WO2015151591A1 - コンデンサ用二軸延伸ポリプロピレンフィルム - Google Patents
コンデンサ用二軸延伸ポリプロピレンフィルム Download PDFInfo
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- WO2015151591A1 WO2015151591A1 PCT/JP2015/053681 JP2015053681W WO2015151591A1 WO 2015151591 A1 WO2015151591 A1 WO 2015151591A1 JP 2015053681 W JP2015053681 W JP 2015053681W WO 2015151591 A1 WO2015151591 A1 WO 2015151591A1
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- molecular weight
- polypropylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
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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
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/14—Organic dielectrics
- H01G4/18—Organic dielectrics of synthetic material, e.g. derivatives of cellulose
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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
- H01G4/32—Wound capacitors
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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
- H01G4/33—Thin- or thick-film capacitors (thin- or thick-film circuits; capacitors without a potential-jump or surface barrier specially adapted for integrated circuits, details thereof, multistep manufacturing processes therefor)
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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
- B32B2250/00—Layers arrangement
- B32B2250/02—2 layers
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
- B32B2255/205—Metallic coating
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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
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
-
- 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
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/204—Di-electric
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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
- B32B2307/70—Other properties
- B32B2307/704—Crystalline
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Definitions
- the present invention relates to a biaxially stretched polypropylene film for a capacitor having high withstand voltage at high temperatures and excellent dielectric breakdown characteristics. More specifically, the present invention relates to a biaxially oriented polypropylene film for a capacitor that can be suitably used for a high-capacitance capacitor to which a high voltage is applied at a high temperature, and preferably has a small thickness.
- Biaxially stretched polypropylene film makes use of the excellent electrical properties such as voltage resistance and low dielectric loss properties of polypropylene film and high moisture resistance, in electronic and electrical equipment, for example, high voltage capacitors, various switching power supplies, converters and It is preferably used as a dielectric film for a capacitor such as a filter capacitor such as an inverter and a smoothing capacitor.
- Polypropylene films have begun to be used as capacitors for inverter power supply devices that control drive motors of electric vehicles and hybrid vehicles, for which demand has been increasing in recent years.
- Such a capacitor for an inverter power supply device used in an automobile or the like is required to be further reduced in size and weight as the vehicle is reduced in size and weight.
- a polypropylene film having a high stretching performance as the capacitor film and to make it extremely thin, for example, to a thickness of 1 to 6 ⁇ m.
- the film is extremely thin, it is required to have a high withstand voltage that does not break down even when a higher voltage is applied at a higher temperature, and based on such a film.
- Capacitors have a high withstand voltage even when a high voltage is applied in a wide temperature range of ⁇ 40 ° C. to 90 ° C., particularly at high temperatures, and particularly have a high initial withstand voltage and a long-term withstand voltage. Is required.
- Patent Document 1 discloses a predetermined number average molecular weight (Mn), molecular weight distribution (Mw / Mn or Mz / Mn) in order to obtain a capacitor film having excellent electrical insulation properties, antiblocking properties and mechanical properties. It has been proposed to obtain a polypropylene film by biaxially stretching a polypropylene resin having a melt flow rate. However, the film described in Patent Document 1 is not supposed to be used as a dielectric film for a capacitor, and no study has been made on the influence on the voltage resistance at high temperatures.
- Mn number average molecular weight
- Mw / Mn or Mz / Mn molecular weight distribution
- Patent Document 2 in order to obtain an ultrathin roughened biaxially stretched polypropylene film excellent in winding processability, an isotactic polypropylene homopolymer (A) having a specific melt flow index (MFR) is used.
- a biaxially stretched polypropylene film comprising a resin mixture obtained by adding 1% by mass to 30% by mass of an isotactic polypropylene homopolymer (B) whose MFR is 1 to 30 g / 10 min greater than that of the resin (A). Proposed.
- the polypropylene film made of a resin having a large composition of low molecular weight components is in response to the high demand from the market in recent years regarding further downsizing of the capacitor element itself and high initial voltage resistance and long-term durability under high temperature. In some cases, it was not always sufficient.
- an object of the present invention is to provide a biaxially stretched polypropylene film for a capacitor having voltage resistance at high temperatures and excellent in dielectric breakdown characteristics. It is another object of the present invention to provide a biaxially oriented polypropylene film for a capacitor that can be suitably used for a high-capacitance capacitor to which a high voltage is applied at a high temperature, and is preferably thin.
- the present invention provides a metallized polypropylene film for a capacitor in which the above-mentioned biaxially stretched polypropylene film for a capacitor is subjected to metal vapor deposition, and a capacitor having a withstand voltage at a high temperature manufactured using such a polypropylene film. It is to be.
- the crystallite size of the polypropylene film is 12.2 nm or less calculated from the half width of the ⁇ crystal (040) plane reflection peak measured by wide-angle X-ray diffraction method using the Scherrer equation.
- the polypropylene film is obtained by biaxially stretching a polypropylene resin composition, and the polypropylene resin composition includes a polypropylene resin having a melt flow rate of 4 g / 10 min or less and a polypropylene resin contained in the polypropylene resin composition.
- the biaxially oriented polypropylene film for capacitors according to [1] or [2], which is contained in an amount of 1% by mass to 70% by mass based on the total amount of resin.
- the polypropylene film is obtained by biaxially stretching a polypropylene resin composition.
- the polypropylene resin composition has a number average molecular weight (Mn) of 40,000 to 150,000 and a Z average molecular weight of 1,200,000 to 260. Any one of [1] to [3] above, wherein a polypropylene resin that is 10,000 or less is contained in an amount of 1 to 70% by mass based on the total amount of polypropylene resin contained in the polypropylene resin composition.
- Biaxially oriented polypropylene film for capacitors is described by biaxially oriented polypropylene film for capacitors.
- a metallized polypropylene film for a capacitor wherein metal deposition is performed on one or both sides of the biaxially stretched polypropylene film for a capacitor according to any one of [1] to [4].
- a biaxially stretched polypropylene film for a capacitor having a high withstand voltage at a high temperature and excellent in dielectric breakdown characteristics it is possible to provide a biaxially oriented polypropylene film for a capacitor that can be suitably used for a high-capacity capacitor to which a high voltage is applied at a high temperature, and preferably has a small thickness.
- a capacitor having high voltage resistance at high temperatures can be obtained.
- the number average molecular weight (Mn) of the polypropylene resin constituting the polypropylene film of the present invention is 40,000 or more and 100,000 or less.
- the number average molecular weight (Mn) of the polypropylene resin is preferably 41,000 or more, more preferably 42,000 or more, from the viewpoint of the thermo-mechanical properties and stretchability of the film.
- the number average molecular weight (Mn) of the polypropylene resin is preferably 80,000 or less, and more preferably 60,000 or less, from the viewpoint of film thickness accuracy.
- the Z average molecular weight (Mz) of the polypropylene resin constituting the polypropylene film of the present invention is 950,000 to 1,500,000.
- the Z average molecular weight (Mz) of the polypropylene resin is preferably 960,000 or more, and more preferably 980,000 or more, from the viewpoint of voltage resistance.
- the Z-average molecular weight (Mz) of the polypropylene resin is preferably 14.45 million or less, more preferably 1.4 million or less, from the viewpoint of stretchability.
- the number average molecular weight (Mn) and the Z average molecular weight (Mz) of the polypropylene resin can be measured by a gel permeation chromatography (GPC) method.
- the GPC apparatus used in the GPC method is not particularly limited, and is a commercially available high-temperature GPC measuring instrument capable of analyzing the molecular weight of polyolefins, for example, a high-temperature GPC measuring instrument with a built-in differential refractometer (RI) manufactured by Tosoh Corporation. HLC-8121GPC-HT or the like can be used.
- a GPC column manufactured by Tosoh Corporation, with three TSKgel GMHHR-H (20) HT connected is used, the column temperature is set to 140 ° C., and trichlorobenzene is used as an eluent. Measured at a flow rate of 1.0 ml / min.
- a calibration curve is prepared using standard polystyrene, and a number average molecular weight (Mn) and a Z average molecular weight (Mz) are obtained by polystyrene conversion.
- Mn number average molecular weight
- Mz Z average molecular weight
- the logarithmic value of the weight average molecular weight thus obtained is referred to as logarithmic molecular weight (“Log (M)”).
- the subtracted difference is -15% or more and 11% or less.
- the difference is preferably ⁇ 10% to 11%, more preferably ⁇ 8 to 11%.
- Such a polypropylene resin contains a component having a molecular weight of about 10,000 to 100,000 at a predetermined ratio with respect to a high molecular weight component having a molecular weight of about 1 million.
- the difference in the differential distribution value described above is the component having a molecular weight of 10,000 to 100,000 (hereinafter referred to as “low molecular weight component”) that is close to the number average molecular weight (Mn) value (40,000 to 100,000) of the polypropylene resin.
- low molecular weight component the component having a molecular weight of 10,000 to 100,000
- Mn number average molecular weight
- Mz Z average molecular weight
- a differential distribution value of Log (M) 6.0 is used as a representative distribution value of the preceding and following components (hereinafter also referred to as “high molecular weight component”), and the logarithmic molecular weight Log (M) is between 4 and 5 (low
- the distribution value of the molecular weight component means that the logarithmic molecular weight Log (M) is a predetermined ratio compared to the distribution value of around 6 (high molecular weight component).
