WO2012121256A1 - 二軸延伸ポリプロピレンフィルム、金属化フィルム、およびフィルムコンデンサ - Google Patents
二軸延伸ポリプロピレンフィルム、金属化フィルム、およびフィルムコンデンサ Download PDFInfo
- Publication number
- WO2012121256A1 WO2012121256A1 PCT/JP2012/055708 JP2012055708W WO2012121256A1 WO 2012121256 A1 WO2012121256 A1 WO 2012121256A1 JP 2012055708 W JP2012055708 W JP 2012055708W WO 2012121256 A1 WO2012121256 A1 WO 2012121256A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- biaxially stretched
- stretched polypropylene
- polypropylene film
- protrusions
- Prior art date
Links
- -1 polypropylene Polymers 0.000 title claims abstract description 170
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 168
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 167
- 239000003990 capacitor Substances 0.000 title claims abstract description 79
- 239000010408 film Substances 0.000 title claims description 342
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- 230000003746 surface roughness Effects 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
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- 239000011127 biaxially oriented polypropylene Substances 0.000 claims description 10
- 229910052774 Proactinium Inorganic materials 0.000 claims description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 238000012545 processing Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
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- ROHFBIREHKPELA-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]prop-2-enoic acid;methane Chemical compound C.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O ROHFBIREHKPELA-UHFFFAOYSA-N 0.000 description 1
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-hydroxyoctadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 1
- MBSRTKPGZKQXQR-UHFFFAOYSA-N 2-n,6-n-dicyclohexylnaphthalene-2,6-dicarboxamide Chemical compound C=1C=C2C=C(C(=O)NC3CCCCC3)C=CC2=CC=1C(=O)NC1CCCCC1 MBSRTKPGZKQXQR-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- NMLSKYOPDGYLLU-UHFFFAOYSA-N 4-[[2,3-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]phenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C(=C(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C=CC=2)CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 NMLSKYOPDGYLLU-UHFFFAOYSA-N 0.000 description 1
- PCBPVYHMZBWMAZ-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C)CC1C=C2 PCBPVYHMZBWMAZ-UHFFFAOYSA-N 0.000 description 1
- WNEYWVBECXCQRT-UHFFFAOYSA-N 5-methylhept-1-ene Chemical compound CCC(C)CCC=C WNEYWVBECXCQRT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical class N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 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 1
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- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- PJJZFXPJNUVBMR-UHFFFAOYSA-L magnesium benzoate Chemical compound [Mg+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 PJJZFXPJNUVBMR-UHFFFAOYSA-L 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
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- 230000035515 penetration Effects 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical group 0.000 description 1
- 229930015698 phenylpropene Natural products 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
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- 239000011342 resin composition Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
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- 239000011701 zinc 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
- H01G4/08—Inorganic dielectrics
-
- 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
- B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
- B29L2031/3406—Components, e.g. resistors
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
- Y10T428/24521—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness with component conforming to contour of nonplanar surface
- Y10T428/24529—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness with component conforming to contour of nonplanar surface and conforming component on an opposite nonplanar surface
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
- Y10T428/24521—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness with component conforming to contour of nonplanar surface
- Y10T428/24545—Containing metal or metal compound
Definitions
- the present invention relates to a biaxially stretched polypropylene film suitable for packaging, industrial use, and the like, more specifically, a biaxially stretched polypropylene film excellent in high voltage resistance and suitable element workability as a dielectric for capacitors, And a metallized film and a film capacitor using the biaxially oriented polypropylene film.
- Biaxially stretched polypropylene films are excellent in transparency, mechanical properties, electrical properties, etc., and are therefore used in various applications such as packaging, tapes, cable wrapping and electrical applications including capacitors.
- the capacitor application is particularly preferably used for high voltage capacitors because of its 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.
- Such a biaxially stretched polypropylene film needs to be appropriately roughened from the viewpoint of voltage endurance and device processability, and this is particularly effective in improving the slipping property and oil impregnation property of the film or in the deposition capacitor. It is particularly important for imparting sex.
- the term “security” refers to a metal-deposited capacitor that uses a metal-deposited film formed on the dielectric film as an electrode. In the event of abnormal discharge, the deposited metal scatters due to discharge energy, thereby recovering insulation and preventing short circuits. Thus, the function of the capacitor is maintained or prevented from being destroyed, and it is an extremely useful function from the viewpoint of safety.
- Such roughening methods include mechanical methods such as embossing and sandblasting, chemical methods such as chemical etching with solvents, methods of stretching sheets mixed with different types of polymers such as polyethylene, and generating ⁇ crystals.
- a method of stretching a sheet (see, for example, Patent Documents 1 and 2) has been proposed.
- the mechanical method and the chemical method reduce the roughness density, and the method of stretching the sheet that has formed ⁇ crystals tends to generate coarse protrusions. Therefore, the roughness density, the coarse protrusions, and the number of protrusions are not necessarily required. In some cases, it was not enough. Further, the film roughened by these methods may be insufficiently impregnated with oil between the film layers at the time of capacitor formation, and partly unimpregnated portions are likely to be formed, and the capacitor life may be reduced. In the method of stretching a sheet blended with a different polymer such as polyethylene, there is little remaining of bubbles at the time of capacitor formation, but when the film is recycled, the different polymer may adversely affect and there is a problem that the recyclability is poor. .
- a different polymer such as polyethylene
- the biaxially stretched polypropylene film produced by any of the methods is not sufficiently safe under the severe use conditions of the capacitor having a potential gradient of 350 V / ⁇ m or more, and may cause problems in terms of reliability.
- the potential gradient is obtained by dividing the voltage applied to the dielectric film by the film thickness, and is the applied voltage per unit film thickness.
- Patent Document 5 discloses a biaxially stretched polypropylene film whose surface roughness is controlled and a method for producing the biaxially stretched polypropylene film. The two surfaces of the film are finely roughened, and the heights of protrusions on the front and back of the film are controlled. However, this method is insufficient and difficult.
- Patent Documents 6 and 7 that define the roughness on the film surface of at least one side, as a method of forming a fine rough surface, the ⁇ crystal fraction of the cast raw sheet is within a predetermined range, It is said that the element winding property and the pressure resistance can be balanced.
- the production method cannot sufficiently control the roughness of both surfaces of the film, and the fine roughness of the obtained film sufficiently satisfies the pressure resistance and device processability particularly required for automotive applications. It was not a thing.
- the present inventors have arrived at the present invention as a result of intensive studies to solve the above-mentioned problems.
- the present invention is intended to provide a biaxially stretched polypropylene film, a metallized film, and a film capacitor that exhibit excellent voltage resistance and reliability even in high voltage capacitor applications and ensure stable device processability. It is.
- the biaxially stretched polypropylene film of the present invention is a biaxially stretched polypropylene film having protrusions on both sides, and has a thickness t1 of 1 ⁇ m to 3 ⁇ m and has a longitudinal direction.
- the tensile strength is 120 MPa to 250 MPa
- the transverse tensile strength is 250 MPa to 400 MPa
- the minimum protrusion height P min is 100 nm or more for any surface
- the maximum protrusion height P max is 1,600 nm.
- all of the following formulas (1) to (3) are satisfied.
- Pa 250-450 means the number of protrusions having a height of 250 nm or more and less than 450 nm present on the A plane per 0.1 mm 2
- Pb 450-1600 is the B plane
- Pa means the number of protrusions existing on the A surface per 0.1 mm 2
- Pb is on the B surface. It means the number of existing protrusions per 0.1 mm 2 .
- the biaxially stretched polypropylene film of the present invention is characterized in that, in the above invention, Pa and Pb satisfy the following formula (5).
- the biaxially stretched polypropylene film of the present invention is characterized in that, in the above invention, the ten-point average roughness (SRz) is 500 nm or more and 1,500 nm or less for any surface.
- SRz ten-point average roughness
- the biaxially stretched polypropylene film of the present invention is characterized in that, in the above invention, the center line surface roughness (SRa) is 20 nm or more and 50 nm or less for any surface.
- SRa center line surface roughness
- the SRz / SRa value which is the ratio of the center line surface roughness (SRa) to the ten-point average roughness (SRz), is 20 for any surface. It is characterized by being 40 or less.
- the biaxially stretched polypropylene film of the present invention is characterized in that, in the above-mentioned invention, 0.05 to 10% by mass of branched polypropylene is contained.
- the metallized film of the present invention is characterized in that a metal film is provided on at least one surface of the biaxially stretched polypropylene film described in any one of the above.
- the metallized film of the present invention is characterized in that, in the above invention, a metal film is provided on both sides.
- the metallized film of the present invention is characterized in that, in the above invention, the surface electrical resistance of the metal film is in the range of 1 to 20 ⁇ / ⁇ .
- the film capacitor of the present invention is characterized by using the metallized film described above.
