WO2016159330A1 - コンデンサ用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コンデンサ - Google Patents
コンデンサ用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コンデンサ Download PDFInfo
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- WO2016159330A1 WO2016159330A1 PCT/JP2016/060854 JP2016060854W WO2016159330A1 WO 2016159330 A1 WO2016159330 A1 WO 2016159330A1 JP 2016060854 W JP2016060854 W JP 2016060854W WO 2016159330 A1 WO2016159330 A1 WO 2016159330A1
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- WIPO (PCT)
- Prior art keywords
- tan
- polypropylene
- film
- polypropylene film
- capacitor
- Prior art date
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 390
- -1 polypropylene Polymers 0.000 title claims abstract description 370
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- 239000003990 capacitor Substances 0.000 title claims abstract description 194
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/33—Thin- or thick-film capacitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/32—Wound capacitors
Definitions
- the present invention relates to a biaxially stretched polypropylene film for a capacitor, and more particularly to a biaxially stretched polypropylene film for a capacitor in which a decrease in capacitance is small in a long-term withstand voltage test at a high temperature.
- polypropylene films have been widely used in electrical applications such as film capacitors because they are superior in electrical properties such as dielectric loss (hereinafter also referred to as tan ⁇ ) and voltage resistance to other plastic films.
- tan ⁇ dielectric loss
- polypropylene films are generally unsuitable for capacitors used at high temperatures because of their low heat resistance.
- Patent Document 1 for the purpose of improving heat resistance and voltage resistance, a capacitor with improved voltage resistance and device workability is controlled by controlling the surface roughness, protrusion height, and number of protrusions on both sides of a polypropylene film.
- Biaxially oriented polypropylene films have been proposed.
- Patent Document 2 proposes a biaxially stretched polypropylene film for a capacitor using a polypropylene resin raw material having a specific mesopentad fraction, a weight average molecular weight and a molecular weight distribution.
- Patent Document 3 proposes a roughened polypropylene film mainly composed of a polypropylene resin having a specific weight average molecular weight.
- Patent Document 4 as a result of paying attention to the relationship between the internal structure of the polypropylene film and the leakage current when a high voltage is applied, the voltage resistance of the polypropylene film is improved by making the crystallite size fine and highly oriented. Improved biaxially oriented polypropylene films for capacitors have been proposed.
- Patent Document 5 proposes a polypropylene film for a capacitor having a stable tan ⁇ characteristic with a small decrease in capacitance during high temperature and long-term charging by keeping the heat shrinkage stress value of the polypropylene film within a certain range.
- JP 2011-122142 A JP 2012-149171 A JP 2014-77057 A JP 2014-231584 A JP 2009-88492 A
- Patent Documents 1 to 3 have the effect of improving the dielectric breakdown strength and the healing characteristics (security) by reducing the number of coarse protrusions on the surface of the polypropylene film and forming a finely and uniformly roughened surface shape. It is disclosed that it can be obtained.
- the present inventors have found that none of the polypropylene films described in the cited documents 1 to 3 is sufficiently suppressed with respect to a decrease in capacitance that occurs when used for a long time under high voltage and high temperature. I found out.
- cited document 4 discloses that the effect of improving the withstand voltage of the polypropylene film can be obtained by reducing the crystallite size and increasing the orientation.
- an object of the present invention is to provide a biaxially stretched polypropylene film for a capacitor that can suppress a decrease in capacitance even when a high voltage is applied to the capacitor over a long period of time at a high temperature. .
- the inventors of the present invention have made studies to suppress a decrease in capacitance that occurs when a capacitor is used over a long period of time at a high voltage and a high temperature, and as a result, a polypropylene in which the increase in tan ⁇ of the capacitor element is delayed. It has been found that the film has a smaller capacitance change rate ⁇ C and a decrease in capacitance with time.
- the tan ⁇ of the capacitor element is composed of dielectric loss caused by molecular motion of polypropylene molecules constituting the dielectric, and electrode loss such as resistance at electrodes and leakage current between electrodes.
- electrode loss such as resistance at electrodes and leakage current between electrodes.
- the inventors of the present invention use one or more polypropylene resins having a specific range of molecular weight distribution and mesopentad fraction as an example of the increase in dielectric loss caused by molecular motion of the capacitor element.
- the crystallite size is controlled to be equal to or smaller than a specific size, and the birefringence value in the thickness direction is suppressed by the biaxially stretched polypropylene film controlled to a specific range.
- the present inventors have a density such as a circular shape or an elliptical shape formed on the surface as crater-like fine irregularities. That is, it has been found that a surface shape characterized by a relatively small elliptical density is preferable, and a surface shape characterized by a large number of coarse protrusions having a relatively high protrusion height is preferable.
- These features in the surface shape are an ellipse shape that is finely and uniformly roughened to improve the dielectric breakdown strength and healing characteristics (security) disclosed in the prior arts such as Patent Documents 1 to 4, and has a low protrusion height. This is greatly different from the characteristics of the surface with the increased number of and the like, and the surface of the surface that is finely and uniformly roughened by suppressing the number of coarse protrusions.
- tan ⁇ [measured during an elapsed time of 0 to 500 hours in a long-term durability test in which a voltage of 600 V is applied at 105 ° C. %] Normalized by the initial value tan ⁇ 0 [%] measured at an elapsed time of 0 hour, and the rate of change of tan ⁇ / tan ⁇ 0 with respect to time is 5.0 ⁇ 10 ⁇ 4 [1 / hour] or less.
- the capacitor is used for a long time at a high voltage and high temperature, it is found that the increase in tan ⁇ of the capacitor element can be suppressed, and as a result, the decrease in the capacitance can be suppressed, and the present invention is completed. I came to let you.
- the present invention includes the following.
- [1] In a long-term durability test in which a voltage of 600 V is applied at 105 ° C., tan ⁇ [%] measured during an elapsed time of 0 hours to 500 hours is an initial value tan ⁇ 0 measured at an elapsed time of 0 hours.
- the polypropylene film according to any one of [1] to [3] above, which is 0.50 or more.
- a capacitor comprising the metallized film according to [9].
- tan ⁇ [%] measured during an elapsed time of 0 to 500 hours is measured at an elapsed time of 0 hours.
- tan ⁇ [%] measured during an elapsed time of 0 to 500 hours is measured at an elapsed time of 0 hours.
- the method of using a film, wherein the rate of change of the value tan ⁇ / tan ⁇ 0 normalized by the initial value tan ⁇ 0 [%] with respect to time is 5.0 ⁇ 10 ⁇ 4 [1 / hour] or less.
- tan ⁇ [%] measured during an elapsed time of 0 hours to 500 hours is an initial value tan ⁇ 0 measured at an elapsed time of 0 hours.
- a method for producing a biaxially stretched polypropylene film for a capacitor wherein a rate of change with respect to time of a value tan ⁇ / tan ⁇ 0 normalized by [%] is 5.0 ⁇ 10 ⁇ 4 [1 / hour] or less, (1) Step 1 of heating the polypropylene resin composition, (2) Step 2 for extruding the molten polypropylene resin composition obtained in Step 1 above, (3) Step 3 in which the polypropylene resin composition obtained in Step 2 is brought into contact with at least one metal drum, and (4) Step of biaxially stretching the cast raw sheet obtained in Step 3 4 Including, in order.
- step 3 The method according to [13], wherein in step 3, the surface temperature of at least one metal drum is maintained at a temperature of 90 ° C. to 140 ° C.
- step 4 the cast raw sheet is stretched at a temperature of 100 to 160 ° C.
- the capacitor using the biaxially stretched polypropylene film for a capacitor of the present invention has a small increase in tan ⁇ even when a high voltage is applied at a high temperature for a long time, and as a result, a decrease in capacitance is small (suppressed). .
- the polypropylene film of the present invention also has an internal structure excellent in dielectric breakdown characteristics. Therefore, according to the present invention, a biaxially stretched polypropylene film for capacitors having a long-term durability (long life) at high temperatures and high voltages can be obtained.
- FIG. 1 shows the result of observation by an optical microscope of the surface of the polypropylene film of the present invention stretched with the direction of arrow MD as the flow direction and the direction of arrow TD as the width direction.
- FIG. 2 is a schematic (a) perspective view (image diagram), (b) transverse sectional view, and (c) (b) longitudinal sectional view taken along line II ′ of FIG. .
- FIG. 3 shows an example in which the number of ellipses on the surface of the polypropylene film of FIG. 1 is counted.
- the symbol “/” means “ ⁇ ” (provided that “2 ⁇ / ⁇ ”, “and / or”, “HLC-8121GPC / HT type” “ /"except for).
- 1 / time refers to 1 ⁇ time (hour)
- tan ⁇ / tan ⁇ 0 means tan ⁇ ⁇ tan ⁇ 0. ⁇ 1.
- Biaxially stretched polypropylene film for capacitors of the present invention >> The polypropylene film of the present invention was measured in a long-term durability test in which a voltage of 600 V was applied at 105 ° C., and tan ⁇ [%] measured during an elapsed time of 0 hours to 500 hours was measured at an elapsed time of 0 hours.
- the rate of change of the value tan ⁇ / tan ⁇ 0 normalized by the initial value tan ⁇ 0 with respect to time (hereinafter also simply referred to as the rate of change of tan ⁇ / tan ⁇ 0 with respect to time) is 5.0 ⁇ 10 ⁇ 4 [1 / time] or less. It is a biaxially stretched polypropylene film for capacitors.
- tan ⁇ [%] refers to a dielectric loss tangent (dielectric loss) measured when a direct current is passed through a capacitor using the polypropylene film of the present invention as a dielectric. Therefore, tan [delta is the tan [delta of the capacitor element, the initial value tan [delta 0 is the initial value tan [delta 0 of the capacitor element.
- the polypropylene film of the present invention is a biaxially stretched polypropylene film for a capacitor, and in a long-term durability test of a capacitor including the polypropylene film to which a voltage of 600 V is applied at 105 ° C., 0 to 500 hours.
- the rate of change of the value tan ⁇ / tan ⁇ 0 with respect to the time obtained by normalizing the tan ⁇ [%] of the capacitor measured during the elapsed time of 0 with the initial value tan ⁇ 0 [%] of the capacitor measured at the elapsed time of 0 hours is 5. It is a polypropylene film that is 0 ⁇ 10 ⁇ 4 [1 / hour] or less.
- the capacitance change rate ⁇ C of the capacitor element is the ratio of the difference obtained by subtracting the initial capacitance from the capacitance after the lapse of a predetermined time, measured in the long-term durability test, to the initial capacitance. Calculated as [%].
- the long-term durability test can be performed as follows. The initial capacitance and tan ⁇ 0 before the long-term durability test are measured. Next, a DC voltage of 600 V is applied to the capacitor element for 100 hours in a constant temperature bath at 105 ° C. Thereafter, the capacitor element is taken out from the thermostatic chamber. The capacitance and tan ⁇ of the capacitor element after 100 hours are measured at room temperature. Thereafter, the capacitor element is returned to the thermostat. This operation is repeated every predetermined time, for example, every 100 hours or every 500 hours. In the present invention, the average value of capacitance and tan ⁇ measured at a predetermined time for five capacitor elements is calculated.
- an air-conditioning dryer FC-610 manufactured by Advantech can be used as the thermostatic bath.
- tan ⁇ and capacitance can be measured using, for example, an LCR high tester 3522-50 manufactured by Hioki Electric Co., Ltd.
- a constant temperature dryer FC-610 manufactured by Advantech was used as a thermostatic chamber.
- tan ⁇ and capacitance were measured using an LCR high tester 3522-50 manufactured by Hioki Electric Co., Ltd.
- the rate of change with time of the tan [delta / tan [delta 0 is calculated as the slope of a primary approximate straight line obtained by the least square method from the point it plotted against the the / tan [delta 0 measurement time in the long-term durability test.
- the rate of change of tan ⁇ / tan ⁇ 0 with respect to time is It can also be expressed as
- the capacitor is kept at high voltage and high temperature for a long time. It is possible to suppress a decrease in capacitance when used, and as a result, it is possible to improve the long-term durability of the capacitor.
- the tan ⁇ of the capacitor element is composed of dielectric loss caused by molecular motion of polypropylene molecules constituting the dielectric, and electrode loss such as resistance at electrodes and leakage current between electrodes. Both of these two losses have the property of increasing irreversibly once they start increasing.
- the dielectric loss due to molecular motion increases, it is considered that the higher-order crystal structure in the polypropylene has changed due to internal heat generation of the capacitor. Therefore, in general, it does not return to the original, and the dielectric loss continues to increase.
- electrode loss it is thought that loss increases by the partial destruction of the electrode part inside a film capacitor, or structural change. Therefore, it is considered that the electrode loss does not start to decrease once it starts increasing. Therefore, the present inventors have thought that when the capacitor is used for a long period of time at a high voltage and at a high temperature, suppressing the increase in tan ⁇ of the capacitor element as much as possible leads to improvement of long-term durability.
- the present invention has been completed.
- the reason why the biaxially stretched polypropylene film of the present invention is excellent in the effects of the present invention is specified here as being within the scope of the present invention even if it is different from the above-mentioned reason.
- the rate of change with respect to time of tan ⁇ / tan ⁇ 0 is preferably 4.9 ⁇ 10 ⁇ 4 or less, more preferably 4.8 ⁇ 10 ⁇ 4 or less, and further preferably 4.7 ⁇ 10 ⁇ 4. Or less, particularly preferably 4.5 ⁇ 10 ⁇ 4 or less, and particularly preferably 4.0 ⁇ 10 ⁇ 4 or less.
- the lower limit value of the rate of change with respect to time of tan ⁇ / tan ⁇ 0 is usually 0 or more, for example, 0.1 ⁇ 10 ⁇ 8 or more, 0.1 ⁇ 10 ⁇ 5 or more, 0.1 ⁇ 10 ⁇ 4 or more, 1.0 ⁇ 10 ⁇ 4 or more.
- the rate of change with respect to time of tan ⁇ / tan ⁇ 0 is in the range of any combination of the above upper limit value and lower limit value, for example, 0 or more and 5.0 ⁇ 10 ⁇ 4 or less, 0.1 ⁇ 10 ⁇ 8 or more and 4.9 ⁇ 10 ⁇ 4 or less, 0.1 ⁇ 10 ⁇ 5 or more and 4.8 ⁇ 10 ⁇ 4 or less, 0.1 ⁇ 10 ⁇ 4 or more and 4.7 ⁇ 10 ⁇ 4 or less, 1.0 ⁇ 10 -4 or more and 4.0 ⁇ 10 -4 or less is preferable.
- the rate of change of tan ⁇ / tan ⁇ 0 with respect to time in the present invention is, for example, (1) selection of raw materials (particularly resin components), (2) metal drum temperature for cooling and solidifying when forming a cast raw sheet (3) It can be adjusted by the temperature at the time of stretching when the cast raw sheet is stretched.
- the increase in tan ⁇ of the capacitor element can be significantly suppressed when the increase in both the dielectric loss and the electrode loss due to the molecular motion of the capacitor element is suppressed.
- the raw material it is possible to suppress dielectric loss due to molecular motion of the capacitor element.
- the metal drum temperature for cooling and solidifying the cast original sheet and the temperature during stretching when the cast original sheet is stretched, the elliptic density on at least one surface, and high
- the total protrusion volume of 0.4 ⁇ m or more becomes a desired value, and the dielectric loss of the capacitor element can be suppressed.
- the biaxially stretched polypropylene film for capacitors of the present invention (hereinafter also simply referred to as “polypropylene film”) is preferably roughened by fine crater-like irregularities on at least one surface.
- polypropylene film having ⁇ -type spherulites is stretched, the ⁇ -type spherulites are transformed into ⁇ -type spherulites with higher density. As a result, crater-like fine irregularities are formed on the film surface at the portion where the crystal transformation has occurred.
- arc shapes and arcuate shapes are formed by, for example, using an optical microscope or the like to collect two arcuate or substantially arcuate shapes that are curved in opposite directions (hereinafter referred to as arc shapes and arcuate shapes).
- arc shape Arcuate shape
- FIG. 1 When two (substantially) arc-shaped portions forming an observed pair are complemented (interpolated) and connected, an elliptical shape or a substantially elliptical shape (hereinafter referred to as an elliptical shape and a substantially elliptical shape, Is also called).
