analyzed using a bearing function that is an analysis tool of the image analysis software VS-Viewer of VertScan 2.0.
- the valley side height threshold was set to ⁇ 50 nm (that is, a valley side void having a depth of 0.05 ⁇ m or more was designated), and then the value described as the valley side void volume was read. The read value was rounded off to 2 significant figures.
- Ash content (W 1 / W 0 ) ⁇ 1,000,000 (ppm)
- Example 1 A Production of Polypropylene Resin Composition Anhydrous magnesium chloride, decane and 2-ethylhexyl alcohol were mixed, and phthalic anhydride was added to the heated solution, followed by further stirring. The solution was cooled and then added dropwise to titanium tetrachloride cooled to ⁇ 20 ° C. Next, the temperature of the mixture was raised, diisobutyl phthalate was added and stirred, and then a solid was obtained by filtration. The obtained solid was washed with decane and hexane to obtain a titanium catalyst used for propylene polymerization.
- Propylene polymerization was performed using the above titanium catalyst, triethylaluminum as a co-catalyst, and hydrogen as a chain transfer agent.
- the obtained product was deactivated and then thoroughly washed with a propylene monomer to obtain a polypropylene resin.
- the polypropylene resin had an MFR of 2.5 g / 10 min and a mesopentad fraction (mmmm) of 0.980.
- BHT as an antioxidant
- Irganox-1010 as an antioxidant to 0.2 mass% to 99.7 mass% of the obtained polypropylene resin, at a temperature of 260 ° C. Kneading and pelletizing were performed to obtain a polypropylene resin composition.
- the surface temperature of CD1 and CD2 was 30 ° C., and the surface temperature of CD3 and CD4 was 90 ° C.
- the time for which the cast drums of CD1, CD2, CD3, and CD4 and the molten sheet were in close contact with each other was 0.4 seconds.
- An air knife and end spot air were used to bring the sheet into close contact with CD1, the first cast drum.
- the temperature of the air knife was adjusted to 30 ° C.
- the atmospheric temperature of the casting process was also adjusted to 30 ° C.
- the cast sheet was preheated using a heated roll, heated so that the film temperature was 145 ° C., and then stretched 5.5 times in the longitudinal direction.
- the stretching speed in the longitudinal direction was 2,000,000% / min, and the neck-down rate was 98%.
- the edge part was hold
- heat treatment was performed at 158 ° C. for 7 seconds, and 12% relaxation was performed in the width direction. Thereafter, after cooling to room temperature, one side of the film was subjected to corona discharge treatment at a treatment strength of 25 W ⁇ min / m 2 , and the film ears held by the clips were cut and removed.
- the surface in contact with CD1, the surface subjected to corona discharge treatment was the A surface, the surface in contact with the other CD2, and the surface not subjected to corona discharge was defined as the B surface.
- the film from which the end portion was removed was wound up by a winder to obtain a biaxially oriented polypropylene film having a thickness of 2.5 ⁇ m. Table 1 shows the physical properties of the obtained film.
- Example 2 A biaxially oriented polypropylene film having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the surface temperature of CD1 and CD2 was 45 ° C. Table 1 shows the physical properties of the obtained film.
- Example 3 A biaxially oriented polypropylene film having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the surface temperature of CD1 and CD2 was 50 ° C. Table 1 shows the physical properties of the obtained film.
- Example 4 A biaxially oriented polypropylene film having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the surface temperature of CD1 and CD2 was 25 ° C. Table 1 shows the physical properties of the obtained film.
- Example 5 A biaxially oriented polypropylene film having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the surface temperature of CD3 and CD4 was changed to 70 ° C. Table 1 shows the physical properties of the obtained film.
- Example 6 A biaxially oriented polypropylene film having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the surface temperature of CD3 and CD4 was changed to 50 ° C. Table 1 shows the physical properties of the obtained film.
- Example 7 A biaxially oriented polypropylene film having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the surface temperature of CD3 and CD4 was 100 ° C. Table 1 shows the physical properties of the obtained film.
