WO2012099167A1 - コンデンサー用ポリプロピレンフィルム - Google Patents
コンデンサー用ポリプロピレンフィルム Download PDFInfo
- Publication number
- WO2012099167A1 WO2012099167A1 PCT/JP2012/050965 JP2012050965W WO2012099167A1 WO 2012099167 A1 WO2012099167 A1 WO 2012099167A1 JP 2012050965 W JP2012050965 W JP 2012050965W WO 2012099167 A1 WO2012099167 A1 WO 2012099167A1
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- WIPO (PCT)
- Prior art keywords
- molecular weight
- film
- biaxially stretched
- polypropylene film
- stretched polypropylene
- Prior art date
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- -1 Polypropylene Polymers 0.000 title claims abstract description 108
- 239000003990 capacitor Substances 0.000 title claims abstract description 107
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 104
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- 238000000034 method Methods 0.000 claims description 77
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- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical group ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
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- ZVVFVKJZNVSANF-UHFFFAOYSA-N 6-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]hexyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCCCCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 ZVVFVKJZNVSANF-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
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- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
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- 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
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- WZSYKGHOYGNHKS-UHFFFAOYSA-N 1,2-ditert-butyl-4-methylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CCC(O)(C(C)(C)C)C(C(C)(C)C)=C1 WZSYKGHOYGNHKS-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- VFBJXXJYHWLXRM-UHFFFAOYSA-N 2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethylsulfanyl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCSCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 VFBJXXJYHWLXRM-UHFFFAOYSA-N 0.000 description 1
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/14—Organic dielectrics
- H01G4/18—Organic dielectrics of synthetic material, e.g. derivatives of cellulose
-
- 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
-
- 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
- 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
- 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.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
Definitions
- the present invention relates to an improvement in heat resistance and voltage resistance of ultra-thin capacitor films used in electronic and electrical equipment. More specifically, the present invention relates to withstand voltage characteristics at high temperatures (improvement of breakdown voltage value) or high voltage.
- a biaxially stretched polypropylene film for capacitors that is suitable for high-capacity capacitors with excellent long-term durability under high temperatures when loaded (so-called long life, high life performance) and a very thin film thickness It is.
- the biaxially stretched polypropylene film is widely used as a dielectric film for capacitors by taking advantage of its excellent electric characteristics such as withstand voltage performance and low dielectric loss characteristics, and in addition, high moisture resistance.
- Polypropylene films for capacitors are used for capacitors such as high voltage capacitors, various switching power supplies and converters, filters for inverters, etc., and smoothing. In recent years, capacitors have become smaller and have higher capacities. The demand is very strong and the demand for thinner films is increasing.
- polypropylene film capacitors have begun to be widely used as smoothing capacitors in inverter power supply circuits that control drive motors used in electric vehicles and hybrid vehicles, for which demand is increasing in recent years.
- Such a capacitor for an inverter power supply device used in an automobile or the like has a small size, light weight, and high capacity, and can stably operate (statically) in a wide temperature range of ⁇ 40 ° C. to 90 ° C. while withstanding a high DC voltage for a long time. (Maintenance of electric capacity) must be continued.
- the capacitor dielectric film used is 1-5 ⁇ m thick and extremely thin (high stretch performance), and even when a higher DC voltage (voltage) is applied at a higher temperature (temperature), it breaks down (insulation) High breakdown voltage characteristics (improved dielectric breakdown voltage) that are not destroyed) have become necessary. Furthermore, in a capacitor made of such a film, a higher voltage is applied at a higher temperature for a longer time (time). It has become essential to improve long-term durability (minimization of change in capacitance with time) that is not destroyed even if the load is continued.
- Patent Document 1 discloses a capacitor made of a highly stereoregular polypropylene resin containing an antioxidant.
- Patent Document 2 and the like disclose a technique relating to a film and a capacitor thereof that realizes control of high melt crystallization temperature (high crystallinity) and surface smoothness performance by using a high melt tension polypropylene resin.
- high crystallization temperature high crystallinity
- surface smoothness performance by using a high melt tension polypropylene resin.
- a simple increase in stereoregularity / high crystallinity leads to a decrease in stretchability, and the film is likely to break during the stretching process.
- the capacitor market has not been fully met.
- Patent Document 3 discloses a fine-roughened film stretched from a cast raw material having a relatively low ⁇ crystal weight, using a resin that balances the molecular weight distribution and stereoregularity in a specific range. ing.
- This stretched micro-roughened film is a thin film having withstand voltage characteristics, and since it has an appropriate surface roughening property, it is a micro-roughened film that has reached a satisfactory level with respect to the above three characteristics.
- Patent Document 4 discloses that by adjusting the molecular weight distribution by containing a low molecular weight component, it is possible to achieve both high withstand voltage performance and thin film formation without increasing the stereoregularity.
- Patent Document 4 discloses that by adjusting the molecular weight distribution by containing a low molecular weight component, it is possible to achieve both high withstand voltage performance and thin film formation without increasing the stereoregularity.
- the long-term durability and withstand voltage performance required by the market and it cannot be said that it is sufficiently satisfactory.
- Patent Document 1 discloses a technique for suppressing dielectric loss to a low level by an appropriate combination and blending amount of phenolic antioxidants.
- Patent Document 6 discloses a technique for improving the insulation resistance at high temperatures by using an antioxidant having a high melting point.
- long-term withstand voltage at high temperature and high voltage load there is no illustration or suggestion regarding long-term withstand voltage at high temperature and high voltage load.
- JP-A-10-119127 page 2-5) JP 2006-93689 A (page 2-4) JP 2007-137988 (page 2-4) International Publication No. WO2009-060944 (page 3-11) JP 2007-146026 A (page 2-3) Japanese Unexamined Patent Publication No. 2009-231705 (page 2-4)
- the purpose of the present invention is for an ultra-thin capacitor having a high dielectric breakdown voltage characteristic at a high temperature with little decrease in capacitance even when a high DC voltage is continuously applied for a long time at a high temperature.
- the object is to provide a biaxially oriented polypropylene film.
- the present invention includes the following aspects.
- the mesopentad fraction ([mmmm]) determined by high temperature nuclear magnetic resonance (high temperature NMR) measurement has a degree of stereoregularity of 94% or more and less than 98%, and is a gel permeation chromatograph (GPC).
- a biaxially oriented polypropylene film having a difference obtained by subtracting the differential distribution value when Log (M) 6 from the differential distribution value when 5 is 9% or more and 15% or less, and the composition of the molecular weight distribution is polypropylene resin
- the biaxially stretched polypropylene film contains at least one hindered phenol antioxidant having a carbonyl group, and the residual content in the film is 4000 ppm (mass basis) or more and 6000 ppm (mass basis) or less.
- the at least one surface of the biaxially stretched polypropylene film has a surface roughness of 0.05 ⁇ m or more and 0.15 ⁇ m or less in terms of centerline average roughness (Ra), and a maximum height
- a metallized polypropylene film for capacitors obtained by performing metal vapor deposition on one or both sides of the biaxially oriented polypropylene film for capacitors described in any one of the above items (1) to (4).
- the biaxially stretched polypropylene film for capacitors according to the present invention contains a low molecular weight component having an average molecular weight of about several tens of thousands more than usual by using a raw material polypropylene resin whose molecular weight distribution is adjusted by peroxidative decomposition treatment, and has a unique molecular weight distribution. Therefore, it has the effect of exhibiting high dielectric breakdown strength and excellent resistance when a high voltage is applied at a high temperature.
- the specific antioxidant according to the present invention within the range described in the present invention, resistance when a high voltage is applied for a long time at a high temperature is greatly improved.
- the structure of the unique molecular weight distribution has an effect on the stretchability of the resin, so that it is extremely excellent in realizing a capacitor film having a very thin film thickness of 1 to 5 ⁇ m.
- the usable temperature of the polypropylene film capacitor can be effectively increased, the rated voltage can be increased, the service life can be extended (long-term durability), and the size and capacity can be increased effectively.
- the biaxially stretched polypropylene film for capacitors according to the first aspect of the present invention has a mesopentad fraction ([mmmm]) determined by high temperature nuclear magnetic resonance (high temperature NMR) measurement of 94% or more and less than 98%.
- a polypropylene raw material resin is used which is a polypropylene film and the constitution of the molecular weight distribution is adjusted by a peroxide decomposition treatment of the polypropylene resin.
