Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G4/00—Fixed capacitors; Processes of their manufacture
  • H01G4/002—Details
  • H01G4/018—Dielectrics
  • H01G4/06—Solid dielectrics
  • H01G4/14—Organic dielectrics
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/14—Monomers containing five or more carbon atoms
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
  • C08K5/1535—Five-membered rings
• • 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
  • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
  • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
• • 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

Definitions

• Hydrocarbon-based resins such as polyethylene terephthalate (PET), polypropylene (PP), polyphenylene sulfide (PPS), polyethylene naphthalate (PEN), polymethylpentene (PMP), and cycloolefin polymer (COP) have traditionally been used as resins for such film capacitor films.
• films for film capacitors using the above-mentioned hydrocarbon-based resins and fillers, etc. are being developed with the aim of improving physical properties such as dielectric constant, dielectric tangent, heat resistance, and breaking strength (for example, Patent Documents 1 to 5).
• the reflow soldering method is widely used in surface mounting technology for film capacitors. Because solder has a relatively high melting temperature, the temperature of the object must be set high at 260°C or higher during reflow soldering.
• films made of resins with low heat resistance are difficult to surface mount.
• films made of PPS, PET, etc. are known to be surface mountable, but their dielectric properties are insufficient and they are not suitable for use at high frequencies.
• films made of PP, PMP, COP, etc. are known to have excellent electrical properties, but because their heat resistance is insufficient, it is difficult to say that these resins are suitable for surface mounting technology.
• the objective of the present invention is to provide a film for film capacitors that has a low dielectric constant and low dielectric tangent, and that can be surface mounted.
• the present inventors have conceived the following invention and found that the problems can be solved. That is, the present invention is as follows.
• a film for a film capacitor comprising a resin composition containing a 3-methyl-1-butene polymer.
• the 3-methyl-1-butene polymer is at least one selected from the group consisting of a 3-methyl-1-butene homopolymer and a copolymer of 3-methyl-1-butene with ethylene or an ⁇ -olefin, and the ⁇ -olefin has 3 to 20 carbon atoms.
• the content ratio of the structural unit derived from the ethylene or the ⁇ -olefin in the copolymer is more than 0 mol% and 10 mol% or less.
• [6] The film for film capacitors according to any one of [1] to [5], wherein the 3-methyl-1-butene polymer has a melting point of 260 to 310° C.
• the present invention provides a film for film capacitors that has a low dielectric constant and a low dielectric tangent, and is capable of being surface mounted.
• the film for a film capacitor of the present embodiment is characterized in that it contains a resin composition containing a 3-methyl-1-butene polymer. That is, the film for a film capacitor of the present embodiment contains a 3-methyl-1-butene polymer.
• the resin composition contained in the film for film capacitors contains a 3-methyl-1-butene polymer, which allows surface mounting such as reflow soldering while having a low relative dielectric constant and a low dielectric loss tangent. Furthermore, since the resin composition contained in the film for film capacitors has excellent heat resistance, it can be molded into any shape, and is expected to suppress an increase in the dielectric loss tangent while ensuring the suppression of blisters during surface mounting.
• the film for a film capacitor of the present embodiment is less susceptible to the use environment and can exhibit stable physical properties. Furthermore, since the 3-methyl-1-butene polymer has a relatively low specific gravity, the film for a film capacitor of the present embodiment can also contribute to reducing the weight of the film capacitor.
• the resin composition contained in the film for a film capacitor of the present embodiment contains a 3-methyl-1-butene polymer.
• the ⁇ -olefin means an ⁇ -olefin other than 3-methyl-1-butene, and is also expressed as ⁇ -olefin (excluding 3-methyl-1-butene).
• the unsaturated hydrocarbon is preferably ethylene or an ⁇ -olefin having 3 to 20 carbon atoms.
• the ⁇ -olefin having 3 to 20 carbon atoms may be one type or multiple types.
• the copolymer of 3-methyl-1-butene with ethylene or an ⁇ -olefin having 3 to 20 carbon atoms means, in other words, a copolymer of 3-methyl-1-butene with ethylene or a copolymer of 3-methyl-1-butene with an ⁇ -olefin having 3 to 20 carbon atoms.
