WO2015046125A1 - 非オーム性を有する樹脂材料及びその製造方法、並びに該樹脂材料を用いた非オーム性抵抗体 - Google Patents
非オーム性を有する樹脂材料及びその製造方法、並びに該樹脂材料を用いた非オーム性抵抗体 Download PDFInfo
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08L81/02—Polythioethers; Polythioether-ethers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/10—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
- H01C7/105—Varistor cores
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/10—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
- H01C7/12—Overvoltage protection resistors
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Definitions
- the present invention relates to a non-ohmic resin material having a non-ohmic property excellent in surge resistance, and a non-ohmic resistor using the resin material, which protects an electrical device from a surge voltage generated by lightning or circuit switching. About.
- a varistor is a non-ohmic device in which current increases rapidly as voltage increases.
- a varistor is used for the purpose of protecting an electric circuit from a surge voltage by utilizing such non-ohmicity. Specifically, by connecting the varistor in parallel to the protected device, the varistor maintains insulation against the ground under normal voltage, but if a surge voltage occurs in the electrical circuit, both ends of the varistor Since the current can be released to the ground without increasing the voltage, the voltage of the electric circuit is prevented from exceeding the withstand voltage of the protected device.
- varistor materials For example, ceramics fired by adding metal oxides such as Bi, Sb, Co, Mn to ZnO (zinc oxide), the main component.
- This material is a polycrystalline body composed of zinc oxide particles as the main phase and a grain boundary layer mainly composed of bismuth oxide, and has a microstructure in which spinel particles composed of Zn and Sb are randomly scattered in the polycrystalline body. Transition metal oxides such as Co and Mn are present in solid solution in these main phase, grain boundary layer, and spinel particles. In this material, the current passes through the interface between the zinc oxide particles and the grain boundary layer, thereby exhibiting non-ohmic properties.
- such materials are ceramics, they have the disadvantages that the degree of freedom in molding is low and the impact resistance is low because they are hard and brittle.
- Patent Document 1 describes a non-ohmic resistor containing an insulating matrix based on a polymer such as an epoxy resin and a powdery filler embedded in the matrix.
- the filler is a mixture of non-ohmic particles such as micro-varistors and conductive particles, which are heat-treated to bond the conductive particles contacting the surface of the micro-varistor with the micro-varistor. It is used.
- a micro-varistor uses particles having a nearly spherical shape made of the above ceramics.
- the conductive particles are particles that are smaller in size and higher in conductivity (for example, made of Ni) than the microvaristor, and have an aspect ratio such as a plate shape, flake shape, and short fiber shape that easily contacts the surface of the microvaristor. Those having a high shape are used.
- the number of microvaristors is increased as a means for forming a current path, and two types of microvaristors having different particle diameters are used, so that the smaller one is inserted in the gap between the larger microvaristors.
- Micro varistors enter, thereby increasing the concentration of the micro varistors.
- this non-ohmic resistor contains a matrix based on a polymer
- the surface of a part of an electrical device such as a switch is coated with the non-ohmic resistor using a casting method, or the surface is covered with the non-ohmic resistor.
- the component itself can be used as a varistor.
- the invasion of the matrix between adjacent microvaristors can be reduced, but in this case, there is a portion not covered with the matrix on the surface of the microvaristor. As a result, good insulation characteristics for a small current cannot be obtained. Furthermore, the portion not covered with the matrix becomes voids (bubbles) and causes dielectric breakdown due to discharge.
- the concentration of the solid varistor is increased because the concentration of the microvaristor is increased in order to obtain a current path. Therefore, with this non-ohmic resistor, it becomes difficult to apply an injection molding method generally used for resin molding, and the impact resistance is also lowered.
- a problem to be solved by the present invention is a non-ohmic resin material that has good characteristics as a varistor, is capable of injection molding, has a high degree of freedom in molding, and has high impact resistance. And a manufacturing method thereof, and a non-ohmic resistor using the resin material.
- the present invention made to solve the above problems is a resin material having a non-ohmic property in which current rapidly increases with an increase in voltage, a) an insulating matrix made of the first resin material; b) It is made of a conductive second resin material that is incompatible with the first resin material and has higher wettability to the micro-varistor described later than the first resin material, and is dispersed in islands in the matrix. And an island-shaped conductive dispersed phase having a volume fraction of less than 16% in the total resin material, c) Ceramic particles having non-ohmic properties, comprising a micro varistor dispersed in the matrix and in electrical contact with each other through the island-like conductive dispersed phase.
