WO2010107052A1 - フィルムコンデンサ用ポリプロピレン、フィルムコンデンサ用ポリプロピレンシート、それらの製造方法、およびその用途 - Google Patents
フィルムコンデンサ用ポリプロピレン、フィルムコンデンサ用ポリプロピレンシート、それらの製造方法、およびその用途 Download PDFInfo
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- WO2010107052A1 WO2010107052A1 PCT/JP2010/054519 JP2010054519W WO2010107052A1 WO 2010107052 A1 WO2010107052 A1 WO 2010107052A1 JP 2010054519 W JP2010054519 W JP 2010054519W WO 2010107052 A1 WO2010107052 A1 WO 2010107052A1
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- WIPO (PCT)
- Prior art keywords
- film
- polypropylene
- film capacitor
- propylene homopolymer
- sheet
- Prior art date
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- -1 Polypropylene Polymers 0.000 title claims abstract description 124
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 119
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- 238000000034 method Methods 0.000 title claims description 17
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
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- 241001315609 Pittosporum crassifolium Species 0.000 description 6
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- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
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- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 4
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- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
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- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
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- 125000004386 diacrylate group Chemical group 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
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- MPJPKEMZYOAIRN-UHFFFAOYSA-N 1,3,5-tris(2-methylprop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound CC(=C)CN1C(=O)N(CC(C)=C)C(=O)N(CC(C)=C)C1=O MPJPKEMZYOAIRN-UHFFFAOYSA-N 0.000 description 2
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 2
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- FQMIAEWUVYWVNB-UHFFFAOYSA-N 3-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OC(C)CCOC(=O)C=C FQMIAEWUVYWVNB-UHFFFAOYSA-N 0.000 description 2
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
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- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
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- GIYLECFPSJNUDC-UHFFFAOYSA-N (2,3-diethoxy-4-propylphenyl) 2-methylprop-2-enoate Chemical compound CCCC1=CC=C(OC(=O)C(C)=C)C(OCC)=C1OCC GIYLECFPSJNUDC-UHFFFAOYSA-N 0.000 description 1
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- SWHLOXLFJPTYTL-UHFFFAOYSA-N [2-methyl-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(COC(=O)C(C)=C)COC(=O)C(C)=C SWHLOXLFJPTYTL-UHFFFAOYSA-N 0.000 description 1
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- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to polypropylene for film capacitors, polypropylene sheets for film capacitors, polypropylene films for film capacitors, and film capacitors. More specifically, the present invention relates to a polypropylene for a film capacitor or a polypropylene sheet for a film capacitor suitable for a polypropylene film for a film capacitor having excellent stretchability when the film is stretched and having a high dielectric breakdown voltage and a low thermal shrinkage.
- Polypropylene is widely used as a film for film capacitors because it has excellent stretching properties, insulation properties, and voltage resistance.
- the demand for film capacitors is increasing mainly in the fields of automobiles and home appliances, and there is a demand for further miniaturization. Therefore, there is a demand for further improvement in dielectric breakdown voltage with respect to the films used.
- a film for a film capacitor for example, a film made of a composition mainly composed of highly stereoregular polypropylene (Patent Document 1), ash contained in polypropylene is 40 ppm by weight or less, and chlorine is 2 ppm by weight or less.
- High stereoregularity of polymer insulating material Patent Document 2
- a film made of propylene polymer having an aluminum residual content of less than 25 ppm and a boron residual content of less than 25 ppm Patent Document 3
- a polypropylene having a long chain branch as a masterbatch A film obtained by adding to polypropylene and biaxially stretching (Patent Document 4) is disclosed.
- a film for a film capacitor is disclosed in which the polypropylene film is irradiated with ultraviolet rays or an electron beam, and the thermal shrinkage in the longitudinal direction of the film is regulated within a specific range.
- the polypropylene used in the examples has a stereoregularity of about 91%, when such a stereoregularity of about 91% is used, “wrinkles” are generated using this method. Even if suppressed, a film capacitor having a sufficient dielectric breakdown voltage cannot be obtained.
- JP 61-110906 A JP-A-6-236709 Special table 2009-500479 JP 2006-93688 A JP 54-109160 A
- the present invention is intended to solve the problems associated with the prior art as described above, and is excellent in stretchability when stretching a film. Further, the dielectric breakdown voltage (BDV) of the resulting film (hereinafter referred to as BDV) is obtained. It is an object of the present invention to provide a polypropylene film for a film capacitor or a polypropylene sheet for a film capacitor, which is suitable for a film capacitor including a film capacitor and a film capacitor including the film.
- specific propylene homopolymers for example, powders, granules or pellets
- radiation preferably electron beams or gamma rays
- a sheet obtained from polypropylene for a film capacitor obtained by irradiating an electron beam or a specific propylene homopolymer is irradiated with radiation, preferably an electron beam or a gamma ray, more preferably an electron beam at a specific absorbed dose.
- the polypropylene sheet for film capacitors obtained by irradiating is excellent in stretchability when stretching a film, and the polypropylene film for film capacitors obtained by biaxial stretching of polypropylene for film capacitors or polypropylene sheet for film capacitors is , Insulation breakdown Pressure is high, the thermal shrinkage rate is small and found to be suitable for a film capacitor, thereby completing the present invention.
- the present invention includes the following matters.
- the polypropylene for a film capacitor of the present invention has (1) a melt flow rate (MFR) measured at 230 ° C. and a 2.16 kg load in the range of 1 to 10 g / 10 min in accordance with ASTM D1238, 2)
- MFR melt flow rate
- the pentad isotactic fraction (mmmm fraction) measured using 13 C-NMR is 94% or more
- the ash content obtained by complete combustion in air is 30 ppm or less.
- a propylene homopolymer having a chlorine content of 10 ppm or less measured by ion chromatography is irradiated with an absorbed dose of 0.1 to 500 kGy.
- the polypropylene sheet for a film capacitor of the present invention has (1) a melt flow rate (MFR) measured at 230 ° C. and a 2.16 kg load in the range of 1 to 10 g / 10 min in accordance with ASTM D1238. Yes, (2) The pentad isotactic fraction (mmmm fraction) measured using 13 C-NMR is 94% or more, and (3) the amount of ash obtained by complete combustion in air. 30) or less, and (4) a sheet obtained from a propylene homopolymer having a chlorine content measured by ion chromatography of 10 ppm or less, which is irradiated with an absorbed dose of 0.1 to 500 kGy. And
- the method for producing polypropylene for a film capacitor of the present invention is as follows: (1) Melt flow rate (MFR) measured at 230 ° C. and 2.16 kg load is in the range of 1 to 10 g / 10 min in accordance with ASTM D1238. Yes, (2) The pentad isotactic fraction (mmmm fraction) measured using 13 C-NMR is 94% or more, and (3) the amount of ash obtained by complete combustion in air.
- the propylene homopolymer having a chlorine content of 10 ppm or less as measured by ion chromatography is irradiated with an absorbed dose of 0.1 to 500 kGy.
- the method for producing a polypropylene sheet for a film capacitor of the present invention is as follows: (1) Melt flow rate (MFR) measured at 230 ° C. under a 2.16 kg load in accordance with ASTM D1238 is in the range of 1 to 10 g / 10 min. (2) The pentad isotactic fraction (mmmm fraction) measured using 13 C-NMR is 94% or more, and (3) the amount of ash obtained by complete combustion in air. (4) A sheet obtained from a propylene homopolymer having a chlorine content measured by ion chromatography of 10 ppm or less is irradiated with an absorbed dose of 0.1 to 500 kGy.
- the method for producing a polypropylene film for a film capacitor of the present invention is as follows: (1) Melt flow rate (MFR) measured at 230 ° C. under a 2.16 kg load in accordance with ASTM D1238 is in the range of 1 to 10 g / 10 min. (2) The pentad isotactic fraction (mmmm fraction) measured using 13 C-NMR is 94% or more, and (3) the amount of ash obtained by complete combustion in air.
- a step (I) of producing a propylene homopolymer having a chlorine content of 10 ppm or less measured by ion chromatography Then, the process (II) which manufactures a sheet
- the propylene homopolymer obtained in the step (I) or the sheet obtained in the step (II) includes a step of irradiating with an electron beam at an absorbed dose of 0.1 to 500 kGy.
- the radiation is preferably an electron beam or a gamma ray.
- the crosslinking agent is added in an amount of 0.01 to 10% by weight based on 100% by weight of the propylene homopolymer.
- the absorbed dose of radiation is 1 to 300 KGy.
- the propylene homopolymer is any of powder, granule, and pellet.
- the polypropylene sheet for a film capacitor of the present invention is preferably obtained from the polypropylene for a film capacitor.
- the polypropylene film for film capacitors of the present invention is obtained by biaxially stretching the polypropylene sheet for film capacitors.
- the film capacitor of the present invention includes the polypropylene film for a film capacitor.
- the polypropylene film for a film capacitor obtained from the polypropylene for a film capacitor or the polypropylene sheet for a film capacitor of the present invention has a small thermal shrinkage, a high dielectric breakdown voltage, and excellent stretchability, so that a thin film can be obtained. Therefore, it is possible to provide a small-sized and large-capacity capacitor, which can greatly contribute to, for example, higher output, smaller size, and lighter weight of a hybrid vehicle.