- the two (substantially) arc-shaped portions forming this pair form a protrusion and a recess between the protrusions (see FIG. 2 (a)).
- the protrusions and depressions form the crater-like fine irregularities (see FIGS. 2B and 2C).
- the two (substantially) arc shapes are combined to form a circular shape or a substantially circular shape (hereinafter collectively referred to as “(substantially) circular shape”) or (substantially) elliptical shape. There may be.
- the cross section of the protrusion in this case is circular or substantially annular (hereinafter collectively referred to as "(substantially) annular”), or elliptical or substantially elliptical (hereinafter elliptical and A substantially elliptical ring is collectively referred to as “(substantially) elliptical ring”). Moreover, it may be observed as a single (substantially) arc shape without making a pair.
- the protrusions forming the crater-like fine irregularities have a total protrusion volume of 0.4 ⁇ m or more in height of 50 ⁇ m 3 or more and 150 ⁇ m 3 or less per 1 mm 2 on at least one surface.
- the polypropylene film of the present invention, in at least one surface, or more projections total volume height 0.4 ⁇ m is 1 mm 2 per 60 [mu] m 3 or more 140 .mu.m 3 or less, more preferably 70 [mu] m 3 or more 130 .mu.m 3 or less, particularly preferably is 80 ⁇ m 3 more than 120 ⁇ m 3 below.
- the electrode loss of the capacitor element is reduced as long as the total volume of protrusions having a height of 0.4 ⁇ m or more is in the range of 50 ⁇ m 3 or more and 150 ⁇ m 3 or less per 1 mm 2 on at least one surface. Even when a high voltage current is applied for a long time at a high temperature, a capacitor having a small capacitance change rate ⁇ C can be easily obtained, which is preferable.
- the total protrusion volume refers to the total volume of protrusions forming the crater-like fine irregularities in a certain range on the surface of polypropylene.
- the protrusions in the total volume of the protrusions are observed as two (substantially) arcuate shapes that form pairs that are curved in opposite directions, and the two protrusions are combined to be observed as a (substantially) circular or (substantially) elliptical shape. Projections that are observed as single (substantially) arcuate shapes that are not paired.
- the total protrusion volume can be obtained by measuring the surface shape using a three-dimensional surface roughness evaluation method using an optical interference type non-contact surface shape measuring instrument.
- the gap between the films can be evaluated three-dimensionally. Therefore, it is possible to grasp local fine changes and variations on the measurement target surface, and to evaluate more accurate surface roughness. It is possible to evaluate the gap between the films by using the total volume of the three-dimensional protrusions, not just the height of the protrusions (two-dimensional surface roughness evaluation based on a general centerline average roughness Ra). it can.
- the total volume of protrusions with a height of 0.4 ⁇ m or more is measured using, for example, “VertScan 2.0 (model: R5500GML)” manufactured by Ryoka System Co., Ltd. as an optical interference type non-contact surface shape measuring instrument. Can do.
- “VertScan 2.0 (model: R5500 GML)” manufactured by Ryoka System Co., Ltd. was used as an optical interference type non-contact surface shape measuring instrument.
- the surface of the film to be measured is 240 ⁇ m ⁇ 180 ⁇ m per field of view. Measure at any 10 points.
- the obtained data is subjected to noise removal processing by a median filter. Thereafter, Gaussian filter processing with a cutoff value of 30 ⁇ m is performed. Next, the swell component is removed. Thereby, it is set as the state which can measure the state of a roughening surface appropriately.
- the “peak side height threshold” is set to 0.4 ⁇ m.
- mountain side volume is the total protrusion volume per field of view. This measurement was performed at 10 locations, and the total volume of protrusions per field obtained by dividing the average value by the area of one field of view was the total volume of protrusions of 0.4 ⁇ m or more per 1 mm 2 [unit: ⁇ m 3 / mm. 2 ].
- the polypropylene film of the present invention has a (substantially) circular shape composed of two (substantially) arcuate shapes on the surface that are observed using a digital scope or the like, for example, a digital microscope VHX-2000 manufactured by Keyence Corporation.
- the elliptical density which is the shape and the number of (substantially) elliptical shapes per unit area, is preferably 60 / mm 2 or more and 80 / mm 2 or less on at least one surface.
- An elliptic density of 60 pieces / mm 2 or more and 80 pieces / mm 2 or less is preferable because a capacitor having a small capacitance change rate ⁇ C can be easily obtained even when a high voltage is applied for a long time at a high temperature.
- the elliptic density is configured by combining two (substantially) arcuate projections that form the above-mentioned pair, which are observed using a digital microscope or the like, for example, a digital microscope VHX-2000 manufactured by Keyence Corporation (The number of (substantially) elliptical shapes formed by interpolating and connecting the (substantially) circular shape or the (substantially) elliptical shape and the two (substantially) circular arc shapes forming the above pair (two (a pair of ( (Substantially) density of (substantially) circular and (substantially) elliptical shapes formed from arcuate projections).
- a (substantially) elliptical shape two (substantially) arcuate shapes forming a pair are combined to form a (substantially) elliptical shape, and a pair of (substantially) arcuate shapes having a length of 1 to 200 ⁇ m. Also included is a (substantially) elliptical shape by interpolating between them, the major axis of the (substantially) ellipse may be in the range of 1 to 250 ⁇ m, and the minor axis may be in the range of 1 to 150 ⁇ m. .
- the number of (substantially) circular and (substantially) elliptical shapes is eight (see FIG. 3).
- the elliptical density is 60 / mm 2 or more and 80 / mm 2 or less, the electrode loss of the capacitor element is reduced. As a result, even when a high voltage is applied for a long time at a high temperature, the capacitance change rate ⁇ C Is preferable because a capacitor having a small size can be easily obtained.
- the elliptic density is more preferably 65 pieces / mm 2 or more, and still more preferably 68 pieces / mm 2 or more.
- the elliptic density is more preferably 80 pieces / mm 2 or less, and still more preferably 78 pieces / mm 2 .
- the polypropylene film of the present invention preferably has an elliptic density of 65 pieces / mm 2 or more and 80 pieces / mm 2 or less, more preferably 68 pieces / mm 2 or more and 78 pieces / mm 2 or less.
- the elliptic density was measured using a digital microscope VHX-2000 manufactured by Keyence Corporation at a lens magnification of 100 times, a measurement method: reflection measurement, and a visual field range: 3.4 mm ⁇ 2.6 mm.
- Polypropylene film of the present invention in the value tan [delta / tan [delta 0 normalized by the initial value tan [delta 0 the measured tan [delta between the elapsed time of 0 hours to 1500 hours in the long-term durability test, prior to the expiration of 1,500 hours the measured tan [delta from the maximum value of the value tan [delta / tan [delta 0 normalized by the initial value tan [delta 0, as a difference obtained by subtracting the value tan [delta / tan [delta 0 normalized the tan [delta measured at elapsed 1,500 hours at an initial value tan [delta 0
- the calculated ⁇ (tan ⁇ ) (hereinafter also simply referred to as ⁇ (tan ⁇ )) is preferably ⁇ 10.0 or more and 0.50 or less.
- the capacitor has ⁇ (tan ⁇ ) of ⁇ 10.0 or more and 0.50 or less, a capacitor having a small capacitance change rate ⁇ C can be easily obtained even when a high-voltage current is applied for a long time at a high temperature.
- the polypropylene film of the present invention has an upper limit of ⁇ (tan ⁇ ) of 0.45 or less, more preferably 0.40 or less, more preferably 0.35 or less.
- the lower limit value of ⁇ (tan ⁇ ) is more preferably ⁇ 5.0 or more, further preferably ⁇ 3.0 or more, more preferably ⁇ 1.5 or more.
- ⁇ (tan ⁇ ) has a range of any combination of the above upper limit value and lower limit value, for example, ⁇ 5.0 to 0.45, ⁇ 3.0 to 0.40, ⁇ 1 0.5 or more and 0.35 or less.
- the polypropylene film of the present invention preferably has a maximum protrusion height (Sp) of 0.5 ⁇ m or more and 1.0 ⁇ m or less, more preferably 0.5 ⁇ m or more and 0.9 ⁇ m or less, and still more preferably 0.00 on at least one surface. It is 6 ⁇ m or more and 0.9 ⁇ m or less, particularly preferably 0.6 ⁇ m or more and 0.8 or less ⁇ m, and particularly preferably 0.7 ⁇ m or more and 0.8 ⁇ m or less.
- the maximum protrusion height of the surface shape refers to the maximum value of protrusions forming the crater-like fine irregularities in a certain range on the surface of polypropylene.
- the maximum protrusion height (Sp) can be measured using, for example, an optical interference type non-contact surface shape measuring instrument.
- the optical interference type non-contact surface shape measuring instrument include “VertScan 2.0 (model: R5500GML)” manufactured by Ryoka System Co., Ltd.
- “VertScan 2.0 (model: R5500 GML)” manufactured by Ryoka System Co., Ltd. was used as an optical interference type non-contact surface shape measuring instrument.
- the WAVE mode is used, and the measurement target film is 240 ⁇ m ⁇ 180 ⁇ m per field of view using a 530 white filter and a ⁇ 20 objective lens. Measure at any 10 locations on the surface.
- the obtained data is subjected to noise removal processing by a median filter. Thereafter, Gaussian filter processing with a cutoff value of 30 ⁇ m is performed. Next, the swell component is removed. Thereby, it will be in the state which can measure the state of a roughening surface appropriately.
- various three-dimensional roughness parameters including the maximum protrusion height (Sp) are calculated.
- the average value is calculated from the values measured at 10 locations.
- the polypropylene film of the present invention preferably has a crystallite size determined by Scherrer's formula from the half-value width of the ⁇ crystal (040) plane reflection peak measured by wide-angle X-ray diffraction method, and is 122 mm or less, and optical
- the birefringence value ⁇ Nyz in the thickness direction obtained by birefringence measurement is 7.0 ⁇ 10 ⁇ 3 or more and 10.0 ⁇ 10 ⁇ 3 or less.
- the crystallite size is a Scherrer equation described later using a diffraction reflection peak of an ⁇ crystal (040) plane of a polypropylene film, which is measured using a wide-angle X-ray diffraction method (XRD method).
- XRD method wide-angle X-ray diffraction method
- the polypropylene film of the present invention has a crystallite size of preferably 122 mm or less, more preferably 120 mm or less.
- the crystallite size is preferably 100 mm or more, more preferably 110 mm or more, and particularly preferably 115 mm or more. Accordingly, the crystallite size is more preferably 110 to 120 mm, and particularly preferably 115 to 120 mm.
- the lower limit of the crystallite size is usually considered to be around 100 mm.
- the crystallite size of the polypropylene film of the present invention can be determined as follows. First, wide-angle X-ray diffraction measurement of the biaxially stretched polypropylene film and its metallized film is performed, and the half width of the diffraction reflection peak of the obtained ⁇ crystal (040) plane is obtained.
- D K ⁇ ⁇ / ( ⁇ ⁇ Cos ⁇ ) (1)
- ⁇ the crystallite size
- K a constant (shape factor)
- ⁇ the wavelength of the X-ray used
- ⁇ the half-value width of the diffraction reflection peak of the ⁇ crystal (040) plane
- ⁇ the half-value width of the diffraction Bragg angle of the ⁇ crystal (040) plane
- the crystallite size is calculated using the Scherrer equation shown in FIG.
- a desktop X-ray diffractometer MiniFlex300 (trade name) manufactured by Rigaku Corporation can be used.
- a desktop X-ray diffraction apparatus MiniFlex300 (trade name) manufactured by Rigaku Corporation was used.
- a CuK ⁇ ray (wavelength: 1.5418 mm) monochromatized by a light-receiving monochromator is collimated by a slit and irradiated to a measurement film.
- the diffraction intensity is measured by using a scintillation counter and scanning with 2 ⁇ / ⁇ interlocking using a goniometer.
- the integrated powder X-ray analysis software PDXL attached as standard to the apparatus, the half width of the diffraction reflection peak of the ⁇ crystal (040) plane is obtained using the obtained data.
- the crystallite size can be obtained by using the Scherrer equation (1) using the diffraction reflection peak ⁇ and the half width obtained by the above measurement.
- the crystallite size can be controlled by cooling conditions and stretching conditions when obtaining a cast raw sheet.
- the crystallite size tends to decrease as the temperature of the metal drum group in forming the cast raw sheet decreases, and the crystallite size decreases as the draw ratio increases.
- the group of metal drums means an assembly of metal drums constituted by two or more metal drums for cooling the cast raw sheet. Therefore, the temperature of the metal drum group means the temperature of all the metal drums constituting the metal drum group.
- the birefringence value ⁇ Nyz relative to the thickness direction of the polypropylene film refers to the birefringence value ⁇ Nyz relative to the thickness direction determined by optical birefringence measurement.
- the main axes in the in-plane direction of the film are the x-axis and the y-axis, and the thickness direction of the film (normal direction to the in-plane direction) is the z-axis, and the refractive index is higher in the in-plane direction.
- a value obtained by subtracting the three-dimensional refractive index in the z-axis direction from the three-dimensional refractive index in the y-axis direction is a birefringence value ⁇ Nyz.
- the value of the birefringence value ⁇ Nyz can be used as an index of the strength of film orientation.
- the orientation strength of the film is strong, the three-dimensional refractive index in the y-axis direction, which is the in-plane refractive index, is high, and the three-dimensional refractive index in the z-axis direction, which is the refractive index in the thickness direction, is low.
- the value of ⁇ Nyz increases.
- the birefringence value ⁇ Nyz in the thickness direction of the biaxially stretched polypropylene film for capacitors of the present invention is preferably 7.0 ⁇ 10 ⁇ 3 or more and 10.0 ⁇ 10 ⁇ 3 or less. It is more preferably 7.0 ⁇ 10 ⁇ 3 or more and 9.0 ⁇ 10 ⁇ 3 or less, and further preferably 7.5 ⁇ 10 ⁇ 3 or more and 9.0 ⁇ 10 ⁇ 3 or less.
- the birefringence value ⁇ Nyz is 7.0 ⁇ 10 ⁇ 3 or more, the orientation of the film is sufficient, and the withstand voltage and the withstand voltage over a long period are sufficient.
- a phase difference measuring device RE-100 manufactured by Otsuka Electronics Co., Ltd. in order to measure the “birefringence value ⁇ Nyz” in the thickness direction of the polypropylene film, for example, a phase difference measuring device RE-100 manufactured by Otsuka Electronics Co., Ltd. can be used.
- a phase difference measuring device RE-100 manufactured by Otsuka Electronics Co., Ltd. is used.
- Retardation (phase difference) is measured using a gradient method. More specifically, the main axes in the in-plane direction of the film are the x-axis and the y-axis, and the thickness direction of the film (normal direction to the in-plane direction) is the z-axis. The slow axis in the higher direction is the x axis.
- Retardation values when tilted by 10 ° with respect to the z axis in the range of 0 ° to 50 ° with the x axis as the tilt axis are obtained. From the obtained retardation value, the y-axis direction relative to the thickness direction (z-axis direction) was determined using the method described in the non-patent document “Hiroshi Hiroya, Introduction to Polarizing Microscope of Polymer Materials, pp. 105-120, 2001”. The birefringence ⁇ Nyz of is calculated.
- the TD direction becomes the slow axis (x axis)
- the MD direction is y. It becomes an axis.
- the refractive index Nz in the thickness direction changes, the birefringence ⁇ Nyz increases, and the withstand voltage improves (the dielectric breakdown voltage increases). This is considered to be due to the following reason.
- the refractive index Nz in the thickness direction is lowered.
- the electrical conductivity in the thickness direction of the film is low because it is transmitted between molecular chains.
- the polypropylene molecular chain is oriented in the plane direction (birefringence ⁇ Nyz is large), the polypropylene molecular chain is not oriented in the plane direction (birefringence ⁇ Nyz is small), that is, electrical conductivity is within the molecular chain. It is considered that the withstand voltage is improved as compared with the case of transmission in the case of
- the “birefringence value ⁇ Nyz” can be controlled by changing the orientation of the polypropylene molecular chain by changing the film forming conditions (high stretching ratio, etc.). Further, the “birefringence value ⁇ Nyz” can be controlled by changing the characteristics of the polypropylene resin.
