JP7311605B2 - 破壊強度が改善された二軸配向ポリプロピレンフィルム - Google Patents
破壊強度が改善された二軸配向ポリプロピレンフィルム Download PDFInfo
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- JP7311605B2 JP7311605B2 JP2021534152A JP2021534152A JP7311605B2 JP 7311605 B2 JP7311605 B2 JP 7311605B2 JP 2021534152 A JP2021534152 A JP 2021534152A JP 2021534152 A JP2021534152 A JP 2021534152A JP 7311605 B2 JP7311605 B2 JP 7311605B2
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- film
- biaxially oriented
- polypropylene composition
- oriented polypropylene
- weight
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- 239000011127 biaxially oriented polypropylene Substances 0.000 title claims description 72
- 229920006378 biaxially oriented polypropylene Polymers 0.000 title claims description 70
- -1 polypropylene Polymers 0.000 claims description 117
- 229920001155 polypropylene Polymers 0.000 claims description 92
- 239000004743 Polypropylene Substances 0.000 claims description 91
- 239000000203 mixture Substances 0.000 claims description 86
- 230000015556 catabolic process Effects 0.000 claims description 68
- 229920001384 propylene homopolymer Polymers 0.000 claims description 58
- 238000009826 distribution Methods 0.000 claims description 47
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- 239000003484 crystal nucleating agent Substances 0.000 claims description 36
- 239000003990 capacitor Substances 0.000 claims description 24
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- 239000010408 film Substances 0.000 description 132
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 41
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- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 3
- 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 3
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000005025 cast polypropylene Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
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- RIZMRRKBZQXFOY-UHFFFAOYSA-N ethion Chemical compound CCOP(=S)(OCC)SCSP(=S)(OCC)OCC RIZMRRKBZQXFOY-UHFFFAOYSA-N 0.000 description 2
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- 230000007246 mechanism Effects 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 2
- QPFMBZIOSGYJDE-QDNHWIQGSA-N 1,1,2,2-tetrachlorethane-d2 Chemical compound [2H]C(Cl)(Cl)C([2H])(Cl)Cl QPFMBZIOSGYJDE-QDNHWIQGSA-N 0.000 description 1