- the polypropylene resin used for the biaxially stretched polypropylene film for capacitors of this embodiment is a crystalline isotactic polypropylene resin, which is a homopolymer of propylene.
- the mesopentad fraction ([mmmm]), which is the degree of stereoregularity determined by high temperature nuclear magnetic resonance (NMR) measurement, is 94% or more and less than 98%, and more preferably 95% or more and 97. It is a biaxially stretched polypropylene film for capacitors having a molecular characteristic of not more than%.
- the mesopentad fraction [mmmm] is 94% or more, the crystallinity of the resin is improved due to the high stereoregularity component, and high withstand voltage characteristics are exhibited.
- the mesopentad fraction [mmmm] is less than 94%, the voltage resistance and mechanical heat resistance tend to be inferior.
- the mesopentad fraction [mmmm] is 98% or more, the speed of solidification (crystallization) at the time of forming the cast raw sheet becomes too fast, and peeling from the metal drum for forming the sheet is likely to occur. Or stretchability decreases.
- the high-temperature NMR apparatus for measuring the mesopentad fraction ([mmmm]), and a commercially available high-temperature nuclear magnetic resonance (NMR) apparatus capable of the degree of stereoregularity of polyolefins
- NMR nuclear magnetic resonance
- a high temperature type Fourier transform nuclear magnetic resonance apparatus (high temperature FT-NMR) and JNM-ECP500 manufactured by JEOL Ltd. can be used.
- the observation nucleus is 13 C (125 MHz)
- the measurement temperature is 135 ° C.
- the method by high temperature NMR can be performed by a known method, for example, the method described in “Japan Analytical Chemistry / Polymer Analysis Research Roundtable, New Edition Polymer Analysis Handbook, Kinokuniya, 1995, p. 610”. .
- the pentad fraction representing the degree of stereoregularity is a combination of a pentad of a consensus “meso (m)” arranged in the same direction and a consensus “rasemo (r)” arranged in the same direction (mmmm or mrrm). Etc.) is calculated as a percentage from the integrated intensity value of each signal derived from. Regarding the attribution of each signal derived from mmmm, mrrm, etc., reference is made to the description of the spectrum such as “T. Hayashi et al., Polymer, 29, 138 (1988)”.
- the moderate inclusion of the low molecular weight component maintains a high withstand voltage even if the mesopentad fraction does not have a very high degree of stereoregularity exceeding 98% as in the prior art. As it is, stretchability is imparted.
- the mesopentad fraction [mmmm]) can be controlled by appropriately adjusting the aforementioned polymerization conditions, the type of catalyst, the amount of catalyst, and the like.
- the film of this embodiment has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) method of 250,000 to 450,000. Preferably, it is 250,000 or more and 400,000 or less.
- the molecular weight distribution calculated from the weight average molecular weight (Mw) / number average molecular weight (Mn) ratio obtained by the GPC method is 4 or more and 7 or less, preferably 4.5 or more and 7 or less, more preferably 5 It is 7 or less.
- the weight average molecular weight exceeds 450,000, the resin fluidity is remarkably lowered, and it becomes difficult to control the thickness of the cast raw sheet, and a very thin stretched film, which is the object of the present invention, is accurately produced in the width direction. This is not preferable for practical use.
- the weight average molecular weight is less than 250,000, the extrusion moldability is excellent, but the sheet and film thickness unevenness is likely to occur, and the stretchability and the mechanical properties and thermo-mechanical characteristics of the resulting sheet are reduced. Is significantly reduced, and it is not preferable because biaxial stretch molding cannot be performed, resulting in difficulty in production and product performance.
- the gel permeation chromatograph (GPC) apparatus for obtaining molecular weight / molecular weight distribution measurement values of a biaxially stretched polypropylene film is not particularly limited, and is a commercially available high-temperature GPC apparatus capable of analyzing the molecular weight of polyolefins.
- GPC gel permeation chromatograph
- RI differential refractometer
- HLC-8121GPC-HT high-temperature GPC measuring machine
- the molecular weight / molecular weight distribution measurement value is measured at a flow rate of 1.0 ml / min. Standard polystyrene manufactured by Tosoh Corporation is used for the production of the calibration curve, and the measurement results are converted into polypropylene values.
- the logarithmic value of the weight average molecular weight thus obtained is referred to as logarithmic molecular weight (Log (M)).
- the distribution structure is adjusted to have a wide molecular weight distribution, and at the same time, the distribution structure includes a component having a molecular weight of 10,000 to 100,000 with a certain ratio more than a component having a molecular weight of 1,000,000. Therefore, both stretchability and voltage resistance are achieved.
- this difference exceeds 15% there are too many low molecular weight components, which causes problems in film forming properties and mechanical heat resistance, which is not preferable in practice.
- the differential distribution value is generally obtained as follows in the GPC method.
- a time curve (generally referred to as an elution curve) of an intensity distribution detected by a differential refraction (RI) detector of GPC is obtained with respect to logarithmic molecular weight (Log (M)) using a calibration curve obtained from a substance having a known molecular weight.
- the distribution curve since the RI detection intensity is proportional to the component concentration, an integral distribution curve with respect to the logarithmic molecular weight Log (M) when the total area of the distribution curve is 100% can be obtained.
- the differential distribution curve is obtained by differentiating the integral distribution curve with Log (M). Therefore, the differential distribution here means a differential distribution with respect to the molecular weight of the concentration fraction. From this curve, the differential distribution value at a specific Log (M) is read, and the relationship according to this aspect can be obtained.
- Is present in a larger amount than components having a molecular weight M of 1 million (Log (M) 6). It is indicated that in a film having the same degree of stereoregularity and molecular weight distribution, the lower the molecular weight, the higher the dielectric breakdown voltage (the better the voltage resistance).
- the voltage resistance of the biaxially stretched polypropylene film can be improved by allowing many low molecular weight components to exist while maintaining the molecular weight distribution within the above range.
- a method by peroxidation treatment with a decomposing agent such as hydrogen peroxide or organic oxide is preferable.
- a peroxide is added to a collapsible polymer such as polypropylene, a hydrogen abstraction reaction occurs from the polymer, and the resulting polymer radical partially recombines to cause a crosslinking reaction, but most radicals undergo secondary decomposition ( ⁇ cleavage). ) And is divided into two polymers having smaller molecular weights. Therefore, decomposition proceeds with a high probability from the high molecular weight component, and therefore, the low molecular weight component increases and the structure of the molecular weight distribution can be adjusted.
- Examples of the method for obtaining a resin containing a moderately low molecular weight component by peroxide decomposition include the following methods.
- Polymerized powder or pellets of polypropylene resin obtained by polymerization and, as an organic peroxide, for example, 1,3-bis- (tertiary-butyl peroxide isopropyl) -benzene and the like are 0.001% by mass to 0.5%. Adjusting and adding about mass%, considering the composition (configuration) of the target high molecular weight component and low molecular weight component, and performing melt kneading at a temperature of about 180 ° C. to 300 ° C. in a melt kneader machine. I can do it.
- composition of low molecular weight component amount it can be achieved, for example, by adjusting the concentration (amount) of the organic oxide, the time of the melt-kneading treatment, and the rotational speed.
- concentration (amount) of the organic oxide concentration of the organic oxide
- the total ash resulting from the melt reaction treatment, polymerization catalyst residue, and the like contained in the polypropylene raw material resin of this embodiment is preferably as small as possible in order to improve electrical characteristics, and is 50 ppm or less, preferably 40 ppm or less. .
- polymerization methods for producing a polypropylene resin for producing the polypropylene stretched film of this embodiment generally known polymerization methods can be used without any limitation.
- generally known polymerization methods include, for example, a gas phase polymerization method, a bulk polymerization method, and a slurry polymerization method. Further, it may be a multistage polymerization reaction using at least two polymerization reactors, or a polymerization method in which hydrogen or a comonomer is added as a molecular weight regulator in the reactor.
- the catalyst used is not particularly limited, and generally known Ziegler-Natta catalysts are widely applied. Further, a promoter component and a donor may be included. The molecular weight distribution can be controlled by appropriately adjusting the catalyst and polymerization conditions.
- the long-term durability of such a capacitor element is evaluated by promoting the life (long-term durability) by loading the capacitor element at a higher temperature and voltage than the actual use temperature and voltage.