- the propylene homopolymer as a raw material for the film capacitor polypropylene or the film capacitor polypropylene sheet of the present invention satisfies the following requirements (1) to (4). Further, it is more preferable to satisfy the following requirements (1) to (6) because the moldability is improved and the withstand voltage is improved.
- the melt flow rate (MFR) measured at 230 ° C. under a 2.16 kg load is 1 to 10 g / 10 minutes, preferably 2 to 5 g / 10 minutes, in accordance with ASTM D1238. If the MFR is less than 1 g / 10 min, the film formability is inferior and stretching is not easy, and if it exceeds 10 g / 10 min, breakage may occur during stretching of the film, which is not preferable. This is considered to be caused by a lack of melt tension.
- the pentad isotactic fraction (mmmm fraction) measured using 13 C-NMR is 94% or more, preferably 96% or more, more preferably 98% or more.
- the pentad isotactic fraction (mmmm fraction) of the polypropylene homopolymer is less than 94%, a polypropylene film for a film capacitor having a high dielectric breakdown voltage even when irradiated with radiation, and a film capacitor including the film are provided. I can't get it. This is presumed to be due to the fact that there are many amorphous parts that easily conduct electricity because the pentad isotactic fraction is low.
- the upper limit of the pentad isotactic fraction is not particularly limited, but is usually 99.5% or less.
- the amount of ash obtained by complete combustion in air is 30 ppm or less, preferably 25 ppm or less, more preferably 20 ppm or less.
- a polypropylene film for a film capacitor having a high dielectric breakdown voltage cannot be obtained. This is presumed to be due to the fact that voids tend to form when there is a large amount of ash, thus affecting the breakdown voltage.
- the amount of chlorine measured by ion chromatography is 10 ppm or less, preferably 5 ppm or less, more preferably 2 ppm or less.
- the amount of chlorine exceeds 10 ppm, a polypropylene film for a film capacitor having a high dielectric breakdown voltage cannot be obtained. This is presumed to be because chlorine becomes hydrochloric acid and gradually destroys polypropylene, affecting the breakdown voltage during long-term use.
- the melting point (Tm) obtained by differential scanning calorimeter (DSC) measurement is 155 ° C. or higher, preferably 160 ° C. or higher, more preferably 163 ° C. or higher.
- the upper limit of Tm is not particularly limited, but is usually 170 ° C. or lower.
- the molecular weight distribution Mw / Mn (Mw: weight average molecular weight, Mn: number average molecular weight) measured by gel permeation chromatography (GPC) is 4.0 or more, preferably 4.5 to 9.0. More preferably, it is 4.5 to 7.5. It is preferable for the molecular weight distribution Mw / Mn to be in the above range because of excellent film moldability and stretchability.
- the propylene homopolymer according to the present invention can be produced by a propylene polymerization method using a known propylene polymerization catalyst, and among them, a production method using a supported titanium catalyst is preferred.
- the supported titanium catalyst includes, for example, a solid titanium catalyst component containing titanium, magnesium, halogen and an internally added electron donating compound, and a metal selected from Groups I, II, and III of the periodic table.
- a polymerization catalyst comprising an organometallic compound and an externally added electron donating compound is preferably used.
- a catalyst used for industrially producing a propylene polymer containing polypropylene is used.
- a material in which titanium trichloride or titanium tetrachloride is supported on a support such as magnesium halide and an organoaluminum compound are used.
- a catalyst that is highly active and has a low titanium component is particularly preferable.
- the propylene homopolymer according to the present invention is used for a film capacitor application, when the amount of polymer produced per unit amount of the catalyst is small, it is necessary to perform post-treatment to remove the catalyst residue. Further, even when the amount of polymer produced is large due to the high activity of the catalyst, it is preferable to carry out post-treatment to remove the catalyst residue.
- the post-treatment method include a method of washing a propylene homopolymer obtained by polymerization with liquid propylene, butane, hexane, heptane or the like.
- water, alcohol compounds, ketone compounds, ether compounds, ester compounds, amine compounds, organic acid compounds or inorganic acid compounds may be added to solubilize and easily extract catalyst components such as titanium and magnesium. Good. It is also preferable to wash with a polar compound such as water or alcohol.
- the propylene homopolymer obtained by the above polymerization is preferably dehalogenated.
- dehalogenation treatment using an epoxy compound is preferable.
- the epoxy compound for example, alkoxy oxides such as ethylene oxide, propylene oxide, butene oxide or cyclohexene oxide, glycidyl alcohol, glycidyl acid or glycidyl ester are preferably used.
- a dechlorination treatment of a propylene homopolymer using these epoxy compounds it is very effective to use a compound having an hydroxyl group (OH group) of equimolar or more with the epoxy compound.
- the compound having an OH group include water and alcohol.
- the propylene homopolymer used in the present invention is obtained by polymerizing propylene in the presence or absence of hydrogen in the presence of a supported titanium catalyst, so that the propylene homopolymer part has two or more stages. It can be produced by multistage polymerization. Moreover, when producing a propylene homopolymer, preliminary polymerization can be carried out in advance.
- the polymerization conditions are a polymerization temperature in the range of about ⁇ 50 to + 200 ° C., preferably about 20 to 100 ° C., and a polymerization pressure of normal pressure to 9.8 MPa (gauge pressure), preferably about 0.2 to 4.9 MPa. It is appropriately selected within the range of (gauge pressure).
- a polymerization pressure of normal pressure to 9.8 MPa (gauge pressure), preferably about 0.2 to 4.9 MPa. It is appropriately selected within the range of (gauge pressure).
- gauge pressure normal pressure
- liquid propylene may be used as the polymerization medium.
- the method for adjusting the molecular weight is not particularly limited, but a method using hydrogen as the molecular weight adjusting agent is preferred.
- the propylene homopolymer according to the present invention may be in the form of powder, granules or pellets.
- the powder and granule are obtained from a propylene homopolymer, and the pellet is obtained by granulating the powder and granule.
- the sheet according to the present invention can be obtained by a known method, for example, melt extrusion molding or press molding of powder, granules and pellets.
- the propylene homopolymer according to the present invention is a powder, granule or pellet
- the average particle size is, for example, about 50 to 150 ⁇ m and is a granule.
- the average particle diameter is usually about 150 to 2000 ⁇ m, for example, and it is not particularly limited as long as it is a pellet, but usually the average particle diameter is about 2 to 10 mm and the height is about 1 to 5 mm. It is.
- the thickness of the sheet according to the present invention is not particularly limited, but is usually preferably about 80 to 800 ⁇ m, and more preferably about 120 to 500 ⁇ m. When the thickness of the sheet is less than 80 ⁇ m, the sheet may be broken at the time of stretching, and when it exceeds 800 ⁇ m, a thin film cannot be obtained, which may not be suitable for a film capacitor.
- the polypropylene for a film capacitor according to the present invention has an absorption dose of 0.1 to 500 kGy, preferably 1 to 300 kGy, more preferably 1 to 1 to radiation, preferably an electron beam or a gamma ray, more preferably an electron beam. It is obtained by irradiating with 100 kGy.
- the absorbed dose of radiation is less than 0.1 kGy, the effect of irradiation cannot be obtained, so that it is not possible to obtain polypropylene for a film capacitor having excellent stretchability when stretching a film, and a high dielectric breakdown voltage.
- ⁇ rays, ⁇ rays, ⁇ rays, X rays, electron rays, positron rays, and the like preferably electron rays or gamma rays, and more preferably electron rays.
- gamma radiation sources include 60 Co and 137 Cs.
- the absorbed dose (kGy) of the electron beam is a value calculated by the product of the acceleration voltage, current, and irradiation time of the electron beam irradiation apparatus. Further, the absorbed dose (kGy) of gamma rays can be measured with an alanine dosimeter, a PMMA (Polymethylmethacrylate) dosimeter, or the like, specifically, using a Harwell ⁇ Red 4034 Perspex Dosimeter. In addition, the absorbed dose of radiation is a total amount, which may be irradiated only once or a plurality of times, and may be a total amount using a plurality of types of lines, but preferably only with an electron beam. It is to irradiate. Moreover, the irradiation condition of a radiation will not be specifically limited if a predetermined absorbed dose is irradiated.
- powder, granules or pellets are irradiated with radiation, preferably electron beams or gamma rays, more preferably electron beams with an absorbed dose of 0.1 to 500 kGy, preferably with improved breakdown voltage, irradiation. It is also possible to obtain an absorbed dose of 1 to 100 kGy because of the resin deterioration due to the above.
- the powder, granule or pellet with radiation it is preferable to arrange the powder, granule or pellet so as not to overlap each other. Irradiation to the pellet may be performed on any surface, and may be performed on only one surface, both surfaces, or the side surface.
- the polypropylene sheet for a film capacitor of the present invention has an absorption dose of 0.1 to 500 kGy, preferably 1 to the sheet obtained from the propylene homopolymer according to the present invention, with radiation, preferably electron beam or gamma ray, more preferably electron beam. It can be obtained by irradiating with ⁇ 300 kGy, more preferably 1-100 kGy. The reason for the upper and lower limits of the radiation absorbed dose is the same as described above. Irradiation to the sheet according to the present invention may be performed on any surface, and may be performed on only one surface or both surfaces. When the shape is a sheet, radiation can be more uniformly applied at a low output voltage, and a polypropylene film for a film capacitor having a uniform breakdown voltage (non-uniformity) can be obtained. Therefore, it is preferable.