- the volume ratio of the island-like conductive dispersed phase in the resin material is 16% or more, theoretically, percolation occurs, so that the characteristics as a varistor cannot be obtained. Therefore, in the present invention, the volume ratio of the island-like conductive dispersed phase is set to less than 16%.
- the first resin material and the second resin material are kneaded, the first resin material and the second resin material are incompatible with each other. An island is formed.
- the sea made of the first resin material is called “matrix”, and the island made of the second resin material is called “island-like conductive dispersed phase”.
- the second resin material has higher wettability with respect to the microvaristor than the first resin material, and therefore, between the microvaristor and the island-like conductive dispersed phase. Intrusion of the matrix is prevented. Therefore, the microvaristors are in electrical contact with each other through the island-like conductive dispersed phase without being insulated by the matrix. Therefore, in the resin material of the present invention, characteristics excellent in surge resistance against a large current can be obtained.
- the second resin material satisfies the condition that the wettability with respect to the microvaristor is higher than that of the first resin material, it is not necessary to use a material with low wettability with respect to the microvaristor as the first resin material. No voids (bubbles) are formed on the surface of the microvaristor, so that good insulation characteristics on the surface of the microvaristor can be obtained and the occurrence of dielectric breakdown due to discharge can be prevented.
- a non-ohmic resistor having a desired shape, such as a housing for an electronic component or an electric device, a substrate for an electric circuit, a sheath for an electric cable, and an electric wire covering. Injection molding can be suitably used for producing these products.
- the island-like conductive dispersed phase in the resin material needs to be controlled, and the volume ratio may be 1% or more. desirable.
- thermoplastic resin for the first resin material and the second resin material.
- the resin material is cured in the shape by mixing the cross-linking agent using the material obtained by kneading the first resin material and the second resin material and the material kneading the microvaristor. Can do.
- the second resin material a resin having conductivity itself (for example, polyacetylene) can be used, but a resin imparted with conductivity by adding a conductive powder to an insulating resin can also be used.
- a resin having conductivity itself for example, polyacetylene
- a resin imparted with conductivity by adding a conductive powder to an insulating resin can also be used.
- the present invention uses a nonpolar resin as the first resin material as the matrix and a polar resin as the second resin material as the dispersed phase.
- the method of kneading these nonpolar resin and polar resin and conductive powder simultaneously is a method in which the conductive powder once mixed in the matrix resin is gradually taken into the dispersed phase to make the dispersed phase conductive. Can be adopted. By doing so, it becomes possible to easily obtain a dispersed phase having high conductivity.
- Polyolefin resin, polyphenylene sulfide, polystyrene, or the like can be used as the nonpolar resin that is the first resin material.
- examples of the polyolefin resin include polyethylene and polypropylene.
- the polar resin used as the second resin material include nylon, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polycarbonate.
- the conductive powder can be used as it is without any special treatment, but it is also possible to use a conductive powder whose surface is treated with a coupling agent on the surface of the particles of the conductive powder so as to be easily adapted to the polar resin.
- the conductive powder includes carbon powder, metal powder such as gold, silver, copper, nickel, palladium and platinum, conductive oxide powder such as tin oxide and oxide superconducting material, and conductive powder such as silicon carbide.
- a conductive carbide powder, a conductive nitride powder such as titanium nitride, or the like can be used.
- microvaristor a material mainly composed of zinc oxide, barium titanate, strontium titanate, silicon carbide, tin oxide or the like can be used.
- the micro varistor is preferably at least partially non-spherical. Thereby, the number of contact points (via the island-like conductive dispersed phase) between the microvaristors can be increased as compared with the case where the microvaristors are spherical.
- the method for producing a resin material according to the present invention is a method for producing a resin material having non-ohmic properties in which current increases rapidly with an increase in voltage, and includes an insulating first resin material and the first resin.
- a conductive second resin material that is incompatible with the material and has higher wettability to the microvaristor than the first resin material is kneaded, and the kneaded product and the microvaristor are kneaded.
- a nonpolar resin is used as the first resin material as a matrix
- a polar resin is used as the second resin material as a dispersed phase
- the conductive resin once mixed in the matrix resin is kneaded simultaneously with the conductive powder. It is possible to adopt a method in which the conductive powder is gradually taken into the dispersed phase to make the dispersed phase conductive. By doing so, it became possible to easily obtain a dispersed phase having high conductivity.