- the polypropylene film of the present invention can be obtained by biaxially stretching a polypropylene resin composition containing a polypropylene resin.
- the polypropylene resin is not limited, and for example, a polypropylene resin that forms ⁇ -type spherulites when used as a cast raw sheet is preferable.
- One type of polypropylene resin may be sufficient and two or more types of polypropylene resins may be sufficient.
- polypropylene resin A is preferable.
- the polypropylene resin A preferably has a weight average molecular weight of 250,000 to 450,000, more preferably 250,000 to 400,000. Since the polypropylene resin A has a weight average molecular weight of 250,000 or more and 450,000 or less, the resin fluidity is appropriate, the thickness of the cast raw sheet can be easily controlled, and a thin stretched film can be easily produced. . Furthermore, unevenness is less likely to occur in the thickness of the sheet and film, and an appropriate stretchability is obtained, which is preferable.
- the polypropylene resin A preferably has a molecular weight distribution (weight average molecular weight / number average molecular weight (Mw / Mn)) of 7.0 or more and 12.0 or less, and (Mw / Mn) of 7.5 or more and 12.0 or less. More preferably, it has (Mw / Mn) of 7.5 or more and 11.0 or less, particularly preferably (Mw / Mn) of 8.0 or more and 11.0 or less, and 9.0 or more. It is particularly preferable to have (Mw / Mn) of 11.0 or less.
- the polypropylene resin A preferably has a molecular weight distribution (Z average molecular weight / number average molecular weight (Mz / Mn)) of 20.0 or more and 70.0 or less, and a molecular weight distribution (Mz / Mn) of 25.0 or more and 60.0 or less. It is more preferable to have a molecular weight distribution (Mz / Mn) of 25.0 or more and 50.0 or less.
- the content of the polypropylene resin A is preferably 55% by weight or more and 90% by weight or less, more preferably 60% by weight or more and 85% by weight or less when the entire polypropylene resin is 100% by weight, and 60% by weight. % To 80% by weight is particularly preferable.
- the weight average molecular weight (Mw), number average molecular weight (Mn), Z average molecular weight and molecular weight distribution (Mw / Mn and Mz / Mn) of the polypropylene resin are determined by gel permeation chromatograph (GPC) apparatus such as Tosoh Corporation. It can be measured using a differential refractometer (RI) built-in type high temperature GPC measuring machine HLC-8121GPC-HT. As the GPC column, for example, three TSKgel GMHHR-H (20) HT manufactured by Tosoh Corporation can be connected and used.
- GPC gel permeation chromatograph
- a differential refractometer (RI) built-in type high temperature GPC measuring machine HLC-8121GPC-HT manufactured by Tosoh Corporation was used.
- As the GPC column three TSKgel GMHHR-H (20) HT manufactured by Tosoh Corporation were connected and used. The measurement can be performed as follows. The column temperature is set to 140 ° C. and trichlorobenzene is allowed to flow as an eluent at a flow rate of 1.0 ml / 10 minutes to obtain measured values of Mw and Mn.
- a calibration curve related to the molecular weight M is prepared using standard polystyrene manufactured by Tosoh Corporation, and the measured values are converted into polystyrene values to obtain Mw, Mn and Mz. Furthermore, the logarithm of the bottom 10 of the molecular weight M of standard polystyrene is referred to as the logarithmic molecular weight (“Log (M)”).
- the polypropylene resin A according to the present invention has a broad molecular weight distribution, and at the same time, a component having a molecular weight of 10,000 to 100,000 is not less than 8.0% and not more than 18.0% compared to a component having a molecular weight of 1,000,000. It is preferable to contain many by a ratio.
- the differential distribution value at 0 100% (reference)
- it is 8.0% or more and 18.0% or less. Therefore, when the low molecular weight component is compared with the high molecular weight component, it is 8.0% or more and 18.0%. Therefore, the crystallite size becomes smaller, and it becomes easier to obtain a desired orientation and a roughened surface, which is preferable.
- Such a differential distribution value can be obtained as follows using GPC.
- a curve (generally also referred to as “elution curve”) showing the intensity with respect to time obtained by a differential refraction (RI) detector of GPC is used.
- the elution curve is converted into a curve showing the intensity with respect to Log (M) by converting the time axis into logarithmic molecular weight (Log (M)). Since the RI detection intensity is proportional to the component concentration, an integral distribution curve with respect to the logarithmic molecular weight Log (M) can be obtained when the total area of the curve indicating the intensity is 100%.
- the differential distribution curve is obtained by differentiating the integral distribution curve with Log (M). Therefore, “differential distribution” 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 the present invention can be obtained.
- the polypropylene resin A has a mesopentad fraction ([mmmm]) of preferably 94.0% or more and 99.5% or less, more preferably 94.0% or more and 99.0% or less, and 94.0% or more and 98.5%. % Or less is more preferable, 94.0% or more and less than 98.0% is particularly preferable, and 95.0% or more and 97.0% or less is more preferable. Regarding the lower limit value of the mesopentad fraction, 94.0% or more is preferable, 94.5% or more is more preferable, and 95% or more is more preferable.
- the crystallinity of the resin is appropriately improved due to a reasonably high stereoregularity, and in the film of the present invention, the desired rate of change of tan ⁇ / tan ⁇ 0 with respect to time can be obtained. Easy to obtain. Therefore, the initial withstand voltage property and the withstand voltage property over a long period tend to be appropriately improved. On the other hand, the speed of solidification (crystallization) at the time of forming the cast original fabric sheet is appropriate, and it can have appropriate stretchability.
- the mesopentad fraction ([mmmm]) is an index of stereoregularity that can be obtained by high temperature nuclear magnetic resonance (NMR) measurement.
- the mesopentad fraction ([mmmm]) can be measured, for example, using a high temperature Fourier transform nuclear magnetic resonance apparatus (high temperature FT-NMR) JNM-ECP500 manufactured by JEOL Ltd.
- the measurement method by high temperature NMR can be carried out by referring to the method described in, for example, “Japan Analytical Chemistry / Polymer Analysis Research Roundtable, New Edition Polymer Analysis Handbook, Kinokuniya, 1995, p. 610”.
- a high-temperature Fourier transform nuclear magnetic resonance apparatus (high-temperature FT-NMR) JNM-ECP500 manufactured by JEOL Ltd. was used, “Japan Analytical Chemistry / Polymer Analysis Research Roundtable, New Edition Polymer Analysis Handbook, The measurement was performed according to the method described in Kinokuniya, 1995, page 610.
- the pentad fraction representing the degree of stereoregularity is a combination of mm (5 mm) and mrrm (5 mm and mrrm) of a consensus “meso (m)” arranged in the same direction and a consensus “lacemo (r)” arranged in the opposite direction. Etc.) based on the integrated value of the intensity of each signal derived from.
- mmmm, mrrm, etc. can be attributed with reference to, for example, “T. Hayashi et al., Polymer, 29, 138 (1988)”.
- the polypropylene resin composition may use polypropylene resin B together with polypropylene resin A.
- the Mw of the polypropylene resin B is preferably 300,000 or more and 400,000 or less, and more preferably 330,000 or more and 380,000 or less.
- the molecular weight distribution (Mw / Mn) of the polypropylene resin B is preferably 7.0 or more and 9.0 or less, more preferably 7.5 or more and 8.9 or less, and further preferably 7.5 or more and 8.5 or less. .
- Mw / Mn The molecular weight distribution of the polypropylene resin B is within the preferable range, the desired change rate of the tan ⁇ / tan ⁇ 0 with respect to time can be easily obtained in the film of the present invention.
- the differential distribution value is 100% (reference)
- it is 1.0% or more and less than 8.0%, preferably 3.0% or more and 7.5% or less, % To 7.5% is more preferable.
- the polypropylene resin B preferably has a molecular weight distribution (Z average molecular weight / number average molecular weight (Mz / Mn)) of 20.0 or more and 70.0 or less, and a molecular weight distribution (Mz / Mn) of 25.0 or more and 60.0 or less. Mn) is more preferable, and a molecular weight distribution (Mz / Mn) of 25.0 to 50.0 is particularly preferable.
- Polypropylene resin B preferably has a mesopentad fraction ([mmmm]) of 94.0% or more and less than 98.0%, and more preferably 95.0% or more and 97.0% or less. Regarding the lower limit value of the mesopentad fraction, 94.0% or more is preferable, 94.5% or more is more preferable, and 95% or more is more preferable.
- the content of the polypropylene resin B is preferably 10% by weight or more and 45% by weight or less when the polypropylene resin is 100% by weight, and 15% by weight. It is more preferably 40% by weight or less and further preferably 20% by weight or more and 40% by weight or less.
- the total of the polypropylene resins is based on 100% by weight.
- the polypropylene resin contains polypropylene resins A and B
- the difference between the differential distribution values of polypropylene A and B is different, that is, the structure of the molecular weight distribution is different.
- the polypropylene film obtained by mixing and molding is slightly different in the quantitative relationship between the high molecular weight component and the low molecular weight component, so it takes a kind of fine mixing (phase separation) state and the crystal size becomes finer. It is easy and preferable. Furthermore, even if the draw ratio is the same (without increasing the draw ratio), it tends to be highly oriented, and it is considered preferable that fine roughening can be easily obtained on the surface.
- the polypropylene resin contains both the polypropylene resin A and the polypropylene resin B
- the present invention is considered to have an excellent effect for the reasons described above, but the present invention is not limited at all by such reasons. There is no.
- the polypropylene resin used in the present invention is preferable when both of the polypropylene resins A and B are included, because a capacitor having a small capacitance change rate ⁇ C can be easily obtained even when a high-voltage current is applied for a long time at a high temperature.
- the above case is preferable because the above-described crystallite size and birefringence ⁇ Nyz can be easily satisfied.
- the polypropylene resin composition used in the present invention and the polypropylene film of the present invention can contain a polypropylene resin other than the polypropylene resins A and B (hereinafter also referred to as “other polypropylene resins”).
- the “other polypropylene resin” is a resin generally used as a polypropylene resin, and is not particularly limited as long as the biaxially stretched polypropylene film for a capacitor intended by the present invention can be obtained.
- Other polypropylene resins can include, for example, long chain branched polypropylene (branched polypropylene) for the purpose of improving heat resistance.
- the polypropylene resin according to the present invention can contain such other polypropylene resin in an amount that does not adversely affect the biaxially stretched polypropylene film for capacitors that is the object of the present invention.
- the polypropylene resin composition used in the present invention and the polypropylene film of the present invention can further contain a resin other than the polypropylene resin (hereinafter also referred to as “other resin”).
- the “other resin” is generally a resin other than a polypropylene resin as a main component resin, and a biaxially stretched polypropylene film for a capacitor intended by the present invention is obtained.
- Examples of other resins include polyolefins other than polypropylene, such as polyethylene, poly (1-butene), polyisobutene, poly (1-pentene), and poly (1-methylpentene), ethylene-propylene copolymers, propylene- ⁇ -olefin copolymer such as butene copolymer, ethylene-butene copolymer, vinyl monomer-diene monomer random copolymer such as styrene-butadiene random copolymer, styrene-butadiene-styrene And vinyl monomers-diene monomers-vinyl monomer random copolymers such as block copolymers.
- polyolefins other than polypropylene such as polyethylene, poly (1-butene), polyisobutene, poly (1-pentene), and poly (1-methylpentene
- ethylene-propylene copolymers such as polyethylene, poly (1-butene), polyisobut
- the polypropylene resin composition used in the present invention can contain such other resins in an amount that does not adversely affect the biaxially stretched polypropylene film for capacitors that is the object of the present invention.
- the polypropylene resin composition may contain 10 parts by weight or less, and more preferably 5 parts by weight or less, of other resins with respect to 100 parts by weight of the polypropylene resin. Further, the polypropylene resin composition may preferably contain 0.1 part by weight or more, and more preferably 1 part by weight or more with respect to 100 parts by weight of the polypropylene resin.
- the polypropylene resin used in the present invention can be produced using a generally known polymerization method, and is not particularly limited as long as the polypropylene resin can be produced.
- a polymerization method include a gas phase polymerization method, a bulk polymerization method, and a slurry polymerization method.
- Polymerization may be single-stage (one-stage) polymerization using one polymerization reactor, or multi-stage polymerization using at least two polymerization reactors. Furthermore, hydrogen or comonomer may be added to the reactor as a molecular weight modifier.
- the catalyst is not particularly limited as long as a generally known Ziegler-Natta catalyst can be used and the polypropylene resin according to the present invention can be obtained.
- the catalyst can also contain a promoter component and a donor.
- the molecular weight, molecular weight distribution, stereoregularity, etc. can be controlled by adjusting the catalyst and polymerization conditions.
- “Differential distribution value difference” means, for example, by adjusting the polymerization conditions and adjusting the molecular weight distribution, by using a decomposing agent and selectively decomposing high molecular weight components, It can be adjusted to a desired value by mixing the resin.
- the polymerization catalyst described later When adjusting the structure of the molecular weight distribution depending on the polymerization conditions, it is preferable to use the polymerization catalyst described later, because the molecular weight distribution and the structure of the molecular weight can be easily adjusted. In this case, it can be freely contained, which is preferable.
- Examples of the method obtained by the multistage polymerization reaction include the following methods.
- polymerization is performed at a high temperature in a plurality of reactors of a high molecular weight polymerization reactor and a low molecular weight or medium molecular weight reactor.
- the high molecular weight component and the low molecular weight component of the product resin are prepared regardless of the order in the reactor.
- propylene and a catalyst are supplied to the first polymerization reactor.
- hydrogen as a molecular weight modifier is mixed in an amount necessary to reach the required polymer molecular weight.
- the reaction temperature is about 70 to 100 ° C.
- the residence time is about 20 to 100 minutes.
- Multiple reactors can be used, for example, in series, in which case the polymerization product of the first step is sent continuously to the next reactor along with additional propylene, catalyst, and molecular weight modifier. Then, the 2nd superposition
- the yield (production amount) of the first and second reactors the composition (configuration) of the high molecular weight component and the low molecular weight component can be adjusted.
- a general Ziegler-Natta catalyst is preferable. 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.
- a method by peroxidation treatment with a decomposing agent such as hydrogen peroxide or organic peroxide is preferable.
- a decomposing agent such as hydrogen peroxide or organic peroxide
- peroxide is added to a collapsible polymer such as polypropylene, a hydrogen abstraction reaction from the polymer occurs.
- the generated polymer radicals are partly recombined to cause a crosslinking reaction, but most radicals are known to undergo secondary decomposition ( ⁇ -cleavage) and to be separated into two polymers having smaller molecular weights.
- decomposition proceeds with a high probability from the high molecular weight component, so that the low molecular weight component increases and the structure of the molecular weight distribution can be adjusted.
- Examples of a method for obtaining a resin containing moderately low molecular weight components by peroxidative decomposition include the following methods.
- 1,1-bis- (tertiary-butyl peroxide isopropyl) -benzene or the like as an organic peroxide is added to the polymer powder or pellets of polypropylene resin obtained by polymerization in an amount of 0.001% by mass to 0.5% by mass. It is added by adjusting the amount in consideration of the composition (configuration) of the target high molecular weight component and low molecular weight component. These can be carried out by melt kneading at about 180 ° C. to 300 ° C. in a melt kneader.
- a two-polypropylene mixed system in which about 1 to 40% by mass of a main resin and an additive resin having a higher or lower average molecular weight is mixed is preferable because the amount of low molecular weight components can be easily adjusted. Used.
- melt flow rate (MFR) may be used as a measure of the average molecular weight.
- MFR melt flow rate
- the difference in MFR between the main resin and the additive resin is preferably about 1 to 30 g / 10 minutes from the viewpoint of convenience during adjustment.
- polypropylene resins for example, polypropylene resin A as a main component and polypropylene resin B as an auxiliary component (addition component)
- a method of preparing a polypropylene resin composition As the method, the polymer powder or pellets of polypropylene resin are dry blended using a mixer or the like, or the polymer powder or pellets of main resin polypropylene resin A and added polypropylene resin B are supplied to a kneader and melted. There are methods of kneading to obtain a blended resin (that is, melt blending method), and any method may be used.