- the propylene homopolymer or a sheet obtained from the propylene homopolymer according to the present invention is irradiated with radiation, preferably an electron beam, at a desired absorbed dose
- radiation preferably an electron beam
- the propylene homopolymer or molecules in the amorphous part of the sheet are crosslinked.
- the entanglement between the molecules increases and the molecules do not move easily, so that the passage of electrons is blocked. Therefore, it is estimated that the dielectric breakdown voltage of the obtained polypropylene film for film capacitors is remarkably improved.
- radiation preferably electron beam irradiation, cuts a part of the molecules in the amorphous part at the same time as the cross-linking, so that the fluidity during stretching is improved and the stretching orientation after spherulite collapse is promoted. It is estimated that the stretchability of the polypropylene film for film capacitors is improved.
- the polypropylene for a film capacitor or the polypropylene sheet for a film capacitor of the present invention is obtained by adding a crosslinking agent to the propylene homopolymer before irradiating with radiation, preferably an electron beam or a gamma ray, more preferably an electron beam. Kneading and cross-linking the propylene homopolymer is preferable because a polypropylene film for a film capacitor having a higher dielectric breakdown voltage can be obtained.
- the molecular dose of the propylene homopolymer is reduced by being cross-linked with a cross-linking agent, so that the absorbed dose can be increased to a point where the effect of the dielectric breakdown voltage is more manifested.
- the absorbed dose can be 0.1 to 500 kGy, preferably 10 to 300 kGy, and if it is a sheet, the absorbed dose is 0.1 to 500 kGy, preferably 10 to It can be 300 kGy.
- the addition amount of the crosslinking agent is not particularly limited, but is 0.01 to 10% by weight, preferably 0.5 to 5% by weight with respect to 100% by weight of the propylene homopolymer. If the amount of the crosslinking agent is less than 0.01% by weight, the effect of adding the crosslinking agent may not be obtained so much. If it exceeds 10% by weight, it may be difficult to form a propylene homopolymer containing a crosslinking agent.
- the crosslinking agent is preferably a crosslinkable monomer having two or more polymerizable double bonds.
- crosslinkable monomers examples include polyethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,6-butylene glycol diacrylate, 1,4-butanediol diacrylate. 1,6-hexanediol diacrylate, 1,6-hexaneglycol diacrylate, neopentyl glycol diacrylate, 1,9-nonanediol diacrylate, polypropylene glycol diacrylate, 2,2′-bis (4-acryloxy) Diacrylate compounds such as propyloxyphenyl) propane and 2,2′-bis (4-acryloxydiethoxyphenyl) propane; Triacrylate compounds such as trimethylolpropane triacrylate, trimethylolethane triacrylate, tetramethylolmethane triacrylate, Tetraacrylate compounds such as ditrimethylol tetraacrylate, tetramethylol methane tetraacrylate, pentaery
- the propylene homopolymer used as the raw material for the film capacitor polypropylene or the film capacitor polypropylene sheet of the present invention is a weather resistant stabilizer, heat stabilizer, antistatic agent, anti-slip agent, anti-antioxidant, as long as the object of the invention is not impaired. It may be obtained by adding additives such as blocking agents, antifogging agents, nucleating agents, lubricants, pigments, dyes, plasticizers, anti-aging agents, hydrochloric acid absorbents and antioxidants.
- the polypropylene film for a film capacitor of the present invention is formed by stretching the polypropylene for a film capacitor or the polypropylene sheet for a film capacitor of the present invention, has a high dielectric breakdown voltage, and has a low thermal shrinkage rate. Moreover, since the polypropylene for film capacitors or the polypropylene sheet for film capacitors of the present invention is excellent in stretchability, the resulting polypropylene film for film capacitors can be made into a thin film.
- the polypropylene sheet for a film capacitor of the present invention is uniformly irradiated with radiation, preferably an electron beam or a gamma ray, and more preferably an electron beam. No) Since a polypropylene film for a film capacitor can be obtained, it is preferable from the viewpoint of productivity and economy.
- the polypropylene film for a film capacitor of the present invention has a higher dielectric breakdown voltage and excellent stretchability than conventional polypropylene films. Therefore, sufficient performance can be exhibited for a small-sized large-capacitance capacitor, and for example, it can greatly contribute to increase in output and weight of a hybrid vehicle.
- the polypropylene film for a film capacitor of the present invention is cut into a length of 10 mm and a length of 100 mm in the resin flow direction (MD direction), put in a 120 ° C. hot air oven, heated for 15 minutes, and contracted to the original length.
- the thermal shrinkage rate (%) when calculated by the ratio of the length is -2.0 to + 2.0%, preferably -1.5 to + 1.5%. If the thermal shrinkage rate is lower, there is a possibility that the tightening is insufficient and it is difficult to maintain the shape, or that voids are generated and the device is deteriorated. When the thermal shrinkage rate is exceeded, the element is deformed, and a gap due to the deformation is generated, and the element may be deteriorated or further destroyed.
- the thickness of the polypropylene film according to the present invention is preferably 1 to 20 ⁇ m, more preferably 1 to 15 ⁇ m, still more preferably 2 to 8 ⁇ m, and particularly preferably 2 to 4 ⁇ m.
- a polypropylene film having a thickness in the above range (preferably 8 ⁇ m or less, particularly preferably 4 ⁇ m or less) exhibits better electrical characteristics (dielectric breakdown voltage) than when a conventionally known material is used. Films with a thickness below the above range may be difficult to mold with current technology, and when a film with a thickness above the above range is used, the film capacitor becomes large and the current capacitor is downsized. May not be able to meet the demands for.
- the polypropylene film for a film capacitor according to the present invention may be added to the polypropylene for a film capacitor according to the present invention, if necessary, with various antioxidants (Irganox 1010, BHT (dibutylhydroxytoluene), Irgaphos 168, etc.), calcium stearate and the like. While adding additives, melt extrusion in the range of 180 to 280 ° C., and, for example, in the case of uniaxial stretching, the obtained raw sheet is 2 to 10 times at 100 to 160 ° C. (preparing the original sheet) In the biaxial stretching, the film obtained by the uniaxial stretching is further machined under the same conditions as the uniaxial stretching.
- antioxidants Irganox 1010, BHT (dibutylhydroxytoluene), Irgaphos 168, etc.
- the polypropylene film for film capacitors of the present invention is prepared by adding various antioxidants (Irganox 1010, BHT (dibutylhydroxytoluene), Irgaphos 168, etc.), calcium stearate to the propylene homopolymer according to the present invention as necessary.
- various antioxidants Irganox 1010, BHT (dibutylhydroxytoluene), Irgaphos 168, etc.
- calcium stearate to the propylene homopolymer according to the present invention as necessary.
- the obtained raw sheet is irradiated with radiation at a desired absorbed dose, the polypropylene sheet for film capacitor obtained continuously, It can also be produced using uniaxial stretching or biaxial stretching described in 1.
- a polypropylene film for a film capacitor can be obtained by various known simultaneous biaxial or sequential biaxial stretching methods such as a tubular film method and a tenter method.
- the molten sheet melt-extruded from the T-die is solidified with a cooling roll, preheated if necessary, and then introduced into the stretching zone, and then 3 to 7 times in the machine direction at a temperature of 100 to 160 ° C. Stretched 5 to 11 times in the transverse direction.
- the total stretched surface magnification is 20 to 70 times, preferably 30 to 50 times. If it is less than 20 times, the film strength does not increase, and if it exceeds 70 times, voids are likely to occur, and the strength in the width direction becomes low. , Easy to tear in the length direction.
- the biaxially stretched film may be heat-set at 160 to 190 ° C. if necessary.
- the above-described polypropylene film for a film capacitor can be used for a known film capacitor.
- the polypropylene film for a film capacitor of the present invention exhibits a high dielectric breakdown voltage even in a thin film, and a high capacitor capacity can be obtained even in a small capacitor.
- each physical property was measured as follows.
- MFR Melt flow rate
- Chlorine content About 0.7 g of sample (propylene homopolymer) is set in the sample combustion device (QF-02 manufactured by Mitsubishi Chemical Corporation), and slowly burned under the condition of complete combustion, and the combustion that has come out The gas was passed through an absorption liquid (ultra pure water) to collect chlorine.
- the absorbing solution was introduced into an ion chromatograph equipped with a concentrator (DX-300 manufactured by Nippon Dionex Co., Ltd.), and the amount of chlorine was calculated from the area of the obtained chromatogram.
- the detection limit is 1 ppm.
- Mw / Mn The molecular weight distribution (Mw / Mn) was measured as follows using a gel permeation chromatograph Alliance GPC-2000 manufactured by Waters.
- the separation column has two TSKgel GNH6-HT and two TSKgel GNH6-HTL, the column size is 7.5 mm in diameter and 300 mm in length, the column temperature is 140 ° C., and the mobile phase is o -Using dichlorobenzene and BHT 0.025% by weight as an antioxidant, moving at 1.0 ml / min, sample (propylene homopolymer) concentration 15 mg / 10 mL, sample injection volume 500 ⁇ L, differential as detector A refractometer was used.
