Nonlinear resistance resin material, nonlinear resistor, overvoltage protection device, and method for producing nonlinear resistance resin material

Abstract

A nonlinear resistive resin material (1A) comprises: a plurality of first particles (2) that have nonlinear resistance characteristics, that show insulating properties when a voltage less a threshold is applied and that show electroconductivity when a voltage equal to or greater than the threshold is applied; and a first resin phase (3) that contains semi-electroconductive or electroconductive second particles and that covers at least a portion of the surfaces of some or all of the plurality of first particles (2); and a second resin phase (5) that has insulating properties and that fills gaps (4) formed in an area where the first particles (2) and the first resin phase (3) are absent. Adjacent first particles (2) are joined to each other via the first resin phase (3) and are electrically connected.

Description

[Technical field]

[0001] The present disclosure relates to a nonlinear resistance resin material having nonlinear resistance characteristics, a nonlinear resistor using this nonlinear resistance resin material, an overvoltage protection device including this nonlinear resistor, and a method for manufacturing the nonlinear resistance resin material. [Background technology]

[0002] Conventionally, devices with high electric field parts are designed to keep the electric field below the allowable value. The smaller the electric field is below the allowable value, the shorter the insulation distance can be, which allows for the miniaturization of the device. Therefore, reducing the electric field leads to the miniaturization of the device.

[0003] Conventionally, as a technique for relaxing an electric field, a technique is known in which a nonlinear resistance resin material having nonlinear resistance characteristics that shows insulation when a voltage below a threshold is applied and shows conductivity when a voltage equal to or above the threshold is applied is placed in a high electric field portion of a device. For example, Patent Document 1 discloses an electric field relaxation agent in which particles having nonlinear resistance characteristics are mixed with semiconductive whiskers and one type of resin. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2015-101714 A Summary of the Invention [Problem to be solved by the invention]

[0005] In the electric field relaxation agent disclosed in Patent Document 1, since the semiconductive whiskers are dispersed throughout the resin, a large amount of semiconductive whiskers must be added to obtain sufficient conductivity. However, the more the amount of semiconductive whiskers added increases, the easier it becomes for the semiconductive whiskers to join together and to pass electricity in the thickness direction. This may result in a decrease in resistance value compared to the designed nonlinear resistance characteristics, and the electric field relaxation agent may function as an insulator under conditions in which it should function as an insulator. The thickness direction refers to the Z direction of the XYZ coordinate system, and is, for example, the pressing direction when a nonlinear resistance resin material is pressed, and the thickness direction of the film thickness of the nonlinear resistance resin material when the nonlinear resistance resin material is applied.

[0006] The present disclosure has been made in consideration of the above, and aims to obtain a nonlinear resistance resin material that can prevent a decrease in its function as an insulator under conditions in which it should function as an insulator. [Means for solving the problem]

[0007] In order to solve the above problems and achieve the object, the nonlinear resistance resin material according to the present disclosure includes a plurality of first particles having nonlinear resistance characteristics that show insulation when a voltage below a threshold is applied and show conductivity when a voltage equal to or above the threshold is applied, a first resin phase that includes semiconductive or conductive second particles and covers at least a part of the surface of some or all of the plurality of first particles, and a second resin phase that fills voids formed in the portions other than the first particles and the first resin phase and has insulation properties. Adjacent first particles are bonded to each other and electrically connected via the first resin phase. Effect of the Invention

[0008] According to the present disclosure, it is possible to prevent a decrease in the function as an insulator under conditions in which the insulator should function. [Brief description of the drawings]

[0009] [Figure 1]FIG. 1 is a schematic diagram showing a nonlinear resistance resin material according to a first embodiment. [Diagram 2] An enlarged view of part A shown in FIG. [Diagram 3] FIG. 1 is a diagram illustrating a first particle and a first resin phase according to a first embodiment; [Figure 4] An enlarged view of part B shown in FIG. [Diagram 5] 1 is a diagram showing the current-voltage characteristics of a first particle of the nonlinear resistance resin material according to the first embodiment, the current-voltage characteristics of a material in a state close to an insulator, and the current-voltage characteristics of a material in a state close to a conductor. [Figure 6] FIG. 1 is a schematic diagram showing a nonlinear resistance resin material according to a first modification of the first embodiment; [Figure 7] An enlarged view of part C shown in FIG. [Figure 8] FIG. 1 is a schematic diagram showing a nonlinear resistance resin material according to a second modification of the first embodiment; [Figure 9] FIG. 13 is a diagram showing a current path of a nonlinear resistance resin material according to a second modification of the first embodiment. [Figure 10] FIG. 13 is a schematic diagram showing a nonlinear resistance resin material according to a third modification of the first embodiment. [Figure 11] FIG. 13 is a schematic diagram showing an example of a connection between an overvoltage protection device and a protected device according to a second embodiment, in which a voltage less than a threshold value is applied; [Figure 12] FIG. 13 is a schematic diagram showing an example of a connection between an overvoltage protection device and a protected device according to a second embodiment, in which a voltage equal to or higher than a threshold value is applied; [Figure 13] FIG. 13 is a schematic diagram showing a nonlinear resistor of an overvoltage protection device according to a second embodiment; FIG. 14 is a diagram showing a nonlinear resistor using the nonlinear resistance resin material according to the first embodiment; [Figure 14] FIG. 13 is a schematic diagram of a nonlinear resistor of an overvoltage protection device according to a second embodiment, and shows a nonlinear resistor using a nonlinear resistance resin material according to a first modification of the first embodiment. [Figure 15] FIG. 13 is a schematic diagram showing a nonlinear resistance resin material according to a third embodiment. [Figure 16] FIG. 13 is a diagram showing a particle size distribution of the first particles of the nonlinear resistance resin material according to the third embodiment. [Figure 17] FIG. 13 is a diagram showing the relationship between the mixing ratio and the filling rate of the first particles of the nonlinear resistance resin material according to the third embodiment. [Figure 18] FIG. 13 is a diagram showing a current path of a nonlinear resistance resin material according to a third embodiment. [Figure 19] FIG. 13 is a diagram showing the current-voltage characteristics of the first particles of the nonlinear resistance resin material according to the third embodiment and the current-voltage characteristics of the first particles of the nonlinear resistance resin material according to the first embodiment. [Figure 20] FIG. 13 is a schematic diagram showing a nonlinear resistance resin material according to a modification of the third embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A nonlinear resistive resin material, a nonlinear resistor, an overvoltage protection device, and a method for manufacturing a nonlinear resistive resin material according to embodiments will be described in detail below with reference to the drawings.