- a trace amount electroconductive powder may remain in the 1st resin material, since percolation does not arise with such a trace amount electroconductive powder, the characteristic as a varistor is maintained.
- a non-ohmic resin material having good characteristics as a varistor, capable of injection molding, having a high degree of freedom in molding, and having high impact resistance, and a method for producing the same, and A non-ohmic resistor using the resin material can be obtained.
- the flowchart which shows the manufacturing method of the resin material which is one Example of this invention.
- the schematic diagram (a) of the resin material of this example, and the diagram (b) showing the main current paths in the resin material. 6 is a graph showing measurement results of voltage-current (V-I) characteristics of the sample manufactured in Experiment 1.
- the graph which shows so that the measurement result of the VI characteristic of the sample produced in Experiment 2 may be compared with the difference in a microvaristor particle size.
- the graph which shows so that the measurement result of the VI characteristic of the sample produced in Experiment 2 may be compared with the volume ratio of a microvaristor.
- non-ohmic resin material hereinafter simply referred to as “resin material”
- manufacturing method thereof and a non-ohmic resistor according to the present invention will be described with reference to FIGS.
- the first resin material is polyethylene
- the second resin material is nylon (main phase resin) mixed with carbon powder (conductive powder)
- the microvaristor contains ZnO.
- polycrystalline particles obtained by sintering reaction were used.
- the carbon powder may be obtained by subjecting the surface of the particles to a hydrophilic surface treatment with a coupling agent, but may be used as it is without performing such a treatment.
- the microvaristor one obtained by firing a product obtained by a general spray drying method and passing through a sieve having a predetermined size of eyes (described later) was used.
- the volume of the second resin material was less than 16% of the total volume of the second resin material and the first resin material.
- the first resin material and the second resin material are kneaded at a temperature of 190 to 230 ° C. (step S1). At that time, the main resin and the conductive powder are mixed to produce the second resin material, and then the first resin material and the second resin material are mixed.
- the time can be shortened and a dispersed phase having a high concentration of the conductive powder can be easily obtained.
- step S2 the obtained mixture is formed into pellets (step S2).
- step S3 the pellet and the microvaristor are kneaded (step S3).
- the resin material 10 of a present Example is obtained.
- a non-ohmic resistor is obtained by performing injection molding after adding a crosslinking agent (step S4).
- first resin material polyethylene and the second resin material main phase resin nylon are incompatible with each other, the first resin material and the second resin material are separated from each other even when mixed. Further, since polyethylene is a nonpolar resin and nylon is a polar resin, carbon as a conductive material is unevenly distributed toward nylon. Thereby, in the obtained resin material 10, as shown in FIG. 2 (a), in the matrix 11 made of the first resin material, islands made of the second resin material having a volume smaller than that of the first resin material. The conductive dispersed phase 12 is formed in a dispersed manner.
- the island-shaped conductive dispersed phase 12 and the microvaristor 13 are in contact with each other, and the microvaristors 13 are electrically connected to each other via the island-shaped conductive dispersed phase 12.
- a path of current 19 is formed.
- the electrical characteristics (that is, non-ohmic properties) of the resin material 10 are manifested by current flowing through the interface between the ZnO particles 131 and the grain boundary layers 132 in the microvaristor 13.
- the second resin material nylon has higher wettability to the microvaristor 13 than the first resin material polyethylene. Therefore, the matrix 11 is prevented from entering between the microvaristor 13 and the island-shaped conductive dispersed phase 12, and the microvaristors 13 are in electrical contact with each other via the island-shaped conductive dispersed phase 12. .
- the resin material 10 of the present embodiment characteristics excellent in surge resistance against a large current can be obtained.
- the polyethylene of the first resin material has lower wettability with respect to the microvaristor 13 than the second resin material as described above, but is not so repelled on the surface of the microvaristor 13. Therefore, the matrix 11 can cover the surface of the microvaristor 13 except for the contact point where the microvaristors 13 are in contact with each other via the island-shaped conductive dispersed phase 12. As a result, it is possible to prevent a current from flowing through the surface layer of the microvaristor 13, and to obtain good insulation characteristics against a small current.