- Example 8 A biaxially oriented polypropylene having a thickness of 2.5 ⁇ m was produced in the same manner as in Example 1 except that the time for which the cast drums of CD1, CD2, CD3, and CD4 and the molten sheet were in close contact with each other was 0.3 seconds. A film was obtained. Table 1 shows the physical properties of the obtained film.
- Example 9 A biaxially oriented polypropylene having a thickness of 2.5 ⁇ m was prepared in the same manner as in Example 1 except that the time when the cast drums of CD1, CD2, CD3, and CD4 and the molten sheet were in close contact with each other was 0.7 seconds. A film was obtained. Table 1 shows the physical properties of the obtained film.
- Example 10 A biaxially oriented polypropylene having a thickness of 2.5 ⁇ m was prepared in the same manner as in Example 1 except that the time when the cast drums of CD1, CD2, CD3, and CD4 and the molten sheet were in close contact with each other was 0.8 seconds. A film was obtained. Table 1 shows the physical properties of the obtained film.
- Example 11 A biaxially oriented polypropylene film having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the air temperature of the air knife was 50 ° C. Table 1 shows the physical properties of the obtained film.
- Example 12 A biaxially oriented polypropylene film having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the atmospheric temperature in the casting step was 50 ° C. Table 1 shows the physical properties of the obtained film.
- Example 13 A biaxially oriented polypropylene film having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the surface temperature of CD1 and CD2 was 40 ° C. Table 1 shows the physical properties of the obtained film.
- Example 14 A biaxially oriented polypropylene having a thickness of 2.5 ⁇ m was prepared in the same manner as in Example 1 except that the time during which the cast drums of CD1, CD2, CD3, and CD4 were in close contact with the molten sheet was 0.6 seconds. A film was obtained. Table 1 shows the physical properties of the obtained film.
- Comparative Example 2 Other than supplying 99.5% by mass of the polypropylene resin composition described in Example 1 and 0.5% by mass of sol-gel silica particles (average particle size 0.3 ⁇ m) manufactured by Tokuyama Corporation to a uniaxial melt extruder. Was produced in the same manner as in Comparative Example 1 to obtain a biaxially oriented polypropylene film having a thickness of 2.5 ⁇ m. Table 2 shows the physical properties of the obtained film.
- Example 3 The number of cast drums is set to two so that one side and the other side of the cast sheet are alternately in contact with the two cast drums, and the surface temperature of the first cast drum is 30 ° C.
- the surface temperature of the cast drum was set to 95 ° C., and at that time, each cast drum was prepared in the same manner as in Example 1 except that the time during which the molten sheet was in close contact was 0.8 seconds.
- a biaxially oriented polypropylene film was obtained.
- the surface in contact with the first cast drum the surface subjected to the corona discharge treatment is the A surface, the surface in contact with the other second cast drum, and the surface not treated with the corona discharge is defined as the B surface.
- Table 2 shows the physical properties of the obtained film.
- Example 4 A biaxially oriented polypropylene film having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the surface temperature of CD1 and CD2 was 55 ° C. Table 2 shows the physical properties of the obtained film.
- Example 5 A biaxially oriented polypropylene film having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the surface temperature of CD3 and CD4 was 45 ° C. Table 2 shows the physical properties of the obtained film.
- Example 6 A biaxially oriented polypropylene film having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the surface temperature of CD3 and CD4 was changed to 105 ° C. Table 2 shows the physical properties of the obtained film.
- Example 7 A biaxially oriented polypropylene having a thickness of 2.5 ⁇ m was prepared in the same manner as in Example 1 except that the time when the cast drums of CD1, CD2, CD3, and CD4 and the molten sheet were in close contact with each other was 0.2 seconds. A film was obtained. Table 2 shows the physical properties of the obtained film.
