JPH02504333A - conductive polymer composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] conductive polymer composition Kadan 1 field of invention The present invention provides a conductive polymer comprising particulate conductive fillers dispersed in an organic polymer. mer compositions.

Related technology Particulate conductive particles dispersed in organic polymers (this term includes polysiloxanes) Sexual fillers are known. Such compositions are known as "conductive polymer compositions". It is being STATEMENT REGARDING CONDUCTIVE POLYMER COMPOSITIONS AND DEVICES COMPRISING THE SAME Examples of contributions include: United States Patent No. 2,9 52,761.2.978,665.3.243.753.3,351,882 ．． 3,571.777.3,591,526.3.757.086.3.793 ゜716.3,823,217.3,858,144.3,861,029.3 ．． 950,604.4,017,715.4. o72. s4g, 4,085.2 86.4,117,312.4,177.376.4.177゜446.4,1 88,276.4,237,441.4,242,573.4.246,468 ．． 4.250.400.4.252.692.4, 255.698.4, 271 , 350.4, 272, 471.4, 304°987.4, 309, 596.4 ,309,5971.4,314,230.4.314,231.4,315, 237.4,317. ．． 027.4,318.881.4,327,351,4 ,330,704.4,334゜351.4,352,083.4,361,7 99.4,388,607.4.398,084.4,413,301,4,4 25,397.4,426.339.4,426,633.4,427,877 ．． 4,435°639.4,429,216.4,442,139.4,459 ,473.4.470,898.4,481,498.4,476.450.4 ,502,929.4,514,620,4,517,449.4,529°8 66.4, 534, 889.4, 545, 926.4, 562, 313.4.5 70,055.4,582,983.4,591,700,4,624.990 and No. 4,661,687; Klason and Kubat Kubat), Journal of Applied Polymer Science (J. Applied Polymer 5science) 19+813-815(1 975); Narkis et al., Polymer Engineering and 0 Science (Polymer Engineering and Science nce) 18+ 649-653 (1978); Japanese Patent Publication 51-3298 3.51-32984.57-228128.60-115678 and 61- 123665; West German Patent Publication No. 2,821,799; European Patent Application Publication No. 38,718; published as European Patent Application Publication No. 63°440 European Patent Application No. 656,046, now abandoned. United States Patent Application No. 30, published as Patent Application Publication No. 74.281 0,709 and 423,589, U.S. Patent No. 4.700,0 No. 54, now abandoned U.S. Patent Application No. 780.524, U.S. Pat. United States Patent No. 4.724.417, United States Patent Application No. 720,11 No. 7, American patent application published as European Patent Application Publication No. 157,759. US Patent Application No. 720.118, European Patent Application Publication No. 220,003 No. 784,288, published as U.S. Pat. Grant No. 4.689°475, United States Patent Application No. 913.290.024 , 783.021.820, 061.353, 061,354, o64. No. 287 and No. 061.259. The descriptions in these documents are cited as references.

Conductive polymer compositions are used in electrically conductive elements such as heaters and circuit protection devices. shielding or other equipment for high voltage cables and other high voltage electrical equipment. is used as a stress grading element and as an antistatic material . These are PTC (positive temperature coefficient), ZTC (zero temperature coefficient) or NTC (negative temperature coefficient). degree coefficient) behavior. The phrase "rprc behavior" refers to operating temperature an R14 value of at least 2.5 or is at least 10 R1°. value, preferably both, or at least 6 As used herein to mean a composition preferably having an R5° value of are doing. Here, R14 is in the temperature range of 14°C where the increase in resistivity is the largest. It represents the ratio of the initial and final resistivity, RIo. is 100' where the resistivity increase is the largest RmD represents the ratio of the initial and final resistivity in the temperature range of C, where RmD is the resistivity increase It represents the ratio of initial and final resistivity in the largest temperature range of 30°C. “NTC The phrase "behavior" refers to a composition that does not exhibit PTC behavior over the operating temperature range. As used herein to mean, in the operating temperature range, at 0°C. whose resistivity is at least twice, preferably at least 5 times, the resistivity at high temperature. be. The phrase "rZTC behavior" as used herein refers to PTC behavior or N eZTC composition refers to a composition that does not exhibit any of the C behavior. It may exhibit PTC behavior at temperatures above the temperature range.