- the island-shaped conductive dispersed phases 12 are almost spherical, percolation between the island-shaped conductive dispersed phases 12 is unlikely to occur, and can be made high in concentration. Therefore, since the volume ratio of the microvaristor 13 that is a solid content can be reduced, injection molding becomes possible, and the degree of freedom in molding can be increased. Furthermore, impact resistance can also be improved.
- VI characteristics were measured for each sample in Table 1.
- a DC voltage was applied to the sample in the range where the current obtained was approximately 1 ⁇ 10 ⁇ 2 A / 10 cm 2 or less, and in the range where the current generally exceeded 1 ⁇ 10 ⁇ 2 A / 10 cm 2 .
- An impulse voltage was applied to the sample so that a large current could flow.
- the measurement results are shown in FIG. In any sample, even when the current is almost zero, the voltage has a high value of several tens to several hundreds V per mm. This means that it has good insulation properties for small currents.
- the voltage is shown in a linear scale with respect to the logarithmic scale current, which means that the increase in voltage can be suppressed even if the current increases. That is, this measurement result indicates that Samples 1 to 4 have non-ohmic properties.
- Example 2 Next, a sample having a higher content of the second resin material than that in Experiment 1 was prepared, and the results of measuring VI characteristics are shown.
- a sample first, 91.3% by volume of polyethylene, 8.0% by volume of nylon, and 0.680% by volume of carbon (the sum of these numbers does not add up to 100% by volume due to significant figures), 200 ° C Were simultaneously kneaded to prepare a polymer alloy.
- a sample was obtained by mixing the polymer alloy and the ZnO microvaristor 13 at a volume ratio shown in Table 2 at a temperature of 190 ° C.
- Three types of microvaristors 13 having particle sizes in the range of 10 to 20 ⁇ m, 20 to 30 ⁇ m, and 30 to 44 ⁇ m were used by passing through a sieve.
- FIG. 4 summarizes samples having the same volume fraction of the microvaristor 13 into one graph (the number of graphs is three), and shows the difference in VI characteristics due to the difference in the particle size of the microvaristor 13 in each graph. From the graph of FIG. 4, when samples having the same volume ratio of the microvaristor 13 are compared, in each case, the sample with a particle size of 20 to 30 ⁇ m, which is the middle of the three types, is small. In addition to the best insulation characteristics in current (high voltage), the non-ohmic index ⁇ is large.
- FIG. 5 summarizes samples having the same particle size of the microvaristor 13 in one graph (the number of graphs is three), and shows the difference in VI characteristics due to the difference in volume ratio of the microvaristor 13 in each graph. From the graph of FIG. 5, when samples having the same particle size of the microvaristor 13 are compared, in any case, the volume is within the range of the volume ratio of the microvaristor 13 in the prepared sample (10 to 30% by volume). It can be said that the lower the rate, the better the insulation characteristics at a small current (high voltage).
- the non-ohmic index ⁇ is the largest for a 20% by volume sample in which the volume fraction of the microvaristor 13 is the middle of the three types.
- Example 3 Next, as shown in Table 3, three types of polymer alloys having different volume fractions of polyethylene, nylon, and carbon were prepared, and each of these polymer alloys was mixed with a ZnO microvaristor 13 to obtain three types of samples ( Samples 21 to 23) were prepared. Each material was mixed at 200 ° C. when producing a polymer alloy. A microvaristor having a particle size of 10 to 20 ⁇ m was used. The polymer alloy and the microvaristor 13 were mixed at 190 ° C. The mixing ratio was 70% by volume for the polymer alloy and 30% by volume for the microvaristor 13. One of these three types of samples (sample 23 in Table 3) is the same as sample 17 in Table 2.
- the volume ratio (concentration) of the island-shaped conductive dispersed phase 12 is within a range of 0.5 vol% to 16 vol%.
- Different samples consisting of a matrix 11 and an island-like conductive dispersed phase 12 were prepared.
- the microvaristor 13 is not kneaded with this sample.
- the raw materials for the matrix 11 and the island-like conductive dispersed phase 12 the same materials as those used in Experiments 1 to 3 were used.
- FIG. 7 the result of having measured the volume resistivity of the whole resin material in each sample is shown.
- the volume resistivity is on the order of 10 8 ⁇ cm for the sample in which the volume ratio of the island-like conductive dispersed phase 12 is 16% by volume (hereinafter referred to as “16% sample”), while other than the 16% sample.
- the volume ratio of the island-like conductive dispersed phase 12 is 0.5 to 12% by volume
- Samples other than the 16% sample show no significant difference in volume resistivity depending on the volume ratio of the island-like conductive dispersed phase 12.