- polypropylene resin composition with which each said polypropylene resin was mixed by supplying the polymer powder or pellet of each polypropylene resin directly to an extruder, and kneading in an extruder.
- the mixer and kneader are not particularly limited, and the kneader may be either a single screw type, a twin screw type, or a multi-screw type higher than that. Furthermore, in the case of a screw type having two or more axes, either a kneading type rotating in the same direction or rotating in a different direction may be used.
- the kneading temperature is not particularly limited as long as good kneading can be obtained, but is generally in the range of 200 ° C to 300 ° C, preferably 230 ° C to 270 ° C.
- a too high kneading temperature is not preferable because it causes deterioration of the resin.
- the kneader may be purged with an inert gas such as nitrogen.
- the melt-kneaded resin is generally pelletized to a suitable size using a known granulator, whereby mixed polypropylene raw resin pellets can be obtained.
- the total ash due to the polymerization catalyst residue and the like contained in the polypropylene raw material resin of this embodiment is as small as possible in order to improve electrical characteristics.
- the total ash content is preferably 100 ppm or less, more preferably 50 ppm or less, still more preferably 40 ppm or less, and particularly preferably 30 ppm or less, based on polypropylene resin (100 parts by weight). Since it is preferable that the total ash content is as low as possible, the lower limit is not particularly limited, but is, for example, 0 ppm or more, 0.01 ppm, 0.1 ppm, or the like.
- the polypropylene resin composition may further contain an additive.
- the “additive” is generally an additive used for a polypropylene resin composition, and is not particularly limited as long as the biaxially stretched polypropylene film for a capacitor targeted by the present invention can be obtained. Absent. Additives include, for example, necessary stabilizers such as antioxidants, chlorine absorbers and ultraviolet absorbers, lubricants, plasticizers, flame retardants, antistatic agents and the like.
- the polypropylene resin composition used in the present invention can contain such additives in an amount that does not adversely affect the biaxially stretched polypropylene film for capacitors that is the object of the present invention.
- the “antioxidant” is generally referred to as an antioxidant and is not particularly limited as long as it can be used for polypropylene and can obtain a biaxially stretched polypropylene film for a capacitor which is an object of the present invention.
- Antioxidants are generally used for two purposes. One purpose is to suppress thermal deterioration and oxidation deterioration in the extruder, and the other purpose is to contribute to suppression of deterioration and improvement of capacitor performance in long-term use as a capacitor film.
- An antioxidant that suppresses thermal degradation and oxidative degradation in the extruder is also referred to as a “primary agent”, and an antioxidant that contributes to improving capacitor performance is also referred to as a “secondary agent”.
- antioxidants Two types of antioxidants may be used for these two purposes, or one type of antioxidant may be used for the two purposes.
- the polypropylene resin composition contains, as a primary agent, for example, 2,6-di-tert-butyl-para-cresol (100 parts by weight) based on the polypropylene resin.
- BHT 2,6-di-tert-butyl-para-cresol
- BHT can preferably be contained in an amount of about 100 ppm to 10,000 ppm (more preferably 1000 ppm to 4000 ppm).
- 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 can be used.
- the “hindered phenol-based antioxidant having a carbonyl group” is usually a hindered phenol-based antioxidant having a carbonyl group, and the biaxially stretched polypropylene film for a capacitor intended by the present invention can be obtained. There is no particular limitation.
- 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), pentaerythritol tetrakis [3- ( 3,5-di-tertiarybutyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1010), 2,2-thio-diethylenebis [3- (3,5-di-tertiary-butyl-4 -Hydroxyphenyl) propionate] (trade name: Irganox 1035), octadec -3- (3,5-di-tertiary-butyl-4-
- the polypropylene resin composition preferably contains 1000 ppm (mass basis) or more and 10000 ppm (mass basis) or less of a hindered phenol-based antioxidant having a carbonyl group based on the polypropylene resin as a basis (100 parts by weight). More preferably, it is contained in an amount of not less than 7000 ppm (mass basis) and more preferably not more than 5500 ppm (mass basis) and not more than 7000 ppm (mass basis). This is because a hindered phenolic antioxidant having a carbonyl group is consumed in the extruder.
- the polypropylene resin composition does not contain a primary agent, more hindered phenol antioxidants having a carbonyl group can be used. Since the consumption of hindered phenolic antioxidants having a carbonyl group increases in the extruder, the polypropylene resin composition is a hindered phenolic antioxidant having a carbonyl group based on the polypropylene resin (100 parts by weight). Is preferably 6000 ppm (mass basis) or more and 8000 ppm (mass basis) or less.
- the polypropylene film of the present invention may contain one or more hindered phenolic antioxidants (secondary agents) having a carbonyl group for the purpose of suppressing deterioration that progresses with time during long-term use.
- the content of the antioxidant in the polypropylene film of the present invention is preferably 1000 ppm (mass basis) or more and 10000 ppm (mass basis) or less, preferably 4000 ppm (mass basis), based on the polypropylene resin (100 parts by weight). More preferably, it is 6000 ppm (mass basis) or less, more preferably 4500 ppm (mass basis) or more and 6000 ppm (mass basis) or less.
- the content in the film is more preferably 4000 ppm (mass basis) or more and 6000 ppm (mass basis) or less from the viewpoint of appropriate effects.
- Capacitor films containing hindered phenolic antioxidants with carbonyl groups that have good compatibility with polypropylene at the molecular level in an optimal amount within the specified range are the internal structure (crystallite size) and orientation described above. (Birefringence), while maintaining the high withstand voltage performance obtained by surface roughening (projection volume), even in a very high temperature (life) acceleration test of 110 ° C. or higher, over a long period exceeding 100 hours It is preferable because the electrostatic capacity is not lowered (deterioration does not proceed) and long-term durability is improved.
- the polypropylene resin composition undergoes thermal degradation (oxidation degradation) and shear degradation.
- the degree of deterioration depends on the nitrogen purge in the extruder (suppression of oxidation), the screw shape (shearing force) in the extruder, and the internal shape of the T-die during casting (shearing) Force), the amount of antioxidant added (suppression of oxidation), the winding speed during casting (extension force), and the like.
- the “chlorine absorbent” is generally called a chlorine absorbent and is not particularly limited as long as it is used for polypropylene and can achieve the object of the present invention.
- Examples of the chlorine absorbent include metal soaps such as calcium stearate.
- a “raw original cast sheet”, that is, an unstretched cast original sheet (hereinafter also referred to as a cast original sheet or a polypropylene cast original sheet) is a known method.
- Can be molded using for example, polypropylene resin pellets, dry-mixed polypropylene resin pellets (and / or polymerized powder), or mixed polypropylene resin pellets prepared by melt-kneading in advance, that is, pellet-shaped polypropylene resin compositions are supplied to an extruder.
- the supplied polypropylene resin pellets and the like are melted by heating to a temperature of preferably 170 ° C.
- the melted polypropylene resin composition may be passed through a filtration filter.
- the molten polypropylene resin composition is extruded from the T die by heating to a temperature of preferably 170 ° C. to 320 ° C., more preferably 200 ° C. to 300 ° C., and even more preferably 230 ° C. to 270 ° C.
- the extruded polypropylene resin composition is solidified by cooling with at least one metal drum held at 80 to 140 ° C., preferably 90 to 140 ° C., more preferably 90 to 105 ° C. This is done by bringing the extruded polypropylene resin composition into contact with a metal drum. Thereby, an unstretched cast original fabric sheet can be shape
- the unstretched cast raw sheet thus obtained is preferably a polypropylene cast sheet in which ⁇ -type spherulites are generated.
- the polypropylene film of the present invention in order to obtain a desired surface shape, that is, an unstretched cast raw sheet for producing a polypropylene film having an elliptic density of 60 pieces / mm 2 or more and 80 pieces / mm 2 or less.
- the temperature of the metal drum group during molding is preferably maintained at 90 to 140 ° C. (particularly 90 ° C. to 105 ° C.).
- the polypropylene film of the present invention in order to obtain a desired surface shape, that is, in order to set the total volume of protrusions having a height of 0.4 ⁇ m or more to a range of 50 ⁇ m 3 or more and 150 ⁇ m 3 or less per 1 mm 2 , unstretched It is preferable to maintain the temperature of the metal drum group at the time of forming the cast original fabric sheet at 90 to 140 ° C. (especially 90 to 105 ° C.). (1) Method of heating polypropylene resin (polypropylene resin composition), (2) Kind of extruder, extrusion conditions, etc., (3) Method and conditions of contacting extruded polypropylene resin composition with metal drum, etc.
- the temperature of the metal drum group is 80 ° C to 140 ° C, preferably 90 ° C to 140 ° C, more preferably 90 ° C to 120 ° C, and still more preferably 90 to 105 ° C.
- the ⁇ crystal fraction of the obtained cast raw sheet is 1% to 50%, preferably 5% to 30%, more preferably 5% to 20% by X-ray method. It is about the following. This value is a value when no ⁇ crystal nucleating agent is included.
- the above-mentioned ⁇ crystal fraction range is preferable because both physical properties of the capacitor characteristics and element winding workability can be satisfied.
- the ⁇ crystal fraction is obtained by X-ray diffraction intensity measurement, and can be calculated by the method described in “A. Turner-Jones et al., Makromol. Chem., 75, 134 (1964)”. Can be called the 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 average radius of ⁇ -type spherulites is preferably 0.1 ⁇ m to 10 ⁇ m, more preferably 0.5 ⁇ m to 8 ⁇ m. More preferably, it is 1 ⁇ m to 5 ⁇ m.
- the average radius of ⁇ -type spherulites is the average of radii measured for all ⁇ -type spherulites confirmed in one field of view (460 ⁇ 620 ⁇ m) using a polarizing microscope (Nikon “ECLIPSE E200”). Value.
- image analysis software “ImagePro” manufactured by Nippon Rover was used.
- the thickness of the cast raw sheet is not particularly limited as long as the biaxially stretched polypropylene film for a capacitor intended by the present invention can be obtained, but is usually 0.05 mm to 2 mm. Preferably, it is 0.1 mm to 1 mm.
- the polypropylene film of the present invention can be produced by subjecting the polypropylene cast raw sheet to stretching treatment.
- the stretching is preferably biaxial stretching in which the longitudinal and lateral orientations are biaxially oriented, and the sequential biaxial stretching method is preferred as the stretching method.
- the sequential biaxial stretching method first, the cast raw sheet is kept at a temperature of 100 to 180 ° C., preferably 140 to 160 ° C., and passed between rolls provided with a speed difference in a flow direction (longitudinal direction) of 3 to 7
- the film is stretched twice, preferably 3.5 to 6 times, more preferably 3.8 to 6 times, and immediately cooled to room temperature.
- the ⁇ crystal melts and transitions to the ⁇ crystal, and the unevenness becomes obvious.
- the stretched film is guided to a tenter and stretched at a temperature of 160 ° C. or more in the width direction (lateral direction) 3 to 11 times, more preferably 5 to 10.5 times, and even more preferably 7 to 10 times, Relieve and heat fix and take up.
- the wound film can be cut to a desired product width after being aged in an atmosphere of about 20 to 45 ° C.
- the elliptical density in the polypropylene film of the present invention can also be achieved by using a known roughening method such as an embossing method and an etching method.
- the surface roughening method used is preferably used.
- the production ratio of ⁇ crystals can be adjusted by changing characteristics such as the molecular structure of the polypropylene resin used. Further, the ⁇ crystal ratio can also be controlled by the casting temperature, that is, the drawing conditions such as the temperature of the metal drum group and the rotation speed of the metal drum group when forming the cast raw sheet. Further, the melting rate of the ⁇ crystal can be controlled at the roll temperature in the longitudinal stretching step.
- the surface property can be controlled by selecting optimum production conditions for the two parameters of ⁇ crystal formation and melting.
- the total volume of the protrusions having a height of 0.4 ⁇ m or more in the polypropylene film of the present invention can be achieved by using a known roughening method such as an embossing method and an etching method. It is preferable to use a surface roughening method using ⁇ crystals.
- the production ratio of ⁇ crystals can be adjusted by changing characteristics such as the molecular structure of the polypropylene resin used. Further, the ⁇ crystal ratio can also be controlled by the casting temperature, that is, the drawing conditions such as the temperature of the metal drum group and the rotation speed of the metal drum group when forming the cast raw sheet. Further, the melting rate of the ⁇ crystal can be controlled at the roll temperature in the longitudinal stretching step.
- the surface property can be controlled by selecting optimum production conditions for the two parameters of ⁇ crystal formation and melting.
- the polypropylene film of the present invention is preferably a biaxially stretched film of a polypropylene cast sheet in which ⁇ -type spherulites are generated.
- a corona discharge treatment can be performed on-line or off-line after completion of the stretching and heat-setting steps for the purpose of enhancing the adhesive properties in a later process such as a metal deposition process.
- the corona discharge treatment can be performed using a known method. It is preferable to use air, carbon dioxide gas, nitrogen gas and a mixed gas thereof as the atmospheric gas.
- the polypropylene film thus obtained preferably has a thickness of 1.0 ⁇ m to 6.0 ⁇ m, more preferably 1.5 ⁇ m to 4.0 ⁇ m, and more preferably 1.8 ⁇ m to 3.
- the thickness is more preferably 5 ⁇ m or less, and particularly preferably 1.8 ⁇ m or more and less than 3.0 ⁇ m.
- the polypropylene film of the present invention is preferably a very thin film.
- the thickness is a value measured using a micrometer (JIS-B7502) in accordance with JIS-C2330.
- Step 1 of heating the polypropylene resin composition (2) Step 2 for extruding the molten polypropylene resin composition obtained in Step 1 above, (3) Step 3 in which the polypropylene resin composition obtained in Step 2 is brought into contact with at least one metal drum, and (4) Step of biaxially stretching the cast raw sheet obtained in Step 3 4 In order.
- Step 1 of heating the polypropylene resin composition (2) Step 2 for extruding the molten polypropylene resin composition obtained in Step 1 above, (3) Step 3 in which the polypropylene resin composition obtained in Step 2 is brought into contact with at least one metal drum, and (4) Step of biaxially stretching the cast raw sheet obtained in Step 3 4
- the above-described film of the present invention can be suitably produced.
- the manufacturing method of this invention includes the process 1 which heats a polypropylene resin composition. According to step 1, a molten resin composition is obtained.
- the melted polypropylene resin composition may contain only one kind of polypropylene resin or may contain two or more kinds.
- the polypropylene resin composition is preferably 85% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, and still more preferably 95% by mass to 100% by mass, based on the total mass of the polypropylene resin composition. %, Particularly preferably 98% by mass to 100% by mass.
- the temperature at which the polypropylene resin composition is heated is not particularly limited as long as the polypropylene resin composition can be melted, but is preferably 170 to 320 ° C, more preferably 200 to 300 ° C, and still more preferably. It is within the range of 230 ° C to 270 ° C.
- the polypropylene resin composition is heated at a temperature within the above range, the polypropylene resin composition can be uniformly melted, and the polypropylene resin and other resins are unlikely to deteriorate.
- the molten polypropylene resin composition may be passed through a filtration filter.
- the polypropylene resin composition can be heated by a conventionally known method.
- the polypropylene resin composition can be heated by using an extruder equipped with a heating device.
- Such an extruder is not particularly limited as long as the polypropylene resin composition can be heated.
- a polypropylene resin composition produced by a dry blend method is used, a polyaxial screw type is preferable because the polypropylene resin composition is sufficiently mixed and a uniformly melted polypropylene resin composition is obtained.
- an extruder is used, deterioration due to oxidation of the polypropylene resin can be suppressed by purging the inside of the extruder with an inert gas such as nitrogen.
- Process 2 The production method of the present invention includes Step 2 for extruding the molten polypropylene resin composition obtained in Step 1 above. By the process 2, the resin composition extruded into the sheet form is obtained.
- the resin composition extruded into a sheet is preferably a molten resin composition extruded in a thickness of 0.05 mm to 23 mm, more preferably 0.1 mm to 2 mm, and still more preferably 0.15 mm to 1 mm. It is.