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- MSTDXOZUKAQDRL-UHFFFAOYSA-N 4-Chromanone Chemical compound C1=CC=C2C(=O)CCOC2=C1 MSTDXOZUKAQDRL-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 208000006670 Multiple fractures Diseases 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 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
- 150000007513 acids Chemical class 0.000 description 1
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- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
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- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
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- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
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- 229920000098 polyolefin Polymers 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000011593 sulfur Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 229960000984 tocofersolan Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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Classifications
-
- 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
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Description
(i)前記ポリプロピレン組成物の総重量に基づいて、93~98%のアイソタクチックペンタッド分率の含有量および0.4~10g/10minのメルトフローレートMFR2を有する90~99.99重量%のプロピレンホモポリマーと、
(ii)ポリプロピレン組成物の総重量に基づいて、0.0000001~1重量%の高分子α晶造核剤と、
を含み、前記二軸配向ポリプロピレンフィルムは、
・厚さ3.8~4.2μmのフィルムで、250V/sのDC電圧上昇速度を使用して、2.84cm2の有効電極面積で測定された50の結果に基づいて、適合した2パラメータワイブル分布の尺度パラメータαとして取得された絶縁破壊電界強度Eb63.2が少なくとも595kV/mmであり、
・好ましくは厚さが2~5μmで、さらに前記フィルムは機械方向と横方向に同時に引き伸ばされる。
プロピレンの高アイソタクチックホモポリマー(i)は、ポリプロピレン組成物の主成分である。ポリプロピレン組成物は、90~99.99重量%、好ましくは95~99.9重量%、より好ましくは98~99.99重量%、特に99~99.9重量%のプロピレンの高アイソタクチックホモポリマー(i)を含む。
ポリプロピレン組成物は、ポリマーα核剤晶造核剤(ii)を含む。高分子α晶造核剤(ii)は、式CH2=CH-CHR6R7のビニル化合物のポリマーであり、R6とR7は一緒になって、5員または6員の飽和、不飽和、または芳香族環を形成するか、独立して1~4個の炭素原子を含むアルキル基を表す。好ましくは、高分子α晶造核剤(ii)は、式CH2=CH-CHR6R7のビニル化合物のホモポリマーである。
したがって、本発明の好ましい実施形態によれば、ポリプロピレン組成物は、
(iii)ポリプロピレン組成物の総重量に基づいて、プロピレンホモポリマー(i)以外の、すなわちプロピレンの高アイソタクチックホモポリマー(i)以外に、最大で9.99重量%のプロピレンホモポリマーまたはコポリマーをさらに含む。
本発明の好ましい実施形態によれば、ポリプロピレン組成物は、
(iv)ポリプロピレン組成物の総重量に基づいて、0.01~1重量%、好ましくは0.05~0.8重量%の従来の添加剤をさらに含む。
ポリプロピレン組成物は、90~99.99重量%、好ましくは90~99.9重量%、より好ましくは95~99.9重量%、特に99~99.9重量%のプロピレンの高アイソタクチックホモポリマー(i)を含む。さらに、ポリプロピレン組成物は、0.0000001~1重量%の高分子系α晶造核剤(ii)を含む。ポリプロピレン組成物は、好ましくは、0.01~1.0重量%の従来の添加剤(iv)も含む。
本発明による二軸配向ポリプロピレンフィルムは、少なくとも595kV/mmの絶縁破壊電界強度Eb63.2を有し、これは、厚さ3.8~4.2μmのフィルムで250V/sのDC電圧上昇速度を使用して、2.84cm2の有効電極面積で、測定された50の結果に基づいて適合された2パラメータワイブル分布の尺度パラメータαとして得られる。
さらなる態様による本発明は、上記で詳述したように、二軸配向ポリプロピレンフィルムの層を含む絶縁フィルムを含むコンデンサに関する。
さらなる態様による本発明は、二軸配向ポリプロピレンフィルムの製造プロセスに関し、このプロセスは、