[0011] Embodiment 1 FIG. 1 is a schematic diagram of a nonlinear resistance resin material 1 according to the first embodiment. FIG. 2 is an enlarged view of a portion A shown in FIG. 1. As shown in FIG. 1, the nonlinear resistance resin material 1 includes a plurality of first particles 2 and a first resin phase 3 covering a part or all of the surfaces of the plurality of first particles 2. In this embodiment, the first resin phase 3 covers all of the surfaces of the plurality of first particles 2. Adjacent first particles 2 are bonded to each other via the first resin phase 3 and are electrically connected. A void 4 is formed in a portion of the nonlinear resistance resin material 1 other than the first particles 2 and the first resin phase 3. The void 4 is formed between the outer edge of the nonlinear resistance resin material 1 and the first particle 2. Also, as shown in FIG. 2, the void 4 is formed in a portion surrounded by three adjacent first particles 2. Although FIG. 1 illustrates a state in which the first particles 2 of the same particle size are regularly aligned, when the first particles 2 having a plurality of particle size distributions are used, the first particles 2 of various sizes will be densely bound together.

[0012] FIG. 3 is a diagram showing a schematic diagram of the first particle 2 and the first resin phase 3 in the first embodiment. FIG. 4 is an enlarged diagram of part B shown in FIG. 3. The first particle 2 shown in FIG. 3 has a nonlinear resistance characteristic in which it shows insulating properties when a voltage below a threshold is applied, and shows conductivity when a voltage equal to or above the threshold is applied. That is, the first particle 2 shows nonlinear resistance characteristics in which it shows insulating properties when a voltage below a threshold is applied, and shows conductivity when a voltage equal to or above the threshold is applied. th It has the property of reversibly changing between an insulator and a conductor at the boundary. Therefore, while general materials follow Ohm's law, the first particles 2 do not follow Ohm's law and are commonly called "varistors." In particular, varistors with a particle shape like the first particles 2 are called "microvaristors."

[0013] FIG. 5 is a diagram showing the current-voltage characteristics of the first particle 2 of the nonlinear resistance resin material 1 according to the first embodiment, the current-voltage characteristics of the material in a state close to an insulator, and the current-voltage characteristics of the material in a state close to a conductor. The horizontal axis of FIG. 5 is current (A), and the vertical axis is voltage (V). Line L1 shown in FIG. 5 represents the current-voltage characteristics of the first particle 2. Line L2 shown in FIG. 5 represents the current-voltage characteristics of the material in a state close to an insulator. Line L3 shown in FIG. 5 represents the current-voltage characteristics of the material in a state close to a conductor.

[0014] As shown in FIG. 5, the first particle 2 has a threshold voltage V th It can be seen that the electrical resistance changes and a current flows suddenly at the boundary of the applied voltage V th If the applied voltage is less than the threshold voltage V th When the electric resistance value is larger than 100 kV, the electric resistance value decreases rapidly and the electric conductivity is exhibited. It can be seen that the current-voltage characteristics of the first particle 2 are different from the current-voltage characteristics of a state close to an insulator and a state close to a conductor according to Ohm's law.

[0015] In this disclosure, the nonlinear resistance index, which is a numerical representation of the nonlinear resistance characteristic, is the threshold voltage V thIt represents the degree to which electrical resistance changes suddenly, and is calculated from the slope of two points on the current-voltage characteristics. It is generally expressed by the following formula (1). Nonlinear resistance exponent = (logI 2 -logI 1 ) / (logV 2 -logV 1 ) · · · (1)

[0016] The better the nonlinear resistance characteristic, the larger the nonlinear resistance index. th When the current flows suddenly at the boundary, it can be said that the nonlinear resistance characteristics are good and the nonlinear resistance index is large. On the other hand, in the case of a material that has small nonlinear resistance characteristics and is close to an insulator, as shown by line L2 in Figure 5, it can be said that the nonlinear resistance characteristics are poor and the nonlinear resistance index is small. Also, in the case of a material that has no nonlinear resistance characteristics and is close to a conductor, as shown by line L3 in Figure 5, it can be said that there is no nonlinear resistance characteristics and the nonlinear resistance index is small.

[0017] The first particle 2 shown in FIG. 3 is made of a material obtained by adding a small amount of several kinds of subcomponents to a main component and sintering the mixture. The threshold voltage V th It is possible to control performance such as the size of the first particles 2, the volume resistance when the particles are insulators, and the nonlinear resistance characteristics. For example, zinc oxide or silicon carbide is used as the main component of the first particles 2. From the viewpoint of sufficiently ensuring the nonlinear resistance characteristics of the first particles 2, it is preferable that the first particles 2 contain 80 wt% or more of zinc oxide or silicon carbide. It is preferable to use zinc oxide, which has higher nonlinear resistance characteristics than silicon carbide, as the main component of the first particles 2. For example, the minor components of the first particles 2 include bismuth oxide, antimony oxide, chromium oxide, nickel oxide, manganese oxide, cobalt oxide, and silicon oxide, and the composition is adjusted according to the application.

[0018] Here, a method for producing the first particles 2 will be described. Assume that the main component of the first particles 2 is zinc oxide powder. First, 95.8 mol% of zinc oxide powder, which is the main component, is weighed out. Next, 0.5 mol% of bismuth oxide, 1.2 mol% of antimony oxide, 0.5 mol% of chromium oxide, 0.5 mol% of nickel oxide, 0.5 mol% of manganese oxide, 0.5 mol% of cobalt oxide, and 0.5 mol% of silicon oxide are weighed out as auxiliary components, and the weighed auxiliary components are added to the zinc oxide powder. These raw materials are pulverized and mixed using water as a medium. At this time, it is preferable to pulverize and mix the raw materials so that the raw materials are uniform and have the same average particle size. Next, the pulverized and mixed raw materials are sprayed into a high-temperature atmosphere of 100°C or more, and the raw materials are spray-dried. As a result, spherical granules in which raw materials such as zinc oxide powder, bismuth oxide, antimony oxide, chromium oxide, nickel oxide, manganese oxide, cobalt oxide, and silicon oxide are uniformly aggregated are obtained. Next, the granules are placed in a sagger and fired at a temperature of 1200° C. After firing, the granules are aggregated, so pressure is applied to break up the aggregates and disintegrate them. Through the above steps, the first particles 2 having nonlinear resistance characteristics are obtained.

[0019] The first particles 2 are spherical and made up of primary particles of zinc oxide or silicon carbide, and are generally spherical, although in reality some small irregularities are observed. The particle size of the first particles 2 can be adjusted by the solids concentration when crushing and mixing using water as a medium, the pressure when spraying, etc., and may be changed appropriately depending on the application of the nonlinear resistance resin material 1. The average particle size of the primary particles constituting the main component of the first particles 2 is set to 1 / 1000th of a second, which is the threshold voltage V th From the viewpoint of the size and adhesive strength with the first resin phase 3, it is preferable that the size is less than 20 μm.