- the melted polypropylene resin composition can be extruded by a conventionally known method, for example, using a T-die.
- the type and shape of the T die are not particularly limited.
- the extrusion temperature of the T die is preferably 170 ° C to 320 ° C, more preferably 200 ° C to 300 ° C, and further preferably 230 ° C to 270 ° C.
- Process 3 The manufacturing method of the film of this invention includes the process 3 which makes the polypropylene resin composition obtained by the said process 2 contact at least 1 metal drum. By step 3, an unstretched cast original fabric sheet is obtained.
- the thickness of the original cast sheet is not particularly limited as long as the biaxially stretched polypropylene film for capacitors intended by the present invention can be obtained, but it is usually preferably 0.05 mm to 2 mm. More preferably, the thickness is 0.1 mm to 1 mm.
- the extruded polypropylene resin composition As a method of bringing the extruded polypropylene resin composition into contact with at least one metal drum, for example, discharging the resin composition extruded in a sheet shape onto a rotated metal roll can be mentioned. . More specifically, by discharging the extruded resin composition onto a metal roll, the resin composition is applied to at least one, preferably 2 to 5, more preferably 2 to 3 metal drums. Wrap around.
- the surface temperature of the metal drum is preferably maintained at a temperature of 80 ° C to 140 ° C, more preferably 90 ° C to 140 ° C, still more preferably 90 ° C to 120 ° C, and particularly preferably 90 ° C to 105 ° C. Can do.
- the surface temperature of the metal drum is within the above range, it becomes easy to adjust the ⁇ crystal fraction of the cast raw sheet to the following range, and as a result, the elliptic density within the range of the present invention is achieved. Further, it becomes easy to obtain the total volume of the protrusions. As a result, in the film of the present invention, it is easy to obtain a desired rate of change of tan ⁇ / tan ⁇ 0 with respect to time. Therefore, it is preferable to perform step 3 in the surface temperature range of each preferable metal drum.
- the ⁇ crystal fraction of the obtained cast original fabric sheet is preferably 1% or more and 50% or less, more preferably 5% or more and 30% or less, and further preferably 5% or more and 20% or less by the X-ray method. This value is a value when no ⁇ crystal nucleating agent is included.
- the ⁇ crystal fraction can be measured as described above.
- the method for producing a film of the present invention includes a step 4 of biaxially stretching the original cast sheet obtained in the step 3.
- step 4 a biaxially stretched polypropylene film is obtained.
- Step 4 includes a so-called flow direction stretching step and a width direction stretching step.
- a stretching method for biaxially stretching the cast raw fabric sheet a known method such as a method of stretching between rolls having a difference in peripheral speed, a tenter method, a tubular method, or the like can be used.
- a stretching direction uniaxial stretching, biaxial stretching, biaxial stretching in an oblique direction, and the like can be performed.
- biaxial or more stretching both sequential stretching and simultaneous stretching are applicable.
- the simultaneous biaxial stretching method by the tenter method the sequential biaxial stretching method by the tenter method, and the longitudinal (flow, MD) stretching between rolls provided with a peripheral speed difference, and then the lateral (width, TD) by the tenter method
- a sequential biaxial stretching method of stretching is preferred, and a sequential biaxial stretching method of longitudinal (flow, MD) stretching between rolls provided with a peripheral speed difference and then transverse (width, TD) stretching by a tenter method is more preferred.
- step 4 it is preferable to include a step of stretching the cast raw sheet at a temperature of 100 to 180 ° C, preferably 140 to 160 ° C.
- the sequential biaxial stretching method it is necessary to adjust the stretching temperature and the stretching ratio according to the melting point and glass transition temperature of the resin used.
- the original cast sheet is preferably maintained at a temperature of 100 to 180 ° C, more preferably 140 to 160 ° C, more preferably 144 to 160 ° C, and still more preferably 144 ° C to 150 ° C. If the temperature of the cast raw sheet is within the above range, the ⁇ crystal melts in this longitudinal direction, in other words, the stretching process in the flow direction, and changes to ⁇ crystal by crystal transformation, resulting in crater-like irregularities.
- the cast original fabric sheet is preferably passed 3 to 7 times, more preferably 3.5 to 6.5 times in the longitudinal direction (flow direction) by passing between rolls having a difference in peripheral speed or by the tenter method. More preferably, the film is stretched 3.8 to 6 times. After stretching, a uniaxially stretched film is obtained by relaxing the tension applied to the film.
- the film stretched in the uniaxial direction is preferably maintained at a temperature of 140 ° C. or higher, more preferably 150 ° C. or higher, and still more preferably 160 ° C. or higher.
- a preferable upper limit of the stretching temperature of the uniaxially stretched film is, for example, 180 ° C. If the temperature of the film stretched in the uniaxial direction is within the above range, a uniformly biaxially stretched film can be obtained.
- in the stretching process in the lateral direction in other words, in the width direction, (substantially) circular and elliptical shapes with the elliptical density and total protrusion volume of the present invention.
- the film stretched in the uniaxial direction is preferably stretched 3 to 11 times, more preferably 5 to 10.5 times, still more preferably 7 to 10 times in the transverse direction (width direction).
- a biaxially stretched film is obtained by relaxing the tension applied to the film.
- the obtained biaxially stretched film was measured for tan ⁇ [%] measured during an elapsed time of 0 to 500 hours at an elapsed time of 0 hours in a long-term durability test in which a voltage of 600 V was applied at 105 ° C.
- This is a biaxially stretched polypropylene film for capacitors having a rate of change with respect to time of the value tan ⁇ / tan ⁇ 0 normalized by the initial value tan ⁇ 0 [%] of 5.0 ⁇ 10 ⁇ 4 [1 / hour] or less.
- the obtained biaxially stretched film is ⁇ 1. It has the same thickness as the thickness described in the item of the biaxially oriented polypropylene film for capacitors of the present invention >>.
- the film production method of the present invention can include other steps in addition to the above steps 1 to 4.
- Examples of other processes include a cutting process, a winding process, a roughening process, and a metal vapor deposition process.
- the cutting step is preferably performed after the biaxial stretching step and before winding the biaxially stretched film. By the cutting process, it can be cut into an arbitrary product width.
- the film production method of the present invention may further include a metal deposition processing step of depositing a metal film on one side or both sides of the biaxially stretched polypropylene sheet.
- a metal deposition processing step of depositing a metal film on one side or both sides of the biaxially stretched polypropylene sheet.
- a step of performing a corona discharge treatment online or offline after the drawing and heat setting step may be further included for the purpose of enhancing the adhesive properties.
- the corona discharge treatment can be performed using a known method. It is preferable to use air, carbon dioxide gas, nitrogen gas and a mixed gas thereof as the atmospheric gas.
- the biaxially stretched film can be wound to a desired length.
- the polypropylene film of the present invention has high initial voltage resistance and excellent long-term voltage resistance. Furthermore, since the surface is appropriately roughened, the element winding aptitude is excellent. Furthermore, since it can be made very thin, it is easy to develop a high capacitance. Therefore, the polypropylene film of the present invention can be used very suitably for a small capacitor having a high capacity of 5 ⁇ F or more, preferably 10 ⁇ F or more, more preferably 20 ⁇ F or more.
- the capacitor including the metallized film of the present invention has little decrease in capacitance even when a voltage is applied for a long time at a high temperature. For example, even when a voltage of 600 V is applied as a direct current for 1500 hours in an atmosphere of 105 ° C., the capacitance change rate ⁇ C is 0% to ⁇ 20%. Therefore, the polypropylene film of the present invention can be suitably used for a capacitor.
- the type of the capacitor that can use the polypropylene film of the present invention is not particularly limited, but may be, for example, a flat type.
- the polypropylene film of the present invention is, for example, a high-voltage capacitor, various switching power supplies, a filter, a smoothing capacitor for an inverter, an inverter power supply circuit smoothing capacitor for controlling a drive motor used in an electric vehicle, a hybrid vehicle, etc. Etc. can be used.
- an electrode can be attached to the polypropylene film of the present invention for processing as a capacitor.
- Such an electrode is not particularly limited as long as the objective capacitor of the present invention can be obtained, and an electrode usually used for manufacturing a capacitor can be used.
- the electrode include metal foil, paper having at least one side metallized, and a plastic film.
- capacitors are further required to be smaller and lighter, it is preferable to form an electrode by directly metallizing one or both sides of the film of the present invention.
- a film having a metal film on one or both sides of the polypropylene film of the present invention is obtained.
- the metal used for the metal film for example, simple metals such as zinc, lead, silver, chromium, aluminum, copper, and nickel, a mixture of plural kinds thereof, and alloys thereof can be used.
- the metal used for the metal film is preferably at least one selected from the group consisting of zinc and aluminum.
- the film resistance of the metal deposition film is preferably 1 to 100 ⁇ / ⁇ from the viewpoint of the electrical characteristics of the capacitor. A higher value within this range is desirable from the viewpoint of self-healing (self-healing) characteristics, and the film resistance is more preferably 5 ⁇ / ⁇ or more, and further preferably 10 ⁇ / ⁇ or more. Further, from the viewpoint of safety as a capacitor element, the membrane resistance is more preferably 50 ⁇ / ⁇ or less, and further preferably 20 ⁇ / ⁇ or less.
- the film resistance of a metal vapor deposition film can be measured during metal vapor deposition, for example, by the two-terminal method known to those skilled in the art.
- the film resistance of the metal vapor deposition film can be adjusted by adjusting the evaporation amount by adjusting the output of the evaporation source, for example.
- the thickness of the metal film is not particularly limited, but is preferably 10 nm to 100 nm.
- an insulating margin is formed without vapor-depositing a certain width from one end of the film so that it becomes a capacitor when the film is wound.
- the film resistance of the heavy edge is preferably 2 to 8 ⁇ / ⁇ . More preferably, it is 3 to 6 ⁇ / ⁇ .
- a vacuum deposition method and a sputtering method can be exemplified, and the method is not particularly limited as long as a capacitor intended by the present invention can be obtained. From the viewpoint of productivity and economy, the vacuum deposition method is preferable.
- a vacuum deposition method a crucible method, a wire method, etc. can be generally exemplified, but there is no particular limitation as long as a capacitor intended by the present invention can be obtained, and an optimal one is selected as appropriate. be able to.
- the margin pattern for metallization by vapor deposition is not particularly limited, but a pattern including a so-called special margin such as a fish net pattern or a T margin pattern is used in order to improve characteristics such as the safety of the capacitor. It can be applied on one side of the inventive film. When a pattern is formed on one surface of the film of the present invention, the safety of the capacitor is enhanced, and the destruction of the capacitor and the prevention of a short circuit tend to be suppressed.
- a generally known method such as a tape method or an oil method can be used without any limitation.
- the film of the present invention to which an electrode is attached or metallized is wound alone or in combination of two or more, preferably in combination of two.
- the number of windings can be appropriately selected according to the use of the capacitor, but for example, in the case of a flat capacitor, it may be about 500 to 2000 times. Winding can be performed using an automatic winder.
- the element wound element can be heat-treated under pressure and / or heating.
- the pressure may be 200 to 1000 kPa, for example.
- the temperature may be 60 to 130 ° C., for example.
- Zinc metal is sprayed onto the heat-treated element end face. Thereby, a flat capacitor can be obtained.
- Capacitor of the present invention is a capacitor
- the capacitor of the present invention may be small and have a high capacity of 5 ⁇ F or more, preferably 10 ⁇ F or more, more preferably 20 ⁇ F or more.
- the capacitor of the present invention has little decrease in capacitance even when a voltage is applied for a long time at a high temperature. For example, even when a voltage of 600 V is applied as a direct current for 1500 hours in an atmosphere of 105 ° C., the capacitance change rate ⁇ C is 0% to ⁇ 20%.
- the capacitor type of the present invention is not particularly limited, but may be a flat type, for example.
- Applications of the capacitor of the present invention include high-voltage capacitors, various switching power supplies, filters, smoothing capacitors for converters, inverters, etc., inverter power supply circuit smoothing capacitors for controlling drive motors used in electric vehicles, hybrid vehicles, etc. It may be.
- the capacitor of the present invention can be manufactured using a conventionally known method.
- condenser of this invention can be manufactured using the metallized film which has a metal film on the single side
- Capacitance change rate ⁇ C Capacitances of the capacitor elements produced in the following examples and comparative examples were measured at a predetermined time between 0 hours and 1500 hours using an LCR high tester 3522-50 manufactured by Hioki Electric Co., Ltd. For five capacitor elements, the ratio of the difference obtained by subtracting the initial capacitance (capacitance at elapsed time 0 hours) from the capacitance at each measurement time to the initial capacitance (capacitance at elapsed time 0 hours) [%] was calculated as a capacitance change rate ⁇ C [%]. The average value of the change rate ⁇ C [%] of the capacitance of five capacitor elements at each measurement time was determined.
- Total volume of protrusions of 0.4 ⁇ m or more per 1 mm 2 The total protrusion volume was measured for the polypropylene films prepared in the following examples and comparative examples as follows. “VertScan 2.0 (model: R5500 GML)” manufactured by Ryoka System Co., Ltd. was used as an optical interference type non-contact surface shape measuring instrument. A 530 white filter and a ⁇ 20 (20 ⁇ ) objective lens were used in the WAVE mode. Measurements of 240 ⁇ m ⁇ 180 ⁇ m per field of view were made at any 10 locations on the film surface to be measured. About the obtained data, the noise removal process by a median filter was performed. Thereafter, Gaussian filter processing with a cutoff value of 30 ⁇ m was performed.
- the total volume of the protrusion was determined using the plug-in function “bearing” of the analysis software “VS-Viewer” of “VertScan 2.0”.
- the reference plane at each measurement location was set to the height of the “swell component” when performing the Gaussian filter processing.
- the ⁇ crystal fraction was evaluated using the K value obtained by X-ray diffraction intensity measurement.
- H ⁇ I is the intensity (height) of the peak corresponding to the crystal diffraction of the ⁇ crystal (110) plane
- H ⁇ II is ⁇
- H ⁇ III is the peak intensity (height) corresponding to the crystal diffraction on the ⁇ crystal (130) plane.
- the intensity (height) after subtracting amorphous scattering was used for all.
- the maximum protrusion height (Sp) of the polypropylene films produced in the following examples and comparative examples was measured as follows. “VertScan 2.0 (model: R5500 GML)” manufactured by Ryoka System Co., Ltd. was used as an optical interference type non-contact surface shape measuring instrument. A 530 white filter and a ⁇ 20 (20 ⁇ ) objective lens were used in the WAVE mode. Measurements of 240 ⁇ m ⁇ 180 ⁇ m per field of view were measured at any 10 locations on the film surface to be measured. About the obtained data, the noise removal process by a median filter was performed. Thereafter, Gaussian filter processing with a cutoff value of 30 ⁇ m was performed. This removed the swell component. In this way, the surface of the roughened surface can be appropriately measured. The average value of the values measured at the 10 locations was calculated. The average value was defined as the maximum protrusion height (Sp).
- the supplied PP resin A and PP resin B were kneaded in an extruder to obtain a polypropylene resin composition.
- a polypropylene resin composition made of polypropylene resin was melted at a resin temperature of 250 ° C. Thereafter, the molten polypropylene resin composition was extruded using a T-die.
- the extruded polypropylene resin composition was solidified by winding it around a metal drum maintained at a surface temperature of 97 ° C. This produced the cast original fabric sheet.
- the obtained cast original fabric sheet had an average radius of ⁇ -type spherulites of 1.7 ⁇ m and a ⁇ crystal fraction of 13%.
- a capacitor was produced as follows. Aluminum vapor deposition was performed on a biaxially stretched polypropylene film with a T margin vapor deposition pattern at a vapor deposition resistance of 15 ⁇ / ⁇ . This obtained the metallized film. This metallized film was slit to a width of 60 mm. Two metallized films were combined. The combined metallized film was wound 1076 turns at a winding tension of 200 g by using an automatic winder 3KAW-N2 manufactured by Minato Co., Ltd. The element wound element was heat-treated at 120 ° C. for 15 hours while being pressed. Thereafter, zinc metal was sprayed onto the element end face. Thus, a flat capacitor was obtained. Lead wires were soldered to the end face of the flat capacitor. Thereafter, the flat capacitor was sealed with an epoxy resin. The completed capacitor had a capacitance of 75 ⁇ F ( ⁇ 5 ⁇ F).