- Standard polystyrene used was manufactured by Tosoh Corporation for molecular weights of Mw ⁇ 1000 and Mw> 4 ⁇ 10 6 , and used by Pressure Chemical Co. for 1000 ⁇ Mw ⁇ 4 ⁇ 10 6 .
- Thermal contraction rate The biaxially stretched film was cut into a length of 10 mm and a length of 100 mm in the MD direction. The cut one was placed in a 120 ° C. hot air oven and heated for 15 minutes. The thermal contraction rate (%) was determined by the ratio of the contracted length to the original length.
- Dielectric breakdown voltage In accordance with JIS C2330, a biaxially stretched film (250 mm) with a voltage increase of 100 to 500 V / sec at a temperature of 80 ° C. using a 6-point DC / AC switching type 15 KV pressure tester manufactured by Kasuga Electric Co., Ltd. X300 mm, thickness 15 ⁇ m) was applied to measure the dielectric breakdown voltage to obtain the withstand voltage characteristics.
- the upper electrode was a brass cylinder having a mass of 500 g and 25 mm ⁇ as the (+) electrode, and the lower electrode was wound around silicon rubber with an aluminum foil defined in JIS-H-4160, which was used as the ( ⁇ ) electrode.
- the measurement was performed on 6 sheets for 1 film and 3 sheets, and the average value was defined as the BDV value.
- the dielectric breakdown voltage is obtained by dividing the measured breakdown voltage (V) by the film thickness ( ⁇ m).
- undrawn means that a portion that is not stretched remains.
- the solid titanium catalyst component thus adjusted is stored as a hexane slurry. A portion of this hexane slurry was dried and the catalyst composition was examined.
- the solid titanium catalyst component contained 2% by weight of titanium, 57% by weight of chlorine, 21% by weight of magnesium and 20% by weight of DIBP. .
- the resulting slurry was deactivated and then sent to a liquid propylene washing tank to wash the propylene homopolymer powder. After the slurry was vaporized, gas-solid separation was performed to obtain a propylene homopolymer.
- the resulting propylene homopolymer was introduced into a conical dryer and vacuum dried at 80 ° C. Subsequently, 35.9 g of pure water and 0.63 L of propylene oxide were added to 100 kg of the product, dechlorinated at 90 ° C. for 2 hours, and then vacuum-dried at 80 ° C. to obtain a propylene homopolymer I got a powder.
- Example 1 Propylene homopolymer obtained in the above production example (MFR: 4.2 g / 10 min, mmmm: 98%, ash content: 20 ppm, chlorine content: 1 ppm, Tm: 166 ° C., Mw / Mn: 6.5) Pellets (average particle size 3 mm) are uniformly laid out so that the pellets do not overlap each other, and an electron beam irradiation machine (EBC800-35 manufactured by NHV Corporation) is used to absorb the electron beam with an absorbed dose of 1 kGy (acceleration voltage). : 800 kV, current: 0.5 mA, irradiation speed: 2 m / min).
- EBC800-35 electron beam irradiation machine
- the pellets after irradiation were subjected to a preheating / heating temperature of 210 ° C., a preheating time of 5 minutes, a heating pressure of 10 MPa, and a pressure heating time of 2 minutes. Pressing was performed under the conditions to obtain a 0.5 mm press sheet.
- This press sheet is cut into 85 mm x 85 mm, and using a biaxial stretching machine (KARO IV, manufactured by Bruckner), a preheating temperature of 152 ° C, a preheating time of 60 seconds, a stretching temperature of 152 ° C, and a stretching ratio of 5x7 times (MD Direction: 5 times, TD direction: 7 times) and a stretching speed of 6 m / min were sequentially biaxially stretched to obtain a biaxially stretched film having a thickness of 15 ⁇ m.
- KARO IV manufactured by Bruckner
- Table 1 shows the results of the obtained film.
- Example 2 a film was produced in the same manner as in Example 1 except that the absorbed dose of the electron beam was 10 kGy (acceleration voltage: 800 kV, current: 1.3 mA, irradiation rate: 2 m / min).
- Example 3 the absorbed dose of the electron beam was 100 kGy (50 kGy (acceleration voltage: 800 kV, current: 4.9 mA, irradiation speed: 2 m / min) was irradiated twice) and Example 1 A film was prepared in the same manner.
- Table 1 shows the results of the obtained film.
- Example 1 A film was produced in the same manner as in Example 1 without irradiating the electron beam. The results are shown in Table 1 for the obtained film.
- Example 4 Propylene homopolymer (MFR: 4.2 g / 10 min, mmmm: 98%, ash content: 20 ppm, chlorine content: 1 ppm, Tm: 166 ° C., Mw / Mn: 6.5) pellets (average particle size 3 mm) Using a 30 mm ⁇ extruder (extruded sheet molding machine manufactured by GM Engineering Co., Ltd.), melted at a molding temperature of 210 ° C., extruded from a T-die, and taken by a cooling roll held at a cooling temperature of 30 ° C. The sheet was cooled at a speed of 1.0 m / min to obtain a sheet having a thickness of 0.5 mm.
- MFR 4.2 g / 10 min, mmmm: 98%, ash content: 20 ppm, chlorine content: 1 ppm, Tm: 166 ° C., Mw / Mn: 6.5
- the sheet is cut into 85 mm ⁇ 85 mm, and the electron beam is irradiated with 1 kGy (acceleration voltage: 300 kV, current: 1.9 mA) using an electron beam irradiator (EBC300-60 manufactured by NHV Corporation). The sheet was irradiated at a speed of 50 m / min.
- the sheet after irradiation was pre-heated at a preheating temperature of 152 ° C., a preheating time of 60 seconds, a drawing temperature of 152 ° C., and a draw ratio of 5 ⁇ 7 times (MD direction: 5 times, TD) using a biaxial drawing machine (KARO IV IV manufactured by Bruckner). (Direction: 7 times) and a stretching speed of 6 m / min were sequentially biaxially stretched to obtain a biaxially stretched film having a thickness of 15 ⁇ m.
- Table 1 shows the results of the obtained film.
- Example 5 a film was produced in the same manner as in Example 4 except that the absorbed dose of the electron beam was 10 kGy (acceleration voltage: 300 kV, current: 18.7 mA, irradiation rate: 50 m / min).
- Example 6 a film was produced in the same manner as in Example 4 except that the absorbed dose of the electron beam was 100 kGy (acceleration voltage: 300 kV, current: 37.4 mA, irradiation rate: 10 m / min).
- Example 7 a film was produced in the same manner as in Example 4 except that the absorbed dose of the electron beam was 300 kGy (the above 100 kGy condition was irradiated three times).
- Table 1 shows the results of the obtained film.
- Example 8 Propylene homopolymer (MFR: 2.9 g / 10 min, mmmm: 94%, ash content: 23 ppm, chlorine content: 1 ppm, Tm: 163 ° C., Mw / Mn: 5.0) pellets (average particle size 3 mm)
- MFR 2.9 g / 10 min, mmmm: 94%, ash content: 23 ppm, chlorine content: 1 ppm, Tm: 163 ° C., Mw / Mn: 5.0
- pellets average particle size 3 mm
- Comparative Example 6 A film was produced in the same manner as in Comparative Example 5, except that the absorbed dose of the electron beam was 10 kGy (acceleration voltage: 300 kV, current: 18.7 mA, irradiation rate: 50 m / min). The results are shown in Table 1 for the obtained film.
- This pellet was melted at a molding temperature of 210 ° C. using a 30 mm ⁇ extruder (extruded sheet molding machine manufactured by GM Engineering Co., Ltd.), extruded from a T-die, and cooled by a cooling roll held at a cooling temperature of 30 ° C. The sheet was cooled at a take-up speed of 1.0 m / min to obtain a sheet having a thickness of 0.5 mm.
- this sheet was preheated at a temperature of 152 ° C., preheated for 60 seconds, stretched at a temperature of 152 ° C., and stretched at a magnification of 5 ⁇ 7 (MD direction: 5 times, TD direction: 7 times) and a biaxially stretched film having a thickness of 15 ⁇ m was obtained by sequentially biaxially stretching under conditions of a stretching speed of 6 m / min.
- Table 1 shows the results of the obtained film.
- the dielectric breakdown voltage of the polypropylene film for a film capacitor of the present invention has a very high dielectric breakdown voltage as shown in the examples and comparative examples of the present invention.
- Example 9 Pellets of propylene homopolymer (MFR: 4.2 g / 10 min, mmmm: 98%, ash content: 20 ppm, chlorine content: 1 ppm, Tm: 166 ° C., Mw / Mn: 6.5) (average particle size 3 mm) Using 100% by weight and 1% by weight of triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd., TAIC) as a crosslinking agent, a twin screw extruder (HYPERKTX30, 30 mm ⁇ ⁇ 2 manufactured by Kobe Steel) The mixture was melt-kneaded at a molding temperature of 210 ° C. to obtain pellets.
