Thin film for film capacitor, metal laminate, film capacitor, power control unit, electric automobile, and electric airplane

Abstract

A film for a film capacitor having two resin layers with different thicknesses, when a layer with a smaller thickness is provided as a resin layer A and a layer with a larger thickness is provided as a resin layer B, has the resin layer A on at least one side of the resin layer B, XA calculated based on formula (i) from the atomic fractions of H, C, S, Si, N, and O in the resin layer A is 0.050 to 0.80, the dielectric loss tangent measured at 23°C and 10 kHz is 0.50% or less, and at least one of the following conditions 1 and 2 is satisfied, formula (i): XA = (atomic fraction of C + atomic fraction of N + atomic fraction of S + atomic fraction of Si) / (atomic fraction of H + atomic fraction of O). Condition 1: the melting point measured by DSC is 180°C or higher, Condition 2: the glass transition temperature measured by DSC is 130°C or higher and 370°C or lower. A film for a film capacitor is provided that has high heat resistance and self-repairing properties and can reduce performance degradation caused by heat when used as a capacitor.

Description

Technical Field

[0001] This invention relates to films used as dielectrics in film capacitors, metal laminates, film capacitors, power control units, electric vehicles, and electric aircraft. Background Technology

[0002] In recent years, due to environmental issues and other reasons, the market for electric motor-driven vehicles such as hybrid electric vehicles (HEVs) and plug-in hybrid electric vehicles (PHEVs), or electric electric vehicles (EVs) and fuel cell vehicles (FCVs) has been expanding. However, as the market for these electric motor-driven vehicles expands, the demand for film capacitors used in these vehicles is also increasing rapidly.

[0003] Film capacitors are capacitors that use a resin-based thin film as the dielectric, exhibiting excellent frequency characteristics and temperature stability. Examples of films used in film capacitors include polypropylene (PP) resin films, polyethylene terephthalate (PET) resin films, polyethylene naphthalate (PEN) resin films, and other polyester resin films; thermoplastic resin films such as polyphenylene sulfide (PPS) resin films; and amorphous thermoplastic resin films such as polyetherimide (PEI) resin films.

[0004] Among these films, polyetherimide resin films have attracted attention (Patent Documents 1 and 2). This is because when film capacitors are used in hybrid electric vehicles or electric vehicles, heat resistance is sometimes required to withstand environments above 120°C. If films made of polyetherimide resin with a glass transition temperature (Tg) of 200°C or higher are used, excellent electrical properties such as heat resistance, voltage withstand properties, or dielectric properties can be obtained.

[0005] On the other hand, films such as polyetherimide and polyphenylene sulfide, which have excellent heat resistance, generally suffer from poor self-healing (SH) properties and a decrease in capacitor capacitance over prolonged use. To address this issue, techniques are known to improve self-healing properties by applying a coating to the substrate film (Patent Document 3). Furthermore, when using films such as polyetherimide and polyethylene naphthalate as capacitor films, they generate significant heat, posing a risk of performance degradation.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2007-300126

[0009] Patent Document 2: Japanese Patent Application Publication No. 2018-163950

[0010] Patent Document 3: International Publication No. 2007 / 080757 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] However, the prior art shown in Patent Document 3, because the silicone-based self-healing coating used to balance heat resistance and self-healing properties contains Si, has the problem of generating siloxanes that may cause poor wiring in the circuit during insulation breakdown, thus impairing the characteristics of the capacitor. Therefore, in view of the background of the above-mentioned prior art, the present invention provides a film for a thin-film capacitor that has high heat resistance and self-healing properties and can reduce the performance degradation caused by heat generation when used as a capacitor.

[0013] Problem-solving methods

[0014] The aforementioned problem can be solved by the following invention. That is, the thin film for a thin film capacitor of the present invention is a thin film capacitor having two resin layers with different thicknesses. In the two resin layers, the layer with a smaller thickness is designated as resin layer A, and the layer with a larger thickness is designated as resin layer B. Resin layer A is provided on at least one side of resin layer B. Based on the atomic fractions of hydrogen atoms (H), carbon atoms (C), sulfur atoms (S), silicon atoms (Si), nitrogen atoms (N), and oxygen atoms (O) contained in resin layer A, XA calculated based on the following formula (i) is 0.050 or more and 0.80 or less. The dielectric loss tangent measured at 10 kHz in an atmosphere at 23°C is 0.50% or less. And at least one of the following conditions 1 and 2 is satisfied.

[0015] Equation (i)XA = (atomic fraction of carbon atom C + atomic fraction of nitrogen atom N + atomic fraction of sulfur atom S + atomic fraction of silicon atom Si) / (atomic fraction of hydrogen atom H + atomic fraction of oxygen atom O)

[0016] Condition 1: The melting point determined by DSC is above 180℃.

[0017] Condition 2: The glass transition temperature determined by DSC is above 130℃ and below 370℃.

[0018] Invention Effects

[0019] According to the present invention, a thin film for a thin-film capacitor with high heat resistance and self-healing properties can be provided. Detailed Implementation

[0020] The following is a detailed description of the thin film for a thin film capacitor according to the present invention. The thin film for a thin film capacitor according to the present invention is a thin film capacitor having two resin layers with different thicknesses. In the two resin layers, the layer with a smaller thickness is designated as resin layer A, and the layer with a larger thickness is designated as resin layer B. Resin layer A is present on at least one side of resin layer B. Based on the atomic fractions of hydrogen atoms (H), carbon atoms (C), sulfur atoms (S), silicon atoms (Si), nitrogen atoms (N), and oxygen atoms (O) contained in resin layer A, XA calculated based on the following formula (i) is 0.050 or more and 0.80 or less. The dielectric loss tangent measured at 10 kHz in an atmosphere at 23°C is 0.50% or less, and at least one of the following conditions 1 and 2 is satisfied.

[0021] Equation (i)XA = (atomic fraction of carbon atom C + atomic fraction of nitrogen atom N + atomic fraction of sulfur atom S + atomic fraction of silicon atom Si) / (atomic fraction of hydrogen atom H + atomic fraction of oxygen atom O)

[0022] Condition 1: The melting point determined by DSC is above 180℃.

[0023] Condition 2: The glass transition temperature determined by DSC is above 130℃ and below 370℃.

[0024] The thin-film capacitor of the present invention has two resin layers with different thicknesses. Here, "different thicknesses" means a thickness difference of 0.10 μm or more, and "two resin layers" means two resin layers with different compositions. A resin layer is a layer in which resin is the main component, and a main component is a component that has a content of more than 50% by mass and less than 100% by mass in the layer (hereafter, the same explanation applies to main components). Furthermore, "different compositions" means that the components constituting each layer differ by 10% by mass and less than 100% by mass, preferably with different main components.

[0025] In the thin film capacitor of the present invention, when the thin film has two resin layers, the layer with a smaller thickness is used as resin layer A and the layer with a larger thickness is used as resin layer B, the resin layer A is present on at least one side of resin layer B. It is important that XA calculated based on the following formula (i) is 0.050 or more and 0.80 or less, according to the atomic fractions of hydrogen atoms (H), carbon atoms (C), sulfur atoms (S), silicon atoms (Si), nitrogen atoms (N), and oxygen atoms (O) contained in resin layer A.

[0026] Equation (i)XA = (atomic fraction of carbon atom C + atomic fraction of nitrogen atom N + atomic fraction of sulfur atom S + atomic fraction of silicon atom Si) / (atomic fraction of hydrogen atom H + atomic fraction of oxygen atom O).

[0027] XA is the ratio of atoms in resin layer A that are difficult to evaporate during insulation breakdown to atoms that are easy to evaporate. Setting it to 0.80 or less improves self-healing properties and capacitor reliability, while setting it to 0.050 or more suppresses oxidation and degradation of the metal layer during lamination. From this perspective, XA is preferably 0.70 or less, more preferably 0.65 or less, even more preferably 0.60 or less, and particularly preferably 0.55 or less. On the other hand, from the viewpoint of ease of implementation, XA is preferably 0.20 or more, more preferably 0.40 or more. The atomic content in resin layer A can be determined by analyzing the atomic fraction using Rutherford backscattering / hydrogen forward scattering analysis (Pelletron 3SDH manufactured by National Electrostatics Corporation), the detailed steps of which are described below.

[0028] The thin film for the thin film capacitor of the present invention satisfies at least one of the following conditions 1 and 2. Condition 1: The melting point determined by DSC is 180°C or higher. Condition 2: The glass transition temperature determined by DSC is 130°C or higher and 370°C or lower. Furthermore, the melting point and glass transition temperature determined by DSC will sometimes be referred to simply as "melting point" and "glass transition temperature," respectively.

[0029] The film for the film capacitor of the present invention, by satisfying at least one of conditions 1 and 2 above, is unlikely to cause poor insulation due to thermal shrinkage or film rupture when used as a film capacitor. From the above viewpoint, the melting point is preferably 205°C or higher, more preferably 215°C or higher. On the other hand, from the viewpoint of processability, the melting point is preferably 370°C or lower, more preferably 360°C or lower. From the above viewpoint, the glass transition temperature is preferably 150°C or higher, more preferably 165°C or higher, and even more preferably 180°C or higher. On the other hand, from the viewpoint of processability, the glass transition temperature is preferably 350°C or lower.

[0030] The melting point mentioned here is based on JIS K-7122 (1987). Differential scanning calorimetry (DSC) was used to obtain the highest melting peak temperature among the melting peak temperatures calculated according to the method described in JIS K-7121 (1987). Furthermore, Tmax (°C) was initially set to 350°C for measurement, and then set to 380°C for measurement again if no melting point was observed. If no melting point was observed at Tmax = 380°C, it was considered that there was no melting point.