- the range of the molecular weight distribution Mz / Mn for example, it merely represents the width of the molecular weight distribution range, and the quantitative relationship between the high molecular weight component and the low molecular weight component therein is shown. It does not represent.
- the polypropylene resin constituting the polypropylene film of the present invention has the above-mentioned predetermined number average molecular weight and Z average molecular weight, and at the same time, as described above, a component having a molecular weight of 10,000 to 100,000 with respect to a component having a molecular weight of 1,000,000. At a ratio of the predetermined range.
- RI detector differential refraction detector
- the weight average molecular weight (Mw) of the polypropylene resin constituting the polypropylene film is preferably 250,000 to 450,000.
- Mw weight average molecular weight
- an appropriate resin fluidity can be obtained during biaxial stretching, and the thickness of the cast raw sheet can be easily controlled. For example, it is very thin and suitable for a small and high capacity type capacitor. It is preferable because a biaxially stretched polypropylene film can be easily obtained. Moreover, since it becomes difficult to generate
- the weight average molecular weight (Mw) of the polypropylene resin is preferably 270,000 or more, more preferably 290,000 or more from the viewpoints of thickness uniformity, mechanical properties, thermo-mechanical properties, etc. of the biaxially oriented polypropylene film. Is more preferable.
- the weight average molecular weight (Mw) of the polypropylene resin is more preferably 400,000 or less from the viewpoint of the fluidity of the polypropylene resin composition and the stretchability when obtaining an ultrathin biaxially stretched polypropylene film.
- the molecular weight distribution (Mw / Mn) calculated as the ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polypropylene resin constituting the polypropylene film is preferably 6 or more and 12 or less.
- the molecular weight distribution (Mw / Mn) is more preferably 7 or more, and further preferably 7.5 or more.
- the molecular weight distribution (Mw / Mn) is more preferably 11 or less, and still more preferably 10 or less.
- Use of such a polypropylene resin is preferable because appropriate resin fluidity can be obtained at the time of biaxial stretching, and it becomes easy to obtain a very thin biaxially stretched propylene film having no thickness unevenness.
- Such a polypropylene resin composition is also preferable from the viewpoint of voltage resistance of the biaxially stretched polypropylene film.
- the molecular weight distribution (Mz / Mn) calculated as the ratio of the Z average molecular weight (Mz) and the number average molecular weight (Mn) of the polypropylene resin constituting the polypropylene film contains a polypropylene resin that is 20 or more and 70 or less. Is preferred.
- the molecular weight distribution (Mz / Mn) is more preferably 24 or more.
- the molecular weight distribution (Mz / Mn) is more preferably 60 or less, and further preferably 50 or less.
- Use of such a polypropylene resin is preferable because appropriate resin fluidity can be obtained at the time of biaxial stretching, and it becomes easy to obtain a very thin biaxially stretched propylene film having no thickness unevenness.
- Such a polypropylene resin composition is also preferable from the viewpoint of voltage resistance of the biaxially stretched polypropylene film.
- the weight average molecular weight (Mw) of a polypropylene resin can be measured by gel permeation chromatography (GPC) method similarly to said number average molecular weight (Mn) and Z average molecular weight (Mz).
- the molecular weight distribution (Mw / Mn) is calculated as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), the weight average molecular weight (Mw) / number average molecular weight (Mn).
- Mn) is calculated as the ratio of Z average molecular weight (Mz) to number average molecular weight (Mn), Z average molecular weight (Mz) / number average molecular weight (Mn).
- polypropylene resin constituting the polypropylene film examples include homopolymers of polypropylene such as isotactic polypropylene and syndiotactic polypropylene, and copolymers of polypropylene and polyethylene.
- the polypropylene resin is preferably isotactic polypropylene, and more preferably isotactic polypropylene obtained by homopolymerizing polypropylene in the presence of an olefin polymerization catalyst.
- the biaxially stretched polypropylene film for capacitors of the present invention can be obtained by biaxially stretching a polypropylene resin composition.
- polypropylene resin contained in the polypropylene resin composition examples include polypropylene homopolymers such as isotactic polypropylene and syndiotactic polypropylene, and copolymers of polypropylene and polyethylene.
- the polypropylene resin is preferably isotactic polypropylene, and more preferably isotactic polypropylene obtained by homopolymerizing polypropylene in the presence of an olefin polymerization catalyst.
- the polypropylene resin contained in the polypropylene resin composition is particularly limited as long as the polypropylene resin constituting the polypropylene film of the present invention has a difference in the number average molecular weight (Mn), Z average molecular weight (Mz) and differential distribution value.
- Mn number average molecular weight
- Mz Z average molecular weight
- differential distribution value e.g., it may be one type of polypropylene resin obtained by multistage polymerization or the like, or may be a blend of polypropylene resins obtained by combining two or more types of polypropylene resins.
- Examples of a method for adjusting the number average molecular weight (Mn), the Z average molecular weight (Mz), and the difference in differential distribution value of the polypropylene resin constituting the polypropylene film of the present invention include, for example, polymerization of polypropylene resin contained in the polypropylene resin composition
- Examples thereof include a method by adjusting the molecular weight distribution by adjusting conditions, a method using a decomposing agent, a method of selectively decomposing high molecular weight components, and a method of blending resins having different molecular weights.
- the polymerization catalyst described later When adjusting the number average molecular weight (Mn), the Z average molecular weight (Mz), the difference in the differential distribution value, and the like depending on the polymerization conditions, it is preferable to use a polymerization catalyst described later from the viewpoint of easy adjustment.
- the following method can be exemplified.
- the polymerization reaction is carried out in a plurality of reactors, a polymerization reactor for high molecular weight components and a reactor for low molecular weight or medium molecular weight components. Multiple reactors can be used, for example, in series or in parallel. First, propylene and a catalyst are supplied into the reactor.
- a first polymerization reaction is carried out by mixing a molecular weight adjusting agent, for example, hydrogen, in an amount necessary to reach the required molecular weight of the polymer.
- a molecular weight adjusting agent for example, hydrogen
- the reaction temperature is about 70 to 100 ° C.
- the residence time is about 20 to 100 minutes.
- the product of the first polymerization reaction is sent sequentially or continuously to the next reactor together with additional propylene, a catalyst, and a molecular weight regulator so that a product having a lower molecular weight or higher molecular weight than the first polymerization reaction can be obtained.
- the second polymerization reaction is carried out. By adjusting the yield (production amount) of the first and second polymerization reactions, the composition (configuration) of the high molecular weight component and the low molecular weight component can be adjusted.
- a relatively high molecular weight polypropylene can be produced by the former polymerization, and a relatively low molecular weight polypropylene can be produced by the latter polymerization.
- the intrinsic viscosity [ ⁇ 2nd ] is 0.1 to 5 dl / g, preferably 0.3 to 3 dl / g.
- polypropylene in such an amount that the content in the finally obtained polypropylene resin is 99.5 to 60% by mass.
- polypropylene having an intrinsic viscosity [ ⁇ 2nd ] of 0.1 to 5 dl / g, preferably 0.3 to 3 dl / g is finally obtained.
- the intrinsic viscosity [ ⁇ 3rd ] is 0.001 to 5 dl / g, preferably 0.05 to 3 dl.
- / G of polypropylene is preferably produced in such an amount that the content in the finally obtained polypropylene resin is 0.5 to 40% by mass.
- the catalyst a general Ziegler-Natta catalyst is preferably used.
- the catalyst used may contain a promoter component and a donor.
- the molecular weight distribution can be controlled by appropriately adjusting the catalyst and polymerization conditions.
- a method of performing a peroxidation treatment using a decomposing agent such as hydrogen peroxide or organic peroxide it is preferable to adopt.
- a peroxide is added to a collapsible polymer such as polypropylene, a hydrogen abstraction reaction occurs from the polymer, and the resulting polymer radical partially recombines to cause a crosslinking reaction, but most radicals undergo secondary decomposition ( ⁇ cleavage). ) And is divided into two polymers having smaller molecular weights.
- a method for obtaining a resin containing a low molecular weight component appropriately by oxidative decomposition include the following methods. That is, polypropylene resin powder or pellets obtained by the polymerization reaction and, as an organic peroxide, for example, 1,3-bis- (tertiary-butyl peroxide isopropyl) -benzene or the like is 0.001% by mass to 0%.
- the polypropylene resin composition in one embodiment of the present invention in which a polypropylene resin composition is obtained by blending resins, preferably contains the polypropylene resin A described below.
- the weight average molecular weight of the polypropylene resin A is preferably 250,000 or more and 450,000 or less, and more preferably 250,000 or more and 400,000 or less.
- the resin fluidity is appropriate, the thickness of the cast raw sheet can be easily controlled, and a thin stretched film can be easily produced. .
- seat can have moderate stretchability, it is preferable.
- the molecular weight distribution (Mw / Mn) calculated as a ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polypropylene resin A is preferably 7.0 or more and 12.0 or less.
- the molecular weight distribution (Mw / Mn) is more preferably 7.0 or more and 11.0 or less, and further preferably 7.2 or more and 10.0 or less.
- the molecular weight distribution (Mz / Mn) calculated as a ratio of the Z average molecular weight (Mz) and the number average molecular weight (Mn) of the polypropylene resin A is preferably 20 or more and 70 or less.
