WO2022220248A1 - 金属化ポリプロピレンフィルム - Google Patents
金属化ポリプロピレンフィルム Download PDFInfo
- Publication number
- WO2022220248A1 WO2022220248A1 PCT/JP2022/017622 JP2022017622W WO2022220248A1 WO 2022220248 A1 WO2022220248 A1 WO 2022220248A1 JP 2022017622 W JP2022017622 W JP 2022017622W WO 2022220248 A1 WO2022220248 A1 WO 2022220248A1
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- WO
- WIPO (PCT)
- Prior art keywords
- polypropylene film
- film
- metallized
- polypropylene
- dielectric breakdown
- Prior art date
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
- B32B2307/518—Oriented bi-axially
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
- B32B2307/737—Dimensions, e.g. volume or area
- B32B2307/7375—Linear, e.g. length, distance or width
- B32B2307/7376—Thickness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/24—Aluminium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2323/00—Polyalkenes
- B32B2323/10—Polypropylene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/16—Capacitors
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/228—Terminals
- H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor
- H01G4/2325—Terminals electrically connecting two or more layers of a stacked or rolled capacitor characterised by the material of the terminals
Definitions
- the present invention relates to a metallized polypropylene film (also referred to as a metal layer-integrated polypropylene film).
- Polypropylene film has excellent electrical properties such as voltage resistance and low dielectric loss properties, as well as high moisture resistance. Taking advantage of these properties, it is preferably used as a dielectric film for capacitors such as high-voltage capacitors, various switching power sources, filter capacitors such as converters and inverters, and smoothing capacitors in electronic and electrical equipment.
- capacitors such as high-voltage capacitors, various switching power sources, filter capacitors such as converters and inverters, and smoothing capacitors in electronic and electrical equipment.
- polypropylene films have begun to be used as capacitors for inverter power supply devices that control drive motors for electric vehicles, hybrid vehicles, and the like, for which demand has been increasing in recent years.
- the present invention has been made in view of the above, and an object of the present invention is to provide a metallized polypropylene film that is excellent in dielectric breakdown resistance.
- the inventors of the present invention have found that the above object can be achieved by controlling the number of dielectric breakdown points measured by a specific measuring method to a certain number or less, and have completed the present invention. Completed.
- the present invention includes, for example, the subject matter described in the following sections.
- Item 1 A metallized polypropylene film in which a first metal film is formed on at least one side of a biaxially stretched polypropylene film, The metallized polypropylene film has a thickness of 0.5 to 4.0 ⁇ m, A metallized polypropylene film having a thickness-equivalent dielectric breakdown score of 1.90 [(pieces/cm 2 ) ⁇ m] or less measured under the following dielectric breakdown score measurement conditions.
- a 22 ⁇ m-thick polypropylene insulating film having an opening of 10 mm ⁇ 100 mm is placed on the aluminum foil side of a conductive substrate comprising a brass plate, conductive rubber, and aluminum foil laminated in this order.
- the metallized polypropylene film is brought into contact with the insulating film and the opening is It is also brought into contact with the aluminum foil through.
- an electrode is placed on the surface of the first metal film, and 391 (V/ ⁇ m), 435 (V/ ⁇ m), 478 (V/ ⁇ m) between the first metal film and the conductive substrate. ), 521 (V/ ⁇ m), 565 (V/ ⁇ m), and 609 (V/ ⁇ m) are applied in this order for a total of 6 times for 1 minute, and the accumulated dielectric breakdown points are counted up to the third time.
- the value obtained by dividing this count number by the area (1000 mm 2 ) of the opening of the insulating film is defined as the dielectric breakdown score, and the value obtained by multiplying the dielectric breakdown score by the thickness of the metallized polypropylene film is the thickness conversion dielectric breakdown score.
- Item 2 When the surface shape of the biaxially stretched polypropylene film is measured using an optical interference non-contact surface profiler in a range of 240 ⁇ m ⁇ 180 ⁇ m per field of view, the total protrusions with a height of 0.02 ⁇ m or more Item 1.
- the metallized polypropylene film according to Item 1 having a volume of 950 to 1300 ⁇ m 3 per field of view.
- Item 3 A metallized polypropylene film having a polypropylene film and a metal layer laminated on one or both sides of the polypropylene film, wherein the cumulative dielectric breakdown point density after a cumulative DC voltage application test of 20 ° C.
- Item 4 Item 4. The metallized polypropylene film according to Item 3, wherein the polypropylene film has a thickness of 1.0 to 3.0 ⁇ m.
- Item 5 The polypropylene film has a heat shrinkage rate of 0 to 8% in the first direction and a heat shrinkage rate of -2 to 2% in the second direction orthogonal to the first direction under the treatment conditions of 120 ° C. for 15 minutes.
- Item 3 or 4 the metallized polypropylene film.
- the polypropylene film has a heat shrinkage rate of 0 to 10% in the first direction and a heat shrinkage rate of -1 to 5% in the second direction orthogonal to the first direction under the treatment conditions of 140 ° C. for 15 minutes. , the metallized polypropylene film according to any one of items 3 to 5.
- Item 7 Item 7. The metal according to any one of Items 3 to 6, wherein the polypropylene film has a tensile elastic modulus of 1.5 GPa or more in a first direction and a tensile elastic modulus of 3 GPa or more in a second direction orthogonal to the first direction. Polypropylene film.
- Item 8 Item 8.
- Item 9 Item 9. The metallized polypropylene film according to any one of Items 3 to 8, wherein the polypropylene film is a monolayer film.
- Item 10 Item 10. The metallized polypropylene film according to any one of Items 1 to 9, which is used for capacitors.
- Item 11 A capacitor comprising the metallized polypropylene film according to any one of Items 1 to 10.
- Item 12 12 comprising a winding of the metallized polypropylene film of any one of claims 1-11.
- the metallized polypropylene film of the present invention has excellent dielectric breakdown resistance.
- FIG. 1 is a schematic diagram illustrating the measurement of the dielectric breakdown point of the metallized polypropylene film of the present invention
- (a) is a side view of the device used in the measurement method
- (b) is a plan view of the device
- (c) is A cross-sectional view of the device
- (d) a perspective view of an insulating film incorporated in the device.
- (A) and (B) show the measurement results of the dielectric breakdown points of Production Examples 1 to 4 and Production Examples 5 to 8, respectively.
- 1 is a schematic diagram of an apparatus for measuring cumulative dielectric breakdown point density; FIG.
- FIG. 2 is a schematic diagram for explaining a method for producing a metal layer-integrated polypropylene film according to Examples and Comparative Examples.
- the present specification also exemplifies ranges in which the upper limits and/or lower limits are arbitrarily exchanged between a plurality of ranges based on the ranges consisting of the upper limits and/or lower limits described for each parameter.
- X or more is a range consisting of X to 0 and a value greater than 0.
- X or less is a range consisting of X and a negative value having a larger absolute value than X.
- the metallized polypropylene film of the present invention includes metallized polypropylene film X and metallized polypropylene film Y below.
- the metallized polypropylene film X is A first metal film is formed on one side of the biaxially stretched polypropylene film, the thickness of the metallized polypropylene film is 0.5 to 4.0 ⁇ m, and the procedure described in ⁇ Conditions for measuring dielectric breakdown point> described later.
- the measured thickness-equivalent dielectric breakdown point is 1.90 [(pieces/cm 2 ) ⁇ m] or less.
- ⁇ Measurement conditions for the number of dielectric breakdown points> A 22 ⁇ m-thick polypropylene insulating film having an opening of 10 mm ⁇ 100 mm is placed on the aluminum foil side of a conductive substrate comprising a brass plate, conductive rubber, and aluminum foil laminated in this order.
- the metallized polypropylene film By placing the metallized polypropylene film on the upper surface of the insulating film so that the first metal film is exposed on the surface side, the metallized polypropylene film is brought into contact with the insulating film and the opening is It is also brought into contact with the aluminum foil through. Next, an electrode is placed on the surface of the first metal film, and 391 (V/ ⁇ m), 435 (V/ ⁇ m), 478 (V/ ⁇ m) between the first metal film and the conductive substrate. ), 521 (V/ ⁇ m), 565 (V/ ⁇ m), and 609 (V/ ⁇ m) are applied in this order for a total of 6 times for 1 minute, and the accumulated dielectric breakdown points are counted up to the third time.
- the value obtained by dividing this count number by the area (1000 mm 2 ) of the opening of the insulating film is defined as the dielectric breakdown score, and the value obtained by multiplying the dielectric breakdown score by the thickness of the metallized polypropylene film is the thickness conversion dielectric breakdown score.
- the metallized polypropylene film Y is A metallized polypropylene film having a polypropylene film and a metal layer laminated on one or both sides of the polypropylene film, wherein the cumulative dielectric breakdown point density after a cumulative DC voltage application test of 20 ° C. and 350 to 425 V / ⁇ m is 1000 pieces/m 2 or less.
- the metallized polypropylene film X and the metallized polypropylene film Y will be described in detail below.
- the metallized polypropylene film X is formed by providing a metal film on one side of a biaxially stretched polypropylene film.
- the metal film formed on one side of the biaxially stretched polypropylene film is referred to as "first metal film”.
- a biaxially oriented polypropylene film refers to a film formed by biaxially oriented polypropylene resin.
- a biaxially stretched polypropylene film has a polypropylene resin as a main component.
- the "main component” is 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more in terms of solid content in the biaxially stretched polypropylene film. , and more preferably 99% by mass or more.
- the type of polypropylene resin is not particularly limited, and for example, a wide range of polypropylene resins that are used to form biaxially oriented polypropylene films for capacitors can be used.
- polypropylene resins include propylene homopolymers such as isotactic polypropylene and syndiotactic polypropylene; copolymers of propylene and ethylene; long chain branched polypropylene; and ultrahigh molecular weight polypropylene.
- a preferred polypropylene resin is a propylene homopolymer, and isotactic polypropylene is more preferred from the viewpoint of easily improving heat resistance, and isotactic polypropylene obtained by homopolymerizing polypropylene in the presence of an olefin polymerization catalyst is further preferred. preferable.
- the metallized polypropylene film X contains a highly stereoregular polypropylene resin, so that the free volume and the relative free volume are easily adjusted to the desired values described above.
- the polypropylene resin contained in the biaxially stretched polypropylene film may be of one type alone, or may be of two or more different types.
- the metallized polypropylene film tends to improve the dielectric breakdown resistance.
- the polypropylene resin contained in the biaxially stretched polypropylene film includes polypropylene resin A having Mw/Mn of 8 or more (preferably 8.5 or more, more preferably 9 or more) and Mw/Mn of less than 8 (preferably 7.9 or less, more preferably 7.8 or less).
- the polypropylene resin contained in the biaxially oriented polypropylene film may consist of polypropylene resin A and polypropylene resin B alone.
- the Mw/Mn of polypropylene resin A is, for example, 15 or less, preferably 13 or less, more preferably 12 or less, and the Mw/Mn of polypropylene resin B is, for example, 5 or more, preferably 6 or more.
- the content ratio of polypropylene resin A and polypropylene resin B is not particularly limited. 20:80 to 80:20 is more preferred, and 30:70 to 70:30 is particularly preferred.
- the polypropylene resin as the main component and the polypropylene other than the main component It means both with resin.
- the weight average molecular weight Mw of the polypropylene resin is preferably 250,000 or more and 450,000 or less. and that the weight average molecular weight Mw of the polypropylene resin other than the main component is preferably 250,000 or more and 450,000 or less.
- the weight average molecular weight Mw of the polypropylene resin is preferably 250,000 or more and 450,000 or less, more preferably 250,000 or more and 400,000 or less.
- the weight average molecular weight Mw of the polypropylene resin is 250,000 or more and 450,000 or less, the resin fluidity becomes appropriate. As a result, it is easy to control the thickness of the original cast sheet, and it becomes easy to produce a thin stretched film with good thickness uniformity.
- the weight average molecular weight Mw is preferably 250,000 or more and 450,000 or less from the viewpoint of the mechanical properties, thermo-mechanical properties, stretch moldability, etc. of the biaxially stretched polypropylene film.
- the polypropylene resin preferably has a number average molecular weight Mn of 30,000 or more and 53,000 or less, more preferably 33,000 or more and 52,000 or less.
- the z-average molecular weight Mz of the polypropylene resin is preferably from 500,000 to 2,100,000, more preferably from 700,000 to 1,700,000.
- the molecular weight distribution [(weight average molecular weight Mw)/(number average molecular weight Mn)] of the polypropylene resin is preferably 5 or more and 12 or less, more preferably 5 or more and 11 or less. , 5 or more and 10 or less.
- the molecular weight distribution [(weight average molecular weight Mw) / (number average molecular weight Mn)] of the polypropylene resin is 5 or more and 12 or less, moderate resin fluidity is obtained during biaxial stretching, and ultra-thinness without thickness unevenness It is preferable because it becomes easy to obtain a biaxially stretched propylene film that has been stretched.
- the molecular weight distribution [(z average molecular weight Mz)/(number average molecular weight Mn)] of the polypropylene resin is preferably 10 or more and 70 or less, more preferably 15 or more and 60 or less. , 15 or more and 50 or less.
- the weight average molecular weight (Mw), number average molecular weight (Mn), z average molecular weight (Mz), and molecular weight distribution (Mw/Mn and Mz/Mn) of the polypropylene resin are determined by gel permeation chromatography. It is a value measured using a graph (GPC) apparatus (the same applies to the metallized polypropylene film Y described later). More specifically, it is a value measured using HLC-8121GPC-HT (trade name), a differential refractometer (RI) built-in high-temperature GPC measuring instrument manufactured by Tosoh Corporation. As a GPC column, three TSKgel GMHHR-H(20)HT manufactured by Tosoh Corporation are used by connecting them.
- GPC graph
- the column temperature is set to 140° C., and trichlorobenzene is passed as an eluent at a flow rate of 1.0 ml/10 minutes to obtain measured values of Mw and Mn.
- a standard polystyrene manufactured by Tosoh Corporation is used to prepare a calibration curve for the molecular weight M, and the measured values are converted into polystyrene values to obtain Mw, Mn and Mz.
- the base 10 logarithm of the molecular weight M of standard polystyrene is referred to as the logarithmic molecular weight ("Log(M)").
- differential distribution value difference DM is preferably -5% or more and 14% or less, more preferably -4% or more and 12% or less, -4% or more It is more preferably 10% or less.
- the polypropylene resin has a differential distribution value difference of -5% when a component with a molecular weight of 10,000 to 100,000 is compared with a component with a molecular weight of 1,000,000. It is preferable to use a polypropylene resin so that the ratio is 14% or less.
- the differential distribution value is a value obtained as follows using GPC.
- a curve of intensity against time also commonly referred to as an "elution curve” obtained by a GPC differential refractometer (RI) detector is used.
- the elution curve is converted to a curve showing intensity versus Log(M) by transforming the time axis to logarithmic molecular weight (Log(M)). Since the RI detection intensity is proportional to the component concentration, if the total area of the intensity curve is set to 100%, an integral distribution curve for the logarithmic molecular weight Log(M) can be obtained.
- a differential distribution curve is obtained by differentiating this integral distribution curve by Log(M). Therefore, "differential distribution” means the differential distribution of the concentration fraction with respect to the molecular weight. From this curve, a differential distribution value at a specific Log(M) is read.
- the mesopentad fraction ([mmmm]) of the polypropylene resin is preferably less than 98.0%, more preferably 97.5% or less, and 97.4% or less. It is more preferable that the content is 97.0% or less. Moreover, the mesopentad fraction is preferably 94.0% or more, more preferably 94.5% or more, and even more preferably 95.0% or more.
- the crystallinity of the resin is moderately improved due to moderately high stereoregularity, and the initial voltage resistance and long-term voltage resistance are improved.
- the desired stretchability can be obtained by a moderate solidification (crystallization) speed during molding.
- the mesopentad fraction ([mmmm]) is an index of stereoregularity that can be obtained by high temperature nuclear magnetic resonance (NMR) measurement.
- NMR nuclear magnetic resonance
- the mesopentad fraction ([mmmm]) is a value measured using a high-temperature Fourier transform nuclear magnetic resonance spectrometer (high-temperature FT-NMR) JNM-ECP500 manufactured by JEOL Ltd.
- ODCB o-dichlorobenzene
- the heptane-insoluble content (HI) of the polypropylene resin is preferably 96.0% or more, more preferably 97.0% or more.
- the heptane-insoluble content (HI) of the polypropylene resin is preferably 99.5% or less, more preferably 99.0% or less.
- the higher the heptane-insoluble content the higher the stereoregularity of the resin.
- the rate of solidification (crystallization) during cast raw sheet molding is moderate, and it has moderate stretchability.
- the method for measuring the heptane insolubles (HI) is according to the method described in Examples.
- the melt flow rate (MFR) of the polypropylene resin is preferably 1.0 to 8.0 g/10 min, more preferably 1.5 to 7.0 g/10 min, More preferably, it is 2.0 to 6.0 g/10 min.
- the method for measuring the melt flow rate of the polypropylene resin is according to the method described in Examples.
- the polypropylene resin as the main component has at least a weight average molecular weight Mw of 250,000 or more and less than 345,000, and an MFR of 4. It is preferably ⁇ 8 g/10 min.
- the polypropylene resin contained in the polypropylene film is two or more types, the polypropylene resin other than the main component has at least a weight average molecular weight Mw of 345,000 or more and 450,000 or less, and an MFR of 1 g/10 min or more and 4 g. /10 min (more preferably 1 g/10 min or more and 3.9 g/10 min or less).