- the result of having measured the average particle diameter of the island-like electroconductive dispersion phase 12 in each sample is shown.
- the average particle diameter a value (median value) of 50% in the cumulative frequency distribution obtained by analyzing a scanning electron microscope (SEM) image of the resin material 10 was used.
- SEM scanning electron microscope
- the size of the island-like conductive dispersed phase is read from the two-dimensional image obtained by SEM, the actual size cannot be accurately measured if the shape is broken from the spherical shape. Theoretically, the size is infinite at 16%.
- the volume ratio of the island-like conductive dispersed phase 12 is set to avoid such a range. It is desirable to do.
- the number of island-shaped conductive dispersed phases is extremely small, the heterogeneity of the island-shaped conductive dispersed phases in the matrix increases.
- FIG. 8 shows that when the volume ratio of the island-shaped conductive dispersed phase 12 is close to 1%, the particle diameter is extremely reduced as the volume ratio decreases.
- the volume ratio of the island-like conductive dispersed phase is desirably 1% or more.
- the diameter r 2 of the island-like conductive dispersed phase 12 is determined by the conditions for kneading the first resin material and the second resin material during the production of the resin material 10 and the MFR (Melt of the first resin material and the second resin material). This is a value that depends on the flow rate) and surface energy.
- the total number of microvaristors 13 included in the entire resin material 10 is n 1
- the total number of island-like conductive dispersed phases 12 is n 2 .
- the average number of island-like conductive dispersed phases 12 in contact with one microvaristor 13 is n
- the ratio of the number of island-like conductive dispersed phases 12 in contact with the microvaristor 13 is p
- n p ⁇ n 2 / n 1 (1) It becomes.
- n 2 / n 1 is represented by x, y, r 1 , and r 2
- n 2 / n 1 (y / x) ⁇ (r 1 / r 2 ) 3 ... Equation (2) It becomes.
- Equation (5) (1 / p) ⁇ (r 2 / r 1 ) 2 ⁇ (y / x) ⁇ (r 1 / r 2 ) ⁇ (1 / p) ⁇ 4 ⁇ Equation (5) It becomes. Therefore, if the parameters p and ⁇ can be obtained by computer simulation or the like, the appropriate ranges of values of x, y, r 1 and r 2 can be obtained.
- the present invention is not limited to the above embodiment.
- the first resin material, the second resin material, and the material of the microvaristor 13 are not limited to those described in the embodiment, and various combinations described above can be used.
- the MFR that affects the particle size of the microvaristor 13 itself, the firing temperature that affects the particle size of the crystal grains in the microvaristor 13, or the particle size of the island-like conductive dispersed phase 12 is not limited to the above. .
- the fired microvaristor 13 is used as it is.
- a microvaristor obtained by coating ZnO nanorods with Co or Mn thermally diffused by heat treatment with bismuth oxide may be used. Thereby, the number of contact points (via the island-shaped conductive dispersed phase 12) between the microvaristors 13 can be increased as compared with the case where the microvaristors 13 are spherical.
- a part of the island-like conductive dispersed phase 12 may be replaced with particles made of conductive powder such as carbon. It is desirable to use particles having the same size as a microvaristor. In addition, it is desirable that the particles are spherical in that percolation hardly occurs.
- an insulating material having a high thermal conductivity shown below to the matrix, it is possible to equalize the heat in the matrix.
- examples of such an insulating material include aluminum nitride, aluminum oxide, silicon nitride, boron nitride, and magnesium oxide.
- the resin material 10 can be used in addition to the varistor by replacing the microvaristor 13 with another functional powder such as a high thermal conductivity insulating material.