- the molecular weight distribution (Mz / Mn) is more preferably 25 or more and 60 or less, and further preferably 25 or more and 50 or less.
- the weight average molecular weight (Mw), number average molecular weight (Mn), and Z average molecular weight (Mz) of the polypropylene resin A are the same as the weight average molecular weight (Mw) of the above-mentioned polypropylene resin. It can be measured by the (GPC) method.
- the molecular weight distribution (Mw / Mn) is calculated as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), the weight average molecular weight (Mw) / number average molecular weight (Mn).
- Mn) is calculated as the ratio of Z average molecular weight (Mz) to number average molecular weight (Mn), Z average molecular weight (Mz) / number average molecular weight (Mn).
- melt flow rate can be used as a measure of average molecular weight.
- the MFR of the polypropylene resin A is preferably 7 g / 10 minutes or less and more preferably 6 g / 10 minutes or less from the viewpoint of stretchability.
- it is preferable that it is 4 g / 10min or more from a viewpoint of raising the precision of the thickness of the biaxially stretched polypropylene film of this invention, and it is more preferable that it is 4.5 g / 10min or more.
- the mesopentad fraction ([mmmm]) of the polypropylene resin A is preferably 94.0% or more and 98.0% or less.
- the mesopentad fraction is more preferably 95.0% or more and 97.0% or less.
- 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
- measurement can be performed using a high temperature Fourier transform nuclear magnetic resonance apparatus (high temperature FT-NMR), JNM-ECP500 manufactured by JEOL Ltd.
- the observation nucleus is 13 C (125 MHz), the measurement temperature is 135 ° C.
- ODCB o-dichlorobenzene
- the measurement method by high temperature NMR is, for example, the method described in “Japan Analytical Chemistry / Polymer Analysis Research Roundtable, New Edition Polymer Analysis Handbook, Kinokuniya, 1995, p. 610”. Can be done with reference to.
- the pentad fraction representing the degree of stereoregularity is a combination of the quintet (pentad) of the consensus “meso (m)” arranged in the same direction and the consensus “rasemo (r)” arranged in the opposite direction (mmmm and mrrm). Etc.) based on the integrated value of the intensity of each signal derived from.
- Each signal derived from mmmm, mrrm, etc. can be attributed with reference to, for example, “T. Hayashi et al., Polymer, 29, 138 (1988)”.
- the polypropylene resin composition preferably contains 55% by mass or more and 90% by mass or less of polypropylene resin A based on the total amount of polypropylene resin contained in the polypropylene resin composition, and is 60% by mass or more and 85% by mass or less. It is more preferable to include it, and it is especially preferable to include 60 mass% or more and 80 mass% or less.
- the polypropylene resin composition has a number average molecular weight (Mn) of 40,000 to 150,000 from the viewpoint of reducing the crystallite size and obtaining a capacitor film having high voltage resistance. It is preferable to contain polypropylene resin B1 having an average molecular weight of 1,200,000 to 2.6 million.
- the number average molecular weight (Mn) of the polypropylene resin B1 is preferably 40,000 to 150,000, and more preferably 45,000 to 130,000, from the viewpoint of stretchability.
- the Z average molecular weight of the polypropylene resin B1 is preferably 1.2 million or more and 2.6 million or less, more preferably 1.2 million or more and 2.4 million or less, from the viewpoint of increasing the accuracy of the thickness of the biaxially stretched polypropylene film of the present invention. More preferably, it is 1.2 million or more and 2 million or less, and particularly preferably 1.25 million or more and 1.9 million or less.
- the polypropylene resin B1 having a number average molecular weight (Mn) and a Z average molecular weight within the above ranges is a polypropylene resin contained in the polypropylene resin composition from the viewpoint of reducing the crystallite size and obtaining a capacitor film having high voltage resistance. Based on the total amount, it is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50%. It is preferably contained in an amount of not more than mass%.
- melt flow rate can be used as a measure of average molecular weight.
- the polypropylene resin composition preferably includes a polypropylene resin B2 having a melt flow rate of 4 g / 10 min or less from the viewpoint of reducing the crystallite size and obtaining a capacitor film having high voltage resistance.
- the melt flow rate of the polypropylene resin B2 is preferably 4 g / 10 minutes or less, more preferably 3.5 g / 10 minutes or less, from the viewpoint of reducing the crystallite size and obtaining a capacitor film with high voltage resistance. It is particularly preferably 2.0 g / 10 min or less.
- the melt flow rate is preferably 0.1 g / 10 min or more, more preferably 0.2 g / 10 min or more from the viewpoint of increasing the thickness accuracy of the biaxially stretched polypropylene film of the present invention. More preferably, it is 0.3 g / 10 min or more.
- the polypropylene resin B2 having a melt flow rate in the above range is preferably based on the total amount of the polypropylene resin contained in the polypropylene resin composition from the viewpoint of reducing the crystallite size and obtaining a capacitor film with high voltage resistance. 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less. It is preferable that
- polypropylene resin B1 having a higher molecular weight or the polypropylene resin B2 having a lower MFR is dried or melted with respect to the polypropylene resin A. It is preferable to mix in a state to obtain a polypropylene resin composition.
- polypropylene resin B1 or B2 is preferably mixed in an amount of 1 to 70% by mass, more preferably 5 to 60% by mass, and further preferably 10 to 50% by mass with respect to 100% by mass of polypropylene resin A as a main component.
- the method of obtaining the polypropylene resin composition which is 2 types of polypropylene resin mixing systems is preferably employ
- these resins may be mixed freely without limitation, including a method of dry blending the polymerized powder or pellets with a mixer or the like, a method of melt-kneading the polymerized powder or pellets with a kneader to obtain a blended resin, and the like. You may mix according to the method.
- a resin other than the polypropylene resin may be mixed with the polypropylene resin composition within a range not impairing the effects of the present invention.
- the “other resin” is not particularly limited, and a conventionally known resin that is a resin other than a polypropylene resin and is suitable for a capacitor application can be appropriately used in the present invention.
- resins include, for example, polyolefins other than polypropylene, such as polyethylene, poly (1-butene), polyisobutene, poly (1-pentene), poly (1-methylpentene), ethylene-propylene copolymers, propylene -Copolymers of ⁇ -olefins such as butene copolymers and ethylene-butene copolymers, vinyl monomers such as styrene-butadiene random copolymers, random copolymers of diene monomers, styrene-butadiene -Vinyl monomer such as styrene block copolymer-Diene monomer-Random copolymer of vinyl monomer. It is preferable that the compounding quantity of such other resin is 10 mass parts or less based on the total amount of the polypropylene resin contained in a polypropylene resin composition, More preferably, it is 5 mass parts or less.
- the polypropylene resin composition may contain at least one additive as required in addition to the polypropylene resin.
- the additive is not particularly limited as long as it is an additive used for a polypropylene resin.
- additives include, for example, stabilizers such as antioxidants, chlorine absorbers, ultraviolet absorbers, lubricants, plasticizers, flame retardants, antistatic agents, colorants and the like. You may add such an additive to a polypropylene resin composition within the range which does not impair the effect of this invention.
- the “antioxidant” is not particularly limited as long as it is normally used for polypropylene. Antioxidants are generally used for two purposes. One purpose is to suppress thermal deterioration and oxidation deterioration in the extruder, and the other purpose is to contribute to suppression of deterioration and improvement of capacitor performance in long-term use as a film capacitor.
- An antioxidant that suppresses thermal degradation and oxidative degradation in the extruder is also referred to as a “primary agent”, and an antioxidant that contributes to improvement of capacitor performance is also referred to as a “secondary agent”. Two types of antioxidants may be used for these two purposes, and one type of antioxidant may be used for the two purposes.
- the polypropylene resin composition is prepared by using, for example, 2,6-di-tert-butyl-para-cresol (generic name: BHT) as the primary agent, and polypropylene resin.
- BHT 2,6-di-tert-butyl-para-cresol
- Most of the antioxidant for this purpose is consumed in the molding process in the extruder, and hardly remains in the film after film formation (generally, the residual amount is less than 100 ppm).
- a hindered phenol-based antioxidant having a carbonyl group can be used as the secondary agent.
- the hindered phenol-based antioxidant having a carbonyl group that can be used in the present invention is not particularly limited.
- triethylene glycol-bis [3- (3-tertiary-butyl-5-methyl-4-hydroxyphenyl] ) Propionate] (trade name: Irganox 245)
- 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 259)
- Pentaerythrityl tetrakis [3- (3,5-di-tertiarybutyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1010)
- 2,2-thio-diethylenebis [3- (3 5-di-tertiary-butyl-4-hydroxyphenyl) propionate] product) :
- pentaerythryl tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate has a high molecular weight, is highly compatible with polypropylene, has low volatility and is excellent in heat resistance. ] Is most preferred.
- the hindered phenol-based antioxidant having a carbonyl group is preferably not less than 2000 ppm and not more than 7000 ppm based on the total amount of polypropylene resin contained in the polypropylene resin composition, considering that it is consumed in the extruder. Preferably, it is contained in the polypropylene resin composition in an amount of 3000 ppm to 7000 ppm.
- the polypropylene resin composition does not contain a primary agent
- more hindered phenol antioxidants having a carbonyl group can be used.
- the hindered phenol-based antioxidant having a carbonyl group in the extruder increases the consumption amount of the hindered phenol-based antioxidant having a carbonyl group. It is preferable to add in the following amounts.
