Resin material having non-OHMIC properties, method for producing same, and non-OHMIC resistor using said resin material

Abstract

Provided is a resin material having non-ohmic properties which has favorable characteristics as a varistor and has a high degree of molding freedom and impact resistance. A resin material 10 comprises: an insulating matrix 11 made of a first resin material; an island-form conductive dispersed phase 12 made of a conductive second resin material which is incompatible with the first resin material and is more wettable to a microvaristor 13 described later than the first resin material is, wherein the island-form conductive dispersed phase is dispersed in an island form in the matrix and has a volume ratio of less than 16% in the whole resin material; and a microvaristor 13 comprising ceramic particles having non-ohmic properties, wherein the ceramic particles are dispersed in the matrix 11 and electrically contacted with each other via the island-form conductive dispersed phase 12.

Claims

1. A resin material having non-ohmic properties in which current rapidly increases with increase in voltage, comprising: a) an insulating matrix made of a first resin material; b) an island-form conductive dispersed phase made of a conductive second resin material which is incompatible with the first resin material and is more wettable to a microvaristor than the first resin material is, wherein the island-form conductive dispersed phase is dispersed in an island form in the matrix and has a volume ratio of less than 16% in the whole resin material; and c) the microvaristor comprising ceramic particles having non-ohmic properties, wherein the ceramic particles are dispersed in the matrix and electrically contacted with each other via the island-form conductive dispersed phase.

2. The resin material according to claim 1, wherein the volume ratio of the island-form conductive dispersed phase in the whole resin material is 1% or more.

3. The resin material according to claim 1, wherein at least a portion of the microvaristor particles is nonspherical.

4. The resin material according to claim 1, wherein the second resin material is a main-phase resin in which a conductive powder is mixed.

5. The resin material according to claim 4, wherein the first resin material is a nonpolar resin, and the main-phase resin is a polar resin.

6. The resin material according to claim 5, wherein the first resin material is a resin selected from polyethylene, polypropylene, polyphenylene sulfide, and polystyrene, the main-phase resin is a resin selected from nylon, polyethylene terephthalate, polybutylene terephthalate, and polycarbonate, and the conductive powder is made of a material selected from carbon, gold, silver, copper, nickel, palladium, platinum, tin oxide, an oxide superconductive material, silicon carbide, and titanium nitride.

7. A non-ohmic resistor obtained by molding a resin material according to claim 1 into a predetermined shape.

8. The non-ohmic resistor according to claim 7, wherein the predetermined shape is a shape of any of a housing of an electronic component or electrical equipment, a board for an electric circuit, a sheath of an electric cable, and a coating of an electric wire.

9. A method for producing a resin material having non-ohmic properties in which current rapidly increases with increase in voltage, comprising kneading an insulating first resin material with a conductive second resin material which is incompatible with the first resin material and is more wettable to a microvaristor than the first resin material is, and kneading the resulting kneaded product with a microvaristor.

10. A method for producing a resin material having non-ohmic properties in which current rapidly increases with increase in voltage, comprising kneading an insulating and nonpolar first resin material with a main-phase resin as a main raw material for a second resin material and a conductive powder at a same time and kneading the resulting kneaded product with a microvaristor.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a flowchart showing a method for producing a resin material, which is one Example of the present invention.

(2) FIG. 2A is a schematic diagram of the resin material of the present Example. FIG. 2B is a diagram showing a main current pathway in the resin material.

(3) FIG. 3 is a graph showing results of measuring the voltage-current (V-I) characteristics of samples prepared in Experiment 1.

(4) FIG. 4 is a graph showing results of measuring the V-I characteristics of samples prepared in Experiment 2 compared on the basis of difference in microvaristor particle size.

(5) FIG. 5 is a graph showing the results of measuring the V-I characteristics of samples prepared in Experiment 2 compared on the basis of volume ratio of the microvaristor.

(6) FIG. 6 is a graph showing results of measuring the V-I characteristics of samples prepared in Experiment 3.

(7) FIG. 7 is a graph showing results of measuring volume resistivity of the whole resin material as to a plurality of samples differing in the volume ratio of an island-form conductive dispersed phase 12, prepared in Experiment 4.

(8) FIG. 8 is a graph showing results of measuring the average particle size (median) of the island-form conductive dispersed phase 12 as to the samples prepared in Experiment 4.