[0031] The glass transition temperature mentioned here is based on JIS K-7122 (1987). The film capacitor film was heated from 25°C to Tmax (°C) at a heating rate of 20°C / min, and the resin was heated at the same rate of 20°C / min (round 1). After holding this state for 5 minutes, it was rapidly cooled to below 25°C, and then heated again from 25°C to Tmax (°C) at a heating rate of 20°C / min (round 2). This yielded a second round of differential scanning calorimetry (DSC) measurements. The highest intermediate glass transition temperature among the intermediate glass transition temperatures determined based on the method described in JIS K-7121 (1987) was used. Furthermore, Tmax (°C) was initially set to 350°C for measurement. If no glass transition temperature was observed, it was set to 380°C for measurement again. If no glass transition temperature was observed at Tmax = 380°C, it was considered that no glass transition temperature occurred.

[0032] The method for making the thin film of the thin film capacitor of the present invention satisfy at least one of conditions 1 and 2 is not particularly limited. For example, a method can be listed where a material satisfying at least one of conditions 1 and 2 is selected as the raw material for resin layer B, and the thickness of resin layer A is 30% or less of the thickness of resin layer B. Alternatively, a method can be listed where a material satisfying at least one of conditions 1 and 2 is selected as the raw material for resin layer A and resin layer B.

[0033] From the viewpoint of improving heat resistance when used as a capacitor, the resin layer B preferably satisfies at least one of conditions 1 and 2 above. By satisfying at least one of conditions 1 and 2 above, it is difficult to cause poor insulation due to thermal shrinkage or film rupture when used as a film capacitor. From the above viewpoint, the melting point is preferably 205°C or higher, more preferably 215°C or higher. On the other hand, from the viewpoint of molding processability, the melting point is preferably 370°C or lower, more preferably 360°C or lower. From the above viewpoint, the glass transition temperature is preferably 150°C or higher, more preferably 165°C or higher, and even more preferably 180°C or higher. On the other hand, from the viewpoint of molding processability, the glass transition temperature is preferably 370°C or lower, more preferably 350°C or lower. Regarding the melting point and glass transition temperature of the resin layer B, except that 3.0 mg of resin layer B is scraped and used instead of 3.0 mg of film, the same method as the method for measuring the melting point and glass transition temperature of the film described later can be used for measurement.

[0034] It is important that the dielectric loss tangent of the thin film capacitor of the present invention, measured at 10 kHz in an atmosphere at 23°C, is 0.50% or less. By making the dielectric loss tangent 0.50% or less, the heat generated when used as a capacitor can be reduced, and the performance degradation caused by heat generation can be mitigated. From the above viewpoint, the dielectric loss tangent is preferably 0.30% or less. There is no particular limitation on the lower limit of the dielectric loss tangent, but from the viewpoint of feasibility, 0.0010% is preferred, 0.010% is more preferred considering manufacturing cost, and 0.10% is particularly preferred.

[0035] There are no particular limitations on the method for setting the dielectric loss tangent of the thin film capacitor of the present invention to be 0.50% or less. For example, it can be achieved by forming resin layer B with a raw material having a dielectric loss tangent of 0.50% or less, and forming resin layer A on one side of it with a thickness within the range described below. In addition, the dielectric loss tangent referred to here means the value measured according to JIS C2138-2007, the detailed measurement method of which is described below.

[0036] The thin film for the thin-film capacitor of the present invention, when subjected to thermal decomposition GC-MS measurement at 400°C under the conditions described later, preferably has a peak with an intensity of 25,000 or more in the range of retention time of 2 minutes to 20 minutes. More preferably, this range contains a peak with an intensity of 50,000 or more; even more preferably, it contains a peak with an intensity of 90,000 or more; and particularly preferably, it contains a peak with an intensity of 210,000 or more. The number of peaks contained in the above range can be one or more. The presence of a peak with an intensity of 25,000 or more means that the film contains a large amount of components that evaporate during insulation breakdown, thereby improving the self-healing properties of the capacitor film. As a method to achieve a peak with an intensity of 25,000 or more in the above range, examples include adjusting the dielectric loss tangent to the above range, so that the thin resin layer A contains components that easily evaporate during insulation breakdown.

[0037] From the viewpoint of improving self-healing properties, when the thermogravimetric change rate of the film capacitor of the present invention is measured under a nitrogen atmosphere at a heating rate of 10°C / min, the 10% mass reduction temperature is preferably 390°C or lower. Hereinafter, the 10% mass reduction temperature when measuring the thermogravimetric change rate of the resin layer A under a nitrogen atmosphere at a heating rate of 10°C / min is sometimes referred to as the "10% mass reduction temperature of resin layer A". From the above viewpoint, the 10% mass reduction temperature of resin layer A is more preferably 355°C or lower, further preferably 325°C or lower, and particularly preferably 295°C or lower. A 10% mass reduction temperature of resin layer A of 390°C or lower, or within the above-mentioned preferred range, means that a greater amount of the components that evaporate during insulation breakdown are contained in the capacitor film (especially resin layer A), and by adopting this method, the self-healing properties of the capacitor film can be improved.

[0038] The 10% mass reduction temperature of resin layer A can be determined according to the following steps. First, the sample of resin layer A is stored in an environment of 23°C and 50% RH for 24 hours. After storage, the sample is heated from 23°C to 500°C in a thermogravimetric analyzer under a nitrogen atmosphere at a heating rate of 10°C / min, and the change in thermogravimetric weight is measured. Based on the obtained change in thermogravimetric weight, the thermogravimetric weight at 170°C is set as 100% mass, and the rate of change of thermogravimetric weight at each temperature is calculated. The temperature at which the thermogravimetric weight becomes 90% of its mass is set as the 10% mass reduction temperature of resin layer A. Furthermore, any apparatus capable of performing the above-described measurement can be used; a suitable known apparatus can be selected, such as the TGA-50 (manufactured by Shimadzu Corporation).

[0039] As a method to reduce the temperature by 10% by mass of resin layer A to below 390°C, one example is using a raw material in resin layer A that reduces the temperature by 10% by mass to below 390°C when measuring the rate of change of thermogravimetric analysis. Examples of such raw materials include, for instance, urethane acrylate polymers, acrylate polymers, urethane methacrylate polymers, methacrylate polymers, aliphatic polyethers, aliphatic polyesters, aliphatic polyamides, polyurethanes, and polyureas.

[0040] From the viewpoint of improving self-healing properties, when the rate of change of thermogravimetric analysis (CGA) of the thin-film capacitor of the present invention is measured under a nitrogen atmosphere at a heating rate of 10°C / min, the 1% mass reduction temperature is preferably 430°C or lower. Furthermore, hereinafter, the 1% mass reduction temperature when measuring the rate of change of thermogravimetric analysis (CGA) under a nitrogen atmosphere at a heating rate of 10°C / min is sometimes referred to as the "1% mass reduction temperature of the thin film." From the above viewpoint, the 1% mass reduction temperature of the thin film is more preferably 380°C or lower, further preferably 370°C or lower, particularly preferably 355°C or lower, and most preferably 340°C or lower. A 1% mass reduction temperature of 430°C or lower, or within the above-mentioned preferred range, means that the capacitor film contains a high proportion of components that evaporate during insulation breakdown. In cases where the thickness of resin layer A is large, especially when the thickness of resin layer A is designed to be 5% or more of the overall film thickness, this improves the self-healing properties of the capacitor film.

[0041] The 1% mass reduction temperature of the film can be measured in the same way as the 10% mass reduction temperature of resin layer A, except that the sample being measured is a film and the temperature read is the temperature at which the thermogravimetric change rate becomes 99% of its mass. As a method for setting the 1% mass reduction temperature of the film to 430°C or below, from the viewpoint of controlling the dielectric loss tangent within the aforementioned range, it is preferable to control this through the design of resin layer A. Examples include using a raw material for resin layer A with a low 10% mass reduction temperature when measuring the thermogravimetric change rate, and increasing the thickness of resin layer A. By designing resin layer A using the above methods, the amount of resin layer A decomposes at 430°C or below when heating the film increases, and the mass reduction of the film also increases.

[0042] The thin film for the thin-film capacitor of the present invention preferably has a resin layer A (n is an integer greater than or equal to 1) having any one of the partial structures represented by structures r1 to r8 as structural units. "Having any one of the partial structures represented by structures r1 to r8 as structural units" means that at least one of the resins constituting the resin layer A contains a partial structure represented by structures r1 to r8. Furthermore, a partial structure refers to a group of atoms that constitutes part or all of the molecular structure and is bonded by chemical bonds. In this case, it may contain two or more components containing the same or different partial structures shown by structures r1 to r8, or it may contain components containing two or more partial structures shown by structures r1 to r8 within one molecule. The partial structures represented by structures r1 to r8 are structures that easily evaporate during insulation breakdown; by having a resin layer A having this structure, the self-healing property of the thin film for the thin-film capacitor can be improved.

[0043]

[0044] Regarding the content of the partial structures represented by the structures r1 to r8 mentioned above, when the mass of resin layer A is set to 100% by mass, the proportion of the mass of the partial structures in resin layer A corresponding to the structures r1 to r8 mentioned above is set to W. R From a self-healing perspective, the above W... R Preferably, it is 5.0% by mass or more, more preferably 15% by mass or more, and even more preferably 45% by mass or more. Additionally, W R There is no specific upper limit, but from a feasibility standpoint, it is set to 100% by mass. Similarly, when the mass of resin layer A is set to 100% by mass, the proportion of the mass of a portion of the structure in resin layer A, equivalent to at least one structure selected from structures r5, r7, and r8, is set as W. 578 Let W be the proportion of the mass of a portion of the resin layer A, which is equivalent to at least one of the structures r7 or r8. 78 .

[0045] From the viewpoint of self-healing properties in the partial structures shown in structures r1 to r8, resin layer A preferably contains at least one structure selected from the more easily evaporating structures r5, r7, and r8, and particularly preferably contains at least one of the easily evaporating structures r7 or r8. From the same viewpoint, W 578 More preferably, it is 1% by mass or more, and even more preferably 10% by mass or more. 78 More preferably, it is 1% by mass or more, particularly preferably 10% by mass or more. Additionally, W 578 and W 78 There is no specific upper limit, but from a feasibility point of view, it is 100% mass.

