JP5944304B2 - Polyurea and method for producing the same, capacitor element and method for producing the same - Google Patents

Description

  The present invention relates to a polyurea and a method for producing the same, and a capacitor element and a method for producing the same, and in particular, a polyurea preferably used in the form of a thin film, an advantageous method for producing such a polyurea, and a dielectric comprising such a polyurea. The present invention relates to a capacitor element having a film layer and an advantageous method for producing such a capacitor element.

  Conventionally, a vapor deposition polymerization method is known as a kind of method for forming a polymer thin film. In this vapor deposition polymerization method, for example, as disclosed in JP-A-61-78463 (Patent Document 1), vapors of two or more kinds of raw material monomers are polymerized in a vacuum, for example, on a substrate. Thus, a polymer thin film made of a vapor deposition polymer is formed. The thin film of the vapor-deposited polymer formed by such vapor-deposition polymerization method can control the film thickness on the nano order, and since it is formed in a vacuum, the impurities in the film are extremely reduced. Excellent characteristics are demonstrated.

  By the way, when manufacturing polyurea which is a kind of polymer, various methods are employed, and among them, a manufacturing method using the above-described vapor deposition polymerization method is preferably employed. This is because the polyurea produced by the vapor deposition polymerization method is not only highly pure and can be made into a nano-order thin film as described above, but also heat treatment in the polymerization of raw material monomers (diisocyanate and diamine, etc.). Is unnecessary, and since the polyaddition polymerization reaction proceeds, there is no elimination of water or alcohol. Therefore, when polyurea is produced by vapor deposition polymerization, equipment for carrying out heat treatment during the polymerization of raw material monomers, water, alcohol, etc. desorbed by the polymerization reaction are removed from the vacuum chamber in which the polymerization reaction proceeds. This is because there is no need for equipment for removal, and cost reduction and simplification of manufacturing equipment can be advantageously achieved.

  In recent years, the use of polyurea having excellent characteristics obtained by such vapor deposition polymerization method has been sought. For example, such polyurea can be used as a dielectric film layer of a film capacitor element or a solid electrolyte of a solid secondary battery. Application to a layer or the like has been studied.

  Under such circumstances, the present inventor conducted various tests on the polyurea produced by the conventional vapor deposition polymerization method, and the following became clear. That is, the polyurea produced by the conventional method using the vapor deposition polymerization method has sufficient heat resistance, but has poor flexibility or high flexibility, but only has poor heat resistance, and is high. It has been found that there is no combination of heat resistance and flexibility. In addition, when a film capacitor element is manufactured using a dielectric film layer made of polyurea produced by a conventional vapor deposition polymerization method, a dielectric film layer made of polyurea having low heat resistance but high flexibility is used. It is also clear that the obtained film capacitor element is inferior in self-healing compared to a film capacitor element obtained using a dielectric film layer made of polyurea having low heat resistance, although it has high flexibility. It became. Self-healing means that when a dielectric breakdown occurs in the dielectric film layer, the surrounding metal vapor deposition film layer is evaporated and scattered by the energy generated by the short-circuit current, and an insulating part is formed around it. The property that immediately restores the capacitor function.

  In JP-A-8-148281 (Patent Document 2), by performing a vapor deposition polymerization method using a raw material monomer having two functional groups and a raw material monomer having three or more functional groups. It is possible to obtain a vapor-deposited polymer thin film whose molecular structure is a network structure, and to apply such a vapor-deposited polymer thin film to an electroluminescent layer or a charge injection / transport layer of an organic thin film electroluminescent device. Can improve the heat resistance and durability of the electroluminescent layer and charge injection / transport layer.

  However, the inventors have verified the performance of the vapor-deposited polymer disclosed in JP-A-8-148281, and as a result, the vapor-deposited polymer whose molecular structure is simply a network structure is, for example, a dielectric film. It has been found that it is difficult to sufficiently enhance the self-recovery property of the film capacitor element applied to the layer. Moreover, since the vapor deposition polymer disclosed in this publication uses carboxylic acid chloride as a raw material monomer, hydrochloric acid is generated during the reaction. Therefore, when a vapor deposition polymer obtained using a raw material monomer composed of such a carboxylic acid chloride is applied to a dielectric film layer to obtain a film capacitor element, hydrochloric acid is impure in the dielectric film. It has also been clarified by the study of the present inventor that a problem arises in that the withstand voltage is lowered due to being mixed in as a result.

JP-A-61-78463 JP-A-8-148281

  Here, the present invention has been made in the background of the above-mentioned circumstances, and the problem to be solved thereof is that it has excellent heat resistance and flexibility, and further, a dielectric film of a film capacitor element. It is an object of the present invention to provide a polyurea that can sufficiently enhance the self-healing property of an applied film capacitor element when applied to a layer and the like, and a method that can advantageously produce such a polyurea. In addition, the present invention provides a film capacitor element in which high heat resistance and flexibility are sufficiently ensured in the dielectric film layer, and excellent self-recovery properties are advantageously exhibited, and such a film capacitor element. Another object of the present invention is to provide an advantageous manufacturing method.

  In the course of conducting various tests and studies to solve the above-mentioned problems, the present inventor has polyurea produced using two or more kinds of raw material monomers composed of aromatic monomers, having sufficient heat resistance. , Tending to be low in flexibility, and polyurea produced using two or more raw material monomers composed of aliphatic monomers tends to be inferior in heat resistance, while exhibiting high flexibility. I found out. As a result of further research by the inventor, if only a raw material monomer composed of an aliphatic monomer is used as a polyurea raw material monomer, and the polyurea molecular structure is a network structure, the Excellent flexibility and heat resistance are improved, and when polyurea is applied to the dielectric film layer of the film capacitor element, the self-healing property of the applied film capacitor element is improved. We have obtained the knowledge that can be sufficiently achieved.

  The present invention has been completed based on the above knowledge, and the gist thereof is a polyurea produced by a vapor deposition polymerization method in which vapors of two or more kinds of raw material monomers are polymerized in vacuum. All of the two or more raw material monomers are composed of an aliphatic monomer, and at least one of the two or more raw material monomers has a function of another raw material monomer that is polymerized with the at least one raw material monomer. The polyurea is characterized by having three or more functional groups capable of reacting with a group and having a network structure as a molecular structure. The polyurea referred to here includes a polyurea simple substance and a copolymer of polyurea and other polymer compound mainly composed of polyurea. Hereinafter, they are used in the same meaning.

  Further, in the present invention, a polyurea is produced by a vapor deposition polymerization method in which vapors of two or more kinds of raw material monomers are polymerized in a vacuum, and all of the two or more kinds of raw material monomers are aliphatic monomers. And a functional group capable of reacting with a functional group of another raw material monomer that is polymerized with at least one raw material monomer on at least one of the two or more raw material monomers made of the aliphatic monomer. The gist of the method for producing polyurea is characterized in that the vapor of two or more kinds of raw material monomers is polymerized in vacuum using a material having three or more groups.

  According to the present invention, there is provided a film capacitor element using a laminate formed by laminating a dielectric film layer made of polyurea and a metal vapor deposition film layer, wherein the dielectric film layer made of polyurea is deposited. Formed by a polymerization method, the molecular structure of the polyurea is a network structure, and the raw material monomer for forming the dielectric film layer made of the polyurea is composed of only two or more types of aliphatic monomers, and At least one of the two or more types of aliphatic monomers has three or more functional groups capable of reacting with functional groups of other raw material monomers that are polymerized with the at least one raw material monomer. The film capacitor element is also the gist of the film capacitor element.