- MFR 4.2 g / 10 min, mmmm: 98%, ash content: 20 ppm, chlorine content: 1 ppm, Tm: 166 ° C., Mw / Mn: 6.5
- TAIC triallyl isocyanurate
- the pellets are uniformly laid out so that the pellets do not overlap each other, and an electron beam irradiation machine (EBC800-35 manufactured by NHV Corporation) is used to absorb the electron beam with an absorbed dose of 10 kGy (acceleration voltage: 800 kV, current: Irradiation was performed at 1.3 mA and an irradiation speed of 2 m / min.
- EBC800-35 manufactured by NHV Corporation
- the pellets after irradiation were subjected to a preheating / heating temperature of 210 ° C., a preheating time of 5 minutes, a heating pressure of 10 MPa, and a pressure heating time of 2 minutes. Pressing was performed under the conditions to obtain a 0.5 mm press sheet.
- This press sheet is cut into 85 mm ⁇ 85 mm, and using a biaxial stretching machine (KARO IV IV, manufactured by Brookner Co.), a preheating temperature of 152 ° C., a preheating time of 60 seconds, a stretching temperature of 152 ° C., and a stretching ratio of 5 ⁇ 7 times (MD Direction: 5 times, TD direction: 7 times) and a stretching speed of 6 m / min were successively biaxially stretched to obtain a biaxially stretched film having a thickness of 15 ⁇ m.
- KARO IV IV manufactured by Brookner Co.
- Table 2 shows the results of the obtained film.
- Example 10 A film was produced in the same manner as in Example 9 except that the absorbed dose of the electron beam was 50 kGy (acceleration voltage: 800 kV, current: 4.9 mA, irradiation rate: 2 m / min). The results are shown in Table 2 for the obtained film.
- Example 11 Propylene homopolymer (MFR: 4.2 g / 10 min, mmmm: 98%, ash content: 20 ppm, chlorine content: 1 ppm, Tm: 166 ° C., Mw / Mn: 6.5) pellets (average particle size 3 mm) 100 wt% and TAIC 1 wt% as a crosslinking agent were melt-kneaded at a molding temperature of 210 ° C. using a twin screw extruder (HYPERKTX30, 30 mm ⁇ ⁇ 2 manufactured by Kobe Steel) to obtain pellets .
- HYPERKTX30, 30 mm ⁇ ⁇ 2 manufactured by Kobe Steel twin screw extruder
- This pellet was melted at a molding temperature of 210 ° C. using a 30 mm ⁇ extruder (extruded sheet molding machine manufactured by GM Engineering Co., Ltd.), extruded from a T-die, and cooled by a cooling roll held at a cooling temperature of 30 ° C. The sheet was cooled at a take-up speed of 1.0 m / min to obtain a sheet having a thickness of 0.5 mm.
- the sheet is cut into 85 mm ⁇ 85 mm, and the electron beam is irradiated with 1 kGy (acceleration voltage: 300 kV, current: 1.9 mA) using an electron beam irradiator (EBC300-60 manufactured by NHV Corporation). The sheet was irradiated at a speed of 50 m / min.
- the sheet after irradiation was pre-heated at a preheating temperature of 152 ° C., a preheating time of 60 seconds, a drawing temperature of 152 ° C., and a draw ratio of 5 ⁇ 7 times (MD direction: 5 times, TD) using a biaxial drawing machine (KARO IV IV manufactured by Bruckner). (Direction: 7 times) and a stretching speed of 6 m / min were sequentially biaxially stretched to obtain a biaxially stretched film having a thickness of 15 ⁇ m.
- Table 2 shows the results of the obtained film.
- Example 12 a film was produced in the same manner as in Example 11 except that the absorbed dose of the electron beam was 10 kGy (acceleration voltage: 300 kV, current: 18.7 mA, irradiation rate: 50 m / min).
- Example 13 a film was produced in the same manner as in Example 11 except that the absorbed dose of the electron beam was 100 kGy (acceleration voltage: 300 kV, current: 37.4 mA, irradiation rate: 10 m / min).
- Table 2 shows the results of the obtained film.
- Example 14 a film was produced in the same manner as in Example 12 except that 4% by weight of TAIC was used as a crosslinking agent.
- Example 15 a film was produced in the same manner as in Example 13 except that 4% by weight of TAIC was used as a crosslinking agent.
- Example 16 a film was produced in the same manner as in Example 12 except that 5% by weight of TAIC was used as a crosslinking agent.
- Example 17 a film was produced in the same manner as in Example 13 except that 5% by weight of TAIC was used as a crosslinking agent.
- Example 18 a film was produced in the same manner as in Example 11 except that 5% by weight of a crosslinking agent (TAIC) was used and the absorbed dose of the electron beam was 300 kGy (the above-mentioned 100 kGy condition was irradiated three times). .
- TAIC crosslinking agent
- Table 2 shows the results of the obtained film.
- Comparative Example 11 In Comparative Example 11, a film was produced in the same manner as Example 11 without irradiating the electron beam. The results are shown in Table 2 for the obtained film.
- Comparative Examples 12 to 14 In Comparative Example 12, a film was produced in the same manner as in Comparative Example 11 except that 4% by weight of TAIC was used as a crosslinking agent.
- Comparative Example 13 a film was produced in the same manner as in Comparative Example 11 except that 5% by weight of TAIC was used as a crosslinking agent.