[0020] For the first particles 2, zinc oxide or silicon carbide that is partially crushed into spheres may be used. Partially crushed means that zinc oxide or silicon carbide is not crushed into primary particles, and the agglomeration of the primary particles of zinc oxide or silicon carbide remains. In other words, the first particles 2 may be an agglomeration of two or more primary particles. When such first particles 2 are used, the nonlinear resistance characteristics are inferior compared to when spherical first particles 2 are used, but the degree of freedom of pressure during the crushing process during production is increased, so that the productivity of the first particles 2 can be improved. Furthermore, for the first particles 2, zinc oxide or silicon carbide that is not partially broken down into spheres may be used. Even when such first particles 2 are used, the degree of freedom of pressure during the crushing process during production is increased, so that the productivity of the first particles 2 can be improved. However, if partially crushed zinc oxide or silicon carbide, or zinc oxide or silicon carbide that is not partially detached, is used, the viscosity increases when mixed with the resin, so the zinc oxide or silicon carbide used for the first particles 2 should be selected appropriately depending on the application of the nonlinear resistance resin material 1.

[0021] The first resin phase 3 shown in Fig. 3 has semiconductive or conductive properties and covers at least a part of the surface of each of the first particles 2. As shown in Fig. 4, the first resin phase 3 contains a first matrix resin 31 and a plurality of second particles 32 having conductive or semiconductive properties.

[0022] For the first matrix resin 31, a resin insoluble in a solvent may be used, but it is preferable to use a resin soluble in a solvent such as polyvinyl alcohol resin, polyvinyl butyral, or polylactic acid. For example, water can be used as a solvent for polyvinyl alcohol resin, ethanol can be used as a solvent for polyvinyl butyral, and chloroform can be used as a solvent for polylactic acid. From the viewpoint of the safety and workability of the solvent, it is preferable to use polyvinyl alcohol resin for the first matrix resin 31. In this embodiment, polyvinyl alcohol resin is used for the first matrix resin 31.

[0023] For example, metal powder, carbon powder, or conductive ceramic powder is used for the second particles 32. From the viewpoint of ease of mixing, it is preferable to use carbon powder for the second particles 32. In this embodiment, carbon powder is used for the second particles 32.

[0024] The first resin phase 3 may cover the entire surface of the first particle 2 as shown in FIG. 3, but it is not necessary to cover the entire surface of the first particle 2, and may cover at least a part of the surface of the first particle 2. From the viewpoint of bonding adjacent first particles 2 to each other in a later process, the first resin phase 3 preferably covers 50% or more of the surface of the first particle 2, and more preferably covers 70% or more of the surface of the first particle 2. The average particle size of the second particles 32 is preferably 1 / 10 or less of the average particle size of the first particles 2. With such a size relationship, the second particles 32 can easily cover the surface of the first particles 2.

[0025] As shown in FIG. 2, each first particle 2 has a contact portion 21 that contacts the adjacent first particle 2 through the first resin phase 3, and a non-contact portion 22 that does not contact the adjacent first particle 2. The contact portion 21 is a portion that is electrically connected to the adjacent first particle 2 through the first resin phase 3. In this specification, "electrically connected" means a state in which adjacent first particles 2 are conductive through the first resin phase 3. The contact portions 21 of adjacent first particles 2 are bonded to each other through the first resin phase 3. In this specification, "bonding" means that the first resin phase 3 is cured while being in close contact with each of the adjacent first particles 2, so that adjacent first particles 2 are connected to each other through the first resin phase 3. The first resin phase 3 penetrates into minute irregularities in the first particles 2 and may be attached to the first particles 2 by physical bonds such as an anchor effect, or may be attached to the first particles 2 by chemical bonds such as hydrogen bonds caused by the influence of moisture due to moisture absorption. A thin first resin phase 3 exists between the contact portions 21 of adjacent first particles 2.

[0026] If the volume ratio of the first particles 2 in the nonlinear resistance resin material 1 is small, the first particles 2 do not easily bond to each other. Therefore, from the viewpoint of the ease of bonding between the first particles 2 and the closest packing, the volume ratio of the first particles 2 in the nonlinear resistance resin material 1 is preferably 25 vol% or more and 74 vol% or less. If the volume ratio of the second particles 32 in the first resin phase 3 is less than 1 vol%, the conductive components are insufficient, and the first particles 2 may not adhere to each other sufficiently, and may become closer to an insulator. On the other hand, if the volume ratio of the second particles 32 in the first resin phase 3 exceeds 40 vol%, the conductive components are excessive, and may become closer to a conductor. Therefore, the volume ratio of the second particles 32 in the first resin phase 3 is preferably 1 vol% or more and 40 vol% or less. In addition, the volume ratio of the second particles 32 in the nonlinear resistance resin material 1 is preferably 0.2 vol% or more and 2 vol% or less. The volume of the voids 4 in the nonlinear resistance resin material 1 is preferably larger than the volume of the first resin phase 3 in the nonlinear resistance resin material 1 .

[0027] Next, a method for producing the nonlinear resistance resin material 1 according to the present embodiment will be described with reference to Fig. 1 to Fig. 4. The method for producing the nonlinear resistance resin material 1 includes a mixing step, a pressure molding step, and a curing step. Note that these steps are merely examples, and are not intended to limit the method for producing the nonlinear resistance resin material 1.

[0028] The mixing step is a step of mixing a plurality of first particles 2 having nonlinear resistance characteristics that show insulation when a voltage below a threshold is applied and show conductivity when a voltage equal to or higher than the threshold is applied with a first resin phase 3 having semiconductivity or conductivity, and covering at least a part of the surface of a part or all of the plurality of first particles 2 with the first resin phase 3. In the mixing step, the first particles 2 shown in FIG. 3, the polyvinyl alcohol resin as the first matrix resin 31 shown in FIG. 4, and the carbon powder as the second particles 32 are weighed and then mixed. In this embodiment, "GL-05" manufactured by Mitsubishi Chemical Corporation was used as the polyvinyl alcohol resin. In this embodiment, "CCE03PB" manufactured by Kojundo Chemical Laboratory Co., Ltd. was used as the carbon powder. The mixing method is not particularly limited, and may be appropriately selected from known mixing methods. In this embodiment, the first particles 2, the first matrix resin 31 in a liquid state made into a 5 wt% aqueous solution, and the second particles 32 were uniformly mixed using a machine. It is preferable to control the pressure during mixing so as not to crush the first particles 2. By the mixing process, a nonlinear resistance resin material 1 before molding is obtained, which includes the first particles 2 covered with the first resin phase 3 shown in FIG.

[0029] The pressure molding process is a process of molding the nonlinear resistance resin material 1 having the first particles 2 covered with the first resin phase 3 into a predetermined shape. The molding method is not particularly limited, and may be appropriately selected from among known molding methods according to the shape of the nonlinear resistance resin material 1 to be produced. For example, the nonlinear resistance resin material 1 having the first particles 2 covered with the first resin phase 3 may be filled into a mold, and molding pressure may be applied to the nonlinear resistance resin material 1 by a press device to mold the nonlinear resistance resin material 1 into a predetermined shape. In addition, the nonlinear resistance resin material 1 may be molded into a predetermined shape by applying molding pressure to the nonlinear resistance resin material 1 by increasing the gas pressure. In this embodiment, the nonlinear resistance resin material 1 is filled into a mold, and molding pressure is applied to the nonlinear resistance resin material 1 to mold the nonlinear resistance resin material 1 into a predetermined shape.