- a biaxially stretched polypropylene film having excellent uniformity of surface protrusions suitable for capacitors and the like, having a high roughness density, a surface having few coarse protrusions, and a surface having a large number of coarse protrusions uniformly. Can do. Furthermore, the biaxially stretched polypropylene film of the present invention has excellent surface characteristics, so that it is excellent in processability even for a thin film, and has a wide range of atmospheric temperature from low temperature ( ⁇ 40 ° C.) to high temperature (115 ° C.). Since it can exhibit high voltage resistance even under conditions, it can be suitably used particularly as a capacitor for automobiles, preferably as a film capacitor for automobiles.
- the biaxially stretched polypropylene film of the present invention has protrusions on both sides and has a thickness t1 of 1 ⁇ m to 3 ⁇ m. In addition, this thickness is the thickness by a micrometer method so that it may mention later.
- the tensile strength in the longitudinal direction of the biaxially stretched polypropylene film of the present invention is 120 MPa to 250 MPa, and the tensile strength in the width direction is 250 MPa to 400 MPa.
- the biaxially stretched polypropylene film of the present invention has a minimum protrusion height Pmin of 100 nm or more and a maximum protrusion height Pmax of 1,600 nm or less for any surface, and one surface is an A-plane, When the other surface is a B surface, all of the following formulas (1) to (3) are satisfied.
- Pa 250-450 means the number of protrusions having a height of 250 nm or more and less than 450 nm present on the A plane per 0.1 mm 2
- Pb 450-1600 is the B plane
- Pa means the number of protrusions existing on the A surface per 0.1 mm 2
- Pb is on the B surface. It means the number of existing protrusions per 0.1 mm 2 .
- the biaxially stretched polypropylene film of the present invention preferably has a film thickness of 1 ⁇ m to 3 ⁇ m by the micrometer method from the viewpoints of capacitor element size and film formation stability.
- the film thickness by the micrometer method is more preferably 1.2 ⁇ m to 2.8 ⁇ m, and particularly preferably 1.5 ⁇ m to 2.5 ⁇ m. If the film is too thin, the mechanical strength and dielectric breakdown strength may be inferior. On the other hand, if the film is too thick, it becomes difficult to form a film having a uniform thickness, and when used as a capacitor dielectric, the capacity per volume is reduced.
- the tensile strength in the longitudinal direction of the biaxially stretched polypropylene film of the present invention is preferably 120 MPa to 250 MPa, and the tensile strength MPa in the width direction is preferably 250 MPa to 400 MPa. If the tensile strength is too low, film breakage may occur at the time of winding the film, or the withstand voltage of the film itself is lowered, and the withstand voltage is likely to be lowered. If the tensile strength is too high, the voltage resistance of the film itself is increased, and the Joule heat at the time of film breakage is increased, so that the films are fused together, and it is difficult to maintain the security.
- the biaxially stretched polypropylene film of the present invention preferably has a minimum protrusion height P min of 100 nm or more for any surface. If the minimum protrusion height P min is less than 100 nm, the film cannot be wound well due to poor air removal under the conventional winding conditions, and also during the deposition process, slit process and capacitor element winding process, The stability of the film becomes poor, and the phenomenon of meandering and hesitation is liable to occur and scratches. For this reason, wrinkles tend to occur particularly in the capacitor element winding process, local interlayer adhesion occurs, and the breakdown voltage tends to decrease due to electric field concentration.
- the biaxially stretched polypropylene film of the present invention preferably has a maximum protrusion height P max of 1,600 nm or less for any surface.
- P max the maximum protrusion height
- the biaxially stretched polypropylene film of the present invention satisfies the following formulas (1) to (3) when one surface is an A plane and the other surface is a B plane.
- Pa 250-450 means the number of protrusions having a height of 250 nm or more and less than 450 nm present on the A plane per 0.1 mm 2
- Pb 450-1600 is the B plane
- Pa means the number of protrusions existing on the A surface per 0.1 mm 2
- Pb is on the B surface. It means the number of existing protrusions per 0.1 mm 2 .
- the biaxially stretched polypropylene film of the present invention satisfies the following formula (5). 600 ⁇ Pa + Pb ⁇ 1,200 (5)
- the value of Pa + Pb is preferably 700 to 1,100. If the number of protrusions on both sides is too small, the smooth portion of the film base surface will increase and the proportion of the area per area will increase. Therefore, the gap between the film layers will tend to narrow locally, and the security of the capacitor will be maintained and secured. It becomes difficult. If the number of protrusions is too large, dielectric breakdown is likely to occur at the protrusions.
- Pa and Pb satisfy
- is preferably 200 or more. More preferably, it is 250 or more. When the above value is 100 or more, a sufficient gap between film layers can be maintained in applications in which the safety and reliability as a capacitor are important, and the self-healing property is good and the security is ensured. Can do.
- the technical background of the film capacitor in which the biaxially stretched polypropylene film of the present invention is mainly used will be described.
- the uniformity of the gap between the films and the ease of slipping between the films or the transport roll are important. It is required to reduce adhesion and residual stress.
- index which cannot be expressed with the conventional 2-dimensional or 3-dimensional centerline surface roughness is employ
- the biaxially stretched polypropylene film of the present invention preferably has a 10-point average roughness (SRz) on both sides of 500 nm or more. If the SRz is less than 500 nm, the film cannot be wound up due to poor air escape or the like, the roll shape may be disturbed, and the slit process and capacitor element formation may not be performed properly. On the other hand, when SRz exceeds 1,500 nm, the dielectric breakdown voltage may decrease, and SRz is preferably 500 nm to 1,500 nm. SRz is more preferably from 600 nm to 1,400 nm, particularly preferably from 700 nm to 1,300 nm. This makes it possible to obtain a film with improved workability and improved workability in the slit process and the capacitor element process. It becomes possible.
- SRz 10-point average roughness
- the biaxially oriented polypropylene film of the present invention preferably has a center line average roughness (SRa) of 50 nm or less on both sides. If the center line average roughness (SRa) is greater than 50 nm, air may easily enter between the layers when the films are laminated, leading to deterioration of the capacitor element. Further, when a metal layer is formed on the film, a hole or the like is generated in the metal layer, and the dielectric breakdown strength and device life at high temperatures are reduced, or charges are concentrated when a voltage is applied, which easily causes insulation defects.
- SRa center line average roughness
- the center line average surface roughness (SRa) on both surfaces of the film is preferably 20 nm to 50 nm, particularly preferably 25 nm to 45 nm, and more preferably 30 nm to 40 nm.
- the biaxially stretched polypropylene film of the present invention preferably has a ten-point average roughness (SRz) within a certain range with respect to the centerline average surface roughness (SRa). That is, in any plane, the ratio of SRz to SRa (SRz / SRa) is preferably in the range of 20 to 40, more preferably in the range of 22 to 32, and particularly preferably in the range of 25 to It is within the range of 29.
- SRz centerline average surface roughness
- this ratio (SRz / SRa) If the value of this ratio (SRz / SRa) is too large, the ratio of coarse protrusions increases, so that air may enter between layers when the films are laminated, leading to deterioration of the capacitor element. Further, when a metal layer is formed on the film, a hole or the like is generated in the metal layer, and the dielectric breakdown strength and device life at high temperatures are reduced, or charges are concentrated when a voltage is applied, which easily causes insulation defects. On the other hand, if this ratio (SRz / SRa) is too small, handling properties and stability during film conveyance may be inferior.
- the biaxially stretched polypropylene film of the present invention defined for the surface protrusion is excellent in the uniformity of the protrusion height on the surface and has different protrusion distributions on the front and back of the film. And if a capacitor is produced using such a biaxially stretched polypropylene film, even if dielectric breakdown occurs, a sufficient film inter-layer gap is kept for the deposited metal to scatter, so self-healing ( The self-healing process is excellent, and the capacitor has a safety function that can maintain the capacitor life for a long time without causing dielectric breakdown and can stably exhibit the safety.
- the biaxially stretched polypropylene film of the present invention preferably contains 0.05 to 10% by mass of branched polypropylene.
- the branched polypropylene referred to here is a polypropylene having 5 or less internal 3-substituted olefins per 10,000 carbon atoms constituting the branched polypropylene.
- the presence of the internal trisubstituted olefin can be confirmed by the proton ratio in the 1 H-NMR spectrum.
- the size of the spherulite generated in the cooling process of the melt-extruded resin sheet can be easily controlled to be small, and the generation of insulation defects generated in the stretching process can be reduced.
- a polypropylene film having excellent voltage resistance can be obtained.
- the branched polypropylene can act as an ⁇ crystal nucleating agent, and can form a rough surface by crystal transformation as long as the addition amount is within a certain range.
- a biaxially oriented polypropylene film having a typical surface roughness can be provided.
- the content of branched polypropylene is more preferably 0.05 to 2% by mass.
- the content of the branched polypropylene is in the above range, a film excellent in element workability and capacitor characteristics can be obtained with improved winding properties and voltage resistance.
- a typical method is to obtain the desired protrusions and surface roughness by using crystal transformation from the viewpoint that electrical characteristics such as dielectric breakdown voltage are not deteriorated without adding electrical impurities. Can be adopted.