- one or more hindered phenol antioxidants (secondary agents) having a carbonyl group may be contained for the purpose of suppressing deterioration that progresses with time during long-term use of the biaxially stretched polypropylene film.
- the content of the hindered phenolic antioxidant in the film is preferably 1000 ppm or more and 6000 ppm or less, more preferably 1500 ppm or more and 6000 ppm or less, based on the total amount of polypropylene resin contained in the polypropylene resin composition. preferable.
- Film capacitors containing hindered phenolic antioxidants with carbonyl groups that have good compatibility with polypropylene at the molecular level and in the optimum specified range are very high temperatures while maintaining high withstand voltage performance. This life test is also preferable because the electrostatic capacity is not lowered (deterioration does not progress) and long-term durability is improved over a long period of time.
- the polypropylene resin composition may contain a phosphorus antioxidant as an antioxidant.
- the phosphorus-based antioxidant can suppress the uniform cleavage of the organic peroxide and suppress the deterioration of the resin.
- Examples of phosphorus antioxidants include tris (2,4-di-t-butylphenyl) phosphite (trade name: Irgaphos 168), bis (2,4-di-t-butyl-6-methylphenyl) ethyl. And phosphite (trade name: Irgaphos 38).
- the phosphorus-based antioxidant is preferably added in an amount of about 1000 ppm to 2000 ppm based on 100 parts by mass of the polypropylene resin.
- the polypropylene resin composition may contain the above-mentioned antioxidant alone as an antioxidant, or may contain, for example, a combination of BHT and a hindered phenol antioxidant, and a phosphorus antioxidant. And BHT and / or a hindered phenol antioxidant may be contained in combination.
- the combined use of a phosphorus antioxidant and a hindered phenol antioxidant is preferable because a strong synergistic effect is obtained.
- Chlorine absorbent is not particularly limited as long as it is normally used for polypropylene.
- Examples of the chlorine absorbent include metal soaps such as calcium stearate.
- the “ultraviolet absorber” is not particularly limited as long as it is normally used for polypropylene.
- examples of the ultraviolet absorber include benzotriazole (such as Tinuvin 328 manufactured by BASF), benzophenone (such as Cysorb UV-531 manufactured by Cytec), and hydroxybenzoate (such as UV-CHEK-AM-340 manufactured by Ferro).
- “Lubricant” is not particularly limited as long as it is usually used for polypropylene.
- examples of lubricants include primary amides (such as stearic acid amides), secondary amides (such as N-stearyl stearic acid amides), ethylene bisamides (such as N, N'-ethylene bisstearic acid amides), and the like.
- Plasticizer is not particularly limited as long as it is usually used for polypropylene. As a plasticizer, PP random copolymer etc. can be illustrated, for example.
- “Flame retardant” is not particularly limited as long as it is usually used for polypropylene.
- Examples of the flame retardant include halogen compounds, aluminum hydroxide, magnesium hydroxide, phosphates, borates, and antimony oxides.
- the “antistatic agent” is not particularly limited as long as it is usually used for polypropylene.
- examples of the antistatic agent include glycerin monoester (glycerin monostearate and the like), ethoxylated secondary amine and the like.
- the “colorant” is not particularly limited as long as it is usually used for polypropylene.
- Examples of the colorant include cadmium and chromium-containing inorganic compounds to azo and quinacridone organic pigments.
- the polypropylene resin contained in the polypropylene resin composition can be produced using a conventionally known method, and examples of the polymerization method include a gas phase polymerization method, a bulk polymerization method, and a slurry polymerization method.
- the polymerization may be one-stage polymerization using one polymerization reactor, or may be multistage polymerization using two or more polymerization reactors. Moreover, you may superpose
- a conventionally known Ziegler-Natta catalyst can be used as the polymerization catalyst, and the polymerization catalyst may contain a promoter component and a donor.
- the molecular weight, molecular weight distribution, stereoregularity and the like of the polypropylene resin can be controlled by appropriately adjusting the polymerization catalyst and other polymerization conditions.
- the mixing method is not particularly limited. For example, a method of dry blending each resin in powder form or pellet form with a mixer or the like And a method of obtaining a blended resin by melting and kneading each resin in powder form or pellet form in a kneader.
- mixers there are no particular restrictions on the mixers that can be used, and Henschel mixers, ribbon blenders, Banbury mixers, and the like can be used. Moreover, there is no restriction
- the kneading temperature is not particularly limited as long as even good kneading can be obtained, but it is generally in the range of 200 ° C to 300 ° C, preferably 230 ° C to 270 ° C. Kneading at an excessively high temperature is not preferable because the resin may be deteriorated. In order to suppress deterioration during resin kneading and mixing, an inert gas such as nitrogen may be purged into the kneader. The melt-kneaded resin is pelletized to an appropriate size using a known granulator, whereby mixed polypropylene raw material resin pellets can be obtained.
- the total ash resulting from the polymerization catalyst residue and the like contained in the polypropylene raw material resin is as small as possible in order to improve electrical characteristics.
- the total ash content is preferably 200 ppm or less, more preferably 100 ppm or less, and particularly preferably 75 ppm or less, based on the polypropylene resin (100 parts by mass).
- the biaxially stretched polypropylene film for capacitors of the present invention is a polypropylene film formed by biaxially stretching the above polypropylene resin composition.
- the biaxially stretched polypropylene film for capacitors of the present invention is calculated from the half-value width of the ⁇ -crystal (040) plane reflection peak measured by wide-angle X-ray diffractometry from the viewpoint of voltage endurance using the Scherrer equation. It preferably has a crystallite size of 2 nm or less.
- the “crystallite size” of the polypropylene film is determined from the half-value width of the diffraction reflection peak of the ⁇ crystal (040) plane of the polypropylene film, which is measured using a wide-angle X-ray diffraction method (XRD method). It refers to the crystallite size calculated using the Scherrer equation described below.
- the crystallite size of the polypropylene film is more preferably 12.0 nm or less.
- the crystallite size of the polypropylene film is preferably 10.0 nm or more, and more preferably 10.5 nm or more.
- the “crystallite size” of the polypropylene film of the present invention can be determined as follows. First, wide-angle X-ray diffraction of the biaxially stretched polypropylene film or its metallized film was performed, and the half width of the diffraction reflection peak of the obtained ⁇ crystal (040) plane was determined. Next, from the half width of the diffraction reflection peak of the obtained ⁇ crystal (040) plane, the crystallite size was determined using the Scherrer equation shown in the following equation (1). In the present invention, the shape factor constant K is 0.94. [Where D is the crystallite size (nm), K is a constant (shape factor), ⁇ is the used X-ray wavelength (nm), ⁇ is the calculated half-value width, and ⁇ is the diffraction Bragg angle. ]
- the biaxially stretched polypropylene film of the present invention can be obtained by biaxially stretching the above polypropylene resin composition according to a usual method.
- a known method For example, after supplying polypropylene resin pellets, dry-mixed polypropylene resin pellets and / or powder, or mixed polypropylene resin pellets prepared by pre-melting and kneading to an extruder, heating and melting, and passing through a filtration filter 170 ° C. to 320 ° C., preferably 200 ° C.
- An unstretched cast raw sheet can be formed by cooling and solidifying with at least one held metal drum.
- the thickness of the cast original fabric sheet is preferably 0.05 mm to 2 mm, and more preferably 0.1 mm to 1 mm.
- the biaxially stretched polypropylene film can be produced by subjecting the polypropylene cast original fabric sheet to stretching treatment. Stretching is performed biaxially orienting vertically and horizontally in a biaxial manner. Examples of the stretching method include simultaneous or sequential biaxial stretching methods, and a sequential biaxial stretching method is preferred.
- a sequential biaxial stretching method for example, the cast raw sheet is first maintained at a temperature of 100 to 160 ° C., passed between rolls provided with a speed difference, stretched 3 to 7 times in the flow direction, and immediately cooled to room temperature. To do. Subsequently, the stretched film is guided to a tenter, stretched 3 to 11 times in the width direction at a temperature of 160 ° C. or higher, and then relaxed and heat-set, and wound up. The wound film can be cut to a desired product width after being subjected to an aging treatment in an atmosphere of about 20 to 45 ° C.
- the thickness of the biaxially stretched polypropylene film used for producing the metallized polypropylene film is preferably 1 to 6 ⁇ m from the viewpoint of obtaining a small and large capacity capacitor element. It is more preferable to use a biaxially stretched polypropylene film having a thickness of 1.5 ⁇ m or more. Moreover, it is desirable that the biaxially stretched polypropylene film to be used is extremely thin, and the thickness thereof is preferably 5 ⁇ m or less, more preferably 4 ⁇ m or less, and further preferably 3 ⁇ m or less. The thickness of the film can be measured according to JIS-C2330 using, for example, a paper thickness measuring instrument, a micrometer (JIS-B7502), or the like.
- the surface of the biaxially stretched polypropylene film is preferably provided with an appropriate surface roughness that improves the winding properties and also improves the capacitor characteristics.
- the biaxially stretched polypropylene film preferably has a surface roughness of 0.03 ⁇ m or more and 0.08 ⁇ m or less in centerline average roughness (Ra) on at least one surface, and a maximum height (Rz, It is preferable that the surface is finely roughened to 0.3 ⁇ m or more and 0.8 ⁇ m or less as Rmax) in the old JIS definition.