[0046] When the composition of the raw materials is unknown, whether resin layer A contains some of the structures shown in structures r1 to r8 can be determined by examining the scraped resin layer A using a solid... 1 H-NMR, solid-state 13 The analysis was performed using well-known analytical methods such as nuclear magnetic resonance (NMR) and pyrolysis gas chromatography-mass spectrometry (GC-MS). The above analysis can be performed according to the following steps.

[0047] The quantitative analysis of structures r1–r4 is presented. First, the n-values ​​of these structures are determined by pyrolysis GC-MS. Then, solid-state analysis is performed using the DD / MAS (Dipolar Decoupling / Magic Angle Spinning) method. 1 ¹H-NMR analysis was used to quantify the number of hydrogen atoms bonded to the carbonyl carbon adjacent to the carbonyl carbon in this structure, based on the peak area detected from 2.0 to 2.8 ppm. The number of other atoms in the structure was then calculated based on the obtained number of hydrogen atoms, used for W...R Calculations. Through solids 1 H- 13 CCross-polarization-Heteronuclear Single Quantum Correlation (CP-HSQC) determines which of the peaks detected in the 2.0–2.8 ppm range corresponds to a hydrogen atom on the carbon adjacent to the carbonyl carbon in the structure.

[0048] The quantitative analysis of structures r5 and r6 is explained. The n value of this structure was determined by pyrolysis GC-MS. Then, solid-state analysis was performed using the DD / MAS method. 1 ¹H-NMR analysis, based on the peak area detected in the 3.5–4.5 ppm range, quantifies the number of hydrogen atoms bonded to the carbon adjacent to the ether oxygen in this structure. The number of other atoms in the structure is then calculated based on the obtained number of hydrogen atoms, for use in W... R W 578 The calculation. From solids. 1 H- 13 C Cross-polarization-Heteronuclear Single Quantum Correlation (CP-HSQC) determines which of the peaks detected in the 3.5–4.5 ppm range corresponds to a hydrogen atom on a carbon adjacent to the ether oxygen in the structure.

[0049] The quantitative analysis of structures r7 and r8 is explained. Solids were analyzed using the DD / MAS method. 13 C-NMR analysis was used to quantify the number of carbonyl carbon atoms in the structure based on the peak area detected at 150–160 ppm. The number of other atoms in the structure was then calculated based on the obtained carbon atom count, used for W... R W 578 W 78 The calculation.

[0050] The raw material for resin layer A in the capacitor film of the present invention is not particularly limited. From the viewpoint of improving self-healing properties by making XA between 0.050 and 0.80, it is preferable to contain at least one compound selected from urethane acrylate polymers, acrylate polymers, urethane methacrylate polymers, methacrylate polymers, aliphatic polyethers, aliphatic polyesters, aliphatic polyamides, polyurethanes, and polyureas. From the viewpoint of improving self-healing properties by containing urethane or urea bonds that tend to lower the decomposition temperature, it is more preferable to contain at least one compound selected from urethane acrylate polymers, urethane methacrylate polymers, polyurethanes, and polyureas. From the viewpoint of improving resistance to damp heat, it is even more preferable to contain at least one urethane acrylate polymer or urethane methacrylate polymer. An urethane acrylate polymer refers to a compound formed by polymerizing acrylates containing urethane bonds. An acrylate polymer is a compound formed by polymerizing acrylates, but it is a compound other than urethane acrylate polymers. Aliphatic polyethers, aliphatic polyesters, and aliphatic polyamides refer to compounds with structures in which aliphatic hydrocarbon groups are linked by ether bonds, ester bonds, and amide bonds, respectively.

[0051] Two or more compounds from the compound group can be selected for mixing, or at least one compound containing "two or more structural units from the compound group". The structural unit of the compound group refers to the following structure. In the above compound group, urethane acrylate polymer and urethane methacrylate polymer are two structural units; if both structures are present, it is considered as containing one structural unit of the above compound. Furthermore, in the case of compounds having multiple structural units, each compound is judged to meet certain criteria. For example, a resin layer containing compounds having structures 1, 2, and 3 as structural units is treated as a substance containing urethane acrylate polymer, acrylate polymer, urethane methacrylate polymer, and methacrylate polymer. The compound may also contain components containing structures other than those described below. When the mass of resin layer A is set to 100% by mass, it is preferable that the resin layer A contains components corresponding to the following structures 1 to 7 at a mass ratio W. A The compound comprises 1% or more of the above-mentioned compound group. However, the mass of the X, Y, and Z portions of structures 1 to 6 is not included in W. A In the middle. The above W A Preferably, it is 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 40% by mass or more. Additionally, W A There is no specific upper limit, but theoretically it is 100% of the mass.

[0052] Carbamate acrylate polymers: Structure 1 and Structure 2

[0053] Acrylic polymers: Structure 1

[0054] Carbamate methacrylic polymers: Structure 2 and Structure 3

[0055] Methacrylate polymers: Structure 3

[0056] Aliphatic polyether: Structure 4

[0057] Aliphatic polyester: Structure 5

[0058] Aliphatic polyamide: Structure 6

[0059] Polyurethane: Structure 2

[0060] Polyurea: Structure 7

[0061]

[0062] Additionally, n here is an integer greater than or equal to 1. R1 and R2 represent aliphatic hydrocarbon groups, and X, Y, and Z represent arbitrary chemical structures. They can have the same chemical structure or all of them can be different chemical structures.

[0063] Whether resin layer A contains the above-mentioned structural units can be determined by, for example... 1 Methods commonly used for polymer structure analysis include H-NMR (also known as nuclear magnetic resonance), time-of-flight secondary ion mass spectrometry (also known as TOF-SIMS), and Fourier transform infrared spectroscopy (also known as FT-IR).

[0064] The raw materials used in the resin layer B of the film capacitor of the present invention are not particularly limited, and examples include polyolefins such as polystyrene (PS), polymethylpentene (PMP), cyclic olefins (COP), and cyclic olefin copolymers (COC); polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN); and polyamide 6 (PA6), polyamide 66 (PA66), polyamide 46 (PA46), and polyamide 4T (PA66, PA ... Polyamides such as PA4T, polyamide 6T (PA6T), modified polyamide 6T (modified PA6T), polyamide 9T (PA9T), polyamide 10T (PA10T), and polyamide 11T (PA11T); polysulfones such as polysulfone (power source); polyethersulfone (PES); polyphenylene sulfone (PPSU); polysulfones such as polyphenylene sulfide (PPS); polyphenylene sulfide ketone; polyphenylene sulfide sulfone; polyphenylene sulfide ketone sulfone; polyaryl sulfides such as polyimide (PI); polyetherimide (PEI); and polyamide imide (PAI). Polyimide (PI), polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyetheretherketoneketone (PEEKK), polyetherketoneketone (PEKEKK), and other polyaryletherketones; polytetrafluoroethylene (PTFE) (also known as tetrafluoroethylene), polytetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) (also known as tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), tetrafluoroethylene-hexafluoropropylene copolymer (FEP) (also known as tetrafluoroethylene-hexafluoropropylene copolymer), and tetrafluoroethylene... Fluoropolymers such as ethylene-ethylene copolymer (ETFE) (also known as tetrafluoroethylene-ethylene copolymer), polychlorotrifluoroethylene (PCTFE) (also known as trifluoroethylene), polyvinylidene fluoride (PVDE) (also known as vinylidene fluoride), vinylidene fluoride / tetrafluoroethylene / hexafluoropyrene copolymer, polyacetal, liquid crystal polymer (LCP), polycarbonate (PC), polyarylate (PAR), phenolic resin, polyurea, melamine resin, epoxy resin, alkyd resin, mixtures of syndiotactic polystyrene and polyphenylene ether, polyurethane, etc.

[0065] Preferably, the capacitor film of the present invention satisfies at least one of conditions 1 and 2, and has excellent heat resistance at 150°C. Other suitable materials include polyetherimide, polycarbonate, polyarylene sulfide, polyethersulfone, and polyphenylsulfone, as well as polysulfone, polyimide, polymethylpentene, polyetheretherketone, polyetherketoneketone, polyarylene etherketone, fluorene-containing polyester, syndiotactic polystyrene, mixtures of syndiotactic polystyrene and polyphenylene ether, and polyurethane.

[0066] Furthermore, from the viewpoint of controlling at least one of the melting point and glass transition temperature of the film used in the film capacitor under the aforementioned conditions to improve heat resistance, reduce the dielectric loss tangent, and suppress heat generation during use as a capacitor, resin layer B particularly preferably contains at least one resin selected from polyarylene sulfide, polyethersulfone, polysulfone, and especially polyimide, and its total amount is 50% by mass or more and 100% by mass or less. From the above viewpoint, the combined amount of polyarylene sulfide and polyimide is more preferably 70% by mass or more, and even more preferably 90% by mass or more. These resins can be homopolymers, but modified forms, derivatives, and copolymers with other compounds can also be used. In addition, they can be used alone or in combination. Furthermore, here, the term "polymer of polyarylene sulfide" refers to a resin containing more than 50 mol% and less than 100 mol% of arylene sulfide units and more than 0 mol% and less than 50 mol% of other structural units when all structural units constituting the resin are set to 100 mol%. The same interpretation applies to copolymers of polyimide.

[0067] The thin film for the thin-film capacitor of the present invention may contain antioxidants, light stabilizers, ultraviolet absorbers, plasticizers, lubricants, crosslinking agents, flame retardants, antistatic agents, heat resistance improvers, colorants, slip agents, anti-blocking agents, inorganic particles, resin particles, inorganic compounds, organic compounds, etc., without impairing its properties. Furthermore, these components may be used individually or in combination as needed, and may also be used in either resin layer A or resin layer B.