In conventional methods of making conductive bomber compositions, heated polymer matrices Disperse homogeneous conductive granular filler (in this specification, π homogeneous filler) The term refers to fillers in which each particle has a single phase, such as carbon black, means graphite, metal, metal oxide, ceramic or other conductive inorganic material. ) . Although this conventional method is used to produce a variety of manufactured goods, polymer matrices Reproducible results in a range of resistivities for many combinations of glass and conductive fillers. It is difficult to obtain effective results. Because the "filling curve", i.e., combined with the filler volume % Graphs showing the relationship between the resistivity of the composition and the logarithm of the resistivity of the matrix polymer are always It has a short, fairly flat upper section corresponding to the drag, then drops off steeply; Furthermore, the resistivity of the composition becomes flat as it approaches its asymptotic value. such a filling The curve is shown as curve 1 in FIG. Desired resistivity is in the steep part of the filling curve In some cases, small changes in processing conditions or starting materials can significantly change the resistivity of the manufactured product. become For example, a conductive polymer can be used as a layered PTC heating element sandwiched between layered electrodes. It is powered by a fairly high voltage (typically over 100V) power supply. Carbon black filled polymer used in pressure applied PTC heaters - For PTC compositions, resistivity in the steep part of the filling curve is desirable.

For such use, especially if the composition is first energized, it may cause damage. resistivity of 103 to 10@Ω・cm to avoid high “inrush” currents. (23°C) is preferred.

Other known methods of making conductive polymer compositions include carbon black and powdered polyester. Dry mix the polymers to ensure that the polymer particles coalesce but do not lose their identity. sintering the mixture. Such a method uses ultra-high molecular weight polyethylene. For the production of ZTC conductive polymers comprising any non-melt processable polymers (See examples in U.S. Patent Application No. 720,117). However, it is not applicable in general.

United States Patent No. 3,591,526 (Kawashima), Special Publication No. 51-329 No. 83 and No. 51-32984, the conductive filler is not a homogeneous material, but a carbon material. -bon black is melt mixed with a thermoplastic polymer to make a PTC composition, and then A conductive bottle is a composite filler manufactured by casting a mixture into a fine shape. mer compositions are disclosed. The composite fillers described in these documents have high content. The composition contains a high content of composite filler.

As a result, the composition (carbon black-containing conductive polyester) 100 to 200 Ω・cIll or less at 23°C, and as a function of the resistivity of the filler itself, about 10 times the resistivity of the filler or more. It has a low resistivity of: The composition is described as being useful as a resistor. .

We conducted extensive research on conductive polymer compositions as agents. Composite filler means that each particle granules comprising an organic polymer and a homogeneous conductive filler dispersed therein. means a conductive filler. Therefore, the conductive polymer composition is (a) a first organic polymer (also referred to herein as matrix polymer); (b) each particle comprises a second organic polymer (herein filler polymer) and a second particle dispersed in a second polymer. It consists of conductive fillers that are dispersed within a matrix and have unique properties within them. First particulate conductive filler (also referred to herein as composite filler) It consists of

The inventors aim to combine particles so that they coalesce without completely losing their identity. A muddler comprising sintered organic polymer particles.

conducted intensive research on conductive polymers in which granular conductive fillers are dispersed in .

In conducting this research, the inventors used U.S. Patent No. 3. +91, No. 526 and Japanese Patent Publications No. 51-32983 and 51-32984 or other subordinates. We have made a very interesting and useful discovery not described or suggested in the prior art.

These discoveries include:

(1) The filling curve of the composite filler has a different shape from the conventional filling curve.