- Ra and Rz are in the above-mentioned preferable ranges, the surface can be a finely roughened surface, and during capacitor processing, it is difficult to cause winding wrinkles in element winding processing, and the surface can be preferably wound up. it can. Furthermore, since uniform contact is also possible between the films, the voltage resistance and the voltage resistance over a long period of time can be improved.
- Ra and Rz are, for example, stylus type surface roughness meters that are generally widely used by the method defined in JIS-B0601: 2001, etc.
- the value measured using a stylus type surface roughness meter for example, a diamond needle.
- “Ra” and “Rz” are, for example, a method defined in JIS-B0601: 2001 using a three-dimensional surface roughness meter Surfcom 1400D-3DF-12 manufactured by Tokyo Seimitsu Co., Ltd. It can be determined in compliance.
- various known roughening methods such as an embossing method and an etching method can be employed, and among them, a roughening using ⁇ crystals that do not require the incorporation of impurities.
- the surface method is preferred.
- the production rate of ⁇ crystals can be generally controlled by changing the casting temperature and the casting speed.
- the melting / transition ratio of the ⁇ crystal can be controlled by the roll temperature in the longitudinal stretching process, and fine roughening can be achieved by selecting optimum production conditions for these two parameters of ⁇ crystal formation and its melting / transition. Surface property can be obtained.
- the biaxially stretched polypropylene film can be subjected to a corona discharge treatment online or offline after the stretching and heat setting processes for the purpose of enhancing the adhesive properties in the subsequent processes such as a metal vapor deposition process.
- the corona discharge treatment can be performed using a known method.
- As the atmospheric gas it is preferable to use air, carbon dioxide gas, nitrogen gas, and a mixed gas thereof.
- a metal vapor deposition film is formed on one side of the biaxially stretched polypropylene film.
- a method for providing a metal vapor deposition film on a biaxially stretched polypropylene film include a vacuum vapor deposition method and a sputtering method, and the vacuum vapor deposition method is preferable from the viewpoint of productivity and economy.
- a vacuum vapor deposition method it carries out by selecting suitably from well-known systems, such as a crucible system and a wire system.
- the metal constituting the metal vapor deposition film it is possible to use a single metal such as zinc, lead, silver, chromium, aluminum, copper, nickel, a mixture or an alloy composed of a plurality of kinds of metals selected from these metals. it can. From the standpoints of environment, economy, and film capacitor performance, especially temperature characteristics and frequency characteristics of capacitance and insulation resistance, a simple metal or metal selected from zinc and aluminum as the metal constituting the metal deposition film It is preferable to employ a mixture or an alloy.
- the film resistance of the metal deposition film is preferably 1 to 100 ⁇ / ⁇ from the viewpoint of the electrical characteristics of the capacitor. A higher value within this range is desirable from the viewpoint of self-healing (self-healing) characteristics, and the film resistance is more preferably 5 ⁇ / ⁇ or more, and further preferably 10 ⁇ / ⁇ or more. Further, from the viewpoint of safety as a capacitor element, the membrane resistance is more preferably 50 ⁇ / ⁇ or less, and further preferably 20 ⁇ / ⁇ or less.
- the film resistance of a metal vapor deposition film can be measured during metal vapor deposition, for example, by the two-terminal method known to those skilled in the art. The film resistance of the metal vapor deposition film can be adjusted by adjusting the evaporation amount by adjusting the output of the evaporation source, for example.
- an insulating margin is formed without depositing a certain width from one end of the film so that a capacitor is formed when the film is wound. Furthermore, in order to strengthen the bonding between the metallized polypropylene film and the metallicon electrode, it is preferable to form a heavy edge structure at the end opposite to the insulation margin, and the film resistance of the heavy edge is usually 2 to 8 ⁇ / ⁇ . Yes, preferably 3 to 6 ⁇ / ⁇ .
- the margin pattern of the metal vapor deposition film to be formed is not particularly limited, but from the viewpoint of the security of the film capacitor, a pattern including a so-called special margin such as a fish net pattern or a T margin pattern is preferable. It is preferable to form a metal vapor-deposited film with a pattern including a special margin on one side of a biaxially stretched polypropylene film because the security of the obtained film capacitor is improved and the breakdown and short-circuit of the film capacitor can be suppressed.
- a known method such as a tape method in which masking is performed with a tape at the time of vapor deposition or an oil method in which masking is performed by application of oil can be used without any limitation.
- the biaxially stretched polypropylene film provided with the metal vapor-deposited film is processed into a metallized polypropylene film capacitor through a winding process in which the film is wound along the longitudinal direction of the film. That is, two metallized polypropylene films prepared as described above are paired and wound so that metal vapor deposition films and polypropylene films are alternately laminated, and then paired by metal spraying on both end faces.
- a metal capacitor electrode is formed to produce a film capacitor element.
- the film is wound.
- two pairs of metallized polypropylene films are overlapped and wound so that metal vapor deposition portions and polypropylene films are alternately laminated, and further, the insulation margin portions are on the opposite side.
- the winding machine to be used is not particularly limited, and for example, an automatic winder 3KAW-N2 manufactured by Minato Seisakusho Co., Ltd. can be used.
- the optimum value of the applied pressure varies depending on the thickness of the polypropylene film and the like, but is preferably 10 ⁇ 10 4 to 450 ⁇ 10 4 Pa, more preferably 30 ⁇ 10 4 to 300 ⁇ 10 4 Pa. More preferably, it is 40 ⁇ 10 4 to 150 ⁇ 10 4 Pa.
- the heat treatment temperature is preferably 100 to 120 ° C.
- the time for performing the heat treatment is preferably 5 hours or more, more preferably 10 hours or more from the viewpoint of obtaining mechanical and thermal stability, but it prevents molding defects such as heat wrinkles and molding. In this respect, it is preferably 20 hours or less, and more preferably 15 hours or less.
- a film capacitor element is manufactured by spraying metal on both end faces of the wound material to provide metallicon electrodes.
- a lead wire is usually welded to the metallicon electrode.
- the metallized polypropylene film capacitor element produced by the method described above is further subjected to a predetermined heat treatment. That is, the film capacitor element is subjected to heat treatment at a temperature of 80 to 115 ° C. for 1 hour or longer (hereinafter sometimes referred to as “thermal aging”).
- the temperature of the heat treatment is preferably 80 ° C. or higher and preferably 90 ° C. or higher, while 115 ° C. or lower and 110 ° C. or lower. preferable.
- the effect of heat aging can be obtained by performing heat treatment at the above temperature. Specifically, the gap between the films constituting the capacitor element based on the metallized polypropylene film is reduced, corona discharge is suppressed, and metal It is considered that the internal structure of the fluorinated polypropylene film changes and crystallization proceeds, and as a result, the withstand voltage is improved.
- the temperature of the heat treatment is lower than the predetermined temperature, the above effect due to thermal aging cannot be obtained sufficiently.
- the temperature of the heat treatment is higher than a predetermined temperature, the polypropylene film may be thermally decomposed or oxidized and deteriorated.
- a method for performing heat treatment on the film capacitor element for example, from a known method including a method using a thermostatic bath or a method using high-frequency induction heating in an air atmosphere, a vacuum atmosphere, or an inert gas atmosphere Although it may be selected as appropriate, it is preferable to employ a method using a thermostatic bath.
- the capacitor element obtained by the above method is a small and large-capacity film capacitor element based on a metallized polypropylene film, and has high voltage resistance at high temperature and long-term durability at high temperature.
- test methods for examining the durability of the capacitor element include “step-up test”, “life test”, and the like, both of which are test methods for evaluating the durability at a high temperature of 100 ° C. or higher.
- “Step-up test” is a test method in which a constant voltage is repeatedly applied to a capacitor element for a certain period (short time) while gradually increasing the voltage value. This is an evaluation method from the viewpoint of voltage.
- the “life test” is a test method in which a constant voltage is applied to the capacitor element over a long period of time, and the long-term voltage resistance, that is, the durability of the capacitor element is reduced by the capacitance. It is a method of evaluation from the viewpoint of the time when no runaway occurs. Details of each test method are as described later.
- the capacitance change rate ⁇ C (after 200 hours) after voltage application evaluated according to the “life test” is preferably ⁇ 10% or more, more preferably ⁇ 8% or more. Preferably, it is ⁇ 6% or more, more preferably ⁇ 5% or more.
- the rated voltage of a high voltage type capacitor for a hybrid vehicle is generally 400 to 800 V DC .
- the “life test” may be performed with an applied voltage of 600 V DC .
- Measuring instrument manufactured by Tosoh Corporation, differential refractometer (RI) built-in high-temperature GPC apparatus, HLC-8121GPC-HT type Column: manufactured by Tosoh Corporation, connecting three TSKgel GMHHR-H (20) HT Column temperature: 140 ° C Eluent: Trichlorobenzene Flow rate: 1.0 ml / min
- RI differential refractometer
- HLC-8121GPC-HT type Column manufactured by Tosoh Corporation
- Eluent Trichlorobenzene
- Flow rate 1.0 ml / min
- the measurement result was obtained by polystyrene conversion using the standard polystyrene by Tosoh Corporation for preparation of a calibration curve.
- the molecular weight was converted to the molecular weight of polypropylene using a Q-factor.