- a direct current was applied to the obtained capacitor in an air-conditioning dryer FC-610 manufactured by Advantech at a test environment temperature of 105 ° C. and a voltage of 600 V for 1500 hours.
- the capacitance and tan ⁇ were measured at 0 hours, 100 hours, 200 hours, 300 hours, 400 hours, 500 hours, 1000 hours and 1500 hours.
- the rate of change of tan ⁇ / tan ⁇ 0 with respect to time, ⁇ (tan ⁇ ), and the rate of change ⁇ C in capacitance were determined. The results are shown in Table 1.
- Table 2 shows tan ⁇ measured at each time.
- Example 2 A biaxially stretched polypropylene film and a capacitor were produced in the same manner as in Example 1 except that the surface temperature of the metal drum used for producing the cast original fabric sheet was maintained at 100 ° C. instead of 97 ° C. Next, the produced biaxially stretched polypropylene film and capacitor were evaluated. The results are shown in Tables 1 and 2.
- Example 3 In the production of the biaxially stretched polypropylene film, the unstretched cast original sheet was stretched in the flow direction while maintaining the temperature at 144 ° C., that is, in the flow direction when the biaxially stretched polypropylene film was produced.
- a biaxially stretched polypropylene film and a capacitor were prepared in the same manner as in Example 1 except that the unstretched cast original fabric sheet was stretched while maintaining the holding temperature at 144 ° C instead of 145 ° C. The results are shown in Tables 1 and 2.
- Example 4 In the same manner as in Example 1 except that a cast raw fabric sheet was produced using PP resin A alone as a raw material instead of producing a cast raw fabric sheet using PP resin A and PP resin B as raw materials. A biaxially stretched polypropylene film and a capacitor were produced. Next, the produced biaxially stretched polypropylene film and capacitor were evaluated. The results are shown in Tables 1 and 2.
- Example 5 A biaxially stretched polypropylene film and a capacitor were produced in the same manner as in Example 1, except that the surface temperature of the metal drum used for producing the cast original fabric sheet was maintained at 95 ° C. instead of 97 ° C. Next, the produced biaxially stretched polypropylene film and capacitor were evaluated. The results are shown in Tables 1 and 2.
- Example 6 The surface temperature of the metal drum used for the production of the cast original fabric sheet was maintained at 100 ° C. instead of 97 ° C., and the unstretched cast original fabric sheet was kept at a temperature of 144 ° C. in the production of the biaxially oriented polypropylene film. Stretching in the direction, that is, while maintaining the temperature of holding the unstretched cast raw sheet at 144 ° C. instead of 145 ° C. with respect to the stretching in the flow direction when producing a biaxially stretched polypropylene film A biaxially stretched polypropylene film and a capacitor were produced in the same manner as in Example 1 except that the above was performed. Next, the produced biaxially stretched polypropylene film and capacitor were evaluated. The results are shown in Tables 1 and 2.
- Example 7 The surface temperature of the metal drum used for the production of the cast original fabric sheet was kept at 95 ° C. instead of 97 ° C., and the unstretched cast original fabric sheet was kept at a temperature of 144 ° C. in the production of the biaxially oriented polypropylene film. Stretching in the direction, that is, while maintaining the temperature of holding the unstretched cast raw sheet at 144 ° C. instead of 145 ° C. with respect to the stretching in the flow direction when producing a biaxially stretched polypropylene film A biaxially stretched polypropylene film and a capacitor were produced in the same manner as in Example 1 except that the above was performed. Next, the produced biaxially stretched polypropylene film and capacitor were evaluated. The results are shown in Tables 1 and 2.
- Example 8 Instead of producing a cast original fabric sheet using PP resin A and PP resin B as raw materials, a cast sheet was produced using PP resin A alone as a raw material, and metal used for producing a cast original fabric sheet A biaxially stretched polypropylene film and a capacitor were produced in the same manner as in Example 1 except that the drum surface temperature was maintained at 95 ° C. instead of 97 ° C. Next, the produced biaxially stretched polypropylene film and the capacitor were evaluated. The results are shown in Tables 1 and 2.
- Example 9 Instead of supplying PP resin A and PP resin B as raw materials to the extruder at a weight ratio of 65:35 in the production of the cast raw sheet, PP resin A, PP resin B, and PP are used as raw materials.
- Resin C1 long-chain branched polypropylene resin, WB135HMS manufactured by Borealis Co., Ltd.
- the embodiment was carried out except that the stretching temperature was maintained at 144 ° C. instead of 145 ° C.
- a biaxially stretched polypropylene film and a capacitor were produced.
- the produced biaxially stretched polypropylene film and the capacitor were evaluated. The results are shown in Tables 1 and 2.
- Comparative Example 1 The surface temperature of the metal drum used for the production of the cast original fabric sheet was kept at 88 ° C. instead of 97 ° C., and the unstretched cast original fabric sheet was kept at a temperature of 138 ° C. in the production of the biaxially oriented polypropylene film. While maintaining the temperature of holding the unstretched cast original sheet at 138 ° C. instead of 145 ° C. A biaxially stretched polypropylene film and a capacitor were produced in the same manner as in Example 1 except that the stretching was performed. Next, the produced biaxially stretched polypropylene film and the capacitor were evaluated. The results are shown in Tables 1 and 2.
- Comparative Example 2 The surface temperature of the metal drum used for the production of the cast original fabric sheet was kept at 88 ° C. instead of 97 ° C., and the unstretched cast original fabric sheet was kept at a temperature of 140 ° C. in the production of the biaxially oriented polypropylene film. With respect to the stretching in the direction, that is, the stretching in the flow direction performed in the production of the biaxially stretched polypropylene film, the holding temperature of the unstretched cast original fabric sheet is maintained at a temperature of 140 ° C. instead of 145 ° C. A biaxially stretched polypropylene film and a capacitor were produced in the same manner as in Example 1 except that the stretching was performed. Next, the produced biaxially stretched polypropylene film and the capacitor were evaluated. The results are shown in Tables 1 and 2.
- Comparative Example 3 The surface temperature of the metal drum used for the production of the cast original fabric sheet was kept at 89 ° C. instead of 97 ° C., and the unstretched cast original fabric sheet was kept at a temperature of 140 ° C. in the production of the biaxially oriented polypropylene film.
- the stretching in the direction that is, the stretching in the flow direction performed in the production of the biaxially stretched polypropylene film
- the holding temperature of the unstretched cast original fabric sheet is maintained at a temperature of 140 ° C. instead of 145 ° C.
- a biaxially stretched polypropylene film and a capacitor were produced in the same manner as in Example 1 except that the stretching was performed. Next, the produced biaxially stretched polypropylene film and the capacitor were evaluated. The results are shown in Tables 1 and 2.
- Comparative Example 5 The surface temperature of the metal drum used for the production of the cast original fabric sheet was maintained at 88 ° C. instead of 97 ° C., and in the production of the biaxially oriented polypropylene film, the unstretched cast original fabric sheet was kept at a temperature of 142 ° C. While maintaining the temperature of holding the unstretched cast raw sheet at 142 ° C. instead of 145 ° C. A biaxially stretched polypropylene film and a capacitor were produced in the same manner as in Example 1 except that the stretching was performed. Next, the produced biaxially stretched polypropylene film and the capacitor were evaluated. The results are shown in Tables 1 and 2.
- Comparative Example 6 The surface temperature of the metal drum used for the production of the cast original fabric sheet was maintained at 89 ° C. instead of 97 ° C., and the unstretched cast original fabric sheet was kept at a temperature of 142 ° C. in the production of the biaxially oriented polypropylene film. While maintaining the temperature of holding the unstretched cast raw sheet at 142 ° C. instead of 145 ° C. A biaxially stretched polypropylene film and a capacitor were produced in the same manner as in Example 1 except that the stretching was performed. Next, the produced biaxially stretched polypropylene film and the capacitor were evaluated. The results are shown in Tables 1 and 2.
- Comparative Example 7 The surface temperature of the metal drum used for the production of the cast original fabric sheet was maintained at 88 ° C. instead of 97 ° C., and the unstretched cast original fabric sheet was kept at a temperature of 143 ° C. in the production of the biaxially oriented polypropylene film. While maintaining the temperature of the unstretched cast original sheet at 143 ° C. in place of 145 ° C. A biaxially stretched polypropylene film and a capacitor were produced in the same manner as in Example 1 except that the stretching was performed. Next, the produced biaxially stretched polypropylene film and the capacitor were evaluated. The results are shown in Tables 1 and 2.