In particular, the steepest part of the curve has a gentler, substantially flat slope, e.g. = 0.2 It is interrupted by the middle part of the slope from 5 to 0. Such a filling curve is shown in Figure 1. Shown as curve 2. This discovery was made with much higher reproducibility than previously possible. Producing conductive polymer compositions with resistivities that fall in the steep part of conventional filling curves make it possible to build The composition produced in this way approaches an asymptotic value. U.S. Pat. No. 3,591., which is a low, fairly flat portion of the filling curve. No. 526 (Kawashima) and Special Publication No. 51-32893 and 51-32894 have a much higher resistivity than those described in No. In such a filling curve a conductive polymer composition that falls within or is more conductive than the intermediate portion; Conductive polymer compositions, especially conductive fillers, forming part of a filling curve such as Conductive polymer compositions in which is a composite filler are novel and form part of the present invention. do. The middle part of the filling curve is at least 100 times the resistivity of the composite filler, typically occurs at a value that is at least 1000 times greater, for example 1000 to 10000 times greater.

Such a filling curve is a matrix where two different conduction mechanisms are possible. Resulting from the use of a trix polymer/conductive filler combination.

One mechanism is that until a conductive path is no longer formed by the mechanism, As the filler content increases, one is superior to the other at lower filler content beyond the middle part. force (or the only mechanism) that causes rapid changes in resistivity. on the other hand mechanism until the conductive path is no longer formed by the other mechanism. As the filler content increases, the filler content reaches a high level beyond the middle part. Provide much less conductive path (or no conductive path at all) until ). At that level, the other mechanism causes the resistivity to change rapidly again. Guidance At the point where no electrical path is formed, the resistivity tends toward that of the filler itself.

(2) ensuring that the composite filler retains its identity in the composition; is desirable, and the smaller the amount of the second conductive filler that escapes into the matrix, the better. It's good. Therefore, matrices, composite fillers and methods of mixing them It is important to be aware of this when choosing. Said Kawashima and Tokuko The measures suggested in the Sho bulletin are inadequate and unsuitable for achieving the desired results. /or exclude many preferred combinations of substances and/or eliminate many preferred combinations of substances; Eliminate unsuitable preparation methods. Ensure that the secondary filler does not escape into the matrix A preferred method of doing so is to subject the composite filler to crosslinking. Crosslinking of composite fillers Relationship between logarithm of resistivity and crosslinking level for a series of compositions that are the same except for If we form a graph that shows the relationship between Ru. Fits the part of the curve of resistivity versus crosslinking level where the slope is −0,25 to 0. If the composite filler is crosslinked at a level such that It was also found that reproducible results could be obtained.

(3) Selecting a matrix with an appropriate spreading factor for the composite filler, e.g. By this, the matrix has a small amount surrounding a substantial portion of the particles of the composite filler. (It is preferable that partial coverage can be formed reliably in both cases.

(4) Compositions comprising composite fillers exhibit nonlinear properties, i.e., depend on voltage stress. For example, as the voltage stress increases (the use of voltage stress may have a decreasing resistivity (over a range). Therefore, the composition It becomes extremely useful as a stress grading material within the range of stress usage. .

(5) New and useful compositions use composite fillers exhibiting ZTC or NTC behavior It can be formed by

(6) New and useful compositions include two or more composite fillers or one filler. of composite fillers and one or more homogeneous fillers dispersed in the matrix. It can be formed by

(7) Novel and useful compositions that respond to changes in temperature, voltage stress, or frequency. granular filler (this may or may not be a composite filler) to change its resistivity. good. ) in a sintered polymer matrix.

(8) Novel and useful composite fillers that generate crosslinking of polymers during mixing and form particulate Crosslinking of homogeneous conductive fillers, e.g. carbon black, under conditions to form products a thermoplastic polymer, preferably a thermoplastic polymer. Ru. The components that are mixed together must include a chemical crosslinker that decomposes at the mixing temperature. is preferred.

(9) Novel and useful compositions are created under conditions such that the composite filler retains its identity. Under the condition that mixing is carried out, a composite filler is used instead of a homogeneous filler. It can be formed by the method described in (8).