- Polypropylene resin For the production of polypropylene films of Examples and Comparative Examples, the number average molecular weight (Mn), weight average molecular weight (Mw), Z average molecular weight (Mz), molecular weight distribution (Mw / Mn), molecular weight distribution (shown in Table 1 below) A polypropylene resin with Mz / Mn) and MFR was used. These values are values measured in accordance with the above measurement method in the form of raw material resin pellets.
- Polypropylene resin PP-1 Isotactic polypropylene (manufactured by Prime Polymer Co., Ltd.)
- Polypropylene resin PP-2 Isotactic polypropylene (manufactured by Nippon Polypro Co., Ltd.)
- Polypropylene resin PP-3 Isotactic polypropylene (manufactured by Korea Oil Chemical Co., Ltd.)
- Polypropylene resin PP-5 Isotactic polypropylene (manufactured by Prime Polymer Co., Ltd.)
- Polypropylene resin PP-6 Isotactic polypropylene (manufactured by Korea Oil Chemical Co., Ltd.)
- Polypropylene resin PP-7 Isotactic polypropylene (manufactured by Prime Polymer Co., Ltd.)
- Polypropylene resin PP-8 Isotactic polyprop
- All of the polypropylene resins PP-1 to PP-8 are 2,6-di-t-butyl-p-cresol (generic name: BHT) 2000 ppm as an antioxidant (primary agent), hindered having a carbonyl group Pentaerysutyl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1010) 3000-6500 ppm as a phenolic antioxidant (secondary agent), And at least one antioxidant selected from the group consisting of 1000 to 2000 ppm of tris (2,4-di-t-butylphenyl) phosphite (trade name: Irgaphos 168), which is a phosphorus-based antioxidant. contains.
- BHT 2,6-di-t-butyl-p-cresol
- polypropylene resin compositions having the compositions shown in Table 2 and Table 3 were prepared according to the following method.
- the obtained polypropylene resin compositions were biaxially stretched to produce polypropylene films of Examples 1 to 6 and Comparative Examples 1 to 4.
- the physical properties of the polypropylene resin constituting each film were measured according to the above measuring method.
- the dielectric breakdown voltage and the crystallite size were evaluated by the method shown below. The obtained results are shown in Tables 2 and 3.
- the cast raw sheet is stretched 5 times in the flow direction at a temperature of 140 ° C., immediately cooled to room temperature, and then stretched 10 times in the lateral direction at a temperature of 165 ° C. by a tenter to obtain a thickness of 2.
- a very thin biaxially oriented polypropylene film of 3 ⁇ m was obtained.
- Comparative Example 1 A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that the resin PP-1 was used alone.
- Comparative Example 2 A cast original fabric sheet was produced in the same manner as in Example 1 except that the resin PP-2 was used alone. The cast original fabric sheet was attempted to be biaxially stretched in the same manner as in Example 1, but it was broken in the stretching step, and a biaxially stretched polypropylene film was not obtained.
- Comparative Example 3 A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that the resin PP-4 was used alone.
- Comparative Example 4 A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that the resin PP-5 was used alone.
- Film thickness can be measured in accordance with JIS-C2330 using, for example, a paper thickness measuring instrument, a micrometer (JIS-B7502) or the like.
- Crystallite size The crystallite size of the biaxially stretched polypropylene film was measured according to the following using an XRD (wide angle X-ray diffraction) apparatus.
- Measuring device Disstop X-ray diffractometer “MiniFlex300” manufactured by Rigaku Corporation X-ray generation output: 30KV, 10mA
- Irradiation X-ray Monochromator monochromated CuK ⁇ ray (wavelength 0.15418 nm)
- Detector scintillation counter goniometer scan: 2 ⁇ / ⁇ interlocking scan From the obtained data, diffraction reflection of ⁇ crystal (040) plane using analysis computer and integrated powder X-ray analysis software PDXL The half width of the peak was calculated.
- the crystallite size was determined using the Scherrer equation of the following equation (1).
- the shape factor constant K is 0.94.
- D is the crystallite size (nm)
- K is a constant (shape factor)
- ⁇ is the used X-ray wavelength (nm)
- ⁇ is the calculated half-value width
- ⁇ is the diffraction Bragg angle.
- Dielectric breakdown voltage The dielectric breakdown voltage value was measured at 100 ° C. using a DC power source in accordance with JIS C2330 (2001) 7.4.11.2 B method (plate electrode method). The average breakdown voltage value (V DC ) of 12 measurements is divided by the film thickness ( ⁇ m), and the average value of 8 times excluding the upper 2 times and lower 2 times is obtained as the breakdown voltage (V DC). / ⁇ m).
- Capacitor element life test (long voltage resistance) The capacitor element was preheated at 105 ° C. in advance, and the initial capacitance before the test was evaluated at room temperature using an LCR high tester 3522-50 manufactured by Hioki Electric Co., Ltd. Next, in a high temperature bath at 105 ° C., a voltage of DC 600V was continuously applied to the capacitor element for 200 hours. The capacity of the element after 200 hours was measured at room temperature with an LCR tester, and the capacity change rate before and after voltage loading was calculated. The rate of change in capacity after the elapse of 200 hours was evaluated based on the average value of three elements. The rate of change in capacity after 200 hours was -1.9% in Example 1, -1.0% in Example 2, and -3.0% in Example 3. The capacity change rate after 200 hours has passed is preferably ⁇ 5% or more.
- the biaxially stretched polypropylene film of the present invention has an excellent dielectric breakdown voltage and an excellent withstand voltage at high temperatures.
- a small and high-capacitance type capacitor that has been confirmed to have the above-mentioned excellent voltage resistance while being a very thin biaxially stretched polypropylene film having a thickness of 2.3 ⁇ m, a high voltage resistance is required. It is extremely suitable as a biaxially stretched polypropylene film.
- the polypropylene films of Comparative Examples 1 and 3 were not composed of a polypropylene resin having a differential distribution value difference within a predetermined range, and sufficient voltage resistance was not obtained.
- the polypropylene films of Comparative Examples 3 and 4 made of a polypropylene resin having a small high molecular weight component and not having a predetermined Z average molecular weight, the dielectric breakdown voltage was very low.
- the polypropylene film of Comparative Example 2 could not be stretched into a film.
- the biaxially stretched polypropylene film for capacitors of the present invention is excellent in dielectric breakdown voltage, by producing a capacitor using this film, the withstand voltage at high temperatures, particularly the initial withstand voltage and the long-term withstand voltage are improved. Improvement is expected. Furthermore, since the biaxially stretched polypropylene film for capacitors of the present invention is excellent in dielectric breakdown voltage and can be reduced in thickness, it can be preferably used for small and high-capacity capacitors that require high voltage resistance. is there.