[0068] The thickness of the resin layer A in the capacitor film of the present invention is preferably 1.0 nm or more and 500 nm or less. By making the thickness of the resin layer A 1.0 nm or more, self-healing properties can be improved; by making it 500 nm or less, the dielectric loss tangent is more easily controlled within the aforementioned range. From the above viewpoint, the thickness of the resin layer A is more preferably 200 nm or less. Similarly, from the above viewpoint, the thickness of the resin layer A is more preferably 5.0 nm or more, and even more preferably 15 nm or more.

[0069] Generally, materials with low XA are known to tend to have a high dielectric loss tangent. Therefore, as described above, if this were the case, they would generate excessive heat when used as capacitors, making them unsuitable for use. However, in this invention, by using this material as a resin layer A that is thinner than resin layer B, it is possible to improve self-healing properties while suppressing heat generation when used as a capacitor. In particular, by controlling the thickness of resin layer A within the aforementioned range, heat generation can be further reduced.

[0070] The thickness of resin layer B is not particularly limited as long as it is greater than that of resin layer A, but it is preferably 0.50 μm or more and 9.0 μm or less. By making the thickness of resin layer B 9.0 μm or less, it is easier to miniaturize the film capacitor when used as a film capacitor. By making the thickness of resin layer B 0.50 μm or more, film breakage during the processing of the film capacitor material into a film capacitor can be reduced. From the above viewpoint, the thickness of resin layer B is preferably 7.5 μm or less, more preferably 5.5 μm or less, and more preferably 4.5 μm or less. The thickness of resin layer B is preferably 1.0 μm or more, and more preferably 1.5 μm or more.

[0071] Here, the thickness of each layer can be observed in the width-thickness cross-section using a field emission scanning electron microscope, and measured using its length measurement function. The detailed steps are described below.

[0072] From the viewpoint of processability in manufacturing capacitors, the arithmetic mean roughness Sa of at least one side of the thin film for the thin film capacitor of the present invention is preferably 5.0 nm or more and 1000 nm or less, more preferably 5.0 nm or more and 300 nm or less. By making Sa of at least one side 5.0 nm or more, the thin film capacitor can be imparted with sliding properties, making it easier to manufacture into a thin film capacitor. By making Sa of at least one side 1000 nm or less, the withstand voltage when used as a thin film capacitor can be improved. The method of controlling Sa within this range is not particularly limited, but in order to increase Sa, it is effective to add particles to resin layer B or to add two phase-separated components to resin layer A. Conversely, in order to reduce Sa, it is effective to perform extrusion molding on a smooth mirror roller or to form resin layer B on a smooth solution film substrate. From the viewpoint of imparting sliding properties to the thin film capacitor of the present invention, it is more preferable that the Sa of both sides of the thin film capacitor of the present invention is 5.0 nm or more and 1000 nm or less, and even more preferably that the Sa of both sides is 5.0 nm or more and 300 nm or less.

[0073] The following describes the metal laminate for a thin-film capacitor according to the present invention. From an integration viewpoint, the metal laminate of the present invention has a metal layer on at least one surface of the thin film for a thin-film capacitor. Furthermore, to improve self-healing properties, it is more preferable to form a metal laminate having a resin layer B, a resin layer A, and a metal layer in sequence. Here, "having a resin layer B, a resin layer A, and a metal layer in sequence" refers to all arrangements in which the resin layer B, resin layer A, and metal layer are formed in that order, regardless of whether there are other layers between resin layer B and resin layer A, between resin layer A and metal layer, or on the outside of resin layer B or the metal layer.

[0074] The thickness of the metal layer is preferably 1 nm to 100 nm, more preferably 5 nm to 80 nm, and even more preferably 10 nm to 50 nm. Furthermore, the surface resistivity of the metal layer is preferably 0.1 Ω / sq to 10 Ω / sq, more preferably 2 Ω / sq to 8 Ω / sq, and even more preferably 3 Ω / sq to 6 Ω / sq. This is because when the surface resistivity of the metal layer is less than 0.1 Ω / sq, the self-healing property decreases, which is therefore undesirable. Conversely, a value exceeding 10 Ω / sq is preferable because the dielectric loss tangent may deteriorate. Moreover, adjusting the surface resistivity of the metal layer is simply a matter of adjusting the thickness of the metal layer.

[0075] The thin film used in the thin-film capacitor of the present invention is preferably used as a dielectric thin film for capacitors, but the type of capacitor is not limited. Specifically, from the viewpoint of electrode structure, it can be any of foil-wound capacitors or metal vapor-deposited film capacitors, and it is also well used in oil-immersed capacitors impregnated with insulating oil or dry-type capacitors without any insulating oil. In addition, from the viewpoint of shape, it can be either wound or laminated. Among these, based on the characteristics of the thin film of the present invention, it is preferred to use it as a metal vapor-deposited film thin-film capacitor containing a metal laminate. As a method for forming the metal layer, vacuum evaporation, sputtering, ion plating, and deposition methods can be used, for example. Among these methods, vacuum evaporation, which has excellent productivity, is preferred. In the case of vapor-depositing the metal layer, oil or strip methods are used as the evaporation method. The evaporation pattern of the metal layer is not particularly limited, but preferred patterns include, for example, T-margin patterns, honeycomb patterns, and mosaic patterns.

[0076] The metal composition of the aforementioned metal layer is not particularly limited, but aluminum or an alloy of aluminum and zinc is preferred. Alternatively, other metal components such as nickel, copper, gold, silver, and chromium can be deposited simultaneously or sequentially with aluminum as the metal layer. Furthermore, a protective layer such as oil can be applied to the deposited film. When depositing metal layers onto a thin film composed of resin layer A and resin layer B by vapor deposition, surface treatments such as corona discharge treatment can be performed on the deposited surface of the thin-film capacitor film before vapor deposition. Such surface treatment improves the adhesion of the deposited metal to the surface.

[0077] The thin-film capacitor of the present invention will now be described. The thin-film capacitor of the present invention is formed using the metal laminate of the present invention. The thin-film capacitor of the present invention can be part of an automotive inverter and / or converter (e.g., an inverter for a hybrid electric vehicle, a converter for a hybrid electric vehicle, an inverter for an electric vehicle, a converter for an electric vehicle, etc.).

[0078] The following describes the power control unit, electric vehicle, and electric aircraft of the present invention. The power control unit of the present invention includes the thin-film capacitor of the present invention. The power control unit is a system that manages power in an electric vehicle or electric aircraft, etc., which has a mechanism for electric drive. By mounting the thin-film capacitor of the present invention on the power control unit, it is possible to achieve miniaturization, improved heat resistance, and higher efficiency of the power control unit itself, resulting in improved fuel consumption performance.

[0079] The electric vehicle of the present invention includes the power control unit of the present invention. Here, electric vehicle refers to an electric vehicle, hybrid vehicle, fuel cell vehicle, or other vehicle with an electric drive mechanism. As described above, the power control unit of the present invention is not only miniaturized but also exhibits excellent heat resistance and efficiency. Therefore, by incorporating the power control unit of the present invention, electric vehicles can improve fuel efficiency, etc.

[0080] The electric aircraft of the present invention includes the power control unit of the present invention. Here, an electric aircraft refers to an aircraft such as a manned electric aircraft or an unmanned aerial vehicle that has a mechanism driven by electricity. As described above, the power control unit of the present invention not only enables miniaturization but also exhibits excellent heat resistance and efficiency. Therefore, by incorporating the power control unit of the present invention, the electric aircraft can achieve improved fuel efficiency, etc.

[0081] Next, an example of a method for manufacturing a thin film for a thin-film capacitor according to the present invention will be described. Furthermore, the following example is a two-layer structure consisting of resin layer A and resin layer B, but the thin film for a thin-film capacitor according to the present invention only needs to have resin layer A and resin layer B; it can be a two-layer structure or a structure with three or more layers in addition to the above.

[0082] Firstly, as a method for forming resin layer B, examples include feeding the raw material of resin layer B to an extruder, melting and extruding it from a slit-shaped die such as a T-die, and solidifying it on a cooling drum to form resin layer B; or coating a solution or liquid raw material of resin layer B onto a film used for solution film making substrates such as polyolefin film, polyethylene terephthalate film, polyimide film, or films to which silicone coating has been applied to improve release properties using a coating machine, followed by drying or polymerization and curing to form resin layer B; or casting the liquid onto a casting tape, drying or polymerization, and curing to form resin layer B. From the viewpoint of improving the uniformity of resin layer B thickness, it is preferable to use any of the following methods: coating the raw material of the solution or liquid resin layer B onto the film for solution film formation substrate using a coating machine, and then forming the resin layer B by drying; or feeding the raw material to an extruder, melting and extruding it from a slit die such as a T-die, solidifying it into a thin film on a cooling drum, and then stretching it uniaxially or biaxially to obtain the resulting film as resin layer B. When resin layer B is formed on the film for solution film formation substrate, it can be peeled off from the film for solution film formation substrate before forming resin layer A, or it can be left unpeeled. However, from the viewpoint of improving transportability, it is preferable to form resin layer A without peeling.

[0083] As an example of a method for forming resin layer B, a method is described when a biaxially oriented PPS layer is used as resin layer B. As raw material, PPS, vacuum-dried at 170°C to 190°C, is fed to an extruder and melted at 310°C to 330°C under a nitrogen atmosphere, then introduced into a T-die. Next, it is extruded from the T-die into a sheet to form a molten monolayer sheet, which is then ejected onto a casting roller maintained at a surface temperature of 10°C to 30°C. The sheet is then cooled and solidified by electrostatic application to achieve adhesion, thereby casting an unstretched film. Using a longitudinal stretching machine consisting of multiple heated roller sets, the unstretched film is stretched along its length at a ratio of 2.0 to 5.0 times the circumferential speed of the rollers, utilizing the difference in circumferential speed. Then, the obtained uniaxially stretched film is clamped at both ends in the width direction and fed into a tenter frame, where it is stretched at a stretching temperature of 95℃~105℃ at a ratio of 2.5 to 5.0 times in the width direction. Next, it is heat-treated at 270℃~290℃, followed by a relaxation treatment of 1%~10%, and cooled to room temperature. Then, the film surface (the side in contact with the casting roller) is stretched at 20 W·min / m 2 ~30W·min / m 2 The film is subjected to corona discharge treatment in the atmosphere, and then the film edge is removed to obtain a biaxially oriented PPS film with a thickness of 1μm to 8μm, which is used as resin layer B.