(A)ポリプロピレン組成物であって、
(i)前記ポリプロピレン組成物の総重量に基づいて、93~98%のアイソタクチックペンタッド分率の含有量および0.4~10g/のメルトフローレートMFR2を有する90~99.99重量%のプロピレンホモポリマーと、
(ii)前記ポリプロピレン組成物の総重量に基づいて、0.0000001~1重量%の高分子α晶造核剤と、を含む、
ポリプロピレン組成物を提供するステップと、
(B)前記ポリプロピレン組成物を平坦フィルムに押し出すステップと、
(C)前記平坦フィルムを機械方向と横方向に同時に配向させて、前記二軸配向ポリプロピレンフィルムを取得するステップと、
(D)前記二軸配向ポリプロピレンフィルムを回収するステップと、を含む。
(iii)前記ポリプロピレン組成物の総重量に基づいて、前記プロピレンホモポリマ(i)以外に、最大で9.99重量%のプロピレンホモポリマーまたはコポリマーを
さらに含む。
(iv)前記ポリプロピレン組成物の総重量に基づいて、0.01~1重量%の従来の添加剤を
さらに含む。
・厚さ3.8~4.2μmのフィルムで、250V/sのDC電圧上昇速度を使用して、2.84cm2の有効電極面積で測定された50の結果に基づいて、適合した2パラメータワイブル分布の尺度パラメータαとして取得された絶縁破壊電界強度Eb63.2が少なくとも595kV/mmで、好ましくは600kV/mmであり、
・好ましくは、絶縁破壊電界強度Eb10.0が少なくとも535kV/mmで、より好ましくは少なくとも540kV/mmであり、
・好ましくは、厚さが2~5μmで、さらに好ましくは3~5μmで、またさらに好ましくは3.5~4.5μmである。
さらなる態様による本発明は、コンデンサの絶縁フィルムの層として、上記で詳述したように、本発明の二軸配向ポリプロピレンフィルムの使用に関する。
一般
絶縁破壊強度Eb、または電界(kV/mm)は、気体、液体、および固体の特性である。電界がEbを超えると、電極を接続する材料を通る放電チャネルによって破壊が発生する。固体では、放電によって材料が不可逆的に破壊されるが、気体および液体では、損傷は一時的で可逆的である。
固体の絶縁破壊強度は、通常、電極間に薄い試験片(平板、シート、またはフィルム)を挟み、絶縁破壊が発生するまで、電圧を(線形、指数関数的に、段階的になど)上昇させることにより、短時間昇圧試験で試験され、これにより、試験片の絶縁破壊電圧(kV)が得られる(IEC60234-1(2013)「絶縁材料の破壊強度・試験方法・第1部:電力周波数による試験」を参照)。次に、絶縁破壊スポットでの試験片の厚さを測定して、絶縁破壊強度Eb(kV/mm)を取得する。この試験は、材料の絶縁破壊分布を得るために、同じように準備された材料の試験片で繰り返される(R Rytoluoto I.; Gitsas A.; Pasanan S.; Lahti K. Effect of film structure and morphology on the dielectric breakdown characteristics of cast and biaxially oriented polypropylene films. European Polymer Journal,2017,95,606-624を参照)。
電圧上昇試験から得られた破壊分布は、通常、正規分布ではなく、極値分布に従い、ワイブル分布が一般的に使用される(Dissado L. A.; Fothergill J. C. “Electrical degradation and breakdown in polymers”, IEEE Materials and Devices Series 9, Peter Peregrinus Ltd.,1992,およびIEC62539(2007)「電気絶縁破壊データの統計分析のためのガイド」を参照)。ワイブル分布は、最初に提案されたように、3つのパラメータ、すなわち、尺度パラメータα、形状パラメータβ、および位置パラメータδを使用する。尺度パラメータαは、ワイブル分布の平均であり、正規分布の平均と類似しているが、同等ではない。平均は正規分布の50パーセンタイルであるが、尺度パラメータαは、ワイブル分布の63.2パーセンタイルである。材料の絶縁破壊強度を意味する場合、ほとんどの著者は、本質的に尺度パラメータαを参照する。形状パラメータβは、その名前が示すように、ワイブル分布の形状に影響を与える。ワイブル分布は、低βの場合は指数分布のように見え、高βの場合は正規分布のようにほぼベル型になる。そのため、βが高いということは、分散が低く、ベル形状であることを意味する。位置パラメータδは、実験分布を原点に移動するため、「シフト定数」である。つまり、Eb-δ=0の場合、故障確率はゼロである。しかしながら、δは不要であることが多く、ゼロと見なされ、著者は、ワイブル分布を、2つのパラメータで、すなわち、αとβのみを使用して適用する。