- Example 8 A biaxially oriented polypropylene having a thickness of 2.5 ⁇ m was produced in the same manner as in Example 1 except that the time for which the cast drums of CD1, CD2, CD3, and CD4 and the molten sheet were in close contact with each other was 1.0 second. A film was obtained. Table 2 shows the physical properties of the obtained film.
- Example 9 A biaxially oriented polypropylene film having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the temperature of the air temperature of the air knife was turned off to obtain the desired temperature (55 ° C.). Table 2 shows the physical properties of the obtained film.
- Example 10 A biaxially oriented polypropylene film having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the temperature of the atmospheric temperature in the casting process was cut off to obtain the desired temperature (55 ° C.).
- Table 2 shows the physical properties of the obtained film.
- the biaxially oriented polypropylene film of the present invention is provided as a biaxially oriented polypropylene film not only excellent in device processability but also in high temperature withstand voltage characteristics because the surface shape is controlled when used as a capacitor dielectric. can do.
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Abstract
Description
せん断速度(sec-1)=6Q/ρWt2 ・・・(1)
Q:流量(kg/sec)
ρ:比重(kg/cm3)
W:Tダイの溝幅(cm)
t:Tダイの溝間隙(cm)
延伸速度(%/分)=(MDX-1)×100/(L/V) ・・・(2)
MDX:長手方向の延伸倍率(倍)
L:延伸区間(m)
V:延伸後の製膜速度(m/分)
ポリプロピレン樹脂試料を溶媒に溶解し、13C-NMRを用いて、以下の条件にてメソペンタッド分率(mmmm)を求めた(参考文献:新版 高分子分析ハンドブック 社団法人日本分析化学会・高分子分析研究懇談会 編 1995年 P609~611)。
A.測定条件
装置:Bruker社製 DRX-500
測定核:13C核(共鳴周波数:125.8MHz)
測定濃度:10wt%
溶媒:ベンゼン/重オルトジクロロベンゼン=質量比1:3混合溶液
測定温度:130℃
スピン回転数:12Hz
NMR試料管:5mm管
パルス幅:45°(4.5μs)
パルス繰り返し時間:10秒
データポイント:64K
換算回数:10,000回
測定モード:complete decoupling
B.解析条件