• the copolymer of 3-methyl-1-butene with ethylene or an ⁇ -olefin will also be referred to simply as "copolymer”.
• the copolymer may be a random copolymer, a block copolymer, or an alternating copolymer.
• the method for producing the copolymer is not limited as long as it does not impair the effects of the present invention, and any known copolymerization method can be used.
• the ⁇ -olefin having 3 to 20 carbon atoms is preferably a linear ⁇ -olefin, more preferably at least one selected from the group consisting of 1-butene, 1-octene, 1-nonene, and 1-decene, even more preferably at least one selected from the group consisting of 1-octene, 1-nonene, and 1-decene, and even more preferably 1-decene.
• the ethylene or ⁇ -olefin having 3 to 20 carbon atoms may be used alone or in combination of two or more kinds.
• the melting point of the 3-methyl-1-butene polymer is preferably 260 to 310° C.
• the resin composition can be easily molded by extrusion molding or the like, and the warping, melting, and blistering of the film for film capacitors due to surface mounting such as reflow soldering can be further suppressed, i.e., the heat resistance is improved.
• the melting point of the 3-methyl-1-butene polymer means a peak temperature measured by using a differential scanning calorimeter to raise the temperature of a test piece (3-methyl-1-butene polymer) from 30° C. to 320° C.
• the melting point can be measured by the method described in the Examples. From the viewpoint of a balance between processability and heat resistance, the melting point of the 3-methyl-1-butene polymer is preferably 270 to 305°C, more preferably 280 to 305°C, and further preferably 280 to 300°C.
• the melt viscosity of the 3-methyl-1-butene polymer means a value measured using a capillary rheometer under conditions of a barrel temperature of 320° C. and a shear rate of 1220 sec ⁇ 1 (capillary: inner diameter 1.0 mm ⁇ length 10 mm, extrusion rate 10 mm/min), and specifically, can be measured by the method described in the Examples.
• the resin composition may contain an alkyl radical scavenger in order to exhibit better mechanical properties.
• the film for a film capacitor of the present embodiment also contains the alkyl radical scavenger or a reaction product thereof or a decomposition product thereof.
• the term "alkyl radical scavenger” refers to a compound that reacts with an alkyl radical derived from a 3-methyl-1-butene polymer and has a function of stabilizing the radical thereafter, and serves to suppress a chain reaction of main chain scission initiated by the alkyl radical.
• the resin composition may contain additives other than the alkyl radical scavenger and the antioxidant, so long as the effects of the present invention are not impaired.
• additives include antacids, fillers, light stabilizers, antistatic agents, flame retardants, pigments, polymerization inhibitors, heavy metal deactivators, ultraviolet absorbers, nucleating agents, clarifying agents, lubricants, fluorescent brightening agents, rust inhibitors, and sliding agents.
• the other additives may be used alone or in combination of two or more.
• the content of the ultraviolet absorber in the resin composition relative to 100 parts by mass of the 3-methyl-1-butene polymer can be determined appropriately, and may be, for example, 0.001 to 5 parts by mass, or 0.01 to 1 part by mass.
• the content of the ultraviolet absorber in the film for film capacitors is the same as above.
• the resin composition may or may not contain a resin other than the 3-methyl-1-butene polymer.
• the resin composition may contain, as a resin other than the 3-methyl-1-butene polymer, other resins such as vinyl acetate-ethylene copolymers and modified polyolefins in which polyolefins are partially oxidized and/or modified with reactive functional groups such as maleic acid, from the viewpoint of improving the dispersibility of additives containing polar groups.
• polyolefins constituting modified polyolefins modified with reactive functional groups include polyethylene, polypropylene, and polyolefins having ⁇ -olefins having 3 to 20 carbon atoms as structural units.
• the melting point of the resin composition of the present embodiment is preferably 260 to 310° C. When the melting point of the resin composition is within the above range, molding can be performed more easily, and reflow heat resistance can be further improved.
• the melting point of the resin composition means a peak temperature measured by a method similar to the method for measuring the melting point of a 3-methyl-1-butene polymer, and specifically, the melting point can be measured by the method for measuring the melting point of a 3-methyl-1-butene polymer described in the Examples.