DESCRIPTION OF EMBODIMENTS

(9) Examples of the resin material having non-ohmic properties (hereinafter, simply referred to as the resin material) and the method for producing the same, and the non-ohmic resistor according to the present invention will be described with reference to FIGS. 1 to 8.

EXAMPLES

(10) First, Example of the method for producing a resin material and a non-ohmic resistor will be described with reference to FIG. 1. In the present Example, a polyethylene was used as the first resin material; nylon (main-phase resin) in which a carbon powder (conductive powder) was mixed was used as the second resin material; and polycrystal particles obtained by the sintering reaction of ZnO with an additive was used as the microvaristor. The carbon powder may be used after hydrophilic surface treatment of the particles with a coupling agent, but may be used as it is without such treatment. The microvaristor was obtained by a general spray drying method and used after being sintered and passing through a sieve having a mesh (mentioned later) of a predetermined size. The volume of the second resin material was set to less than 16% of the total volume of the second resin material and the first resin material.

(11) The first resin material and the second resin material are kneaded at a temperature of 190 to 230 C. (step S1). In this operation, two-stage mixing of mixing the main-phase resin and the conductive powder to prepare the second resin material and then mixing the second resin material with the first resin material may be carried out. Alternatively, the kneading of three materials, i.e., the first resin material, the main-phase resin, and the conductive powder, at the same time can shorten the amount of time and, furthermore, can easily yield a dispersed phase having a high density of the conductive powder.

(12) Then, the obtained mixture is molded into pellet (step S2). Next, this pellet is kneaded with the microvaristor (step S3). In this way, a resin material 10 of the present Example is obtained. Then, a cross-linking agent is added thereto, followed by injection molding to obtain a non-ohmic resistor (step S4).

(13) Since polyethylene used as the first resin material and nylon used as the main-phase resin of the second resin material are incompatible with each other, the first resin material and the second resin material are separate from each other even after mixing. Also, since polyethylene is a nonpolar resin and nylon is a polar resin, the conductive material carbon is unevenly distributed in the nylon. As a result, in the obtained resin material 10, as shown in FIG. 2A, an island-form conductive dispersed phase 12 made of the second resin material having a smaller volume than that of the first resin material is formed in a dispersed manner in a matrix 11 made of the first resin material.

(14) In the resin material 10, as shown in FIG. 2B, the island-form conductive dispersed phase 12 and a microvaristor 13 are contacted with each other to form a pathway of current 19 where the particles of the microvaristor 13 are electrically connected with each other via the island-form conductive dispersed phase 12. The electrical characteristics (i.e., non-ohmic properties) of the resin material 10 are exerted when the current flows in the interface between ZnO particles 131 and a grain boundary layer 132 in the microvaristor 13.

(15) In the resin material 10 of the present Example, nylon as the second resin material is more wettable to the microvaristor 13 than polyethylene as the first resin material is. This prevents the matrix 11 from entering between the microvaristor 13 and the island-form conductive dispersed phase 12. The particles of this microvaristor 13 are electrically contacted with each other via the island-form conductive dispersed phase 12. In this way, the resin material 10 of the present Example produces characteristics of excellent surge resistance to large current.

(16) The wettability of polyethylene as the first resin material to the microvaristor 13 is lower than that of the second resin material, as mentioned above, but is not low enough to be rejected by the surface of the microvaristor 13. Hence, the matrix 11 can cover the surface of the microvaristor 13 at sites other than the points of contact where the particles of the microvaristor 13 are contacted with each other via the island-form conductive dispersed phase 12. This can prevent the current from flowing in the surface layer of the microvaristor 13. Thus, favorable insulating characteristics against small current can be obtained.

(17) Since the island-form conductive dispersed phase 12 has nearly spherical particles, percolation rarely occurs between the particles of the island-form conductive dispersed phase 12. Thus, the island-form conductive dispersed phase 12 can have a high density. Hence, the microvaristor 13, which is solid matter, can have a small volume ratio. This permits injection molding and can enhance the degree of molding freedom. This can also enhance impact resistance.

(18) Hereinafter, results of experiments conducted on samples prepared in the present Example will be described.

Experiment 1

(19) In Experiment 1, four samples differing in parameters (1) to (3) related to materials given below were prepared. The microvaristor 13 was used after passing through a sieve having a mesh size of 45 m.