LB(ラインブロードニングファクター)を1.0としてフーリエ変換を行い、mmmmピークを21.86ppmとした。WINFITソフト(Bruker社製)を用いて、ピーク分割を行う。その際に、高磁場側のピークから以下のようにピーク分割を行い、さらに付属ソフトの自動フィッティングを行った。ピーク分割の最適化を行った上で、mmmmのピーク分率の合計を求めた。なお、上記測定を5回行い、その平均値を本試料のメソペンタッド分率(mmmm)とした。
ピーク
(a)mrrm
(b)(c)rrrm(2つのピークとして分割)
(d)rrrr
(e)mrmr
(f)mrmm+rmrr
(g)mmrr
(h)rmmr
(i)mmmr
(j)mmmm
JIS K7210(1995)の条件M(230℃、2.16kg)に準拠して測定した。
JIS B-0601(1982)により、株式会社小坂研究所社製非接触三次元微細形状測定器(ET-30HK)、および三次元粗さ分析装置(MODEL SPA-11)を用いて測定した。測定は長手方向に10回繰り返し、その平均値として算術平均粗さSRa、最大谷深さSRv、最大山高さSRpを求めた。1回の測定の詳細条件については下記の通りとした。
A.測定条件
測定面処理:測定面にアルミニウムを真空蒸着し、非接触法とした。
測定方向:フィルムの幅方向
幅方向送り速度:0.1mm/秒
測定範囲(幅方向×長さ方向):1.0mm×0.249mm
高さ方向寸法の基準面:LOWER(下側)
幅方向サンプリング間隔:2μm
長さ方向サンプリング間隔:10μm
長さ方向サンプリング本数:25本
カットオフ:0.25mm/秒
幅方向拡大倍率:200倍
長さ方向拡大倍率:20,000倍
うねり、粗さカット:なし
B.測定方法
フィルム測定には専用のサンプルホルダーを使用する。サンプルホルダーは中心に円形の穴が空いた脱着可能な2枚の金属板であり、その間にサンプルを挟んでサンプルホルダーの四方までフィルムを張って装着することでフィルムを固定し、中央円形部のフィルムにおいて測定を行った。
株式会社菱化システム社製非接触表面・層断面形状測定システムVertScan2.0(型式:R3300GL-Lite-AC)を用いて測定した。測定は任意の箇所において10回繰り返し、その平均値として谷側空隙体積を求めた。1回の測定の詳細条件については下記の通りとした。なお、一回の測定に対して一視野(視野面積は1,252×939μm)の観察を行った。また、一視野当たりの視野面積は、対物レンズの精度によって異なる場合があり、5%以内の誤差が生じる場合がある。
A.測定条件
CCDカメラ:SONY HR-57 1/2
対物レンズ:10X
鏡筒:0.5X BODY
波長フィルター:530 white
測定モード:Wave
視野サイズ:640×480
スキャンレンジ:スタート5μm、ストップ-0.5μm
B.測定方法
フィルム測定には専用のサンプルホルダーを使用する。サンプルホルダーは中心に円形の穴が空いた脱着可能な2枚の金属板であり、その間にサンプルを挟んでサンプルホルダーの四方までフィルムを張って装着することでフィルムを固定し、中央円形部のフィルムについて測定を行った。ついで、得られたデータについて4次多項式近似による面補正を行い、うねり成分を除去した後、補間処理として完全補間を実施した。
C.解析方法
上記により得られた画像データについて、VertScan2.0の画像解析ソフトVS-Viewerの解析ツールであるベアリング機能を用いて解析した。高さ領域指定において、谷側高さ閾値を-50nmに設定(つまり、深さ0.05μm以上の谷側空隙を指定)した後、谷側空隙体積と記載された値を読み取った。また、読み取った値は、有効数字2桁となるように四捨五入した。
JIS K7105(1981)に準じ、スガ試験機株式会社製デジタル変角光沢計UGV-5Dを用いて入射角60°、受光角60°の条件で測定した。なお、本測定を5回行い、その平均値を本発明の二軸配向ポリプロピレンフィルムの光沢度とした。
JIS C2330(2001)の7.4.1.1に準じ、マイクロメーター法厚みを測定した。
JIS C2330(1995)に従い、初期質量W0の二軸配向ポリプロピレンフィルムを白金坩堝に入れ、まずガスバーナーで十分に燃焼させた後、750~800℃の電気炉で1時間処理して完全に灰化し、得られた灰の質量W1を測定し、下記式から算出した。
灰分=(W1/W0)×1,000,000(ppm)