In one aspect, the invention provides: (a) a continuous matrix comprising a first organic polymer; and (b) each particle. comprises a second organic polymer and a second particulate conductive filler dispersed in the second polymer. a first particulate guide, which is dispersed in the matrix and maintains its identity; A composition comprising an electrically conductive filler, The following conditions (1) the composition has a resistivity of at least 100 times the resistivity of the first filler; Also 1000 times, for example 1000 to 100000 times, especially 1000 to 10000 times have twice the resistivity; this condition reflects two facts: first, that At resistivities such as Second, prior art compositions containing composite fillers have very low resistance. have a rate; (2) the first particulate filler is at least 250 psi (as measured as described below); , preferably at least 300 psi, especially at least 450 psi This condition requires a substantial amount of the second conductive filler to be present in the matrix. heating above the melting point of the second polymer and/or The first filler is filled so that it can be subjected to mixing conditions that include (3) reflects the fact that the first polyester is preferably cross-linked; the viscosity of the first filler at the same temperature. have a viscosity not exceeding 0.2 times; this condition requires that the first filler the first filling is fairly viscous at at least some temperatures above the melting point of without losing the identity of the agent particles (the first polymer can be melt-mixed with the first filler). reflects the fact that; (4) the second polymer has a melting point or softening point of at least 30 °C, preferably at least 60 °C higher; this condition is such that the melting point or softening point of the second polymer is lower than the melting point or softening point of the first polymer. If the first polymer is sufficiently high, without losing the identity of the particles of the first filler. , reflecting the fact that it can be melt-mixed with the first filler; (5) the matrix; The number of particles of the second filler in the filler is less than 450 particles per 100 square microns. preferably less than 400 particles; the number of particles is as described in Example 1 below. This condition is such that the particles of the second filler are in the matrix. (6) reflects the desirability of limiting the extent to which the composition escapes into IJ; comprising a sock-dispersed third particulate filler; this condition is electrically conductive or Adding one or more additional particulate fillers, which may be non-conductive (7) Tomato The first organic polymer is sintered together without completely losing its uniqueness. containing particles of reamer; this condition can be achieved by using composite fillers. reflects the fact that novel sintered compositions can be formed using (8) The first particulate filler exhibits ZTC or NTC behavior; this condition is Novel compositions are formed by using composite fillers exhibiting C or NTC behavior. (9) the composition is in the form of a heat recoverable article; or the composition is in the form of a flexible tape or sheet without electrodes; or the composition is fixed to a substrate that is deformable from a first shape to a second shape; or included in the substrate, thereby allowing the conductive composition to be applied to the second substrate; or the composition is connected to a high voltage device and subjected to electrical stress in an area of high electric field force. This condition requires that the composition containing the composite filler be non-linear. discovered and used such compositions to limit electrical stress in high-voltage equipment. Articles that can be used to apply such compositions to high voltage equipment is meant to be formed from such a composition: Provided is a composition that satisfies at least one of the following.

According to the second gist, the present invention includes: (a) a continuous matrix of a first organic polymer; and (b) a matrix. The first grain is preferably a composite filler, which is dispersed in the powder and retains its identity. A composition comprising a conductive filler in the form of The composition has a resistivity that is less than 061 times the resistivity of the first polymer and a resistivity of the first filler. and the method by which the composition is prepared, having a resistivity that is at least 100 times that of the and the components in the composition include (i) a slightly greater or slightly greater volume % of the first filler; Many other combinations have been made by similar methods using similar ingredients except that they are much smaller. prepare a composition; (ii) measuring the resistivity of the composition and other compositions; and (iii) measuring the resistivity of the composition and other compositions; For the composition and other compositions, the vertical axis is the logarithm of the resistivity, and the horizontal axis is the volume of the first conductive filler. When creating a graph that is filler volume %, the slope of the graph is the filler volume % of the composition. 10 in.

25-0, preferably -0,15-0. . This aspect of the invention is that these compositions are in the fairly flat middle part of the filling curve. This reflects the fact that they are particularly useful because they can be manufactured reproducibly. Ru.

According to the third aspect, the present invention includes: has a resistivity of at least 1.000Ω·Cl11, and (a) the first organic polymer (b) a continuous matrix consisting of a first particulate electrically conductive filler, preferably a composite filler; It is a thing, The method by which the composition was prepared, and the components of the composition include (i) the amount of conductive filler; except that the % varies from a very small amount to the maximum amount that can be dispersed in the matrix. A number of other compositions were prepared by similar methods using similar ingredients and (11 ) measuring the resistivity of the composition and other compositions; and (iii) measuring the resistivity of the composition and other compositions. and other compositions, the vertical axis is the logarithm of the resistivity, and the horizontal axis is the volume % of the first conductive filler. If the resistivity is less than 0.1 times the resistivity of the first polymer, There are two distinct regions of the graph whose slopes are -0,25=,O. However, the slope of the graph is less than -0,5 and the resistivity is less in the distinct region. both by a factor of 100, preferably at least 1000 and at least 10' Compositions separated by regions varying in the smaller of Ω cm submit a poem. This gist forms part of a filling curve with a fairly flat middle part This reflects the fact that these compositions are novel and useful.