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Abstract
Description
本発明は、高温下での高い耐電圧性を有する、絶縁破壊特性に優れたコンデンサ用二軸延伸ポリプロピレンフィルムに関する。さらにより詳細には、高温下、高電圧が印加される高容量型コンデンサに好適に使用可能であり、好ましくは厚さの薄い、コンデンサ用二軸延伸ポリプロピレンフィルムに関する。
そこで、本発明の目的は、高温下での耐電圧性を有する、絶縁破壊特性に優れたコンデンサ用二軸延伸ポリプロピレンフィルムを提供することである。さらに、高温下で高電圧が印加される高容量のコンデンサに好適に使用可能である、好ましくは厚さの薄い、コンデンサ用二軸延伸ポリプロピレンフィルムを提供することである。さらに、上記のコンデンサ用二軸延伸ポリプロピレンフィルムに金属蒸着が施されたコンデンサ用金属化ポリプロピレンフィルム、ならびに、このようなポリプロピレンフィルムを用いて製造した、高温下での耐電圧性を有するコンデンサを提供することである。
すなわち、本発明は、以下の好適な態様を包含する。
〔1〕コンデンサ用二軸延伸ポリプロピレンフィルムであって、該ポリプロピレンフィルムを構成するポリプロピレン樹脂は、
・数平均分子量が4万以上10万以下、
・Z平均分子量が95万以上150万以下、
・分子量分布曲線において、対数分子量Log(M)=4.5のときの微分分布値からLog(M)=6.0のときの微分分布値を引いた差が-15%以上11%以下
である、ポリプロピレンフィルム。
〔2〕前記ポリプロピレンフィルムの結晶子サイズは、広角X線回折法により測定したα晶(040)面反射ピークの半価幅からScherrerの式を用いて算出して12.2nm以下である、前記〔1〕に記載のコンデンサ用二軸延伸ポリプロピレンフィルム。
〔3〕前記ポリプロピレンフィルムはポリプロピレン樹脂組成物を二軸延伸してなり、該ポリプロピレン樹脂組成物は、メルトフローレートが4g/10分以下であるポリプロピレン樹脂を、該ポリプロピレン樹脂組成物に含まれるポリプロピレン樹脂の総量に基づいて1質量%以上70質量%以下の量で含有する、前記〔1〕または〔2〕に記載のコンデンサ用二軸延伸ポリプロピレンフィルム。
〔4〕前記ポリプロピレンフィルムはポリプロピレン樹脂組成物を二軸延伸してなり、該ポリプロピレン樹脂組成物は、数平均分子量(Mn)が4万以上15万以下であり、Z平均分子量が120万以上260万以下であるポリプロピレン樹脂を、該ポリプロピレン樹脂組成物に含まれるポリプロピレン樹脂の総量に基づいて1質量%以上70質量%以下の量で含有する、前記〔1〕~〔3〕のいずれかに記載のコンデンサ用二軸延伸ポリプロピレンフィルム。
〔5〕前記〔1〕~〔4〕のいずれかに記載のコンデンサ用二軸延伸ポリプロピレンフィルムの片面または両面に金属蒸着が施された、コンデンサ用金属化ポリプロピレンフィルム。
〔6〕前記〔5〕に記載のコンデンサ用金属化ポリプロピレンフィルムを用いて製造したコンデンサ。
また3段重合の場合、第1段目において極限粘度[η1st]が2.5~10dl/g、好ましくは2.5~7dl/gのポリプロピレンを最終的に得られるポリプロピレン樹脂中の含有量が0.5~40質量%となる量で製造し、次いで第2段目において極限粘度[η2nd]が0.1~5dl/g、好ましくは0.3~3dl/gのポリプロピレンを最終的に得られるポリプロピレン樹脂中の含有量が20~99質量%となる量で製造し、次いで第3段目において極限粘度[η3rd]が0.001~5dl/g、好ましくは0.05~3dl/gのポリプロピレンを最終的に得られるポリプロピレン樹脂中の含有量が0.5~40質量%となる量で製造することが好ましい。
(1)重量平均分子量(Mw)、数平均分子量(Mn)、Z平均分子量(Mz)および微分分布値
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、ポリプロピレン樹脂の平均分子量および分布曲線の微分分布値を測定した。
測定機:東ソー株式会社製、示差屈折計(RI)内蔵高温GPC装置、HLC-8121GPC-HT型
カラム:東ソー株式会社製、TSKgel GMHHR-H(20)HTを3本連結
カラム温度:140℃
溶離液:トリクロロベンゼン
流速:1.0ml/分
なお、検量線の作製には東ソー株式会社製の標準ポリスチレンを用い、ポリスチレン換算により測定結果を得た。ただし、分子量はQ-ファクターを用いてポリプロピレンの分子量へ換算した。
JIS K 7210-1999に準拠して230℃にて測定した。
実施例および比較例のポリプロピレンフィルムの製造に、下記の表1に示す数平均分子量(Mn)、重量平均分子量(Mw)、Z平均分子量(Mz)、分子量分布(Mw/Mn)、分子量分布(Mz/Mn)およびMFRを有するポリプロピレン樹脂を使用した。なお、これらの値は、原料樹脂ペレットの形態で、上記の測定方法に従い測定した値である。
なお、PP-4は、Mw=30万、Mw/Mn=5.2、MFR=4.0g/10分のアイソタクチックポリプロピレン樹脂(プライムポリマー製)を80質量%、MFR=10.0g/10分のアイソタクチックポリプロピレン樹脂(プライムポリマー製)を20質量%混合して得た。
ポリプロピレン樹脂PP-2:アイソタクチックポリプロピレン(日本ポリプロ株式会社製)
ポリプロピレン樹脂PP-3:アイソタクチックポリプロピレン(大韓油化社製)
ポリプロピレン樹脂PP-4:アイソタクチックポリプロピレン
ポリプロピレン樹脂PP-5:アイソタクチックポリプロピレン(プライムポリマー株式会社製)
ポリプロピレン樹脂PP-6:アイソタクチックポリプロピレン(大韓油化社製)
ポリプロピレン樹脂PP-7:アイソタクチックポリプロピレン(プライムポリマー株式会社製)
ポリプロピレン樹脂PP-8:アイソタクチックポリプロピレン(プライムポリマー株式会社製)
樹脂PP-1(酸化防止剤としてイルガノックス1010を5000ppm添加)と樹脂PP-2(酸化防止剤としてイルガノックス1010を5000ppm添加)を、PP-1/PP-2=80/20(質量比)で、連続的に計量混合したドライブレンド体を、押出機に供給した。ドライブレンド体を250℃の温度で溶融した後、Tダイから押し出し、表面温度を92℃に保持した金属ドラムに巻きつけて固化させて、厚さ約125μmの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140℃の温度で、流れ方向に5倍に延伸し、直ちに室温まで冷却した後、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の非常に薄い二軸延伸ポリプロピレンフィルムを得た。
樹脂PP-1と樹脂PP-2を、PP-1/PP-2=65/35(質量比)で計量混合したこと以外は、実施例1と同様にして、二軸延伸ポリプロピレンフィルムを得た。
樹脂PP-1と樹脂PP-3を、PP-1/PP-3=65/35(質量比)で計量混合したこと以外は、実施例1と同様にして、二軸延伸ポリプロピレンフィルムを得た。
樹脂PP-1と樹脂PP-6を、PP-1/PP-6=65/35(質量比)で計量混合したこと以外は、実施例1と同様にして、二軸延伸ポリプロピレンフィルムを得た。
樹脂PP-1と樹脂PP-7を、PP-1/PP-7=65/35(質量比)で計量混合したこと以外は、実施例1と同様にして、二軸延伸ポリプロピレンフィルムを得た。
樹脂PP-1と樹脂PP-8を、PP-1/PP-8=65/35(質量比)で計量混合したこと以外は、実施例1と同様にして、二軸延伸ポリプロピレンフィルムを得た。
樹脂PP-1を単独で使用したこと以外は、実施例1と同様にして、二軸延伸ポリプロピレンフィルムを得た。
樹脂PP-2を単独で使用したこと以外は、実施例1と同様にして、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実施例1と同様にして二軸延伸することを試みたが、延伸工程で破断し、二軸延伸ポリプロピレンフィルムは得られなかった。
樹脂PP-4を単独で使用したこと以外は、実施例1と同様にして、二軸延伸ポリプロピレンフィルムを得た。
樹脂PP-5を単独で使用したこと以外は、実施例1と同様にして、二軸延伸ポリプロピレンフィルムを得た。
(1)フィルムの厚み
フィルムの厚さは、例えば紙厚測定器、マイクロメータ(JIS-B7502)等を用いて、JIS-C2330に準拠して測定することができる。
二軸延伸ポリプロピレンフィルムの結晶子サイズを、XRD(広角X線回折)装置を用いて、以下に従い測定した。
測定機:リガク社製のディストップX線回折装置「MiniFlex300」
X線発生出力:30KV、10mA
照射X線:モノクローメーター単色化CuKα線(波長0.15418nm)
検出器:シンチュレーションカウンター
ゴニオメーター走査:2θ/θ連動走査
得られたデータから、解析コンピューターを用い、装置標準付属の統合粉末X線解析ソフトウェアPDXLを用い、α晶(040)面の回折反射ピークの半価幅を算出した。
得られたα晶(040)面の回折反射ピークの半価幅から、下記(1)式のScherrerの式を用いて、結晶子サイズを求めた。なお、本発明では、形状因子定数Kは、0.94を用いた。
JIS C2330(2001)7.4.11.2 B法(平板電極法)にならって、直流電源を使用し、100℃で、絶縁破壊電圧値を測定した。12回の測定の平均絶縁破壊電圧値(VDC)を、フィルムの厚み(μm)で割り、上位2回および下位2回の値を除いた8回の平均値を、絶縁破壊電圧(VDC/μm)とした。
上記の実施例1~3で得た二軸延伸ポリプロピレンフィルムに、特殊マージン蒸着パターンを蒸着抵抗15Ω/□にてアルミニウム蒸着を施し、金属化フィルムを得た。小幅にスリットした後に、2枚の金属化フィルムを相合わせて、株式会社皆藤製作所製、自動巻取機 3KAW-N2型を用い、1100ターン巻回を行った。
素子巻きした素子に、プレスしながら120℃にて熱処理を施した後、素子端面に亜鉛金属を溶射し、扁平型コンデンサを得た。出来上がったコンデンサの静電容量は、75μF(±2μF)であった。
(1)コンデンサ素子のライフ試験(長期間にわたる耐電圧性)
上記のコンデンサ素子を、予め105℃にて予熱した後、試験前の初期の静電容量を日置電機株式会社製LCRハイテスター3522-50にて、室温で評価した。次に、105℃の高温槽中にて、コンデンサ素子に直流600Vの電圧を200時間負荷し続けた。200時間経過後の素子の容量をLCRテスターにて室温で測定し、電圧負荷前後の容量変化率を算出した。200時間経過後の容量変化率を、素子3個の平均値により評価した。200時間経過後の容量変化率は、実施例1で-1.9%、実施例2で-1.0%、実施例3で-3.0%であった。なお、200時間経過後の容量変化率は、-5%以上であることが好ましい。
Claims (6)
- コンデンサ用二軸延伸ポリプロピレンフィルムであって、該ポリプロピレンフィルムを構成するポリプロピレン樹脂は、
・数平均分子量が4万以上10万以下、
・Z平均分子量が95万以上150万以下、
・分子量分布曲線において、対数分子量Log(M)=4.5のときの微分分布値からLog(M)=6.0のときの微分分布値を引いた差が-15%以上11%以下
である、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結晶子サイズは、広角X線回折法により測定したα晶(040)面反射ピークの半価幅からScherrerの式を用いて算出して12.2nm以下である、請求項1に記載のコンデンサ用二軸延伸ポリプロピレンフィルム。
- 前記ポリプロピレンフィルムはポリプロピレン樹脂組成物を二軸延伸してなり、該ポリプロピレン樹脂組成物は、メルトフローレートが4g/10分以下であるポリプロピレン樹脂を、該ポリプロピレン樹脂組成物に含まれるポリプロピレン樹脂の総量に基づいて1質量%以上70質量%以下の量で含有する、請求項1に記載のコンデンサ用二軸延伸ポリプロピレンフィルム。