- a DC high voltage for example, 600 to 900 V
- the change rate of the capacitance of the capacitor element is increased over a long period (for example, 2000 hours). : About 80 days).
- a capacitor using a film with little progress of deterioration and good long-term durability (long life) has little decrease in capacitance even when a high voltage is applied for 2,000 hours because the degree of deterioration of the film is small.
- the capacity reduction tends to increase with time.
- the long-term durability test of capacitor films is evaluated by the change in capacitance when a high temperature and high voltage are continuously applied for a predetermined time (long term: several tens of days) as a capacitor element, and this improvement is important.
- Another aspect of the present invention contains one or more hindered phenolic antioxidants having a carbonyl group for the purpose of suppressing deterioration that progresses with time during long-term use, and the residual content in the film is It is a biaxially stretched polypropylene film for capacitors having a concentration of 4000 ppm (mass basis) to 6000 ppm (mass basis).
- hindered phenol-based antioxidant having a carbonyl group for example, triethylene glycol-bis [3- (3-tertiary-butyl-5-methyl-4-hydroxyphenyl) propionate) (product) Name: Irganox 245), 1,6-hexanediol-bis [3- (3,5-di-tertiary-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 259), pentaerythritol Tetrakis [3- (3,5-di-tertiary-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1010), 2,2-thio-diethylenebis [3- (3,5-di- Tertiary-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1 035), octadecyl-3- (3,5-di-tertiary-butyl-5-methyl-4-
- the content (residual amount in the film) of the hindered phenol-based antioxidant having a carbonyl group contained in the biaxially stretched polypropylene film for capacitors of this embodiment is 4000 ppm (mass basis) or more and 6000 ppm (mass basis) or less. It is.
- the content of the hindered phenolic antioxidant having a carbonyl group (residual amount in the film) is less than 4000 ppm (mass basis), the effect of suppressing oxidative degradation during the long-term life test is insufficient, and the high temperature / high The effect of improving long-term durability under voltage is not sufficiently exhibited, which is not preferable.
- the antioxidant itself may become a charge carrier (a certain kind of impurity), resulting in generation of current under high voltage, thermal runaway or bursting, etc.
- the phenomenon that leads to destruction occurs, which is not preferable because long-term resistance is lost.
- it is 4500 ppm (mass basis) or more and 6000 ppm (mass basis) or less, More preferably, it is 5000 ppm (mass basis) or more and 6000 ppm (mass basis) or less.
- Capacitor films containing hindered phenolic antioxidants with carbonyl groups that have good compatibility with polypropylene at the molecular level and containing an optimal amount in a specific range have a high withstand voltage obtained by adjusting the molecular weight distribution described above. Even in a very high temperature (life) accelerated test of 100 ° C or higher while maintaining the property (dielectric breakdown voltage value), the capacitance is decreased over a long period exceeding 1000 hours (40 days or more). (Deterioration does not progress) and long-term durability is improved.
- the molecular characteristics (molecular weight, molecular weight distribution, composition of molecular weight distribution, degree of stereoregularity) of the biaxially stretched polypropylene film of the above-described embodiment are not the values of the resin for film production itself, It is necessary to be the value of the resin forming the film after the film forming process.
- the resin forming this film has undergone decomposition during the film-forming process, generating heat / oxidation degradation, shear degradation, elongation degradation, and the like in the extruder. Accordingly, the molecular weight / molecular weight distribution and stereoregularity are often different between the raw resin and the resin forming the film after film formation. What affects the voltage resistance and heat resistance of the film is the molecular characteristics of the resin in the film state.
- the degree of deterioration that is, the change in molecular weight distribution and stereoregularity, is the nitrogen purge in the extruder (suppression of oxidation), the screw shape in the extruder (shearing force), the internal shape of the T-die during casting (shearing force), It can be adjusted by the amount of antioxidant added (suppression of oxidation), the winding speed (extension force) during casting, and the like.
- antioxidants to suppress deterioration in the extruder necessary stabilizers such as chlorine absorbers and ultraviolet absorbers, lubricants, plasticizers, flame retardants, antistatic agents Additives such as may be added as long as the effects of the present invention are not impaired.
- Antioxidants added to the resin include antioxidants for the purpose of suppressing heat and oxidative deterioration in the extruder (hereinafter also referred to as primary agents), and deterioration in long-term use as a capacitor film. It is used for at least two purposes of an antioxidant (hereinafter also referred to as a secondary agent) that contributes to suppression and improvement of capacitor performance. Different types of antioxidants may be used for these two purposes, or two types of antioxidants may be used for one purpose.
- antioxidants for example, 1,6-di-tert-butyl-para-cresol (generic name: BHT) is used as a primary agent for suppressing deterioration in the extruder from 1000 ppm to About 4000 ppm can be added. Most of the antioxidant for this purpose is consumed in the molding process in the extruder, and hardly remains in the film after film formation (generally, the residual amount is less than 100 ppm).
- a hindered phenol-based antioxidant having a carbonyl group is added as a secondary agent that contributes to suppressing deterioration and improving performance in the long-term use as a capacitor, which is the object of the present invention.
- hindered phenol-based antioxidant having a carbonyl group for example, triethylene glycol-bis [3- (3-tertiary-butyl-5-methyl-4-hydroxyphenyl) propionate] (trade name: Irganox 245 ), 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 259), pentaerythryl tetrakis [3- ( 3,5-di-tertiary-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1010), 2,2-thio-diethylenebis [3- (3,5-di-tertiary-butyl- 4-hydroxyphenyl) propionate) (trade name: Irganox 1035), Octade 3- (3,5-di-tertiary-butyl-4-hydroxyphenyl) propionate (trade name: Irg
- the addition amount needs to be added in the range of 5000 ppm (mass basis) to 7000 ppm (mass basis) with respect to the total mass of the resin. Preferably, it is 5500 ppm (mass basis) or more and 7000 ppm (mass basis) or less.
- the residual amount in the film of the hindered phenol-based antioxidant having a carbonyl group contained in the biaxially stretched polypropylene film for capacitors according to the present invention is 4000 ppm (mass basis) or more and 6000 ppm (mass basis) or less. Therefore, it is necessary to make the above-mentioned addition amount.
- hindered phenolic antioxidants having a carbonyl group are also consumed in the extruder regardless of the presence or absence of the primary agent for the purpose of suppressing deterioration in the extruder. is there.
- the consumption amount of the hindered phenol-based antioxidant having a carbonyl group in the extruder is usually about 1000 ppm to 2000 ppm.
- the amount of hindered phenolic antioxidant having a carbonyl group is less than 5000 ppm, the remaining amount of antioxidant in the biaxially stretched polypropylene film for capacitors is less than 4000 ppm. The effect of improving the properties is not sufficiently exhibited, which is not preferable.
- the amount of hindered phenol antioxidant having a carbonyl group is more than 7000 ppm, the residual amount in the film exceeds 6000 ppm, and as described above, the antioxidant itself is charged carriers (some impurities). However, it tends to lose long-term tolerance.
- a hindered phenol antioxidant having a carbonyl group is substituted as the antioxidant for this purpose.
- the hindered phenol-based antioxidant having a carbonyl group is considerably consumed for suppressing deterioration in the molding process in the extruder, so the amount added is 6000 ppm (mass basis) with respect to the total mass of the resin. It is preferable to add more than 7000 ppm (mass basis).
- the method of forming the cast raw sheet before stretching for producing the biaxially stretched polypropylene film of the present invention various known methods can be employed. For example, dry-mixed polypropylene resin pellets (and / or polymerized powder) or raw material pellets made of mixed polypropylene resin pellets prepared by pre-melting and kneading are supplied to an extruder, heated and melted, and passed through a filtration filter. Thereafter, it is heated and melted at 170 ° C. to 320 ° C., preferably 200 ° C. to 300 ° C., melt-extruded from the T die, and cooled and solidified with at least one metal drum held at 80 ° C. to 140 ° C.
- a method of forming a stretched cast raw sheet can be employed.
- the ⁇ crystal fraction of the obtained cast raw sheet is 1 by the X-ray method. % To 50%, preferably 5% to less than 30%. This value is a value when no ⁇ crystal nucleating agent is included. As described above, a ⁇ crystal fraction that is too low tends to be inferior in workability such as element winding because the film surface is smoothed, but the capacitor characteristics such as withstand voltage characteristics are improved. However, when the ⁇ crystal fraction is within the above range, both physical properties of the capacitor characteristics and the element winding workability can be sufficiently satisfied.