  According to the present invention, in the method of manufacturing a film capacitor element using a laminate formed by laminating a dielectric film layer made of polyurea and a metal vapor deposition film layer, Dielectrics comprising two or more types of aliphatic monomers each having a group, and at least one of the two or more types of aliphatic monomers having three or more functional groups, respectively, the polyurea A dielectric film layer made of the polyurea by performing a step of preparing as a raw material monomer for the film layer, and (b) a vapor deposition polymerization method in which vapors of two or more kinds of raw material monomers made of the aliphatic monomer are polymerized in a vacuum. Forming a metal vapor deposition film layer by performing a vapor deposition method using a metal material; and (d) a dielectric film layer made of the polyurea and a front layer. A method for producing a film capacitor element, comprising: laminating a metal vapor deposition film layer to obtain the laminate; and (e) producing the film capacitor element using the laminate. Is also the gist of this.

  That is, in the polyurea according to the present invention, all of the two or more kinds of raw material monomers are composed of aliphatic monomers, and since the molecular structure is a network structure, more excellent flexibility is exhibited, The heat resistance can be improved, and when applied to the dielectric film layer of the film capacitor element, the self-healing property of the applied film capacitor element can be effectively and sufficiently improved.

  In addition, according to the method for producing a polyurea according to the present invention, the film capacitor element has excellent heat resistance and flexibility, and when applied to the dielectric film layer of the film capacitor element, the self-healing of the applied film capacitor element Polyurea that can sufficiently enhance the properties can be produced very advantageously.

  Furthermore, in the film capacitor element according to the present invention, high heat resistance and flexibility are sufficiently ensured in the dielectric film layer, and excellent self-healing properties can be advantageously exhibited.

  In addition, according to the method for manufacturing a film capacitor element according to the present invention, a film capacitor element in which high heat resistance and flexibility are sufficiently ensured in the dielectric film layer, and excellent self-recovery can be advantageously exhibited. Can be produced very advantageously.

It is a section explanatory view showing one embodiment of a film capacitor element which has a structure according to the present invention. FIG. 2 is a schematic diagram of a molecular structure of polyurea constituting a dielectric film layer of the film capacitor element shown in FIG. 1. It is explanatory drawing which shows an example of the manufacturing apparatus which manufactures the film capacitor | condenser element shown by FIG. FIG. 2 is a cross-sectional explanatory view showing a film capacitor manufactured using the film capacitor element shown in FIG. 1.

  Hereinafter, in order to clarify the present invention more specifically, embodiments of the present invention will be described in detail with reference to the drawings.

  First, FIG. 1 shows an embodiment of a film capacitor element having a structure according to the present invention in its longitudinal sectional form. As is apparent from FIG. 1, the film capacitor element 10 of the present embodiment has a resin film 12 as a base dielectric film layer. And the 1st metal vapor deposition film layer 14, the dielectric material film layer 16, and the 2nd metal vapor deposition film layer 18 are laminated | stacked and formed in that order on one surface of the thickness direction of the resin film 12. FIG. That is, here, one laminated body formed by alternately laminating the first and second metal vapor-deposited film layers 14 and 18 and one dielectric film layer 16 on one surface of the resin film 12. At 20, the film capacitor element 10 is configured.

  More specifically, the resin film 12 is composed of a long biaxially stretched film made of polypropylene and has a thickness of about 1 to 10 μm. As the resin film 12, any resin film constituting the dielectric film layer of a conventional film capacitor can be used. For example, a resin film made of polyethylene terephthalate, polyphenylene sulfide, polyethylene naphthalate, polyvinylidene fluoride, or the like can be used. Further, these resin films are not necessarily biaxially stretched films.

  Both the first metal vapor deposition film layer 14 and the second metal vapor deposition film layer 18 are made of aluminum. The first metal vapor-deposited film layer 14 and the second metal vapor-deposited film layer 18 constitute an internal electrode of a film capacitor produced using the film capacitor element 10, and are formed on the resin film 12 according to a known method. And the dielectric film layer 16 are stacked. That is, the first and second metal vapor deposition film layers 14 and 18 are formed by using a publicly known vapor deposition method belonging to the category of PVD or CVD, using a known metal material forming an internal electrode of a film capacitor as a vapor deposition material. By carrying out, it is laminated on the resin film 12 or the dielectric film layer 16. Therefore, the 1st metal vapor deposition film layer 14 and the 2nd metal vapor deposition film layer 18 are not limited to aluminum, For example, you may consist of zinc etc. The first metal vapor deposition film layer 14 and the second metal vapor deposition film layer 18 may be composed of different metal materials.

  Here, the widths of the first metal vapor-deposited film layer 14 and the second metal vapor-deposited film layer 18 (dimensions in the left-right direction in FIG. 1) are made smaller than the width of the resin film 12 by a predetermined dimension. And the 1st metal vapor deposition film layer 14 is laminated | stacked on the part except the edge part of the width direction one side (left side of FIG. 1) of the resin film 12, while the 2nd metal vapor deposition film layer 18 is a dielectric material. The film layer 16 is laminated on a portion excluding an end portion on the other side in the width direction (right side in FIG. 1). As a result, the first margin portion 22 made of a portion where the first metal vapor deposition film layer 16 is not formed is formed at one end in the width direction of the resin film 12 so as to extend along the length direction of the resin film 12. Has been. In addition, a second margin portion 24 formed of a portion where the second metal vapor deposition film layer 18 is not formed is provided at the end of the dielectric film layer 16 on the other side in the width direction opposite to the first margin portion 22 side. It is formed so as to extend along the length direction of the film layer 16 (resin film 12). In the present embodiment, a part of the second metal vapor-deposited film layer 18 is laminated on the edge of one side in the width direction of the resin film 12 where the first metal vapor-deposited film layer 14 is not formed. Thereby, only the part which entered only the predetermined dimension in the width direction inside from the edge part except the formation part of the 2nd metal vapor deposition film layer 18 among the edge parts of the width direction one side of resin film 12 is the first. The margin portion 22 is used.

  On the other hand, the dielectric film layer 16 is made of polyurea. The dielectric film layer 16 made of polyurea is laminated on the first metal vapor deposition film layer 14 by a known vapor deposition polymerization method in which vapors of two or more kinds of raw material monomers are polymerized in vacuum. In such a dielectric film layer 16, good quality with few impurities is ensured, and the thickness thereof is sufficiently thinner than the thickness of the resin film 12. As a result, the film capacitor produced using the film capacitor element 10 can be effectively reduced in size and performance.

  The dielectric film layer 16 has a smaller width than the resin film 12, and is disposed on the resin film 12 at the center in the width direction. Thereby, no dielectric film layer 16 is provided at the end of the first metal vapor-deposited film layer 14 on the side opposite to the first margin portion 22 side, and such first metal vapor-deposited film layer 14 is not provided. The first end 26 is connected to one of two metallicon electrodes on the positive electrode side and the negative electrode side which will be described later. Further, the end portion of the second metal vapor deposition film layer 18 on the side opposite to the second margin portion 24 side is directly laminated on the end portion of the resin film 12 on the first margin portion 22 side, which will be described later. The second connecting portion 28 is connected to the other of the two metallicon electrodes.