ポリプロピレンフィルム試料5gを135℃のキシレン1,000mlに溶解し、高温に保持したままでろ過を実施した。不溶部を取り出し、135℃のキシレンで十分洗浄した。100℃に昇温した減圧乾燥機内にて12時間静置させた後、重量を測定した(Y(g))。試料5gの精量値(Y0(g))を用いて下記式から算出した。
粒子含有量(質量%)=(Y/Y0)×100
後述する各実施例、および比較例において得られた二軸配向ポリプロピレンフィルムの片面に、株式会社ULVAC社製真空蒸着機でアルミニウムを8Ω/□となるように真空蒸着した。その際、長手方向に走るマージン部を有するストライプ状にアルミニウムを蒸着した(蒸着部の幅39.0mm、マージン部の幅1.0mmの繰り返し)。ついで、各蒸着部の中央と各マージン部の中央に刃を入れてスリットし、左右いずれかの端部に0.5mmのマージン部を有する全幅20mmのテープ状巻取リールを作製した。得られたリールの左マージン、および右マージンのもの各1本ずつを幅方向に蒸着部分がマージン部より0.5mmはみ出すように2枚を重ね合わせて巻回し、静電容量10μFの巻回体を得た。素子巻回には株式会社皆藤製作所社製KAW-4NHBを使用した。
上記コンデンサ製造の際、巻き始めから巻き終わりまでを目視で観察し、シワやずれが発生したものを不合格とし、不合格となったものの数により素子加工性を評価した。なお、コンデンサ素子は50個作製し、下記判断基準により評価した。
○(優良):不良品なし
△(良好):不良品1~2個
×(不可):不良品3個以上
JIS C2330(2001)に準じて、125℃に温調した熱風オーブン中に電極を設置し、二軸配向ポリプロピレンフィルムの絶縁破壊電圧を測定した。なお、本測定を5回行い、その平均値を求め、上記で求めたフィルム厚みで除して1μm当たりの高温絶縁破壊電圧(V/μm)を求めた。高温耐電圧特性は、上記高温絶縁破壊電圧を下記の基準により評価した。
○(優良):450V/μm以上
△(良好):400V/μm以上、450V/μm未満
×(不可):400V/μm未満
A.ポリプロピレン樹脂組成物の製造
無水塩化マグネシウム、デカン、2-エチルヘキシルアルコールを混合し、加熱した溶液に無水フタル酸を添加し、さらに撹拌した。前記溶液を冷却した後、-20℃に冷却した四塩化チタンに滴下した。ついで、前記混合物を昇温し、フタル酸ジイソブチルを加え撹拌した後、ろ過により固体を得た。得られた固体をデカンおよびヘキサンで洗浄し、プロピレン重合に使用するチタン触媒を得た。
上記チタン触媒、および助触媒としてトリエチルアルミニウム、連鎖移動剤として水素を用いてプロピレン重合を行った。得られた生成物は失活した後、プロピレンモノマーで十分に洗浄を行い、ポリプロピレン樹脂を得た。このポリプロピレン樹脂のMFRは2.5g/10分、メソペンタッド分率(mmmm)は0.980であった。
得られたポリプロピレン樹脂99.7質量%に酸化防止剤としてBHTが0.1質量%、同じく酸化防止剤としてIrganox-1010が0.2質量%となるように添加した後、260℃の温度で混練、ペレット化し、ポリプロピレン樹脂組成物を得た。
前記ポリプロピレン樹脂組成物100質量%を単軸の溶融押出機に供給し、250℃で溶融押出を行い、25μmカットの焼結フィルターで異物除去を行った。なお、押出の際のTダイでかかるせん断速度は300sec-1であった。Tダイから吐出された溶融ポリプロピレン樹脂組成物を4つの連続したキャストドラム上に密着させ溶融シートを得た。この際、連続したキャストドラムの径は同じであり、装置上流からCD1、CD2、CD3、CD4とし、キャストシートのそれぞれの面が、それぞれのキャストドラムに交互に接触するようなフィルムパスとした。CD1およびCD2の表面温度は30℃、CD3およびCD4の表面温度は90℃であった。また、CD1、CD2、CD3、CD4のそれぞれのキャストドラムと溶融シートが密着していた時間はそれぞれ0.4秒であった。シートを最初のキャストドラムであるCD1上に密着させるためにエアーナイフおよび端部スポットエアーを用いた。この際、エアーナイフのエアー温度は30℃になるように温度調整した。さらに、キャスト工程の雰囲気温度も30℃に温度調整した。