[0084] Methods for forming resin layer A on one side of resin layer B include coating resin layer A (in solution or liquid form) onto resin layer B using a coating machine and then drying it, and vacuum evaporating resin layer A onto resin layer B. When resin layer A is formed by coating one side of resin layer B with resin layer A, surface treatments such as corona discharge treatment can be performed on the coated surface that forms the thin film of resin layer B beforehand. By performing surface treatments such as corona discharge treatment, the wettability of the coating composition used to form resin layer A on the coated surface can be improved. As a result, pits in the coating composition are suppressed, and a uniform coating thickness is easily achieved.

[0085] When forming resin layer A, it is preferable to use crosslinking of the components of the coating composition used to form resin layer A. The crosslinking method is not particularly limited, and examples include using a composition having multiple reaction sites as the coating composition for forming resin layer A, performing a crosslinking reaction by heat or ultraviolet light, or performing crosslinking by electron beams after applying the coating composition for forming resin layer A. Examples of compositions having multiple reaction sites include acrylates or urethane acrylates having two or more vinyl groups, epoxy compounds having two or more epoxy groups, condensates of melamine and formaldehyde, mixtures of compounds having two or more isocyanate groups and compounds having three or more hydroxyl groups, and mixtures of compounds having two or more isocyanate groups and compounds having three or more amino groups. From the viewpoint of promoting the decomposition of resin layer A during insulation breakdown and improving self-healing properties, it is preferable to use acrylates or urethane acrylates having two or more vinyl groups, mixtures of compounds having two or more isocyanate groups and compounds having three or more hydroxyl groups, or mixtures of compounds having two or more isocyanate groups and compounds having three or more amino groups.

[0086] To promote the crosslinking reaction, additives such as catalysts (e.g., acids or bases), cationic initiators, anionic initiators, and free radical initiators can be added during the formation of resin layer A, depending on the reactivity of the reaction sites. For example, when using an acrylate having two or more vinyl groups as a coating composition for forming resin layer A, a coating liquid containing a free radical initiator capable of generating free radicals via ultraviolet light can be prepared. After coating the resin layer B with this coating liquid, ultraviolet light is irradiated, thereby promoting the crosslinking reaction. There are no particular limitations on the free radical initiator; hydroxyalkylphenyl ketone type initiators, aminoacetophenone type initiators, etc., capable of generating free radicals via ultraviolet light can be used. By forming a crosslinked structure on resin layer A in this way, the heat resistance of the film for the thin-film capacitor of the present invention can be easily improved.

[0087] As an example, a method for forming resin layer A using a bar coater is described. A coating solution is prepared by mixing 100 parts by weight of acrylate, 1 to 5 parts by weight of α-hydroxyalkylphenyl ketone, and 800 to 1000 parts by weight of 2-butanone. The prepared coating solution is then applied to the corona-treated surface of resin layer B formed by the above method using a bar coater to a cured film thickness of 50 nm to 500 nm. The film is then placed in a drying oven at 80°C to 100°C for 30 seconds to 2 minutes. Next, it can be placed in a UV irradiation device at an illuminance of 40 mW / cm². 2 ~70mW / cm 2 0.1 J / cm 2 ~0.3J / cm 2 The coating is cured under conditions of oxygen concentration of 100ppm to 300ppm to form resin layer A. Furthermore, by winding the resulting laminate of resin layer A and resin layer B, the thin film for the thin-film capacitor of the present invention can be obtained.

[0088] On a thin film capacitor composed of resin layer A and resin layer B obtained in this way, metal laminates of the present invention can be obtained by laminating metals such as aluminum or aluminum-zinc alloys by vacuum evaporation, sputtering, ion plating, or deposition.

[0089] Example

[0090] The following examples will specifically describe the thin film for the thin-film capacitor of the present invention. Furthermore, the methods for measuring the characteristic values ​​and evaluating the effects are as follows.

[0091] (1) Thin film thickness

[0092] The thickness of the film was measured at 10 random locations using a contact-type electronic micrometer (K-312A type) manufactured by Anlitz Co., Ltd., under an atmosphere of 23°C and 65% RH. The arithmetic mean of the thicknesses at these 10 locations was taken as the film thickness.

[0093] (2) Thickness of resin layer A, thickness of resin layer B

[0094] Using a sectioning method, an ultrathin section with a cross-sectional area of ​​5 mm in the width-thickness direction of the thin film was prepared, and platinum was coated on this section as the observation sample. Next, a field emission scanning electron microscope (S-4800) manufactured by Hitachi was used to observe the film cross-section at an accelerating voltage of 1.0 kV. The thicknesses of resin layer A and resin layer B were measured from any part of the observed image. Furthermore, the thicker layer was designated as resin layer B, and the thinner layer as resin layer A, with an observation magnification of 10000x. A total of 20 such measurements were performed, and the average values ​​were taken as the thicknesses of resin layer A and resin layer B, respectively.

[0095] (3) Melting point of the film

[0096] Based on JIS K-7122 (1987), 3.0 mg of the film was weighed and heated from 25°C to Tmax (°C) using a differential scanning calorimeter (EXSTAR DSC 6220 manufactured by Seiko Instrument) at a heating rate of 20°C / min, obtaining a differential scanning calorimeter. Based on the obtained differential scanning calorimeter, the melting peak temperature was determined according to the method described in JIS K-7121 (1987). The highest melting peak temperature obtained was taken as the melting point of the film. Initially, Tmax (°C) was set to 350°C for measurement; if no melting point was observed, it was set to 380°C for measurement again. If no melting point was observed at Tmax = 380°C, it was considered that there was no melting point.

[0097] (4) Glass transition temperature of thin film

[0098] Based on JIS K-7122 (1987), 3.0 mg of the film was weighed. Using a differential scanning calorimeter (EXSTAR DSC 6220 manufactured by Seiko Instrument), the resin was heated from 25°C to Tmax [°C] at a heating rate of 20°C / min. This heating was repeated at a rate of 20°C / min (first round), held for 5 minutes, and then rapidly cooled to below 25°C. The temperature was then increased again from 25°C to Tmax (°C) at a rate of 20°C / min (second round) to obtain the differential scanning calorimetry chart for the second round. The intermediate glass transition temperature was determined according to the method described in JIS K-7121 (1987), and the highest intermediate glass transition temperature was taken as the glass transition temperature of the film. Tmax (°C) was initially set to 350°C for measurement, and when no glass transition temperature was observed, it was set to 380°C for measurement again. If no glass transition temperature is observed at Tmax = 380℃, it is considered that there is no glass transition temperature.

[0099] (5) The atomic fractions of hydrogen atoms (H), carbon atoms (C), sulfur atoms (S), silicon atoms (Si), nitrogen atoms (N), and oxygen atoms (O) in resin layer A, and the content of oxygen atoms (O) and silicon atoms (Si) in layer B.

[0100] The surface of the resin layer A side of the thin film was analyzed using Rutherford backscattering / hydrogen forward scattering analysis (Pelletron 3SDH, National Electrostatics Corporation), yielding the atomic yields Y(H), Y(C), Y(S), Y(Si), Y(N), and Y(O) of resin layer A. Based on these values, calculations were performed using the following formula, and the resulting values ​​were taken as the atomic fractions of hydrogen (H), carbon (C), sulfur (S), silicon (Si), nitrogen (N), and oxygen (O) in resin layer A.

[0101] <Calculation Formula>

[0102] Y(All)=Y(C)+Y(S)+Y(Si)+Y(N)+Y(O)+Y(H).

[0103] The atomic fraction of hydrogen (H) = Y(H) / Y(All)

[0104] The atomic fraction of carbon (C) = Y(C) / Y(All)

[0105] The atomic fraction of sulfur atoms (S) = Y(S) / Y(All)

[0106] The atomic fraction of silicon (Si) = Y(Si) / Y(All)

[0107] The atomic fraction of nitrogen (N) = Y(N) / Y(All)

[0108] The atomic fraction of oxygen (O) is Y(O) / Y(All).

[0109] In addition, the measurement conditions are as follows.

[0110] Incident ions: 4 He ++

[0111] Incident energy: 2300keV

[0112] Angle of incidence: 75 degrees

[0113] Scattering angle: 160°

[0114] Rebound angle: 30 degrees

[0115] Sample current: 4nA

[0116] Beam diameter:

[0117] In-plane rotation: None

[0118] Irradiation dose: 0.5μC, C×20 points.

[0119] (6)XA

[0120] Using the values ​​obtained by the method described in (5), XA is calculated by the following formula (i).

[0121] Equation (i)XA = (atomic fraction of carbon atom C + atomic fraction of nitrogen atom N + atomic fraction of sulfur atom S + atomic fraction of silicon atom Si) / (atomic fraction of hydrogen atom H + atomic fraction of oxygen atom O).

[0122] (7) Pyrolysis GC-MS

[0123] 50 μg of the thin film was weighed and analyzed using the pyrolysis GC-MS apparatus set according to the following scheme to obtain a GC map. The average signal intensity at retention times of 5.0 s (10th scan), 15.0 s (30th scan), and 25.0 s (50th scan) in the obtained map was taken as the baseline intensity. The difference between the intensity of each point in the GC map and the baseline intensity was used to construct a baseline-corrected GC map. The intensity of the region with a retention time of 2 minutes to 20 minutes in the baseline-corrected GC map was recorded as 5.0 × 10⁻⁶. 3 The intensity of the highest peak among the above peaks (maximum peak intensity). Additionally, no peaks with an intensity of 5.0 × 10⁻⁶ were found. 3 When the above-mentioned peak intensities are reached, the same measurement is performed three times, and the average value of the obtained maximum peak intensity is taken as the measurement value of the membrane.