- the total ash content due to polymerization catalyst residues and the like contained in the polypropylene resin is preferably 50 ppm or less based on the polypropylene resin (100 parts by mass).
- the total ash content (total ash content contained in the polypropylene resin) is preferably 5 ppm or more and 35 ppm or less, and 5 ppm or more and 30 ppm or less in order to improve the electrical characteristics as a capacitor while suppressing the generation of polar low-molecular-weight components. is more preferable, and 10 ppm or more and 25 ppm or less is even more preferable.
- the manufacturing method of the polypropylene resin is not particularly limited, and for example, a wide range of known manufacturing methods can be adopted.
- the polypropylene resin can be produced using various polymerization methods such as gas phase polymerization, bulk polymerization and slurry polymerization.
- polypropylene resin can also be obtained from a commercial item etc., for example.
- the biaxially stretched polypropylene film can contain other resins besides polypropylene resin.
- the biaxially oriented polypropylene film can contain additives.
- the "additive” is generally an additive used for polypropylene resin, and is not particularly limited as long as a desired polypropylene film can be obtained. Examples of additives include antioxidants, stabilizers such as chlorine absorbers and ultraviolet absorbers, lubricants, plasticizers, flame retardants, antistatic agents, colorants, and the like. Known additives applied to polypropylene films can be widely applied.
- the biaxially oriented polypropylene film preferably has a thickness of, for example, 0.5 to 4.0 ⁇ m in that the capacitor tends to have a high capacity.
- Such thickness is a value measured in accordance with JIS K 7130:1999 A method using an outside micrometer (Mitsutoyo Corporation, high-precision Digimatic Micrometer MDH-25MB).
- the total volume of protrusions of the biaxially stretched polypropylene film is not particularly limited.
- the total protrusions with a height of 0.02 ⁇ m or more The volume is preferably 950-1300 ⁇ m 3 per field of view.
- the dielectric breakdown property of the metallized polypropylene film over a long period of time is likely to be improved, and when the element is wound, winding wrinkles do not occur and the film can be wound optimally. As a result, a uniform contact between the films is produced, thereby improving voltage resistance and voltage resistance over a long period of time.
- the total volume of the protrusions is obtained by measuring the surface shape using a three-dimensional surface roughness evaluation method using an optical interference non-contact surface shape measuring instrument. Since the "three-dimensional surface roughness evaluation method" evaluates the height of the entire surface of the film, the voids between the films are evaluated three-dimensionally. Therefore, it is possible to grasp local fine changes and variations of the surface to be measured, and to evaluate the surface roughness more accurately. Evaluate the voids between films using the total volume of three-dimensional protrusions rather than simply the height of protrusions (two-dimensional surface roughness evaluation based on general center line average roughness Ra, etc.) Next, better voltage resistance and long-term voltage resistance can be obtained.
- the total volume of the protrusions is measured using Ryoka System's "VertScan 2.0 (model: R5500GML)" as an optical interference non-contact surface shape measuring instrument.
- R5500GML optical interference non-contact surface shape measuring instrument.
- WAVE mode is used, a 530 white filter and a ⁇ 20 objective lens are used, and measurements of 240 ⁇ m ⁇ 180 ⁇ m per field are performed at arbitrary 10 locations on the surface of the film to be measured.
- the obtained data is subjected to noise removal processing using a median filter, and then to Gaussian filtering processing with a cutoff value of 30 ⁇ m to remove undulation components. As a result, the state of the roughened surface can be appropriately measured.
- the total projection volume can be obtained as follows using the plug-in function "bearing” of the analysis software "VS-Viewer” of "VertScan 2.0". After setting the "mountain side height threshold" to a predetermined height (ie, 0.02 ⁇ m), what is displayed as the “mountain side volume” is the total projection volume per field of view. This measurement is performed at 10 locations, and the average value is taken as the total projection volume per field of view.
- the total volume of projections of the biaxially stretched polypropylene film can be adjusted using known roughening methods such as embossing and etching.
- a surface roughening method using ⁇ crystals which does not require the mixing of impurities.
- the proportion of ⁇ crystals produced can be adjusted by changing the properties such as the molecular structure of the polypropylene resin used.
- the ratio of ⁇ crystals can also be controlled by stretching conditions such as casting temperature and casting speed.
- the melting ratio of ⁇ crystals can be controlled by the roll temperature in the longitudinal stretching step.
- the surface property can be controlled by selecting the optimum manufacturing conditions for the two parameters of ⁇ -crystal formation and melting.
- the method for producing the biaxially stretched polypropylene film is not particularly limited, and for example, a wide range of known methods for producing a biaxially stretched polypropylene film can be employed.
- a biaxially stretched polypropylene film is preferably produced using an unstretched original sheet. Therefore, the method for producing a biaxially oriented polypropylene film can include a step of stretching an unstretched raw sheet.
- the method for producing the unstretched raw fabric sheet is not particularly limited, and for example, widely known methods can be applied.
- an unstretched raw sheet is obtained by supplying a raw material containing a polypropylene resin to an extruder, heat-melting it, melt-extruding it from a T-die, and cooling and solidifying it with a metal drum.
- the polypropylene resin for obtaining the unstretched raw sheet can be, for example, in the form of pellets. Specifically, polypropylene resin pellets, dry-mixed polypropylene resin pellets (and/or polymerized powder), or pre-melted Mixed polypropylene resin pellets made by kneading can be used.
- the polypropylene resin contained in the raw material containing the polypropylene resin may be of one type alone, or may be of two or more different types. When two or more different polypropylene resins are contained in the polypropylene resin-containing raw material, the types thereof are not particularly limited, and various polypropylene resins can be combined.
- raw materials containing polypropylene resin can contain additives.
- additives include antioxidants, stabilizers such as chlorine absorbers and ultraviolet absorbers, lubricants, plasticizers, flame retardants, antistatic agents, colorants, and the like.
- Known additives applied to polypropylene films can be widely applied.
- the temperature (melting temperature) at which the raw material containing the polypropylene resin is melted by the extruder is, for example, 170° C. or higher and 320° C. or lower, preferably 200° C. or higher and 300° C. or lower, more preferably 220° C. or higher and 250° C. or lower. .
- the raw material containing polypropylene resin After heating and melting the raw material containing polypropylene resin with an extruder, it is preferable to pass it through a polymer filter and then melt-extrude it with a T-die. In other words, it is preferable to install a polymer filter between the extruder and the T-die when manufacturing the unstretched raw sheet.
- the finally obtained metallized polypropylene film of the present invention tends to have a lower dielectric breakdown point.
- the filtration accuracy of the polymer filter is 20 ⁇ m (98% cut size) in that the value of the dielectric breakdown point according to the measurement is likely to be smaller and the dielectric breakdown resistance is likely to be improved. It is preferably less than 15 ⁇ m, more preferably 10 ⁇ m or less, even more preferably 5 ⁇ m or less, particularly preferably 5 ⁇ m or less. However, in order to prevent deterioration of ejection stability, it is necessary not to make the opening size of the polymer filter too small.
- the type of filter medium used in the polymer filter is not particularly limited, and a wide range of known filter mediums can be used.
- a sintered metal nonwoven fabric fiber sintered body
- a laminated sintered wire mesh a powder sintered body, or the like
- filter types leaf disc filters, candle filters, pack filters, etc. can be used without limitation.
- the leaf disk type filter using sintered metal non-woven fabric is preferably used because it does not increase the differential pressure (pressure loss), provides stable discharge, and has a long service life. can.
- the T-die temperature is not particularly limited, and can be, for example, 170°C to 320°C, preferably 200°C to 300°C.
- the heated and melted raw material is melted and extruded from a T-die, then cooled and solidified in a metal drum. As a result, an unstretched cast material sheet is formed. At the time of this cooling and solidification, it is also possible to blow air onto the resin using an air knife.
- the cooling temperature is not particularly limited. For example, by cooling and solidifying with at least one or more metal drums maintained at 80 to 140° C., an unstretched cast raw fabric sheet can be formed.
- the metal drum temperature is preferably 90°C to 120°C, more preferably 90°C to 105°C.
- the thickness of the unstretched raw sheet obtained is, for example, preferably 0.05 mm or more and 2 mm or less, more preferably 0.1 mm or more and 1 mm or less.
- a biaxially stretched polypropylene film can be produced by stretching the obtained unstretched raw sheet.
- the stretching is preferably biaxial stretching in which the film is biaxially oriented longitudinally and transversely, and the stretching method is preferably a sequential biaxial stretching method.
- An example of the sequential biaxial stretching method is as follows. First, an unstretched raw sheet is kept at a temperature of 100 to 160° C., stretched 3 to 7 times in the machine direction by being passed between rolls provided with a speed difference, and immediately cooled to room temperature. Subsequently, the stretched film is led to a tenter and stretched 3 to 11 times in the width direction at a temperature of 160° C. or higher, then relaxed, heat-set, and wound up. The wound film can be cut into a desired product width after being subjected to aging treatment in an atmosphere of about 20 to 45° C., for example.
- the surface of the biaxially stretched polypropylene film obtained by the above method can be subjected to unevenness treatment, if necessary.
- Various known roughening methods such as an embossing method and an etching method can be employed as a method for providing unevenness.
- a roughening method using ⁇ crystals, which does not require the mixing of impurities, is preferable.
- the ⁇ -crystal formation rate can generally be controlled by changing the casting temperature (cooling temperature by the metal drum described above) and casting speed.
- the melting/transition ratio of ⁇ crystals can be controlled by the roll temperature in the longitudinal stretching process, and by selecting the optimum production conditions for these two parameters of ⁇ crystal formation and its melting/transition, fine coarsening can be achieved. Surface properties can be obtained.
- At least one surface of the biaxially stretched polypropylene film preferably has a center line average roughness (Ra) of 0.03 ⁇ m or more and 0.08 ⁇ m or less, and , the maximum height (Rz, Rmax in the old JIS definition) is preferably finely roughened to 0.3 ⁇ m or more and 0.8 ⁇ m or less.
- Ra and Rz are in the preferred ranges described above, the surface can be a finely roughened surface, and during capacitor processing, winding wrinkles are less likely to occur during element winding processing, and winding is preferable. can. Furthermore, uniform contact between the films may be possible, so voltage resistance and long-term voltage resistance may be improved.
- Ra and Rz refer to stylus-type surface roughness meters (for example, A value measured using a stylus-type surface roughness meter using a diamond stylus, etc.).
- Ra and Rz are, more specifically, for example, using a three-dimensional surface roughness meter Surfcom 1400D-3DF-12 manufactured by Tokyo Seimitsu Co., Ltd., according to the method specified in JIS-B0601: 2001. Ra and Rz (Rmax in the old JIS definition) can be determined according to the standard.
- the biaxial polypropylene film obtained by the above method can be subjected to corona discharge treatment on-line or off-line, if necessary.
- corona discharge treatment for example, known methods can be widely adopted.
- the corona discharge treatment may be performed, for example, in any atmosphere of air, carbon dioxide gas, nitrogen gas, and mixed gases thereof.
- Metalized polypropylene film X In the metallized polypropylene film X of the present invention, the first metal film is formed only on one side of the biaxially stretched polypropylene film.
- the first metal film may be simply referred to as "metal film”.
- the metal film functions as an electrode when the metallized polypropylene film is used as a capacitor.
- the metal used for the metal film for example, single metals such as zinc, lead, silver, chromium, aluminum, copper, and nickel, mixtures of multiple types thereof, and alloys thereof can be used. , economy and capacitor performance, etc., zinc and aluminum are preferred.
- the thickness of the metal film is not particularly limited, and can be the same as a known metallized polypropylene film used as a capacitor.
- examples of methods for laminating a metal film on one side of the biaxially stretched polypropylene film include a vacuum deposition method and a sputtering method.
- a vacuum deposition method is preferable from the viewpoint of productivity and economy.
- examples of the vacuum deposition method include a crucible method and a wire method in general, but the method is not particularly limited, and an optimum method can be selected as appropriate.
- the temperature of the cooling roll is preferably ⁇ 20° C. or less, more preferably ⁇ 23° C. or less, from the viewpoint of preventing heat loss of the polypropylene film.
- the thickness of the metal film is controlled by film resistance.
- the film resistance is preferably 25 ⁇ /sq or less, more preferably 20 ⁇ /sq or less, from the viewpoint of suppressing the loss of the capacitor element.
- the film resistance is preferably 1 ⁇ /sq or more, more preferably 5 ⁇ /sq or more, from the viewpoint of self-healing properties.
- a zinc film it is preferably 1 ⁇ /sq or more, more preferably 2 ⁇ /sq or more.
- the thickness (film resistance) of the metal film can be adjusted by the vapor deposition line speed and the temperature of the evaporation source.
- the margin pattern when laminating metal films by vapor deposition is not particularly limited. is preferably a structure (special margin pattern) connected by a metal film (so-called fuse). Security is improved, and it is also effective in terms of prevention of capacitor destruction and short circuit. Generally known methods such as a tape method and an oil method can be used without any limitation for forming the margin.
- the metallized polypropylene film X of the present invention has a thickness of 0.5-4.0 ⁇ m.
- the thickness of the metallized polypropylene film of the present invention is a value measured in accordance with JIS K 7130:1999 A method using an outer micrometer (Mitsutoyo Corporation, high-precision Digimatic Micrometer MDH-25MB). be.
- the metallized polypropylene film X of the present invention has a thickness-converted dielectric breakdown point of 1.90 [(pieces/cm 2 ) ⁇ m] or less measured by the above-described measuring method, and thus has excellent voltage resistance. Therefore, it can be suitably used for various capacitor element applications.
- the thickness-equivalent dielectric breakdown point of the metallized polypropylene film of the present invention is preferably 1.8 [(pieces/cm 2 ) ⁇ m] or less, more preferably 1.7 [(pieces/cm 2 ) ⁇ m] or less. is more preferably 1.6 [(pieces/cm 2 ) ⁇ m] or less, and particularly preferably 1.5 [(pieces/cm 2 ) ⁇ m] or less.
- FIG. 1 is a schematic diagram illustrating a method for measuring the dielectric breakdown score of a metallized polypropylene film of the present invention, in which (a) is a side view of an apparatus used in the measurement method, and (b) is the apparatus. , and FIG. 1(c) shows a sectional view of the device. Specifically, the cross-sectional view of FIG. 1(c) is a cross-sectional view taken along the line aa in FIG. 1(b).
- FIG. 1(a) shows a circuit provided for application in step 1, the illustration of the circuit is omitted in (b) and (c).
- the measurement method includes a conductive substrate 2, a polypropylene insulating film 3 having openings, and the metallized polypropylene film X (the metallized polypropylene film of the present invention). Measurements are performed using laminate A. As shown in FIGS. 1(a), (b) and (c), in this laminate A, an insulating film 3 is arranged between the conductive substrate 2 and the metallized polypropylene film 1 . Moreover, in the laminate A, the first metal film 1b formed on one side of the metallized polypropylene film 1 is arranged so as to be exposed on the surface side of the laminate A. As shown in FIG. The conductive base material 2 and the insulating film 3 constituting the laminate A will be described below.
- the conductive base material 2 is a base material that functions as a conductor in the laminate A, and is a base material that functions, so to speak, as a lower conductor.
- the conductive base material 2 is a three-layer laminate in which a brass plate, conductive rubber and aluminum foil are laminated in this order. In the laminate A, the aluminum foil is arranged on the insulating film 3 side.
- the type of the conductive rubber is not particularly limited, and for example, a wide range of known conductive rubbers can be used.
- the material of the conductive rubber is also not particularly limited as long as it has appropriate softness and sufficient conductivity.
- a resistor may be connected to the laminate A, so a conductive rubber having a resistance value lower than that of the resistor is preferably employed.
- the insulating film 3 is a layer arranged between the conductive base material 2 and the metallized polypropylene film 1 in the laminate A as described above, and between the conductors (between the lower conductor and the upper conductor described later) ) to provide insulation. Therefore, it is preferable that a conductive material such as the metal film of the metallized resin film 1 is not formed on either side of the insulating film 3 .
- the insulating film 3 is a polypropylene film with openings.
- the insulating film 3 is preferably sufficiently thicker than the metallized polypropylene film to be measured, so the thickness is set to 22 ⁇ m.
- the insulating film 3 is partially cut out to form an opening 3a.
- the opening 3 a is formed in a rectangular shape (10 mm ⁇ 100 mm) in a plan view of the insulating film 3 .
- the opening 3a is formed so as to penetrate the insulating film 3 in its thickness direction.
- frame portion 3b the film portion outside the opening 3a is referred to as "frame portion 3b".
- the formation position of the opening 3a is not particularly limited as long as it is formed inside the insulating film 3, and the occurrence of creeping discharge described later can be more easily suppressed, as shown in FIG. 1(d). Moreover, it is preferably formed inside the insulating film 3 so as to include the central portion.
- the insulating film 3 is placed on the conductive base material 2, which is the lower conductor. Specifically, the insulating film 3 is placed on the aluminum foil of the conductive substrate 2 .
- the metallized polypropylene film 1 is a film to be measured, and is the aforementioned "metallized polypropylene film X". Therefore, the metallized polypropylene film 1 is composed of a biaxially stretched polypropylene film 1a and a first metal film 1b formed on one side thereof.
- the first metal film 1b is arranged so as to be exposed on the surface side of the laminate A. That is, the metallized polypropylene film 1 is arranged on the insulating film 3 so that the surface on the side of the first metal film 1b is located on the opposite side of the insulating film 3 .