ついで、加熱したロールを用いてキャストシートを予熱し、フィルム温度が145℃になるように加熱した後、長手方向に5.5倍延伸した。この際の長手方向の延伸速度は2,000,000%/分であり、ネックダウン率は98%であった。次に端部をクリップで把持して155℃で幅方向に延伸速度30,000%/分で10倍延伸した。さらに、158℃で7秒間の熱処理を行い、幅方向に12%の弛緩を行った。その後、室温まで除冷した後にフィルムの片面に25W・min/m2の処理強度でコロナ放電処理を施し、クリップで把持したフィルムの耳部をカットして除去した。なお、CD1に接した面であり、コロナ放電処理した面をA面、もう片方のCD2に接した面であり、コロナ放電未処理面をB面とした。端部を除去したフィルムを巻取機で巻取り、厚み2.5μmの二軸配向ポリプロピレンフィルムを得た。得られたフィルムの物性を表1に示す。
CD1およびCD2の表面温度を45℃とした以外は実施例1と同様に作製し、厚み2.5μmの二軸配向ポリプロピレンフィルムを得た。得られたフィルムの物性を表1に示す。
CD1およびCD2の表面温度を50℃とした以外は実施例1と同様に作製し、厚み2.5μmの二軸配向ポリプロピレンフィルムを得た。得られたフィルムの物性を表1に示す。
CD1およびCD2の表面温度を25℃とした以外は実施例1と同様に作製し、厚み2.5μmの二軸配向ポリプロピレンフィルムを得た。得られたフィルムの物性を表1に示す。
CD3およびCD4の表面温度を70℃とした以外は実施例1と同様に作製し、厚み2.5μmの二軸配向ポリプロピレンフィルムを得た。得られたフィルムの物性を表1に示す。
CD3およびCD4の表面温度を50℃とした以外は実施例1と同様に作製し、厚み2.5μmの二軸配向ポリプロピレンフィルムを得た。得られたフィルムの物性を表1に示す。
CD3およびCD4の表面温度を100℃とした以外は実施例1と同様に作製し、厚み2.5μmの二軸配向ポリプロピレンフィルムを得た。得られたフィルムの物性を表1に示す。
CD1、CD2、CD3、CD4のそれぞれのキャストドラムと溶融シートが密着していた時間がそれぞれ0.3秒であった以外は実施例1と同様に作製し、厚み2.5μmの二軸配向ポリプロピレンフィルムを得た。得られたフィルムの物性を表1に示す。
CD1、CD2、CD3、CD4のそれぞれのキャストドラムと溶融シートが密着していた時間がそれぞれ0.7秒であった以外は実施例1と同様に作製し、厚み2.5μmの二軸配向ポリプロピレンフィルムを得た。得られたフィルムの物性を表1に示す。
CD1、CD2、CD3、CD4のそれぞれのキャストドラムと溶融シートが密着していた時間がそれぞれ0.8秒であった以外は実施例1と同様に作製し、厚み2.5μmの二軸配向ポリプロピレンフィルムを得た。得られたフィルムの物性を表1に示す。
エアーナイフのエアー温度を50℃とした以外は実施例1と同様に作製し、厚み2.5μmの二軸配向ポリプロピレンフィルムを得た。得られたフィルムの物性を表1に示す。
キャスト工程の雰囲気温度を50℃とした以外は実施例1と同様に作製し、厚み2.5μmの二軸配向ポリプロピレンフィルムを得た。得られたフィルムの物性を表1に示す。
CD1およびCD2の表面温度を40℃とした以外は実施例1と同様に作製し、厚み2.5μmの二軸配向ポリプロピレンフィルムを得た。得られたフィルムの物性を表1に示す。
CD1、CD2、CD3、CD4のそれぞれのキャストドラムと溶融シートが密着していた時間がそれぞれ0.6秒であった以外は実施例1と同様に作製し、厚み2.5μmの二軸配向ポリプロピレンフィルムを得た。得られたフィルムの物性を表1に示す。
キャストドラムの数を1つにして、キャストシートの片面のみが表面温度が30℃のキャストドラムに接触するようにし、キャストドラムと溶融シートが密着していた時間が1.6秒であった以外は実施例1と同様に作製し、厚み2.5μmの二軸配向ポリプロピレンフィルムを得た。なお、キャストドラムに接した面であり、コロナ放電処理した面をA面、もう片方のキャストドラムに接しておらず、コロナ放電未処理面をB面とした。得られたフィルムの物性を表2に示す。
実施例1に記載のポリプロピレン樹脂組成物99.5質量%と、株式会社トクヤマ社製ゾルゲル法シリカ粒子(平均粒子径0.3μm)0.5質量%を単軸の溶融押出機に供給した以外は比較例1と同様に作製し、厚み2.5μmの二軸配向ポリプロピレンフィルムを得た。得られたフィルムの物性を表2に示す。