  The film thickness of the dielectric film layer 16 is not particularly limited, but is preferably about 0.001 to 10 μm. This is because it is not easy to form the dielectric film layer 16 with a film thickness of less than 0.001 μm. Therefore, the film thickness of the dielectric film layer 16 is practically 0.001 μm or more. Further, when the thickness of the dielectric film layer 16 exceeds 10 μm, it is difficult to promote downsizing of the film capacitor having the dielectric film layer 16 as a dielectric.

  The polyurea constituting the dielectric film layer 16 not only has a higher dielectric constant than that of the resin film 12, but also does not require heat treatment when polymerizing raw material monomers (diisocyanate and diamine, etc.) It is formed in a polyaddition polymerization reaction with no elimination of alcohol or alcohol. Therefore, the equipment for carrying out the heat treatment at the time of polymerization of the raw material monomers is not necessary here, and cost reduction can be realized. Moreover, it can be advantageously avoided that the heat loss during heat treatment causes the resin film 12 to be deformed, so-called heat loss. Furthermore, it is not necessary to remove water, alcohol, and the like released by the polymerization reaction from the vacuum chamber in which the polymerization reaction proceeds. Therefore, facilities for removing the desorbed water, alcohol, etc. are not required. This also makes it possible to advantageously reduce costs. In addition, the polyurea resin film has excellent moisture resistance. Thereby, the high withstand voltage of the dielectric film layer 16 can be secured more stably.

  In the film capacitor element 10 of the present embodiment, in particular, the two or more kinds of raw material monomers used when forming such a dielectric film layer 16 by vapor deposition polymerization are all composed of aliphatic monomers. In addition, at least one of the two or more types of raw material monomers has three or more functional groups capable of reacting with the functional groups of other aliphatic monomers of the two or more types of aliphatic monomers. doing.

  That is, in the film capacitor element 10, since the dielectric film layer 16 is made of polyurea, at least one kind of aliphatic amine and aliphatic isocyanate are used as raw material monomers for forming the dielectric film layer 16. At least one kind is used. And at least any one of the two or more kinds of raw material monomers composed of the aliphatic amine and the aliphatic isocyanate has a function that other aliphatic amines or aliphatic isocyanates of the two or more kinds of raw material monomers have. It has three or more functional groups that react with the group. In other words, all of the aliphatic amine and aliphatic isocyanate used as raw material monomers are trifunctional monomers, or only some but not all of them are difunctional monomers or monofunctional monomers. It is said.

Among the raw material monomers forming the dielectric film layer 16 made of polyurea, the aliphatic amine having three or more functional groups capable of reacting with the functional groups of other raw material monomers includes, for example, three or more functional groups. Are tris (2-aminoethyl) amine and trisaminomethane, all of which are composed of amino groups (—NH ₂ ), and three or more functional groups are amino groups (—NH ₂ ) and hydroxyl groups (— 1,3-diamino-2-propanol composed of OH), trishydroxymethylaminomethane and the like, and 3,3 or more functional groups composed of an amino group (—NH ₂ ) and a carboxyl group (—COOH) -Diaminopropanoic acid, 2,6-diaminopimelic acid, etc. are mentioned. In the case where an aliphatic amine having three or more functional groups consisting of an amino group (—NH ₂ ) and a hydroxyl group (—OH) and an aliphatic isocyanate are used as raw material monomers, the dielectric film layer 16 is composed of polyurea and It will be composed of a polyurethane copolymer.

  Moreover, as the aliphatic isocyanate having three or more functional groups capable of reacting with the functional groups of other raw material monomers among the raw material monomers forming the dielectric film layer 16 made of polyurea, for example, three or more functional groups 1,3,6-triisocyanate hexane, 1,3,5-triisocyanate hexane, 1,3,5-trimethylisocyanate cyclohexane, all of which is composed of an isocyanate group (—NCO).

  Among the raw material monomers forming the dielectric film layer 16 made of polyurea, aliphatic amines or aliphatic isocyanates having only one or two functional groups capable of reacting with the functional groups of other raw material monomers include polyurea. When forming by the vapor deposition polymerization method, any of aliphatic amines and aliphatic isocyanates generally used conventionally can be used.

In the film capacitor element 10 of this embodiment, the dielectric film layer 16 made of polyurea is specifically tris (2-aminoethyl) which is an aliphatic amine having three amino groups (—NH ₂ ). ) And a raw material monomer comprising 1'3-bis (isocyanatomethyl) cyclohexane, which is an aliphatic isocyanate having two isocyanate groups (-NCO). Even if the dielectric film layer 16 is made of polyurea, tris (2-aminoethyl) amine and 1′3-bis (isocyanatomethyl) cyclohexane are used as an aliphatic amine and aliphatic isocyanate as raw material monomers. Of course, it is possible to use only another or in addition to them.

  Thus, in the film capacitor element 10 according to the present embodiment, the dielectric film layer 16 does not contain any aromatic amine or aromatic isocyanate, and vapor deposition polymerization method using a raw material monomer composed only of aliphatic amine and aliphatic isocyanate. The high reactivity at the time of vapor deposition polymerization of those raw material monomers is ensured more stably.

  In particular, in the present embodiment, one of the aliphatic amine and the aliphatic isocyanate as the raw material monomer of the dielectric film layer 16 (here, aliphatic amine) is composed of a trifunctional monomer, while the other is bifunctional. Since it is composed of monomers, the molecular structure of polyurea constituting the dielectric film layer 16 in which these trifunctional monomers and bifunctional monomers are vapor-deposited and polymerized is a network structure that is cross-linked to each other as schematically shown in FIG. ing. On the other hand, in the conventional film capacitor element, for example, polyurea constituting a dielectric film layer in which a diamine and a diisocyanate each having two functional groups (amino group and isocyanate group) that can react with each other are vapor-deposited. The molecular structure is a chain structure that is not cross-linked.

  Thus, in the film capacitor element 10 of the present embodiment, the dielectric film layer 16 made of polyurea having a network molecular structure as shown in FIG. 2 is formed in the chain shape of the conventional film capacitor element. Compared with a dielectric film layer made of polyurea having a molecular structure, it has clearly different physical properties. In addition, the dielectric film layer 16 uses only aliphatic amine and aliphatic isocyanate as raw material monomers, and this also makes the physical properties clear between the dielectric film layer of the conventional film capacitor element. There are significant differences.

  That is, in the conventional film capacitor element, the dielectric film layer obtained by vapor deposition polymerization using only aliphatic amine and aliphatic isocyanate as raw material monomers is vapor deposition using only aromatic amine and aromatic isocyanate as raw material monomers. Compared to a dielectric film layer obtained by polymerization, the heat resistance is inferior. However, the dielectric film layer 16 of the film capacitor element according to this embodiment uses a trifunctional monomer as a raw material monomer for one of an aliphatic amine and an aliphatic isocyanate (here, an aliphatic amine). Thus, the molecular structure is a network structure. Therefore, even though only aliphatic amines and aliphatic isocyanates are used as raw material monomers, they are equivalent to or more than dielectric film layers obtained by vapor deposition polymerization using only aromatic amines and aromatic isocyanates as raw material monomers. The heat resistance of is realized. This is because the molecular structure of the dielectric film layer 16 is a network structure, so that the molecular motion of the polyurea constituting the dielectric film layer 16 is constrained, and as a result, aliphatic amine and aliphatic isocyanate are separated. This is probably because the heat resistance of the vapor deposited polyurea is advantageously increased.