- the surface formation method by crystal transformation is, for example, a surface using two crystal systems possessed by polypropylene as described in M. Fujiyama, Journal of Applied Polymer Science 36, P.985-1948 (1988).
- ⁇ crystal monoclinic crystal system, crystal density 0.936 g / cm 2
- ⁇ crystal hexagonal system, crystal density 0.922 g / cm 2
- It is formed in an unstretched sheet, and irregularities are formed on the film surface by transforming thermally unstable ⁇ crystals into ⁇ crystals in the stretching step.
- the shape may exhibit a crater shape formed in an elliptical shape or an arc shape by the projection group.
- the surface shape obtained by the crystal transformation may be formed by the existence of many crater shapes, and may have a crater shape by connecting individual protrusions in an elliptical shape or an arc shape.
- the unevenness is not formed and it is relatively flat.
- the crater-shaped protrusions described above change corresponding to the ratio of the vertical and horizontal stretching ratios when biaxially stretching, and the aspect ratio is 1, that is, substantially circular when isotropic stretching, and flattened as the aspect ratio increases.
- the shape usually obtained by the sequential biaxial stretching method has a major axis in the transverse direction of the film (the width direction of the film roll).
- a plurality of craters having different shapes may be overlapped, and the arc may be arcuate or semi-arc shaped without being circularly closed.
- the present invention as one of the methods for generating the surface shape related to Pa and Pb as defined above, a method of increasing the nucleation ability by adding a raw material having a nucleating agent effect can be adopted. As a result, the number of nuclei is increased so that many small fine protrusions are present, and relatively flat portions (parts where no protrusions are present) are reduced, so that a surface form in which protrusions are uniformly formed as a whole can be obtained. . Since such a surface has projections densely formed, it is easy to satisfy the above-described surface shape defined by the present invention.
- Examples of the raw material having a nucleating agent effect include the above-described branched polypropylene. Since the crater shape can be controlled by controlling the amount of branched polypropylene added and the film forming conditions, the characteristic surface shape of the above-described biaxially stretched polypropylene film of the present invention is generated as a result. It becomes possible.
- the biaxially stretched polypropylene film of the present invention is preferably composed of a mixture of the above-described branched polypropylene and linear polypropylene.
- the melt crystallization temperature of ordinary polypropylene is about 110 ° C., but can be increased to 115 ° C. or higher. That is, in the capacitor self-healing (self-recovery process), the melt crystallization temperature is high, so that the safety is easily recovered, and the dielectric strength does not break down and the withstand voltage is improved.
- the vapor deposition metal around the discharge part is scattered by the discharge energy generated when the dielectric film causes dielectric breakdown for some reason, and the film itself partially melts due to partial high temperature at that time.
- High crystallization temperature makes it easy to recrystallize immediately and to recover the insulating property.
- the ambient temperature of the capacitor becomes high, it is difficult to recrystallize normally and it is difficult to recover the insulation.
- melt crystallization temperature as described above, it is easy to recrystallize at high temperatures during dielectric breakdown. Thus, security can be improved.
- the surface roughness for example, by roughening the surface and securing a gap between the film layers, the insulating property is further improved and the withstand voltage is further improved.
- the branched polypropylene is not particularly limited, but the melt tension is preferably in the range of 1 cN to 30 cN, more preferably in the range of 2 cN to 20 cN from the viewpoint of film forming property. As the melt tension is higher, the uniformity of the protrusion height tends to improve, and this ratio (SRz / SRa) tends to decrease, resulting in dense surface formation (the number of protrusions per unit area is large). Cheap. When the melt tension is less than 1 cN, the uniformity of the protrusion height is inferior, while when it is 30 cN or more, the preferable protrusion height cannot be maintained.
- a method of blending an oligomer or polymer having a branched structure, a method of introducing a long chain branched structure into a polypropylene molecule as described in JP-A-62-1121704, or A method as described in Japanese Patent No. 2869606 is preferably used.
- Specific examples of the branched polypropylene that can be obtained include “Profax PF-814” manufactured by Basell, and “Daploy HMS-PP” manufactured by Borealis.
- the resin obtained by the electron beam cross-linking method includes It is preferably used because the gel component in the resin is small.
- melt crystallization temperature of PP is usually around 110 ° C., but rises to a range of 115 to 130 ° C. That is.
- the content of the branched polypropylene in the entire film is preferably 10% by mass, and more preferably contained.
- the amount is 0.05 to 2% by mass, more preferably 0.05 to 1% by mass.
- the linear polypropylene which is the main component of the biaxially stretched polypropylene film of the present invention
- the linear polypropylene is usually used for a packaging material or a capacitor, but preferably has a cold xylene-soluble part (hereinafter referred to as CXS) of 4% by mass or less.
- CXS cold xylene-soluble part
- the cold xylene soluble part (CXS) is a polypropylene component dissolved in xylene after the sample is completely dissolved in heated xylene and then cooled to room temperature, and the undissolved portion deposited by cooling is separated by filtration. Yes, it is considered that it corresponds to a component that is difficult to crystallize due to low stereoregularity or low molecular weight.
- CXS is preferably 4% by mass or less, more preferably 3% by mass or less, and particularly preferably 2% by mass or less. The above range is preferably satisfied for the linear polypropylene to be used, but it is also preferable that the entire film containing the polymer as a constituent component is satisfied.
- the mesopentad fraction of the linear polypropylene is preferably 0.95 or more, more preferably 0.97 or more.
- the mesopentad fraction is an index indicating the stereoregularity of the crystal phase of polypropylene measured by a nuclear magnetic resonance method (NMR method). The higher the numerical value, the higher the crystallinity, the higher the melting point, and the higher the temperature.
- the upper limit of the mesopentad fraction is not particularly specified.
- a method of washing the resin powder obtained as described above with a solvent such as n-heptane is exemplified.
- the linear polypropylene according to the present invention preferably has a melt flow index (melt flow rate: MFR) of 1 g / 10 min to 10 g / 10 min (230 ° C., 21.18 N load), particularly preferably 2 g / 10.
- MFR melt flow index
- the range of from 5 to 10 g / 10 min (230 ° C., 21.18 N load) is preferable from the viewpoint of film forming property.
- MFR melt flow index
- a method of controlling the average molecular weight or the molecular weight distribution is employed.
- the linear polypropylene according to the present invention is a polypropylene copolymer containing other unsaturated hydrocarbons as a copolymer component in addition to a propylene homopolymer, as long as the object of the present invention is not impaired.
- a polypropylene copolymer containing an unsaturated hydrocarbon as a copolymerization component may be blended with a homopolymer of propylene.
- Examples of such a copolymer component and a monomer component constituting the blend include ethylene, propylene (in the case of a copolymer blend), 1-butene, 1-pentene, 3-methyl-1-pentene, 3- Methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 5-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, vinylcyclohexene, styrene, allylbenzene, cyclopentene, norbornene, Examples include 5-methyl-2-norbornene.
- the blending amount of the copolymer component or the blend amount of the copolymer is less than 1 mol% in the blending amount of the copolymer component and less than 10% by weight in the blend amount of the copolymer from the viewpoint of dielectric breakdown resistance and dimensional stability. It is preferable that
- the linear polypropylene has various additives such as a crystal nucleating agent, an antioxidant, a heat stabilizer, a slip agent, an antistatic agent, an antiblocking agent, and a filler as long as the object of the present invention is not impaired. , A viscosity modifier, a coloring inhibitor, and the like can also be contained.
- the selection of the type and content of the antioxidant may be preferable for 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. Specific examples thereof include various compounds such as 2,6-di-t-butyl-p-cresol (BHT: molecular weight 220.4) and 1,3,5-trimethyl-2,4,6.
- BHT 2,6-di-t-butyl-p-cresol
- Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene eg Irganox® 1330: molecular weight 775.2 from Ciba Geigy
- tetrakis [methylene-3- (3,5-di- t-butyl-4-hydroxyphenyl) propionate] methane for example, Irganox 1010 manufactured by Ciba Geigy, Inc., molecular weight 1,177.7
- the total content of these antioxidants is preferably in the range of 0.03 to 1% by mass relative to the total amount of polypropylene. If the amount of the antioxidant is too small, the long-term heat resistance may be poor. If the amount of the antioxidant is too large, the capacitor element may be adversely affected by blocking at a high temperature due to bleeding out of these antioxidants.
- a more preferable content is 0.1 to 0.9% by mass, particularly preferably 0.2 to 0.8% by mass.
- a crystal nucleating agent can be added as long as it does not contradict the purpose of the present invention.
- branched polypropylene already has an ⁇ -crystal or ⁇ -crystal nucleating agent effect itself, but another ⁇ -crystal nucleating agent (dibenzylidene sorbitols, sodium benzoate, etc.), It is also preferable to add ⁇ crystal nucleating agents (amide compounds such as potassium 1,2-hydroxystearate, magnesium benzoate, N, N′-dicyclohexyl-2,6-naphthalene dicarboxamide, quinacridone compounds, etc.) and the like. .