- Comparative Example 8 The surface temperature of the metal drum used for the production of the cast original fabric sheet was maintained at 89 ° C. instead of 97 ° C., and the unstretched cast original fabric sheet was kept at a temperature of 143 ° C. in the production of the biaxially oriented polypropylene film. While maintaining the temperature of the unstretched cast original sheet at 143 ° C. in place of 145 ° C. A biaxially stretched polypropylene film and a capacitor were produced in the same manner as in Example 1 except that the stretching was performed. Next, the produced biaxially stretched polypropylene film and the capacitor were evaluated. The results are shown in Tables 1 and 2.
- Comparative Example 9 The surface temperature of the metal drum used for the production of the cast original fabric sheet was kept at 87 ° C. instead of 97 ° C., and in the production of the biaxially oriented polypropylene film, the unstretched cast original fabric sheet was kept at a temperature of 143 ° C. While maintaining the temperature of the unstretched cast original sheet at 143 ° C. in place of 145 ° C. A biaxially stretched polypropylene film and a capacitor were produced in the same manner as in Example 1 except that the stretching was performed. Next, the produced biaxially stretched polypropylene film and the capacitor were evaluated. The results are shown in Tables 1 and 2.
- the biaxially stretched polypropylene film of the present invention suppresses the increase in tan ⁇ even when used for a long time under high voltage and high temperature when used in a capacitor. It is understood that the decrease in electric capacity is suppressed.
Abstract
Description
本発明は、コンデンサ用二軸延伸ポリプロピレンフィルム、詳しくは高温下での長期耐電圧試験において静電容量の低下が少ないコンデンサ用二軸延伸ポリプロピレンフィルムに関する。
また、引用文献4には、結晶子サイズを微細化するとともに高配向化することによりポリプロピレンフィルムの耐電圧性を向上させるという効果が得られることが開示されている。しかしながら、上記ポリプロピレンフィルムにおいても、高電圧および高温下で長期間にわたり使用した場合に生じる静電容量の低下は十分に抑えられていないことが分かった。
さらに、引用文献5には、ポリプロピレンフィルムの熱収縮応力値を一定の範囲とすることにより、高温および長期荷電時に静電容量の低下が小さく、tanδ特性の安定したコンデンサ用ポリプロピレンフィルムが得られることが開示されている。しかしながら、本発明者らは、上記ポリプロピレンフィルムでは、高電圧および高温下で長期間にわたり使用した場合に生じる静電容量の低下は、十分に抑えられていないことを突き止めた。また、引用文献5では、フィルムの表面形状とコンデンサ素子のtanδとの関係性については検討されていない。
したがって、本発明の目的は、コンデンサに高電圧を高温下で長期間にわたり印加した場合でも、静電容量の低下を抑制することができるコンデンサ用二軸延伸ポリプロピレンフィルムを提供することを課題とする。
[1]105℃にて600Vの電圧を印加する長期耐用性試験において、0時間~500時間の経過時間の間に測定されたtanδ[%]を経過時間0時間において測定された初期値tanδ0[%]で規格化した値tanδ/tanδ0の時間に対する変化率が5.0×10-4[1/時間]以下であるコンデンサ用二軸延伸ポリプロピレンフィルム。
[2]少なくとも一方の面において、高さ0.4μm以上の突起総体積が1mm2当たり50μm3以上150μm3以下である、上記[1]に記載のポリプロピレンフィルム。
[3]少なくとも一方の面において、楕円密度が60個/mm2以上80個/mm2以下である、上記[1]または[2]に記載のポリプロピレンフィルム。
[4]前記長期耐用性試験において0時間~1500時間の経過時間の間に測定されたtanδ[%]を経過時間0時間において測定された初期値tanδ0[%]で規格化した値tanδ/tanδ0において、1500時間の経過前に測定されたtanδ/tanδ0の最大値から、1500時間経過時に測定されたtanδ/tanδ0を差し引いた差分として算出されるΔ(tanδ)が-10.0以上0.50以下である、上記[1]~[3]のいずれかに記載のポリプロピレンフィルム。
[5]前記少なくとも一方の面において、最大突起高さが0.5μm以上1.0μm以下である、上記[2]または[3]に記載のポリプロピレンフィルム。
[6]β型球晶が生成したポリプロピレンキャストシートの二軸延伸フィルムである、上記[1]~[5]のいずれかに記載のポリプロピレンフィルム。
[7]前記ポリプロピレンキャストシートはβ晶分率が5%~30%である、上記[6]に記載のポリプロピレンフィルム。
[8]1.0μm以上6.0μm以下の厚みを有する、上記[1]~[7]のいずれかに記載のポリプロピレンフィルム。
[9]上記[1]~[8]のいずれかに記載のポリプロピレンフィルムの片面又は両面に金属膜を有する金属化フィルム。
[10][9]に記載の金属化フィルムを含むコンデンサ。
[11]コンデンサ用フィルムとして用いる、105℃にて600Vの電圧を印加する長期耐用性試験において、0時間~500時間の経過時間の間に測定されたtanδ[%]を経過時間0時間において測定された初期値tanδ0[%]で規格化した値tanδ/tanδ0の時間に対する変化率が5.0×10-4[1/時間]以下であるフィルムの使用。
[12]コンデンサ用フィルムとして用いる、105℃にて600Vの電圧を印加する長期耐用性試験において、0時間~500時間の経過時間の間に測定されたtanδ[%]を経過時間0時間において測定された初期値tanδ0[%]で規格化した値tanδ/tanδ0の時間に対する変化率が5.0×10-4[1/時間]以下であるフィルムの使用方法。
[13]105℃にて600Vの電圧を印加する長期耐用性試験において、0時間~500時間の経過時間の間に測定されたtanδ[%]を経過時間0時間において測定された初期値tanδ0[%]で規格化した値tanδ/tanδ0の時間に対する変化率が5.0×10-4[1/時間]以下であるコンデンサ用二軸延伸ポリプロピレンフィルムの製造方法であって、
(1)ポリプロピレン樹脂組成物を加熱する工程1、
(2)前記工程1により得られた溶融したポリプロピレン樹脂組成物を押し出す工程2、
(3)前記工程2により得られたポリプロピレン樹脂組成物を、少なくとも1個の金属ドラムに接触させる工程3、および
(4)前記工程3により得られたキャスト原反シートを、二軸延伸する工程4
を順に含む、方法。
[14]工程3において、少なくとも1個の金属ドラムの表面温度を90℃~140℃の温度に保持する、[13]に記載の方法。
[15]工程4において、キャスト原反シートを、100~160℃の温度において延伸する工程を含む、[13]または[14]に記載の方法。
[16]少なくとも一方の面において、高さ0.4μm以上の突起総体積が1mm2当たり50μm3以上150μm3以下であるポリプロピレンフィルムであって、105℃にて600Vの電圧を印加する長期耐用性試験において、0時間~500時間の経過時間の間に測定されたtanδ[%]を経過時間0時間において測定された初期値tanδ0[%]で規格化した値tanδ/tanδ0の時間に対する変化率が5.0×10-4[1/時間]以下であるコンデンサ用二軸延伸ポリプロピレンフィルム。
[17]少なくとも一方の面において、楕円密度が60個/mm2以上80個/mm2以下であるポリプロピレンフィルムであって、105℃にて600Vの電圧を印加する長期耐用性試験において、0時間~500時間の経過時間の間に測定されたtanδ[%]を経過時間0時間において測定された初期値tanδ0[%]で規格化した値tanδ/tanδ0の時間に対する変化率[1/時間]が5.0×10-4以下であるコンデンサ用二軸延伸ポリプロピレンフィルム。
[18]105℃にて600Vの電圧を印加する長期耐用性試験において、0時間~500時間の経過時間の間に測定されたtanδ[%]を経過時間0時間において測定された初期値tanδ0[%]で規格化した値tanδ/tanδ0の時間に対する変化率が5.0×10-4[1/時間]以下であるコンデンサ用二軸延伸ポリプロピレンフィルムの片面又は両面に金属膜を有する金属化フィルムを含むコンデンサ。
20a、20b 突起
20c 窪み
≪1.本発明のコンデンサ用二軸延伸ポリプロピレンフィルム≫
本発明のポリプロピレンフィルムは、105℃にて600Vの電圧を印加する長期耐用性試験において、0時間~500時間の経過時間の間に測定されたtanδ[%]を経過時間0時間において測定された初期値tanδ0で規格化した値tanδ/tanδ0の時間に対する変化率(以下、単にtanδ/tanδ0の時間に対する変化率ともいう)が5.0×10-4[1/時間]以下であるコンデンサ用二軸延伸ポリプロピレンフィルムである。
上述の通り、コンデンサ素子のtanδの上昇は、コンデンサ素子の分子運動起因の誘電損失および電極損失の両方の上昇を抑制した場合に著しく抑制することができる。原料を適宜選定することにより、コンデンサ素子の分子運動起因の誘電損失を抑えることができる。
また、キャスト原反シートを成形する際に冷却して固化させるための金属ドラム温度およびキャスト原反シートを延伸する際の延伸時温度を調整することにより、少なくとも一方の面における楕円密度、および高さ0.4μm以上の突起総体積が所望の値となり、コンデンサ素子の誘電損失を抑えることができる。
本発明では、楕円密度は、株式会社キーエンス製デジタルマイクロスコープVHX-2000を用いて、レンズ倍率:100倍、測定方法:反射測定、視野範囲:3.4mm×2.6mmにて計測した。
D=K×λ/(β×Cosθ) (1)
〔ここで、Dは結晶子サイズ(Å)、Kは定数(形状因子)、λは使用X線の波長(Å)、βはα晶(040)面の回折反射ピークの半価幅、θはα晶(040)面の回折ブラッグ角である〕
で示されるScherrerの式を用いて、結晶子サイズを計算する。
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としては、例えば、トリエチレングリコール-ビス[3-(3-ターシャリー-ブチル-5-メチル-4-ヒドロキシフェニル)プロピオネート](商品名:イルガノックス245)、1,6-ヘキサンジオール-ビス[3-(3,5-ジ-ターシャリー-ブチル-4-ヒドロキシフェニル)プロピオネート](商品名:イルガノックス259)、ペンタエリスルチル・テトラキス[3-(3,5-ジ-ターシャリーブチル-4-ヒドロキシフェニル)プロピオネート](商品名:イルガノックス1010)、2,2-チオ-ジエチレンビス[3-(3,5-ジ-ターシャリー-ブチル-4-ヒドロキシフェニル)プロピオネート](商品名:イルガノックス1035)、オクタデシル-3-(3,5-ジ-ターシャリー-ブチル-4-ヒドロキシフェニル)プロピオネート(商品名:イルガノックス1076)、N,N’-ヘキサメチレンビス(3,5-ジ-ターシャリー-ブチル-4-ヒドロキシ-ヒドロシンナマミド)(商品名:イルガノックス1098)などが挙げられるが、高分子量であり、ポリプロピレンとの相溶性に富み、低揮発性かつ耐熱性に優れたペンタエリスルチル・テトラキス[3-(3,5-ジ-ターシャリーブチル-4-ヒドロキシフェニル)プロピオネート]が最も好ましい。
なお、(1)ポリプロピレン樹脂組成物を加熱する方法、(2)押出機の種類、押出条件等、(3)押し出されたポリプロピレン樹脂組成物を金属ドラムに接触させる方法および条件等、(4)キャスト原反シートの物性等、(5)延伸条件、延伸方法等、などの各説明は、上述した事項以外にも後述の≪2.本発明のコンデンサ用二軸延伸ポリプロピレンフィルムの製造方法≫における記載を参照されたい。
本発明の製造方法は、105℃にて600Vの電圧を印加する長期耐用性試験において、0時間~500時間の経過時間の間に測定されたtanδ[%]を経過時間0時間において測定された初期値tanδ0[%]で規格化した値tanδ/tanδ0の時間に対する変化率が5.0×10-4[1/時間]以下であるコンデンサ用二軸延伸ポリプロピレンフィルムの製造方法であって、
(1)ポリプロピレン樹脂組成物を加熱する工程1、
(2)前記工程1により得られた溶融したポリプロピレン樹脂組成物を押し出す工程2、
(3)前記工程2により得られたポリプロピレン樹脂組成物を、少なくとも1個の金属ドラムに接触させる工程3、および
(4)前記工程3により得られたキャスト原反シートを、二軸延伸する工程4
を順に含む方法である。この本発明のフィルムの製造方法によれば、上述の本発明のフィルムを好適に製造することができる。
本発明の製造方法は、ポリプロピレン樹脂組成物を加熱する工程1を含む。工程1により、溶融された樹脂組成物が得られる。
本発明の製造方法は、前記工程1により得られた溶融したポリプロピレン樹脂組成物を押し出す工程2を含む。工程2により、シート状に押し出された樹脂組成物が得られる。
本発明のフィルムの製造方法は、前記工程2により得られたポリプロピレン樹脂組成物を、少なくとも1個の金属ドラムに接触させる工程3を含む。工程3により、未延伸のキャスト原反シートが得られる。
本発明のフィルムの製造方法は、前記工程3により得られたキャスト原反シートを、二軸延伸する工程4を含む。工程4により、二軸延伸ポリプロピレンフィルムが得られる。工程4は、いわゆる流れ方向の延伸工程及び幅方向の延伸工程を含む。
逐次二軸延伸方法を用いる場合には、使用する樹脂の融点およびガラス転移温度により延伸温度や延伸倍率を調整する必要がある。まず、キャスト原反シートを好ましくは100~180℃、より好ましくは140~160℃、より好ましくは144~160℃、さらに好ましくは144℃~150℃の温度に保つ。キャスト原反シートの温度が上記範囲内であれば、この縦方向、言い換えれば流れ方向の延伸工程においてβ晶が融解し、結晶変態によりα晶に変化し、その結果、クレーター状の凹凸が生じる。そのため、本発明における所望の楕円密度及び/又は突起総体積を得ることが容易となる。その結果、本発明フィルムにおいて、所望の上記tanδ/tanδ0の時間に対する変化率を得られやすいので、上記各好ましい延伸時温度範囲で工程4における上記流れ方向の延伸を行うことは好ましい態様である。
キャスト原反シートは、周速差を設けたロール間に通して、あるいはテンター法にて、縦方向(流れ方向)に好ましくは3~7倍、より好ましくは3.5~6.5倍、さらに好ましくは3.8~6倍に延伸する。
延伸後、フィルムにかけられた張力を緩和することにより、一軸延伸されたフィルムが得られる。
次に、当該一軸方向に延伸されたフィルムを、好ましくは140℃以上、より好ましくは150℃以上、さらに好ましくは160℃以上の温度に保つ。一軸延伸フィルムの延伸温度の好ましい上限値は、例えば180℃である。当該一軸方向に延伸されたフィルムの温度が上記範囲内であれば均一に二軸延伸されたフィルムを得ることができる。その結果、縦方向の延伸工程にて形成されたクレーター状の凹凸から、横方向、言い換えれば幅方向の延伸工程において、本発明の楕円密度及び突起総体積にて(略)円形状および楕円形状等として観察される突起が形成される。テンター法において、当該一軸方向に延伸されたフィルムを、横方向(幅方向)に好ましくは3~11倍、より好ましくは5~10.5倍、さらに好ましくは7~10倍に延伸する。延伸後、フィルムにかけられた張力を緩和を行うことにより、二軸延伸されたフィルムが得られる。
本発明のフィルムの製造方法は、上記工程1~工程4以外に、その他の工程を含むことができる。その他の工程としては、断裁工程、巻き取り工程、粗面化工程、金属蒸着加工工程などが挙げられる。
本発明のポリプロピレンフィルムの使用又は使用方法は、それぞれ、コンデンサ用フィルムとして用いる、105℃にて600Vの電圧を印加する長期耐用性試験において、0時間~500時間の経過時間の間に測定されたtanδ[%]を経過時間0時間において測定された初期値tanδ0[%]で規格化した値tanδ/tanδ0の時間に対する変化率が5.0×10-4[1/時間]以下であるフィルムの使用又は使用方法である。
本発明のコンデンサは、上述の本発明のフィルムの片面又は両面に金属膜を有する金属化フィルムを含むコンデンサである。即ち、本発明のコンデンサは、上述の本発明のコンデンサ用二軸延伸ポリプロピレンフィルムを含む。
本発明のコンデンサは、小型かつ、5μF以上、好ましくは10μF以上、さらに好ましくは20μF以上の高容量であってよい。
本発明のコンデンサの用途としては、高電圧コンデンサ、各種スイッチング電源、コンバーター、インバーター等のフィルター用または平滑用コンデンサ、電気自動車やハイブリッド自動車等に用いられる駆動モーターを制御するインバーター電源回路平滑用コンデンサであってよい。
以下の実施例および比較例において作製したコンデンサ素子のtanδを、日置電機株式会社製LCRハイテスター3522-50を用いて経過時間0時間~1500時間の間の所定の時間において測定した。コンデンサ素子5個について、各測定時間におけるtanδを初期値tanδ0(経過時間0時間のtanδ)で規格化することによりtanδ/tanδ0を算出した。各測定時間におけるコンデンサ素子5個のtanδ/tanδ0の平均値を求めた。
以下の実施例および比較例において作製したコンデンサ素子の静電容量を、日置電機株式会社製LCRハイテスター3522-50を用いて経過時間0時間~1500時間の間の所定の時間において測定した。コンデンサ素子5個について、各測定時間における静電容量から初期静電容量(経過時間0時間の静電容量)を引いた差分の、初期静電容量(経過時間0時間の静電容量)に対する割合[%]を静電容量の変化率ΔC[%]として算出した。各測定時間におけるコンデンサ素子5個の静電容量の変化率ΔC[%]の平均値を求めた。
以下の実施例および比較例において作製したポリプロピレンフィルムについて突起総体積を以下の通り測定した。光干渉式非接触表面形状測定器として株式会社菱化システム製の「VertScan2.0(型式:R5500GML)」を用いた。WAVEモードにより、530whiteフィルターおよび×20(20倍)対物レンズを用いた。一視野あたり240μm×180μmの計測を計測対象のフィルム表面の任意の10箇所について行った。得られたデータについて、メディアンフィルタによるノイズ除去処理を行った。その後、カットオフ値30μmによるガウシアンフィルタ処理を行った。これによりうねり成分を除去した。このようにして粗面化表面の状態を適切に計測できる状態とした。突起部総体積は、「VertScan2.0」の解析ソフトウェア「VS-Viewer」のプラグイン機能「ベアリング」を用いて求めた。「山側高さ閾値」を、0.4μmに設定した。「山側体積」として表示されるものを一視野あたりの突起総体積とした。この測定を10箇所について行った。得られた突起総体積の平均値を求めた。次いで平均値を一視野の面積(0.237mm×0.178mm=0.0422mm2)で割ることにより、「1mm2あたりの0.4μm以上の突起総体積(単位:μm3/mm2)」を算出した。なお、それぞれの測定箇所における基準面は、ガウシアンフィルタ処理を行う際における「うねり成分」の高さとした。