[0030] The curing process is a process in which the nonlinear resistance resin material 1 molded into a predetermined shape is heated and cured. By heating and curing the nonlinear resistance resin material 1, adjacent first particles 2 are bound and electrically connected via the first resin phase 3 as shown in FIG. 2. The method for curing the nonlinear resistance resin material 1 is not particularly limited and may be appropriately selected from known curing methods. Through the above process, the nonlinear resistance resin material 1 is manufactured.

[0031] Next, the effects of the nonlinear resistance resin material 1 according to this embodiment will be described.

[0032] In this embodiment, as shown in FIG. 1, the nonlinear resistance resin material 1 includes a plurality of first particles 2 having nonlinear resistance characteristics that show insulation when a voltage below a threshold is applied and show conductivity when a voltage equal to or higher than the threshold is applied, and a first resin phase 3 that includes a semiconductive or conductive second particle 32 and covers at least a part of the surface of a part or all of the plurality of first particles 2. In addition, in this embodiment, as shown in FIG. 2, adjacent first particles 2 are bonded to each other via the first resin phase 3 and electrically connected. In this way, the first resin phase 3 having semiconductivity or conductivity is suppressed from being connected to each other, making it difficult for electricity to flow in the thickness direction. This suppresses the resistance value from decreasing below the designed nonlinear resistance characteristics, and prevents the nonlinear resistance resin material 1 from functioning as an insulator under conditions where it should function as an insulator.

[0033] In this embodiment, as shown in Fig. 4, the first resin phase 3 contains semiconductive or conductive second particles 32. In this embodiment, the volume ratio of the first particles 2 in the nonlinear resistance resin material 1 is 25 vol% or more and 74 vol% or less, and the volume ratio of the second particles 32 in the first resin phase 3 is 1 vol% or more and 40 vol% or less. In this way, the nonlinear resistance characteristics of the nonlinear resistance resin material 1 can be fully exhibited.

[0034] In this embodiment, the volume ratio of the second particles 32 in the nonlinear resistance resin material 1 is 0.2 vol% or more and 2 vol% or less, and the volume of the voids 4 in the nonlinear resistance resin material 1 is larger than the volume of the first resin phase 3 in the nonlinear resistance resin material 1. In this way, the nonlinear resistance characteristics of the nonlinear resistance resin material 1 can be fully exhibited.

[0035] In this embodiment, the average particle size of the second particles 32 is 1 / 10 or less of the average particle size of the first particles 2, so that the surfaces of the first particles 2 are easily covered with the second particles 32.

[0036] In this embodiment, the first particles 2 contain 80 wt % or more of zinc oxide or silicon carbide, so that the nonlinear resistance characteristics of the first particles 2 can be sufficiently ensured.

[0037] In this embodiment, since the first particles 2 are agglomerates of two or more primary particles, the degree of freedom in the pressure during the crushing process during production is increased, and therefore the productivity of the first particles 2 can be improved.

[0038] In this embodiment, the average particle size of the primary particles constituting the main component of the first particles 2 is less than 20 μm, so that the adhesive strength between the first particles 2 and the first resin phase 3 can be increased.

[0039] Next, a nonlinear resistance resin material 1A according to Modification 1 of the first embodiment will be described with reference to FIG. 6 and FIG. 7. FIG. 6 is a schematic diagram of the nonlinear resistance resin material 1A according to Modification 1 of the first embodiment. FIG. 7 is an enlarged diagram of part C shown in FIG. 6. The nonlinear resistance resin material 1A according to Modification 1 is different from the nonlinear resistance resin material 1 according to the first embodiment in that it includes a second resin phase 5. In Modification 1, the same reference numerals are used for the parts that overlap with the nonlinear resistance resin material 1 according to the first embodiment, and the description thereof will be omitted. Note that FIG. 6 and FIG. 7 show a state in which the part that was the void 4 in FIG. 1 and FIG. 2 is filled with the second resin phase 5. For convenience of description, both the reference numerals 4 and 5 are written in FIG. 6 and FIG. 7.

[0040] The second resin phase 5 fills the gaps 4 formed in the nonlinear resistance resin material 1A other than the first particles 2 and the first resin phase 3, and has insulating properties. The volume ratio of the second resin phase 5 in the nonlinear resistance resin material 1A is preferably larger than the volume ratio of the first resin phase 3 in the nonlinear resistance resin material 1A.

[0041] The second resin phase 5 may be incompatible with the first resin phase 3. For example, epoxy, polycarbonate, polypropylene, acrylic, phenol, polyvinyl chloride, polystyrene, unsaturated polyester, polyimide, and acrylonitrile-butadiene-styrene copolymer are used for the second resin phase 5. These resins may be used alone or in combination of two or more. In addition, a varnish in which these resins are dissolved in a solvent may be used for the second resin phase 5. For example, when polyvinyl alcohol is used for the first resin phase 3, it is preferable to use an epoxy resin for the second resin phase 5 from the viewpoint of handling, and an epoxy resin is used in this modification. In this modification, "CY230" manufactured by Nagase ChemteX Corporation was used as the base agent for the epoxy resin. In this modification, "HY951" manufactured by Nagase ChemteX Corporation was used as the curing agent for the epoxy resin. According to experiments and research by the present inventors, it has been confirmed that there is no difference in current-voltage characteristics between the nonlinear resistance resin material 1A having the second resin phase 5 and the nonlinear resistance resin material 1 not having the second resin phase 5. This is presumably because there is no change in the current path between the nonlinear resistance resin material 1A having the second resin phase 5 and the nonlinear resistance resin material 1 not having the second resin phase 5.

[0042] When manufacturing the nonlinear resistance resin material 1A including the second resin phase 5, a compounding process is performed after the above-mentioned curing process. The compounding process is a process of compounding the molded nonlinear resistance resin material 1A with the second resin phase 5 having insulating properties. That is, the nonlinear resistance resin material 1A after the curing process is impregnated with the second resin phase 5 in a liquid state, and the voids 4 are filled with the second resin phase 5. The compounding process can be performed under vacuum to impregnate even finer voids 4. After the compounding process, a new curing process is performed in which the nonlinear resistance resin material 1A including the second resin phase 5 is heated and cured.

[0043] In this modification, the nonlinear resistance resin material 1A includes the second resin phase 5, which fills the voids 4 formed in the portions other than the first particles 2 and the first resin phase 3 and has insulating properties, so that a structure having even higher mechanical strength can be fabricated. In addition, the occurrence of internal discharge when a high electric field is applied can be suppressed.

[0044] Next, a nonlinear resistance resin material 1B according to Modification 2 of the first embodiment will be described with reference to Fig. 8 and Fig. 9. Fig. 8 is a diagram showing a schematic diagram of the nonlinear resistance resin material 1B according to Modification 2 of the first embodiment. Fig. 9 is a diagram showing a current path Z of the nonlinear resistance resin material 1B according to Modification 2 of the first embodiment. In Modification 2, parts that overlap with the nonlinear resistance resin material 1 according to the first embodiment described above are given the same reference numerals and description thereof will be omitted.