- the amount is preferably less than 0.1% by mass, more preferably not substantially added.
- the glossiness of the biaxially stretched polypropylene film surface of the present invention is preferably in the range of 100 to 130%, more preferably 110 to 120%. That is, lowering the gloss level means increasing the light scattering density on the film surface, that is, increasing the unevenness of the film surface, increasing the number of protrusions per unit area and increasing the roughness density. . However, if the gloss level is lowered to less than 100%, the liquid impregnation property is improved. However, the number of protrusions increases due to the formation of dense protrusions, so that the amount of air pool between the protrusions increases, and the film layers are slippery and the elements are wound. The property deteriorates and it becomes difficult to wind the film into a roll.
- the glossiness exceeds 130%, it is difficult to form a flat capacitor element that is difficult to slip between the film layers, and the safety is deteriorated because sufficient clearance between the film layers cannot be maintained. Arise.
- the glossiness of 110 to 120% is more preferable because the element winding property, pressure resistance, and security are improved.
- the ash content of the biaxially stretched polypropylene film of the present invention is preferably 50 ppm or less (weight basis, the same shall apply hereinafter), more preferably 30 ppm. Or less, particularly preferably 20 ppm or less. If the ash content is too large, the dielectric breakdown resistance of the film is lowered, and the dielectric breakdown strength may be lowered when a capacitor is used.
- the biaxially stretched polypropylene film of the present invention is preferably used as a dielectric film for a capacitor, but is not limited to the type of capacitor.
- a foil wound capacitor or a metal vapor deposition film capacitor may be used, and it is also preferably used for an oil immersion type capacitor impregnated with insulating oil or a dry type capacitor not using insulating oil at all. It is done.
- it may be a winding type or a laminated type.
- it is particularly preferably used as a metal vapor deposition film capacitor because of the characteristics of the film of the present invention.
- the biaxially stretched polypropylene film of the present invention is preferably subjected to surface treatment in advance for the purpose of improving the metal adhesion.
- Specific examples of the surface treatment include corona discharge treatment, plasma treatment, glow treatment, and flame treatment.
- the surface wetting tension of a polypropylene film is about 30 mN / m, but by these surface treatments, the wetting tension is 37 to 50 mN / m, preferably 39 to 48 mN. / M is preferable because the adhesion to the metal film is excellent and the safety is improved.
- the biaxially stretched polypropylene film of the present invention is obtained by biaxially stretching under a predetermined condition using a raw material that can give the above-described characteristics.
- the biaxial stretching method can be obtained by any of the inflation simultaneous biaxial stretching method, the stenter simultaneous biaxial stretching method, and the stenter sequential biaxial stretching method. Among them, the film forming stability, the thickness uniformity, In terms of controlling the surface shape, it is preferable to employ a stenter sequential biaxial stretching method.
- branched polypropylene is blended with linear polypropylene resin at a predetermined ratio, melt-extruded, passed through a filtration filter, extruded from a slit die at a temperature of 220 to 280 ° C., solidified on a cooling drum, and unstretched Get a film.
- Any method of electrostatic contact, contact using water surface tension, air knife method, press roll method, underwater cast method, etc. may be used as the method of close contact with the cooling drum, The air knife method is preferable because it is good and the surface roughness can be controlled.
- the conventional technique includes surface roughness control by an air knife method.
- the projection distribution to some extent can be controlled by the air knife method, since the temperature range of the air knife is from room temperature to 120 ° C., the present invention can be achieved by simply blowing the air in this temperature range and bringing the unstretched film into close contact with the cooling drum. It is difficult to obtain a polypropylene film having a projection distribution on both sides of the film.
- an unstretched sheet is brought into close contact with the cooling drum at a predetermined temperature with an air knife, and the periphery of the cooling drum is It is important to control the temperature holding time on the drum surface side and the non-drum surface side by controlling the speed, and to control the amount and size of ⁇ crystals formed on the front and back of the film.
- the temperature holding time refers to the time for the unstretched film to contact the cooling drum.
- the amount of ⁇ crystals generated on the film surface and the height of the protrusions can be controlled. Since the surface in contact with the cooling drum is maintained at a temperature at which ⁇ crystals are easily generated, the amount of ⁇ crystals generated is large and the size is reduced. On the other hand, the surface that is not in contact with the cooling drum is kept at a temperature at which the heat of the cooling drum is transferred through the film and is likely to generate ⁇ crystals. The holding time is shortened, the amount of ⁇ crystals generated is small, and the protrusion height and fibril dimensions are increased.
- the temperature of the cooling drum is preferably 70 to 135 ° C., more preferably. It is in the range of 80 to 120 ° C., particularly preferably 85 to 110 ° C.
- the temperature holding time is preferably 1.5 seconds or more, particularly preferably 2.0 seconds or more.
- this unstretched film is biaxially stretched to be biaxially oriented.
- the unstretched film is preheated by passing it through a roll maintained at 120 to 150 ° C., then the sheet is kept at a temperature of 130 ° C. to 160 ° C. and passed between rolls with a difference in peripheral speed, and 4.0 in the longitudinal direction. After stretching to 5.5 times, quench. At the time of stretching, it is preferable to install a radiation heater in the stretching section to supplement the amount of heat from one side of the film.
- the temperature of the cooling drum and the temperature holding time are controlled, and the film surface A surface in the longitudinal stretching step, It is important to optimize the draw ratio after controlling the amount of heat from both sides of the B side.
- the roll temperature of the stretched portion in the longitudinal direction is preferably a temperature of 130 ° C. to 160 ° C. at which ⁇ crystals in the unstretched film melt and protrusions are formed on the film surface. More preferably, it is 135 ° C to 155 ° C, particularly preferably 140 ° C to 150 ° C. If the roll temperature of the stretched part is too high, the film is fused to the roll, and film breakage occurs. On the other hand, if the roll temperature is too low, stretching unevenness may occur, or the ⁇ crystals may not melt and projections on the film surface cannot be formed.
- the application of heat by the radiation heater in the stretching section is the application of heat in the non-contact manner of the film, unlike the application of heat at the time of surface contact with a roll, and can be controlled directly and with high accuracy in the formation of protrusions on the surface. Therefore, the biaxially stretched polypropylene film of the present invention enables the formation of a predetermined distribution of projections on the front and back of the film by controlling the application of heat in a non-contact manner together with the application of heat to the film by a conventional roll.
- the output of the radiation heater is preferably 1.5 kW to 13 kW at which the ⁇ crystal is melted and projections are formed on the film surface in the same manner as the application of heat by the roll.
- the film melts and the film is broken.
- the film may be broken, or the surface projections on the side to which the amount of heat is applied by the radiation heater will be small, and the desired projection distribution on the film surface may not be formed.
- the amount of heat can be directly and non-contacted with the film being stretched. Since it can be provided, surface protrusions can be efficiently generated at the heat application portion of the film being stretched, and the protrusion distribution on the film surface of the present invention can be easily achieved.
- the longitudinal draw ratio is preferably 4.0 to 5.5 times in order to assist the melting of ⁇ crystals. More preferably, it is 4.3 times to 5.2 times. Since the projection on the film surface is stretched by stretching, the size of the projection can be controlled by controlling the stretching ratio. When the longitudinal draw ratio is higher than 6 times, the film is easily broken and film formation becomes difficult. On the other hand, when the draw ratio is low, the projection size on the film surface becomes small and the tensile strength becomes low. If the draw ratio is lower than 4, it becomes difficult to obtain a desired tensile strength, and the voltage resistance is impaired.
- quenching immediately after stretching in the longitudinal direction of the film is important for controlling the protrusion distribution.
- quenching to 30 to 50 ° C. is preferable.
- melting of ⁇ crystals can be stopped, and the projection distribution on the film surface formed during stretching can be maintained.
- the cooling temperature is higher than 50 ° C.
- the distribution of protrusions on the surface of the film formed by stretching cannot be maintained, and when the cooling temperature is lower than 30 ° C., the film becomes brittle because the solidification of the film proceeds rapidly, and the protrusions Since it becomes easy to be crushed, it is difficult to obtain a projection distribution on the film surface of the present invention.
- As a rapid cooling method it can cool rapidly with a cooling roll or air.
- the stretched film After stretching in the longitudinal direction, the stretched film is guided to a stenter, stretched 5 to 15 times in the width direction at a temperature of 150 to 170 ° C., and then given a relaxation of 2 to 20% in the width direction. Heat set at a temperature of 170 ° C. After heat setting, in order to improve the adhesion of the deposited metal, the surface on which the stretched film is deposited is subjected to corona discharge treatment in air, nitrogen, carbon dioxide gas, or a mixed gas thereof, so that biaxial A stretched polypropylene film can be obtained.
- the method for forming a metallized film by providing a metal film on the surface of the above-mentioned biaxially stretched polypropylene film is not particularly limited.