- the ⁇ crystal fraction is obtained by X-ray diffraction intensity measurement, and is calculated by the method described in “A. Turner-Jones et al., Makromol. Chem., Vol. 75, p. 134 (1964)”. It is a value and is a value called a K value. That is, the ratio of the ⁇ crystal is expressed by the ratio of the sum of the heights of the three diffraction peaks derived from the ⁇ crystal and the single diffraction peak derived from the ⁇ crystal.
- the thickness of the cast original fabric sheet is not particularly limited, but it is usually 0.05 mm to 2 mm, preferably 0.1 mm to 1 mm.
- the biaxially stretched polypropylene film for capacitors of the present invention can be produced by subjecting the polypropylene cast original fabric sheet to a stretching treatment.
- the stretching is preferably biaxial stretching in which the longitudinal and lateral orientations are biaxial, and the sequential biaxial stretching method is preferred as the stretching method.
- a sequential biaxial stretching method first, a cast raw sheet is maintained at a temperature of 100 to 160 ° C., passed between rolls provided with a speed difference, stretched 3 to 7 times in the flow direction, and immediately cooled to room temperature.
- the stretched film is guided to a tenter, stretched 3 to 11 times in the width direction at a temperature of 160 ° C. or higher, and then relaxed and heat-set, and wound.
- the wound film is subjected to an aging treatment in an atmosphere of about 20 to 45 ° C., and can be cut to a desired product width.
- a stretching process a film having excellent mechanical strength and rigidity is obtained, and the unevenness of the surface is further clarified, resulting in a stretched film that is finely roughened.
- the surface of the film of the present invention is imparted with an appropriate surface roughness that improves capacitor characteristics while improving the element winding suitability.
- the surface roughness of at least one surface of the biaxially stretched polypropylene film is 0.05 ⁇ m or more and 0.15 ⁇ m or less in terms of centerline average roughness (Ra), and That is, the surface is finely roughened to 0.5 ⁇ m or more and 1.5 ⁇ m or less at the maximum height (Rz, Rmax in the old JIS definition).
- Ra and Rz Rmax defined in the former JIS definition
- a film is formed because an appropriate gap is generated between the films in the element winding process during winding, rewinding, and capacitor processing. Slips moderately, making it difficult for wrinkles to be taken up in winding, and also preventing lateral displacement.
- Ra and Rz can be measured using, for example, a stylus type or non-contact type surface roughness meter that is widely used by the method defined in JIS-B0601: 2001, etc. Measured. There are no restrictions on the manufacturer or model of the device. In the examination in the present invention, a universal surface shape measuring instrument SE-30 manufactured by Kosaka Laboratory Co., Ltd. was used, and a roughness analyzer AY-41 was used to determine Ra according to the method defined in JIS-B0601: 2001. And Rz (Rmax of the old JIS definition) were obtained. Either the contact method (stylus type using a diamond needle) or the non-contact method (non-contact detection using a laser beam or the like) can be measured. In the present invention, the measurement is performed using the contact method and the reliability of the value is measured. Was supplemented with non-contact method values as necessary.
- various known surface roughening methods such as embossing and etching can be adopted, but among them, there is no need to mix impurities, and ⁇ crystals are used.
- the roughening method is preferable.
- the ratio of ⁇ crystals can be controlled by the casting temperature and the casting speed.
- the roll temperature in the longitudinal stretching process can control the melting / transition ratio of the ⁇ crystal, and by selecting the optimum manufacturing conditions for these two parameters of ⁇ crystal formation and its melting / transition, fine roughening can be achieved. Surface properties can be obtained.
- a characteristic microcrystal formation state is expressed by a change in crystallization behavior due to a low molecular weight component within the range according to the present invention, which is also useful for generating a ⁇ crystal for obtaining fine surface irregularities.
- An effect can be obtained. That is, even if the production conditions of the polypropylene biaxially stretched film for adjusting the ratio of ⁇ crystal production is not greatly changed from the conventional conditions, the structure of the characteristic molecular weight distribution according to the present invention has a small spherulite size, and It is possible to control the spherulite density which is not too much, and thus, it is possible to realize the surface roughness according to the present invention, and to effectively impart winding workability without impairing other performances. .
- the thickness of the biaxially stretched polypropylene film of the present invention is 1 ⁇ m or more and 5 ⁇ m or less, preferably 1.5 ⁇ m or more and 4 ⁇ m or less, more preferably 1.8 ⁇ m or more and 3.5 ⁇ m or less. It is an ultrathin biaxially oriented polypropylene film for capacitors.
- a corona discharge treatment may be performed online or offline after the stretching / heat setting process for the purpose of improving adhesive properties. Absent.
- a known method can be used as the corona discharge treatment, but it is desirable to perform treatment in air, carbon dioxide gas, nitrogen gas, or a mixed gas thereof as the atmospheric gas.
- a necessary stabilizer such as a chlorine absorbent is added to the biaxially stretched polypropylene film for a capacitor of the present invention within a range that does not affect the capacitor characteristics.
- a metal soap such as calcium stearate is preferably used as the chlorine absorbent.
- the total ash content in the biaxially stretched polypropylene film for capacitors of the present invention is preferably as small as possible in order to improve the electrical characteristics, and is 50 ppm or less, preferably 40 ppm or less.
- the electrode when processing the biaxially stretched polypropylene film for a capacitor of the present invention as a capacitor is not particularly limited, and may be, for example, a metal foil, or a paper or plastic film metallized at least on one side.
- an electrode obtained by directly metallizing one or both surfaces of the film of the present invention is preferable.
- the metal used for metalization at this time can be used alone, such as zinc, lead, silver, chromium, aluminum, copper, nickel, a mixture of a plurality of types, an alloy, etc., but the environment and economy In consideration of the capacitor performance, zinc or aluminum is preferable.
- Examples of the method for directly metallizing the biaxially stretched polypropylene film for a capacitor of the present invention include a vacuum deposition method and a sputtering method, but are not limited to these, such as productivity and economy. From the viewpoint, the vacuum deposition method is preferable. Examples of the vacuum deposition method generally include a crucible method and a wire method, but are not particularly limited, and an optimum method may be selected as appropriate.
- the margin pattern for metallization by vapor deposition is not particularly limited, but a pattern including a so-called special margin such as a fishnet pattern or a T margin pattern is used in order to improve characteristics such as the safety of the capacitor. When it is applied on one side of the film of the invention, it is preferable from the standpoints of improving the safety and preventing the destruction of the capacitor and the short circuit.
- a method of forming the margin a generally known method such as a tape method or an oil method can be used without any limitation.
- This biaxially stretched polypropylene film for capacitors has a finely roughened surface, so it has excellent element winding properties, high withstand voltage characteristics, and is a very thin film, so it exhibits high capacitance. Since it is easy and excellent in long-term durability, it is extremely suitable for a small-sized capacitor having a high capacity of 5 ⁇ F or more, preferably 10 ⁇ F or more, more preferably 20 ⁇ F or more.
- Measuring instrument manufactured by JEOL Ltd., high temperature FT-NMR JNM-ECP500 Observation nucleus: 13 C (125 MHz) Measurement temperature: 135 ° C
- Solvent Ortho-dichlorobenzene [ODCB: Mixed solvent of ODCB and deuterated ODCB (4/1)]
- the description of spectra such as “T. Hayashi et al., Polymer, 29, 138 (1988)” was referred to.
- the withstand voltage of the biaxially stretched film is JIS-C2330 7.4.11.2 (dielectric breakdown voltage / plate electrode method: B method). It evaluated by measuring the dielectric breakdown voltage value according to it. The boosting speed was 100 V / sec, the breaking current at the time of breakdown was 10 mA, and the number of measurements was 18 times. Here, what measured the average voltage value divided by the thickness of the film was used for evaluation as dielectric breakdown strength. A film and an electrode jig were set in the air circulation type high temperature bath, and the measurement was performed at an evaluation temperature of 100 ° C. A high-temperature dielectric breakdown strength of 450 V / ⁇ m or more is desirable for practical use, and 450 V / ⁇ m or more is a more preferable withstand voltage.