[0045] The nonlinear resistance resin material 1B includes a plurality of first particles 2 having different particle sizes. The average particle size of the first particles 2 is not particularly limited, but is 50 μm in this embodiment. The first particles 2 are manufactured by spraying the raw material described in the first embodiment and spray-drying the raw material. The particle size distribution of the first particles 2 can be changed by the amount of spray when spraying the raw material. The smaller the amount of spray and the smaller the size of the droplets, the smaller the particle size of the first particles 2. As shown in FIG. 9, adjacent first particles 2 are bonded to each other via the first resin phase 3, thereby forming a current path Z that electrically connects the first particles 2 to each other. This modification can also achieve the same effect as the first embodiment.

[0046] Fig. 10 is a schematic diagram showing a nonlinear resistance resin material 1C according to Modification 3 of the embodiment 1. As shown in Fig. 10, the nonlinear resistance resin material 1C differs from the nonlinear resistance resin material 1B according to Modification 2 of the embodiment 1 in that it includes a second resin phase 5. The nonlinear resistance resin material 1C may include a second resin phase 5 that fills voids 4 formed in portions other than the first particles 2 and the first resin phase 3 and has insulating properties.

[0047] Embodiment 2 Next, the overvoltage protection device 6 according to the second embodiment will be described with reference to Figs. 11 to 13. Fig. 11 is a diagram showing a connection example between the overvoltage protection device 6 according to the second embodiment and the protected device 7, showing the case where a voltage less than a threshold value is applied. Fig. 12 is a diagram showing a connection example between the overvoltage protection device 6 according to the second embodiment and the protected device 7, showing the case where a voltage equal to or greater than a threshold value is applied. Fig. 13 is a diagram showing a nonlinear resistor 61 of the overvoltage protection device 6 according to the second embodiment, showing the nonlinear resistor 61 using the nonlinear resistance resin material 1 according to the first embodiment. In the second embodiment, the same reference numerals are used for the parts overlapping with the first embodiment, and the description thereof will be omitted. The arrow Y shown in Figs. 11 and 12 indicates the flow of electricity.

[0048] The overvoltage protection device 6 shown in Fig. 11 and Fig. 12 is a device that prevents an overvoltage from being applied to a protected device 7. As shown in Fig. 11 to Fig. 13, the overvoltage protection device 6 includes a nonlinear resistor 61 and wiring 63 electrically connected to the protected device 7. The nonlinear resistor 61 shown in Fig. 13 includes the nonlinear resistance resin material 1 according to the first embodiment described above and a plurality of electrodes 62 attached to the nonlinear resistance resin material 1.

[0049] The shape of the nonlinear resistance resin material 1 is not particularly limited, but is cylindrical in this embodiment. The number of electrodes 62 is not particularly limited, but is two in this embodiment. The electrodes 62 are attached along both ends in the short direction of the nonlinear resistance resin material 1. The shape of the electrodes 62 is not particularly limited, but is circular in this embodiment. When distinguishing between the two electrodes 62, one electrode 62 is referred to as electrode 62a and the other electrode 62 is referred to as electrode 62b. The electrode 62a is connected to a wiring 63, and the electrode 62b is grounded. For the electrode 62, for example, a silver paste that can be hardened at room temperature, or an aluminum spray material if it has sufficient heat resistance, is used. The nonlinear resistor 61 is built into the overvoltage protection device 6 shown in FIG. 11 and FIG. 12.

[0050] The overvoltage protection device 6 and the protected device 7 are electrically connected in parallel. When one electrode 62a shown in Fig. 13 is energized and the other electrode 62b is grounded and an overvoltage is applied to the electrode 62a on the energized side, the nonlinear resistance resin material 1 of the nonlinear resistor 61 becomes an insulator when a voltage less than the threshold shown in Fig. 11 is applied, whereas the nonlinear resistance resin material 1 of the nonlinear resistor 61 becomes a conductor when a voltage equal to or greater than the threshold shown in Fig. 12 is applied, thereby lowering the inter-terminal voltage and protecting the protected device 7.

[0051] FIG. 14 is a diagram showing a schematic diagram of a nonlinear resistor 61 of an overvoltage protection device 6 according to the second embodiment, and shows a nonlinear resistor 61 using a nonlinear resistance resin material 1A according to the first modification of the first embodiment. The nonlinear resistor 61 includes the nonlinear resistance resin material 1A according to the first modification of the first embodiment and a plurality of electrodes 62 attached to the nonlinear resistance resin material 1A. Even when the nonlinear resistance resin material 1A includes a second resin phase 5, the same effect as that of the present embodiment can be achieved. That is, the nonlinear resistance resin material 1 according to the first embodiment, the nonlinear resistance resin material 1A according to the first modification of the first embodiment, the nonlinear resistance resin material 1B according to the second modification of the first embodiment, or the nonlinear resistance resin material 1C according to the third modification of the first embodiment can be used for the nonlinear resistor 61 in which an electric field is applied by providing a potential difference between the electrodes 62a and 62b, such as by applying a voltage to one electrode 62a and grounding the other electrode 62b.

[0052] Embodiment 3 Next, the nonlinear resistance resin material 1D according to the third embodiment will be described with reference to FIG. 15 to FIG. 19. FIG. 15 is a schematic diagram of the nonlinear resistance resin material 1D according to the third embodiment. FIG. 16 is a diagram showing the particle size distribution of the first particles 2 of the nonlinear resistance resin material 1D according to the third embodiment. FIG. 17 is a diagram showing the relationship between the mixing ratio and the filling rate of the first particles 2 of the nonlinear resistance resin material 1D according to the third embodiment. FIG. 18 is a diagram showing the current path Z of the nonlinear resistance resin material 1D according to the third embodiment. FIG. 19 is a diagram showing the current-voltage characteristic of the first particles 2 of the nonlinear resistance resin material 1D according to the third embodiment and the current-voltage characteristic of the first particles 2 of the nonlinear resistance resin material 1 according to the first embodiment. The nonlinear resistance resin material 1D according to the third embodiment is different from the nonlinear resistance resin material 1B according to the second modification of the first embodiment in that the nonlinear resistance resin material 1D according to the third embodiment includes two types of first particles 2 having different particle size distributions. In the third embodiment, the parts that overlap with those of the nonlinear resistance resin material 1B according to the second modification of the first embodiment described above are given the same reference numerals and the description thereof will be omitted.