- 前記ポリプロピレンフィルムはポリプロピレン樹脂組成物を二軸延伸してなり、該ポリプロピレン樹脂組成物は、数平均分子量(Mn)が4万以上15万以下であり、Z平均分子量が120万以上260万以下であるポリプロピレン樹脂を、該ポリプロピレン樹脂組成物に含まれるポリプロピレン樹脂の総量に基づいて1質量%以上70質量%以下の量で含有する、請求項1に記載のコンデンサ用二軸延伸ポリプロピレンフィルム。
- 請求項1~4のいずれかに記載のコンデンサ用二軸延伸ポリプロピレンフィルムの片面または両面に金属蒸着が施された、コンデンサ用金属化ポリプロピレンフィルム。
- 請求項5に記載のコンデンサ用金属化ポリプロピレンフィルムを用いて製造したコンデンサ。
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP15773270.2A EP3127945A4 (en) | 2014-03-31 | 2015-02-10 | Biaxially stretched polypropylene film for capacitors |
| US15/129,513 US10093792B2 (en) | 2014-03-31 | 2015-02-10 | Biaxially stretched polypropylene film for capacitors |
| CN201580017559.8A CN106133035B (zh) | 2014-03-31 | 2015-02-10 | 电容器用双轴拉伸聚丙烯薄膜 |
| KR1020167025990A KR102244757B1 (ko) | 2014-03-31 | 2015-02-10 | 콘덴서용 2축 연신 폴리프로필렌 필름 |
| US16/118,934 US10294356B2 (en) | 2014-03-31 | 2018-08-31 | Biaxially stretched polypropylene film for capacitors |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-073192 | 2014-03-31 | ||
| JP2014073192 | 2014-03-31 | ||
| JP2014132997A JP6217542B2 (ja) | 2014-03-31 | 2014-06-27 | コンデンサ用二軸延伸ポリプロピレンフィルム |
| JP2014-132997 | 2014-06-27 |
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|---|---|---|---|
| US15/129,513 A-371-Of-International US10093792B2 (en) | 2014-03-31 | 2015-02-10 | Biaxially stretched polypropylene film for capacitors |
| US16/118,934 Continuation US10294356B2 (en) | 2014-03-31 | 2018-08-31 | Biaxially stretched polypropylene film for capacitors |
Publications (1)
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| WO2015151591A1 true WO2015151591A1 (ja) | 2015-10-08 |
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| US (2) | US10093792B2 (ja) |
| EP (1) | EP3127945A4 (ja) |
| JP (1) | JP6217542B2 (ja) |
| KR (1) | KR102244757B1 (ja) |
| CN (1) | CN106133035B (ja) |
| WO (1) | WO2015151591A1 (ja) |
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| WO2018181938A1 (ja) * | 2017-03-31 | 2018-10-04 | 王子ホールディングス株式会社 | ポリプロピレンフィルム、金属層一体型ポリプロピレンフィルム、及び、フィルムコンデンサ |
| JPWO2017159103A1 (ja) * | 2016-03-17 | 2019-01-17 | 東レ株式会社 | 二軸配向ポリプロピレンフィルム、金属膜積層フィルムおよびフィルムコンデンサ |
| JP2019167513A (ja) * | 2017-07-20 | 2019-10-03 | 王子ホールディングス株式会社 | ポリプロピレンフィルム、金属層一体型ポリプロピレンフィルム、及び、フィルムコンデンサ |
| JP2019167512A (ja) * | 2017-03-31 | 2019-10-03 | 王子ホールディングス株式会社 | ポリプロピレンフィルム、金属層一体型ポリプロピレンフィルム、及び、フィルムコンデンサ |
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| JP6217542B2 (ja) * | 2014-03-31 | 2017-10-25 | 王子ホールディングス株式会社 | コンデンサ用二軸延伸ポリプロピレンフィルム |
| EP3202825B1 (en) * | 2014-09-30 | 2019-03-27 | Oji Holdings Corporation | Biaxially stretched polypropylene film for capacitor |
| KR102184883B1 (ko) * | 2016-09-23 | 2020-12-01 | 오지 홀딩스 가부시키가이샤 | 2축 연신 폴리프로필렌 필름, 콘덴서용 금속화 필름 및 콘덴서 |
| JP7088019B2 (ja) * | 2017-03-30 | 2022-06-21 | 東レ株式会社 | ポリプロピレンフィルム、金属膜積層フィルムおよびフィルムコンデンサ並びにそれらの製造方法 |
| CN110461914A (zh) * | 2017-04-03 | 2019-11-15 | 王子控股株式会社 | 聚丙烯薄膜、金属层一体型聚丙烯薄膜及薄膜电容器 |
| KR102362917B1 (ko) * | 2017-08-02 | 2022-02-14 | 오지 홀딩스 가부시키가이샤 | 폴리프로필렌 필름, 금속층 일체형 폴리프로필렌 필름 및 필름 콘덴서 |
| EP3728460B1 (en) | 2017-12-22 | 2024-02-07 | SABIC Global Technologies B.V. | Polypropylene composition for non-pressurized pipes |
| US11492475B2 (en) * | 2017-12-26 | 2022-11-08 | Oji Holdings Corporation | Polypropylene film, metal layer-integrated polypropylene film, film capacitor and film roll |
| KR102772244B1 (ko) | 2017-12-26 | 2025-02-21 | 오지 홀딩스 가부시키가이샤 | 폴리프로필렌 필름, 금속층 일체형 폴리프로필렌 필름, 필름 콘덴서 및 필름 롤 |
| JP7192973B2 (ja) * | 2019-04-22 | 2022-12-20 | 王子ホールディングス株式会社 | ポリプロピレンフィルム、金属層一体型ポリプロピレンフィルム、及び、フィルムコンデンサ |
| JP7676746B2 (ja) * | 2020-09-30 | 2025-05-15 | 王子ホールディングス株式会社 | 金属層一体型ポリプロピレンフィルム、フィルムコンデンサ、及び金属層一体型ポリプロピレンフィルムの製造方法 |
| WO2022220248A1 (ja) * | 2021-04-12 | 2022-10-20 | 王子ホールディングス株式会社 | 金属化ポリプロピレンフィルム |
| CN115116747B (zh) * | 2022-06-09 | 2024-07-23 | 佛山佛塑科技集团股份有限公司 | 一种用于油浸式电力电容器的粗化膜及其制备方法 |
| KR20250168334A (ko) | 2023-07-27 | 2025-12-02 | 인비스타 텍스타일스 (유.케이.) 리미티드 | 열기계적 특성이 개선된 폴리아미드 산업용 얀 |
| WO2025249506A1 (ja) * | 2024-05-30 | 2025-12-04 | 王子ホールディングス株式会社 | 二軸延伸ポリプロピレンフィルム、コンデンサ用二軸延伸ポリプロピレンフィルム、コンデンサ用金属化フィルム、コンデンサ |
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- 2015-02-10 WO PCT/JP2015/053681 patent/WO2015151591A1/ja not_active Ceased
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| JPWO2017159103A1 (ja) * | 2016-03-17 | 2019-01-17 | 東レ株式会社 | 二軸配向ポリプロピレンフィルム、金属膜積層フィルムおよびフィルムコンデンサ |
| EP3431530A4 (en) * | 2016-03-17 | 2019-11-20 | Toray Industries, Inc. | BIAXIALLY POSITIONED POLYPROPYLENE FOIL, METAL FOIL LAMINATE FOIL AND FILM CONDENSER |
| JP7135320B2 (ja) | 2016-03-17 | 2022-09-13 | 東レ株式会社 | 二軸配向ポリプロピレンフィルム、金属膜積層フィルムおよびフィルムコンデンサ |
| WO2018181938A1 (ja) * | 2017-03-31 | 2018-10-04 | 王子ホールディングス株式会社 | ポリプロピレンフィルム、金属層一体型ポリプロピレンフィルム、及び、フィルムコンデンサ |
| JP2019167512A (ja) * | 2017-03-31 | 2019-10-03 | 王子ホールディングス株式会社 | ポリプロピレンフィルム、金属層一体型ポリプロピレンフィルム、及び、フィルムコンデンサ |
| JP2019167513A (ja) * | 2017-07-20 | 2019-10-03 | 王子ホールディングス株式会社 | ポリプロピレンフィルム、金属層一体型ポリプロピレンフィルム、及び、フィルムコンデンサ |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6217542B2 (ja) | 2017-10-25 |
| EP3127945A4 (en) | 2017-10-18 |
| US20170121515A1 (en) | 2017-05-04 |
| JP2015201610A (ja) | 2015-11-12 |
| US10294356B2 (en) | 2019-05-21 |
| US10093792B2 (en) | 2018-10-09 |
| CN106133035A (zh) | 2016-11-16 |
| EP3127945A1 (en) | 2017-02-08 |
| US20180371223A1 (en) | 2018-12-27 |
| CN106133035B (zh) | 2020-03-24 |
| KR102244757B1 (ko) | 2021-04-26 |
| KR20160140632A (ko) | 2016-12-07 |
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