- Capacitor element life test (high temperature and long-term durability) The obtained capacitor element was assumed to be used at an environmental maximum temperature of 90 ° C. and a maximum voltage of 700 V as an inverter for controlling an automobile driving motor, and a life promotion test was performed according to the following procedure. The element was preheated for 1 hour in advance at the test environment temperature (105 ° C. (assumed maximum temperature + 15 ° C.)), and then the initial capacitance before the test was evaluated with an LCR tester AG4311 manufactured by Ando Electric Co., Ltd.
- a high-voltage power supply was used, and a voltage of DC 750 V (assumed maximum voltage +50 V) was continuously applied to the capacitor element for 500 hours.
- the capacitance of the element after 500 hours was measured with an LCR tester, and the capacitance change rate before and after voltage loading was calculated.
- the device was returned to the high temperature bath again, and further, voltage loading was performed for 500 hours to obtain a capacity change (cumulative) after 1000 hours (cumulative), and this was repeated until 2000 hours had elapsed.
- the capacity change rate after 2000 hours was obtained, and the average value of three elements was adopted for evaluation.
- the capacity change rate is preferably within ⁇ 5% after 2000 hours.
- Polypropylene resin Molecular weight distribution unadjusted polypropylene resin E (melt flow index 4 g / 10 min, weight average molecular weight 300,000, mesopentad fraction 96%) was obtained from Prime Polymer Co., Ltd. Further, this polypropylene resin E and an organic peroxide were melt-kneaded to carry out a peroxide decomposition treatment to obtain molecular weight distribution adjusting resins A to D. Furthermore, a molecular weight distribution adjusting resin F subjected to a peroxide decomposition treatment was obtained by melt-kneading a low stereoregular polypropylene resin (mesopentad fraction 93.5%) with an organic peroxide.
- a polypropylene resin G having a molecular weight distribution adjusted by adding and mixing a high melt flow resin based on the resin E was obtained.
- Antioxidants (secondary agents) were added to the polypropylene resins A to G.
- Table 1 shows the presence or absence of peroxide decomposition treatment of biaxially stretched polypropylene films obtained from these resins, molecular weight differential distribution difference, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), degree of stereoregularity (mesopentad). Fraction) and the remaining amount of antioxidant (secondary agent).
- these values in Table 1 are analysis values of the film.
- Example 1 Add 5,000 ppm of Irganox (registered trademark) 1010 and 20 ppm of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane as secondary antioxidant to resin E manufactured by Prime Polymer Co., Ltd. and melt in a granulator
- the raw material resin A which has been subjected to peroxide decomposition treatment by kneading to adjust the molecular weight distribution is supplied to an extruder, melted at a resin temperature of 250 ° C., extruded using a T-die, and the surface temperature is set to 95 ° C.
- Example 2 Raw material resin obtained by adding Irganox (registered trademark) 1010, which is a secondary antioxidant, in the same manner as in Example 1 to molecular weight distribution-adjusted resin B subjected to peroxidative decomposition treatment instead of raw material resin A in Example 1
- Irganox registered trademark
- Table 1 summarizes the molecular properties of the film obtained and the physical properties of the film.
- evaluation results as a capacitor film are summarized in Table 2.
- the molecular weight differential distribution value difference, the molecular weight (Mw), the molecular weight distribution (Mw / Mn), the mesopentad fraction, and the secondary antioxidant remaining amount in Table 1 are the analytical values of the film.
- Example 3 In place of the raw material resin A of Example 1, a raw material resin C obtained by adding 5500 ppm of Irganox (registered trademark) 1010, which is a secondary antioxidant, to the molecular weight distribution adjustment resin C subjected to peroxidative decomposition treatment is used as an extruder. A very thin biaxially stretched polypropylene film having a thickness of 2.8 ⁇ m was obtained in the same manner as in Example 1 except that it was supplied. Table 1 summarizes the molecular properties of the film obtained and the physical properties of the film. Moreover, the evaluation results as a capacitor film are summarized in Table 2. In addition, the molecular weight differential distribution value difference, the molecular weight (Mw), the molecular weight distribution (Mw / Mn), the mesopentad fraction, and the secondary antioxidant remaining amount in Table 1 are the analytical values of the film.
- Irganox registered trademark
- 1010 which is a secondary antioxidant
- Example 4 In place of the raw material resin A of Example 1, a raw material resin D obtained by adding 6000 ppm of Irganox (registered trademark) 1010, which is a secondary antioxidant, to the molecular weight distribution adjustment resin D subjected to peroxidative decomposition treatment was used as an extruder. A very thin biaxially stretched polypropylene film having a thickness of 2.8 ⁇ m was obtained in the same manner as in Example 1 except that it was supplied. Table 1 summarizes the molecular properties of the film obtained and the physical properties of the film. Moreover, the evaluation results as a capacitor film are summarized in Table 2. In addition, the molecular weight differential distribution value difference, the molecular weight (Mw), the molecular weight distribution (Mw / Mn), the mesopentad fraction, and the secondary antioxidant remaining amount in Table 1 are the analytical values of the film.
- Irganox registered trademark
- 1010 which is a secondary antioxidant
- Example 5 The raw material resin A of Example 1 is supplied to an extruder, melted at a resin temperature of 250 ° C., extruded using a T-die, wound around a metal drum maintained at a surface temperature of 95 ° C., and solidified. A cast original fabric sheet having a thickness of about 125 ⁇ m was produced. Subsequently, this unstretched cast original fabric sheet was stretched 5 times in the flow direction at a temperature of 140 ° C., immediately cooled to room temperature, and then stretched 10 times in the transverse direction at a temperature of 165 ° C. with a tenter, A very thin biaxially stretched polypropylene film having a thickness of 2.5 ⁇ m was obtained.
- Table 1 summarizes the molecular properties of the film obtained and the physical properties of the film. Moreover, the evaluation results as a capacitor film are summarized in Table 2. In addition, the molecular weight differential distribution value difference, the molecular weight (Mw), the molecular weight distribution (Mw / Mn), the mesopentad fraction, and the secondary antioxidant remaining amount in Table 1 are the analytical values of the film.
- Example 2 The same as Example 1 except that the raw material resin E ′ in which 5000 ppm of Irganox (registered trademark) 1010 as a secondary antioxidant was added to the resin E whose molecular weight distribution was adjusted by the polymerization method was supplied to the extruder. Thus, a very thin biaxially stretched polypropylene film having a thickness of 2.8 ⁇ m was obtained.
- Table 1 summarizes the molecular properties of the film obtained and the physical properties of the film.
- the evaluation results as a capacitor film are summarized in Table 2.
- the molecular weight differential distribution value difference, the molecular weight (Mw), the molecular weight distribution (Mw / Mn), the mesopentad fraction, and the secondary antioxidant remaining amount in Table 1 are the analytical values of the film.
- Example 3 instead of the raw material resin A of Example 1, a polypropylene resin manufactured by Prime Polymer Co., Ltd. (melt flow index 3 g / 10 min, average molecular weight 350,000, mesopentad fraction 93.5%) is melt kneaded with an organic peroxide.
- Example 1 except that the raw material resin F obtained by adding 5000 ppm of Irganox (registered trademark) 1010, which is a secondary antioxidant, to the molecular weight distribution adjustment resin F that has been subjected to peroxidative decomposition treatment in Example 1 was supplied to the extruder. Thus, a very thin biaxially stretched polypropylene film having a thickness of 2.8 ⁇ m was obtained.
- Table 1 summarizes the molecular properties of the film obtained and the physical properties of the film. Moreover, the evaluation results as a capacitor film are summarized in Table 2. In addition, the molecular weight differential distribution value difference, the molecular weight (Mw), the molecular weight distribution (Mw / Mn), the mesopentad fraction, and the secondary antioxidant remaining amount in Table 1 are the analytical values of the film.
- Example 4 Referring to Example 2 of Patent Document 4 (International Publication No. WO2009-060944), a high melt flow resin (melt flow index 9 g) manufactured by Prime Polymer Co., Ltd. based on Resin E instead of the raw material resin A of Example 1 Except for supplying the raw material resin F in which 4000 ppm of Irganox (registered trademark) 1010, which is a secondary antioxidant, is added to the polypropylene resin G whose molecular weight distribution is adjusted by adding and mixing 15% to 10 minutes) Produced a very thin biaxially oriented polypropylene film having a thickness of 2.8 ⁇ m in the same manner as in Example 1.