- at least one side of the biaxially stretched polypropylene film of the present invention, and if necessary, A method of providing a metal film such as an aluminum vapor deposition film on both surfaces by vapor-depositing aluminum to be an internal electrode of a 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 is preferably in the range of 20 to 100 nm from the viewpoint of electrical characteristics and self-heeling properties of the film capacitor.
- the surface electric resistance value of the metal film is preferably in the range of 1 to 20 ⁇ / ⁇ .
- the surface electrical resistance value can be controlled by the type of metal used and the film thickness. A method for measuring the surface electrical resistance will be described later.
- the metallized film can be subjected to an aging treatment at a specific temperature or a heat treatment. Also, a coating such as polyphenylene oxide can be applied to at least one side of the metallized film for insulation or other purposes.
- the metallized film thus obtained can be laminated or wound by various methods to obtain a film capacitor.
- An example of a preferred method for producing a wound film capacitor is as follows.
- Aluminum is vacuum-deposited on one side of the biaxially stretched polypropylene film of the present invention (deposition process). In that case, it vapor-deposits in the stripe form which has the margin part which runs in a film longitudinal direction.
- a blade is inserted into the center of each vapor deposition section on the surface and the center of each margin section and slit (slit process), and a tape-shaped take-up reel having a margin on one side is created.
- Two tape-shaped take-up reels with margins on the left or right are wound on each other so that the vapor deposition part protrudes from the margin part in the width direction. Is obtained (element winding step).
- the core material is removed from the wound body and pressed, and the metallicon is sprayed on both end faces to form external electrodes, and 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.
- the method for measuring the characteristic value of the biaxially stretched polypropylene film and the method for evaluating the effect in the present invention are as follows.
- B. Analysis condition LB (line broadening factor) was set to 1.0, and Fourier transform was performed to set the mmmm peak to 21.86 ppm.
- Peak splitting is performed using WINFIT software (manufactured by Bruker). At that time, the peak splitting is performed from the peak on the high magnetic field side as follows, and the attached software is automatically fitted to optimize the peak splitting, and then mmmm and ss (mmmm spinning sideband peaks ) was defined as the mesopentad fraction (mmmm). The measurement was performed 5 times, and the average value was defined as the mesopentad fraction.
- CXS Cold xylene soluble part
- Detection values detected by the measuring device are output as histograms at intervals of 50 nm. For example, when a protrusion having a detection value of 100 nm or more and less than 150 nm is present, the slice value (Z) is counted in a column labeled 150 nm.
- the minimum protrusion height is a slice width lower limit value of the slice value (Z) from which the count value is first output.
- the minimum protrusion height Pmin is 100 nm.
- the maximum protrusion height is the slice width lower limit value of the slice value (Z) for which the count value was last output. That is, if the slice value (Z) from which the count value was last output is a column of 1000 nm, the maximum protrusion height P max is 950 nm. (In the case of the A plane, Pa min and Pa max are indicated, and in the case of the B plane, Pb min and Pb max are indicated.)
- the total number of protrusions indicates the sum of all the values obtained by converting the number of protrusions detected at the sampling interval in the width direction and the length direction shown in the measurement condition item to the number per 0.1 mm 2 . Specifically, it is the sum of the count values detected in the histogram obtained by the measuring device.
- 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.
- the film was measured for roughness.
- Table 1 shows examples of measurement results obtained by the above method.
- each parameter of the present invention is read as follows.
- Side A SRa 39.4nm SRz 933nm Pa min 100nm Pa max 1,050 nm Pa 250-450 206 / 0.1mm 2 (rounded off after the decimal point) Pa 383 pcs / 0.1mm 2 (rounded off after decimal point) Pa 250-450 / Pa 0.54
- the capacitance of the capacitor element at this time was 5 ⁇ F.
- a voltage of 500 VDC is applied to the capacitor element at room temperature, and the applied voltage is gradually increased in steps of 50 VDC / 1 minute after 10 minutes at that voltage.
- a so-called step-up test was performed.
- the change in capacitance at this time was measured and plotted on a graph.
- the voltage at which the capacitance reached 70% of the initial value was divided by the micrometer film thickness (described above) to obtain a withstand voltage evaluation, and 300 V / ⁇ m. The above is the usable level.
- Example 1 A linear polypropylene resin manufactured by Prime Polymer Co., Ltd. having a mesopentad fraction of 0.985 and a melt flow rate (MFR) of 2.6 g / 10 min was added to a branched polypropylene resin manufactured by Basell (high melt tension polypropylene).
- Profax PF-8114 was blended in an amount of 0.5% by mass and supplied to an extruder having a temperature of 250 ° C., and melt-extruded into a sheet form from a T-type slit die at a resin temperature of 250 ° C., and the molten sheet was maintained at 90 ° C. It was cooled and solidified on a 1 m cooling drum to obtain an unstretched film.
- the holding time on the cooling roll was 2.5 seconds.
- the unstretched film was gradually preheated to 140 ° C., subsequently passed between rolls maintained at a temperature of 145 ° C. and provided with a peripheral speed difference, and stretched in the longitudinal direction at a stretch ratio of 4.5 times.
- the heat was compensated for stretching using a radiation heater output of 5 kW in the stretching section.
- the film is quenched between rolls kept at 35 ° C.
- the film was guided to a tenter, stretched 10 times in the width direction at a temperature of 158 ° C., then heat-treated at 155 ° C. while giving 6% relaxation in the width direction, and then cooled to a film thickness of 3.0 ⁇ m.
- Example 2 Except for the cooling drum temperature of 75 ° C., a film was formed in the same manner as in Example 1 to obtain a biaxially stretched polypropylene film.
- the stretching conditions of the obtained biaxially stretched polypropylene film are shown in Table 2, and the characteristics of the obtained film are shown in Tables 3 and 4.
- Example 3 A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that the cooling drum temperature was 95 ° C. and the temperature holding time on the cooling drum was 1.7 seconds.
- the stretching conditions of the obtained biaxially stretched polypropylene film are shown in Table 2, and the characteristics of the obtained film are shown in Tables 3 and 4.
- Example 4 Except that the stretching roll temperature was 139 ° C., a film was formed in the same manner as in Example 1 to obtain a biaxially stretched polypropylene film.
- the stretching conditions of the obtained biaxially stretched polypropylene film are shown in Table 2, and the characteristics of the obtained film are shown in Tables 3 and 4.
- Example 5 Except that the output of the radiation heater was 11 kW, a film was formed in the same manner as in Example 1 to obtain a biaxially stretched polypropylene film.
- the stretching conditions of the obtained biaxially stretched polypropylene film are shown in Table 2, and the characteristics of the obtained film are shown in Tables 3 and 4.
- Example 6 The film was formed in the same manner as in Example 1 except that the cooling drum temperature was 85 ° C., the temperature holding time on the cooling drum was 2.0 seconds, the stretching roll temperature was 147 ° C., and the film thickness was 2.0 ⁇ m. A stretched polypropylene film was obtained. The stretching conditions of the obtained biaxially stretched polypropylene film are shown in Table 2, and the characteristics of the obtained film are shown in Tables 3 and 4.
- Example 7 A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that the stretch ratio was 5.3.
- the stretching conditions of the obtained biaxially stretched polypropylene film are shown in Table 2, and the characteristics of the obtained film are shown in Tables 3 and 4.
- Example 8 A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that both the A side and B side of the film were subjected to corona discharge treatment in air at a treatment strength of 25 W ⁇ min / m 2. It was. Aluminum was vapor-deposited on both the A side and B side of the film to obtain a capacitor.
- the stretching conditions of the obtained biaxially stretched polypropylene film are shown in Table 2, and the characteristics of the obtained film are shown in Tables 3 and 4.
- Example 9 A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that the stretching roll temperature was 147 ° C., the cooling temperature after stretching was 45 ° C., and the film thickness was 2.8 ⁇ m.
- the stretching conditions of the obtained biaxially stretched polypropylene film are shown in Table 2, and the characteristics of the obtained film are shown in Tables 3 and 4.
- Example 10 A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that the stretch ratio was 4.2 times.
- the stretching conditions of the obtained biaxially stretched polypropylene film are shown in Table 2, and the characteristics of the obtained film are shown in Tables 3 and 4.
- Example 11 A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that the cooling drum temperature was 95 ° C, the stretching roll temperature was 147 ° C, the radiation heater output was 8 kW, and the cooling temperature after stretching was 45 ° C. It was.
- the stretching conditions of the obtained biaxially stretched polypropylene film are shown in Table 2, and the characteristics of the obtained film are shown in Tables 3 and 4.
- Example 1 Except for the cooling drum temperature of 65 ° C., a film was formed in the same manner as in Example 1 to obtain a biaxially stretched polypropylene film.
- the stretching conditions of the obtained biaxially stretched polypropylene film are shown in Table 2, and the characteristics of the obtained film are shown in Tables 3 and 4.
- Example 2 Except for the cooling drum temperature of 100 ° C. and the temperature holding time of 1.2 seconds, a film was formed in the same manner as in Example 1 to obtain a biaxially stretched polypropylene film.