測定された破壊強度と破壊分布は、直流または交流の使用(Krentz T.; Khani M. M.; Bell M.; Benicewicz B. C.; Nelson J. K.; Zhao S.; Schadler L. S. Morphologically dependent alternating-current and direct-current breakdown strength in silica-polypropylene nanocomposites. Journal of Applied Polymer Science,2017,134)および電圧上昇速度(Rytoluoto I.; Ritamaki M.; Lahti K.; Karttunen M. Ramp rate effect on the breakdown response of SiO2-BOPP Nano composites, IEEE International conference on the properties of applications of dielectric materials,2015,496-499)など、いくつかの実験の詳細に影響を受ける。もう1つの重要な実験の詳細は、測定された体積である。試料の厚さと(電極)面積は、破壊強度に影響を与える(Laihonen S. J. et al. “Area dependence of breakdown strength of polymer films: automatic measurement method.” IEEE Transactions on dielectrics and electrical insulation,2007,14,263-274,およびRytoluoto I.; Lahti K. Effect of film thickness and electrode area on the dielectric breakdown characteristics of metallized film capacitor films, 23rd Nordic Insulation Symposium (Nordis 13),2013,33-38参照)ので、破壊結果とともに報告する必要がある。
以下の用語の定義および決定方法は、別段の定めがない限り、本発明の上記の一般的な説明および以下の実施例に適用される。
メルトフローレートMFR2は、2.16kgの荷重下、230℃でISO1133に従って測定した。
定量核磁気共鳴(NMR)分光法を使用して、プロピレンホモポリマーのアイソタクチシティと位置規則性を定量化した。
ポリマーの灰分含有量は、秤量済み白金るつぼでポリマーを燃焼させて測定した。約100gのポリマーをるつぼの中に入れて秤量する。次いで、ポリマーがゆっくりと燃えるように、るつぼをブンゼンバーナーの火炎で加熱する。ポリマーが完全に燃えた後、るつぼを冷却し、乾燥させて秤量する。灰分含有量は、そのとき、残渣の重量をポリマーサンプルの重量で除した値である。少なくとも2回の測定を行い、測定値間の差が7ppm超である場合、3回目の測定を行う。
動的レオロジー測定を、圧縮成形サンプルについて、Rheometrics RDA-II QCを用いて200℃で窒素雰囲気下、直径25mmの円板・円板の幾何学的形状により行った。振動剪断実験は、ISO6721-10に従って、0.015~300rad/sの周波数で歪みの線形粘弾性範囲内にて行った。
f’(ω)=η’(ω)/[η’(ω)2+η’’(ω)2]および
f’’(ω)=η’’(ω)/[η’(ω)2+η’’(ω)2]
η’=G’’/ωおよびη’’=G’/ω
f’(ω)=G’’(ω)・ω/[G’(ω)2+G’’(ω)2]
f’’(ω)=G’(ω)・ω/[G’(ω)2+G’’(ω)2]
によって定義される。
絶縁破壊電圧(BDV)は、直流(DC)、250V/sの電圧上昇速度、および円筒電極の直径(2.5cm)から、エッジ半径が0.3cmであるために0.6cm減少した2.84cm2の有効電極面積を使用して、DIN IEC60243-2(IEC60243-1および-2の円筒/平板設定。図1aを参照)と概ね一致して決定された。IEC60243-2の標準電極設計は、上部円筒電極と接地電極上に配置されたアルミナ箔で覆われたパッド発泡エラストマーの間にBOPPフィルムを配置するという変更を加えて使用された(図1bを参照)。
破壊分布DBDを評価するために、IEC62539は、2パラメータワイブル分布(2ワイブル)、3パラメータワイブル分布(3ワイブル)、対数正規分布、および第一の極値漸近分布(1AEV)などの極値分布を推奨している。一般に、破壊メカニズムが不明な場合、統計的分布は、主にフィッティング品質によって選択される。しかしながら、ほとんどの著者は、ワイブル分布を使用する。ワイブル分布の3パラメータバリアントの累積密度分布関数は、式1で与えられる。
以下の材料および化合物が実施例で使用されている。
iHPP:特許文献2の参照例1に従って製造されたプロピレンの高アイソタクチックホモポリマー。このポリマーは、多分散性指数PIが6.1 1/Paである。
nPP:特許文献2の参照例3に従って製造された有核プロピレンホモポリマー
W:多分散性指数PIが比較的大きく、6.6 1/PaであるiHPPのバリアントである。
N:多分散性指数PIが比較的狭く、5.8 1/PaであるiHPPのバリアントである。
Rytoluoto I.; Lahti K. New approach to evaluate area-dependent breakdown characteristics of dielectric polymer films, Transactions on Dielectrics and Electrical Insulation,2013,20,937-946。
個々の破壊:N=10、IEC60243電極設計(IEC60243-1、2013、図1c)を使用、電圧上昇速度:250V/s。
Claims (12)
- 連続プロセスで製造するために、ポリプロピレン組成物を含む二軸配向ポリプロピレンフィルムであって、前記ポリプロピレン組成物が、
(i)前記ポリプロピレン組成物の総重量に基づいて、93~98%のアイソタクチックペンタッド分率の含有量および2.16kgの荷重下230℃でISO1133に従って測定される0.4~10g/10minのメルトフローレートMFR2を有する、90~99.99重量%のプロピレンホモポリマーと、