- Irganox registered trademark
- Table 1 summarizes the molecular properties of the film obtained and the physical properties of the film. Moreover, the evaluation results as a capacitor film are summarized in Table 2. In addition, the molecular weight differential distribution value difference, the molecular weight (Mw), the molecular weight distribution (Mw / Mn), the mesopentad fraction, and the secondary antioxidant remaining amount in Table 1 are analytical values of the film.
- the biaxially stretched polypropylene film of the present invention is a very thin film having a high dielectric breakdown voltage value, and the capacitor element obtained by winding the film has a high temperature.
- the film is extremely suitable as a capacitor film.
- the biaxially stretched polypropylene film of the present invention has high withstand voltage characteristics (breakdown voltage value) at high temperatures and excellent long-term durability at high temperatures (long-term withstand voltage characteristics), this biaxially stretched film A film capacitor using a film can not only achieve a long life, but since this film is a particularly thin biaxially stretched film, it can be preferably used for a small and large-capacity capacitor that requires heat resistance. is there.
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Abstract
Description
コンデンサー用ポリプロピレンフィルムは、高電圧コンデンサーをはじめとし、各種スイッチング電源やコンバーターや、インバーター等のフィルター用や、平滑用としてコンデンサー類に好ましく用いられており、近年はコンデンサーの小型化、高容量化の要求が非常に強く、ますます薄いフィルムの要求が高まってきている。
特許文献5では、フェノール系酸化防止剤の適切な組み合わせと配合量によって、誘電損失を低く抑制する技術が開示されている。しかしながら、高電圧負荷時のコンデンサーの寿命(あるいはライフ性能(長期耐用性))、高温下の長期耐電圧性に関しては、例示も示唆もない。また、最近では、特許文献6において、高融点の酸化防止剤を用いる事で、高温下での絶縁抵抗を向上させる技術が開示されている。しかしながら、この文献においても、高温、高電圧負荷時の長期耐電圧性に関しては、例示も示唆もない。
また、その特異な分子量分布の構成は、樹脂の延伸性にも効果を有しているので、厚みが1~5μmの非常に薄いフィルム厚のコンデンサー用フィルムの実現にも極めて優れている。
測定モードは、シングルパルスプロトンブロードバンドデカップリング、パルス幅は、9.1μsec(45°パルス)、パルス間隔5.5sec、積算回数4,500回、シフト基準は、CH3(mmmm)=21.7ppmとされる。
前記メソペンタッド分率([mmmm])は、前出の重合条件や触媒の種類、触媒量など、適宜調整することによって、コントロールすることができる。
ポリプロピレンのような崩壊型ポリマーに過酸化物を添加すると、ポリマーからの水素引抜き反応が起こり、生じたポリマーラジカルは一部再結合し架橋反応も起こすが、殆どのラジカルは二次分解(β開裂)を起こし、より分子量の小さな二つのポリマーに分かれることが知られている。したがって、高分子量成分から高い確率で分解が進行し、よって、低分子量成分が増大し、分子量分布の構成を調整することが出来る。低分子量成分を適度に含有している樹脂を過酸化分解により得る方法としては、例えば、次のような方法が例示できる。
本態様のポリプロピレン原料樹脂中に含まれる溶融反応処理や重合触媒残渣等に起因する総灰分は、電気特性を良化するために可能な限り少ないことが好ましく、50ppm以下、好ましくは40ppm以下である。
また、少なくとも2つ以上の重合反応器を用いた多段重合反応であっても良く、また、反応器中に水素あるいはコモノマーを分子量調整剤として添加して行う重合方法であっても良い。
高温下、高い電圧を負荷し続けると、コンデンサー素子においては、フィルム内で自己発熱が発生し、酸化・熱劣化が時間と共に進行し、コンデンサー性能(コンデンサーの静電容量)が低下する。
このように、コンデンサーフィルムの長期耐用試験は、コンデンサー素子として、高温・高電圧を所定時間(長期:数十日オーダー)負荷し続けた場合の静電容量変化によって評価され、この改善向上が重要な技術要件となる。
カルボニル基を有するヒンダードフェノール系酸化防止剤の含有量(フィルム中における残存量)が、4000ppm(質量基準)未満の場合、長期寿命試験中における酸化劣化抑制効果が不十分であり、高温・高電圧下における長期耐用性の向上効果が十分に発揮されず好ましくない。一方、フィルム中の残存量が6000ppmを超えると、酸化防止剤自身が電荷のキャリア(ある種の不純物)となる場合があり、結果として、高電圧下において電流を発生し、熱暴走あるいは破裂などと呼ばれる破壊に至らしめる現象が発生するため、かえって長期耐性を失うことになるので好ましくない。より好ましくは、4500ppm(質量基準)以上6000ppm(質量基準)以下であり、さらにより好ましくは、5000ppm(質量基準)以上6000ppm(質量基準)以下である。
これら2つの目的に、各々、異なる種類の酸化防止剤を用いても構わないし、1種類の酸化防止剤で2つの目的を持たせても良い。
本発明に係る目的であるコンデンサーとしての長期使用における劣化抑制、性能向上に寄与する2次剤として、カルボニル基を有するヒンダードフェノール系酸化防止剤が添加される。
本発明に係るコンデンサー用2軸延伸ポリプロピレンフィルムに含有される、カルボニル基を有するヒンダードフェノール系酸化防止剤のフィルム中における残存量を、4000ppm(質量基準)以上6000ppm(質量基準)以下とするためには、前記の添加量とする必要がある。これは、前述の様に、押出機内での劣化抑制を目的とする1次剤の有無にかかわらず、押出機内で少なからず、カルボニル基を有するヒンダードフェノール系酸化防止剤も消費されるためである。押出機内でのカルボニル基を有するヒンダードフェノール系酸化防止剤の消費量は、通常1000ppm~2000ppm程度である。
前述したように、低すぎるβ晶分率は、フィルム表面を平滑化するため、素子巻き等の加工適性に劣る傾向にあるが、耐電圧特性などコンデンサーの特性が向上する。しかしながら、前述のβ晶分率の範囲になると、コンデンサー特性と素子巻き加工性の両物性を十分に満足させることができる。
本発明のコンデンサー用2軸延伸ポリプロピレンフィルムは、前記ポリプロピレンキャスト原反シートに延伸処理を行って作製することができる。延伸は、縦及び横に2軸に配向せしめる2軸延伸が良く、延伸方法としては逐次2軸延伸方法が好ましい。逐次2軸延伸方法としては、まずキャスト原反シートを100~160℃の温度に保ち、速度差を設けたロール間に通して流れ方向に3~7倍に延伸し、直ちに室温に冷却する。この縦延伸工程の温度を適切に調整することにより、β晶は融解しα晶に転移し、凹凸が顕在化する。引き続き、当該延伸フィルムをテンターに導いて160℃以上の温度で幅方向に3~11倍に延伸した後、緩和、熱固定を施し巻き取る。