[0124] <Pyrolyzer>

[0125] Device Name: PY-3030D (Made by Frontier Lab)

[0126] Pyrolyzer Temp: 400℃

[0127] <GC>

[0128] Device Name: 7890A (Made by Agilent)

[0129] Column: "Ultra ALLOY" (registered trademark) 5 (MS / HT) 30m × 0.25mm id × 0.25μm 5% diphenyl-95% dimethyl polysiloxane

[0130] Column temperature: 40℃ (3 min) - 320℃ (18 min) (rate 20℃ / min)

[0131] Injection temperature: 300℃

[0132] Injection mode: Split (50:1) 1.5 mL / min const.F

[0133]

[0134] Device Name: JMS-Q1050GC(JEOL)

[0135] Ionization mode: EI+

[0136] Scan range: m / z 10,000-800,000

[0137] Scan rate: 0.5s / scan.

[0138] (8) Thermogravimetric analysis

[0139] 10 mg of the membrane was weighed to determine the rate of change of thermogravimetric analysis (TGA). 10 mg of resin layer A, taken from the membrane containing resin layer A, was used as a sample to determine the TGA of the resin layer A. The sample was stored at 23°C and 50% RH for 24 hours. Then, using a TGA-50 thermogravimetric analyzer (manufactured by Shimadzu Corporation), the stored sample was heated from 23°C to 500°C at a heating rate of 10°C / min under a nitrogen atmosphere, and the change in thermogravimetric analysis was measured. Based on the obtained change in thermogravimetric analysis, the thermogravimetric analysis at 170°C was set as 100% by mass, and the rate of change of thermogravimetric analysis at each temperature was calculated. The temperature at which the thermogravimetric analysis reached 99% by mass was taken as the temperature at which the thermogravimetric analysis reached 1% by mass, and the temperature at which the thermogravimetric analysis reached 90% by mass was taken as the temperature at which the thermogravimetric analysis reached 10% by mass. This measurement was considered one group, and n=5 groups of measurements were performed. The average values ​​of the n=5 groups at which the temperature decreased by 1% by mass and the temperature decreased by 10% by mass were taken as the temperature at which the temperature decreased by 1% by mass and the temperature at which the temperature decreased by 10% by mass for the sample.

[0140] (9) Arithmetic mean roughness Sa

[0141] The arithmetic mean roughness Sa was measured and calculated according to ISO 25178-2:2012 and 25178-3:2012. Measurements were performed using a scanning white interference microscope "VS1540" (manufactured by Hitachi Hitachi Systems Co., Ltd.; measurement conditions and apparatus configuration are described below). The captured image was supplemented (fully supplemented) using the accompanying analytical software. After surface correction using a fourth-order polynomial approximation, a midian filter (3×3 pixels) was applied before measurement. The S-filter Nesting Index was set to 0.455. Measurements were performed on both sides of a 5cm x 5cm square film. The intersection of the diagonals was designated as the first measurement point (starting point). Four points 1cm away from the starting point, pointing towards each corner, were designated as the second to fifth measurement points, totaling five measurement locations. Measurements were taken at each location, and the Sa value was calculated for each location according to the above steps. The average value of these measurements was used as the film's Sa value. For films with resin layer A on one side of resin layer B, the outermost surface relative to resin layer B and resin layer A was designated as the α-side, and the back side as the β-side. For films without resin layer A, the side with the lower Sa value was designated as the α-side, and the back side as the β-side. When Sa values ​​were the same on all sides, one side was designated as the α-side, and the other as the β-side.

[0142] <Measurement Conditions and Device Structure>

[0143] Objective lens: 10x

[0144] Lens tube: 1x

[0145] Zoom lens: 1x

[0146] Filter: 530nm white

[0147] Measurement mode: Wave

[0148] Measurement software: VS-Measure 10.0.4.0

[0149] Analysis software: VS-Viewer 10.0.3.0

[0150] Measurement area: 561.1μm × 561.5μm

[0151] Pixel count: 1024×1024.

[0152] (10) Self-repair (SH) defect rate and self-repairability

[0153] For the α-plane of the thin film, at an atmospheric velocity of 25 W·min / m 2The surface was subjected to corona discharge treatment at a specific intensity. Next, a bell-shaped vacuum evaporation apparatus was used on the corona-treated surface at a pressure of 1.0 × 10⁻⁶. -3 Aluminum was vapor-deposited at Pa and a filament voltage of 2.6kV to form a 50nm vapor-deposited film, resulting in a metal layer laminate. The resulting metal layer laminate was cut into 12cm × 7.5cm rectangles along its long side to serve as test pieces. Next, a 10cm square, 1mm thick Teflon sheet (registered trademark) was placed on a 1m × 2m copper plate, and the test piece was then positioned so that its short side was parallel to one side of the Teflon sheet, with the portion of the test piece 1cm from one end of the short side located on the Teflon sheet. Then, the portion of the test piece located on the Teflon sheet was clamped inwards by 2cm. 2 A 5cm square plate-shaped conductive rubber electrode is placed on a Teflon (registered trademark) sheet in a left-right manner. Then, the electrode is positioned such that its center of gravity falls on the overlapping area of ​​the rubber electrode, the test piece, and the Teflon (registered trademark) sheet. Cylindrical electrodes were used. A DC power supply was connected to both the cylindrical electrode and the copper plate via wires. An initial voltage of 100VDC was applied. After 15 seconds at this voltage, a step-increase test was performed, repeatedly increasing the applied voltage in steps of 100VDC / 30 seconds until reaching the initial voltage +800VDC. This generated multiple insulation breakdown marks on the metal layer film. The insulation breakdown marks were visually observed. Insulation breakdown marks with two or more overlapping marks were considered a single SH (Silicone Detection) defect, while marks not exhibiting this pattern were considered normal. The number of these marks was calculated, and the SH defect rate was determined using the following formula. The same measurement was performed twice, and the average value was used as the SH defect rate of the film. Furthermore, without insulation breakdown, the same measurement was performed with an initial voltage of 900VDC. If no insulation breakdown occurred at 900VDC, the same measurement was repeated with an initial voltage of +800VDC until insulation breakdown occurred. If no insulation breakdown occurred even at an initial voltage of 10000VDC, the SH defect rate was 0%. Self-healing performance was evaluated based on the membrane's SH defect rate using the following criteria.

[0154] <Calculation Formula>

[0155] SH defect rate (%) = 100 × (number of SH defective parts) / (number of normal parts + number of SH defective parts)

[0156] <Evaluation Criteria>

[0157] The defect rate of S:SH is below 10%.

[0158] A: SH's defect rate is greater than 10% but less than 20%.

[0159] B: The defect rate of SH is greater than 20% but less than 35%.

[0160] C:SH has a defect rate greater than 35% but less than 50%.

[0161] D:SH has a defect rate greater than 50%.

[0162] (11) Evaluation of processing

[0163] The surface of the thin film α in the atmosphere at 25 W·min / m 2 The surface was subjected to corona discharge treatment at a specific intensity. Next, a bell-shaped vacuum evaporation apparatus was used on the corona-treated surface at a pressure of 1.0 × 10⁻⁶. -3 Commercially available aluminum was vapor-deposited at Pa and a filament voltage of 2.6 kV to form a 50 nm thick film, resulting in a metal laminate. The metal laminate was cut into 12 cm × 7.5 cm rectangles along its length to serve as test pieces. Using a slip tester manufactured by Toyo Seiki Co., Ltd., the coefficient of kinetic friction between the vapor-deposited and undeposited metal surfaces of the metal laminate was measured three times according to JIS K7125 (1999) at a load of 200 g, 25 °C, and 65% RH. The average value was taken as the coefficient of kinetic friction μM of the metal laminate. Measurements were interrupted when the frictional force detected by the force sensor exceeded 5.9 N; at this point, the measured μM value was >3.0. Based on the obtained μM, the processability of the film was determined according to the following criteria.

[0164] A: μM is below 0.60

[0165] B: μM greater than 0.60 and less than 0.85

[0166] C: μM greater than 0.85 and less than 1.5

[0167] D: μM greater than 1.5.

[0168] (12) Dielectric loss tangent

[0169] The dielectric loss tangent was measured according to JIS C2138-2007. First, a 50mm × 50mm square film was cut. Conductive paste was applied to one side with a diameter of 18mm and to the other side with a diameter of 28mm to form an electrode. The electrode-formed sample was stored at 22°C for 90 hours and then at 60% RH. The dielectric loss tangent was then measured using a precision LCR meter HP-4284A (manufactured by Agilent Technologies) at 22°C, 60% RH, and a frequency of 10kHz with n=5. The average value obtained was taken as the dielectric loss tangent of the film.

[0170] (13) Evaluation of the breakdown voltage of thin film insulation at 150℃

[0171] After heating the film in an oven at 150°C for 1 minute, the film was measured in the same atmosphere according to JIS C2330(2001) 7.4.11.2B method (plate electrode method). Thirty insulation breakdown voltage tests were performed (as described above). The obtained values ​​were divided by the film thickness (as described in (1) above) and converted to (V / μm) to obtain a total of 30 measured values ​​(calculated values). Five points that decrease sequentially from the maximum value and five points that increase sequentially from the minimum value were removed. The average value of 20 points was then taken as the film insulation breakdown voltage at 150°C. Based on the obtained film insulation breakdown voltage at 150°C, the film insulation breakdown voltage at 150°C was evaluated as follows.

[0172] S: The breakdown voltage of the thin-film insulation at 150℃ is above 270V / μm.

[0173] A: The breakdown voltage of thin-film insulation at 150℃ is above 240V / μm and below 270V / μm.