- the first metal film 1b functions as a conductor in the laminate A, so to speak, as an upper conductor. do. Therefore, the laminate A has an upper conductor formed of the first metal film 1b and a lower conductor formed of the conductive substrate 2. As shown in FIG.
- the description of the upper conductor and the lower conductor merely represents the vertical direction when the conductive base material 2 is placed on a test stand or the like as shown in FIG. It is not intended that the metal film 1b of 1 is arranged on the upper side and the conductive substrate 2 is arranged on the lower side.
- the metallized polypropylene film 1 is arranged in contact with the insulating film 3 and also in contact with the conductive substrate 2 through the openings of the insulating film 3 . More specifically, the metallized polypropylene film 1 is in contact with a portion of the insulating film 3 other than the opening 3a, that is, the surface of the frame portion 3b (see FIG. 1(d)), and through the opening 3a. It is also arranged in contact with the exposed surface of the conductive base material 2 . Therefore, as shown in FIG. 1(b), the laminate A has a region where a part of the metallized resin film 1 is fitted into the opening 3a. Hereinafter, this area will be referred to as "area R".
- the metallized polypropylene film 1 is arranged so that the first metal film 1b is positioned over the entire region R. Even if the metallized polypropylene film 1 has a portion (a so-called margin) where no metal film is formed, the margin and the region R are prevented from overlapping each other. This makes it possible to measure the dielectric breakdown point of the metallized polypropylene film 1 with high accuracy.
- the metallized polypropylene film 1 to be measured has a so-called heavy edge in which the metal film is formed thicker than other parts, such a heavy edge should not overlap the region R. This also makes it possible to measure the dielectric breakdown point of the metallized polypropylene film 1 with high accuracy.
- the measurement is performed by applying a voltage to the laminate A.
- an electrical connection is made for application between the conductive substrate 2 (lower conductor) and the first metal film 1b (upper conductor).
- the lower conductor can be easily electrically connected by connecting a conductor wire to the conductive base material 2 .
- the electrode 4 is used to facilitate electrical connection.
- electrical connection can be established by placing the electrode 4 on the metal film 1b.
- the electrode 4 When the electrode 4 is placed on the surface of the first metal film 1b, electrical connection between the first metal film 1b (upper conductor) and the electrode 4 becomes possible due to the weight of the electrode 4 itself.
- the electrode 4 can be placed on any portion of the surface of the first metal film 1b, but it is placed on a portion other than the region R described above.
- a commercially available high-voltage power supply and a resistor are used for applying voltage, and these are connected in series as shown in FIG. conductor) and the first metal film 1b (upper conductor).
- the resistance value of the resistor can be appropriately set according to the test object, and can be, for example, several hundred ⁇ to several hundred k ⁇ .
- the laminate A is smoothed with a static elimination brush.
- a static elimination brush As a result, even if there are gaps between the layers, especially between the polypropylene film 1 and its lower layer, the gaps can be removed. Even if voids remain even after the treatment with such a static elimination brush, electrostatic adsorption occurs due to the application of step 1, so that the voids are further removed and the number of dielectric breakdown points can be measured more accurately. becomes possible. After starting the application, further treatment with the static elimination brush can be unnecessary.
- the dielectric breakdown points are counted visually, counted by sound, counted by light, and counted by a threshold value based on the instantaneous current.
- the metallized polypropylene film 1 after voltage application is visually observed, and visually recognized dielectric breakdown portions are counted.
- a dielectric breakdown occurs at a portion with a weak withstand voltage, and when this dielectric breakdown occurs, the metallized resin film 1 instantly generates heat and the film temperature rises. Due to this temperature rise, the first metal film, which is the upper conductor, evaporates, thereby recovering the insulation, causing a so-called self-healing phenomenon. Since the self-healing trace has lost the metal film, it is visually recognized as whiter than the surroundings due to the light transmission of the corresponding portion. Therefore, the number of dielectric breakdown points of the metallized polypropylene film 1 can be visually counted by counting the number of dielectric breakdown sites (self-healing sites).
- the measurement can be performed near the center of the metallized polypropylene film 1 instead of the periphery, so creeping discharge is easily suppressed.
- the position of the opening 3a is closer to the inner side of the insulating film 3
- the actual measurement point of the metallized resin film 1 is also closer to the inner side of the film, and in this case, unnecessary creeping discharge is more easily suppressed. , the measurement accuracy is high.
- Metallized polypropylene film Y is a metallized polypropylene film having a polypropylene film and a metal layer laminated on one or both sides of the polypropylene film, and after a cumulative DC voltage application test of 20 ° C. and 350 to 425 V / ⁇ m The cumulative dielectric breakdown point density is 1000/m 2 or less.
- the metallized polypropylene film Y is a metallized polypropylene film having a polypropylene film and a metal layer laminated on one or both sides of the polypropylene film. Body shape polypropylene film”.
- the metallized polypropylene film Y is sometimes referred to as "the metal layer-integrated polypropylene film of the present invention”.
- the polypropylene film (that is, the polypropylene film not laminated with a metal layer) included in the metal layer-integrated polypropylene film of the present invention is sometimes referred to herein as the "polypropylene film of the present invention". These are described below.
- the metallized polypropylene film Y has a cumulative dielectric breakdown point density after a cumulative DC voltage application test of 350 to 425 V/ ⁇ m at 20° C. (cumulative dielectric breakdown point density at 425 V/ ⁇ m at 20° C.) of 1000/m 2 or less. is.
- the cumulative dielectric breakdown point density of 1000/m 2 or less not only makes it possible to obtain a capacitor that exhibits a certain level of workability and has a certain level of capacitance stability, and furthermore, It is possible to obtain a capacitor excellent in insulation resistance stability under high temperature and high voltage load.
- Cumulative dielectric breakdown point density is preferably 900/m 2 or less, more preferably 800/m 2 or less, still more preferably 700/m 2 or less, even more preferably 600/m 2 or less, and most preferably 500/m 2 or less, more preferably 400/m 2 or less, even more preferably 300/m 2 or less, even more preferably 200/m 2 or less, particularly preferably 100/m 2 or less is.
- the cumulative dielectric breakdown point density is preferably 50/m 2 or less, more preferably 20/m 2 or less, still more preferably 10/m 2 or less, and even more preferably 5/m 2 or less. m 2 or less, particularly preferably 0/m 2 .
- the cumulative dielectric breakdown point density is measured by setting the metal layer integrated polypropylene film in the measuring device so as to have the configuration shown in FIG. 3 and measuring as follows. After applying a DC voltage of 350 V/ ⁇ m for 1 minute in an environment of 20° C., the number of dielectric breakdown points in the window area (100 mm ⁇ 10 mm) of the insulating polypropylene film is visually counted. After counting, a DC voltage of 375 V/ ⁇ m was applied for 1 minute, and then the number of accumulated dielectric breakdown points in the window area of the insulating polypropylene film was visually counted. Next, the DC voltage is increased by 25 V/ ⁇ m, and this operation is repeated up to 425 V/ ⁇ m, and the DC voltage is applied cumulatively.
- FIG. 3 is a schematic diagram for explaining cumulative dielectric breakdown point density measurement.
- the brass plate 201 (320 mm ⁇ 250 mm), the conductive rubber 202 (280 mm ⁇ 150 mm), and the aluminum foil 203 (280 mm ⁇ 150 mm)
- the outer circumference of the aluminum foil 203 is covered.
- Insulating polypropylene film 204 (300 mm x 210 mm, window 100 mm x 10 mm) having a rectangular (100 mm x 10 mm) cut-out portion (hereinafter referred to as “window 204a”) in the center is sequentially laminated. .
- the metal layer-integrated polypropylene film 1 (metallized polypropylene film Y) is overlaid on the insulating polypropylene film 204 laminated as described above so as not to protrude from the outer circumference of the insulating polypropylene film 204 .
- the metal-deposited surface 10a of the metal-layer-integrated polypropylene film 1 faces upward, and the metal-deposited layer 10a covers the window 204a of the insulating polypropylene film 204.
- the portion overlapping with the window 204a is the portion without the special margin of the metal vapor deposition layer 10a, the so-called solid vapor deposition portion of the metal vapor deposition layer 10a.
- the cooling roll contact surface of the metal layer integrated polypropylene film 1 placed on the insulating polypropylene film 204 as described above contacts the surface of the aluminum foil 203 through the window 204 a of the insulating polypropylene film 204 .
- a cylindrical brass electrode 205 (diameter 25 mm, height 65 mm) is placed on the metal deposition layer 10a at a location away from the window 204a. At this time, the columnar brass electrode 205 comes into contact with the metal deposition layer 3a.
- the cylindrical brass electrode 205 is electrically connected to a DC power supply 207 via a resistive element (10 k ⁇ ) 206 for overcurrent prevention. Also, the brass plate 201 is directly electrically connected to the DC power supply 207 .
- the cumulative dielectric breakdown point density test apparatus 301 is configured as described above.
- the cumulative dielectric breakdown point density of the metal layer integrated polypropylene film 1 is measured by the cumulative dielectric breakdown point density tester 301, even if the capacitor is not manufactured, the capacitor can be obtained at the stage of the metal layer integrated polypropylene film. can be expected.
- the cumulative dielectric breakdown point density test device 301 when a high voltage is applied from the DC power source 207, a dielectric breakdown occurs at a portion of the metal layer integrated polypropylene film 1 weak in terms of withstand voltage. When dielectric breakdown occurs, heat is generated instantaneously, so that the metal deposition layer 10a evaporates and the insulation recovers (self-healing). Since the metal vapor deposition layer 10a disappears, the portion where self-healing occurs is visually recognized as cloudy. After applying a predetermined voltage for a certain period of time, the number of places where self-healing occurred (hereinafter referred to as "dielectric breakdown points”) was counted to evaluate the voltage resistance of the metal layer integrated polypropylene film. can.
- This dielectric breakdown point depends on the voltage resistance of the metal layer integrated polypropylene film 1 and the properties of the metal deposition layer 10a. In other words, whether or not the vapor deposited metal layer 10a is likely to evaporate also affects the magnitude of the dielectric breakdown point. Since the accumulated dielectric breakdown point density test apparatus 301 uses the metal deposition layer 10a as the upper conductor, it is possible to see characteristics close to those of an actual capacitor.
- the voltage is increased stepwise at regular intervals from a predetermined start voltage to the end voltage, applied for a certain period of time, and the number of dielectric breakdown points of the metal layer integrated polypropylene film 1 is cumulatively counted each time.
- the cumulative counted number is hereinafter referred to as the "cumulative number of dielectric breakdown points").
- the metallized polypropylene film Y has a heat shrinkage rate of 0 to 8% (more preferably 0 to 6%, still more preferably 0 to 4%) in the first direction under treatment conditions of 120 ° C. for 15 minutes, and the first It is preferable that the heat shrinkage rate in the second direction perpendicular to the first direction is -2 to 2% (more preferably -1 to 1%).
- the first direction is preferably the MD direction (machine direction) of the polypropylene film
- the second direction is the TD direction (transverse direction) of the polypropylene film.
- the first direction is preferably the MD direction (machine direction) of the polypropylene film
- the second direction is the TD direction (transverse direction) of the polypropylene film.
- the first direction is preferably the MD direction (machine direction) of the polypropylene film
- the second direction is the TD direction (transverse direction) of the polypropylene film.
- the first direction is preferably the MD direction (machine direction
- the thermal contraction rate in the first direction is 0% or more (that is, when the thermal expansion coefficient is 0% or less) under the treatment conditions of 120 ° C. for 15 minutes, and the thermal contraction rate in the second direction is -2% or more (i.e., when the coefficient of thermal expansion is 2% or less), and when the coefficient of thermal expansion in the first direction is 8% or less (i.e., when the coefficient of thermal expansion is -8% or more), and when the heat in the second direction
- the shrinkage rate is 2% or less (that is, when the thermal expansion rate is -2% or more)
- the thermal expansion and thermal contraction of the film on the cooling roll during metal vapor deposition are further suppressed to suppress conveying wrinkles,
- the adhesion of the polypropylene film to the cooling roll can be further improved, thermal damage can be suppressed, and the voltage resistance of the metal layer-integrated polypropylene film can be further improved.
- the thermal shrinkage rate (120°C thermal shrinkage rate) (unit: %) under the treatment condition of 120°C for 15 minutes is measured as follows.
- the sample used for measurement is cut out from a roll, and the size of the sample is 130 mm in the first direction and 20 mm in the second direction when measuring the 120°C heat shrinkage in the first direction.
- the shrinkage rate it is 20 mm in the first direction and 130 mm in the second direction.
- Three samples for measuring the 120° C. heat shrinkage in the first direction and three samples for measuring the 120° C. heat shrinkage in the second direction are prepared.
- marked lines are marked at positions 15 mm from each end of 130 mm in the first direction.
- the interval between the marked lines is 100 mm.
- marked lines are marked at positions 15 mm from each end of 130 mm in the second direction. At this time, the interval between the marked lines is 100 mm. Then, each sample with the marked line is suspended without load in a hot air circulating constant temperature bath at 120° C. so that the direction of the 130 mm cut is vertical, and held for 15 minutes.
- Thermal shrinkage rate (%) (Gauge interval before heating - Gauge interval after heating) / Marked line interval before heating ⁇ 100 is used to calculate the thermal shrinkage rate (%) for each sample.
- the average value of the thermal contraction rates of three samples for which the 120° C. thermal contraction rate in the first direction is measured be the 120° C. thermal contraction rate (%) in the first direction.
- the average value of the thermal contraction rates of three samples for which the 120° C. thermal contraction rates in the second direction are measured is defined as the 120° C. thermal contraction rate (%) in the second direction. Measurement conditions other than those described here conform to "25. Dimensional change" of JIS C 2151:2019.
- the metallized polypropylene film Y has a heat shrinkage rate of 0 to 10% (more preferably 0 to 8%, still more preferably 0 to 7%) in the first direction under treatment conditions of 140 ° C. for 15 minutes, and the first It is preferable that the heat shrinkage rate in the second direction orthogonal to the one direction is -1 to 5% (more preferably 0 to 4%).
- the thermal contraction rate in the first direction is 0% or more (that is, when the thermal expansion coefficient is 0% or less) under the treatment conditions of 140 ° C.
- the thermal contraction rate in the second direction is -1% or more (i.e., when the coefficient of thermal expansion is 1% or less), and when the coefficient of thermal expansion in the first direction is 10% or less (i.e., when the coefficient of thermal expansion is ⁇ 10% or more), and when the heat in the second direction
- the shrinkage rate is 5% or less (that is, when the thermal expansion rate is -5% or more)
- the thermal expansion and thermal contraction of the film on the cooling roll during metal vapor deposition are further suppressed to suppress conveyance wrinkles
- the adhesion of the polypropylene film to the cooling roll can be further improved, thermal damage can be suppressed, and the voltage resistance of the metal layer-integrated polypropylene film can be further improved.
- the metallized polypropylene film Y has a tensile elastic modulus of 1.5 GPa or more (more preferably 2.0 GPa or more) in the first direction, and a tensile elastic modulus of 3.0 GPa or more in the second direction perpendicular to the first direction. (more preferably 4.0 GPa or more).
- the tensile elastic modulus in the first direction is 1.5 GPa or more and the tensile elastic modulus in the second direction is 3.0 GPa or more, wrinkles during transportation during metal vapor deposition are further suppressed, and the polypropylene film adheres to the cooling roll. It is possible to further improve the properties, suppress thermal damage, and further improve the voltage resistance of the metal layer-integrated polypropylene film.
- the upper limit of the tensile modulus of elasticity of the polypropylene film of the present invention is not particularly limited in any direction, but the upper limit can be substantially 6.0 GPa.
- the tensile modulus (unit: GPa) is measured according to JIS K-7127 (1999).
- the sample used for measurement is cut from a roll, and the size of the sample is 200 mm in the first direction and 15 mm in the second direction when measuring the tensile elastic modulus in the first direction.
- 15 mm in the first direction and 200 mm in the second direction When measuring, 15 mm in the first direction and 200 mm in the second direction.
- a tensile test is performed using a tensile compression tester (manufactured by Minebea Co., Ltd.) under the test conditions of a measurement temperature of 23° C., a distance between chucks of 100 mm, and a tensile speed of 200 mm/min.
- the tensile modulus of elasticity (GPa) in the first direction and the tensile modulus of elasticity (GPa) in the second direction are determined by automatic analysis using data processing software incorporated in the tester.
- the thickness of the metallized polypropylene film Y is preferably 9.5 ⁇ m or less, more preferably 6.0 ⁇ m or less, still more preferably 3.0 ⁇ m or less, even more preferably 2.9 ⁇ m or less, and particularly preferably 2.8 ⁇ m or less. , 2.5 ⁇ m or less are particularly preferred.
- the thickness of the polypropylene film of the present invention is preferably 0.8 ⁇ m or more, more preferably 1.0 ⁇ m or more, still more preferably 1.4 ⁇ m or more, even more preferably 1.5 ⁇ m or more, and particularly 1.8 ⁇ m or more. preferable.
- the thickness when the thickness is within the range of 1.0 to 6.0 ⁇ m, 1.0 to 3.0 ⁇ m, 1.0 to 2.9 ⁇ m, etc., although the polypropylene film is very thin, slit process processability and vapor deposition process It is preferable because it is excellent in anti-blocking property and element winding workability. If the thickness is 9.5 ⁇ m or less, the capacitance can be increased, and thus it can be suitably used for capacitors. Moreover, from the viewpoint of manufacturing, the thickness can be set to 0.8 ⁇ m or more.