このような延伸工程によって、機械的強度、剛性に優れたフィルムとなり、また、表面の凹凸もより明確化され、微細に粗面化された延伸フィルムとなる。
本発明のフィルムの表面には、素子巻き適性を向上させつつ、コンデンサー特性を良好とする適度な表面粗さを付与することが好ましい。
RaやRz(旧JIS定義のRmax)がある程度大きい値であると、巻き取り、巻き戻しなどの加工や、コンデンサー加工の際には、素子巻き加工において、フィルム間に適度な空隙が生じるためフィルムが適度にすべり、巻取りにシワが入りにくく、かつ横ズレも起こしにくくなる。しかし、それらの値が大きすぎると、表面光沢性や透明性などに実用上の問題を生じる他、コンデンサーにおいては、フィルム間の層間空隙が大きくなることによる重量厚み低下が起こり、耐電圧性の低下を招くため、好ましくない。逆に、突起体積が低くある程度平滑であると、耐電圧性の面では有利となるが、低い値になりすぎると、フィルムが滑りにくく、巻き加工の際にシワが発生しやすくなり、生産性が低下するため好ましくない上、細かなシワなどはコンデンサーの耐電圧性の悪化をも招くので実用上不適と言える。
本発明のコンデンサー用2軸延伸ポリプロピレンフィルム中に含まれる総灰分は、電気特性を良化するために、可能な限り少ないことが好ましく、50ppm以下、好ましくは、40ppm以下である。
マージンを形成する方法はテープ法、オイル法など、一般に公知の方法が、何ら制限無く使用することが出来る。
実施例における特性値の測定方法及び効果の評価方法はつぎの通りである。
2軸延伸ポリプロピレンフィルムの分子量(Mw)、分子量分布(Mw/Mn)、分布曲線の微分分布値の評価は、GPC(ゲルパーミエーションクロマトグラフィー)を用い、以下の条件で測定し行った。
測定機:東ソー株式会社製、示差屈折計(RI)内蔵高温GPC、HLC-8121GPC-HT型
カラム:東ソー株式会社製、TSKgel GMHHR-H(20)HTを3本連結
カラム温度:140℃、
溶離液:トリクロロベンゼン
流速:1.0ml/min
検量線の作製には、東ソー株式会社製の標準ポリスチレンを用い、測定結果はポリプロピレン値に換算した。
2軸延伸ポリプロピレンフィルムを溶媒に溶解し、高温型フーリエ変換核磁気共鳴装置(高温FT-NMR)を用いて、以下の条件で、メソペンタッド分率([mmmm])を求めた。
測定機:日本電子株式会社製、高温FT-NMR JNM-ECP500
観測核:13C(125MHz)
測定温度:135℃
溶媒:オルト-ジクロロベンゼン〔ODCB:ODCBと重水素化ODCBの混合溶媒(4/1)〕
測定モード:シングルパルスプロトンブロードバンドデカップリング
パルス幅:9.1μsec(45°パルス)
パルス間隔:5.5sec
積算回数:4500回
シフト基準:CH3(mmmm)=21.7ppm
5連子(ペンタッド)の組み合わせ(mmmmやmrrmなど)に由来する各シグナルの強度積分値より、百分率(%)で算出した。mmmmやmrrmなどに由来する各シグナルの帰属に関し、例えば、「T.Hayashi et al.,Polymer,29巻,138頁(1988)」などのスペクトルの記載を参考とした。
2軸延伸ポリプロピレンフィルムを断裁し、溶媒を加え、超音波抽出でフィルム中に残存している酸化防止剤を抽出した。
得られた抽出液を、高速液体クロマトグラフ/紫外線検出器を用いて2次剤の測定を行った。得られたクロマトグラフのピーク強度から、予め求めてある検量線を用いて、2次剤の残存量を計算した。
二軸延伸ポリプロピレンフィルムの中心線平均粗さ(Ra)、及び、最大高さ(Rz)の測定は、小坂研究所社製、万能表面形状測定器SE-30型を用い、粗さ解析装置AY-41型によって、JIS-B0601に定められている方法に準拠して求めた。測定回数は3回行い、その平均値を評価に用いた。本評価では、接触法により測定し、その値の信頼性を、必要に応じて非接触法値により補足、確認した。
2軸延伸ポリプロピレンフィルムの厚さは、マイクロメーター(JIS-B7502)を用いて、JIS-C2330に準拠して測定した。
二軸延伸フィルムの耐電圧性は、JIS-C2330 7.4.11.2(絶縁破壊電圧・平板電極法:B法)に準じて絶縁破壊電圧値を測定することによって評価した。昇圧速度は100V/sec、破壊の際の遮断電流は10mAとし、測定回数は18回とした。ここでは、測定された平均電圧値を、フィルムの厚みで割ったものを、絶縁破壊強度として評価に用いた。送風循環式高温槽内にフィルム及び電極冶具をセットして、評価温度100℃にて、測定を行った。
高温絶縁破壊強度450V/μm以上が実用上望ましく、450V/μm以上が、さらに好ましい耐電圧性であると言える。
2軸延伸ポリプロピレンフィルムに、Tマージン蒸着パターンを蒸着抵抗12Ω/□にてアルミニウム蒸着を施し、金属化フィルムを得た。小幅にスリットした後に、2枚の金属化フィルムを相合わせて、株式会社皆藤製作所製、自動巻取機 3KAW-N2型を用い、巻き取り張力400gにて、1150ターン巻回を行った。
素子巻きの際の加工適性を、目視で定性的に評価した。
素子巻きした素子は、プレスしながら120℃にて6時間熱処理を施した後、素子端面に亜鉛金属を溶射し、扁平型コンデンサーを得た。出来上がったコンデンサーの静電容量は、100μF(±5μF)であった。
得られたコンデンサー素子は、自動車駆動用モーターを制御するインバーターとしては、環境最高温度90℃、最大電圧700Vにて、使用されるものと想定し、ライフ促進試験を以下の手順で行った。
予め素子を試験環境温度(105℃(想定最高温度+15℃))にて1時間予熱した後、試験前の初期の静電容量を安藤電気株式会社製LCRテスターAG4311にて、評価した。次に、105℃の高温槽中にて、高圧電源を用い、コンデンサー素子に直流750V(想定最大電圧+50V)の電圧を500時間負荷続けた。500時間経過後の素子の容量をLCRテスターで測定し、電圧負荷前後の容量変化率を算出した。ついで、素子を再度高温槽内に戻し、さらに、500時間電圧負荷を行い、1000時間経過(累積)の容量変化(累積)を求め、これを2000時間経過後まで繰り返した。2000時間経過後の容量変化率を求め、素子3個の平均値を評価に採用した。容量変化率は、2000時間後で、±5%以内が実用上好ましい。
静電容量向上に必要な5μm以下のフィルムによるコンデンサー素子作製の成否、フィルムの高温での絶縁破壊強度(耐電圧性)、かつフィルムをコンデンサー素子とした際の高温長期耐用特性等、コンデンサー用フィルムとしての好適性を総合的に評価した。従来技術に基づくフィルムより向上したものを「A」、従来と変わらないものを「B」、それより劣るものを「C」とした。
プライムポリマー株式会社より、分子量分布未調整ポリプロピレン樹脂E(メルトフローインデックス4g/10分、重量平均分量30万、メソペンタッド分率96%)を得た。
また、このポリプロピレン樹脂Eと有機過酸化物を溶融混練することで過酸化分解処理を施し、分子量分布調整樹脂A~Dを得た。さらに、低立体規則性ポリプロピレン樹脂(メソペンタッド分率93.5%)を有機過酸化物と溶融混練することで過酸化分解処理を施した分子量分布調整樹脂Fを得た。また、比較のため、樹脂Eをベースに高メルトフロー樹脂を添加混合することによって分子量分布を調整したポリプロピレン樹脂Gを得た。
ポリプロピレン樹脂A~Gには酸化防止剤(2次剤)を添加した。
表1には、これら樹脂より得た二軸延伸ポリプロピレンフィルムの過酸化分解処理の有無、分子量微分分布値差、重量平均分子量(Mw)、分子量分布(Mw/Mn)、立体規則性度(メソペンタッド分率)、酸化防止剤(2次剤)の残存量をまとめた。
なお、表1のこれらの値はフィルムの分析値である。
プライムポリマー社製の樹脂Eに2次酸化防止剤としてイルガノックス(登録商標)1010を5000ppm、2,5-ジメチル-2,5-ジ(t-ブチルペロキシ)ヘキサンを20ppm添加し造粒機で溶融混練することにより過酸化分解処理を施して分子量分布を調整した原料樹脂Aを押出機に供給して、樹脂温度250℃の温度で溶融し、Tダイを用いて押出し、表面温度を95℃に保持した金属ドラムに巻きつけて固化させ、厚さ約140μmのキャスト原反シートを作製した。引き続きこの未延伸キャスト原反シートを140℃の温度で、流れ方向に5倍に延伸し、直ちに室温まで冷却した後、ついでテンターにて165℃の温度で横方向に10倍に延伸して、厚さ2.8μmの非常に薄い2軸延伸ポリプロピレンフィルムを得た。得られたフィルムの分子特性並びにフィルムの物性値を表1にまとめる。また、コンデンサーフィルムとしての評価結果を表2にまとめる。なお、表1の分子量微分分布値差、分子量(Mw)、分子量分布(Mw/Mn)、メソペンタッド分率、2次酸化防止剤残存量はフィルムの分析値である。