- the stretching conditions of the obtained biaxially stretched polypropylene film are shown in Table 2, and the characteristics of the obtained film are shown in Tables 3 and 4.
- Example 3 (Comparative Example 3) Except that the stretching roll temperature was 128 ° C., film formation was performed in the same manner as in Example 1 to obtain a biaxially stretched polypropylene film.
- the stretching conditions of the obtained biaxially stretched polypropylene film are shown in Table 2, and the characteristics of the obtained film are shown in Tables 3 and 4.
- Example 4 A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that the film was stretched in the longitudinal direction without compensating for heat with a radiation heater.
- the stretching conditions of the obtained biaxially stretched polypropylene film are shown in Table 2, and the characteristics of the obtained film are shown in Tables 3 and 4.
- Example 5 A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that the cooling drum temperature was 80 ° C. and the film thickness was 5.0 ⁇ m.
- the stretching conditions of the obtained biaxially stretched polypropylene film are shown in Table 2, and the characteristics of the obtained film are shown in Tables 3 and 4.
- Example 6 (Comparative Example 6) Except that the draw ratio was 3.5, film formation was performed in the same manner as in Example 1 to obtain a biaxially stretched polypropylene film.
- the stretching conditions of the obtained biaxially stretched polypropylene film are shown in Table 2, and the characteristics of the obtained film are shown in Tables 3 and 4.
- Example 7 (Comparative Example 7) Except that the roll temperature (cooling temperature) immediately after stretching was 90 ° C., film formation was performed in the same manner as in Example 1 to obtain a biaxially stretched polypropylene film.
- the stretching conditions of the obtained biaxially stretched polypropylene film are shown in Table 2, and the characteristics of the obtained film are shown in Tables 3 and 4.
- Example 8 Film formation was performed in the same manner as in Example 1 except that the cooling drum temperature was 95 ° C, the temperature holding time was 1.0 second, the stretching roll temperature was 147 ° C, the radiation heater was 14 kW, and the cooling temperature after stretching was 47 ° C. A biaxially stretched polypropylene film was obtained. The stretching conditions of the obtained biaxially stretched polypropylene film are shown in Table 2, and the characteristics of the obtained film are shown in Tables 3 and 4.
- Example 9 A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that the stretching roll temperature was 135 ° C., the heating amount of the radiation heater was 2 kW, and the stretching ratio was 5.7 times.
- the stretching conditions of the obtained biaxially stretched polypropylene film are shown in Table 2, and the characteristics of the obtained film are shown in Tables 3 and 4.
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Abstract
Description
最近では、各種電気設備がインバーター化されつつあり、それに伴いコンデンサの小型化、大容量化の要求が一層強まってきている。そのような市場、特に自動車用途(ハイブリットカー用途を含む)の要求を受け、二軸延伸ポリプロピレンフィルムの耐電圧性や素子加工性を向上させつつ、一層の薄膜化が必須な状況となってきている。
0.5≦Pa250-450/Pa≦1.0 ・・・(1)
0.5≦Pb450-1600/Pb≦1.0 ・・・(2)
600≦Pa+Pb≦1,200 ・・・(3)
|Pa-Pb|≧100 ・・・(4)
さらに、本発明の二軸延伸ポリプロピレンフィルムは、優れた表面特性を有することにより、薄いフィルムであっても加工適性に優れ、低温(-40℃)から高温(115℃)までの広範囲の雰囲気温度条件下でも高耐電圧性を発揮することができるので、特にコンデンサ用途に、好ましくは自動車用のフィルムコンデンサとして好適に使用することができる。
また、本発明の二軸延伸ポリプロピレンフィルムの長手方向の引張強度は120MPa~250MPaであり、かつ幅方向の引張強度が250MPa~400MPaである。
0.5≦Pa250-450/Pa≦1.0 ・・・(1)
0.5≦Pb450-1600/Pb≦1.0 ・・・(2)
600≦Pa+Pb≦1,200 ・・・(3)
上記式(1)~(3)において、Pa250-450は、A面に存在する高さ250nm以上450nm未満の突起の0.1mm2あたりの個数を意味し、Pb450-1600は、B面に存在する高さ450nm以上1600nm未満の突起の0.1mm2あたりの個数を意味し、Paは、A面に存在する突起の0.1mm2あたりの個数を意味し、Pbは、B面に存在する突起の0.1mm2あたりの個数を意味する。
0.5≦Pa250-450/Pa≦1.0 ・・・(1)
0.5≦Pb450-1600/Pb≦1.0 ・・・(2)
600≦Pa+Pb≦1,200 ・・・(3)
上記式(1)~(3)において、Pa250-450は、A面に存在する高さ250nm以上450nm未満の突起の0.1mm2あたりの個数を意味し、Pb450-1600は、B面に存在する高さ450nm以上1600nm未満の突起の0.1mm2あたりの個数を意味し、Paは、A面に存在する突起の0.1mm2あたりの個数を意味し、Pbは、B面に存在する突起の0.1mm2あたりの個数を意味する。
600≦Pa+Pb≦1,200 ・・・(5)
上記式(4)において、Pa+Pbの値は、好ましくは、700~1,100である。両面の突起個数が少なすぎると、フィルムベース面の平滑な部分が多くなり面積当たりの占める割合が高くなるため、フィルム層間間隙が局所的に狭くなり易く、コンデンサの保安性を維持・確保することが困難となる。また、突起個数が多すぎると突起部での絶縁破壊が生じ易くなる。
|Pa-Pb|≧100 ・・・(4)
|Pa-Pb|の値は、好ましくは、200以上である。さらに好ましくは250以上である。上記値が100以上であることにより、コンデンサとしての保安性や信頼性を重要視する用途においては、十分なフィルム層間間隙を維持することができ、セルフヒーリング性が良好で保安性を確保することができる。
代表的な方法として、電気的な不純物を添加せず絶縁破壊電圧等の電気特性を悪化する可能性が低いという観点から、結晶変態を利用して、目的とする突起や表面粗さを得る手法を採用することができる。
直鎖状ポリプロピレンは、通常、包装材やコンデンサ用に使用されるものであるが、好ましくは冷キシレン可溶部(以下CXS)が4質量%以下であることが好ましい。ここで冷キシレン可溶部(CXS)とは、試料を加熱したキシレンで完全溶解した後に室温まで冷却し、冷却により析出した未溶解分をろ過分離した後にキシレン中に溶解しているポリプロピレン成分であり、立体規則性の低い、分子量が低い等の理由で結晶化し難い成分に該当していると考えられる。このような成分が多く樹脂中に含まれているとフィルムの熱寸法安定性に劣ることや、高温での絶縁破壊電圧が低下する等の問題を生じることがある。従って、CXSは4質量%以下であることが好ましいが、更に好ましくは3質量%以下であり、特に好ましくは2質量%以下である。上記範囲は、使用する直鎖状ポリプロピレンについて満足していることが好ましいが、同ポリマーを構成成分とするフィルム全体が満足していることも好ましい。
まず、直鎖状ポリプロピレン樹脂に分岐鎖状ポリプロピレンを所定割合でブレンドして溶融押出し、濾過フィルターを通した後、220~280℃の温度でスリット状口金から押出し、冷却ドラム上で固化させ未延伸フィルムを得る。
冷却ドラムへの密着方法としては静電印加法、水の表面張力を利用した密着方法、エアーナイフ法、プレスロール法、水中キャスト法などのうちいずれの手法を用いてもよいが、平面性が良好でかつ表面粗さの制御が可能なエアーナイフ法が好ましい。
このようにして得られた金属化フィルムは、種々の方法で積層もしくは巻回してフィルムコンデンサを得ることができる。巻回型フィルムコンデンサの好ましい製造方法を例示すると、次のとおりである。