- the film thickness is measured according to JIS-C2330, except that it is measured at 100 ⁇ 10 kPa using a paper thickness measuring instrument MEI-11 manufactured by Citizen Seimitsu.
- the haze value of the metallized polypropylene film Y is not particularly limited, but is, for example, 2.2 to 5.0%, preferably 2.3 to 4.5%, more preferably 2.5 to 4.5%, still more preferably is 2.5 to 4.0%, more preferably 2.5 to 3.5%.
- a haze value is measured as follows. Using a haze meter ("NDH-5000" manufactured by Nippon Denshoku Industries Co., Ltd.), it is measured according to JIS K 7136:2000. The sample size is 50 mm ⁇ 100 mm.
- the metallized polypropylene film Y may be a biaxially stretched film, a uniaxially stretched film, or an unstretched film. Among them, a biaxially stretched film is preferable.
- the layer structure of the polypropylene film is not particularly limited, and may be a single layer consisting of one layer, or may be a plurality of layers having the same or different compositions.
- the polypropylene film is preferably a film consisting of one or more film-like molded layers, more preferably a monolayer film (a film consisting of one film-like molded layer).
- the polypropylene film contains polypropylene resin as a main component.
- the “main component” is the same as the “main component” in the metallized polypropylene film X.
- the polypropylene resin is not particularly limited, and one type may be used alone, or two or more types may be used in combination.
- the polypropylene resin is particularly preferably a polypropylene resin that forms ⁇ -type spherulites when formed into a cast sheet.
- the polypropylene resin is preferably a linear polypropylene resin, more preferably a linear homopolypropylene resin.
- the total ash content is preferably 50 ppm or less, more preferably 40 ppm or less, and even more preferably 30 ppm or less based on the polypropylene resin. Lower limits for total ash are, for example, 2 ppm, 5 ppm, and the like.
- the polypropylene resin may contain, for example, only the first polypropylene resin described below, or may contain the second polypropylene resin described below together with the first polypropylene resin.
- the polypropylene resin can contain the first polypropylene resin.
- the content of the first polypropylene resin is preferably 50% by weight or more, more preferably 55% by weight or more, and still more preferably 60% by weight with respect to 100% by weight of the polypropylene resin. That's it.
- the upper limit of the content of the first polypropylene resin for example, 100% by weight or less, 99% by weight or less, 98% by weight or less, or 95% by weight or less with respect to 100% by weight of the polypropylene resin.
- the polypropylene film of this embodiment can contain the first polypropylene resin as a main component.
- the first polypropylene resin include isotactic polypropylene.
- the weight average molecular weight Mw of the first polypropylene resin is preferably 250,000 or more and less than 400,000, more preferably 260,000 or more and 370,000 or less, and still more preferably 270,000 or more and 350,000 or less.
- Mw is 250,000 or more and less than 400,000
- the resin fluidity becomes moderate, the thickness of the cast raw fabric sheet is easily controlled, and it becomes easy to produce a thin stretched film with good thickness uniformity.
- Mw is 250,000 or more and less than 350,000
- the resin fluidity becomes more moderate, the thickness of the cast raw fabric sheet can be easily controlled, and a thin stretched film with good thickness uniformity can be produced. becomes easier.
- the number average molecular weight Mn of the first polypropylene resin is preferably 30,000 or more and 52,000 or less, more preferably 32,000 or more and 50,000 or less, and still more preferably 34,000 or more and 48,000 or less.
- the z-average molecular weight Mz of the first polypropylene resin is preferably 600,000 or more and 1,650,000 or less, more preferably 700,000 or more and 1,600,000 or less.
- the molecular weight distribution (Mw/Mn) of the first polypropylene resin is preferably 5.0 or more, more preferably 5.5 or more.
- the Mw/Mn of the first polypropylene resin is preferably 11.0 or less, more preferably 10.0 or less.
- moderate resin fluidity can be obtained during biaxial stretching, and an ultra-thin biaxially stretched propylene film without thickness unevenness can be obtained. It is preferable because it becomes easy to obtain.
- the molecular weight distribution Mw/Mn is the ratio of the weight average molecular weight Mw to the number average molecular weight Mn.
- the molecular weight distribution (Mz/Mn) of the first polypropylene resin is preferably 10 or more and 60 or less, more preferably 12 or more and 50 or less, and even more preferably 15 or more and 45 or less.
- the molecular weight distribution Mz/Mn is the ratio of the z-average molecular weight Mz to the number-average molecular weight Mn.
- the weight average molecular weight (Mw), number average molecular weight (Mn), z average molecular weight (Mz), and molecular weight distribution (Mw/Mn and Mz/Mn) of the polypropylene resin are gel It is a value measured using a permeation chromatograph (GPC) device. More specifically, it is a value measured using HLC-8121GPC-HT (trade name), a differential refractometer (RI) built-in high-temperature GPC measuring instrument manufactured by Tosoh Corporation. As a GPC column, three TSKgel GMHHR-H(20)HT manufactured by Tosoh Corporation are used by connecting them.
- GPC permeation chromatograph
- the column temperature is set to 140° C., and trichlorobenzene is passed as an eluent at a flow rate of 1.0 ml/10 minutes to obtain measured values of Mw and Mn.
- a standard polystyrene manufactured by Tosoh Corporation is used to prepare a calibration curve for the molecular weight M, and the measured values are converted into polystyrene values to obtain Mw, Mn and Mz.
- the melt flow rate (MFR) of the first polypropylene resin at 230° C. is preferably 8.0 g/10 minutes or less, more preferably 7.0 g/10 minutes or less, still more preferably 6.0 g/10 minutes or less. It is 0 g/10 minutes or less.
- the melt flow rate at 230° C. is preferably 3.5 g/10 minutes or more.
- the melt flow rate at 230°C is measured at 230°C under a load of 2.16 kg according to JIS K 7210-1999.
- the unit g/10 minutes of the melt flow rate is also called dg/min.
- the heptane-insoluble content of the first polypropylene resin is preferably 97.0% or more.
- the heptane-insoluble content is preferably 98.5% or less.
- the higher the heptane-insoluble content the higher the stereoregularity of the resin.
- the heptane-insoluble content (HI) is 97.0% or more and 98.5% or less, the crystallinity of the polypropylene resin in the polypropylene film is moderately improved due to moderately high stereoregularity, and at high temperatures voltage resistance is improved.
- the rate of solidification (crystallization) during cast raw sheet molding is moderate, and it has moderate stretchability.
- the method for measuring the heptane insolubles (HI) is according to the method described in Examples.
- the total ash content of the first polypropylene resin is as low as possible for electrical properties.
- the total ash content is preferably 50 ppm or less, more preferably 40 ppm or less, still more preferably 30 ppm or less based on the first polypropylene resin. Lower limits for total ash are, for example, 2 ppm, 5 ppm, and the like.
- the polypropylene resin may further contain a second polypropylene resin.
- the polypropylene film of the present embodiment preferably contains a second polypropylene resin in addition to the first polypropylene resin, and more preferably the resins constituting the polypropylene film are the first polypropylene resin and the second polypropylene resin.
- the content of the second polypropylene resin is preferably 50% by weight or less, more preferably 49% by weight or less, more preferably 45% by weight or less, relative to 100% by weight of the polypropylene resin. Preferably, 40% by weight or less is particularly preferred. Further, when the polypropylene resin contains the second polypropylene resin, the content of the second polypropylene resin is, with respect to the lower limit, for example, 1% by weight or more, 2% by weight or more, 5% by weight or more with respect to 100% by weight of the polypropylene resin. etc., preferably 10% by weight or more, more preferably 15% by weight or more, still more preferably 20% by weight or more, relative to 100% by weight of the polypropylene resin. Examples of the second polypropylene resin include isotactic polypropylene.
- the Mw of the second polypropylene resin is preferably 300,000 or more, more preferably 350,000 or more. Mw in the second polypropylene resin is preferably 450,000 or less, more preferably 400,000 or less.
- the Mn of the second polypropylene resin is preferably 40,000 or more and 54,000 or less, more preferably 42,000 or more and 50,000 or less, and still more preferably 44,000 or more and 48,000 or less.
- the Mz of the second polypropylene resin is preferably more than 1,550,000 and 2,000,000 or less, more preferably 1,580,000 or more and 1,700,000 or less.
- the ratio of Mw to Mn is preferably 5.5 or more, more preferably 7.0 or more, and particularly preferably 7.5 or more.
- the upper limit of Mw/Mn in the second polypropylene resin is, for example, 11.0, 10.0, 9.0, 8.5.
- the ratio of Mz to Mn (Mz/Mn) in the second polypropylene resin is preferably 30 or more and 40 or less, more preferably 33 or more and 37 or less.
- the melt flow rate at 230°C of the second polypropylene resin is preferably less than 4.0 g/10 minutes, more preferably 3.9 g/10 minutes or less, even more preferably 3.8 g/10 minutes or less. Also, the melt flow rate at 230° C. is preferably 1.0 g/10 minutes or more, more preferably 1.5 g/10 minutes or more, and even more preferably 2.0 g/10 minutes or more.
- the heptane-insoluble content of the second polypropylene resin is preferably 97.5% or more, more preferably 98.0% or more, still more preferably over 98.5%, and particularly preferably 98.6% or more.
- the heptane insoluble content is preferably 99.5% or less, more preferably 99.0% or less.
- the total ash content of the second polypropylene resin is as low as possible for electrical properties.
- the total ash content is preferably 50 ppm or less, more preferably 40 ppm or less, and even more preferably 30 ppm or less based on the second polypropylene resin. Lower limits for total ash are, for example, 2 ppm, 5 ppm, and the like.
- the total amount of the first polypropylene resin and the second polypropylene resin can be, for example, 90% by weight or more, can be 95% by weight or more, and can be 100% by weight when the entire polypropylene resin is 100% by weight. can also be
- the polypropylene resin can be produced using a generally known polymerization method. There are no particular restrictions as long as the polypropylene resin that can be used for the polypropylene film of the present embodiment can be produced. Examples of such polymerization methods include a gas phase polymerization method, a bulk polymerization method and a slurry polymerization method.
- the polymerization may be single-stage (single-stage) polymerization using one polymerization reactor, or may be multi-stage polymerization using at least two or more polymerization reactors. Furthermore, hydrogen or comonomers may be added to the reactor as molecular weight modifiers.
- a generally known Ziegler-Natta catalyst can be used as the catalyst for polymerization, and is not particularly limited as long as the polypropylene resin can be obtained.
- the catalyst may contain co-catalyst components and donors. Molecular weight, molecular weight distribution and the like can be controlled by adjusting the catalyst and polymerization conditions.
- the molecular weight, molecular weight distribution, etc. of the polypropylene resin are, for example, (i) conditions such as the polymerization method and temperature and pressure during polymerization, (ii) the shape of the reactor during polymerization, and (iii) the use of additives. It can be adjusted by appropriately selecting the presence/absence, type and amount used, (iv) the type and amount used of the catalyst, and the like.
- the molecular weight, molecular weight distribution, etc. of the polypropylene resin can be adjusted, for example, by a multistage polymerization reaction.
- the multistage polymerization reaction include the following methods.
- propylene and a catalyst are supplied to the first polymerization reactor.
- hydrogen as a molecular weight modifier is mixed in the amount necessary to reach the required molecular weight of the polymer.
- 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.
- the polymerization product of the first step is continuously sent to the next reactor along with additional propylene, catalyst, and molecular weight modifier, and subsequently the molecular weight is reduced to a lower or higher molecular weight from the first polymerization step.
- a second, conditioned polymerization is performed. By adjusting the yield (production volume) of the first and second reactors, it is possible to adjust the composition (structure) of the high molecular weight component and the low molecular weight component.
- the molecular weight, molecular weight distribution, etc. of the polypropylene resin can be adjusted by peroxide decomposition.
- peroxide decomposition a method of peroxidation treatment using a decomposing agent such as hydrogen peroxide or organic peroxide can be exemplified.
- a peroxide When a peroxide is added to a collapsible polymer such as polypropylene, a hydrogen abstraction reaction occurs from the polymer, and some of the polymer radicals produced recombine and cause a crosslinking reaction, but most of the radicals undergo secondary decomposition ( ⁇ -cleavage ) and split into two polymers with smaller molecular weights. That is, the higher the molecular weight of the component, the higher the probability that the decomposition proceeds. This increases the low-molecular-weight components and allows the composition of the molecular weight distribution to be adjusted.
- the content of the low-molecular-weight component by blending it is preferable to dry-mix or melt-mix at least two or more different molecular weight resins.
- a two-type polypropylene mixed system in which the main resin is mixed with about 1 to 40% by mass of an additive resin having a higher or lower average molecular weight is preferable because it is easy to adjust the amount of the low molecular weight component. used.
- melt flow rate may be used as a measure of the average molecular weight.
- the difference in MFR between the main resin and the additive resin should be about 1 to 30 g/10 minutes from the viewpoint of convenience during adjustment.
- a commercially available product can also be used as the polypropylene resin.
- the metallized polypropylene film Y may contain resins other than polypropylene resins (hereinafter also referred to as "other resins").
- the "other resin” is generally a resin other than the polypropylene resin that is used as the main component resin, and is not particularly limited as long as the intended polypropylene film can be 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- Butene copolymers, copolymers of ⁇ -olefins such as ethylene-butene copolymers, vinyl monomer-diene monomer random copolymers such as styrene-butadiene random copolymers, styrene-butadiene-styrene Examples thereof include vinyl monomer-diene monomer-vinyl monomer random copolymers such as block copolymers.
- the polypropylene film of the present invention can be contained in an amount that does not adversely affect the intended polypropylene film.
- the polypropylene film of the present invention may contain other resins in an amount of preferably 10 parts by mass or less, more preferably 5 parts by mass or less, based on 100 parts by mass of the polypropylene resin.
- the polypropylene film of the present invention may contain other resins in an amount of preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, based on 100 parts by mass of the polypropylene resin.
- the polypropylene film of the present invention may further contain at least one additive in addition to the resin component.
- the "additive” is an additive generally used for polypropylene, and is not particularly limited as long as the intended polypropylene film can be obtained.
- Additives include, for example, nucleating agents ( ⁇ crystal nucleating agents, ⁇ crystal nucleating agents), antioxidants, necessary stabilizers such as chlorine absorbers and ultraviolet absorbers, lubricants, plasticizers, flame retardants, agents, antistatic agents, inorganic fillers, organic fillers, and the like.
- the inorganic filler include barium titanate, strontium titanate, and aluminum oxide.
- Additives include, for example, a wide variety of additives used in polypropylene films for capacitors.
- the metal layer-integrated polypropylene film 10 shown in FIG. 4 is a schematic perspective view for describing one embodiment of the metallized polypropylene film Y.
- the metal layer-integrated polypropylene film 10 includes a biaxially stretched polypropylene film 20 and an insulating margin 40 (insulating groove: length in the width direction) continuous in the longitudinal direction of the film at one end in the width direction of the film.
- the thickness is not particularly limited as long as the area of the metal deposition electrode 30 is too small to significantly impair the capacitance when used as a capacitor, but for example, 2 mm or more) is laminated on the biaxially oriented polypropylene film 20 and a metal vapor deposition electrode 30 .
- the metal vapor deposition electrode 30 comprises a metal vapor deposition layer 30a laminated on the biaxially stretched polypropylene film 20 so as to be in direct contact with the biaxially stretched polypropylene film 20, and an electrode extraction part 30b formed on a part of the metal vapor deposition layer 30a. and
- the metal deposition layer 30a functions as an electrode when the metal layer-integrated polypropylene film is used as a capacitor.
- the electrode lead-out portion 30b is a so-called heavy edge portion.
- Metals used for the metal vapor deposition layer 30a and the electrode lead-out portion 30b include, for example, single metals such as zinc, lead, silver, chromium, aluminum, copper, and nickel, mixtures thereof, and alloys thereof. Although they can be used, zinc and aluminum are preferred in consideration of the environment, economy and capacitor performance.
- the layer structure of the metal layer is not particularly limited.
- the metal layer may be a single layer consisting of one layer, or may be a plurality of layers having the same or different compositions.
- the thickness of the metal deposition layer 30a and the electrode lead-out portion 30b is controlled by film resistance (resistance value per unit area, unit: ⁇ /sq). Since the resistance value is inversely proportional to the thickness, the lower the film resistance, the thicker the film thickness.
- a dielectric breakdown may occur at a portion of the metal-layer-integrated polypropylene film 10 that is weak in withstand voltage.
- heat is generated instantaneously, so that the metal deposited layer 3a evaporates and the insulation recovers (self-healing). Evaporation of the vapor-deposited metal layer 30a (self-healing occurs) restores the function of the capacitor, making it possible to use it continuously.
- the easiness of evaporation (the easiness of occurrence of self-healing) of the metal deposition layer 30a changes depending on the film resistance (thickness).
- the film resistance of the metal deposition layer 30a is preferably 1 ⁇ /sq or more, more preferably 5 ⁇ /sq or more. If the film resistance is lower than 1 ⁇ /sq, evaporation of the metal deposition layer 30a is difficult to occur (self-healing is difficult to occur), and leakage current flows due to dielectric breakdown, which increases the risk of ignition due to heat generation, which is preferable. do not have.
- the film resistance of the metal deposition layer 30a is preferably 30 ⁇ /sq or less, more preferably 27 ⁇ /sq or less. If the film resistance exceeds 30 ⁇ /sq, evaporation of the vapor-deposited metal layer 30a is likely to occur (self-healing is likely to occur), which is not preferable because the capacity of the capacitor will decrease significantly.