[0174] B: At 150℃, the breakdown voltage of the thin-film insulation is above 210V / μm and below 240V / μm.

[0175] C: At 150℃, the breakdown voltage of the thin-film insulation is above 100V / μm and below 210V / μm.

[0176] D: If the film insulation breakdown voltage is less than 100V / μm at 150℃ or the film shrinkage is large, it cannot be evaluated.

[0177] (14) Evaluation of film capacitor characteristics (reliability at 150℃)

[0178] The α-side of the thin film at 25 W·min / m in the atmosphere 2The material is subjected to corona discharge treatment at a certain intensity. Next, aluminum vapor deposition is performed on the corona-treated surface with a film resistance of 10 Ω / sq (vacuum vapor deposition using an Alback vacuum vapor deposition machine), resulting in a vapor deposition pattern with a so-called T-shaped allowance (formed by masking oil with a length pitch (period) of 17 mm and a wire width (hook width) of 0.5 mm). The resulting vapor deposition body is then cut into strips to obtain vapor deposition spools with a film width of 50 mm (end allowance width of 2 mm). Using these spools, thin-film capacitor elements are wound using a component winding machine (KAW-4NHB) manufactured by Kaito Co., Ltd. After metal sputtering, a heat treatment is performed at 130°C for 8 hours under reduced pressure. Wires are then installed to complete the thin-film capacitor element. Using the 10 capacitor elements obtained in this way, a voltage of 250VDC was applied to the capacitor elements at a high temperature of 150°C. After applying this voltage for 10 minutes, a so-called step test was repeatedly performed, in which the applied voltage was gradually increased in a stepwise manner at 50VDC / 1 minute. After the voltage was increased until the electrostatic capacitance decreased to less than 12% of the initial value, the capacitor elements were disassembled, and the state of damage was investigated. The characteristics of the film capacitor were evaluated according to the following evaluation criteria.

[0179] <Evaluation Criteria>

[0180] S: The shape of the film capacitor element remained unchanged, and no breakdown-like damage was observed.

[0181] A: The shape of the thin-film capacitor element did not change, but breakdown-like damage was observed within 5 layers of the film.

[0182] B: The shape of the thin-film capacitor element did not change, but a breakdown-like damage was observed that broke through 6 to 7 layers of the thin film.

[0183] C: Changes in the shape of the film capacitor element are observed. Or, breakdown-like damage is observed in 8 to 14 layers of the film.

[0184] D: The shape of the film capacitor element has changed significantly and it has been damaged, or the film has poor processability and cannot be used to manufacture film capacitor elements.

[0185] The evaluation results mean that the characteristics of the film capacitor are excellent in the order of S to D, qualified in S to C, and unqualified in D because it is difficult to use the film as a practical capacitor.

[0186] (Raw materials, thin films)

[0187] Acrylate 1: Trade name "Epokisitel 3000A", Bisphenol A diglycidyl ether acrylic adduct, manufactured by Kyoei Chemical Co., Ltd.

[0188] Acrylate 2: Trade name "Viscot" (registered trademark) #300, a condensation of pentaerythritol and acrylic acid, containing 45% by mass of pentaerythritol tetraacrylate and 35% by mass of pentaerythritol triacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.

[0189] Acrylate 3: Trade name "TPGDA", tripropylene glycol diacrylate, manufactured by Daicel Ornex Co., Ltd.

[0190] Carbamate acrylate 1: Trade name "UV-3500BA", butyl acetate dilution of carbamate acrylate, manufactured by Mitsubishi Chemical Corporation.

[0191] In polyurea compound 1: 5.90 parts by weight of dicyclohexylmethane 4,4'-diisocyanate, 5.0 parts by weight of isophorone diisocyanate, 2.6 parts by weight of hydroxyethylacrylamide, 0.012 parts by weight of dioctyltin dilaurate as a catalyst, and 9.0 parts by weight of acryloylmorpholine as a monomer for dilution were added to a 500 mL flask, and the mixture was stirred at room temperature for 1.5 hours. 0.71 parts by weight of monoethanolamine were added dropwise to the stirred reaction solution, and the mixture was stirred further at room temperature for 3 hours. Then, a mixed solution of 12 parts by weight of isopropanol and 3.8 parts by weight of dicyclohexylmethane-4,4'-diamine was added to the stirred reaction solution, and the mixture was stirred at room temperature for another 3 hours to obtain polyurea compound 1 with free radical polymerizable substituents [70% non-volatile content, weight-average molecular weight (Mw) = 1300].

[0192] 2-Butanone: Fujifilm Wako Pure Chemical Industries, Ltd.

[0193] "Omnirad" (registered trademark) 184: Made by IGM Resins BV, 1-hydroxycyclohexylphenyl ketone.

[0194] Polyphenylene sulfide resin particles 1 (PPS particles 1):

[0195] To a 1-liter high-pressure reactor equipped with an engineered stirrer, add 1.00 mol of 48% sodium hydrosulfide, 1.02 mol of 95% sodium hydroxide, 1.54 mol of N-methyl-2-pyrrolidone (NMP), 0.47 mol of sodium acetate, and 140 g of deionized water. While stirring at 250 rpm, gradually heat to 228°C under nitrogen atmosphere at atmospheric pressure for approximately 3 hours. After distilling off 212 g of water and 4 g of NMP, cool the reaction vessel to 160°C. Next, add 1.00 mol of p-dichlorobenzene (p-DCB) and 1.32 mol of NMP, and seal the reaction vessel under nitrogen atmosphere. Then, while stirring at 250 rpm, increase the temperature from 200°C to 235°C at a rate of 0.7°C / min, and continue the reaction at 235°C for 95 minutes. Then, increase the temperature to 270°C at a rate of 0.8°C / min and maintain this temperature for 100 minutes. After reaching 270°C, 1 molar of water was injected into the system over 15 minutes. After maintaining the temperature at 270°C for 100 minutes, the mixture was cooled to 200°C at a rate of 1.0°C / min, and then room temperature cooling water was poured onto the autoclave to cool it to near room temperature. Next, the contents were removed, diluted with 0.4 L of NMP, stirred at 85°C for 30 minutes, and the solvent and solids were filtered through an 80 mesh sieve. Then, 0.5 L of NMP was added to the resulting solids, and the mixture was stirred at 85°C for 30 minutes, and the solids were filtered out. The resulting solids were then washed three times with 0.9 L of warm water and filtered. 1 L of warm water was added to the resulting particles (solids), and the mixture was washed and filtered twice to obtain polymer particles. These particles were then dried with hot air at 80°C and then under reduced pressure at 120°C to obtain polyphenylene sulfide (PPS) resin particles (PPS particles 1) with a melting point of 280°C and a weight-average molecular weight of 70,000.

[0196] PPS raw material 1 for film (PPS1):

[0197] A mixed powder obtained by mixing 100 parts by weight of PPS particles 1, 0.05 parts by weight of calcium carbonate particles 1 (NITOREX #30PS manufactured by Nitto Powdered Chemical Co., Ltd. with an average particle size of 0.7 μm), and 0.2 parts by weight of calcium stearate was granulated to prepare resin particles with PPS as the main component. The obtained resin particles were fed into a co-rotating twin-screw compounding extruder (manufactured by Nippon Steel Corporation, screw diameter 30 mm, screw length / screw diameter = 45.5) with a vent, heated to 320°C, and melt-extruded at a residence time of 90 seconds and a screw speed of 150 rpm, extruding into strands, and cooled with water at 25°C. It was then immediately cut into small sheets to make PPS raw material 1 for film (PPS1).

[0198] PPS raw material 2 for film (PPS2):

[0199] Except for the absence of calcium carbonate particles 1, small sheets are made in the same manner as PPS1 as PPS2 for film production.

[0200] PPS raw material 3 (PPS3) for film:

[0201] Except for replacing calcium carbonate particles 1 with calcium carbonate particles 2 (NITOREX #30PS manufactured by Nitto Powdered Chemical Co., Ltd.) with an average particle size of 1.2 μm, small flakes were made in the same manner as PPS1 to serve as PPS raw material 3 (PPS3) for film production.

[0202] PPS film 1:

[0203] As raw material, PPS1 was vacuum dried at 180°C for 3 hours. Then, it was fed into an extruder, melted at 320°C under a nitrogen atmosphere, and introduced into a T-die. Next, it was extruded from the T-die into a sheet to form a molten monolayer, which was then fed onto a casting roller maintained at a surface temperature of 25°C and a rotational speed of 4.0 m / min. The roller was then electrostatically bonded and cooled to solidify, resulting in an unstretched film. Using a longitudinal stretching machine consisting of multiple heated rollers, the unstretched film was stretched at a stretching temperature of 103°C at a length ratio of 3.2 times, utilizing the difference in circumferential speed of the rollers. Then, the width ends of the resulting uniaxially stretched film were clamped and fed into a tenter frame, where it was stretched at a stretching temperature of 100°C at a width ratio of 3.3 times. Finally, after heat treatment at 280°C, a 2% relaxation treatment was performed, followed by cooling to room temperature. Next, the membrane surface (the side in contact with the casting roller) was treated with a pressure of 25 W·min / m. 2 The film was subjected to corona discharge treatment in the atmosphere, and then the film edges were removed to obtain a biaxially stretched PPS film with a thickness of 4.3 μm.

[0204] PPS film 2:

[0205] In addition to using PPS2 as a raw material and making the stretching ratio of the longitudinal stretching machine 3.4 times, a biaxially stretched PPS film was obtained in the same manner as PPS film 1.

[0206] PPS film 3:

[0207] In addition to using PPS3 as a raw material and setting the stretching ratio of the longitudinal stretching machine to 3.0 times, a biaxially stretched PPS film was obtained in the same manner as PPS film 1.