According to a fourth aspect, the invention provides a method in which each particle is smaller than 10 menosini, preferably is smaller than 60 meshes, especially smaller than 8o meshes (messini dimensions are Standard sieve dimensions. ) dimensions and dispersed in organic polymers and organic polymers A composite particulate conductive filler comprising a second particulate conductive filler, the composite particulate conductive filler comprising: The filler has the following properties (1) have a hot modulus of at least 25 Qpsi; (2) the polymer - is melt processable and has a melting or softening point of at least 250'C; (3) the polymer is amorphous; and (4) it exhibits ZTC or NTC behavior. A composite particulate conductive filler having at least one of the following properties is provided.

This summary of the invention describes the many composite fillers used in the preparation of the compositions of the invention. is novel because it has one or more of the properties (1) to (4) above. It reflects the fact that

According to the fifth gist, the present invention (well, (a) a first organic polymer; and (b) each particle comprising a second organic polymer and a second particulate conductive filler dispersed therein; producing a composition comprising integrally mixing a first particulate conductive filler comprising: A method of manufacturing, the method comprising: (A) heating the first polymer to a temperature higher than its melting point; (B) first granular filling; The filler retains its identity and formula (C): %formula%) [In the formula, γ is the surface tension of the first polymer under mixing conditions, γ is the surface tension of the first filler under mixing conditions. surface tension, and γ1. is the interfacial tension between the first polymer and the first filler under mixing conditions. It is power. Ko the value of is at least O, (D) The following conditions (1) The amount of the first filler is such that the resistivity of the composition is 0.1 times the resistivity of the first polymer. the filler is at least 100 times the amount of the first filler; (2) the first particulate filler has a hot modulus of at least 250 psi; and, (3) Under mixing conditions, the viscosity of the first polymer exceeds 0.2 times the viscosity of the first filler. There is no, (4) the temperature is lower than the melting point or softening point of the second polymer; (5) the third granule (6) the method includes also mixing a filler with the first polymer; mixed with polymer particles, then the particles of the first polymer lose their identity completely consisting of sintering the mixture so that it is sintered together without any 7) The first particulate filler satisfies at least one of exhibiting ZTC or NTC behavior. Provide a way to add. In many respects, this aspect of the invention is directed to the preparation of the composition. This reflects the same conditions as the first gist of the present invention in terms of suitability. conditions( C) is based on different considerations, i.e. the spreading coefficient of the matrix polymer, i.e. jl According to the theory widely adopted in adhesive technology, yt-(γ1÷γ8.) Therefore, the matrix polymer has a value such that the matrix polymer coats the first filler particles. This reflects the preference for using xx polymers. The spread factor is Confirmed under certain conditions. However, the above conditions indicate that the surface and interfacial tensions are Mixed if met at a verifiable or easily measurable temperature of approximately 23°C Usually matches under certain conditions.

According to the sixth aspect, the present invention includes: (a) a continuous matrix comprising a first organic polymer 5; and (b) each particle comprising: a second organic polymer and a second particulate conductive filler dispersed in the second polymer; a first grain comprising a bridge mixture, dispersed in a matrix and retaining its identity; 1. A method of producing a composition comprising a conductive filler, the method comprising: (1) dispersing a second particulate conductive filler in a second organic polymer; (2) step (1); (3) crosslinking and pulverizing the extrudate from step (2); to form a composite granular conductive filler, (4) combining the composition from step (3) with a second polymer that is preferably compatible with the first polymer; machine dispersed in polymer It consists of The ingredients of the composition and the conditions of the method are (i) the level of crosslinking is greater than in step (3) if the level is greater than in step (3); In step (3), a similar but smaller (ii) preparing a number of other compositions by the method; (iii) the resistivity of the composition and other compositions are measured, and (iii) the resistivity of the composition and other compositions is The logarithm of resistivity, the horizontal axis is the crosslinking level (the crosslinking level is the crosslinking performed by irradiation with ionizing radiation). expressed in M rad when the be done. ), the crosslinking level in step (3) and the slope of the graph is -0.25 to 0, preferably -0.15 to 0. Provide a way to be something. This aspect of the invention provides that the composite filler is fully crosslinked. This reflects the fact that more reproducible results can be obtained in some cases.