- the film resistance of the electrode lead-out portion 30b (heavy edge) is preferably 1 ⁇ /sq or more and 7 ⁇ /sq or less, more preferably 2 ⁇ /sq or more and 6 ⁇ /sq or less.
- the polypropylene film is preferably biaxially oriented as described above.
- the biaxially stretched polypropylene film can be produced by a generally known method for producing a biaxially stretched polypropylene film.
- a cast sheet is produced from a polypropylene resin composition obtained by mixing the first polypropylene resin, the second polypropylene resin, or the first polypropylene resin with other resins, additives, etc. as necessary. and then biaxially stretching the cast sheet.
- the heating and melting temperature in cast sheet production is set to a relatively high temperature
- the cooling drum temperature in cast sheet production is set to a relatively high temperature
- longitudinal stretching It is preferable to set the temperature to a relatively high temperature and appropriately adjust the stretching conditions.
- the heating and melting temperature in cast sheet production is set to a relatively high temperature
- the cooling drum temperature or longitudinal stretching temperature in cast sheet production is set to a relatively high temperature. etc. is preferred.
- the method for preparing the polypropylene resin composition is not particularly limited, but the first polypropylene resin, the second polypropylene resin, or the polymerized powder or pellets of the first polypropylene resin are mixed with other resins, if necessary.
- additives etc. a method of dry blending using a mixer or the like, the first polypropylene resin, the second polypropylene resin, or the polymerized powder or pellets of the first polypropylene resin, if necessary, other resins, additives and the like, and a method of supplying to a kneader and melt-kneading to obtain a melt-blended resin composition.
- the mixer and kneader are not particularly limited.
- the kneader may be of single-screw type, twin-screw type, or multi-screw type. In the case of a screw type with two or more shafts, it may be a co-rotating kneading type or a counter-rotating kneading type.
- the kneading temperature is not particularly limited as long as good kneading is obtained, but it is preferably in the range of 170 to 320°C, more preferably in the range of 200 to 300°C, and still more preferably. is in the range of 230°C to 270°C.
- the kneader may be purged with an inert gas such as nitrogen.
- the melt-kneaded resin can be pelletized to an appropriate size using a generally known granulator to obtain pellets of the melt-blended resin composition.
- the primary agent as the antioxidant described in the section on additives can be added.
- the content is preferably 1000 mass ppm to 5000 mass ppm (by mass when the resin component is taken as a whole) relative to the mass of the resin component.
- Most of the antioxidants for this purpose are consumed during the molding process in the extruder, and hardly remain in the film after film formation.
- the hindered phenol-based antioxidant having a carbonyl group described in the section on additives above can be added to the polypropylene resin composition as a secondary agent.
- the polypropylene resin composition contains a hindered phenolic antioxidant having a carbonyl group
- its content is preferably 100 mass ppm to the mass of the resin component (by mass when the resin component is taken as a whole). 10000 mass ppm, more preferably 3000 mass ppm to 7000 mass ppm. Not a little hindered phenolic antioxidants having carbonyl groups are also consumed in the extruder.
- the polypropylene resin composition does not contain a primary agent
- a larger amount of hindered phenol-based antioxidant having a carbonyl group can be used. This is because the consumption of the hindered phenolic antioxidant having a carbonyl group increases in the extruder.
- the polypropylene resin composition does not contain a primary agent and contains a hindered phenolic antioxidant having a carbonyl group, the content is relative to the mass of the resin component (when the resin component is taken as a whole, the mass ) 4000 mass ppm to 8000 mass ppm or less.
- the cast sheet is obtained by supplying pellets of a dry blend resin composition and / or melt blend resin composition prepared in advance to an extruder, heating and melting, passing through a filtration filter, and then relatively high temperature, preferably 255 ° C. ⁇ 320 ° C., more preferably 260 ° C. to 300 ° C., more preferably 265 to 280 ° C. Heat and melt and melt and extrude from a T-die at a relatively high temperature, preferably 96 ° C. to 120 ° C., more preferably 96 ° C. to 110 C., more preferably 96 to 100.degree. At this time, it is preferable to press the melt-extruded resin composition against the metal drum with an air knife.
- the surface on the side that contacts the metal drum is the first surface, and the opposite surface (surface on the air knife side) is the second surface.
- the thickness of the cast sheet is not particularly limited as long as the desired polypropylene film can be obtained, but it is preferably 0.05 mm to 2 mm, more preferably 0.1 mm to 1 mm.
- polypropylene is not a little subjected to thermal deterioration (oxidation deterioration) and shear deterioration.
- the degree of progress of such deterioration is determined by nitrogen purge in the extruder (suppression of oxidation), screw shape in the extruder (shear force), internal shape of the T-die during casting ( shear force), the amount of antioxidant added (suppression of oxidation), the winding speed during casting (elongation force), and the like.
- the biaxially oriented polypropylene film can be produced by stretching the cast sheet.
- a sequential biaxial stretching method is preferable as the stretching method.
- the cast sheet is first kept at a relatively high temperature, preferably 142 to 180° C., more preferably 143 to 160° C., more preferably 144 to 150° C., and rolls provided with a speed difference. It is stretched in the machine direction preferably 3 to 7 times, more preferably 4 to 6 times, and immediately cooled to room temperature.
- the stretched film is led to a tenter, preferably 150 to 160 ° C., more preferably 150 to 159 ° C., still more preferably 150 to 158 ° C., still more preferably 150 to 157 ° C. in the width direction at a temperature of 3 to 157 ° C.
- a tenter preferably 150 to 160 ° C., more preferably 150 to 159 ° C., still more preferably 150 to 158 ° C., still more preferably 150 to 157 ° C. in the width direction at a temperature of 3 to 157 ° C.
- the longitudinal stretching speed is preferably 100-100000%/sec, more preferably 1000-80000%/sec, even more preferably 60000-70000%/sec, and even more preferably 65000-70000%/sec.
- the transverse stretching speed is preferably 10 to 800%/sec, more preferably 100 to 600%/sec, even more preferably 300 to 400%/sec, still more preferably 300 to 350%/sec.
- the film wound in a roll is subjected to aging treatment in an atmosphere of about 20 to 45 ° C., and then slit (cut) to the desired product width by a slitter or the like while being rewound (while being unwound). , respectively, are rewound.
- the polypropylene film is preferably subjected to corona discharge treatment on-line or off-line after completion of the stretching and heat setting steps.
- corona discharge treatment By performing the corona discharge treatment, it is possible to improve the adhesive properties in the post-process such as the metal vapor deposition process.
- Corona discharge treatment can be performed using a known method. It is preferable to use air, carbon dioxide gas, nitrogen gas, or a mixed gas thereof as the atmospheric gas.
- the metallized polypropylene film Y can be obtained, for example, by a method including laminating a metal layer on one side or both sides of the polypropylene film of the present invention.
- methods for laminating a metal layer on one side or both sides of the polypropylene film of the present invention include a vacuum deposition method and a sputtering method.
- a vacuum deposition method is preferable from the viewpoint of productivity and economy.
- Examples of the vacuum deposition method include a crucible method and a wire method in general, but the method is not particularly limited, and an optimum method can be selected as appropriate.
- the thickness of the metal layer is controlled by film resistance.
- the film resistance of the metal vapor deposition layer 3a is preferably 1 ⁇ / ⁇ /sq or more, more preferably 5 ⁇ / ⁇ /sq or more. Also, the film resistance of the vapor-deposited metal layer 3a is preferably 30 ⁇ / ⁇ /sq or less, more preferably 27 ⁇ / ⁇ /sq or less.
- the film resistance of the electrode lead-out portion 3b is preferably 1 ⁇ / ⁇ /sq or more and 7 ⁇ / ⁇ /sq or less, and is preferably 2 ⁇ / ⁇ /sq or more and 6 ⁇ / ⁇ /sq or less. It is more preferable to have
- the margin pattern when laminating the metal layer by vapor deposition is not particularly limited, but from the viewpoint of improving characteristics such as security of the capacitor, a so-called fishnet pattern or T-margin pattern is used. It is preferred to apply a pattern containing special margins on one side of the film. Security is improved, and it is also effective in terms of prevention of capacitor destruction and short circuit.
- a post-heating treatment After laminating a metal layer on one side or both sides of the metallized polypropylene film Y, a post-heating treatment may be performed.
- Conditions for the post-heating treatment include application of silicone oil heated to 120 to 130° C., for example.
- a preferred method for producing the metal layer-integrated polypropylene film (metallized polypropylene film Y) of the present invention will be described below with reference to FIG.
- the vapor deposition conditions mainly, the voltage speed ratio per unit width of the cooling roll and the amount of discharge
- the cumulative dielectric breakdown point density can be suppressed.
- FIG. 5 is a schematic diagram for explaining the manufacturing method of the metal layer-integrated polypropylene film.
- the metal layer-integrated polypropylene film is preferably manufactured using the manufacturing apparatus described below.
- the metal-layer-integrated polypropylene film manufacturing apparatus includes a dielectric film supply section 101, an insulating margin forming section 102, a special vapor deposition pattern margin forming section 103, a metal vapor deposition section 104, a DC magnetron A discharge electrode 105 and a metal layer integrated film winding unit 106 are provided.
- the dielectric film supply unit 101 supports the biaxially stretched polypropylene film roll 2R around which the biaxially stretched polypropylene film 20 is wound, and supplies the biaxially stretched polypropylene film 2.
- the biaxially oriented polypropylene film 20 supplied from the biaxially oriented polypropylene film roll 2R is conveyed to the insulating margin forming section 102. As shown in FIG.
- the insulating margin forming part 102 applies oil in a pattern corresponding to the pattern of the insulating margin 4 to the metal deposition surface 20a of the biaxially stretched polypropylene film 20 to form an oil mask.
- the oil mask is for preventing metal particles from adhering to the insulation margin portion of the metal layer integrated polypropylene film 10 during the vapor deposition process.
- the insulating margin forming part 102 vaporizes the oil stored in the oil tank and directly applies the oil to the metal deposition surface 20a of the polypropylene film 2 from a nozzle (slit) provided in the tank to form an oil mask.
- the special vapor deposition pattern margin forming unit 103 applies oil to the metal vapor deposition surface 20a of the biaxially stretched polypropylene film 2 in a pattern roughly corresponding to the electrode pattern of the metal vapor deposition layer 30a to form an oil mask.
- the oil mask is for preventing metal particles from adhering to the vertical margins and horizontal margins of the metal layer integrated polypropylene film 1 during the vapor deposition process.
- the special deposition pattern margin forming unit 103 has an oil tank 103a, an anilox roll 103b, a transfer roll 103c, a plate roll 103d, and a backup roll 103e.
- the oil tank 103a evaporates the stored oil and ejects it from a nozzle.
- the anilox roll 103b and the transfer roll 103c rotate with the oil jetted from the nozzle of the oil tank 103a adhered to their outer peripheral surfaces.
- the backup roll 103e faces the plate roll 103d through the polypropylene film 2 and contacts the cooling roll contact surface 20b of the biaxially stretched polypropylene film 2. As shown in FIG.
- the biaxially oriented polypropylene film 20 that has passed through the insulating margin forming section 102 and the special vapor deposition pattern margin forming section 103 is conveyed to the vapor deposition section 104 .
- the vapor deposition section 104 includes metal vapor generation sections 104a and 104b, and a cooling roll 104c facing the metal vapor generation sections 104a and 104b with the biaxially stretched polypropylene film 20 interposed therebetween.
- the metal vapor generation unit 104a generates metal vapor by supplying it on a heated boat by passing an electric current through a metal wire that is the material of the metal vapor deposition layer 30a, and the metal vapor is applied to the biaxially stretched polypropylene film 20. is vapor-deposited on the metal vapor-deposited surface 20a.
- the metal vapor generator 104b heats and evaporates the metal that is the material of the electrode extraction part 3b to generate metal vapor.
- the metal vapor deposition layer in the electrode lead-out portion 30b portion becomes thicker than the metal vapor deposition layer in the other portion, and a heavy edge structure is formed.
- the metal vapor generated in the metal vapor generating units 104a and 104b adheres to the portions other than the oil mask formed on the metal vapor deposition surface 20a of the biaxially stretched polypropylene film 20, thereby forming the metal vapor deposition electrode 30.
- a voltage is applied to the chill roll 104C, and the chill roll contact surface 20b of the biaxially stretched polypropylene film 20 is brought into close contact with the chill roll 104C by the voltage application to cool the biaxially stretched polypropylene film 20.
- the degree of close contact of the cooling roll contact surface 2b with the cooling roll 104C is proportional to the voltage (V) applied to the cooling roll 104C and inversely proportional to the width (m) of the cooling roll and the deposition rate (m/min). For this reason, the higher the voltage speed ratio (unit: V min/m 2 ) per unit width of the cooling roll, the closer the cooling roll contact surface 2b of the biaxially oriented polypropylene film 20 is to the cooling roll 104C, and the cooling efficiency increases.
- the voltage speed ratio per unit width of the cooling roll is preferably 0.20 V ⁇ min/m 2 or more and 0.45 V ⁇ min/m 2 or less. If the voltage speed ratio per unit width of the chill roll is smaller than 0.20 V min/m 2 , the chill roll contact surface 20b of the biaxially stretched polypropylene film 2 does not sufficiently adhere to the chill roll 104C, resulting in a decrease in cooling efficiency.
- the biaxially oriented polypropylene film 20 or the metal layer-integrated polypropylene film 10 is thermally damaged, and as a result, the voltage resistance of the metal layer-integrated polypropylene film 1 is lowered, and when it is made into a capacitor Dielectric breakdown and heat generation shorten the life.
- the chill roll contact surface 20b of the biaxially stretched polypropylene film 20 is sufficiently adhered to the chill roll 104C, so the cooling efficiency is improved, and the heat damage of the biaxially oriented polypropylene film 20 or the metal layer-integrated polypropylene film 10 is reduced, but between the biaxially oriented polypropylene film 20 and the roll 104C, or the metal layer-integrated polypropylene film 1 and the roll 104C, and when the discharge occurs, the biaxially stretched polypropylene film 20 or the metal layer integrated polypropylene film 10 is electrically damaged and damaged, and the discharge Even if it does not occur, the metal layer-integrated polypropylene film 10 is likely to be charged, and when the metal layer-integrated polypropylene film 10 is wound into a roll by the metal layer-integrated film winding unit 106, electrical damage due to static electricity discharge of the metal layer-integrated polypropylene film
- the biaxially stretched polypropylene film 20 or the metal layer integrated polypropylene film 10 is damaged by electric damage, the voltage resistance is lowered, and when it is made into a capacitor, the life is likely to be shortened due to dielectric breakdown or heat generation. .
- the slipperiness deteriorates, so wrinkles are likely to occur during the winding at the metal layer integrated film winding unit 106 or during the element winding process for manufacturing a capacitor.
- buckling is likely to occur due to deterioration of slipperiness due to electrification.
- the voltage speed ratio per unit width of the chill roll is more preferably 0.24 V ⁇ min/m 2 or more and 0.41 V ⁇ min/m 2 or less.
- the temperature of the cooling roll 104C is preferably -18°C or lower, more preferably -19°C or lower.
- the metal-layer-integrated polypropylene film 1 formed by forming the metal deposition electrodes 3 on the biaxially stretched polypropylene film 20 in the deposition section 104 passes through the static electricity removal section 105 .
- the static electricity remover 105 includes DC magnetron discharge electrodes 105a, 105b, 105c, and 105d, and power is supplied to the DC magnetron discharge electrodes 105a, 105b, 105c, and 105d while argon gas is supplied. As a result, argon gas ions are generated.
- the static electricity of the metal layer-integrated polypropylene film 1 is neutralized by the argon gas ions, and the metal layer-integrated polypropylene film 1 is discharged.
- the degree of neutralization of static electricity given to the metal layer integrated polypropylene film 10 by the argon gas ions can be represented by the amount of discharge, and the amount of discharge is the total power of the DC magnetron discharge electrode portions 105a, 105b, 105c, and 105d.
- the discharge amount is preferably 1.5 W ⁇ min/m 2 or more and 3.7 W ⁇ min/m 2 or less.
- the amount of discharge is greater than 3.7 W ⁇ min/m 2 , the discharge from the DC magnetron discharge electrode portions 105a, 105b, 105c, and 105d becomes too strong, and the metal layer integrated polypropylene film 10 receives electrical damage. In addition, even when no discharge occurs, the metal layer-integrated polypropylene film 10 is charged by argon gas ions. On the other hand, if the amount of discharge is less than 1.5 W ⁇ min/m 2 , neutralization of static electricity in the metal layer-integrated polypropylene film 10 is insufficient and the film is charged.
- the metal-layer-integrated polypropylene film 1 is damaged by electric damage, the withstand voltage is lowered, and when it is made into a capacitor, the life is likely to be shortened due to dielectric breakdown or heat generation.
- the metal layer-integrated polypropylene film 10 is charged, when the metal layer-integrated polypropylene film 10 is wound into a roll by the metal layer-integrated film winding unit 106, electrical damage occurs due to the discharge of static electricity from the metal layer-integrated polypropylene film 10. It causes damage to the layer-integrated polypropylene film 10 .