Abstract
Description
a) 第1樹脂材料から成る絶縁性のマトリックスと、
b) 前記第1樹脂材料とは非相溶であって、且つ該第1樹脂材料よりも後記マイクロバリスタに対する濡れ性が高い導電性の第2樹脂材料から成り、前記マトリックス内に島状に分散し、全樹脂材料中の体積率が16%未満である島状導電性分散相と、
c) 非オーム性を有するセラミックス製の粒子であって、前記マトリックス内に分散し、前記島状導電性分散相を介して該粒子同士が電気的に接触しているマイクロバリスタと
を備えることを特徴とする。
高い導電率を得るには導電性粉末を高濃度に混ぜ込む必要があるが、微小な粉末は吸油量も大きくなるため高濃度混練は容易ではない。
そこで導電性粉末が極性を持った樹脂に偏在しやすいといった性質を利用し、本発明ではマトリックスとなる第1樹脂材料に無極性樹脂を、分散相となる第2樹脂材料に極性樹脂を使用し、これら無極性樹脂及び極性樹脂と導電性粉末を同時に混練する手法で、一旦マトリックスの樹脂に混ぜ込まれた導電性粉末が次第に分散相内に取り込まれ分散相に導電性を持たせるといった方法を採用することができる。そうすることで容易に高い導電率を持った分散相を得ることが可能となる。
第1樹脂材料である無極性樹脂には、ポリオレフィン系樹脂、ポリフェニレンスルファイド、ポリスチレン等を用いることができる。ここでポリオレフィン系樹脂として、ポリエチレン、ポリプロピレン等が挙げられる。第2樹脂材料となる極性樹脂には、ナイロン、ポリエチレンテレフタラート(PET)、ポリブチレンテレフタラート(PBT)、ポリカーボネート等が挙げられる。導電性粉末は、特段の処理を行うことなくそのまま用いることもできるが、導電性粉末の粒子の表面にカップリング剤によって表面処理を行い、極性樹脂になじみやすくしたものを用いてもよい。
また、導電性粉末には、カーボンの粉末、金、銀、銅、ニッケル、パラジウム、白金などの金属粉末、酸化スズや酸化物超伝導材料などの導電性酸化物の粉末、炭化ケイ素などの導電性炭化物の粉末、窒化チタンなどの導電性窒化物の粉末などを用いることができる。
なお、第1樹脂材料内に微量の導電性粉末が残留することがあるが、そのような微量の導電性粉末によってパーコレーションが生じることはないため、バリスタとしての特性は維持される。
[実験1]
実験1では、材料に関する以下の(1)~(3)のパラメータが異なる4種類の試料を作製した。なお、マイクロバリスタ13は、目の大きさが45μmである篩を通過したものを使用した。
<材料パラメータ>
(1) 原料全体に占める第2樹脂材料の濃度(体積百分率)
(2) カーボンが全て第2樹脂材料に偏在したと想定した場合における、第2樹脂材料に占めるカーボンの濃度(重量百分率)
(3) 原料全体に占めるマイクロバリスタ13の濃度(体積百分率)
各試料における材料パラメータの値を表1に示す。
次に、実験1よりも第2樹脂材料の含有率が高い試料を作製し、V-I特性を測定した結果を示す。試料の作製の際には、まず、ポリエチレンを91.3体積%、ナイロンを8.0体積%、カーボンを0.680体積%(有効数字の関係上、これらの数値の合計は100体積%にはならない)、200℃で同時混練することにより、ポリマーアロイを作製した。次に、このポリマーアロイとZnOのマイクロバリスタ13を表2に示した体積割合で190℃の温度条件において混合することにより、試料を得た。マイクロバリスタ13は、篩にかけることにより、粒径がそれぞれ10~20μm、20~30μm、及び30~44μmの範囲内にある3種類のものを用いた。
次に、表3に示すようにポリエチレン、ナイロン、及びカーボンの体積率が異なる3種類のポリマーアロイを作製し、それらポリマーアロイをそれぞれZnOのマイクロバリスタ13と混合することにより、3種類の試料(試料21~23)を作製した。ポリマーアロイの作製時には200℃で各材料を混合した。また、マイクロバリスタは粒径10~20μmのものを用い、ポリマーアロイとマイクロバリスタ13は190℃で混合し、その混合比は、ポリマーアロイを70体積%、マイクロバリスタ13を30体積%とした。なお、これら3種類の試料のうちの1つ(表3中の試料23)は、表2の試料17と同じものである。
次に、島状導電性分散相12の濃度の上限値、及び望ましい下限値を定めるために、島状導電性分散相12の体積率(濃度)が0.5体積%~16体積%の範囲内で異なる、マトリックス11と島状導電性分散相12から成る試料を作製した。なお、この試料にはマイクロバリスタ13は混練されていない。マトリックス11、島状導電性分散相12の原料には、実験1~3と同じものを用いた。