キャストドラムの数を2つにして、キャストシートの片面と他方の面が2つのキャストドラムに対して交互に接触するようにし、1つ目のキャストドラムの表面温度を30℃、2つ目のキャストドラムの表面温度を95℃とし、その際それぞれのキャストドラムと溶融シートが密着していた時間がそれぞれ0.8秒であった以外は実施例1と同様に作製し、厚み2.5μmの二軸配向ポリプロピレンフィルムを得た。なお、1つ目のキャストドラムに接した面であり、コロナ放電処理した面をA面、もう片方の2つ目のキャストドラムに接した面であり、コロナ放電未処理面をB面とした。得られたフィルムの物性を表2に示す。
CD1およびCD2の表面温度を55℃とした以外は実施例1と同様に作製し、厚み2.5μmの二軸配向ポリプロピレンフィルムを得た。得られたフィルムの物性を表2に示す。
CD3およびCD4の表面温度を45℃とした以外は実施例1と同様に作製し、厚み2.5μmの二軸配向ポリプロピレンフィルムを得た。得られたフィルムの物性を表2に示す。
CD3およびCD4の表面温度を105℃とした以外は実施例1と同様に作製し、厚み2.5μmの二軸配向ポリプロピレンフィルムを得た。得られたフィルムの物性を表2に示す。
CD1、CD2、CD3、CD4のそれぞれのキャストドラムと溶融シートが密着していた時間がそれぞれ0.2秒であった以外は実施例1と同様に作製し、厚み2.5μmの二軸配向ポリプロピレンフィルムを得た。得られたフィルムの物性を表2に示す。
CD1、CD2、CD3、CD4のそれぞれのキャストドラムと溶融シートが密着していた時間がそれぞれ1.0秒であった以外は実施例1と同様に作製し、厚み2.5μmの二軸配向ポリプロピレンフィルムを得た。得られたフィルムの物性を表2に示す。
エアーナイフのエアー温度の温調を切り、成り行きの温度(55℃)とした以外は実施例1と同様に作製し、厚み2.5μmの二軸配向ポリプロピレンフィルムを得た。得られたフィルムの物性を表2に示す。
キャスト工程の雰囲気温度の温調を切り、成り行きの温度(55℃)とした以外は実施例1と同様に作製し、厚み2.5μmの二軸配向ポリプロピレンフィルムを得た。得られたフィルムの物性を表2に示す。
Claims (9)
- ポリプロピレン樹脂を主成分とする二軸配向ポリプロピレンフィルムであって、少なくとも片面の算術平均粗さSRaが0.03~0.10μmであり、少なくとも片面の最大谷深さSRvが0.10~0.50μmであり、かつ、少なくとも片面において、非接触表面形状測定による1,252×939μmの範囲の視野面積中に存在する、深さ0.05μm以上の谷側空隙体積が100~10,000μm3である二軸配向ポリプロピレンフィルム。
- 少なくとも片面の最大山高さSRpが0.30~1.0μmである、請求項1に記載の二軸配向ポリプロピレンフィルム。
- 少なくとも片面の最大谷深さSRvと最大山高さSRpの比SRp/SRvが2.0以上である、請求項1または2に記載の二軸配向ポリプロピレンフィルム。
- フィルム厚みtと少なくとも片面の最大谷深さSRvの比SRv/tが0.30以下である、請求項1~3のいずれかに記載の二軸配向ポリプロピレンフィルム。
- 灰分が50ppm以下である、請求項1~4のいずれかに記載の二軸配向ポリプロピレンフィルム。
- 無機および/または有機粒子の総含有量が1質量%以下である、請求項1~5のいずれかに記載の二軸配向ポリプロピレンフィルム。
- コンデンサ用誘電体として用いられる、請求項1~6のいずれかに記載の二軸配向ポリプロピレンフィルム。
- 請求項1~7のいずれかに記載の二軸配向ポリプロピレンフィルムの少なくとも片面に金属膜を形成してなる金属膜積層フィルム。
- 請求項8に記載の金属膜積層フィルムを巻回してなるフィルムコンデンサ。
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| EP16861821.3A EP3372382B1 (en) | 2015-11-05 | 2016-08-05 | Biaxially oriented polypropylene film, multilayered film including metal film, and film capacitor |