- Comparative Example 14 an attempt was made to produce a film in the same manner as in Example 11 except that 5% by weight of TAIC was used as a crosslinking agent and the absorbed dose of the electron beam was 1000 kGy (100 kGy condition was irradiated 10 times). Since the sample was deteriorated by electron beam irradiation, a film could not be produced.
- Table 2 shows the results of the obtained film.
- Example 19 Propylene homopolymer (MFR: 2.9 g / 10 min, mmmm: 94%, ash content: 23 ppm, chlorine content: 1 ppm, Tm: 163 ° C., Mw / Mn: 5.0) pellets (average particle size 3 mm)
- MFR 2.9 g / 10 min, mmmm: 94%, ash content: 23 ppm, chlorine content: 1 ppm, Tm: 163 ° C., Mw / Mn: 5.0
- pellets average particle size 3 mm
- the polypropylene film for a film capacitor obtained from the polypropylene for a film capacitor or the polypropylene sheet for a film capacitor of the present invention can be a thin film, has a high dielectric breakdown voltage, and a low thermal shrinkage rate. For example, it can greatly contribute to high output, miniaturization, and weight reduction of a hybrid vehicle.
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Abstract
Description
次いで、当該プロピレン単独重合体からシートを製造する工程(II)と、
次いで、当該シートから延伸フィルムを製造する工程(III)と
を含むフィルムコンデンサ用ポリプロピレンフィルムの製造方法であり、
工程(I)で得られるプロピレン単独重合体または工程(II)で得られるシートに、吸収線量0.1~500kGyで電子線照射する工程を含むことを特徴とする。
本発明のフィルムコンデンサ用ポリプロピレンまたはフィルムコンデンサ用ポリプロピレンシートの原料となるプロピレン単独重合体は、以下の(1)~(4)の要件を満たす。また、以下の(1)~(6)の要件を満たすと、成形性が良好となり、耐電圧が向上するため、より好ましい。
本発明に係るプロピレン単独重合体は、公知のプロピレン重合用触媒を用いたプロピレンの重合方法により製造し得るが、なかでも担持型チタン触媒を用いた製造方法が好ましい。
本発明に係るプロピレン単独重合体は、その形状が、粉末、顆粒またはペレットのいずれかであってもよい。粉末、顆粒は、プロピレン単独重合体から得られ、ペレットは、粉末、顆粒を造粒することによって得られる。
本発明に係るプロピレン単独重合体が、粉末、顆粒またはペレットである場合は、粉末であれば、特に限定されないが、通常、平均粒径が、たとえば、50~150μm程度であり、顆粒であれば、特に限定されないが、通常、平均粒径が、たとえば、150~2000μm程度であり、ペレットであれば、特に限定されないが、通常、平均粒径が2~10mm程度、高さが1~5mm程度である。
本発明に係るシートの厚みは、特に限定されないが、通常、80~800μm程度が好ましく、120~500μm程度がさらに好ましい。シートの厚みが、80μm未満であると、延伸時に破断することもあり、800μmを超えると、薄膜を得ることができないため、フィルムコンデンサ用として適さないこともある。
本発明のフィルムコンデンサ用ポリプロピレンは、前記プロピレン単独重合体に、放射線、好ましくは電子線またはガンマ線、より好ましくは電子線を吸収線量0.1~500kGy、好ましくは1~300kGy、さらに好ましくは1~100kGyで照射することによって得られる。放射線の吸収線量が、0.1kGy未満であると、照射による効果を得られないため、フィルムを延伸する場合の延伸性に優れるフィルムコンデンサ用ポリプロピレンを得ることができず、また、高い絶縁破壊電圧を有するフィルムコンデンサ用ポリプロピレンフィルムおよび該フィルムを含むフィルムコンデンサを提供できない。放射線の吸収線量が、500kGyを超えると、プロピレン単独重合体が劣化してしまい、延伸性がなくなり、さらに、照射の出力を上げる必要があるため、生産性および経済性の観点からも妥当ではない。放射線としては、α線、β線、γ線、X線、電子線、陽電子線などが挙げられるが、好ましくは、電子線またはガンマ線、より好ましくは、電子線である。ガンマ線の放射源としては、たとえば、60Co や137Csが挙げられる。
本発明のフィルムコンデンサ用ポリプロピレンまたはフィルムコンデンサ用ポリプロピレンシートは、放射線、好ましくは電子線またはガンマ線、より好ましくは電子線を照射する前に、前記プロピレン単独重合体に架橋剤を添加し、必要に応じて混練して、プロピレン単独重合体を架橋することにより、より高い絶縁破壊電圧を有するフィルムコンデンサ用ポリプロピレンフィルムが得られるので、好ましい。この場合、プロピレン単独重合体の分子切断が、架橋剤で架橋されることにより低減されるため、絶縁破壊電圧の効果がより発現されるところまで吸収線量を増やすことができるためと推定される。たとえば、形状が、粉末、顆粒またはペレットであれば、吸収線量0.1~500kGy、好ましくは10~300kGyとすることができ、シートであれば、吸収線量0.1~500kGy、好ましくは10~300kGyとすることができる。
トリメチロールプロパントリアクリレート、トリメチロールエタントリアクリレート、テトラメチロールメタントリアクリレートなどのトリアクリレート化合物、
ジトリメチロールテトラアクリレート、テトラメチロールメタンテトラアクリレート、ペンタエリスリトールテトラアクリレートなどのテトラアクリレート化合物、
ジペンタエリスリトールヘキサアクリレートなどのヘキサアクリレート化合物、
エチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、ポリエチレングリコールジメタクリレート、1,3-ブチレングリコールジメタクリレート、1,4-ブチレングリコールジメタクリレート、1,6-ヘキサンジオールジメタクリレート、ネオペンチルグリコールジメタクリレート、ジプロピレングリコールジメタクリレート、ポリプロピレングリコールジメタクリレート、ポリブチレングリコールジメタクリレート、2,2'-ビス(4-メタクリロキシジエトキシフェニル)プロパンなどのジメタクリレート化合物、
トリメチロールプロパントリメタクリレート、トリメチロールエタントリメタクリレートなどのトリメタクリレート化合物、
グリセリン-α-アリルエーテル、トリアリルイソシアヌレート、トリメタリルイソシアヌレート、メチレンビスアクリルアミド、ジビニルベンゼンが挙げられる。
本発明のフィルムコンデンサ用ポリプロピレンまたはフィルムコンデンサ用ポリプロピレンシートの原料となるプロピレン単独重合体は、発明の目的を損なわない範囲で、耐候性安定剤、耐熱安定剤、帯電防止剤、スリップ防止剤、アンチブロッキング剤、防曇剤、核剤、滑剤、顔料、染料、可塑剤、老化防止剤、塩酸吸収剤、酸化防止剤などの添加剤を添加して得られてもよい。
本発明のフィルムコンデンサ用ポリプロピレンフィルムは、本発明のフィルムコンデンサ用ポリプロピレンまたはフィルムコンデンサ用ポリプロピレンシートを延伸してなり、高い絶縁破壊電圧を有し、熱収縮率が低い。また、本発明のフィルムコンデンサ用ポリプロピレンまたはフィルムコンデンサ用ポリプロピレンシートは、延伸性に優れるため、得られるフィルムコンデンサ用ポリプロピレンフィルムを薄膜とすることができる。
試料(プロピレン単独重合体)のMFRは、ASTM D 1238に準拠して、230℃で2.16kgの荷重にて測定した。
試料(プロピレン単独重合体)のペンタッドアイソタクティック分率(mmmm分率)は、A.zambelliらのMacromolecules,8,687(1975)に示された帰属に基づき、下記条件で13C-NMRを用いて測定し、メソペンタッド分率=(21.7ppmでのピーク面積)/(19~23ppmでのピーク面積)とした。
種類:JNM-Lambada400(日本電子(株)社製)
分解能:400MHz
測定温度:125℃
溶媒:1,2,4-トリクロロベンゼン/重水素化ベンゼン=7/4
パルス幅:7.8μsec
パルス間隔:5sec
積算回数:2000回
シフト基準:TMS=0ppm
モード:シングルパルスブロードバンドデカップリング
(3)灰分量
100gの試料(プロピレン単独重合体)を磁性ルツボに入れ、電熱器上で加熱し試料を燃焼させ、750℃の電気炉に30分入れ、完全灰化させた。ルツボをデシケーター中で1時間冷却したのち精密天秤で灰分の重量を0.1mg単位まで測定し、試料に対する灰分量(ppm)を算出した。
試料燃焼装置(三菱化学(株)社製QF-02)に試料(プロピレン単独重合体)約0.7gをセットし、完全燃焼する条件でゆっくりと燃焼させ、出てきた燃焼ガスを吸収液(超純水)に通し塩素を捕集した。吸収液を濃縮装置付きのイオンクロマトグラフ(日本ダイオネクス(株)社製DX-300)に導入し、得られたクロマトグラムの面積より塩素量を算出した。なお、検出限界は、1ppmである。
試料(プロピレン単独重合体)0.40g程度を0.2mm厚フィルムの成形金型に入れ、240℃で7分加熱後、冷却プレスしフィルムを作成した。得られたフィルムから5.0mg±0.5mgを切り取り、専用アルミパンでクリンプし測定サンプルとした。サンプルを、パーキンエルマー社製DSC7を用い窒素気流下で、30℃で0.5分間保持したのち、30℃から240℃までを30℃/minで昇温し、240℃で10分間保持したのち、240℃から30℃までを10℃/minで降温し、30℃でさらに2分間保持したのち、次いで10℃/minで昇温する際の吸熱曲線から融点(Tm)を求めた。
分子量分布(Mw/Mn)は、Waters社製ゲル浸透クロマトグラフAlliance GPC-2000型を用い、以下のようにして測定した。分離カラムは、TSKgel GNH6- HTを2本およびTSKgel GNH6- HTLを2本であり、カラムサイズはいずれも直径7.5mm、長さ300mmであり、カラム温度は140℃とし、移動相にはo-ジクロロベンゼンおよび酸化防止剤としてBHT0.025重量%を用い、1.0ml/分で移動させ、試料(プロピレン単独重合体)濃度は15mg/10mLとし、試料注入量は500μLとし、検出器として示差屈折計を用いた。標準ポリスチレンは、分子量がMw<1000およびMw>4×106については東ソー社製を用い、1000≦Mw≦4×106についてはプレッシャーケミカル社製を用いた。