  Further, even in the conventional film capacitor element, when the dielectric film layer is formed by vapor deposition polymerization using only aliphatic amine and aliphatic isocyanate as raw material monomers, the dielectric film layer is It exhibits better flexibility than a dielectric film layer obtained by vapor deposition polymerization using only aromatic amine and aromatic isocyanate as raw material monomers. However, since the dielectric film layer 16 of the film capacitor element 10 according to the present embodiment has a network structure, the flexibility is further enhanced and the occurrence of cracks is also advantageously prevented. This is because the molecular structure of the dielectric film layer 16 is a network structure, so that the bonding force between the polyurea molecules constituting the dielectric film layer 16 is increased. It seems that the decrease in vulnerability will have a major impact.

  In particular, in the dielectric film layer 16 of the film capacitor element 10 according to the present embodiment, the molecular structure is a network structure, and the heat resistance and flexibility are more sufficiently enhanced. A dramatic improvement in recoverability is advantageously realized. This is considered to be due to the following reasons.

  That is, in the dielectric film layer of the conventional film capacitor element, as described above, the dielectric film layer formed by vapor deposition polymerization using only aliphatic amine and aliphatic isocyanate as raw material monomers is composed of aromatic amine and aromatic film. Compared to a dielectric film layer formed by vapor deposition polymerization using only a group isocyanate as a raw material monomer, it has high flexibility. For this reason, the former dielectric film layer exhibits higher self-healing than the latter dielectric film layer. However, in the dielectric film layer only for aliphatic amine and aliphatic isocyanate as the raw material monomer, when dielectric breakdown occurs due to instantaneous application of a large voltage, the peripheral portion of the short-circuit portion Will be broken and broken.

  On the other hand, the dielectric film layer 16 of the film capacitor element 10 according to the present embodiment has a network-like molecular structure, so that the heat resistance is enhanced, and therefore dielectric breakdown occurs. In this case, the degree of damage to the dielectric film layer 16 due to thermal energy generated by the short-circuit current is advantageously suppressed. In addition, since the dielectric film layer 16 has a network-like molecular structure, higher flexibility is exhibited. Therefore, when dielectric breakdown occurs, the peripheral portion of the short-circuit portion contracts. Only fine pores are generated there. This fine hole is made sufficiently smaller than the broken portion formed by breaking and scattering the peripheral portion of the short-circuit portion due to dielectric breakdown. Therefore, in the dielectric film layer 16 of the film capacitor element 10 of the present embodiment, the first and second metal vapor deposited film layers 14 formed on both surfaces of the dielectric film layer 16 after instantaneous application of a large voltage, The time until the insulation state between 18 is restored is shortened to an advantage shorter than that of a dielectric film layer only for aliphatic amine and aliphatic isocyanate as a raw material monomer, and thus better self-healing. Sex is demonstrated.

  By the way, the film capacitor element 10 of this embodiment is manufactured using the manufacturing apparatus 30 which has a structure as shown, for example in FIG.

  As is apparent from FIG. 3, the manufacturing apparatus 30 for the film capacitor element 10 has a vacuum chamber 32. The vacuum chamber 32 is evacuated to a predetermined pressure by operating a vacuum pump (not shown). A rotating drum 34 is disposed in the vacuum chamber 32. The rotary drum 34 is continuously driven to rotate in one direction (here, the clockwise direction and the direction of the white arrow in FIG. 4) by a rotary drive device (not shown) such as an electric motor. The resin film 12 is wound around the outer peripheral surface. Around the rotating drum 34 in the vacuum chamber 32, a first oil layer forming device 36, a first metal vapor deposited film forming device 38, a dielectric film layer forming device 40, a second oil layer forming device 42, The second metal vapor deposition film layer forming device 44 is arranged in the clockwise direction in that order, and is arranged at intervals in the circumferential direction of the rotary drum 34.

  The first oil layer forming device 36 forms an oil layer in a thin film form by vapor deposition or the like only at one end in the width direction of the surface (outer peripheral surface) of the resin film 12 wound around the rotary drum 34. . The second oil layer forming device 42 is a first oil layer forming device among both ends of the surface of the dielectric film layer 16 laminated on the surface of the resin film 12 via the first metal vapor-deposited film 14. An oil layer having a thin film form is formed by vapor deposition or the like only on the other end portion on the opposite side of the width direction from the one end portion of the resin film 12 on which the oil layer is formed at 36.

  The first metal vapor deposition film forming apparatus 38 heats and evaporates a predetermined metal such as aluminum or zinc, and blows the metal vapor onto the surface of the resin film 12 wound around the rotating drum 34, thereby forming a resin film. The first metal vapor deposited film layer 14 is formed on the surface 12. The second metal vapor deposition film layer forming device 44 has the same structure as the first metal vapor deposition film layer forming device 38, and the first metal vapor deposition film layer is formed on the surface of the resin film 12 wound around the rotary drum 34. The second metal vapor deposition film layer 18 is formed on the dielectric film layer 16 laminated via 14.

  The metal vapor blown from the first and second metal vapor deposition film layer forming devices 38 and 44 does not adhere to the oil layers formed by the first and second oil layer forming devices 36 and 42. Thus, the first metal vapor deposition film layer 14 and the second metal vapor deposition film are formed on the oil layers formed at one end in the width direction on the surface of the resin film 12 and the other end in the width direction on the surface of the dielectric film layer 16, respectively. The layer 18 is not stacked.

  The dielectric film layer forming apparatus 40 includes a first monomer pot 46 and a second monomer pot 48. A heater 50 is built in each of the first and second monomer pots 46 and 48. Further, the first monomer pot 46 is configured to heat the raw material monomer 52 made of an aliphatic amine accommodated therein by a heater 50 to generate vapor of the raw material monomer 52 made of an aliphatic amine. On the other hand, in the second monomer pot 48, the raw material monomer 54 made of aliphatic isocyanate accommodated therein is heated by a heater 50 to generate vapor of the raw material monomer 54 made of aliphatic isocyanate.

  In the dielectric film layer forming apparatus 40, the vapors of the two types of raw material monomers 52 and 54 generated in the first and second monomer pots 46 and 48 are wound around the rotating drum 34 through the outlet 56. On the surface of the formed resin film 12 or on the surface of the first metal vapor-deposited film layer 14 formed on the surface of the resin film 12, and on the resin film 12 or the first metal vapor-deposited film layer 14 The vapors of the two kinds of raw material monomers 52 and 54 are polymerized. Thus, the dielectric film layer 16 is formed on the resin film 12 or the first metal vapor deposition film layer 14.

  In addition, here, for example, two kinds of raw material monomers blown out from the blower outlet 56 due to the opening width of the blower outlet 56 of the dielectric film layer forming apparatus 40 being narrower than the width of the resin film 12 or the like. The vapors 52 and 54 are sprayed only on the intermediate portion in the width direction excluding both ends in the width direction of the resin film 12.

  Further, another metal vapor deposition film layer forming device having the same structure as that of the first and second metal vapor deposition film layer forming devices 38 and 44 may be used as needed. They are arranged between the film layer forming device 40 and between the second metal vapor deposited film layer forming device 44 and the first oil layer forming device 36, and are formed by the first metal vapor deposited film layer forming device 38. On the first connection part 26 of the first metal vapor deposition film layer 14 and on the second connection part 28 of the second metal vapor deposition film layer 18 formed by the second metal vapor deposition film layer forming device 44, respectively. A metal vapor deposition film layer may be formed. Thereby, it is also possible to thicken the 1st and 2nd connection parts 26 and 28 and to make them into a heavy edge part.