• the film for a film capacitor of the present embodiment includes the resin composition of the present embodiment.
• the film for a film capacitor of the present embodiment includes a 3-methyl-1-butene polymer.
• the film for a film capacitor of the present embodiment may consist of only the resin composition, or may contain components other than the resin composition.
• the film for a film capacitor of this embodiment has a relative dielectric constant at 1 MHz measured by a capacitance method of 0.5 to 5.0, preferably 1.5 to 4.0, more preferably 2.0 to 3.5.
• the thickness of the film for a film capacitor of this embodiment can be appropriately set depending on the type, size, etc. of the film capacitor.
• the thickness of the film for a film capacitor is preferably 0.01 to 40 ⁇ m, more preferably 0.1 to 40 ⁇ m, and even more preferably 0.1 to 20 ⁇ m.
• the melt-kneading time can be adjusted depending on the size of the kneading device, etc. For example, it may be 1 to 15 minutes, but is not limited to this numerical range of melt-kneading time.
• the "melt-kneading time” refers to the time the mixer is rotating in a batch kneader, and the residence time of the raw materials in the device in the case of a continuous extrusion kneader.
• the step of obtaining a film for a film capacitor is a step of obtaining a film for a film capacitor by molding a resin composition.
• the method of forming the film is not particularly limited as long as it does not impair the effects of the present invention, and a known film forming method can be adopted.
• the above-mentioned resin composition is thermoplastic and can be melt-molded. Therefore, the method of forming the film includes extrusion molding, heat press molding, etc. Among these, from the viewpoint of obtaining a film with excellent ease of production and dimensional accuracy, the method of forming the film is preferably extrusion molding.
• the film capacitor of the present embodiment includes the above-mentioned film for a film capacitor.
• the film capacitor of the present embodiment has at least the above-mentioned film for film capacitors and electrodes, and the film for film capacitors is included as a dielectric.
• the film capacitor may further include a lead terminal, an exterior case for enclosing the film for film capacitors and the electrodes, and the like.
• the film for a film capacitor and the electrodes may be laminated alternately, or the film for a film capacitor may be wound around the electrodes.
• the surface of the film for film capacitors may be subjected to pretreatment such as degreasing treatment, plasma treatment, UV ozone treatment, laser treatment, corona discharge treatment, etc.
• pretreatment such as degreasing treatment, plasma treatment, UV ozone treatment, laser treatment, corona discharge treatment, etc.
• Examples of metal materials constituting the electrodes include copper, silver, gold, platinum, iron, nickel, aluminum, magnesium, titanium, etc. In general, aluminum is preferred from the viewpoints of electrical conductivity, good etching properties, cost, etc.
• the method for providing electrodes on the surface of the film for a film capacitor can be a known method, such as ion plating, sputtering, vacuum deposition, etc.
• the film for film capacitors of this embodiment has a low dielectric constant and a low dielectric tangent, and is highly heat resistant, allowing for surface mounting such as reflow soldering. Therefore, the film capacitor of this embodiment can be used in, for example, environmentally-related equipment such as electric vehicles, hybrid vehicles, solar power generation systems, and wind power generation systems, as well as home appliances such as televisions and refrigerators. In particular, the film capacitor of this embodiment is suitable for surface mounting.
• a calibration curve was prepared from the ratio of the peak area of 1,461 cm ⁇ 1 bending vibration derived from the main chain methylene group of the 3-methyl-1-butene homopolymer to the peak area of 727 cm ⁇ 1 bending vibration derived from the side chain methylene group of the ⁇ -olefin homopolymer, and the addition ratio of each polymer (3-methyl-1-butene copolymer and ⁇ -olefin).
• melt viscosity The melt viscosity (Pa ⁇ s) of the polymers (3-methyl-1-butene copolymers) obtained in Production Examples 1 and 2 was measured using a capillary rheometer ("Capillography 1C" manufactured by Toyo Seiki Seisakusho, Ltd.) under the conditions of a barrel temperature of 320° C. and a shear rate of 1220 sec ⁇ 1 (capillary: inner diameter 1.0 mm ⁇ length 10 mm, extrusion rate 10 mm/min).