- the metal-layer-integrated polypropylene film 10 If the metal-layer-integrated polypropylene film 10 is damaged, the withstand voltage is lowered, and when it is used as a capacitor, the life is likely to be shortened due to dielectric breakdown or heat generation. In addition, when the metal layer integrated polypropylene film 10 is charged, the slipperiness deteriorates, so wrinkles are likely to occur during the winding at the metal layer integrated film winding unit 106 or during the element winding process for manufacturing a capacitor. In addition, in the press processing step after element winding in capacitor production, buckling is likely to occur due to deterioration of slipperiness due to electrification.
- the discharge amount is 1.9 W ⁇ min/m 2 or more and 3.3 W ⁇ min/m 2 or less.
- the metal layer-integrated polypropylene film 10 that has passed through the static electricity removal section 105 is conveyed to the metal layer-integrated film winding section 106 and wound up to become a metal layer-integrated polypropylene film roll 1R.
- the metal-deposited electrode 3 is formed on the metal-deposited surface 20a of the polypropylene film 20, and the metal-layer-integrated polypropylene film 10 can be obtained.
- Capacitor A capacitor (capacitor element) can be formed using the metallized polypropylene film X or the metallized polypropylene film Y (metal layer-integrated polypropylene film) of the present invention.
- the structure of the capacitor is not particularly limited as long as it has the metallized polypropylene film of the present invention.
- the film is wrapped.
- the metal film of the metallized polypropylene film of the present invention and the biaxially stretched polypropylene film are alternately laminated, and further, the insulating margin part is on the opposite side, so that the two metal films are arranged in a pair.
- Polypropylene film is overlapped and wound.
- the winding machine to be used is not particularly limited, and for example, an automatic winding machine 3KAW-N2 type manufactured by Kaito Seisakusho Co., Ltd. can be used.
- the resulting winding is usually pressed. Promoting tight winding and element molding of the capacitor by pressing. From the viewpoint of controlling and stabilizing the interlayer gap, the optimum value of the pressure to be applied varies depending on the thickness of the metallized polypropylene film, and is, for example, 2 to 20 kg/cm 2 .
- a capacitor is produced by thermally spraying a metal on both end surfaces of the winding to provide metallikon electrodes. After that, a predetermined heat treatment may be further applied.
- the capacitor can be heat treated at a temperature of 80 to 125° C. for 1 hour or more under normal pressure or under vacuum (hereinafter sometimes referred to as “thermal aging”).
- the heat-treating temperature is usually 80°C or higher, preferably 90°C or higher.
- the heat treatment temperature is usually 130° C. or lower, preferably 125° C. or lower.
- Examples of methods for heat-treating a capacitor include a method using a constant temperature bath and a method using high-frequency induction heating in a vacuum atmosphere, and it is preferable to adopt a method using a constant temperature bath.
- the heat treatment time is preferably 1 hour or more, more preferably 10 hours or more, from the viewpoint of mechanical and thermal stability, in order to prevent molding defects such as heat wrinkles and molding. , 20 hours or less.
- Lead wires are usually welded to the metallikon electrodes of heat-aged capacitors. Moreover, in order to provide weather resistance and, in particular, to prevent moisture deterioration, it is preferable to enclose the capacitor in a case and pot it with an epoxy resin.
- a capacitor obtained using the metallized polypropylene film X or the metallized polypropylene film Y of the present invention has excellent withstand voltage, durability and reliability.
- the melt passed through the polymer filter was extruded using a T-die, wound around a metal drum whose surface temperature was kept at 96° C., and solidified to produce a cast material sheet having a thickness of about 138 ⁇ m.
- This cast raw fabric sheet was stretched 5 times in the machine direction at a temperature of 146° C., immediately cooled to room temperature, and then stretched 10 times in the transverse direction at a temperature of 165° C. in a tenter to obtain a sheet with a thickness of 2.5.
- a 3 ⁇ m biaxially oriented polypropylene film was obtained.
- a metal layer was laminated on the biaxially stretched polypropylene film by a known method using a vapor deposition apparatus to obtain a metallized polypropylene film.
- Vapor deposition was carried out at a cooling roll temperature of ⁇ 23° C., a film resistance of 20 ⁇ / ⁇ , and a film transport speed of 150 m/min.
- Comparative Example 2a A metallized polypropylene film was obtained in the same manner as in Comparative Example 1a except that the opening size of the polymer filter was changed to 20 ⁇ m.
- Example 1a A metallized polypropylene film X was obtained in the same manner as in Comparative Example 1a except that the opening size of the polymer filter was changed to 10 ⁇ m.
- Example 2a A metallized polypropylene film X was obtained in the same manner as in Comparative Example a1, except that the opening size of the polymer filter was changed to 5 ⁇ m.
- Comparative Example 4a A metallized polypropylene film was obtained in the same manner as in Comparative Example 2a, except that PP resin B was used instead of the polypropylene resin pellets.
- Example 5a A metallized polypropylene film was obtained in the same manner as in Example 1a, except that PP resin B was used instead of the polypropylene resin pellets.
- Example 6a A metallized polypropylene film was obtained in the same manner as in Example 2a except that the polypropylene resin pellets were changed to PP resin B.
- a conductive substrate was formed by laminating a brass plate (320 mm ⁇ 250 mm), conductive rubber (280 mm ⁇ 150 mm) and aluminum foil (280 mm ⁇ 150 mm) in this order.
- An insulating film polypropylene A sheet (outer shape: 280 mm x 150 mm, thickness: 22 ⁇ m) was placed. Then, a laminate was produced by placing a metallized polypropylene film for measurement on the insulating film.
- the metallized polypropylene film for measurement is in contact with the entire surface of the conductive substrate (specifically, the aluminum foil of the conductive substrate) exposed through the opening, and the metal of the metallized polypropylene film It was placed so that the deposition surface was exposed on the surface side. Then, a cylindrical brass electrode (25 mm in diameter and 65 mm in height) was placed on the exposed metal deposition surface.
- the brass plate of the conductive base material and the brass electrode were electrically connected by a DC power supply. Then, in an environment of 20 ° C., after applying a voltage (starting voltage) of 900 V (391 (V / ⁇ m)) for 1 minute, the number of dielectric breakdown points in the area arranged in the opening of the metallized polypropylene film for measurement was counted visually. When dielectric breakdown occurred in the metallized polypropylene film, the dielectric breakdown portion was visually observed as cloudy compared to the non-dielectric breakdown portion, so the number of such portions was counted as the dielectric breakdown portion. After this counting, a voltage of 1000 V was applied for 1 minute, and then the number of dielectric breakdown points was visually counted in the same manner.
- starting voltage 900 V (391 (V / ⁇ m)
- the voltage was increased by 100 V (that is, applied in order of 435 (V/ ⁇ m), 478 (V/ ⁇ m), 521 (V/ ⁇ m), 565 (V/ ⁇ m), and 609 (V/ ⁇ m)).
- the number of dielectric breakdown points generated when each voltage was applied for 1 minute was visually counted, and all applications were terminated.
- the value obtained by dividing the cumulative number of dielectric breakdown points generated by the third application (1100 V, 478 (V / ⁇ m)) after all the applications are completed by the area of the opening (100 mm ⁇ 10 mm 10 cm 2 ), The number of dielectric breakdown points (pieces/cm 2 ) of the metallized polypropylene film was used. In addition, the value obtained by multiplying the dielectric breakdown score (pieces/cm 2 ) by the thickness (2.3 ⁇ m) of the metallized polypropylene film is the thickness-converted dielectric breakdown score (pieces/cm 2 ⁇ m) of the metallized polypropylene film. did.
- the total projection volume was obtained by measuring the surface shape using a three-dimensional surface roughness evaluation method using an optical interference non-contact surface shape measuring machine. Specifically, the total projection volume was measured using "VertScan 2.0 (model: R5500GML)" manufactured by Ryoka Systems as an optical interference non-contact surface shape measuring instrument. In such measurements, WAVE mode was used, a 530 white filter and a ⁇ 20 objective lens were used, and measurements of 240 ⁇ m ⁇ 180 ⁇ m per field were performed at arbitrary 10 locations on the film surface to be measured. The obtained data was subjected to noise removal processing with a median filter, and then subjected to Gaussian filter processing with a cutoff value of 30 ⁇ m to remove undulation components.
- the voltage was increased by 50 V, and this operation was repeated until the rate of change in capacity exceeded -1%, and the voltage was applied cumulatively. From the voltage before and after exceeding -1%, the voltage at -1% was obtained by linear interpolation (interpolation). Two samples were tested, and the average value was calculated.
- the method of measuring the capacitance was as follows.
- a 4-terminal probe 9140 was attached to an LCR Hitester 3522-50 manufactured by Hioki Electric Co., Ltd.
- Two terminals (lead wires) of the capacitor were pinched with a 4-terminal probe 9140, and an AC voltage of 0.1 V and 1 kHz was applied from the built-in power supply of LCR HiTester 3522-50.
- the capacitance value was read. Measurement conditions other than those described here conformed to "4.2.2 Capacitance" of JIS C 5101-16:2009.
- Table 1 shows the measurement conditions and measurement results of the thickness of the metallized polypropylene film and the dielectric breakdown point. Table 1 also shows the measurement results of the total projection volume of the metallized polypropylene film, the ejection stability evaluation results, and the results of the short-time pressure resistance test.
- V1 means the first voltage (starting voltage (V))
- D1 means the thickness ( ⁇ m) of the metallized polypropylene film
- Vn means the ending voltage (sixth applied voltage).
- Figures 2 (A) and (B) show the measurement results of the number of dielectric breakdown points.
- the metallized polypropylene films obtained in Examples 1a and 2a have a low dielectric breakdown point and excellent dielectric breakdown resistance. It was also found that the metallized polypropylene films obtained in Examples 1a and 2a met the standards of metallized polypropylene films in the total projection volume, discharge stability and short-time pressure resistance test.
- the resin A shown in Table 1 is a product manufactured by Prime Polymer Co., Ltd.
- Resin B is S802M manufactured by Daehan Yuka Co., Ltd.
- Resins A and B are both linear homopolypropylene resins.
- Table 1 shows the number average molecular weight (Mn), weight average molecular weight (Mw), z average molecular weight (Mz), molecular weight distribution (Mw/Mn), molecular weight distribution (Mz/Mn), and melt flow of linear homopolypropylene resin. rate (MFR) and heptane insolubles (HI). These values are values in the form of raw material resin pellets.
- the measuring method is as follows.
- HLC-8121GPC-HT a high-temperature GPC device with a built-in differential refractometer (RI) manufactured by Tosoh Corporation.
- RI differential refractometer
- TSKgel GMHHR-H(20)HT manufactured by Tosoh Corporation were used by connecting them.
- trichlorobenzene was used as an eluent and measured at a flow rate of 1.0 ml/min.
- melt flow rate (MFR) For each resin, the melt flow rate (MFR) in the form of raw resin pellets was measured using a melt indexer manufactured by Toyo Seiki Co., Ltd. according to JIS K 7210 condition M. measured by Specifically, first, a sample weighed to 4 g was inserted into a cylinder set to a test temperature of 230° C. and preheated for 3.5 minutes under a load of 2.16 kg. Thereafter, the weight of the sample extruded from the bottom hole was measured for 30 seconds to obtain the MFR (g/10min). The above measurements were repeated three times, and the average value was taken as the measured value of MFR. Table 1 shows the results.
- the resulting unstretched cast sheet was kept at a temperature of 146° C., passed between rolls with a speed difference, stretched 5 times in the machine direction at a stretching speed of 67300%/sec, and immediately cooled to room temperature. Subsequently, the stretched film was led to a tenter and stretched 10 times in the width direction at a temperature of 155° C. at a stretching rate of 335%/sec, followed by relaxation and heat setting. Next, the film surface (metal drum contact side) was subjected to corona discharge treatment in the atmosphere at a treatment rate of 25 W ⁇ min/m 2 , then wound up and subjected to aging treatment in an atmosphere of about 30°C. Thus, a biaxially stretched polypropylene film having a thickness of 2.3 ⁇ m was obtained.
- marked lines are marked at positions 15 mm from each end of 130 mm in the MD direction. At this time, the interval between the marked lines is 100 mm. Also, for the three samples for which the 120° C. heat shrinkage in the TD direction was to be measured, marked lines were marked at positions 15 mm from each end of 130 mm in the TD direction. At this time, the interval between the marked lines is 100 mm. Then, each sample with the marked line was suspended without load in a hot air circulating constant temperature bath at 120° C. so that the direction of the 130 mm cut was vertical, and held for 15 minutes.
- Thermal shrinkage rate (%) (marked line interval before heating - marked line interval after heating) / before heating
- the thermal shrinkage rate (%) was calculated for each sample using the marked line spacing of x 100.
- the average value of the thermal contraction rate of three samples for which the 120°C thermal contraction rate in the MD direction was measured was taken as the 120°C thermal contraction rate (%) in the MD direction.
- the average value of the thermal contraction rate of three samples for which the 120° C. thermal contraction rate in the TD direction was measured was defined as the 120° C. thermal contraction rate (%) in the TD direction.
- the 120°C heat shrinkage in the MD direction of the biaxially stretched polypropylene film was 3.7%, and the 120°C heat shrinkage in the TD direction was 0.4%.
- the 140°C heat shrinkage in the MD direction of the biaxially stretched polypropylene film was 6.1%
- the 140°C heat shrinkage in the TD direction was 3.1%.
- a tensile test was performed using a tensile compression tester (manufactured by Minebea Co., Ltd.) under test conditions (measuring temperature of 23° C., distance between chucks of 100 mm, tensile speed of 200 mm/min). Then, the tensile modulus of elasticity (GPa) in the MD direction and the tensile modulus of elasticity (GPa) in the TD direction were each determined by automatic analysis using data processing software built into the tester.
- the tensile modulus of elasticity in the MD direction of the biaxially stretched polypropylene film was 2.76 GPa
- the tensile elasticity modulus in the TD direction was 4.56 GPa.
- FIG. 4 shows a schematic diagram of the metal layer-integrated polypropylene film. A schematic diagram of the manufacturing apparatus is shown in FIG.
- Example 2b A metal layer-integrated polypropylene film was obtained in the same manner as in Example 1b, except that the voltage speed ratio per unit width of the chill roll was 0.21 V ⁇ min/m 2 .
- Example 3b A metal layer-integrated polypropylene film was obtained in the same manner as in Example 1b, except that the voltage speed ratio per unit width of the chill roll was 0.44 V ⁇ min/m 2 .
- Example 4b A metal layer-integrated polypropylene film was obtained in the same manner as in Example 1b, except that the amount of discharge was 1.6 W ⁇ min/m 2 .
- Example 5b A metal layer-integrated polypropylene film was obtained in the same manner as in Example 1b, except that the amount of discharge was 3.6 W ⁇ min/m 2 .
- Example 1b A metal layer-integrated polypropylene film was obtained in the same manner as in Example 1b, except that the voltage speed ratio per unit width of the chill roll was 0.18 V ⁇ min/m 2 .
- Example 2b A metal layer-integrated polypropylene film was obtained in the same manner as in Example 1b, except that the voltage speed ratio per unit width of the chill roll was 0.47 V ⁇ min/m 2 .
- the two sheets were combined and wound for 1350 turns using an automatic winding machine 3KAW-N2 manufactured by Kaito Seisakusho at a winding speed of 4 m/sec, a winding tension of 180 g, and a contact roller contact pressure of 260 g.
- 3KAW-N2 manufactured by Kaito Seisakusho at a winding speed of 4 m/sec, a winding tension of 180 g, and a contact roller contact pressure of 260 g.
- the wound element was flattened by pressing with a load of 5.9 kgf/cm 2 .
- Capacitor Zinc metal was thermally sprayed onto the end face of the element flattened by pressing in the above (7-1) while the pressing load was being applied.
- the thermal spraying conditions were a feed speed of 20 mm/s, a thermal spraying voltage of 21 V, and a thermal spraying pressure of 0.4 MPa. was heat-treated for 15 hours in a vacuum constant temperature bath to heat cure. A flat film capacitor was thus obtained.
- lead wires were soldered to the element end faces of the flat film capacitor and sealed with epoxy resin. Curing of the epoxy resin was performed by heating at 90° C. for 2.5 hours and then heating at 120° C. for 2.5 hours. All the capacitors produced had a capacitance of 50 ⁇ F ( ⁇ 3 ⁇ F). The resulting capacitors were used in the following six tests.
- Capacitor high temperature short-term withstand voltage test Capacitance change rate
- the initial capacitance (C0) of the obtained capacitor before the test was measured using an LCR Hitester 3522-50 manufactured by Hioki Electric Co., Ltd.
- a DC voltage of 325 V/ ⁇ m was applied to the capacitor for 10 seconds in a constant temperature bath at 105°C.
- Capacitor high voltage application test (insulation resistance value) The resulting capacitor was placed in a constant temperature bath at 105° C. and kept under a DC voltage of 1200 V for 10 minutes.
- a shielding box SME-8350 is connected to a super insulation resistance tester DSM8104 manufactured by Hioki Electric Co., Ltd., a capacitor after 10 minutes is placed in the shielding box, a DC voltage of 500 V is applied, and the insulation resistance value after 1 minute ( IR10) was read.
- Two samples were tested, and the average insulation resistance (IR10) was evaluated according to the following criteria. Tables 3 and 4 show the results.