[0053] The nonlinear resistance resin material 1D shown in FIG. 15 includes two or more kinds of first particles 2 with different particle size distributions. The nonlinear resistance resin material 1D includes two or more kinds of first particles 2 with different average particle sizes. In this embodiment, a case where the first particles 2 with an average particle size of 50 μm and the first particles 2 with an average particle size of 20 μm are mixed and the particle size distribution of the first particles 2 with an average particle size of 50 μm is different from the particle size distribution of the first particles 2 with an average particle size of 20 μm is illustrated. Hereinafter, the first particles 2 with an average particle size of 50 μm may be referred to as large particles 8, and the first particles 2 with an average particle size of 20 μm may be referred to as small particles 9. In FIG. 15, in order to distinguish between the large particles 8 and the small particles 9, the large particles 8 are illustrated in white and the small particles 9 are hatched. The small particles 9 enter the gaps 4 between the large particles 8. The small particles 9 are arranged so as to fill the gaps 4 between the large particles 8. The average particle size of the first particles 2 is not limited to the numerical values ​​given as examples.

[0054] Line A in FIG. 16 shows the particle size distribution of the first particles 2 with an average particle size of 50 μm. Line B in FIG. 16 shows the particle size distribution of the first particles 2 with an average particle size of 20 μm. Line C in FIG. 16 shows the particle size distribution of the entire first particles 2. The horizontal axis in FIG. 16 is the particle size (μm) of the first particles 2, and the vertical axis in FIG. 16 is the proportion (%) of the first particles 2 with each particle size. The particle size distribution of the first particles 2 with an average particle size of 50 μm is different from the particle size distribution of the first particles 2 with an average particle size of 20 μm. The particle size distribution of the entire first particles 2 has two maximum values ​​P at which the proportion of the first particles 2 present is maximized. In other words, when the particle size distribution of the entire first particles 2 is shown by a particle size distribution curve in which the horizontal axis is divided into predetermined particle sizes and the vertical axis is the proportion of first particles 2 of each particle size, the particle size distribution curve has a shape having two maximum values ​​P.

[0055] FIG. 17 shows the relationship between the mixing ratio (vol%) of the first particles 2 having an average particle size of 50 μm and the filling ratio (vol%) of the first particles 2. The horizontal axis of FIG. 17 is the mixing ratio (vol%) of the first particles 2 having an average particle size of 50 μm, and the vertical axis of FIG. 17 is the filling ratio (vol%) of the first particles 2. The filling ratio of the first particles 2 means the volume ratio of the first particles 2 in the nonlinear resistance resin material 1D. As is clear from FIG. 17, the filling ratio of the first particles 2 is maximized when the mixing ratio of the first particles 2 having an average particle size of 50 μm is 60 vol%. When the mixing ratio of the first particles 2 having an average particle size of 50 μm is 60 vol%, the mixing ratio of the first particles 2 having an average particle size of 20 μm is 40 vol%.

[0056] Next, the effects of the nonlinear resistance resin material 1D according to this embodiment will be described.

[0057] As in the second modification of the first embodiment shown in FIG. 8, when only the first particles 2 having an average particle size of 50 μm are used, that is, when the first particles 2 having one type of particle size distribution are used, the gaps 4 between the adjacent first particles 2 become large. In contrast, as in the present embodiment shown in FIG. 15, when the nonlinear resistance resin material 1D includes two types of first particles 2 having different particle size distributions, and the particle size distribution of the entire first particles 2 has two maximum values ​​P at which the ratio of the first particles 2 present becomes maximum, the small particles 9 having a small particle size enter the gaps 4 between the large particles 8 having a large particle size. Therefore, the gaps 4 between the adjacent first particles 2 become smaller or disappear, so that the filling rate of the first particles 2 can be increased. And, by the small particles 9 having a small particle size entering between the large particles 8 having a large particle size, the bonding area between the first particles 2 can be increased. As a result, as shown in FIG. 18, the current paths Z electrically connecting the first particles 2 to each other are increased. That is, since the current flows through the bonded portion of the first particles 2, the current paths Z electrically connecting the first particles 2 can be increased by increasing the bonded area between the first particles 2. When the current paths Z are increased, the threshold voltage V th In the current region beyond this, a large amount of current can flow.

[0058] Line L1' in FIG. 19 shows the current-voltage characteristics of the first particles 2 of the nonlinear resistance resin material 1D when the mixing ratio of the first particles 2 having an average particle size of 50 μm is 60 vol% and the mixing ratio of the first particles 2 having an average particle size of 20 μm is 40 vol%, that is, when the packing ratio of the first particles 2 is maximum. Line L1 in FIG. 19 is the same as L1 shown in FIG. 5, and shows the current-voltage characteristics of the first particles 2 of the nonlinear resistance resin material 1 according to the first embodiment. As is clear from FIG. 19, the slope of line L1' is smaller than the slope of line L1. In other words, in this embodiment, the slope of line L1 can be further reduced to line L1'. Therefore, in this embodiment, the nonlinear resistance characteristics of the nonlinear resistance resin material 1D can be further improved and the nonlinear resistance index of the nonlinear resistance resin material 1D can be further increased compared to the first embodiment described above.

[0059] Fig. 20 is a schematic diagram showing a nonlinear resistance resin material 1E according to a modified example of embodiment 3. As shown in Fig. 20, the nonlinear resistance resin material 1E may include a second resin phase 5 that fills voids 4 formed in portions other than the first particles 2 and the first resin phase 3 and has insulating properties.

[0060] In this embodiment, the nonlinear resistance resin material 1D includes two types of first particles 2 with different particle size distributions, but may include three or more types of first particles 2 with different particle size distributions as long as the filling rate of the first particles 2 can be increased. In other words, the nonlinear resistance resin material 1D may include two or more types of first particles 2 with different particle size distributions. The particle size distribution of the entire first particles 2 may have two or more maximum values ​​P at which the proportion of the first particles 2 present is maximized.

[0061] The first particles 2 having an average particle size of 50 μm may be covered by the first resin phase 3 containing the second particles 32, and the first particles 2 having an average particle size of 20 μm may not be covered by the first resin phase 3. Even in this case, it has been confirmed by the experiments and research of the present inventor that the current-voltage characteristics of the first particles 2 are improved from the line L1 to the line L1' shown in FIG. 19. In addition, when the first particles 2 are not sufficiently bonded to each other, the first particles 2 having an average particle size of 20 μm may be covered by the third resin phase 10 not containing the second particles 32 as shown in FIG. 20. The composition of the third resin phase 10 may be the same as the composition of the first resin phase 3, except that it does not contain the second particles 32. On the other hand, the first particles 2 having an average particle size of 50 μm may not be covered by the first resin phase 3, and the first particles 2 having an average particle size of 20 μm may be covered by the first resin phase 3 containing the second particles 32. Even in this way, it has been confirmed by the experiments and research of the present inventor that the current-voltage characteristics of the first particles 2 improve from line L1 to line L1' shown in FIG. 19. In addition, when the first particles 2 are not sufficiently bonded to each other, the first particles 2 having an average particle size of 50 μm may be covered with the third resin phase 10 that does not include the second particles 32. As described above, when the nonlinear resistance resin material 1D includes two types of first particles 2 having different average particle sizes, at least one type of first particle 2 may be covered with the first resin phase 3 that includes the second particles 32, and at least one type of first particle 2 may not be covered with the first resin phase 3 or may be covered with the third resin phase 10 that does not include the second particles 32. In this way, the amount of the first resin phase 3 that includes the second particles 32 used can be reduced, or the amount of the first resin phase 3 that includes the second particles 32 that is processed can be reduced, thereby improving the productivity of the nonlinear resistance resin material 1D. In addition, when at least one type of first particle 2 is not covered by the first resin phase 3, in the mixing process, at least one type of first particle 2 is mixed with the first matrix resin 31 in a liquid state and the second particles 32 to produce the nonlinear resistance resin material 1D before molding, and then another type of first particle 2 having a different average particle size is mixed into this nonlinear resistance resin material 1D before molding.Furthermore, in the case where at least one type of first particles 2 is covered with the third resin phase 10, in the mixing step, a step of mixing at least one type of first particles 2 with the first matrix resin 31 in a liquid state and the second particles 32 to prepare the nonlinear resistance resin material 1D before molding and a step of mixing another type of first particles 2 having a different average particle size with the matrix resin in a liquid state that will become the third resin phase 10 to prepare the nonlinear resistance resin material 1D before molding may be carried out separately. Then, the nonlinear resistance resin materials 1D before molding that have been separately prepared may be mixed.