(20) <Material Parameter>

(21) (1) Density (volume percentage) of the second resin material occupying the whole raw material

(22) (2) Density (weight percentage) of carbon occupying the second resin material on the assumption that all particles of carbon are unevenly distributed in the second resin material

(23) (3) Density (volume percentage) of the microvaristor 13 occupying the whole raw material

(24) The values of the material parameters of each sample are shown in Table 1.

(25) TABLE-US-00001 TABLE 1 (1) (2) (3) Second resin material Carbon occupying -Varistor occupying second occupying whole Sample whole raw material resin material raw material No. [vol. %] [wt. %] [vol. %] 1 1 15 30 2 3 15 40 3 2 15 40 4 3 20 38 *-varistor = microvaristor

(26) The V-I characteristics were measured for each sample of Table 1. In the present Example, direct-current voltage was applied to the sample when the obtained current fell within the range of approximately 110.sup.2 A/10 cm.sup.2 or lower, and impulse voltage was applied to the sample so as to attain the flow of large current when the current fell within the range of higher than approximately 110.sup.2 A/10 cm.sup.2. The measurement results are shown in FIG. 3. All of the samples have a voltage value as high as tens to hundreds of V per 1 mm even when the current is almost 0. This means that these samples have favorable insulating characteristics against small current. In FIG. 3, the current is indicated at a logarithm scale, whereas the voltage is indicated at a linear scale. This diagram means that a rise in voltage is suppressed even if the current is increased. Specifically, these measurement results indicate that samples 1 to 4 have non-ohmic properties.

Experiment 2

(27) Next, samples having a higher second resin material content than that of the samples of Experiment 1 were prepared, and results of measuring their V-I characteristics are shown. For sample preparation, first, 91.3% by volume of polyethylene, 8.0% by volume of nylon, and 0.680% by volume of carbon (the total of these numeric values is not 100% by volume in terms of the relationship of significant figures) were kneaded at the same time at 200 C. to prepare a polymer alloy. Next, this polymer alloy was mixed with a ZnO microvaristor 13 at a volume ratio shown in Table 2 under temperature conditions of 190 C. to obtain each sample. The microvaristor 13 used was three types having a particle size that fell within the range of 10 to 20 m, 20 to 30 m, or 30 to 44 m by sieving.

(28) TABLE-US-00002 TABLE 2 Nylon Microvaristor Polymer alloy occupying occupying Particle occupying whole whole whole size of Sample raw material raw material raw material microvaristor No. [vol. %] [vol. %] [vol. %] [m] 11 90 7.2 10 10-20 12 90 7.2 10 20-30 13 90 7.2 10 30-44 14 80 6.4 20 10-20 15 80 6.4 20 20-30 16 80 6.4 20 30-44 17 70 5.6 30 10-20 18 70 5.6 30 20-30 19 70 5.6 30 30-44

(29) The results of the experiment of the V-I characteristics are shown in the graphs of FIGS. 4 and 5. In these graphs, the current and the voltage are both indicated at a logarithm scale. In the case where the V-I characteristics can be represented by I=(V/C).sup. (: index of non-ohmic properties, C: constant), the graph has a linear form, and a reciprocal of the slope of the line corresponds to the index of non-ohmic properties. A larger index of non-ohmic properties means better non-ohmic properties in which a rise in voltage is suppressed even if the current is increased.

(30) In FIG. 4, samples having an equal volume ratio of the microvaristor 13 are summarized in one graph (the number of graphs: 3). In each graph, difference in V-I characteristics depending on difference in the particle size of the microvaristor 13 is shown. From the graphs of FIG. 4, when the samples having an equal volume ratio of the microvaristor 13 are compared, the sample having the intermediate particle size of 20 to 30 m of the microvaristor 13 among the three types has the best insulating characteristics (highest voltage) against small current and a large index of non-ohmic properties in all cases.

(31) In FIG. 5, samples having an equal particle size of the microvaristor 13 are summarized in one graph (the number of graphs: 3). In each graph, difference in V-I characteristics depending on difference in the volume ratio of the microvaristor 13 is shown. From the graphs of FIG. 5, when the samples having an equal particle size of the microvaristor 13 are compared, a lower volume ratio offers better insulating characteristics (higher voltage) against small current in all cases within the volume ratio range (10 to 30% by volume) of the microvaristor 13 in the prepared samples. The sample having the intermediate volume ratio (20% by volume) of the microvaristor 13 among the three types has the largest index of non-ohmic properties.