以下の実施例および比較例において作製したポリプロピレンフィルムについて、株式会社キーエンス製デジタルマイクロスコープVHX-2000を用いて視野範囲内の(略)円形状および(略)楕円形状の数を計測した。以下に計測条件を示す。
レンズ倍率: 100倍
測定方法: 反射測定
視野範囲: 3.4mm×2.6mm
GPC(ゲルパーミエーションクロマトグラフィー)を用いて、以下の条件で測定した。
測定器: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本連結した。
カラム温度:145℃。
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。
メソペンタッド分率は、NMR装置を用いて、以下の条件で測定した。
高温型核磁気共鳴(NMR)装置:日本電子株式会社製、高温型フーリエ変換核磁気共鳴装置(高温FT-NMR)、JNM-ECP500
観測核は:13C(125MHz)
測定温度:135℃
溶媒:オルト-ジクロロベンゼン(ODCB)と重水素化ODCBの混合溶媒(混合比=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:4,500回
シフト基準:CH3(mmmm)=21.7ppm
ポリプロピレンキャストシートの突起総体積および楕円密度を測定した表面を偏光顕微鏡(ニコン製「ECLIPSE E200」)で観察した。一視野(460×620μm)中で確認される全てのβ型球晶について半径を計測した。得られた半径の平均値を平均半径として求めた。半径の計測には、日本ローバー製の画像解析ソフト「ImagePro」を用いた。
β晶分率は、X線回折強度測定によって求められるK値を用いて評価した。
X線回折強度測定条件は次の通り行った。
測定装置:リガク社製、デスクトップX線回折装置MiniFlex300
X線源:CuKα線
X線発生出力:30KV-10mA
照射X線:モノクローメーター単色化CuKα線(波長1.5418Å)
検出器:シンチュレーションカウンター
ゴニオメーター走査:2θ/θ連動走査
K値は、得られた強度曲線から、以下の式:
K値(強度比%)=Hβ/(Hβ+HαI+HαII+HαIII)×100
に従うα晶由来の3本の回折ピークの高さの和とβ晶由来の1本の回折ピークの比によって算出した。なお、上記式は、
厚みは、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。
以下の実施例および比較例において作製したポリプロピレンフィルムについて最大突起高さ(Sp)を以下の通り測定した。光干渉式非接触表面形状測定器として株式会社菱化システム製「VertScan2.0(型式:R5500GML)」を用いた。WAVEモードにより、530whiteフィルターおよび×20(20倍)対物レンズを用いた。一視野あたり240μm×180μmの計測を計測対象のフィルム表面の任意の10箇所について測定した。得られたデータについて、メディアンフィルタによるノイズ除去処理を行った。その後、カットオフ値30μmによるガウシアンフィルタ処理を行った。これによりうねり成分を除去した。このようにして粗面化表面の状態を適切に計測できる状態とした。上記10箇所において測定した値の平均値を算出した。その平均値を最大突起高さ(Sp)とした。
[キャスト原反シートの作製]
PP樹脂A〔Mw=32万、Mw/Mn=9.3、差(DM)=11.2%(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、Log(M)=6.0のときの微分分布値を100%(基準)とする)、メソペンタッド分率[mmmm]=95%、プライムポリマー製〕と、PP樹脂B〔Mw=35万、Mw/Mn=7.7、差(DM)=7.2%、メソペンタッド分率[mmmm]=96.5%、大韓油化製〕とを、65:35の重量比で押出機へ供給した。供給したPP樹脂AおよびPP樹脂Bは、押出機中で混練することにより、ポリプロピレン樹脂組成物とした。次いでポリプロピレン樹脂からなるポリプロピレン樹脂組成物を樹脂温度250℃で溶融した。その後、溶融したポリプロピレン樹脂組成物をTダイを用いて押出した。押し出されたポリプロピレン樹脂組成物を、表面温度を97℃に保持した金属ドラムに巻きつけることにより固化させた。これによりキャスト原反シートを作製した。得られたキャスト原反シートは、β型球晶の平均半径が1.7μm、β晶分率が13%であった。
得られた未延伸キャスト原反シートを145℃の温度に保ちながら、速度差を設けたロール間に通した。これにより未延伸キャスト原反シートを流れ方向に3~7倍に延伸した。その後、一軸延伸したフィルムを直ちに室温に冷却した。引き続き、当該一軸延伸フィルムをテンターに導いた。その後一軸延伸フィルムを160℃以上の温度で幅方向に3~11倍に延伸した。こうして二軸延伸されたフィルムを緩和した後、熱固定を施した。次いで二軸延伸フィルムを巻き取った。巻き取った二軸延伸フィルムについて20~45℃程度の雰囲気中でエージング処理を施した。こうして厚み2.3μmの二軸延伸ポリプロピレンフィルムを得た。
得られたポリプロピレンフィルムを用いて、以下の通りコンデンサを作製した。二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15Ω/□にてアルミニウム蒸着を施した。これにより金属化フィルムを得た。この金属化フィルムを60mm幅にスリットした。2枚の金属化フィルムを相合わせた。この相合わせた金属化フィルムを、株式会社皆藤製作所製自動巻取機3KAW-N2型を用いることにより、巻き取り張力200gにて、1076ターン巻回を行った。素子巻きした素子は、プレスしながら120℃にて15時間熱処理を施した。その後、素子端面に亜鉛金属を溶射した。こうして扁平型コンデンサを得た。扁平型コンデンサの端面にリード線をはんだ付けした。その後、扁平型コンデンサをエポキシ樹脂で封止した。出来上がったコンデンサは、静電容量が75μF(±5μF)であった。
キャスト原反シートの作製に用いる金属ドラムの表面温度を97℃に代えて100℃に保持したこと以外は実施例1と同様にして、二軸延伸ポリプロピレンフィルムおよびコンデンサを作製した。次いで、製造した二軸延伸ポリプロピレンフィルムおよびコンデンサの評価を行った。結果を表1および2に示す。
二軸延伸ポリプロピレンフィルムの作製において未延伸キャスト原反シートを144℃の温度に保ちながら流れ方向に延伸を行ったこと、すなわち、二軸延伸ポリプロピレンフィルムの作製の際に行う流れ方向の延伸時に関して、未延伸キャスト原反シートの保持温度を145℃に代えて144℃の温度に保ちながら延伸を行ったこと以外は実施例1と同様にして、二軸延伸ポリプロピレンフィルムおよびコンデンサを作製した。結果を表1および2に示す。
原料としてPP樹脂AとPP樹脂Bを用いてキャスト原反シートを作製したことに代えて原料としてPP樹脂Aを単独で用いてキャスト原反シートを作製したこと以外は実施例1と同様にして、二軸延伸ポリプロピレンフィルムおよびコンデンサを作製した。次いで、製造した二軸延伸ポリプロピレンフィルムおよびコンデンサの評価を行った。結果を表1および2に示す。
キャスト原反シートの作製に用いる金属ドラムの表面温度を97℃に代えて95℃に保持したこと以外は実施例1と同様にして、二軸延伸ポリプロピレンフィルムおよびコンデンサを作製した。次いで、製造した二軸延伸ポリプロピレンフィルムおよびコンデンサの評価を行った。結果を表1および2に示す。
キャスト原反シートの作製に用いる金属ドラムの表面温度を97℃に代えて100℃に保持したこと、および二軸延伸ポリプロピレンフィルムの作製において未延伸キャスト原反シートを144℃の温度に保ちながら流れ方向に延伸を行ったこと、すなわち二軸延伸ポリプロピレンフィルムの作製の際に行う流れ方向の延伸時に関して、未延伸キャスト原反シートの保持温度を145℃に代えて144℃の温度に保ちながら延伸を行ったこと以外は実施例1と同様にして、二軸延伸ポリプロピレンフィルムおよびコンデンサを作製した。次いで、製造した二軸延伸ポリプロピレンフィルムおよびコンデンサの評価を行った。結果を表1および表2に示す。
キャスト原反シートの作製に用いる金属ドラムの表面温度を97℃に代えて95℃に保持したこと、および二軸延伸ポリプロピレンフィルムの作製において未延伸キャスト原反シートを144℃の温度に保ちながら流れ方向に延伸を行ったこと、すなわち二軸延伸ポリプロピレンフィルムの作製の際に行う流れ方向の延伸時に関して、未延伸キャスト原反シートの保持温度を145℃に代えて144℃の温度に保ちながら延伸を行ったこと以外は実施例1と同様にして、二軸延伸ポリプロピレンフィルムおよびコンデンサを作製した。次いで、製造した二軸延伸ポリプロピレンフィルムおよびコンデンサの評価を行った。結果を表1および表2に示す。
原料としてPP樹脂AとPP樹脂Bを用いてキャスト原反シートを作製したことに代えて原料としてPP樹脂Aを単独で用いてキャストシートを作製したこと、およびキャスト原反シートの作製に用いる金属ドラムの表面温度を97℃に代えて95℃に保持したこと以外は実施例1と同様にして、二軸延伸ポリプロピレンフィルムおよびコンデンサを作製した。次いで、製造した二軸延伸ポリプロピレンフィルムおよびコンデンサについて評価を行った。結果を表1および表2に示す。
キャスト原反シートの作製において、原料としてPP樹脂AとPP樹脂Bとを65:35の重量比で押出機へ供給したことに代えて、原料として、PP樹脂Aと、PP樹脂Bと、PP樹脂C1(長鎖分岐ポリプロピレン樹脂、ボレアリス社製WB135HMS)とを64:34:2の質量比で押出機へ供給したこと、金属ドラムの表面温度を97℃に代えて99℃に保持したこと、および二軸延伸ポリプロピレンフィルムの作製の際に行う流れ方向の延伸時に関して、未延伸キャスト原反シートの保持温度を145℃に代えて144℃の温度に保ちながら延伸を行ったこと以外は実施例1と同様にして、二軸延伸ポリプロピレンフィルムおよびコンデンサを作製した。次いで、製造した二軸延伸ポリプロピレンフィルムおよびコンデンサについて評価を行った。結果を表1および表2に示す。
キャスト原反シートの作製に用いる金属ドラムの表面温度を97℃に代えて88℃に保持したこと、および二軸延伸ポリプロピレンフィルムの作製において未延伸キャスト原反シートを138℃の温度に保ちながら流れ方向に延伸を行ったこと、すなわち、二軸延伸ポリプロピレンフィルムの作製の際に行う流れ方向の延伸時に関して、未延伸キャスト原反シートの保持温度を145℃に代えて138℃の温度に保ちながら延伸を行ったこと以外は実施例1と同様にして、二軸延伸ポリプロピレンフィルムおよびコンデンサを作製した。次いで、製造した二軸延伸ポリプロピレンフィルムおよびコンデンサについて評価を行った。結果を表1および表2に示す。
キャスト原反シートの作製に用いる金属ドラムの表面温度を97℃に代えて88℃に保持したこと、および二軸延伸ポリプロピレンフィルムの作製において未延伸キャスト原反シートを140℃の温度に保ちながら流れ方向に延伸を行ったこと、すなわち、二軸延伸ポリプロピレンフィルムの作製の際に行う流れ方向の延伸時に関して、未延伸キャスト原反シートの保持温度を145℃に代えて140℃の温度に保ちながら延伸を行ったこと以外は実施例1と同様にして、二軸延伸ポリプロピレンフィルムおよびコンデンサを作製した。次いで、製造した二軸延伸ポリプロピレンフィルムおよびコンデンサについて評価を行った。結果を表1および表2に示す。
キャスト原反シートの作製に用いる金属ドラムの表面温度を97℃に代えて89℃に保持したこと、および二軸延伸ポリプロピレンフィルムの作製において未延伸キャスト原反シートを140℃の温度に保ちながら流れ方向に延伸を行ったこと、すなわち、二軸延伸ポリプロピレンフィルムの作製の際に行う流れ方向の延伸時に関して、未延伸キャスト原反シートの保持温度を145℃に代えて140℃の温度に保ちながら延伸を行ったこと以外は実施例1と同様にして、二軸延伸ポリプロピレンフィルムおよびコンデンサを作製した。次いで、製造した二軸延伸ポリプロピレンフィルムおよびコンデンサについて評価を行った。結果を表1および表2に示す。
PP樹脂AとPP樹脂Bを用いてキャスト原反シートを作製したことに代えて原料としてPP樹脂C2〔Mw=30万、Mw/Mn=4.1、差(DM)=4.6、メソペンタッド分率[mmmm]=94.0%、プライムポリマー製〕を単独で用いてキャスト原反シートを作製したこと以外は実施例1と同様にして、二軸延伸ポリプロピレンフィルムおよびコンデンサを作製した。次いで、製造した二軸延伸ポリプロピレンフィルムおよびコンデンサについて評価を行った。結果を表1および表2に示す。
キャスト原反シートの作製に用いる金属ドラムの表面温度を97℃に代えて88℃に保持したこと、および二軸延伸ポリプロピレンフィルムの作製において未延伸キャスト原反シートを142℃の温度に保ちながら流れ方向に延伸を行ったこと、すなわち、二軸延伸ポリプロピレンフィルムの作製の際に行う流れ方向の延伸時に関して、未延伸キャスト原反シートの保持温度を145℃に代えて142℃の温度に保ちながら延伸を行ったこと以外は実施例1と同様にして、二軸延伸ポリプロピレンフィルムおよびコンデンサを作製した。次いで、製造した二軸延伸ポリプロピレンフィルムおよびコンデンサについて評価を行った。結果を表1および表2に示す。
キャスト原反シートの作製に用いる金属ドラムの表面温度を97℃に代えて89℃に保持したこと、および二軸延伸ポリプロピレンフィルムの作製において未延伸キャスト原反シートを142℃の温度に保ちながら流れ方向に延伸を行ったこと、すなわち、二軸延伸ポリプロピレンフィルムの作製の際に行う流れ方向の延伸時に関して、未延伸キャスト原反シートの保持温度を145℃に代えて142℃の温度に保ちながら延伸を行ったこと以外は実施例1と同様にして、二軸延伸ポリプロピレンフィルムおよびコンデンサを作製した。次いで、製造した二軸延伸ポリプロピレンフィルムおよびコンデンサについて評価を行った。結果を表1および表2に示す。
キャスト原反シートの作製に用いる金属ドラムの表面温度を97℃に代えて88℃に保持したこと、および二軸延伸ポリプロピレンフィルムの作製において未延伸キャスト原反シートを143℃の温度に保ちながら流れ方向に延伸を行ったこと、すなわち、二軸延伸ポリプロピレンフィルムの作製の際に行う流れ方向の延伸時に関して、未延伸キャスト原反シートの保持温度を145℃に代えて143℃の温度に保ちながら延伸を行ったこと以外は実施例1と同様にして、二軸延伸ポリプロピレンフィルムおよびコンデンサを作製した。次いで、製造した二軸延伸ポリプロピレンフィルムおよびコンデンサについて評価を行った。結果を表1および表2に示す。
キャスト原反シートの作製に用いる金属ドラムの表面温度を97℃に代えて89℃に保持したこと、および二軸延伸ポリプロピレンフィルムの作製において未延伸キャスト原反シートを143℃の温度に保ちながら流れ方向に延伸を行ったこと、すなわち、二軸延伸ポリプロピレンフィルムの作製の際に行う流れ方向の延伸時に関して、未延伸キャスト原反シートの保持温度を145℃に代えて143℃の温度に保ちながら延伸を行ったこと以外は実施例1と同様にして、二軸延伸ポリプロピレンフィルムおよびコンデンサを作製した。次いで、製造した二軸延伸ポリプロピレンフィルムおよびコンデンサについて評価を行った。結果を表1および表2に示す。
キャスト原反シートの作製に用いる金属ドラムの表面温度を97℃に代えて87℃に保持したこと、および二軸延伸ポリプロピレンフィルムの作製において未延伸キャスト原反シートを143℃の温度に保ちながら流れ方向に延伸を行ったこと、すなわち、二軸延伸ポリプロピレンフィルムの作製の際に行う流れ方向の延伸時に関して、未延伸キャスト原反シートの保持温度を145℃に代えて143℃の温度に保ちながら延伸を行ったこと以外は実施例1と同様にして、二軸延伸ポリプロピレンフィルムおよびコンデンサを作製した。次いで、製造した二軸延伸ポリプロピレンフィルムおよびコンデンサについて評価を行った。結果を表1および表2に示す。
原料としてPP樹脂AとPP樹脂Bを用いてキャスト原反シートを作製したことに代えて原料としてPP樹脂C2〔Mw=30万、Mw/Mn=4.1、差(DM)=4.6、メソペンタッド分率[mmmm]=94.0%、プライムポリマー製〕を単独で用いてキャストシートを作製したこと、およびキャスト原反シートの作製に用いる金属ドラムの表面温度を97℃に代えて95℃に保持したこと以外は実施例1と同様にして、二軸延伸ポリプロピレンフィルムおよびコンデンサを作製した。次いで、製造した二軸延伸ポリプロピレンフィルムおよびコンデンサについて評価を行った。結果を表1および表2に示す。
Claims (13)
- 105℃にて600Vの電圧を印加する長期耐用性試験において、0時間~500時間の経過時間の間に測定されたtanδ[%]を経過時間0時間において測定された初期値tanδ0[%]で規格化した値tanδ/tanδ0の時間に対する変化率が5.0×10-4[1/時間]以下であるコンデンサ用二軸延伸ポリプロピレンフィルム。
- 少なくとも一方の面において、高さ0.4μm以上の突起総体積が1mm2当たり50μm3以上150μm3以下である、請求項1に記載のポリプロピレンフィルム。
- 少なくとも一方の面において、楕円密度が60個/mm2以上80個/mm2以下である、請求項1または2に記載のポリプロピレンフィルム。
- 前記長期耐用性試験において0時間~1500時間の経過時間の間に測定されたtanδ[%]を経過時間0時間において測定された初期値tanδ0[%]で規格化した値tanδ/tanδ0において、1500時間の経過前に測定されたtanδ/tanδ0の最大値から、1500時間経過時に測定されたtanδ/tanδ0を差し引いた差分として算出されるΔ(tanδ)が-10.0以上0.50以下である、請求項1~3のいずれかに記載のポリプロピレンフィルム。
- 前記少なくとも一方の面において、最大突起高さが0.5μm以上1.0μm以下である、請求項2または3に記載のポリプロピレンフィルム。
- β型球晶が生成したポリプロピレンキャストシートの二軸延伸フィルムである、請求項1~5のいずれかに記載のポリプロピレンフィルム。
- 前記ポリプロピレンキャストシートはβ晶分率が5%~30%である、請求項6に記載のポリプロピレンフィルム。
- 1.0μm以上6.0μm以下の厚みを有する、請求項1~7のいずれかに記載のポリプロピレンフィルム。
- 請求項1~8のいずれかに記載のポリプロピレンフィルムの片面又は両面に金属膜を有する金属化フィルム。
- 請求項9に記載の金属化フィルムを含むコンデンサ。
- 105℃にて600Vの電圧を印加する長期耐用性試験において、0時間~500時間の経過時間の間に測定されたtanδ[%]を経過時間0時間において測定された初期値tanδ0[%]で規格化した値tanδ/tanδ0の時間に対する変化率が5.0×10-4[1/時間]以下であるコンデンサ用二軸延伸ポリプロピレンフィルムの製造方法であって、
(1)ポリプロピレン樹脂組成物を加熱する工程1、
(2)前記工程1により得られた溶融したポリプロピレン樹脂組成物を押し出す工程2、
(3)前記工程2により得られたポリプロピレン樹脂組成物を、少なくとも1個の金属ドラムに接触させる工程3、および
(4)前記工程3により得られたキャスト原反シートを、二軸延伸する工程4
を順に含む、方法。 - 工程3において、少なくとも1個の金属ドラムの表面温度を90℃~140℃の温度に保持する、請求項11に記載の方法。
- 工程4において、キャスト原反シートを、140~160℃の温度において延伸する工程を含む、請求項11または12に記載の方法。
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EP16773210.6A EP3279908B1 (en) | 2015-03-31 | 2016-03-31 | Biaxially stretched polypropylene film for capacitors, metallized film and capacitor |
JP2017510242A JPWO2016159330A1 (ja) | 2015-03-31 | 2016-03-31 | コンデンサ用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コンデンサ |
US15/562,739 US10910164B2 (en) | 2015-03-31 | 2016-03-31 | Biaxially stretched polypropylene film for capacitors, metallized film, and capacitor |
KR1020177024163A KR101974824B1 (ko) | 2015-03-31 | 2016-03-31 | 콘덴서용 2축 연신 폴리프로필렌 필름, 금속화 필름 및 콘덴서 |
CN201680019601.4A CN107408458B (zh) | 2015-03-31 | 2016-03-31 | 电容器用双轴拉伸聚丙烯薄膜、金属化薄膜和电容器 |
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JP (1) | JPWO2016159330A1 (ja) |
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CN107408458A (zh) | 2017-11-28 |
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