• Test pieces (length: 60 mm, width: 60 mm) were prepared by cutting out each of the films for film capacitors obtained in Examples 1 and 2 and Comparative Examples 1 to 3. The test pieces were dried under reduced pressure at 100° C. for 10 hours, and then stored at 23° C. and 50% RH for 1 week. The water absorption rate of the films was measured using a Karl Fischer moisture meter.
• Test pieces (length: 40 mm, width: 40 mm) were prepared by cutting out each of the films for film capacitors obtained in Examples 1 and 2. Using the test pieces, the relative dielectric constant and the dielectric loss tangent at a measurement frequency of 1 MHz were measured by the capacitance method using a precision LCR meter "Keysight E4980A.” Test pieces (length: 40 mm, width: 40 mm) were prepared by cutting out each of the films for film capacitors obtained in Examples 1 and 2 and Comparative Examples 1 to 3.
• test pieces Using the test pieces, the relative dielectric constant and the dielectric loss tangent at a measurement frequency of 10 GHz were measured by the TE resonance method using a vector network analyzer "Keysight PNA N5227A.” Further, test pieces (length: 40 mm, width: 40 mm) were prepared by cutting out the films for film capacitors obtained in Examples 1 and 2. The relative dielectric constant and the dielectric loss tangent at a measurement frequency of 100 GHz were measured using the test pieces and a vector network analyzer "WR10, manufactured by Virginia Diodes Inc.” by the open-type resonant Fabry-Perot method.
• the pellet-like resin compositions obtained in Examples 1 and 2 were melt-kneaded in a nitrogen atmosphere at 40 rpm and a cylinder temperature of 310° C. using an electric injection molding machine "SE18DU” (manufactured by SUMITOMO Heavy Industries, Ltd.), and injection-molded under conditions of an injection pressure of 45 MPa, a retention time in the mold of 33 seconds, and a mold temperature of 160° C. to prepare test pieces (length: 100 mm, width: 100 mm, thickness: 2 mm). The test pieces were used to measure the relative dielectric constant and dielectric loss tangent at a measurement frequency of 200 GHz by a frequency change method using a vector network analyzer "Anritsu ME7838G 70 kHz-220 GHz".
• the composition of the obtained titanium catalyst component was 4.0 mass % titanium, 56.0 mass % chlorine, 17.0 mass % magnesium, 10.4 mass % ethyl benzoate, and 12.6 mass % of the hydrocarbon solvent consisting of decane and hexane.
• Example 1 A mixture of 100 parts by mass of the copolymer (A) obtained in Production Example 1, 0.2 parts by mass of pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] ("AO-60", manufactured by ADEKA Corporation) as a phenol-based antioxidant, 0.2 parts by mass of 3,9-bis(2,6-di-t-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane ("PEP-36", manufactured by ADEKA Corporation) as a phosphorus-based antioxidant, 0.1 part by mass of 2,4-di-t-amyl-6-[1-(3,5-di-t-amyl-2-hydroxyphenyl)ethyl]phenyl acrylate ("Sumilizer (registered trademark) GS", manufactured by Sumitomo Chemical Co., Ltd.) as
• the unstretched film obtained here was heated with a heating roll at 200 ° C., and stretched three times longitudinally between a pair of rolls with a peripheral speed difference to obtain a uniaxially stretched film.
• both ends of the uniaxial film in the width direction were gripped, the temperature was raised in a heating oven at 200 ° C., and the film was laterally stretched seven times in the width direction to obtain a biaxially stretched film, and a film for a film capacitor (thickness 10 ⁇ m) was produced. Both ends of the obtained film for film capacitor were cut, and then a corona discharge treatment was performed.
• the film for film capacitors containing the resin composition containing the 3-methyl-1-butene polymer of this embodiment has a low relative dielectric constant and a low dielectric tangent, and can be surface mounted. Therefore, the industrial usefulness of the film for film capacitors of this embodiment is extremely high.

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• Medicinal Chemistry (AREA)
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• Microelectronics & Electronic Packaging (AREA)
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• Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2023
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