Experiment 3

(32) Next, as shown in Table 3, three polymer alloys differing in the volume ratios of polyethylene, nylon, and carbon were prepared, and these polymer alloys were each mixed with a ZnO microvaristor 13 to prepare three samples (samples 21 to 23). For polymer alloy preparation, the materials were mixed at 200 C. The microvaristor used had a particle size of 10 to 20 m. The microvaristor 13 and each polymer alloy were mixed at 190 C., and the mixing ratio thereof was set to 70% by volume of the polymer alloy and 30% by volume of the microvaristor 13. One (sample 23 in Table 3) of these three samples is the same as the sample 17 of Table 2.

(33) TABLE-US-00003 TABLE 3 Polyethylene occupying Nylon occupying Carbon occupying Sample polymer alloy polymer alloy polymer alloy No. [vol. %] [vol. %] [vol. %] 21 95.3 4.0 0.68 22 93.3 6.0 0.68 23 (17) 91.3 8.0 0.68 * The total of volume contents in each sample is not 100 vol. % in terms of the relationship of significant figures.

(34) The results of the experiment of the V-I characteristics of the samples 21 to 23 are shown in the graph of FIG. 6. As seen from these experiment results, a smaller content of nylon offers a higher voltage against small current and a larger index of non-ohmic properties.

Experiment 4

(35) Next, in order to determine the upper limit value and desirable lower limit value of the density of the island-form conductive dispersed phase 12, samples each composed of the matrix 11 and the island-form conductive dispersed phase 12 were prepared such that these samples differed in the volume ratio (density) of the island-form conductive dispersed phase 12 within the range of 0.5% by volume to 16% by volume. The microvaristor 13 was not kneaded into these samples. The same raw materials as in Experiments 1 to 3 were used for the matrix 11 and the island-form conductive dispersed phase 12.

(36) FIG. 7 shows results of measuring the volume resistivity of the whole resin material in each sample. The volume resistivity was the order of 10.sup.8 cm for the sample having a volume ratio of 16% by volume of the island-form conductive dispersed phase 12 (hereinafter, referred to as the 16% sample), whereas a volume resistivity of 10.sup.15 to 10.sup.17 cm, which was 7 to 9 number of digits higher, was obtained for the samples (volume ratio of the island-form conductive dispersed phase 12:0.5 to 12% by volume) other than the 16% sample. Significant difference in volume resistivity depending on the volume ratio of the island-form conductive dispersed phase 12 is not observed among the samples other than the 16% sample. These results suggest that the particles of the island-form conductive dispersed phase 12 are electrically separate from each other in the samples other than the 16% sample, whereas percolation occurs due to the island-form conductive dispersed phase 12 in the 16% sample.

(37) FIG. 8 shows results of measuring the average particle size of the island-form conductive dispersed phase 12 in each sample. In this context, the average particle size used was a value of 50% (median) in a cumulative frequency distribution determined by analyzing the scanning electron microscope (SEM) image of the resin material 10. A larger volume ratio of the island-form conductive dispersed phase 12 offers a larger average particle size. In the present Example, the particle sizes of the island-form conductive dispersed phase are read from the two-dimensional image of SEM. If a spherical shape is deformed, the actual size cannot ben correctly measured. Theoretically, the size is infinite at 16%. Percolation might occur due to the island-form conductive dispersed phase 12 in a region around 16% at which the average particle size rapidly increases. It is therefore desirable to set the volume ratio of the island-form conductive dispersed phase 12 outside such a range.

(38) On the other hand, an extremely small ratio of the island-form conductive dispersed phase increases the heterogeneity of the island-form conductive dispersed phase in the matrix. FIG. 8 shows that when the volume ratio of the island-form conductive dispersed phase 12 is close to 1%, the particle size is extremely decreased with decrease in volume ratio.

(39) In a region less than 1%, the particle size is drastically changed, as described above, with slight change in the volume ratio of the island-form conductive dispersed phase. It is therefore difficult to control the particle size of the island-form conductive dispersed phase. This renders the heterogeneity of the island-form conductive dispersed phase more marked. It is therefore desirable that the volume ratio of the island-form conductive dispersed phase is 1% or more.

(40) Next, the relationship of a density x of the microvaristor 13, a density y of the island-form conductive dispersed phase 12 (second resin material), a radius r.sub.1 of the microvaristor 13, and radius r.sub.2 of the island-form conductive dispersed phase 12 will be discussed theoretically. The radius r.sub.2 of the island-form conductive dispersed phase 12 is a value that depends on the kneading conditions for the first resin material and the second resin material during the preparation of the resin material 10, and the MFR (melt flow rate: fluidity index) and surface energy of the first resin material and the second resin material.