実施例1の原料樹脂Aに代えて、過酸化分解処理を施した分子量分布調整樹脂Bに、2次酸化防止剤であるイルガノックス(登録商標)1010を実施例1と同様に添加した原料樹脂Bを押出機に供給した以外は、実施例1と同様にして、厚さ2.8μmの非常に薄い2軸延伸ポリプロピレンフィルムを得た。得られたフィルムの分子特性並びにフィルムの物性値を表1にまとめる。また、コンデンサーフィルムとしての評価結果を表2にまとめる。なお、表1の分子量微分分布値差、分子量(Mw)、分子量分布(Mw/Mn)、メソペンタッド分率、2次酸化防止剤残存量はフィルムの分析値である。
実施例1の原料樹脂Aに代えて、過酸化分解処理を施した分子量分布調整樹脂Cに、2次酸化防止剤であるイルガノックス(登録商標)1010を5500ppm添加した原料樹脂Cを押出機に供給した以外は、実施例1と同様に、厚さ2.8μmの非常に薄い2軸延伸ポリプロピレンフィルムを得た。得られたフィルムの分子特性並びにフィルムの物性値を表1にまとめる。また、コンデンサーフィルムとしての評価結果を表2にまとめる。なお、表1の分子量微分分布値差、分子量(Mw)、分子量分布(Mw/Mn)、メソペンタッド分率、2次酸化防止剤残存量はフィルムの分析値である。
実施例1の原料樹脂Aに代えて、過酸化分解処理を施した分子量分布調整樹脂Dに、2次酸化防止剤であるイルガノックス(登録商標)1010を6000ppm添加した原料樹脂Dを押出機に供給した以外は、実施例1と同様に、厚さ2.8μmの非常に薄い2軸延伸ポリプロピレンフィルムを得た。得られたフィルムの分子特性並びにフィルムの物性値を表1にまとめる。また、コンデンサーフィルムとしての評価結果を表2にまとめる。なお、表1の分子量微分分布値差、分子量(Mw)、分子量分布(Mw/Mn)、メソペンタッド分率、2次酸化防止剤残存量はフィルムの分析値である。
実施例1の原料樹脂Aを押出機に供給して、樹脂温度250℃の温度で溶融し、Tダイを用いて押出し、表面温度を95℃に保持した金属ドラムに巻きつけて固化させ、厚さ約125μmのキャスト原反シートを作製した。引き続きこの未延伸キャスト原反シートを140℃の温度で、流れ方向に5倍に延伸し、直ちに室温まで冷却した後、ついでテンターにて165℃の温度で横方向に10倍に延伸して、厚さ2.5μmの非常に薄い2軸延伸ポリプロピレンフィルムを得た。得られたフィルムの分子特性並びにフィルムの物性値を表1にまとめる。また、コンデンサーフィルムとしての評価結果を表2にまとめる。なお、表1の分子量微分分布値差、分子量(Mw)、分子量分布(Mw/Mn)、メソペンタッド分率、2次酸化防止剤残存量はフィルムの分析値である。
特許文献4(国際公開 WO2009-060944号公報)の実施例2を参考に、重合法によって分子量分布の構成を調整した樹脂Eに、2次酸化防止剤であるイルガノックス(登録商標)1010を4000ppm添加した原料樹脂Eを押出機に供給した以外は、実施例1と同様にして、厚さ2.8μmの非常に薄い2軸延伸ポリプロピレンフィルムを得た。得られたフィルムの分子特性並びにフィルムの物性値を表1にまとめる。また、コンデンサーフィルムとしての評価結果を表2にまとめる。なお、表1の分子量微分分布値差、分子量(Mw)、分子量分布(Mw/Mn)、メソペンタッド分率、2次酸化防止剤残存量はフィルムの分析値である。
重合法によって分子量分布の構成を調整した樹脂Eに、2次酸化防止剤であるイルガノックス(登録商標)1010を5000ppm添加した原料樹脂E’を押出機に供給した以外は、実施例1と同様にして、厚さ2.8μmの非常に薄い2軸延伸ポリプロピレンフィルムを得た。得られたフィルムの分子特性並びにフィルムの物性値を表1にまとめる。また、コンデンサーフィルムとしての評価結果を表2にまとめる。なお、表1の分子量微分分布値差、分子量(Mw)、分子量分布(Mw/Mn)、メソペンタッド分率、2次酸化防止剤残存量はフィルムの分析値である。
実施例1の原料樹脂Aに代えて、プライムポリマー社製、ポリプロピレン樹脂(メルトフローインデックス3g/10分、平均分子量35万、メソペンタッド分率93.5%)を有機過酸化物と溶融混練することで過酸化分解処理を施した分子量分布調整樹脂Fに、2次酸化防止剤であるイルガノックス(登録商標)1010を5000ppm添加した原料樹脂Fを押出機に供給した以外は、実施例1と同様にして、厚さ2.8μmの非常に薄い2軸延伸ポリプロピレンフィルムを得た。得られたフィルムの分子特性並びにフィルムの物性値を表1にまとめる。また、コンデンサーフィルムとしての評価結果を表2にまとめる。なお、表1の分子量微分分布値差、分子量(Mw)、分子量分布(Mw/Mn)、メソペンタッド分率、2次酸化防止剤残存量はフィルムの分析値である。
特許文献4(国際公開 WO2009-060944号公報)の実施例2を参考に、実施例1の原料樹脂Aに代えて、樹脂Eをベースにプライムポリマー社製の高メルトフロー樹脂(メルトフローインデックス9g/10分)を15%添加混合することによって分子量分布を調整したポリプロピレン樹脂Gに、2次酸化防止剤であるイルガノックス(登録商標)1010を4000ppm添加した原料樹脂Fを押出機に供給した以外は、実施例1と同様にして、厚さ2.8μmの非常に薄い2軸延伸ポリプロピレンフィルムを得た。得られたフィルムの分子特性並びにフィルムの物性値を表1にまとめる。また、コンデンサーフィルムとしての評価結果を表2にまとめる。なお、表1の分子量微分分布値差、分子量(Mw)、分子量分布(Mw/Mn)、メソペンタッド分率、2次酸化防止剤残存量はフィルムの分析値である。
2:低分子量領域の構成割合が少ない樹脂
Claims (4)
- 高温型核磁気共鳴(高温NMR)測定によって求められるメソペンタッド分率([mmmm])が、94%以上98%未満である立体規則性度を有するとともに、ゲルパーミエーションクロマトグラフ(GPC)法で測定した重量平均分子量(Mw)が25万以上45万以下で、分子量分布(Mw/Mn)が4以上7以下であり、かつ、分子量分布曲線において、対数分子量Log(M)=4.5のときの微分分布値からLog(M)=6のときの微分分布値を引いた差が9%以上15%以下である2軸延伸ポリプロピレンフィルムであって、前記分子量分布の構成をポリプロピレン樹脂の過酸化分解処理によって調整したポリプロピレン原料樹脂を用いる、コンデンサー用2軸延伸ポリプロピレンフィルム。
- 前記ポリプロピレンフィルムが、カルボニル基を有するヒンダードフェノール系酸化防止剤を少なくとも1種類以上含有し、そのフィルム中の残存含有量が4000ppm(質量基準)以上6000ppm(質量基準)以下ある、請求項1記載のコンデンサー用2軸延伸ポリプロピレンフィルム。
- 前記2軸延伸ポリプロピレンフィルムの少なくとも片方の一面において、その表面粗さが、中心線平均粗さ(Ra)で0.05μm以上0.15μm以下であり、かつ、最大高さ(Rz、旧JIS定義でのRmax)で0.5μm以上1.5μm以下に微細粗面化されている、請求項1に記載のコンデンサー用2軸延伸ポリプロピレンフィルム。
- 前記2軸延伸ポリプロピレンフィルムの厚さが、1μm以上5μm以下である、請求項1に記載のコンデンサー用2軸延伸ポリプロピレンフィルム。
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Also Published As
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DE112012000507B4 (de) | 2023-04-20 |
JP2012149171A (ja) | 2012-08-09 |
US9349538B2 (en) | 2016-05-24 |
CN103329226A (zh) | 2013-09-25 |
DE112012000507T5 (de) | 2014-01-02 |
KR20140024268A (ko) | 2014-02-28 |
KR101863063B1 (ko) | 2018-05-31 |
JP5617655B2 (ja) | 2014-11-05 |
US20130288000A1 (en) | 2013-10-31 |
CN103329226B (zh) | 2016-03-16 |
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