JIS C-2330(2001)の7.4.1.1に従い、マイクロメータ法厚みを測定した。
JIS K-7105(1981)に準じて、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5点のデータの平均値を光沢度とした。
JIS-K7210(1999)に準じて、測定温度230℃、荷重21.18Nで測定した。
JIS-K7210(1999)に示されるMFR測定用の装置に準じて測定した。東洋精機製メルトテンションテスターを用いて、測定対象のポリプロピレンを230℃に加熱し、溶融ポリプロピレンを押出速度15mm/分で吐出しストランドとし、このストランドを6.5m/分の速度で引き取る際の張力を測定し、溶融張力とした。
セイコー社製RDC220示差走査熱量計を用いて、下記以下の条件で測定を行った。
<試料の調製:>
検体5mgを測定用のアルミパンに封入する。尚、フィルムに金属蒸着等が施されている場合は適宜除去する。
以下の(a)→(b)→(c)のステップでフィルムを溶融・再結晶・再溶融させる。樹脂の融点は2nd Runで観測される融解ピークの内で最も高い融解ピーク温度を融点とした。3回測定し、その平均値を融点とした。
(a)1st Run 30℃→280℃(昇温速度20℃/分)
(b)Tmc 280℃で5分保持後に20℃/分で 30℃まで冷却
(c)2nd Run 30℃→280℃(昇温速度20℃/分)
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)。
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
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、更に付属ソフトの自動フィッテイングを行い、ピーク分割の最適化を行った上で、mmmmとss(mmmmのスピニングサイドバンドピーク)のピーク分率の合計をメソペンタッド分率(mmmm)とした。
尚、測定は5回行い、その平均値をメソペンタッド分率とした。
ピーク
(a)mrrm
(b)(c)rrrm(2つのピークとして分割)
(d)rrrr
(e)mrmm+rmrr
(f)mmrr
(g)mmmr
(h)ss(mmmmのスピニングサイドバンドピーク)
(i)mmmm
(j)rmmr
試料を溶媒に溶解し、1H-NMRを用いて、以下の条件にて内部3置換オレフィンの個数を求める。
A.測定条件
装置:日本電子製ECX400P型核磁気共鳴装置
測定核:1H核(共鳴周波数:500MHz)
測定濃度:2wt%
溶媒:重オルトジクロロベンゼン
測定温度:120℃
パルス幅:45°
パルス繰り返し時間:7秒
換算回数:512回
測定モード:non decoupling
オルトジクロロベンゼンの化学シフト7.10ppmを基準とし、5.0~5.2ppm領域のシグナルを内部3置換オレフィンのプロトンと帰属、0.5~2.0ppmのブロードなシグナルとの積分比から内部3置換オレフィンのプロトン比を求める。
ポリプロピレンフィルム試料0.5gを沸騰キシレン100mlに溶解して放冷後、20℃の恒温水槽で1時間再結晶化させた後にろ過液に溶解しているポリプロピレン系成分を液体クロマトグラフ法にて定量する(X(g))。試料0.5gの精量値(X0(g))を用いて以下の式で求める。
CXS(質量%)=(X/X0)×100
JIS B-0601(1982)により、株式会社小坂研究所製「非接触三次元微細形状測定器(ET-30HK)」及び「三次元粗さ分析装置(MODELSPA-11)」を用いて測定した。測定は長手方向に10回繰り返し、その平均値として中心線平均粗さ(SRa)、十点平均粗さ(SRz)、総突起個数、突起個数を求め、更にその比(SRz/SRa)を求めた。1回の測定の詳細条件とデータ処理については下記通りとした。
上記測定器により検出された検出値は、50nm間隔のヒストグラムとして出力される。たとえば検出値として100nm以上150nm未満の突起が存在した場合には、スライス値(Z)として150nmと表記された欄にカウントされる。ここで、最小突起高さは、最初にカウント値が出力されたスライス値(Z)のスライス幅下限値である。すなわち、最初にカウント値が出力されたスライス値(Z)が150nmの欄であれば、最小突起高さPminは100nmとなる。同様に、最大突起高さは、最後にカウント値が出力されたスライス値(Z)のスライス幅下限値である。すなわち、最後にカウント値が出力されたスライス値(Z)が1000nmの欄であれば、最大突起高さPmaxは950nmとなる。
(なお、A面の場合はPamin、Pamax、B面の場合はPbmin、Pbmaxとそれぞれ表記している。)
総突起個数は測定条件の項目に示す幅方向、長さ方向サンプリング間隔で検出された突起個数を0.1mm2あたりの個数に換算した値を全て合計したものを示す。
具体的には、上記測定器により得られるヒストグラムにおいて検出されたカウント値の合計である。
上記ヒストグラムのA面の値について、高さ250nm以上450nm未満に該当する突起検出個数を全て総和したものを示す。具体的には、スライス値(Z)が300~450nmに対応する欄のカウント値の合計である。
上記(c)と同様である。具体的には、ヒストグラムのB面の値について、スライス値(Z)が500~1,600nmに対応する欄のカウント値の合計である。
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
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を粗さ測定した。
上記方法によって得られた測定結果の例を表1に示す。データが表1の場合、本発明の各パラメータは次の通り読みとる。
A面
SRa 39.4nm
SRz 933nm
Pamin 100nm
Pamax 1,050nm
Pa250-450 206個/0.1mm2(小数点以下四捨五入)
Pa 383個/0.1mm2(小数点以下四捨五入)
Pa250-450/Pa 0.54
B面
SRa 41.1nm
SRz 1,120nm
Pbmin 200nm
Pbmax 1,200nm
Pb450-1600 439個/0.1mm2(小数点以下四捨五入)
Pb 584個/0.1mm2(小数点以下四捨五入)
Pb450-1600/Pb 0.75
Pa+Pb 967個/0.1mm2(小数点以下四捨五入)
|Pa-Pb| 201個/0.1mm2(小数点以下四捨五入)
JIS C-2330(2001年)7.4.5に準じて、株式会社オリエンテック製「テンシロン万能試験機(RTC―1310)」を用いて測定した。
金属化フィルムを長手方向に10mm幅方向に全幅(50mm)の長方形にカットして試料とし、4端子法により、幅方向30mm間の金属膜の抵抗を測定し、得られた測定値に測定幅(10mm)を乗じて電極間距離(30mm)を除して、10mm×10mm当たりの膜抵抗(表面電気抵抗)を算出した。(単位:Ω/□)
JIS C2330(2001)7.4.11.2 B法(平板電極法)に準じて、平均値を求め、測定したサンプルのマイクロメータ法フィルム厚み(μm)(上述)で除し、V/μmで表記した。
後述する各実施例および比較例で得られた二軸延伸ポリプロピレンフィルムの片面に、ULVAC製真空蒸着機でアルミニウムを膜抵抗が8Ω/sqとなるようにアルミニウムを真空蒸着した。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)。次に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、左もしくは右に0.5mmのマージンを有する全幅20mmのテープ状に巻取リールにした。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枚重ね合わせて巻回し、静電容量約10μFの巻回体を得た。素子巻回には皆藤製作所製KAW-4NHBを用いた。
上記のコンデンサの製造の際、巻き始めから巻き終わりまでを目視で観察し、しわ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の製造数全体に対する割合を百分率で示し加工性の指標とした(以下素子巻収率と称する)。素子巻収率は高いほど好ましい。95%以上を良好「○」、95%未満80%以上を「△」、80%未満を不良「×」とした。「○」または「△」が実用可能なレベルである。
後述する各実施例および比較例で得られた二軸延伸ポリプロピレンフィルムに、ULVAC製真空蒸着機でアルミニウムを膜抵抗が8Ω/sqで長手方向に垂直な方向にマージン部を設けた所謂T型マージンパターンを有する蒸着パターンを施し、幅50mmの蒸着リールを得た。
次いで、このリールを用いて皆藤製作所製素子巻機(KAW-4NHB)にてコンデンサ素子を巻き取り、メタリコンを施した後、減圧下、105℃の温度で10時間の熱処理を施し、リード線を取り付け、コンデンサ素子を仕上げた。このときのコンデンサ素子の静電容量は5μFであった。
こうして得られたコンデンサ素子10個を用いて、常温下でコンデンサ素子に500VDCの電圧を印加し、該電圧で10分間経過後にステップ状に50VDC/1分で徐々に印加電圧を上昇させることを繰り返す所謂ステップアップ試験を行なった。この際の静電容量変化を測定しグラフ上にプロットして、該容量が初期値の70%になった電圧をマイクロメータ法フィルム厚み(上述)で割り返して耐電圧評価とし、300V/μm以上を使用可能レベルとする。また、静電容量が初期値に対して10%以下に減少するまで電圧を上昇させた後に、コンデンサ素子を解体し破壊の状態を調べて、保安性を以下の通り評価した。
◎:素子形状の変化は無く貫通状の破壊は観察されない。
○:素子形状の変化は無くフィルム10層以内の貫通状破壊が観察される。
△:素子形状に変化が認められる若しくは10層を超える貫通状破壊が観察される。
×:素子形状が破壊する。
◎は問題なく使用できるが、○では条件次第で使用可能である。△、×では実用上の問題を生じる。
メソペンタッド分率が0.985で、メルトフローレイト(MFR)が2.6g/10分であるプライムポリマー(株)製直鎖状ポリプロピレン樹脂に、Basell社製分岐鎖状ポリプロピレン樹脂(高溶融張力ポリプロピレンProfax PF-814)を0.5質量%ブレンドし温度250℃の押出機に供給し、樹脂温度250℃でT型スリットダイよりシート状に溶融押出し、該溶融シートを90℃に保持された直径1mの冷却ドラム上で冷却固化して未延伸フィルムを得た。冷却ロール上での保持時間は2.5秒であった。次いで、該未延伸フィルムを徐々に140℃に予熱し、引き続き145℃の温度に保ち周速差を設けたロール間に通し、延伸倍率4.5倍で長手方向に延伸した。その際、延伸部でラジエーションヒーター出力5kWを用い熱量を補い延伸した。その直後、35℃に保持されたロール間にフィルムを通し急冷する。引き続き該フィルムをテンターに導き、158℃の温度で幅方向に10倍延伸し、次いで幅方向に6%の弛緩を与えながら155℃で熱処理を行ない、その後冷却しフィルム厚みが3.0μmの二軸延伸ポリプロピレンフィルムを得た。さらにフィルムの表面に25W・min/m2の処理強度で大気中でコロナ放電処理を行った。こうして得られた二軸延伸ポリプロピレンフィルムの延伸条件を表2に、得られたフィルムの特性、ならびに該フィルムをコンデンサとした際の耐電圧(絶縁破壊電圧)と素子加工性(素子巻収率)を表3、4に示す。表3および4に示すように、実施例1にかかる二軸延伸ポリプロピレンフィルムから作成したコンデンサは、耐電圧、保安性とも優れるものであった。
冷却ドラム温度75℃以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの延伸条件を表2に、得られたフィルムの特性を表3、4に示す。