  When the film capacitor element 10 is manufactured using the manufacturing apparatus 30 having such a structure, first, predetermined oil is stored in the first and second oil layer forming apparatuses 36 and 42 as a preliminary operation. On the other hand, a predetermined metal material is set in the first and second metal vapor deposition film layer forming devices 38 and 44. In addition, a predetermined amount of the raw material monomer 52 made of aliphatic amine and a predetermined amount of the raw material monomer 54 made of aliphatic isocyanate are respectively prepared, and these are prepared in the first and second monomer pots of the dielectric film layer forming apparatus 40. 46 and 48, respectively. The raw material monomer 52 is, for example, a trifunctional aliphatic amine, such as liquid tris- (2-aminoethyl) amine, and the raw material monomer 54 is, for example, a bifunctional aliphatic isocyanate. Liquid 1′3-bis (isocyanatomethyl) cyclohexane and the like are respectively prepared.

  Next, after the resin film 12 is wound around the rotating drum 34, the vacuum chamber 32 is evacuated. On the other hand, when the rotary drum 34 is rotationally driven in the direction of the white arrow in FIG. 3 and the inside of the vacuum chamber 32 is in a predetermined vacuum state, the first oil layer forming device 36 and the first metal vapor deposition film formation are formed. The apparatus 38, the dielectric film layer forming apparatus 40, the second oil layer forming apparatus 42, and the second metal vapor deposition film layer forming apparatus 44 are operated.

  When the resin film 12 wound around the rotating drum 34 reaches the position corresponding to the position where the first oil layer forming device 36 is disposed by the rotation of the rotating drum 34, the first oil layer forming device 36 An oil layer (not shown) extends continuously over the entire circumference of the resin film 12 at a portion of the one end in the width direction of the surface of the resin film 12 that has entered a predetermined dimension from the edge. To form.

  Thereafter, when the portion of the resin film 12 on which the oil layer is formed reaches the position corresponding to the arrangement position of the first metal vapor deposition film layer forming device 38 by the rotation of the rotary drum 34, the first metal vapor deposition film layer forming device. At 38, aluminum vapor is blown onto the portion of the surface of the resin film 12 excluding the oil layer forming side end. At this time, aluminum vapor does not adhere to the oil layer provided at the end of the surface of the resin film 12. As a result, as shown in FIG. 1, the first margin portion 22 is formed in a portion of the surface of the resin film 12 that has entered a predetermined dimension from one edge in the width direction. A first metal vapor deposition film layer 14 made of aluminum is laminated and formed on the surface portion of the resin film 12 excluding the formation side end.

  Subsequently, as shown in FIG. 3, the resin film 12 portion on which the first metal vapor deposition film layer 14 is formed corresponds to the arrangement position of the dielectric film layer forming apparatus 40 by the further rotation of the rotary drum 34. The vapor of the raw material monomer 52 made of trifunctional aliphatic amine and the vapor of the raw material monomer 54 made of bifunctional aliphatic isocyanate are discharged from the outlet 56 of the dielectric film layer forming apparatus 40 to the resin film. 12 on the first metal vapor deposition film layer 14 portion and the first margin portion 22 except for the end opposite to the first margin portion 22 side in the width direction. The vapors of the monomers 52 and 54 are vapor deposited and polymerized. Thereby, as shown in FIG. 1, the dielectric film layer 16 is formed on the first metal deposition film layer 14 portion and the first margin part 22 except for the end opposite to the first margin part 22 side. Laminate. In addition, in this way, the end of the first metal vapor deposition film layer 14 opposite to the first margin portion 22 side is defined as the first connection portion 26 where the dielectric film layer 16 is not formed.

  Next, as shown in FIG. 3, the portion of the resin film 12 on which the dielectric film layer 16 is formed corresponds to the position where the second oil layer forming device 42 is disposed by the further rotation of the rotating drum 34. Then, the second oil layer forming device 42 forms an oil layer only at the end of the dielectric film layer 16 opposite to the first margin portion 22 side in the width direction. Here, the oil layer is not formed on the first connecting portion 26 of the first metal vapor deposition film layer 14.

  Thereafter, the resin film 12 portion where the oil layer is formed at the end of the dielectric film layer 16 is moved to a position corresponding to the arrangement position of the second metal vapor deposition film layer forming device 44 by the further rotation of the rotary drum 34. If it reaches, the dielectric film layer 16 is not formed in the second metal vapor deposition film layer forming apparatus 44 among the entire dielectric film layer 16 and the end of the resin film 12 on the first margin portion 22 side. Aluminum vapor is sprayed on the edge side portion. At this time, aluminum vapor does not adhere to the oil layer provided at the end of the dielectric film layer 16 opposite to the first margin portion 22 in the width direction. As a result, as shown in FIG. 1, the second margin portion 24 is formed at the end of the dielectric film layer 16 opposite to the first margin portion 22 side in the width direction. At the same time, the end of the surface of the dielectric film layer 16 excluding the second margin portion 24 and the end of the resin film 12 on the first margin portion 22 side where the dielectric film layer 16 is not formed. A second metal vapor deposition film layer 18 that is continuous with the edge-side portion is laminated. At the same time, the second connection portion 28 is formed at the second metal vapor deposition film layer 18 portion formed at the edge portion of the resin film 12 on the first margin portion 22 side.

  Thus, the film capacitor element 10 having the structure shown in FIG. 1 is manufactured while the rotating drum 34 is rotated once.

  A plurality of such film capacitor elements 10 are used to manufacture a film capacitor 58 having a structure as shown in FIG.

  That is, as shown in FIG. 4, when obtaining the film capacitor 58, first, a plurality (here, four) of film capacitor elements 10 are arranged so that the second metal deposition film layer 18 and the resin film 12 are vertically moved. In addition, the protective films 62 and 62 are further laminated on the end surfaces on both sides of the plurality of film capacitor elements 10 laminated on each other. For example, a film made of the same resin as the resin film 12 of the film capacitor element 10 is used for the protective films 62 and 62.

  Then, for example, a metal material such as zinc is sprayed on both side surfaces of the laminate of the plurality of film capacitor elements 10 and the protective films 62 and 62 by a known method to form the metallicon electrodes 60, respectively. To do. The two metallicon electrodes 60, 60 are the first connecting portion 26 of the first metal vapor deposition film layer 14 of the film capacitor element 10 located on the lower side of the film capacitor elements 10, 10 adjacent to each other in the vertical direction, and It penetrates into a gap formed between the second connecting portion 28 of the two-metal vapor deposition film layer 18 and the resin film 12 of the film capacitor element 10 located on the upper side, and the first connecting portion 26 and the second connecting portion. A layer is formed on the portion 28. As a result, the two metallicon electrodes 60 and 60 are electrically and reliably connected to the first metal vapor deposition film layer 14 and the second metal vapor deposition film layer 18 of each film capacitor element 10. Thus, a laminate type film capacitor 58 is manufactured. The film capacitor 58 is connected to terminals or the like (not shown) to the respective metallicon electrodes 60 as necessary.

  In addition, although not shown, a wound type film capacitor can be obtained using the film capacitor element 10. For this purpose, for example, first, the film capacitor element 10 is wound once or a plurality of times so that the resin film 12 is inside, thereby obtaining a wound product. Then, the metallicon electrodes 60 are respectively formed on the end faces on both sides of such a wound product. Thus, a wound type film capacitor is obtained. Also in this winding type film capacitor, a terminal or the like is connected to each metallicon electrode 60 as necessary.