- Laminate 1 Metallized polypropylene film 1a: Biaxially stretched polypropylene film 1b: First metal film 2: Conductive substrate 3: Insulating film 3a: Opening 3b: Frame 4: Electrode
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Abstract
Description
項1
二軸延伸ポリプロピレンフィルムの少なくとも片面に第1の金属膜が形成された金属化ポリプロピレンフィルムであって、
前記金属化ポリプロピレンフィルムの厚みが0.5~4.0μmであり、
下記絶縁破壊点数の測定条件にて測定される厚み換算絶縁破壊点数が1.90[(個/cm2)・μm]以下である、金属化ポリプロピレンフィルム。
<絶縁破壊点数の測定条件>
真鍮板、導電性ゴム及びアルミニウム箔がこの順に積層されてなる導電基材の前記アルミニウム箔側の面に、10mm×100mmの開口を有する22μm厚さのポリプロピレンフィルム製絶縁フィルムを載置する。この絶縁フィルム上面に、前記金属化ポリプロピレンフィルムを、第1の金属膜が表面側に露出するように載置することで、前記金属化ポリプロピレンフィルムを、前記絶縁フィルムに接触させると共に、前記開口部を通じて前記アルミニウム箔にも接触させる。次いで、電極を前記第1の金属膜表面に載置し、前記第1の金属膜と前記導電基材との間で391(V/μm)、435(V/μm)、478(V/μm)、521(V/μm)、565(V/μm)、609(V/μm)の順にそれぞれ計6回を1分間印加し、3回目までの累積の絶縁破壊点数をカウントする。このカウント数を、前記絶縁フィルムの開口部の面積(1000mm2)で除した値を絶縁破壊点数とし、前記絶縁破壊点数に前記金属化ポリプロピレンフィルムの厚さを乗じた値を厚み換算絶縁破壊点数[(個/cm2)・μm]とする。
項2
前記二軸延伸ポリプロピレンフィルムは、一視野あたり240μm×180μmの範囲内で、光干渉式非接触表面形状測定機を用いて表面形状の計測を行った際、高さ0.02μm以上の突起部総体積が、一視野あたり950~1300μm3である、項1に記載の金属化ポリプロピレンフィルム。
項3
ポリプロピレンフィルムと、前記ポリプロピレンフィルムの片面又は両面に積層された金属層とを有する金属化ポリプロピレンフィルムであって、20℃且つ350~425V/μmの累積直流電圧印可試験後の累積絶縁破壊点数密度が1000個/m2以下である、金属化ポリプロピレンフィルム。
項4
前記ポリプロピレンフィルムの厚さが1.0~3.0μmである、項3に記載の金属化ポリプロピレンフィルム。
項5
前記ポリプロピレンフィルムの120℃で15分の処理条件における第1方向の熱収縮率が0~8%であり且つ前記第1方向に直交する第2方向の熱収縮率が-2~2%である、項3又は4に記載の金属化ポリプロピレンフィルム。
項6
前記ポリプロピレンフィルムの140℃で15分の処理条件における第1方向の熱収縮率が0~10%であり且つ前記第1方向に直交する第2方向の熱収縮率が-1~5%である、項3~5のいずれかに記載の金属化ポリプロピレンフィルム。
項7
前記ポリプロピレンフィルムの第1方向の引張弾性率が1.5GPa以上であり且つ前記第1方向に直交する第2方向の引張弾性率が3GPa以上である、項3~6のいずれかに記載の金属化ポリプロピレンフィルム。
項8
前記ポリプロピレンフィルムが二軸延伸フィルムである、項3~7のいずれかに記載の金属化ポリプロピレンフィルム。
項9
前記ポリプロピレンフィルムが単層フィルムである、項3~8のいずれかに記載の金属化ポリプロピレンフィルム。
項10
コンデンサ用である、項1~9のいずれかに記載の金属化ポリプロピレンフィルム。
項11
項1~10のいずれかに記載の金属化ポリプロピレンフィルムを含む、コンデンサ。
項12
項1~11のいずれかに記載の金属化ポリプロピレンフィルムの巻回物を含む、請求項11に記載のコンデンサ。
二軸延伸ポリプロピレンフィルムの片面に第1の金属膜が形成され、前記金属化ポリプロピレンフィルムの厚みが0.5~4.0μmであり、後記する<絶縁破壊点数の測定条件>に記載の手順で測定される厚み換算絶縁破壊点数が1.90[(個/cm2)・μm]以下である。
<絶縁破壊点数の測定条件>
真鍮板、導電性ゴム及びアルミニウム箔がこの順に積層されてなる導電基材の前記アルミニウム箔側の面に、10mm×100mmの開口を有する22μm厚さのポリプロピレンフィルム製絶縁フィルムを載置する。この絶縁フィルム上面に、前記金属化ポリプロピレンフィルムを、第1の金属膜が表面側に露出するように載置することで、前記金属化ポリプロピレンフィルムを、前記絶縁フィルムに接触させると共に、前記開口部を通じて前記アルミニウム箔にも接触させる。次いで、電極を前記第1の金属膜表面に載置し、前記第1の金属膜と前記導電基材との間で391(V/μm)、435(V/μm)、478(V/μm)、521(V/μm)、565(V/μm)、609(V/μm)の順にそれぞれ計6回を1分間印加し、3回目までの累積の絶縁破壊点数をカウントする。このカウント数を、前記絶縁フィルムの開口部の面積(1000mm2)で除した値を絶縁破壊点数とし、前記絶縁破壊点数に前記金属化ポリプロピレンフィルムの厚さを乗じた値を厚み換算絶縁破壊点数とする。
ポリプロピレンフィルムと、前記ポリプロピレンフィルムの片面又は両面に積層された金属層とを有する金属化ポリプロピレンフィルムであって、20℃且つ350~425V/μmの累積直流電圧印可試験後の累積絶縁破壊点数密度が1000個/m2以下である。
二軸延伸ポリプロピレンフィルムは、ポリプロピレン樹脂を主成分とする。本明細書において、「主成分」とは、二軸延伸ポリプロピレンフィルム中に固形分換算で50質量%以上、好ましくは70質量%以上、より好ましくは90質量%以上、さらに好ましくは95質量%以上、よりさらに好ましくは99質量%以上含むことをいう。
金属化ポリプロピレンフィルムXにおいて、二軸延伸ポリプロピレンフィルムの製造方法は特に限定されず、例えば、公知の二軸延伸ポリプロピレンフィルムの製造方法を広く採用することができる。例えば、二軸延伸ポリプロピレンフィルムは、未延伸原反シートを用いて製造することが好ましい。従って、二軸延伸ポリプロピレンフィルムの製造方法は、未延伸原反シートを延伸処理する工程を備えることができる。
本発明の金属化ポリプロピレンフィルムXは、前記二軸延伸ポリプロピレンフィルムの片面のみに第1の金属膜が形成されている。第1の金属膜を単に「金属膜」と表記することもある。
ここで、金属化ポリプロピレンフィルムXの絶縁破壊点数の測定条件を詳述する。
導電基材2は、積層体Aにおいて導体の機能を果たす基材であって、いわば下側導体として機能する基材である。導電基材2は、真鍮板、導電性ゴム及びアルミニウム箔がこの順に積層されてなる3層積層体である。積層体Aにおいては、アルミニウム箔が絶縁フィルム3側に配置される。
絶縁フィルム3は、前述のように積層体Aにおいて、導電基材2及び金属化ポリプロピレンフィルム1の間に配置される層であり、導体間(前記下側導体と、後記する上側導体との間)に絶縁性をもたらすための層である。従って、絶縁フィルム3の両面いずれにも、金属化樹脂フィルム1が有する金属膜のような導電性の材料は形成されていないことが好ましい。
金属化ポリプロピレンフィルム1は、測定対象となるフィルムであって、前述の「金属化ポリプロピレンフィルムX」である。従って、金属化ポリプロピレンフィルム1は、二軸延伸ポリプロピレンフィルム1aと、その片面に形成された第1の金属膜1bとで構成されている。
前記測定は、積層体Aに電圧を印加することで行う。この場合、導電基材2(下側導体)と第1の金属膜1b(上側導体)との間に印加するために電気的に接続する。下側導体には、導電基材2に導線をつなぐことで容易に電気的接続ができる。これに対し、上側導体は金属膜1bであるので、電気的接続を容易にするために電極4を用いる。
金属化ポリプロピレンフィルムYは、ポリプロピレンフィルムと、前記ポリプロピレンフィルムの片面又は両面に積層された金属層とを有する金属化ポリプロピレンフィルムであって、20℃且つ350~425V/μmの累積直流電圧印可試験後の累積絶縁破壊点数密度が1000個/m2以下である。
熱収縮率(%)
=(加熱前の標線間隔-加熱後の標線間隔)
/加熱前の標線間隔×100
を用いて、各々のサンプルについて熱収縮率(%)を算出する。第1方向の120℃熱収縮率を測定するサンプル3本の、熱収縮率の平均値を第1方向の120℃熱収縮率(%)とする。また、第2方向の120℃熱収縮率を測定するサンプル3本の、熱収縮率の平均値を第2方向の120℃熱収縮率(%)とする。なお、ここに記載した以外の測定条件については、JIS C 2151:2019の「25.寸法変化」に準じる。
本発明の金属化ポリプロピレンフィルムX又は金属化ポリプロピレンフィルムY(金属層一体型ポリプロピレンフィルム)を用いてコンデンサ(コンデンサ素子)を形成することができる。コンデンサの構成は、本発明の金属化ポリプロピレンフィルムを備える限りは特に限定されない。
以下、実施例により本発明の金属化ポリプロピレンフィルムXをより具体的に説明するが、本発明はこれら実施例の態様に限定されるものではない。
(比較例1a)
ポリプロピレン樹脂ペレット(PP樹脂A1〔Mw=32万、Mw/Mn=9.3、メソペンタッド分率[mmmm]=95%、プライムポリマー製〕と、PP樹脂A2〔〔Mw=35万、Mw/Mn=7.7、メソペンタッド分率[mmmm]=96.5%、大韓油化製〕とを、質量比67:33で混合された樹脂ペレット)を押出機に供給し、230℃の温度で溶融した後、溶融物を目開き寸法が30μmであるポリマーフィルタを通過させた。ポリマーフィルタを通過させた溶融物をTダイを用いて押出し、表面温度を96℃に保持した金属ドラムに巻きつけて固化させることで、厚さ約138μmであるキャスト原反シートを製造した。このキャスト原反シートを146℃の温度で、流れ方向に5倍に延伸し、直ちに室温まで冷却した後、テンターにて165℃の温度で横方向に10倍に延伸して、厚さ2.3μmの二軸延伸ポリプロピレンフィルムを得た。次いで、蒸着装置を用いて公知の方法で二軸延伸ポリプロピレンフィルムに金属層を積層し、金属化ポリプロピレンフィルムを得た。蒸着は、冷却ロールの温度を-23℃、膜抵抗を20Ω/□、フィルムの搬送速度を150m/分で行った。
ポリマーフィルターの目開き寸法を20μmに変更したこと以外は比較例1aと同様の方法で金属化ポリプロピレンフィルムを得た。
ポリマーフィルターの目開き寸法を10μmに変更したこと以外は比較例1aと同様の方法で金属化ポリプロピレンフィルムXを得た。
ポリマーフィルターの目開き寸法を5μmに変更したこと以外は比較例a1と同様の方法で金属化ポリプロピレンフィルムXを得た。
ポリプロピレン樹脂ペレットを、PP樹脂B〔Mw=34万、Mw/Mn=6.3、メソペンタッド分率=98%、プライムポリマー製〕に変更したこと以外は比較例1aと同様の方法で金属化ポリプロピレンフィルムを得た。
ポリプロピレン樹脂ペレットを、PP樹脂Bに変更したこと以外は比較例2aと同様の方法で金属化ポリプロピレンフィルムを得た。
ポリプロピレン樹脂ペレットを、PP樹脂Bに変更したこと以外は実施例1aと同様の方法で金属化ポリプロピレンフィルムを得た。
ポリプロピレン樹脂ペレットを、PP樹脂Bに変更したこと以外は実施例2aと同様の方法で金属化ポリプロピレンフィルムを得た。
真鍮板(320mm×250mm)、導電性ゴム(280mm×150mm)及びアルミニウム箔(280mm×150mm)をこの順に積層することで導電基材を形成した。この導電基材のアルミニウム箔側の面上に、中央部に四角形状(100mm×10mm)の開口部(以下、当該部分を「開口」または「開口部」と表記する)を有する絶縁フィルム(ポリプロピレンシート、外形は280mm×150mm、厚さは22μm)を載置した。次いで、絶縁フィルムの上に、測定用の金属化ポリプロピレンフィルムを載置することで積層体を作製した。このとき、測定用の金属化ポリプロピレンフィルムは、開口部を通じて露出している導電基材(具体的には、導電基材のアルミニウム箔)の全面に接するように、かつ、金属化ポリプロピレンフィルムの金属蒸着面が表面側に露出するように載置した。次いで、前記露出させた金属蒸着面上に、円柱の真鍮電極(直径25mm、高さ65mm)を載置した。
突起部総体積は、光干渉式非接触表面形状測定機を使用して、三次元表面粗さ評価法を用いて、表面形状を計測することで求めた。具体的に突起部総体積は、菱化システム製の「VertScan2.0(型式:R5500GML)」を光干渉式非接触表面形状測定機として使用して測定した。斯かる測定では、WAVEモードを用い、530whiteフィルター及び×20対物レンズを用いて、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。得られたデータは、メディアンフィルタによるノイズ除去処理を行った後、カットオフ値30μmによるガウシアンフィルタ処理を行い、うねり成分を除去した。
実施例及び比較例で得られた金属化ポリプロピレンフィルムで製作したコンデンサの試験前の初期静電容量を、日置電機株式会社製LCRハイテスター3522-50を用いて測定した。次に、コンデンサに室温で1000Vの直流電圧を10秒印加した。電圧印加後のコンデンサの静電容量を同様に測定し、試験前後の容量変化率を、次の式
(静電容量の変化率)=[(電圧印加後の静電容量)-(初期静電容量)]/(初期静電容量)×100(%)
により算出した。次に、1050Vの直流電圧を10秒印加し、静電容量を同様に測定した。電圧を50Vずつ上げ,容量変化率が-1%を超えるまで、この操作を繰り返し行い、累積的に電圧を印加した。-1%を超える前と超えた後の電圧から、-1%になる電圧を直線補間(内挿)で求めた。試験は2個のサンプルで行い、その平均値を算出した。
表1は金属化ポリプロピレンフィルムの厚さ、絶縁破壊点数の測定条件及び測定結果を示す。合わせて表1には、金属化ポリプロピレンフィルムの突起部総体積の測定結果、吐出安定性の評価結果、及び、短時間耐圧試験の結果も示している。表1中、V1は1回目の電圧(開始電圧(V))、D1は金属化ポリプロピレンフィルムの厚さ(μm)、Vnは終了電圧(6回目の印加電圧)を意味する。
以下、実施例により本発明の金属化ポリプロピレンフィルムY(金属層一体型ポリプロピレンフィルム)をより具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。なお、特記しない限り、部及び%はそれぞれ「質量部」及び「質量%」を示す。
金属化ポリプロピレンフィルムYの実施例及び比較例の二軸延伸ポリプロピレンフィルムを製造するために使用したポリプロピレン樹脂を、表1に示す。
GPC(ゲルパーミエーションクロマトグラフィー)を用い、以下の条件で、各樹脂の数平均分子量(Mn)、重量平均分子量(Mw)、z平均分子量(Mz)、分子量分布(Mw/Mn)、及び、分子量分布(Mz/Mn)を測定した。
各樹脂について原料樹脂ペレットの形態でのメルトフローレート(MFR)を、東洋精機株式会社のメルトインデックサを用いてJIS K 7210の条件Mに準じて測定した。具体的には、まず、試験温度230℃にしたシリンダ内に、4gに秤りとった試料を挿入し、2.16kgの荷重下で3.5分予熱した。その後、30秒間で底穴より押出された試料の重量を測定し、MFR(g/10min)を求めた。上記の測定を3回繰り返し、その平均値をMFRの測定値とした。結果を表1に示す。
各樹脂について、10mm×35mm×0.3mmにプレス成形して約3gの測定用サンプルを作製した。次に、ヘプタン約150mLを加えてソックスレー抽出を8時間行った。抽出前後の試料質量よりヘプタン不溶分を算出した。結果を表2に示す。
樹脂Aと樹脂Bとをドライブレンドした。混合比率は、質量比で(樹脂A):(樹脂B)=75:25とした。その後、ドライブレンドした樹脂を用い、樹脂温度270℃で溶融した後、Tダイを用いて押出し、表面温度を98℃に保持した金属ドラムに巻きつけて固化させた。これにより、厚さ115μmのキャストシートを作製した。この際、溶融押し出しされた樹脂組成物をエアーナイフで金属ドラムに押さえつけながらキャストシートを作製した。得られた未延伸のキャストシートを146℃の温度に保ち、速度差を設けたロール間に通して、延伸速度67300%/秒で、流れ方向に5倍に延伸し、直ちに室温に冷却した。引き続き、延伸フィルムをテンターに導いて、155℃の温度で、延伸速度335%/秒で、幅方向に10倍に延伸した後、緩和、熱固定を施した。次いで、フィルム表面(金属ドラム接触面側)に25W・分/m2の処理速度で大気中でコロナ放電処理を行った後、巻き取り、30℃程度の雰囲気中でエージング処理を施した。これにより、厚さ2.3μmの二軸延伸ポリプロピレンフィルムを得た。