冷却ドラム温度を95℃、冷却ドラム上の温度保持時間を1.7秒とした以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの延伸条件を表2に、得られたフィルムの特性を表3、4に示す。
延伸ロール温度を139℃とした以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの延伸条件を表2に、得られたフィルムの特性を表3、4に示す。
ラジエーションヒーター出力を11kWとした以外は実施例1と同様に製膜を行い二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの延伸条件を表2に、得られたフィルムの特性を表3、4に示す。
冷却ドラム温度を85℃、冷却ドラム上の温度保持時間を2.0秒、延伸ロール温度を147℃、フィルム厚みを2.0μmとした以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの延伸条件を表2に、得られたフィルムの特性を表3、4に示す。
延伸倍率を5.3倍とした以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの延伸条件を表2に、得られたフィルムの特性を表3、4に示す。
フィルムのA面、B面の両面に25W・min/m2の処理強度で大気中でコロナ放電処理を行った以外は、実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。該フィルムのA面、B面の両面にアルミニウム蒸着を施しコンデンサとした。得られた二軸延伸ポリプロピレンフィルムの延伸条件を表2に、得られたフィルムの特性を表3、4に示す。
延伸ロール温度を147℃、延伸後の冷却温度を45℃、フィルム厚みを2.8μmとした以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの延伸条件を表2に、得られたフィルムの特性を表3、4に示す。
延伸倍率を4.2倍とした以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの延伸条件を表2に、得られたフィルムの特性を表3、4に示す。
冷却ドラム温度を95℃、延伸ロール温度を147℃、ラジエーションヒーター出力を8kW、延伸後の冷却温度を45℃とした以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの延伸条件を表2に、得られたフィルムの特性を表3、4に示す。
冷却ドラム温度を65℃以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの延伸条件を表2に、得られたフィルムの特性を表3、4に示す。
冷却ドラム温度を100℃、温度保持時間を1.2秒以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの延伸条件を表2に、得られたフィルムの特性を表3、4に示す。
延伸ロール温度を128℃とした以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの延伸条件を表2に、得られたフィルムの特性を表3、4に示す。
ラジエーションヒーターで熱を補うことなく長手方向に延伸した以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの延伸条件を表2に、得られたフィルムの特性を表3、4に示す。
冷却ドラム温度を80℃、フィルム厚みを5.0μmとした以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの延伸条件を表2に、得られたフィルムの特性を表3、4に示す。
延伸倍率を3.5倍とした以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの延伸条件を表2に、得られたフィルムの特性を表3、4に示す。
延伸直後のロール温度(冷却温度)を90℃とした以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの延伸条件を表2に、得られたフィルムの特性を表3、4に示す。
冷却ドラム温度を95℃、温度保持時間を1.0秒、延伸ロール温度を147℃、ラジエーションヒーターを14kW、延伸後の冷却温度を47℃とした以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの延伸条件を表2に、得られたフィルムの特性を表3、4に示す。
延伸ロール温度を135℃、ラジエーションヒーター熱量を2kW、延伸倍率を5.7倍とした以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの延伸条件を表2に、得られたフィルムの特性を表3、4に示す。
Claims (10)
- 両面に突起を有する二軸延伸ポリプロピレンフィルムであって、厚みt1が1μm~3μmであり、長手方向の引張強度が120MPa~250MPaであり、かつ幅手方向の引張強度が250MPa~400MPaであり、いずれの表面についても最小突起高さPminが100nm以上であり、最大突起高さPmaxが1,600nm以下であり、かつ、一方の表面をA面、他方の面をB面としたとき、下記式(1)~(3)を全て満足していることを特徴とする二軸延伸ポリプロピレンフィルム。
0.5≦Pa250-450/Pa≦1.0 ・・・(1)
0.5≦Pb450-1600/Pb≦1.0 ・・・(2)
600≦Pa+Pb≦1,200 ・・・(3)
上記式(1)~(3)において、
Pa250-450は、A面に存在する高さ250nm以上450nm未満の突起の0.1mm2あたりの個数を意味し、
Pb450-1600は、B面に存在する高さ450nm以上1600nm未満の突起の0.1mm2あたりの個数を意味し、
Paは、A面に存在する突起の0.1mm2あたりの個数を意味し、
Pbは、B面に存在する突起の0.1mm2あたりの個数を意味する。 - PaおよびPbが、下記式(4)を満たすことを特徴とする請求項1に記載の二軸延伸ポリプロピレンフィルム。
|Pa-Pb|≧100 ・・・(4) - 十点平均粗さ(SRz)が、いずれの表面についても500nm以上1,500nm以下であることを特徴とする請求項1または2に記載の二軸延伸ポリプロピレンフィルム。
- 中心線表面粗さ(SRa)が、いずれの表面についても20nm以上50nm以下であることを特徴とする請求項1~3のいずれか一つに記載の二軸延伸ポリプロピレンフィルム。
- 中心線表面粗さ(SRa)と十点平均粗さ(SRz)との比であるSRz/SRa値が、いずれの表面についても20以上40以下であることを特徴とする請求項1~4のいずれかに記載の二軸延伸ポリプロピレンフィルム。
- 分岐鎖状ポリプロピレンを0.05~10質量%含有することを特徴とする、請求項1~5のいずれか一つに記載の二軸延伸ポリプロピレンフィルム。
- 請求項1~6のいずれか一つに記載の二軸延伸ポリプロピレンフィルムの少なくとも片面に金属膜が設けられてなることを特徴とする金属化フィルム。
- 前記二軸延伸ポリプロピレンフィルムの両面に金属膜が設けられてなることを特徴とする請求項7に記載の金属化フィルム。
- 金属膜の表面電気抵抗が1~20Ω/□の範囲内にあることを特徴とする請求項7または8に記載の金属化フィルム。
- 請求項7~9のいずれか一つに記載の金属化フィルムを用いてなることを特徴とするフィルムコンデンサ。
Priority Applications (8)
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ES12754628.1T ES2556607T3 (es) | 2011-03-10 | 2012-03-06 | Película de polipropileno estirada biaxialmente, película metalizada y condensador de película |
BR112013022796A BR112013022796A2 (pt) | 2011-03-10 | 2012-03-06 | filme de polipropileno biaxialmente estirado, filme metalizado, e capacitor de filme |
EP12754628.1A EP2684676B1 (en) | 2011-03-10 | 2012-03-06 | Biaxially stretched polypropylene film, metallized film, and film capacitor |
CN201280012266.7A CN103429416B (zh) | 2011-03-10 | 2012-03-06 | 双轴拉伸聚丙烯膜、金属化膜和薄膜电容器 |
US14/004,068 US9123471B2 (en) | 2011-03-10 | 2012-03-06 | Biaxially stretched polypropylene film, metallized film and film capacitor |
KR1020137024638A KR101901470B1 (ko) | 2011-03-10 | 2012-03-06 | 2축 연신 폴리프로필렌 필름, 금속화 필름 및 필름 콘덴서 |
RU2013145308/05A RU2013145308A (ru) | 2011-03-10 | 2012-03-06 | Двуосноориентированная полипропиленовая пленка, металлизированная пленка и пленочный конденсатор |
JP2012517953A JP5472461B2 (ja) | 2011-03-10 | 2012-03-06 | 二軸延伸ポリプロピレンフィルム、金属化フィルム、およびフィルムコンデンサ |
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EP (1) | EP2684676B1 (ja) |
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KR (1) | KR101901470B1 (ja) |
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Also Published As
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US9123471B2 (en) | 2015-09-01 |
EP2684676A1 (en) | 2014-01-15 |
KR101901470B1 (ko) | 2018-09-21 |
US20140016244A1 (en) | 2014-01-16 |
RU2013145308A (ru) | 2015-04-20 |
CN103429416B (zh) | 2015-08-05 |
EP2684676B1 (en) | 2015-10-28 |
ES2556607T3 (es) | 2016-01-19 |
JPWO2012121256A1 (ja) | 2014-07-17 |
CN103429416A (zh) | 2013-12-04 |
JP5472461B2 (ja) | 2014-04-16 |
EP2684676A4 (en) | 2015-03-11 |
KR20140011344A (ko) | 2014-01-28 |
BR112013022796A2 (pt) | 2016-12-06 |
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