  As is clear from the above description, in the film capacitor element 10 of the present embodiment, the raw material monomer used for forming the dielectric film layer 16 made of polyurea does not contain an aromatic amine or aromatic isocyanate. A functional group comprising at least one aliphatic amine and at least one aliphatic isocyanate, and the at least one aliphatic amine reacts with a functional group possessed by another aliphatic amine or aliphatic isocyanate. 3 or more, the molecular structure of the dielectric film layer 16 is a network structure. As a result, the dielectric film layer 16 can exhibit even more flexibility than the dielectric film layer in the conventional film capacitor element and can advantageously ensure sufficient heat resistance. Moreover, in addition to these, further improvement of self-recovery can be effectively realized.

  Therefore, according to the film capacitor element 10 of this embodiment as described above, by having high flexibility, good handleability is ensured, and furthermore, sufficient heat resistance and extremely high self-healing properties are achieved. Furthermore, it is possible to easily obtain a film capacitor 58 that exhibits even more excellent use durability.

  In the film capacitor element 10, since the raw material monomer used for forming the dielectric film layer 16 made of polyurea is composed only of an aliphatic monomer having a lower evaporation temperature than the aromatic monomer, the dielectric film layer When forming 16, the heating temperature of the raw material monomer can be lowered. As a result, the energy required for heating the raw material monomer can be reduced, and the formation cost of the dielectric film layer 16 and thus the production cost of the film capacitor element 10 can be reduced.

  The specific configuration of the present invention has been described in detail above. However, this is merely an example, and the present invention is not limited by the above description.

  For example, in the said embodiment, one laminated body 20 formed by laminating | stacking the 1st metal vapor deposition film layer 14, the dielectric material film layer 16, and the 2nd metal vapor deposition film layer 18 on the resin film 12 in the order. Thus, the film capacitor element 10 was constructed. However, for example, a film capacitor element is configured by further laminating a plurality of laminates formed by laminating the first metal vapor deposition film layer 14 and the dielectric film layer 16 in that order on the resin film 12. It is also possible to do. Also, the resin film 12 is omitted, and at least one of a laminate formed by alternately laminating at least one of the metal vapor deposited film layers 14 and 18 and at least one of the dielectric film layers 16 is used, and a film capacitor element Can also be configured.

  And when manufacturing the film capacitor element which concerns on the said embodiment, and the various film capacitor element illustrated above, the apparatus different from the illustrated manufacturing apparatus 30 can also be utilized.

  In addition, although not enumerated one by one, the present invention can be carried out in a mode to which various changes, modifications, improvements, etc. are added based on the knowledge of those skilled in the art. It goes without saying that all are included in the scope of the present invention without departing from the spirit of the present invention.

  Hereinafter, some examples of the present invention will be shown and the present invention will be more specifically clarified, but the present invention is not limited by the description of such examples. It goes without saying.

<Example 1>
First, an apparatus having a structure as shown in FIG. 3 was prepared as a target film capacitor element manufacturing apparatus. Further, as raw material monomers for the dielectric film layer, tris- (2-aminoethyl) amine, which is a trifunctional aliphatic amine having three amino groups, and 1 ', which is a bifunctional aliphatic isocyanate having two isocyanate groups, are used. A predetermined amount of 3-bis (isocyanatomethyl) cyclohexane was prepared in a liquid state. Then, a predetermined amount of such trifunctional aliphatic monomer is accommodated in the first monomer pot of the dielectric film layer forming device, while a predetermined amount of bifunctional aliphatic isocyanate is stored in the first layer of the dielectric film layer forming device. Housed in a two-monomer pot.

  As a preliminary operation in manufacturing the film capacitor element, aluminum is accommodated as a vapor deposition material in the first and second metal vapor deposition film layer forming apparatuses of the manufacturing apparatus, and in the first and second oil layer forming apparatuses. Each contained known oils used to form the oil layer. A resin film made of a biaxially stretched film made of polypropylene was wound around the rotating drum.

  Then, after reducing the pressure in the vacuum chamber of the manufacturing apparatus to 0.01 Pa and making the vacuum chamber in a vacuum state, the first and second oil layer forming devices, and the first and second metal deposition film layers Each of the forming apparatus and the dielectric film layer forming apparatus was operated. At this time, while the tris- (2-aminoethyl) amine contained in the first monomer pot of the dielectric film layer device is heated to 45 ° C. by a heater built in the first monomer pot, The 1′3-bis (isocyanatomethyl) cyclohexane contained therein was heated to 55 ° C. by a heater built in the second monomer pot. Thus, the vapor pressure of each of tris- (2-aminoethyl) amine and 1'3-bis (isocyanatomethyl) cyclohexane was set to 1 Pa.

  Next, the rotary drum is driven to rotate, and an oil layer is formed on one end in the width direction of the resin film wound around the rotary drum by the first oil layer forming device, and then the resin is formed by the first metal vapor deposition film layer forming device. A first metal vapor deposition film layer was laminated and formed in a portion other than the oil layer formation portion of the film, and a first margin portion was formed in the oil layer formation portion of the resin film. In addition, the thickness of the 1st metal vapor deposition film layer formed in this way was 100-300 mm.

Thereafter, tris- (2-aminoethyl) amine is applied to the first metal deposited film layer portion and the first margin portion excluding the end opposite to the first margin portion side by the dielectric film layer forming apparatus. First vapor deposition film layer excluding the end opposite to the first margin portion side by simultaneously spraying the vapor of 1′3-bis (isocyanatomethyl) cyclohexane and vapor-depositing them. A dielectric film layer was formed on the part and on the first margin part. The film formation rate of the dielectric film layer thus formed was 1.0 × 10 ⁻⁴ μm / min · mm ² , and the thickness of the dielectric film layer was 0.5 to 3.0 μm.

  Subsequently, an oil layer was formed on the end of the dielectric film layer laminated on the resin film on the side opposite to the first margin portion by the second oil layer forming apparatus. Thereafter, the first metal vapor deposition film layer and the dielectric film layer were not formed in the portion other than the oil layer formation portion of the dielectric film layer and the end portion on the first margin portion side of the resin film without being formed. A second metal vapor deposition film layer was laminated on the portion by a second metal vapor deposition film layer forming apparatus, and a second margin portion was formed in the oil layer formation portion of the dielectric film layer. In addition, the thickness of the 2nd metal vapor deposition film layer was 100-300 mm. Thus, a film capacitor element having a structure as shown in FIG. 1 was obtained. The film capacitor element was designated as Example 1.

<Example 2>
Next, tris- (2-aminoethyl) amine, which is a trifunctional aliphatic amine having three amino groups, and a bifunctional aliphatic amine having two amino groups are used as raw material monomers for the dielectric film layer. A predetermined amount of '4 methylenebiscyclohexylamine and 1'3-bis (isocyanatomethyl) cyclohexane, which is a bifunctional aliphatic isocyanate having two isocyanate groups, were prepared in a liquid state. In addition, as a target film capacitor element manufacturing apparatus, the dielectric film layer forming apparatus is provided with the film capacitor element of Example 1 except that a third monomer pot is provided in addition to the first and second monomer pots. A manufacturing apparatus having the same structure as the manufacturing apparatus used for manufacturing was prepared. And the prepared three types of raw material monomers were separately accommodated in the first, second, and third monomer pots of the dielectric film layer forming apparatus in the manufacturing apparatus.