[0062] When the nonlinear resistance resin material 1D has three or more kinds of first particles 2 with different average particle sizes, at least one kind of the first particles 2 may be covered by the first resin phase 3 containing the second particles 32, and at least one kind of the first particles 2 may not be covered by the first resin phase 3, or may be covered by the third resin phase 10 not containing the second particles 32. Even in this case, it has been confirmed by the experiments and research of the present inventor that the current-voltage characteristics of the first particles 2 improve from the line L1 to the line L1' shown in FIG. 19. In addition, the amount of the first resin phase 3 containing the second particles 32 used can be reduced, and the amount of the first resin phase 3 containing the second particles 32 processed can be reduced, so that the productivity of the nonlinear resistance resin material 1D can be improved.

[0063] In the case where the nonlinear resistance resin material 1D has the first particles 2 having one type of average particle size, at least a part of the first particles 2 may be covered by the first resin phase 3 containing the second particles 32, and at least a part of the first particles 2 may not be covered by the first resin phase 3, or may be covered by the third resin phase 10 not containing the second particles 32. Even in this case, it has been confirmed by the experiments and research of the present inventor that the current-voltage characteristics of the first particles 2 improve from the line L1 to the line L1' shown in FIG. 19. In addition, the amount of the first resin phase 3 containing the second particles 32 used can be reduced, and the amount of the first resin phase 3 containing the second particles 32 processed can be reduced, so that the productivity of the nonlinear resistance resin material 1D can be improved.

[0064] Next, the effects of the present disclosure will be further described with reference to examples and comparative examples.

[0065] (Material composition) Nonlinear resistance resin materials according to Examples 1 to 41 in which molding pressure was applied and nonlinear resistance resin materials according to Comparative Examples 1 to 8 in which molding pressure was not applied were prepared according to the compounding amounts shown in Table 1. A polyvinyl alcohol resin ("GL-05" manufactured by Mitsubishi Chemical Corporation) was used for the first matrix resin constituting the first resin phase. Carbon powder ("CCE03PB" manufactured by Kojundo Chemical Laboratory Co., Ltd.) was used for the second particles constituting the first resin phase. An epoxy resin (base material: "CY230" manufactured by Nagase ChemteX Corporation, hardener: "HY951" manufactured by Nagase ChemteX Corporation) was used for the second resin phase. In Examples 1 to 41, the nonlinear resistance resin material before molding was filled into a mold, and 300 kgf / cm was applied to the nonlinear resistance resin material. 2 The nonlinear resistance resin material was molded by applying a molding pressure of 1000 MPa. By applying pressure to the nonlinear resistance resin material, the first particles are bonded together and electrically connected. In Comparative Examples 1 to 8, in which no molding pressure was applied to the nonlinear resistance resin material, the first particles are not bonded together and are not electrically connected. In the nonlinear resistance resin materials according to Examples 1 to 41 and the nonlinear resistance resin materials according to Comparative Examples 1 to 8, the electrical connection between the first particles having nonlinear resistance characteristics, the pressurization, the volume ratio of the first particles in the nonlinear resistance resin material, the volume ratio of the matrix resin of the first resin phase in the nonlinear resistance resin material, the volume ratio of the second particles in the first resin phase in the nonlinear resistance resin material, the volume ratio of the voids or the second resin phase in the nonlinear resistance resin material, the volume ratio of the second particles in the first resin phase, and the average particle size of the second particles relative to the first particles are changed.

[0066] [Table 1]

[0067] (Test Method) For the nonlinear resistance resin materials according to Examples 1 to 41 and Comparative Examples 1 to 8, the nonlinear resistance characteristics, strength, and discharge start electric field were measured by the test methods shown below, and the nonlinear resistance characteristics, strength, and discharge start electric field were evaluated. Each evaluation was recorded on a 5-point scale. The higher the number, the better, and the lower the number, the worse, with 3 or more indicating an acceptable range. The nonlinear resistance characteristics were expressed as a nonlinear resistance index.

[0068] [Nonlinear resistance index] A voltage was applied to the obtained nonlinear resistance resin material, and the value of the current passing through the material was measured to obtain the current-voltage characteristics, and the nonlinear resistance index was calculated.

[0069] [Strength] The obtained nonlinear resistance resin material was compressed to measure the compressive strength.

[0070] [Discharge starting electric field] A voltage was applied to the obtained nonlinear resistance resin material, and the voltage value at which a discharge occurred was measured.

[0071] As is clear from Table 1, in Examples 1 to 41 in which molding pressure was applied to the nonlinear resistance resin material, the first particles having nonlinear resistance characteristics were bonded together and electrically connected, so the nonlinear resistance index was 3 or more, and nonlinear resistance characteristics were exhibited. On the other hand, in Comparative Examples 1 to 8 in which molding pressure was not applied to the nonlinear resistance resin material, the first particles having nonlinear resistance characteristics were not bonded together and electrically connected, so the nonlinear resistance index was 1 or 2, and nonlinear resistance characteristics were not exhibited. From this, it was found that applying molding pressure to the nonlinear resistance resin material, which causes the first particles having nonlinear resistance characteristics to be bonded together and electrically connected, is effective in improving the nonlinear resistance characteristics.

[0072] In Examples 1, 2, 3, 4, 7, 8, 9, 10, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 36, 38, 39, 40, and 41, in which the volume fraction of the first particles in the nonlinear resistance resin material was 25 vol% or more and 74 vol% or less and the volume fraction of the second particles in the first resin phase was 1 vol% or more and 40 vol% or less, the nonlinear resistance index was 4 or more. On the other hand, in Examples 5, 6, 11, 28, 29, 30, 31, 32, 33, 34, and 35, in which the volume ratio of the first particles in the nonlinear resistance resin material was not 25 vol% or more and 74 vol% or less, or the volume ratio of the second particles in the first resin phase was not 1 vol% or more and 40 vol% or less, the nonlinear resistance index was 3. From this, it was found that the volume ratio of the first particles in the nonlinear resistance resin material being 25 vol% or more and 74 vol% or less, and the volume ratio of the second particles in the first resin phase being 1 vol% or more and 40 vol% or less, is effective in improving the nonlinear resistance characteristics.