二軸延伸フィルムをMD方向に10mm幅で100mmの長さにカットした。カットしたものを120℃熱風オーブンに入れて15分間加熱した。元の長さに対する収縮した長さの割合で熱収縮率(%)を求めた。
JIS C2330に準じ、春日電気(株)社製6点式直流交流切替式15KV耐圧試験機を用い、80℃の温度の基で、100~500V/secの電圧上昇をもって、二軸延伸フィルム(250mm×300mm、厚み15μm)に電圧を印加して絶縁破壊電圧を測定し、耐圧特性を求めた。上部電極は質量500g、25mmφの黄銅製円柱を(+)電極として、下部電極はシリコンゴムに、JIS-H-4160に規定するアルミニウム箔を巻き付けて、これを(-)電極とした。また、測定は、フィルム1枚に対して6点を、シート3枚に対して行い、平均値をBDV値とした。
プレスシートまたはTダイシートを、二軸延伸機(ブルックナー社製KARO IV)を用いて、予熱温度152℃、予熱時間60秒、延伸温度152℃、延伸倍率5×7倍(樹脂の流れ方向(MD方向):5倍、樹脂の流れと垂直方向(TD方向):7倍)、延伸速度6m/分の条件で、逐次二軸延伸した。同条件にて、5枚の二軸延伸フィルムを作製し、次の方法にて、延伸性を評価した。
(1)固体状チタン触媒成分の調製
無水塩化マグネシウム952g、デカン4420mLおよび2-エチルヘキシルアルコール3906gを、130℃で2時間加熱して均一溶液とした。この溶液中に無水フタル酸213gを添加し、130℃でさらに1時間撹拌混合を行って無水フタル酸を溶解させた。得られた均一溶液を23℃まで冷却した後、この均一溶液750mLを-20℃に保持された四塩化チタン2000mL中に1時間かけて滴下した。滴下後、得られた混合液の温度を4時間かけて110℃に昇温し、110℃に達したところでフタル酸ジイソブチル(DIBP)52.2gを加え、同温度で2時間加熱した。次いで、熱時濾過にて固体部を採取し、この固体部を2750mLの四塩化チタンに再懸濁させた後、再び110℃のデカンおよびヘキサンを用いて、洗浄液中にチタン化合物が検出されなくなるまで洗浄した。このようにして調整された固体状チタン触媒成分は、ヘキサンスラリーとして保存される。このヘキサンスラリーの一部を乾燥して触媒組成を調べたところ、固体状チタン触媒成分は、チタン2重量%、塩素を57重量%、マグネシウムを21重量%及びDIBPを20重量%含有していた。
遷移金属触媒成分120g、トリエチルアルミニウム20.5mLおよびヘプタン120Lを内容量200Lの撹拌機付きオートクレーブに入れ、内温5℃に保ちながら、プロピレンを720g加え、60分撹拌して反応させた。重合終了後、固体成分を沈降させ、上澄み液の除去およびヘプタンによる洗浄を2回行った。得られた前重合触媒を精製ヘプタンに再懸濁して、遷移金属触媒成分濃度で1g/Lとなるようにした。この前重合触媒は遷移金属触媒成分1g当り、プロピレン重合体を6g含んでいた。
内容量100Lの撹拌機付きベッセル重合器に、プロピレンを110kg/時間、(2)で製造した触媒スラリーを遷移金属触媒成分として1.4g/時間、トリエチルアルミニウムを5.8mL/時間およびジシクロペンチルジメトキシシランを2.6mL/時間、連続的に供給し、水素を、気相部の水素濃度が0.9mol%になるように供給した。重合温度73℃および圧力3.2MPa/Gで重合を行った。得られたスラリーを内容量1000Lの撹拌機付きベッセル重合器に送り、さらに重合を行った。プロピレンを30kg/時間および水素を、気相部の水素濃度が1.3mol%になるように重合器に供給した。重合温度71℃および圧力3.0MPa/Gで重合を行った。得られたスラリーを内容量500Lの撹拌機付きベッセルに送り、さらに重合を行った。プロピレンを46kg/時間および水素を、気相部の水素濃度が1.3mol%になるように重合器に供給した。重合温度69℃および圧力2.9MPa/Gで重合を行った。得られたスラリーは失活させた後、液体プロピレンによる洗浄槽に送り、プロピレン単独重合体パウダーを洗浄した。このスラリーを気化させた後、気固分離を行い、プロピレン単独重合体を得た。得られたプロピレン単独重合体をコニカル乾燥機に導入して、80℃で真空乾燥した。次いで、この生成物100kgに対し、純水35.9gとプロピレンオキサイド0.63Lとを添加して、90℃で2時間脱塩素処理を行った後に、80℃で真空乾燥し、プロピレン単独重合体パウダーを得た。
上記製造例で得られたプロピレン単独重合体(MFR:4.2g/10分、mmmm:98%、灰分量:20ppm、塩素量:1ppm、Tm:166℃、Mw/Mn:6.5)のペレット(平均粒径3mm)を、ペレット同士が重ならないように均一に敷き並べ、電子線照射機((株)NHVコーポレーション社製EBC800-35)を用いて、電子線を吸収線量1kGy(加速電圧:800kV、電流:0.5mA、照射速度:2m/min)で照射した。
実施例2では、電子線の吸収線量を10kGy(加速電圧:800kV、電流:1.3mA、照射速度:2m/min)とした以外は、実施例1と同様にしてフィルムを作製した。
電子線を照射しないで、実施例1と同様にしてフィルムを作製した。得られたフィルムについて、結果を表1に示す。
プロピレン単独重合体(MFR:4.2g/10分、mmmm:98%、灰分量:20ppm、塩素量:1ppm、Tm:166℃、Mw/Mn:6.5)のペレット(平均粒径3mm)を、30mmφ押出機((株)GMエンジニアリング社製押出シート成形機)を用いて、成形温度210℃にて溶融し、Tダイから押出し、冷却温度30℃にて保持された冷却ロールにより、引取速度1.0m/分の条件で除冷し、厚さ0.5mmのシートを得た。
実施例5では、電子線の吸収線量を10kGy(加速電圧:300kV、電流:18.7mA、照射速度:50m/min)とした以外は、実施例4と同様にしてフィルムを作製した。
電子線を照射しないで、実施例4と同様にしてフィルムを作製した。得られたフィルムについて、結果を表1に示す。
電子線の吸収線量を1000kGy(100kGyの条件を10回照射した)として、実施例4と同様にしてフィルムを作製しようとしたが、電子線照射により試料が劣化したため、フィルムを作製することはできなかった。
プロピレン単独重合体(MFR:2.9g/10分、mmmm:94%、灰分量:23ppm、塩素量:1ppm、Tm:163℃、Mw/Mn:5.0)のペレット(平均粒径3mm)を用い、二軸延伸機の予熱温度を149℃とした以外は、実施例5と同様にしてフィルムを作製した。得られたフィルムについて、結果を表1に示す。
電子線を照射しないで、実施例8と同様にしてフィルムを作製した。得られたフィルムについて、結果を表1に示す。
プロピレン単独重合体(MFR:2.8g/10分、mmmm:91%、灰分量:27ppm、塩素量:3ppm、Tm:160℃、Mw/Mn:8.0)のペレット(平均粒径3mm)を用いて、二軸延伸機の予熱温度を145℃とした以外は、比較例2と同様にしてフィルムを作製した。得られたフィルムについて、結果を表1に示す。
電子線の吸収線量を10kGy(加速電圧:300kV、電流:18.7mA、照射速度:50m/min)とした以外は、比較例5と同様にしてフィルムを作製した。得られたフィルムについて、結果を表1に示す。
プロピレン単独重合体(MFR:4.2g/10分、mmmm:98%、灰分量:20ppm、塩素量:1ppm、Tm:166℃、Mw/Mn:6.5)のペレット(平均粒径3mm)99重量%と、プロピレン単独重合体(バセル社製PF814(商品名)、MFR:3.2g/10分、mmmm:91.0%、灰分量:220ppm、塩素量:24ppm、Tm:158℃、Mw/Mn:8.5)1重量%とを、二軸押出し機(神戸製鋼(株)社製HYPERKTX30、30mmφ×2)を用いて、成形温度210℃にて溶融混練し、ペレットを得た。
プロピレン単独重合体(MFR:3.0g/10分、mmmm:98.5%、灰分量:300ppm、塩素量:70ppm、Tm:167℃、Mw/Mn:6.0)のペレット(平均粒径3mm)を用いた以外は、比較例2と同様にして、フィルムを作製した。得られたフィルムについて、結果を表1に示す。
ペレットとして、プロピレン単独重合体(バセル社製PF814(商品名)、MFR:3.2g/10分、mmmm:91.0%、灰分量:220ppm、塩素量:24ppm、Tm:158℃、Mw/Mn:8.5)を用いた以外は、実施例1と同様にしてフィルムを作製した。得られたフィルムについて、結果を表1に示す。
プロピレン単独重合体(MFR:4.2g/10分、mmmm:98%、灰分量:20ppm、塩素量:1ppm、Tm:166℃、Mw/Mn:6.5)のペレット(平均粒径3mm)100重量%と、架橋剤として、トリアリルイソシアヌレート(日本化成(株)社製、TAIC)1重量%とを、二軸押出し機(神戸製鋼(株)社製HYPERKTX30、30mmφ×2)を用いて、成形温度210℃にて溶融混練し、ペレットを得た。
電子線の吸収線量を50kGy(加速電圧:800kV、電流:4.9mA、照射速度:2m/min)とした以外は、実施例9と同様にしてフィルムを作製した。得られたフィルムについて、結果を表2に示す。
電子線を照射しないで、実施例9と同様にしてフィルムを作製した。得られたフィルムについて、結果を表2に示す。
プロピレン単独重合体(MFR:4.2g/10分、mmmm:98%、灰分量:20ppm、塩素量:1ppm、Tm:166℃、Mw/Mn:6.5)のペレット(平均粒径3mm)100重量%と、架橋剤としてTAIC1重量%とを、二軸押出し機(神戸製鋼(株)社製HYPERKTX30、30mmφ×2)を用いて、成形温度210℃にて溶融混練し、ペレットを得た。
実施例12では、電子線の吸収線量を10kGy(加速電圧:300kV、電流:18.7mA、照射速度:50m/min)とした以外は、実施例11と同様にしてフィルムを作製した。
実施例14では、架橋剤としてTAIC4重量%を用いた以外は、実施例12と同様にしてフィルムを作製した。
比較例11では、電子線を照射しないで、実施例11と同様にしてフィルムを作製した。得られたフィルムについて、結果を表2に示す。
比較例12では、架橋剤としてTAIC4重量%を用いた以外は、比較例11と同様にしてフィルムを作製した。
架橋剤としてTAIC15重量%を用いて、実施例11と同様にしてフィルムを作製しようとしたが、架橋剤の量が多すぎるため、ペレダイズできず、フィルムを作製できなかった。
プロピレン単独重合体(MFR:2.9g/10分、mmmm:94%、灰分量:23ppm、塩素量:1ppm、Tm:163℃、Mw/Mn:5.0)のペレット(平均粒径3mm)を用い、二軸延伸機の予熱温度を149℃とした以外は、実施例12と同様にしてフィルムを作製した。得られたフィルムについて、結果を表2に示す。
プロピレン単独重合体(MFR:2.8g/10分、mmmm:91%、灰分量:27ppm、塩素量:3ppm、Tm:160℃、Mw/Mn:8.0)のペレット(平均粒径3mm)を用いた以外は、実施例19と同様にしてフィルムを作製した。得られたフィルムについて、結果を表2に示す。
Claims (20)
- (1)ASTM D1238に準拠して、230℃、2.16kg荷重にて測定したメルトフローレート(MFR)が、1~10g/10分の範囲にあり、
(2)13C-NMRを用いて測定したペンタッドアイソタクティック分率(mmmm分率)が、94%以上であり、