  Thereafter, the same operation as that for producing the film capacitor element of Example 1 was performed. As a result, a film capacitor element was obtained in which a dielectric film layer was formed by vapor deposition polymerization of the three types of raw material monomers of the trifunctional aliphatic amine, the bifunctional aliphatic amine, and the bifunctional isocyanate. This film capacitor element was designated as Example 2.

In addition, each thickness of the 1st and 2nd metal vapor deposition film layer of this film capacitor element of Example 2 and a dielectric film layer is the 1st and 2nd metal vapor deposition film layer of the film capacitor element of Example 1. The thickness of each of the dielectric film layers was the same. Further, when forming the dielectric film layer of the film capacitor element of Example 2, the heating temperature of the trifunctional aliphatic amine is set to 40 ° C., and the heating temperature of the bifunctional aliphatic amine is set to 50 ° C. The vapor pressures of the trifunctional aliphatic amine and the bifunctional aliphatic amine were each 0.5 Pa. On the other hand, the heating temperature of the bifunctional aliphatic isocyanate was set to 60 ° C., and the vapor pressure of the bifunctional aliphatic isocyanate was set to 1 Pa. The deposition rate of the dielectric film layer was 1.0 × 10 ⁻⁴ μm / min · mm ² .

<Comparative Example 1>
For comparison, first, as a raw material monomer for the dielectric film layer, 4′4 methylenebiscyclohexylamine, which is a bifunctional aliphatic amine, and 1′3-bis (isocyanatomethyl) cyclohexane, which is a bifunctional aliphatic isocyanate, are used. A predetermined amount of each was prepared in a liquid state. Moreover, the manufacturing apparatus which has the same structure as the manufacturing apparatus used when manufacturing the film capacitor element of Example 1 was prepared as a manufacturing apparatus of the target film capacitor element. And the prepared two types of raw material monomers were separately accommodated in the first and second monomer pots of the dielectric film layer forming apparatus in the manufacturing apparatus.

  Thereafter, the same operation as that for producing the film capacitor element of Example 1 was performed. As a result, a film capacitor element in which a dielectric film layer was formed by vapor deposition polymerization of the three kinds of raw material monomers of the bifunctional aliphatic amine and the bifunctional isocyanate was obtained. This film capacitor element was designated as Comparative Example 1.

In addition, each thickness of the 1st and 2nd metal vapor deposition film layer of this film capacitor element of the comparative example 1 and a dielectric film layer is the 1st and 2nd metal vapor deposition film layer of the film capacitor element of Example 1, and The thickness of each of the dielectric film layers was the same. Further, when forming the dielectric film layer of the film capacitor element of Comparative Example 1, the heating temperature of the bifunctional aliphatic amine is set to 55 ° C. and the heating temperature of the bifunctional aliphatic isocyanate is set to 60 ° C. The vapor pressures of the bifunctional aliphatic amine and the bifunctional aliphatic isocyanate were each 1 Pa. The deposition rate of the dielectric film layer was 1.0 × 10 ⁻⁴ μm / min · mm ² .

<Comparative Example 2>
For comparison with the film capacitor element of Comparative Example 1, first, tris- (2-aminoethyl) amine, which is a trifunctional aliphatic amine, and an isocyanate group are used as raw material monomers for the dielectric film layer. A predetermined amount of 4′4-diisocyanatodiphenylmethane, which is a bifunctional aromatic isocyanate having two, was prepared in a liquid state. Moreover, the manufacturing apparatus which has the same structure as the manufacturing apparatus used when manufacturing the film capacitor element of Example 1 was prepared as a manufacturing apparatus of the target film capacitor element. And the prepared two types of raw material monomers were separately accommodated in the first and second monomer pots of the dielectric film layer forming apparatus in the manufacturing apparatus.

  Thereafter, the same operation as that for producing the film capacitor element of Example 1 was performed. As a result, a film capacitor element was obtained in which a dielectric film layer was formed by vapor deposition polymerization of the three types of raw material monomers of the trifunctional aliphatic amine and the bifunctional aromatic isocyanate. This film capacitor element was designated as Comparative Example 2.

The thicknesses of the first and second metal vapor deposition film layers and the dielectric film layer of the film capacitor element of Comparative Example 2 are the same as the first and second metal vapor deposition film layers of the film capacitor element of Example 1. The thickness of each of the dielectric film layers was the same. Further, when forming the dielectric film layer of the film capacitor element of Comparative Example 2, the heating temperature of the trifunctional aliphatic amine is set to 50 ° C., and the heating temperature of the bifunctional aromatic isocyanate is set to 110 ° C. The vapor pressures of the trifunctional aliphatic amine and the bifunctional aromatic isocyanate were each 1 Pa. The deposition rate of the dielectric film layer was 1.0 × 10 ⁻⁴ μm / min · mm ² .

<Comparative Example 3>
For comparison separately from the film capacitor elements of Comparative Examples 1 and 2, first, tris- (2-aminoethyl) amine, which is a trifunctional aliphatic amine, was used as a raw material monomer for the dielectric film layer, and an amino group. A predetermined amount of 4′4 diaminodiphenylmethane, which is a bifunctional aromatic amine having two, and 4′4-diisocyanatodiphenylmethane, which is a bifunctional aromatic isocyanate, were prepared in a liquid state. Moreover, the manufacturing apparatus which has the structure similar to the manufacturing apparatus used when manufacturing the film capacitor element of Example 2 as a manufacturing apparatus of the target film capacitor element was prepared. And the three types of prepared raw material monomers were each accommodated separately in the 1st, 2nd, and 3rd monomer pot of the dielectric material film layer forming apparatus in this manufacturing apparatus.

  Thereafter, the same operation as that for producing the film capacitor element of Example 2 was performed. As a result, a film capacitor element was obtained in which a dielectric film layer was formed by vapor deposition polymerization of the three types of raw material monomers of the trifunctional aliphatic amine, the bifunctional aromatic amine, and the difunctional aromatic isocyanate. This film capacitor element was designated as Comparative Example 3.

The thicknesses of the first and second metal vapor deposition film layers and the dielectric film layer of the film capacitor element of Comparative Example 3 are the same as those of the first and second metal vapor deposition film layers of the film capacitor element of Example 1. The thickness of each of the dielectric film layers was the same. Further, when forming the dielectric film layer of the film capacitor element of Comparative Example 3, the heating temperature of the trifunctional aliphatic amine is set to 40 ° C., and the heating temperature of the bifunctional aromatic amine is set to 100 ° C. The vapor pressures of the trifunctional aliphatic amine and the bifunctional aromatic amine were 0.5 Pa, respectively. On the other hand, the heating temperature of the bifunctional aromatic isocyanate was set to 110 ° C., and the vapor pressure of the bifunctional aromatic isocyanate was set to 1 Pa. The deposition rate of the dielectric film layer was 1.0 × 10 ⁻⁴ μm / min · mm ² .

<Comparative example 4>
For comparison separately from the film capacitor elements of Comparative Examples 1 to 3, first, 4′4 diaminodiphenylmethane which is a bifunctional aromatic amine and 4 which is a bifunctional aromatic isocyanate are used as raw material monomers for the dielectric film layer. A predetermined amount of '4-diisocyanatodiphenylmethane was prepared in a liquid state. Moreover, the manufacturing apparatus which has the same structure as the manufacturing apparatus used when manufacturing the film capacitor element of Example 1 was prepared as a manufacturing apparatus of the target film capacitor element. And the prepared two types of raw material monomers were separately accommodated in the first and second monomer pots of the dielectric film layer forming apparatus in the manufacturing apparatus.