| KR1020187010301A KR102526922B1 (ko) | 2015-11-05 | 2016-08-05 | 2축 배향 폴리프로필렌 필름, 금속막 적층 필름 및 필름 콘덴서 |
| CN201680061876.4A CN108349153B (zh) | 2015-11-05 | 2016-08-05 | 双轴取向聚丙烯膜、金属膜层叠膜和膜电容器 |
| JP2016558166A JP6115687B1 (ja) | 2015-11-05 | 2016-08-05 | 二軸配向ポリプロピレンフィルム、金属膜積層フィルムおよびフィルムコンデンサ |
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| JP7218618B2 (ja) | 2018-03-29 | 2023-02-07 | 東レ株式会社 | 二軸配向ポリプロピレンフィルム、金属膜積層フィルムおよびフィルムコンデンサ |
| JP6753540B1 (ja) * | 2018-10-05 | 2020-09-09 | 東レ株式会社 | ポリオレフィンフィルム、および離型用フィルム |
| JP2020203486A (ja) * | 2018-10-05 | 2020-12-24 | 東レ株式会社 | ポリオレフィンフィルム、および離型用フィルム |
| WO2020071291A1 (ja) * | 2018-10-05 | 2020-04-09 | 東レ株式会社 | ポリオレフィンフィルム、および離型用フィルム |
| JPWO2021112100A1 (ja) * | 2019-12-02 | 2021-06-10 | ||
| WO2021112100A1 (ja) * | 2019-12-02 | 2021-06-10 | 京セラ株式会社 | 金属化フィルムおよびこれを用いたフィルムコンデンサ |
| EP4289615A4 (en) * | 2021-03-23 | 2024-07-31 | JFE Steel Corporation | FILM LAMINATED METAL SHEET, METHOD FOR MANUFACTURING SAME, FLEXIBLE ELECTRONICS SUBSTRATE AND ORGANIC EL SUBSTRATE |
| JP7344413B1 (ja) | 2022-12-21 | 2023-09-13 | フタムラ化学株式会社 | ポリプロピレンフィルム及び蒸着フィルム並びに積層フィルム |
| JP2024089609A (ja) * | 2022-12-21 | 2024-07-03 | フタムラ化学株式会社 | ポリプロピレンフィルム及び蒸着フィルム並びに積層フィルム |
| JP7667367B1 (ja) * | 2024-10-04 | 2025-04-22 | フタムラ化学株式会社 | ポリプロピレンフィルム及び蒸着ポリプロピレンフィルム並びに積層フィルム |
| WO2026074752A1 (ja) * | 2024-10-04 | 2026-04-09 | フタムラ化学株式会社 | ポリプロピレンフィルム及び蒸着ポリプロピレンフィルム並びに積層フィルム |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6115687B1 (ja) | 2017-04-19 |
| CN108349153A (zh) | 2018-07-31 |
| EP3372382B1 (en) | 2021-06-16 |
| KR20180080191A (ko) | 2018-07-11 |
| KR102526922B1 (ko) | 2023-04-28 |
| JPWO2017077752A1 (ja) | 2017-11-02 |
| EP3372382A1 (en) | 2018-09-12 |
| CN108349153B (zh) | 2020-04-03 |
| EP3372382A4 (en) | 2019-06-12 |
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