(3)空気中で完全に燃焼させて得られる灰分量が、30ppm以下であり、
(4)イオンクロマトグラフ法により測定した塩素量が、10ppm以下であるプロピレン単独重合体を、
吸収線量0.1~500kGyで放射線照射してなることを特徴とするフィルムコンデンサ用ポリプロピレン。 - 前記放射線が、電子線またはガンマ線であることを特徴とする請求項1に記載のフィルムコンデンサ用ポリプロピレン。
- (1)ASTM D1238に準拠して、230℃、2.16kg荷重にて測定したメルトフローレート(MFR)が、1~10g/10分の範囲にあり、
(2)13C-NMRを用いて測定したペンタッドアイソタクティック分率(mmmm分率)が、94%以上であり、
(3)空気中で完全に燃焼させて得られる灰分量が、30ppm以下であり、
(4)イオンクロマトグラフ法により測定した塩素量が、10ppm以下であるプロピレン単独重合体から得られるシートを、
吸収線量0.1~500kGyで放射線照射してなることを特徴とするフィルムコンデンサ用ポリプロピレンシート。 - 前記放射線が、電子線またはガンマ線であることを特徴とする請求項3に記載のフィルムコンデンサ用ポリプロピレンシート。
- 前記プロピレン単独重合体に、架橋剤を添加してなることを特徴とする請求項1または2に記載のフィルムコンデンサ用ポリプロピレン。
- 前記プロピレン単独重合体に、架橋剤を添加してなることを特徴とする請求項3または4に記載のフィルムコンデンサ用ポリプロピレンシート。
- 前記架橋剤を、前記プロピレン単独重合体100重量%に対して、0.01~10重量%添加してなることを特徴とする請求項5に記載のフィルムコンデンサ用ポリプロピレン。
- 前記架橋剤を、前記プロピレン単独重合体100重量%に対して、0.01~10重量%添加してなることを特徴とする請求項6に記載のフィルムコンデンサ用ポリプロピレンシート。
- 放射線の吸収線量が、1~300KGyであることを特徴とする請求項1または2に記載のフィルムコンデンサ用ポリプロピレン。
- 放射線の吸収線量が、1~300KGyであることを特徴とする請求項3または4に記載のフィルムコンデンサ用ポリプロピレンシート。
- 前記プロピレン単独重合体が、粉末、顆粒またはペレットのいずれかであることを特徴とする請求項1または2に記載のフィルムコンデンサ用ポリプロピレン。
- 請求項1または2に記載のフィルムコンデンサ用ポリプロピレンから得られるフィルムコンデンサ用ポリプロピレンシート。
- 請求項3または4に記載のフィルムコンデンサ用ポリプロピレンシートを二軸延伸して得られることを特徴とするフィルムコンデンサ用ポリプロピレンフィルム。
- 請求項13に記載のフィルムコンデンサ用ポリプロピレンフィルムを含むフィルムコンデンサ。
- (1)ASTM D1238に準拠して、230℃、2.16kg荷重にて測定したメルトフローレート(MFR)が、1~10g/10分の範囲にあり、
(2)13C-NMRを用いて測定したペンタッドアイソタクティック分率(mmmm分率)が、94%以上であり、
(3)空気中で完全に燃焼させて得られる灰分量が、30ppm以下であり、
(4)イオンクロマトグラフ法により測定した塩素量が、10ppm以下であるプロピレン単独重合体を、
吸収線量0.1~500kGyで放射線照射してなることを特徴とするフィルムコンデンサ用ポリプロピレンの製造方法。 - (1)ASTM D1238に準拠して、230℃、2.16kg荷重にて測定したメルトフローレート(MFR)が、1~10g/10分の範囲にあり、
(2)13C-NMRを用いて測定したペンタッドアイソタクティック分率(mmmm分率)が、94%以上であり、
(3)空気中で完全に燃焼させて得られる灰分量が、30ppm以下であり、
(4)イオンクロマトグラフ法により測定した塩素量が、10ppm以下であるプロピレン単独重合体から得られるシートを、
吸収線量0.1~500kGyで放射線照射してなることを特徴とするフィルムコンデンサ用ポリプロピレンシートの製造方法。 - 前記プロピレン単独重合体に、架橋剤を添加してなることを特徴とする請求項15に記載のフィルムコンデンサ用ポリプロピレンの製造方法。
- 前記プロピレン単独重合体に、架橋剤を添加してなることを特徴とする請求項16に記載のフィルムコンデンサ用ポリプロピレンシートの製造方法。
- (1)ASTM D1238に準拠して、230℃、2.16kg荷重にて測定したメルトフローレート(MFR)が、1~10g/10分の範囲にあり、
(2)13C-NMRを用いて測定したペンタッドアイソタクティック分率(mmmm分率)が、94%以上であり、
(3)空気中で完全に燃焼させて得られる灰分量が、30ppm以下であり、
(4)イオンクロマトグラフ法により測定した塩素量が、10ppm以下であるプロピレン単独重合体を製造する工程(I)と、
次いで、当該プロピレン単独重合体からシートを製造する工程(II)と、
次いで、当該シートから延伸フィルムを製造する工程(III)と
を含むフィルムコンデンサ用ポリプロピレンフィルムの製造方法であり、
工程(I)で得られるプロピレン単独重合体または工程(II)で得られるシートに、
吸収線量0.1~500kGyで電子線照射する工程を含むことを特徴とするフィルムコンデンサ用ポリプロピレンフィルムの製造方法。 - 前記プロピレン単独重合体に、架橋剤を添加してなることを特徴とする請求項19に記載のフィルムコンデンサ用ポリプロピレンフィルムの製造方法。
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JP2011504858A JPWO2010107052A1 (ja) | 2009-03-17 | 2010-03-17 | フィルムコンデンサ用ポリプロピレン、フィルムコンデンサ用ポリプロピレンシート、それらの製造方法、およびその用途 |
CN201080012175.4A CN102356439B (zh) | 2009-03-17 | 2010-03-17 | 膜电容器用聚丙烯、膜电容器用聚丙烯片材、其制造方法及其用途 |
US13/256,622 US9449761B2 (en) | 2009-03-17 | 2010-03-17 | Polypropylene for film capacitor, polypropylene sheet for film capacitor, method for producing the same, and uses of the same |
SG2011066263A SG174386A1 (en) | 2009-03-17 | 2010-03-17 | Polypropylene for film capacitor, polypropylene sheet for film capacitor, method for producing the same, and uses of the same |
EP10753544.5A EP2410539B1 (en) | 2009-03-17 | 2010-03-17 | Polypropylene for film capacitor, polypropylene sheet for film capacitor, methods for producing same, and uses of same |
KR1020117024394A KR101690348B1 (ko) | 2009-03-17 | 2010-03-17 | 필름 콘덴서용 폴리프로필렌, 필름 콘덴서용 폴리프로필렌 시트, 그들의 제조방법, 및 그의 용도 |
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EP (1) | EP2410539B1 (ja) |
JP (2) | JPWO2010107052A1 (ja) |
KR (1) | KR101690348B1 (ja) |
CN (1) | CN102356439B (ja) |
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JP2013249330A (ja) * | 2012-05-30 | 2013-12-12 | Canon Inc | 成形体およびその製造方法 |
JP2014055283A (ja) * | 2012-06-29 | 2014-03-27 | Toyobo Co Ltd | 延伸ポリプロピレンフィルム |
JP2015537083A (ja) * | 2012-11-16 | 2015-12-24 | ボレアリス・アクチェンゲゼルシャフトBorealis Ag | 改善されたboppフィルム特性及び易加工性を有する溶融分布の広い高アイソタクチックpp樹脂 |
US9487634B2 (en) | 2012-11-16 | 2016-11-08 | Borealis Ag | High isotactic PP resin with wide melting distribution having improved BOPP film properties and easy processing characteristics |
WO2016159044A1 (ja) * | 2015-03-31 | 2016-10-06 | 株式会社プライムポリマー | フィルムコンデンサ用ポリプロピレン、フィルムコンデンサ用二軸延伸フィルム、フィルムコンデンサ、およびこれらの製造方法 |
WO2016159069A1 (ja) * | 2015-03-31 | 2016-10-06 | 株式会社プライムポリマー | ポリプロピレン樹脂組成物及びその製造方法、二軸延伸フィルム及びその製造方法、並びにフィルムコンデンサ用キャパシタフィルム |
US10256041B2 (en) | 2015-03-31 | 2019-04-09 | Prime Polymer Co., Ltd. | Polypropylene for film capacitor, biaxially stretched film for film capacitor, film capacitor, and process for producing the same |
Also Published As
Publication number | Publication date |
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JP2014231604A (ja) | 2014-12-11 |
SG174386A1 (en) | 2011-10-28 |
EP2410539A4 (en) | 2015-11-04 |
KR101690348B1 (ko) | 2016-12-27 |
CN102356439B (zh) | 2014-03-26 |
EP2410539B1 (en) | 2019-02-20 |
JPWO2010107052A1 (ja) | 2012-09-20 |
JP5877879B2 (ja) | 2016-03-08 |
CN102356439A (zh) | 2012-02-15 |
US9449761B2 (en) | 2016-09-20 |
KR20110128937A (ko) | 2011-11-30 |
EP2410539A1 (en) | 2012-01-25 |
US20120010318A1 (en) | 2012-01-12 |
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