(41) First, the total number of particles of the microvaristor 13 contained in the whole resin material 10 is defined as n.sub.1, and the total number of particles of the island-form conductive dispersed phase 12 is defined as n.sub.2. The average number of particles of the island-form conductive dispersed phase 12 contacted with one particle of the microvaristor 13 is defined as n, and the ratio of the number of particles of the island-form conductive dispersed phase 12 contacted with the microvaristor 13 to the total number of particles of the island-form conductive dispersed phase 12 is defined as p. The following expression holds:
n=p.Math.n.sub.2/n.sub.1Expression(1)
In this context, n.sub.2/n.sub.1 is indicated by x, y, r.sub.1, and r.sub.2 as follows:
n.sub.2/n.sub.1=(y/x).Math.(r.sub.1/r.sub.2).sup.3Expression(2)

(42) It is desirable that one particle of the microvaristor 13 should be contacted with one or more particles on average of the island-form conductive dispersed phase 12. Therefore, from the expressions (1) and (2), the following expression holds:
1n=p.Math.n.sub.2/n.sub.1=p.Math.(y/x).Math.(r.sub.1/r.sub.2).sup.3,
1/pn.sub.2/n.sub.1=(y/x).Math.(r.sub.1/r.sub.2).sup.3Expression(3)

(43) Next, a model is assumed in which the particles of the microvaristor 13 are approximated to spheres each having the radius r.sub.1, the particles of the island-form conductive dispersed phase 12 are approximated to circles each having the radius r.sub.2, and the surface of each of these spheres is filled with a plurality of the circles. When the ratio of an area S.sub.2 attached with the circles to a surface area S.sub.1 of the sphere exceeds a given value , percolation resulting from the continuous linkage of a large number of particles of the microvaristor 13 via the island-form conductive dispersed phase 12 occurs to form a current pathway by which characteristics as a varistor can be exerted. The condition thereof is
>n.Math.S.sub.2/S.sub.1=(n.Math.r.sub.2.sup.2)/(4r.sub.1.sup.2)Expression(4)

(44) From the Expressions (1), (3), and (4), the following expression holds:
(1/p).Math.(r.sub.2/r.sub.1).sup.2(y/x).Math.(r.sub.1/r.sub.2)<(1/p).Math.4Expression(5)
Thus, the appropriate ranges of the values x, y, r.sub.1, and r.sub.2 can be determined provided that the parameters p and can be determined by computer simulation or the like.

(45) The present invention is not intended to be limited by Examples described above. For example, the materials for the first resin material, the second resin material, and the microvaristor 13 are not limited to those described in Examples, and various combinations of the materials mentioned above can be used. The firing temperature that defines the particle size of the microvaristor 13 itself and the particle size of crystalline grains in the microvaristor 13 or the MFR that defines the particle size of the island-form conductive dispersed phase 12 is not limited to those described above.

(46) In Examples described above, the fired microvaristor 13 was used as it was. Alternatively, a microvaristor obtained by coating with bismuth oxide or a ZnO nanorod in which Co or Mn thermally diffused by heat treatment may be used. This can increase the number of points of contact between the particles of the microvaristor 13 (via the island-form conductive dispersed phase 12) as compared with spherical particles of the microvaristor 13.

(47) A portion of the particles of the island-form conductive dispersed phase 12 may be replaced with particles composed of a conductive powder such as carbon or the like. For these particles, it is desirable to use particles having a size equivalent to the microvaristor particles. It is also desirable that these particles should be spherical, because percolation rarely occurs.

(48) Thermal uniformity within the matrix can be achieved by adding an insulating material having a high thermal conductivity as described below, together with the microvaristor to the matrix. Examples of such an insulating material include aluminum nitride, aluminum oxide, silicon nitride, boron nitride, and magnesium oxide or the like. This can enhance the characteristics as a varistor.

(49) Furthermore, the resin material 10 can be used for purposes other than varistors by replacing the microvaristor 13 with any of other functional powders such as highly thermally conductive insulating materials or the like.

REFERENCE SIGNS LIST

(50) 10 . . . Resin material 11 . . . Matrix 12 . . . Island-form conductive dispersed phase 13 . . . Microvaristor 131 . . . ZnO particle 132 . . . Grain boundary layer 19 . . . Current