一方、島状導電性分散相が極端に少ないと、マトリックス内における島状導電性分散相の不均質性が増大する。図8では島状導電性分散相12の体積率が1%付近になると体積率の減少に伴い粒径が極端に減少することが示されている。
このように1%未満の領域では島状導電性分散相の体積率がわずかに変化しただけで粒径が大幅に変化してしまうため、島状導電性分散相の粒径のコントロールは難しく、島状導電性分散相の不均質性はより顕著になってしまう。そのため、島状導電性分散相の体積率は1%以上であることが望ましい。
n=p・n2/n1 …式(1)
となる。ここで、n2/n1をx, y, r1, 及びr2で表すと、
n2/n1=(y/x)・(r1/r2)3 …式(2)
となる。1個のマイクロバリスタ13に平均で1個以上の島状導電性分散相12が接触することが望ましいことから、式(1)及び(2)より、
1≦n=p・n2/n1=p・(y/x)・(r1/r2)3、
1/p≦n2/n1=(y/x)・(r1/r2)3 …式(3)
となる。
φ>n・S2/S1=(n・πr2 2)/(4πr1 2) …式(4)
である。
(1/p)・(r2/r1)2≦(y/x)・(r1/r2)<(1/p)・4φ …式(5)
となる。従って、コンピュータシミュレーション等によりパラメータp及びφを求めることができれば、x、y、r1及びr2の適切な値の範囲を求めることができる。
11…マトリックス
12…島状導電性分散相
13…マイクロバリスタ
131…ZnO粒子
132…粒界層
19…電流
Claims (10)
- 電圧の増加に伴って急激に電流が増加する非オーム性を有する樹脂材料であって、
a) 第1樹脂材料から成る絶縁性のマトリックスと、
b) 前記第1樹脂材料とは非相溶であって、且つ該第1樹脂材料よりも後記マイクロバリスタに対する濡れ性が高い導電性の第2樹脂材料から成り、前記マトリックス内に島状に分散し、全樹脂材料中の体積率が16%未満である島状導電性分散相と、
c) 非オーム性を有するセラミックス製の粒子であって、前記マトリックス内に分散し、前記島状導電性分散相を介して該粒子同士が電気的に接触しているマイクロバリスタと
を備えることを特徴とする樹脂材料。 - 全樹脂材料中における前記島状導電性分散相の体積率が1%以上であることを特徴とする請求項1に記載の樹脂材料。
- 前記マイクロバリスタの少なくとも一部が非球形であることを特徴とする請求項1又は2に記載の樹脂材料。
- 前記第2樹脂材料が、主相樹脂に導電性粉末を混入させたものであることを特徴とする請求項1~3のいずれかに記載の樹脂材料。
- 前記第1樹脂材料が無極性樹脂であり、前記主相樹脂が極性樹脂であることを特徴とする請求項4に記載の樹脂材料。
- 前記第1樹脂材料がポリエチレン、ポリプロピレン、ポリフェニレンスルファイド、ポリスチレンから選択される樹脂であり、前記主相樹脂がナイロン、ポリエチレンテレフタラート、ポリブチレンテレフタラート、ポリカーボネートから選択される樹脂であり、前記導電性粉末がカーボン、金、銀、銅、ニッケル、パラジウム、白金、酸化スズ、酸化物超伝導材料、炭化ケイ素、窒化チタンから選択される材料から成るものであることを特徴とする請求項5に記載の樹脂材料。
- 電圧の増加に伴って急激に電流が増加する非オーム性を有する樹脂材料の製造方法であって、
絶縁性の第1樹脂材料と、該第1樹脂材料とは非相溶であって該第1樹脂材料よりもマイクロバリスタに対する濡れ性が高い導電性の第2樹脂材料を混練し、それらの混練物とマイクロバリスタを混練することを特徴とする樹脂材料製造方法。 - 電圧の増加に伴って急激に電流が増加する非オーム性を有する樹脂材料の製造方法であって、
絶縁性であって無極性である第1樹脂材料と、第2樹脂材料の主原料である主相樹脂と、導電性粉末を同時に混練し、それらの混練物とマイクロバリスタを混練することを特徴とする樹脂材料製造方法。 - 請求項1~6のいずれかに記載の樹脂材料が所定の形状に成形されていることを特徴とする非オーム性抵抗体。
- 前記所定の形状が、電子部品又は電気機器のハウジング、電気回路用の基板、電気ケーブルのシース及び電線の被覆のうちのいずれかの形状であることを特徴とする請求項9に記載の非オーム性抵抗体。
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