(ii)前記ポリプロピレン組成物の総重量に基づいて、0.0000001~1重量%の高分子α晶造核剤と、
を含み、
前記二軸配向ポリプロピレンフィルムが、
・厚さ3.8~4.2μmのフィルムで、250V/sのDC電圧上昇速度を使用して、2.84cm2の有効電極面積で測定された50の結果に基づいて、適合した2パラメータワイブル分布の尺度パラメータαとして取得された絶縁破壊電界強度Eb63.2が少なくとも595kV/mmであり、
・厚さは2~5μmで、さらに前記フィルムは機械方向と横方向に同時に引き伸ばされる、
二軸配向ポリプロピレンフィルム。 - 前記ポリプロピレン組成物が
(iv)前記ポリプロピレン組成物の総重量に基づいて、0.01~1重量%の従来の添加剤をさらに含み、前記従来の添加剤が、酸化防止剤、安定剤、酸スカベンジャー、およびそれらの混合物からなる群から選択される、請求項1に記載の二軸配向ポリプロピレンフィルム。 - 前記ポリプロピレン組成物が30ppm以下の灰分含有量を有し、および/またはTDまたはMDのいずれかにおける延伸比が少なくとも8.0である、請求項1または2に記載の二軸配向ポリプロピレンフィルム。
- 前記高分子α晶造核剤が、ポリビニルシクロヘキサン、ポリ(3-メチル-1-ブテン)およびそれらの混合物からなる群から選択される、請求項1~3のいずれか一項に記載の二軸配向ポリプロピレンフィルム。
- 前記フィルムが前記ポリプロピレン組成物からなる層を含み、および/または前記フィルムの厚さが2~5μmの間である、請求項1~4のいずれか一項に記載の二軸配向ポリプロピレンフィルム。
- 前記フィルムが金属層も含む、請求項1~5のいずれか一項に記載の二軸配向ポリプロピレンフィルム。
- 絶縁破壊電界強度Eb10.0が少なくとも535kV/mmである、請求項1~6のいずれか一項に記載の二軸配向ポリプロピレンフィルム。
- 請求項1~7のいずれか一項に記載の二軸配向ポリプロピレンフィルムの層を含む絶縁フィルムを含むコンデンサ。
- 二軸配向ポリプロピレンフィルムを製造するためのプロセスであって、
(A)ポリプロピレン組成物であって、
(i)前記ポリプロピレン組成物の総重量に基づいて、93~98%のアイソタクチックペンタッド分率の含有量および2.16kgの荷重下230℃でISO1133に従って測定される0.4~10g/10minのメルトフローレートMFR2を有する、90~99.99重量%のプロピレンホモポリマーと、
(ii)前記ポリプロピレン組成物の総重量に基づいて、0.0000001~1重量%の高分子α晶造核剤と、を含む、
ポリプロピレン組成物を提供するステップと、
(B)前記ポリプロピレン組成物を平坦フィルムに押し出すステップと、
(C)前記平坦フィルムを機械方向と横方向に同時に配向させて、前記二軸配向ポリプロピレンフィルムを取得するステップと、
(D)前記二軸配向ポリプロピレンフィルムを回収するステップと、
を含む、プロセス。 - ポリプロピレン組成物が、
(iv)前記ポリプロピレン組成物の総重量に基づいて、0.01~1重量%の従来の添加剤をさらに含み、前記従来の添加剤が、酸化防止剤、安定剤、酸スカベンジャー、およびそれらの混合物からなる群から選択される、請求項9に記載のプロセス。 - 前記二軸配向ポリプロピレンフィルムを得るための、前記機械方向および前記横方向への前記平坦フィルムの同時配向が、連続プロセスで行われ、および/またはTDまたはMDのいずれかにおける延伸比は、少なくとも8.0である、請求項9または10に記載のプロセス。
- 前記二軸配向ポリプロピレンフィルムが、
・厚さ3.8~4.2μmのフィルムで、250V/sのDC電圧上昇速度を使用して、2.84cm2の有効電極面積で測定された50の結果に基づいて、適合した2パラメータワイブル分布の尺度パラメータαとして取得された絶縁破壊電界強度Eb63.2が少なくとも595kV/mmであり、
・厚さは2~5μmである、
請求項9~11のいずれか一項に記載のプロセス。
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KR20220047832A (ko) | 2019-08-19 | 2022-04-19 | 보레알리스 아게 | 개선된 특성을 갖는 폴리프로필렌 - 폴리에틸렌 배합물 |
ES2952634T3 (es) | 2019-08-19 | 2023-11-02 | Borealis Ag | Combinaciones de polipropileno - polietileno con propiedades mejoradas |
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US20220033631A1 (en) | 2022-02-03 |
CN113195605A (zh) | 2021-07-30 |
KR20210102950A (ko) | 2021-08-20 |
WO2020127861A1 (en) | 2020-06-25 |
US11851552B2 (en) | 2023-12-26 |
JP2022514249A (ja) | 2022-02-10 |
KR102593923B1 (ko) | 2023-10-25 |
EP3898789A1 (en) | 2021-10-27 |
SG11202106418WA (en) | 2021-07-29 |
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