[0073] Among the examples with a nonlinear resistance index of 4 or more, in Examples 1, 2, 3, 8, 9, 10, 17, 18, 19, 25, 26, 27, 38, 39, and 40 in which the volume fraction of the second particles in the nonlinear resistance resin material is 0.2 vol% or more and 2 vol% or less, and the volume of the voids or the second resin phase is larger than the volume of the first resin phase, the nonlinear resistance index was 5. From this, it was found that the volume fraction of the second particles in the nonlinear resistance resin material is 0.2 vol% or more and 2 vol% or less, and the volume of the voids or the second resin phase is larger than the volume of the first resin phase, is effective in improving the nonlinear resistance characteristics.

[0074] Example 1 and Example 36 are different in the average particle size of the second particles relative to the first particles. Similarly, Example 7 and Example 37 are different in the average particle size of the second particles relative to the first particles. In Example 1, where the average particle size of the second particles is 1 / 10 or less of the average particle size of the first particles, the nonlinear resistance index was 5, whereas in Example 36, where the average particle size of the second particles is more than 1 / 10 of the average particle size of the first particles, the nonlinear resistance index was 4. In addition, in Example 7, where the average particle size of the second particles is 1 / 10 or less of the average particle size of the first particles, the nonlinear resistance index was 4, whereas in Example 37, where the average particle size of the second particles is more than 1 / 10 of the average particle size of the first particles, the nonlinear resistance index was 3. From this, it was found that the average particle size of the second particles being 1 / 10 or less of the average particle size of the first particles is effective in improving the nonlinear resistance characteristics.

[0075] The difference between Example 1 and Example 40 is whether the voids are filled with the second resin phase or not. Similarly, the difference between Example 7 and Example 41 is whether the voids are filled with the second resin phase or not. In Example 1, in which the voids are not filled with the second resin phase, the strength and discharge start electric field were 3, whereas in Example 40, in which the voids are filled with the second resin phase, the strength and discharge start electric field were 5. In addition, in Example 7, in which the voids are not filled with the second resin phase, the strength and discharge start electric field were 4, whereas in Example 41, in which the voids are filled with the second resin phase, the strength and discharge start electric field were 5. From this, it was found that filling the voids with the second resin phase is effective in improving the strength and discharge characteristics.

[0076] The only difference between Example 40 and Comparative Example 7, and between Example 41 and Comparative Example 8, is whether or not pressure is applied when the second resin phase is provided. In both Examples 40 and 41 and Comparative Examples 7 and 8, the strength and discharge inception electric field can be maintained at a high level by providing a second resin phase, but in Comparative Examples 7 and 8, where molding pressure was not applied to the nonlinear resistance resin material, the first particles were not bonded together and were not electrically connected, so the nonlinear resistance index was smaller than that of Examples 40 and 41.

[0077] The configurations shown in the above embodiments are merely examples, and may be combined with other known technologies, or the embodiments may be combined with each other. Also, parts of the configurations may be omitted or modified without departing from the spirit of the invention. [Explanation of symbols]

[0078] 1, 1A, 1B, 1C, 1D, 1E nonlinear resistance resin material, 2 first particle, 3 first resin phase, 4 void, 5 second resin phase, 6 overvoltage protection device, 7 protected device, 8 large particle, 9 small particle, 10 third resin phase, 21 contact portion, 22 non-contact portion, 31 first matrix resin, 32 second particle, 61 nonlinear resistor, 62, 62a, 62b electrodes, 63 wiring.

Claims

1. A plurality of first particles having nonlinear resistance characteristics that exhibit insulating properties when a voltage less than a threshold is applied and that exhibit conductive properties when a voltage equal to or greater than the threshold is applied; A first resin phase including semiconductive or conductive second particles and covering at least a portion of a surface of some or all of the first particles; a second resin phase that fills voids formed in a portion other than the first particles and the first resin phase and has insulating properties; A nonlinear resistance resin material, characterized in that adjacent first particles are bound to each other and electrically connected via the first resin phase.

2. a volume ratio of the first particles to the nonlinear resistance resin material is 25 vol% or more and 74 vol% or less, 2. The nonlinear resistance resin material according to claim 1, wherein a volume ratio of the second particles to the first resin phase is 1 vol % or more and 40 vol % or less.

3. a volume ratio of the second particles in the nonlinear resistance resin material is 0.2 vol % or more and 2 vol % or less, 3. The nonlinear resistance resin material according to claim 2, wherein a volume ratio of the second resin phase in the nonlinear resistance resin material is greater than a volume ratio of the first resin phase in the nonlinear resistance resin material.

4. 4. The nonlinear resistance resin material according to claim 3, wherein the average particle size of the second particles is 1 / 10 or less of the average particle size of the first particles.

5. Two or more types of the first particles having different particle size distributions are provided, 5. The nonlinear resistance resin material according to claim 4, wherein the particle size distribution of the entire first particles has two or more maximum values ​​at which the proportion of the first particles present is maximized.

6. Two or more types of the first particles having different average particle sizes are provided, 6. The nonlinear resistance resin material according to claim 5, wherein at least one type of the first particles is covered with the first resin phase containing the second particles.

7. 7. The nonlinear resistance resin material according to claim 6, wherein at least one type of the first particles is covered with a third resin phase that does not include the second particles.

8. 2. The nonlinear resistance resin material according to claim 1, wherein the first particles contain 80 wt % or more of zinc oxide or silicon carbide.

9. The nonlinear resistance resin material according to claim 1 , wherein the first particles are aggregates of two or more primary particles.

10. 2. The nonlinear resistance resin material according to claim 1, wherein the average particle size of the primary particles constituting the first particles is less than 20 μm.

11. The nonlinear resistance resin material according to any one of claims 1 to 10, and a plurality of electrodes attached to the nonlinear resistive resin material.

12. An overvoltage protection device that prevents an overvoltage from being applied to a protected device, A nonlinear resistor according to claim 11; a wiring electrically connected to the protected device; At least one of the plurality of electrodes is grounded, and at least one of the plurality of electrodes is connected to the wiring.

13. a mixing step of mixing a plurality of first particles having nonlinear resistance characteristics that show insulation when a voltage below a threshold is applied and show conductivity when a voltage equal to or higher than a threshold is applied with a first resin phase containing semiconductive or conductive second particles, and covering at least a portion of a surface of some or all of the plurality of first particles with the first resin phase; a pressure molding step of molding the nonlinear resistance resin material having the first particles covered with the first resin phase into a predetermined shape; a compounding step of compounding the molded nonlinear resistance resin material with a second resin phase having insulating properties; A method for producing a nonlinear resistance resin material, comprising:

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