  Thereafter, the same operation as that for producing the film capacitor element of Example 1 was performed. As a result, a film capacitor element was obtained in which a dielectric film layer was formed by vapor deposition polymerization of the two types of raw material monomers, bifunctional aromatic amine and difunctional aromatic isocyanate. This film capacitor element was designated as Comparative Example 4.

The thicknesses of the first and second metal vapor deposition film layers and the dielectric film layer of the film capacitor element of Comparative Example 4 are the same as the first and second metal vapor deposition film layers of the film capacitor element of Example 1. The thickness of each of the dielectric film layers was the same. Further, when forming the dielectric film layer of the film capacitor element of Comparative Example 4, the heating temperature of the bifunctional aromatic amine is set to 105 ° C., and the heating temperature of the bifunctional aromatic isocyanate is set to 110 ° C. The vapor pressures of the bifunctional aromatic amine and the bifunctional aromatic isocyanate were each 1 Pa. The deposition rate of the dielectric film layer was 1.0 × 10 ⁻⁴ μm / min · mm ² .

<Evaluation test>
Next, using the two types of film capacitor elements of Examples 1 and 2 manufactured as described above and the four types of film capacitor elements of Comparative Examples 1 to 4, the ratio of these six types of film capacitor elements was compared. The dielectric constant and the withstand voltage were measured according to a known method. The measurement results are shown in Table 1 below.

  Further, the six types of film capacitor elements of Examples 1 and 2 and Comparative Examples 1 to 4 were used, and the heat resistance, flexibility, and self-healing property of each film capacitor element were examined as follows. The results are shown in Table 1 below.

-Heat resistance-
First, at normal temperature, the surface area and thickness of the dielectric film layer of the film capacitor element are measured according to a known method, and the volume of the dielectric film layer is calculated from the measured value. Then, after heating the film capacitor element to 100 ° C. using a known heater, the surface area and thickness of the dielectric film layer of the film capacitor element heated to 100 ° C. are measured by a known method, and the measurement is performed. The volume of the dielectric film layer is calculated from the value. Then, the ratio of the volume change of the dielectric film layer of the film capacitor element after heating to the volume of the dielectric film layer of the film capacitor element before heating is calculated. As a result, the film capacitor element in which the volume change rate was 5% or more was evaluated as having low heat resistance. On the other hand, the film capacitor element in which the volume change rate was less than 5% was evaluated as having high heat resistance, and the result is shown in Table 1 as “◯”.

-Self-healing-
First, a rated voltage is applied to the film capacitor element, and using a commercially available measuring instrument [trade name: LCR meter E4980A (manufactured by Agilent Technologies)], while measuring the capacitance of the film capacitor element as needed, Every 5 minutes, the applied voltage is increased step by step in units of 100V, and the voltage when the measured capacitance value is reduced by 5% or more from the initial value when the rated voltage is applied is shown in the film. The withstand voltage of the capacitor element was used. Then, before the measured capacitance value decreases due to the increase of the applied voltage, the current is short-circuited and the test cannot be continued, and the withstand voltage value is 1 of the rated voltage. The film capacitor element that was less than 5 times was evaluated as having no self-recovering property or insufficient self-recovering property, and these are shown as x in Table 1 below. On the other hand, a film capacitor element having a withstand voltage value of 1.5 times or more of the rated voltage was evaluated as having sufficient self-healing properties, and is indicated by ○ in Table 1 below.

-Flexibility-
In the self-healing evaluation test, the breakdown portion of the dielectric film layer when dielectric breakdown was caused was magnified at a magnification of 100 times, and the evaluation was made based on the breakdown state of the breakdown portion. Specifically, the film capacitor element in which the broken portion of the dielectric film layer was cracked and scattered was evaluated as being poor in flexibility, and this is shown by x in Table 1 below. Moreover, it was evaluated that the film capacitor element in which the broken portion of the dielectric film layer was a hole formed by shrinkage had sufficient flexibility, and this was indicated by ○ in Table 1 below. . Among the film capacitor elements evaluated as having sufficient flexibility, the film capacitor element having no cracks was evaluated as having particularly excellent flexibility, which is indicated by ◎ in Table 1 below. Indicated.

  As is clear from the results in Table 1, all of the six types of film capacitor elements of Examples 1 and 2 and Comparative Examples 1 to 4 have a high relative dielectric constant of 4.5 or more. The film capacitor elements of Example 1 and Example 2 tend to have higher withstand voltage than the film capacitor elements of Comparative Examples 1 to 4. The film capacitor elements of Examples 1 and 2 have a heat resistance equal to or higher than the film capacitor elements of Comparative Examples 1 to 4, and the self-recovery and flexibility of Examples 1 and 2 are the same. The film capacitor element is superior to the film capacitor elements of Comparative Examples 1 to 4. The film according to the present invention has a dielectric film layer formed by vapor deposition polymerization using two or more kinds of raw material monomers consisting of only aliphatic monomers and at least one of which is a trifunctional monomer. This clearly shows that the capacitor element has both sufficient heat resistance and higher flexibility, and exhibits a self-healing property that is even better than the conventional film capacitor element.

DESCRIPTION OF SYMBOLS 10 Film capacitor | condenser element 12 Resin film 14 1st metal vapor deposition film layer 16 Dielectric film layer 18 2nd metal vapor deposition film layer 20 Laminated body 30 Manufacturing apparatus 52,54 Raw material monomer 58 Film capacitor

Claims (4)

A film capacitor element using a laminate formed by laminating a dielectric film layer made of polyurea and a metal vapor deposition film layer,
Before Ki誘 collector layer are in the form of a thin film layer of a deposition polymer comprising polyurea, raw material monomers for forming the thin film layer of a deposition polymer comprising said polyurea, two or more aliphatic monomers And at least one of the two or more types of aliphatic monomers has three or more functional groups capable of reacting with functional groups of other raw material monomers that polymerize with the at least one raw material monomer. Thus, a film capacitor element characterized in that the molecular structure of the polyurea is a network structure . The film capacitor element according to claim 1, wherein the raw material monomer includes at least one aliphatic amine and at least one aliphatic isocyanate. In a method of manufacturing a film capacitor element using a laminate formed by laminating a dielectric film layer made of polyurea and a metal vapor deposition film layer,
Two or more types of aliphatic monomers each having a functional group capable of reacting with each other, and at least one of the two or more types of aliphatic monomers has a monomer having three or more functional groups, Preparing as a raw material monomer for a dielectric film layer made of polyurea;
Performing a vapor deposition polymerization method in which vapors of two or more kinds of raw material monomers composed of the aliphatic monomer are polymerized in vacuum to form a dielectric film layer composed of the polyurea;
Performing a vapor deposition method using a metal material to form the metal vapor deposition film layer;
Laminating the dielectric film layer made of the polyurea and the metal vapor deposition film layer to obtain the laminate;
Using the obtained laminate, producing the film capacitor element,
A method for producing a film capacitor element, comprising: The laminate is formed by sequentially laminating and forming the metal vapor deposition film layer and the dielectric film layer on a resin film, and further laminating and forming the metal vapor deposition film layer on the dielectric film layer. The manufacturing method of the film capacitor | condenser element of Claim 3.

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