(3-1)二軸延伸ポリプロピレンフィルムの厚さ測定
上記(2)で作製した二軸延伸ポリプロピレンフィルムの厚さ(単位:μm)を測定した。具体的に、シチズンセイミツ社製の紙厚測定器MEI-11を用いて100±10kPaで測定すること以外、JIS-C2330に準拠して測定した。結果、二軸延伸ポリプロピレンフィルムの厚さは、2.3μmであった。
上記(2)で作製した二軸延伸ポリプロピレンフィルムの120℃で15分の処理条件における熱収縮率(120℃熱収縮率)(単位:%)を測定した。具体的には、サンプルをロールより、切り出したが、サンプルの大きさは、MD方向の120℃熱収縮率を測定するサンプルは、MD方向130mm、TD方向20mmとし、TD方向の120℃熱収縮率を測定するサンプルは、MD方向20mm、TD方向130mmとした。MD方向の120℃熱収縮率を測定するサンプル、および、TD方向の120℃熱収縮率を測定するサンプルは、各々3本準備した。次に、MD方向の120℃熱収縮率を測定するサンプル3本については、MD方向130mmの各々の端から15mmの位置に標線を印した。このとき、標線と標線の間隔は100mmとなる。また、TD方向の120℃熱収縮率を測定するサンプル3本については、TD方向130mmの各々の端から15mmの位置に標線を印した。このとき、標線と標線の間隔は100mmとなる。次いで、標線を印した各々のサンプルを、120℃の熱風循環式恒温槽内に130mmに切り出した方向が、鉛直方向になるように、無荷重で吊るして15分間保持した。その後、室温(23℃)で冷却し、標線の間隔を定規で測定し、次の式:熱収縮率(%)=(加熱前の標線間隔-加熱後の標線間隔)/加熱前の標線間隔×100 を用いて、各々のサンプルについて熱収縮率(%)を算出した。
上記(2)で作製した二軸延伸ポリプロピレンフィルムの140℃で15分の処理条件における熱収縮率(140℃熱収縮率)(単位:%)を測定した。120℃熱収縮率の測定方法のうち、120℃の熱風循環式恒温槽を、140℃の熱風循環式恒温槽に変更したこと以外は、120℃熱収縮率と同様の方法で、MD方向の140℃熱収縮率(%)、および、TD方向の140℃熱収縮率(%)を算出した。
上記(2)で作製した二軸延伸ポリプロピレンフィルムの引張弾性率(単位:GPa)は、JIS K-7127(1999)に準拠して測定した。具体的には、サンプルをロールより、切り出したが、サンプルの大きさは、MD方向の引張弾性率を測定するサンプルは、MD方向200mm、TD方向15mmとし、TD方向の引張弾性率を測定するサンプルは、MD方向15mm、TD方向200mmとした。次いで、引張圧縮試験機(ミネベア株式会社製)を用いて、試験条件(測定温度23℃、チャック間距離100mm、引張速度200mm/分)で引張試験を行った。次いで、同試験機に内蔵されたデータ処理ソフトによる自動解析より、MD方向の引張弾性率(GPa)、および、TD方向の引張弾性率(GPa)を各々求めた。
上記(2)で作製した二軸延伸ポリプロピレンフィルムのヘーズ(単位:%)は、ヘーズメータ(日本電色工業株式会社製「NDH-5000」)を用いて、JIS K 7136:2000に準拠して測定した。サンプルは、ロールより切り出したが、サンプルの大きさはMD方向50mm、TD方向100mmとした。結果、二軸延伸ポリプロピレンフィルムのヘーズは、3.1%であった。
上記(2)で作製した二軸延伸ポリプロピレンフィルムのロールからフィルムを巻き出し、幅方向にスリッターにて断裁した。断裁後のポリプロピレンフィルムを巻回する際は、外径が176mmの繊維強化プラスチック製のコアを使用し、接圧ロールを備える巻き取り装置を用いて、ポリプロピレンフィルムに面圧を付与しながら巻回する方式を採用した。断裁条件は、速度300m/min、巻出張力40N/m、巻取張力50N/m、巻取面圧400N/mとし、接圧ロールはゴム製の外径152mm、表面硬度40°のものを使用し、幅620mm、長さ75,000mの二軸延伸ポリプロピレンロール(断裁後フィルムロール)を仕上げた。巻取り中のフィルムを目視観察し、シワの発生がない事を確認した。また、得られた断裁後フィルムロールの端面の観察を行い、2mm以上のズレが発生していない事を確認した。
<実施例1b>
蒸着装置(アルバック社製、製品名:巻取式真空蒸着装置EWE-060)を用い、冷却ロール温度-22℃、冷却ロールの単位幅当たりの電圧速度比0.32V・min/m2、放電量2.5W・min/m2の条件で、上記(4)で作製した断裁後フィルムロールにフィルムコンデンサ保安性を付与するための特殊蒸着パターンマージン、絶縁マージンを形成し、金属膜の表面抵抗率が20Ω/sqになるようにアルミニウム蒸着を施すことにより、金属層一体型ポリプロピレンフィルム(金属化ポリプロピレンフィルムY)を得た。金属層一体型ポリプロピレンフィルムの模式図を図4に示す。製造装置の模式図を図5に示す。
冷却ロールの単位幅当たりの電圧速度比を0.21V・min/m2としたこと以外は、実施例1bと同様にして、金属層一体型ポリプロピレンフィルムを得た。
冷却ロールの単位幅当たりの電圧速度比を0.44V・min/m2としたこと以外は、実施例1bと同様にして、金属層一体型ポリプロピレンフィルムを得た。
放電量を1.6W・min/m2としたこと以外は、実施例1bと同様にして、金属層一体型ポリプロピレンフィルムを得た。
放電量を3.6W・min/m2としたこと以外は、実施例1bと同様にして、金属層一体型ポリプロピレンフィルムを得た。
冷却ロールの単位幅当たりの電圧速度比を0.21V・min/m2、放電量を3.6W・min/m2としたこと以外は、実施例1bと同様にして、金属層一体型ポリプロピレンフィルムを得た。
冷却ロールの単位幅当たりの電圧速度比を0.18V・min/m2としたこと以外は、実施例1bと同様にして、金属層一体型ポリプロピレンフィルムを得た。
冷却ロールの単位幅当たりの電圧速度比を0.47V・min/m2としたこと以外は、実施例1bと同様にして、金属層一体型ポリプロピレンフィルムを得た。
放電量を1.3W・min/m2としたこと以外は、実施例1bと同様にして、金属層一体型ポリプロピレンフィルムを得た。
放電量を3.9W・min/m2としたこと以外は、実施例1bと同様にして、金属層一体型ポリプロピレンフィルムを得た。
冷却ロールの単位幅当たりの電圧速度比を0.18V・min/m2、放電量を3.9W・min/m2としたこと以外は、実施例1bと同様にして、金属層一体型ポリプロピレンフィルムを得た。
冷却ロールの単位幅当たりの電圧速度比を0.47V・min/m2、放電量を3.9W・min/m2としたこと以外は、実施例1bと同様にして、金属層一体型ポリプロピレンフィルムを得た。
実施例1bから実施例6b、および、比較例1bから比較例6bで得られた金属層一体型ポリプロピレンフィルムについて、図3に示す構成で、下記、手順にて、20℃且つ350~425V/μmの累積直流電圧印可試験後の累積絶縁破壊点数密度(425V/μmにおける、20℃の累積絶縁破壊点数密度)を測定した。20℃の環境下、350V/μmの直流電圧を1分間印加した後、絶縁用ポリプロピレンフィルムの窓の領域(100mm×10mm)における絶縁破壊点数を目視で数えた。数えた後、375V/μmの直流電圧を1分間印加した後、絶縁用ポリプロピレンフィルムの窓の領域における累積絶縁破壊点数を目視にて数えた。次いで、直流電圧を25V/μmずつ上げ、425V/μmまで、この操作を繰り返し行い、累積的に直流電圧を印加した。試験は5枚の金属層一体型ポリプロピレンフィルムで行い、425V/μmにおける、20℃の累積絶縁破壊点数の平均値を、絶縁用ポリプロピレンフィルムの窓の面積(100mm×10mm=1,000mm2=0.001m2)で割り、425V/μmにおける、20℃の累積絶縁破壊点数密度(単位:個/m2)を求めた。結果を表3及び表4に示す。
(7-1)プレス処理歩留率評価
実施例、比較例で作製した金属層一体型ポリプロピレンフィルムを30mm幅の小巻にスリットした。次に、30mm幅の金属層一体型ポリプロピレンフィルムの小巻のうち、巻き出し側から見て左側に絶縁マージン(幅方向の長さ2mm)がある小巻1本と、巻き出し側から見て右側に絶縁マージン(幅方向の長さ2mm)がある小巻1本とを用い、互いに、相手の金属層一体型ポリプロピレンフィルムの小巻の絶縁マージンよりも、自身の電極取り出し部がはみ出るように2枚組合せて、皆藤製作所製自動巻取機3KAW―N2型を用い、巻取り速度4m/sec、巻取り張力180g、コンタクトローラー接圧260gにて、1350ターン巻回を行った。
B:100%>□≧80%
C:80%>□。
上記(7-1)でプレス処理を行い扁平化させた素子について、プレス荷重を加えたまま、素子端面に亜鉛金属を溶射した。溶射条件としては、フィード速度20mm/s、溶射電圧21V、溶射圧力0.4MPaとし、厚さ0.6mm~0.7mmになるよう溶射を行い電極取り出し部を形成、真空雰囲気下で、120℃にて15時間の加熱処理を真空恒温槽で施し、熱硬化させた。こうして扁平型フィルムコンデンサを得た。その後、扁平型フィルムコンデンサの、素子端面にリード線をはんだ付けし、エポキシ樹脂で封止した。エポキシ樹脂の硬化は、90℃で2.5時間加熱した後、さらに、120℃で2.5時間加熱して行った。出来上がったコンデンサの静電容量は、すべて50μF(±3μF)であった。得られたコンデンサを、以下の6つの試験で使用した。
得られたコンデンサについて、試験前の初期静電容量(C0)を、日置電機株式会社製LCRハイテスター3522-50を用いて測定した。次に、コンデンサに105℃の恒温槽中にて、325 V/μmの直流電圧を10秒印加した。電圧印加後のコンデンサの静電容量を同様に測定し、試験前後の容量変化率(ΔC)を、次の式:
ΔC=[(電圧印加後の静電容量)-C0]/C0×100(%)
により算出した。
B:-2%>ΔC≧-5%
C:-5%>ΔC
得られたコンデンサの試験前の初期静電容量(C0)を、日置電機株式会社製LCRハイテスター3522-50を用いて測定した。次に、105℃の恒温槽中にて、コンデンサに325 V/μmの直流電圧を1,500時間負荷し続けた。1,500時間経過後のコンデンサの静電容量(C1500H105C)を同様に測定し、電圧負荷前後の容量変化率(ΔC105C)を、次の式:ΔC105C=(C1500H105C-C0)/C0 により算出した。試験は2個のサンプルで行い、その容量変化率(ΔC105C)の平均値を以下の基準を与えて評価した。結果を表3及び表4に示す。
B:-15%>ΔC105C≧-25%
C:-25%>ΔC105C
得られたコンデンサを、105℃の恒温槽中にて、325 V/μmの直流電圧を1,500時間負荷し続けた。日置電機株式会社製超絶縁抵抗計DSM8104に遮蔽箱SME-8350を接続し、遮蔽箱内に1,500時間経過後のコンデンサを入れ、500Vの直流電圧を印加し、1分経過時の絶縁抵抗値(IR105C)を読み取った。試験は2個のサンプルで行い、その絶縁抵抗値(IR105C)の平均値を以下の基準を与えて評価した。結果を表3及び表4に示す。
B:500MΩ>IR105C≧20MΩ
C:20MΩ>IR105C
得られたコンデンサの試験前の初期静電容量(C0)を、日置電機株式会社製LCRハイテスター3522-50を用いて測定した。次に、115℃の恒温槽中にて、コンデンサに325 V/μmの直流電圧を1,500時間負荷し続けた。1,500時間経過後のコンデンサの静電容量(C1500H115C)を同様に測定し、電圧負荷前後の容量変化率(ΔC115C)を、次の式:ΔC115C=(C1500H115C-C0)/C0 により算出した。試験は2個のサンプルで行い、その容量変化率(ΔC115C)の平均値を以下の基準を与えて評価した。結果を表3及び表4に示す。
B:-20%>ΔC115C≧-30%
C:-30%>ΔC115C
得られたコンデンサを、115℃の恒温槽中にて、325 V/μmの直流電圧を1,500時間負荷し続けた。日置電機株式会社製超絶縁抵抗計DSM8104に遮蔽箱SME-8350を接続し、遮蔽箱内に1,500時間経過後のコンデンサを入れ、500Vの直流電圧を印加し、1分経過時の絶縁抵抗値(IR115C)を読み取った。試験は2個のサンプルで行い、その絶縁抵抗値(IR115C)の平均値を以下の基準を与えて評価した。結果を表3及び表4に示す。
B:150MΩ>IR115C≧20MΩ
C:20MΩ>IR115C
得られたコンデンサを、105℃の恒温槽中にて、1200Vの直流電圧を10分負荷し続けた。日置電機株式会社製超絶縁抵抗計DSM8104に遮蔽箱SME-8350を接続し、遮蔽箱内に10分経過後のコンデンサを入れ、500Vの直流電圧を印加し、1分経過時の絶縁抵抗値(IR10)を読み取った。試験は2個のサンプルで行い、その絶縁抵抗値(IR10)の平均値を以下の基準を与えて評価した。結果を表3及び表4に示す。
B:5000MΩ>IR10≧20MΩ
C:20MΩ>IR10
1:金属化ポリプロピレンフィルム
1a:二軸延伸ポリプロピレンフィルム
1b:第1の金属膜
2:導電基材
3:絶縁フィルム
3a:開口部
3b:枠部
4:電極
Claims (12)
- 二軸延伸ポリプロピレンフィルムの少なくとも片面に第1の金属膜が形成された金属化ポリプロピレンフィルムであって、
前記金属化ポリプロピレンフィルムの厚みが0.5~4.0μmであり、
下記絶縁破壊点数の測定条件にて測定される厚み換算絶縁破壊点数が1.90[(個/cm2)・μm]以下である、金属化ポリプロピレンフィルム。
<絶縁破壊点数の測定条件>
真鍮板、導電性ゴム及びアルミニウム箔がこの順に積層されてなる導電基材の前記アルミニウム箔側の面に、10mm×100mmの開口を有する22μm厚さのポリプロピレンフィルム製絶縁フィルムを載置する。この絶縁フィルム上面に、前記金属化ポリプロピレンフィルムを、第1の金属膜が表面側に露出するように載置することで、前記金属化ポリプロピレンフィルムを、前記絶縁フィルムに接触させると共に、前記開口部を通じて前記アルミニウム箔にも接触させる。次いで、電極を前記第1の金属膜表面に載置し、前記第1の金属膜と前記導電基材との間で391(V/μm)、435(V/μm)、478(V/μm)、521(V/μm)、565(V/μm)、609(V/μm)の順にそれぞれ計6回を1分間印加し、3回目までの累積の絶縁破壊点数をカウントする。このカウント数を、前記絶縁フィルムの開口部の面積(1000mm2)で除した値を絶縁破壊点数とし、前記絶縁破壊点数に前記金属化ポリプロピレンフィルムの厚さを乗じた値を厚み換算絶縁破壊点数[(個/cm2)・μm]とする。 - 前記二軸延伸ポリプロピレンフィルムは、一視野あたり240μm×180μmの範囲内で、光干渉式非接触表面形状測定機を用いて表面形状の計測を行った際、高さ0.02μm以上の突起部総体積が、一視野あたり950~1300μm3である、請求項1に記載の金属化ポリプロピレンフィルム。
- ポリプロピレンフィルムと、前記ポリプロピレンフィルムの片面又は両面に積層された金属層とを有する金属化ポリプロピレンフィルムであって、20℃且つ350~425V/μmの累積直流電圧印可試験後の累積絶縁破壊点数密度が1000個/m2以下である、金属化ポリプロピレンフィルム。
- 前記ポリプロピレンフィルムの厚さが1.0~3.0μmである、請求項3に記載の金属化ポリプロピレンフィルム。
- 前記ポリプロピレンフィルムの120℃で15分の処理条件における第1方向の熱収縮率が0~8%であり且つ前記第1方向に直交する第2方向の熱収縮率が-2~2%である、請求項3又は4に記載の金属化ポリプロピレンフィルム。
- 前記ポリプロピレンフィルムの140℃で15分の処理条件における第1方向の熱収縮率が0~10%であり且つ前記第1方向に直交する第2方向の熱収縮率が-1~5%である、請求項3~5のいずれかに記載の金属化ポリプロピレンフィルム。
- 前記ポリプロピレンフィルムの第1方向の引張弾性率が1.5GPa以上であり且つ前記第1方向に直交する第2方向の引張弾性率が3GPa以上である、請求項3~6のいずれかに記載の金属化ポリプロピレンフィルム。
- 前記ポリプロピレンフィルムが二軸延伸フィルムである、請求項3~7のいずれかに記載の金属化ポリプロピレンフィルム。
- 前記ポリプロピレンフィルムが単層フィルムである、請求項3~8のいずれかに記載の金属化ポリプロピレンフィルム。
- コンデンサ用である、請求項1~9のいずれかに記載の金属化ポリプロピレンフィルム。
- 請求項1~10のいずれかに記載の金属化ポリプロピレンフィルムを含む、コンデンサ。
- 請求項1~11のいずれかに記載の金属化ポリプロピレンフィルムの巻回物を含む、請求項11に記載のコンデンサ。
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