[0208] PPS film 4:

[0209] Polyethylene terephthalate (PET) containing 0.5% by mass of spherical silica with a diameter of 500 μm and an intrinsic viscosity of 0.6 was subjected to a temperature of 300°C and a shear rate of 200 s. -1 Polyphenylene sulfide (PPS) with a melt viscosity of 4000 poise was fed into different extruders. While molten, it was guided by a lamination device located above the die to form a two-layer polyethylene terephthalate (PET) / PPS / sulfide stack. The stack was then extruded from a T-die and rapidly cooled by a cooling rotary roller to obtain a PET / PPS / PPS / sulfide two-layer sheet. Next, the double-layer sheet was moved across multiple heated rollers at a surface temperature of 90°C and stretched 3.7 times its length between cooling rollers at a different circumferential speed (30°C) located after the heated rollers. The resulting uniaxially stretched sheet was stretched 3.5 times its width at 100°C using a tenter frame, followed by heat treatment at 260°C for 10 seconds to obtain a biaxially stretched film with a total thickness of 4 μm and a PET layer thickness of 0.1 μm.

[0210] PP film 1:

[0211] A linear polypropylene (PP) polymerized with a Ziegler-Natta catalyst, comprising 0.98 units of five components, with a melting point of 167°C and a melt flow rate (MFR) of 2.6 g / 10 min, was fed into a uniaxial melt extruder. After melt extrusion at 240°C, impurities were removed using an 80 μm cut sintered filter, allowing the molten polymer to exit as a sheet from a T-die. This molten sheet was then electrostatically pressed against a casting roller maintained at 95°C, and cooled and solidified to obtain an unstretched sheet. The unstretched sheet was then gradually preheated to 145°C in multiple roller sets, and then stretched 5.0 times its original length by passing it between rollers with a circumferential speed difference while maintaining the temperature at 145°C. The obtained uniaxially stretched film is then guided to a tenter frame and stretched 8 times its original width at 165°C. Following this, as the first stage of heat treatment and relaxation, an 8% relaxation is applied in the width direction while heat treatment is performed at 130°C. This is then followed by the second stage of heat treatment, where the film is held in the width direction by clamps and heat-treated at 140°C. After a cooling process at 100°C, the film is guided to the outside of the tenter frame, the clamps at the film ends are released, and a 3.0 μm thick film is wound to obtain a biaxially stretched PP film.

[0212] PEI film 1:

[0213] Prepare polyetherimide [manufactured by SABIC Inove Plus, product name: ULTEM1010-1000-NB (hereinafter referred to as "1010-1000")]. Place the molding material in a dehumidifying hot air dryer [manufactured by Matsui Seisakusho, product name: Martijett MJ3] heated to 150°C for 12 hours to dry it. After confirming that the moisture content of the molding material is below 300 ppm, place the molding material in a T-die with a width of 900 mm. The polyetherimide was melt-blended in a single-screw extruder and continuously extruded from the T-die of the single-screw extruder to form a strip. The strip was then cooled and solidified on a mirror roller and wound to obtain a PEI film with a thickness of 6.5 μm.

[0214] PES film 1:

[0215] 100 parts by weight of polyethersulfone resin (Sumitomo Chemicals, Smica Eccell 4800P) with a glass transition temperature of 225°C were fed into the feed inlet of a co-rotating twin-screw extruder to melt it. Calcium carbonate particles 1 were then fed into the side feeder on the die side of the co-rotating twin-screw extruder at a ratio of 5.0 parts by weight relative to 100 parts by weight of the polyethersulfone resin, allowing it to melt, mix, and disperse. The molten mixture was extruded from the die at the front end of the co-rotating twin-screw extruder into a rod shape, water-cooled, and then cut using a granulator to prepare a granular molding material. PES film 1 was obtained in the same manner as PEI film 1, except that this molding material was used instead of polyetherimide.

[0216] (Example 1)

[0217] According to the coating solution formulation in Table 1, 100g of coating solution was prepared by mixing urethane acrylate 1, 2-butanone, and "Omnirad" (registered trademark) 184 in a ratio of 100:900:0.3 (mass ratio). As shown in Table 1, PPS film 1 was used as the substrate film (resin layer B). The coating solution was uniformly applied to the corona-treated surface of the PPS film using a bar coater, so that the cured thickness was the same as that of resin layer A (50nm) shown in Table 1. The film was then dried in a drying oven at 90°C for 1 minute. Next, it was placed in a UV irradiation device at an illuminance of 50mW / cm². 2 0.1 J / cm 2 After the coating was cured to form resin layer A under an oxygen concentration of 100 ppm, a laminate of resin layers A and B was wound to obtain a thin film for a thin-film capacitor. The evaluation results are shown in Table 1.

[0218] (Examples 2-10)

[0219] Except that the coating solution formulation, substrate film, and resin layer A thickness are as shown in Table 1, a thin film for a thin-film capacitor was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1.

[0220] (Comparative Example 1)

[0221] PPS film 1 was used as the film for the film capacitor. The evaluation results are shown in Table 2.

[0222] (Comparative Example 2)

[0223] PPS film 4 was used as the film for the film capacitor. The evaluation results are shown in Table 2.

[0224] (Comparative Example 3)

[0225] PP film 1 was evaluated as a film capacitor. The evaluation results are shown in Table 2.

[0226] (Comparative Example 4)

[0227] PEI film 1 was evaluated as a film capacitor. The evaluation results are shown in Table 2.

[0228] (Comparative Example 5)

[0229] Except that the coating solution formulation was the same as in Example 5, the thickness of resin layer A was 550 nm, and the substrate film was PEI film 1, a thin film for filling capacitors was obtained in the same manner as in Example 1. The evaluation results are shown in Table 2.

[0230]

[0231]

[0232] Furthermore, in Tables 1 and 2, the outermost surface of the resin layer A side was designated as the α surface in Examples 1-10 and Comparative Examples 2 and 5; the surface on the side with lower Sa was designated as the α surface in Comparative Examples 3 and 4; and the inner surface of the roll was designated as the α surface in Comparative Example 1. Since the PPS film 4 is a laminated film consisting of a relatively thick PPS layer and a relatively thin PET layer, the substrate film (resin layer B) of Comparative Example 2 becomes the PPS layer portion of the PPS film 4.

[0233] Industrial availability

[0234] The film for the thin-film capacitor of the present invention is applicable to various applications such as packaging, tape, electrical applications such as cable wrapping or capacitors, and is particularly suitable for high-voltage capacitor applications that require high voltage resistance and reliability at high temperatures.

Claims

1. A thin film for a thin-film capacitor, comprising two resin layers of different thicknesses. When the thinner resin layer is designated as resin layer A and the thicker resin layer is designated as resin layer B, resin layer A is present on at least one side of resin layer B. Based on the atomic fractions of hydrogen (H), carbon (C), sulfur (S), silicon (Si), nitrogen (N), and oxygen (O) contained in the resin layer A, XA calculated using the following formula (i) is 0.050 or more and 0.80 or less. The thin film has a dielectric loss tangent of less than 0.50% measured at 10 kHz in an atmosphere at 23°C, and satisfies at least one of the following conditions 1 and 2. Formula (i): XA = (Atomic fraction of carbon atom C + atomic fraction of nitrogen atom N + atomic fraction of sulfur atom S + atomic fraction of silicon atom Si) / (Atomic fraction of hydrogen atom H + atomic fraction of oxygen atom O) Condition 1: The melting point determined by DSC is above 180℃. Condition 2: The glass transition temperature determined by DSC is above 130℃ and below 370℃. When the film was subjected to pyrolysis GC-MS measurement at 400°C, it exhibited a peak intensity of over 25,000 in the retention time range of more than 2 minutes and less than 20 minutes.

2. The film for a film capacitor as described in claim 1, when the thermogravimetric change rate of the resin layer A is measured at a heating rate of 10°C / min under a nitrogen atmosphere, the temperature at which 10% mass decreases is 390°C or less.

3. The film for a film capacitor as described in claim 1 or 2, when the rate of change of thermogravimetric temperature is measured at a heating rate of 10°C / min under a nitrogen atmosphere, has a 1% mass reduction temperature of 430°C or less.

4. The thin film for a thin-film capacitor as described in claim 1 or 2, wherein the resin layer A has any one of the partial structures represented by structures r1 to r8 as structural units. in, In structures r1 to r6, n is an integer greater than or equal to 1.

5. The film for a thin-film capacitor as described in claim 1 or 2, wherein the resin layer A contains at least one compound selected from urethane acrylate polymers, acrylate polymers, urethane methacrylate polymers, methacrylate polymers, aliphatic polyethers, aliphatic polyesters, aliphatic polyamides, polyurethanes, and polyureas. The urethane acrylate polymer refers to a compound formed by polymerizing acrylates containing urethane bonds. The acrylate polymer is a compound formed by polymerizing acrylates, but it is a compound other than a urethane acrylate polymer.

6. The film for a thin-film capacitor as claimed in claim 1 or 2, wherein the resin layer B contains at least one selected from polyarylene sulfide, polysulfone, and polyimide, and the total amount thereof is 50% by mass or more and 100% by mass or less.

7. The film for a thin-film capacitor as described in claim 6, wherein the polysulfone is polyethersulfone.

8. The thin film for a thin film capacitor as described in claim 1 or 2, wherein the thickness of the resin layer A is 1.0 nm or more and 500 nm or less.

9. The thin film for a thin-film capacitor as described in claim 1 or 2, wherein the arithmetic mean roughness Sa of at least one surface is 5.0 nm or more and 1000 nm or less.

10. A metal laminate having a metal layer on at least one surface of the film for a film capacitor according to any one of claims 1 to 9.

11. The metal laminate as claimed in claim 10, comprising the resin layer B, the resin layer A, and the metal layer in sequence.

12. A thin-film capacitor made using the metal laminate of claim 10 or 11.

13. A power control unit having the thin-film capacitor of claim 12.

14. An electric vehicle having the power control unit as claimed in claim 13.

15. An electric aircraft having the power control unit as claimed in claim 13.

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