According to the seventh aspect, the present invention includes: (a) a continuous matrix comprising a first organic polymer; and (b) each particle comprising: a second organic polymer; and a second particulate conductive filler dispersed in the second organic polymer. A first granule containing 1. A method of producing a composition comprising an electrically conductive filler, the method comprising: The method includes: (1) dispersing a second particulate conductive filler in a second organic polymer; (2) step (1); (3) pulverize the extrudate from step (2) to obtain a first forming a filler; (4) drying the first filler from step (3) with particles of the first polymer; Dry and mix; (5) Expose the mixture obtained in step (4) to heat and pressure to produce (a) the first polyester. the first filler particles to coalesce but not completely lose their uniqueness. The particles are sintered together such that they exist substantially only at the boundaries of the coalesced particles, and (b) causing the particles of the first polymer to completely melt. I will provide a. This aspect of the invention provides that the shear is applied to the matrix from the first filler to the second filler. The shear-free method of composite fillers is highly effective in reflects the fact that useful results can be obtained.

According to the eighth aspect, the present invention includes: (1) The particles are sintered together so that they coalesce without completely losing their identity. a matrix comprising organic polymer particles; and (2) (i) is electrically conductive; (ii) dispersed in the matrix but substantially at or at the boundaries of the coalesced particles; Exists only near the world, (iii) responsive to changes in at least one of the following variables: temperature, voltage and frequency; to change the resistivity First granular filler An electrically conductive composition comprising: The conductive composition as a whole also has conductivity that changes its resistivity in response to changes in variables. A composition is provided. This aspect of the invention demonstrates that the sintering process can produce a wide range of novel compositions. This reflects the fact that it is a useful way to build

According to the ninth aspect, the present invention includes: (a) a continuous matrix comprising a first organic polymer; and (b) each particle comprising: , a second organic polymer, and a second particulate conductive filler dispersed in the second polymer. a first particulate conductive material comprising a first particulate conductive material, which is dispersed in a matrix and retains its identity; A composition comprising an electrically conductive filler, The first particulate conductive filler provides the composition with crosslinking under dynamic mixing conditions. Ru. This aspect of the invention provides that the first particulate filler, under fairly high shear conditions, reflects the fact that they can be easily manufactured by chemically crosslinking at high temperatures. Ru.

The present invention provides at least one, and usually two, electrodes, and an electrical current during use of the device. Also included are electrical devices comprising said conductive polymer compositions in which said electrically conductive polymer compositions flow.

Brief description of the drawing The present invention will be explained with reference to the accompanying drawings, in which Figure 1 shows the composition of the present invention (curve 2) and FIG. 2 is a graph schematically showing the filling curve of the and prior art composition (curve 1). Composite filler particles 4 and third conductive filler particles 6 dispersed in matrix 5 a schematic cross-sectional view of a composition of the invention comprising; Figure 3 shows the logarithm of resistivity versus irradiation for a composition where the only variable is the degree of crosslinking of the composite filler. A graph showing the relationship with crosslinking level, Figure 4, shows that the only variable is the degree of crosslinking of the composite filler. The number of second filler particles migrated into the matrix and the radiation crosslinking rate of the composition are A graph showing the relationship with Bell, FIG. 5 shows composite filler particles 4 dispersed around sintered matrix polymer particles 7. and FIG. 6 is a schematic cross-sectional view of the sintered composition of the present invention showing third conductive filler particles 6. .

Detailed description of the invention As used herein, the hot modulus value is 1 for polymers with no melting point. At 50°C, for polymers that have a melting point, the melting point (i.e., the peak of the differential scanning calorimetry curve) Measure at a temperature 20°C higher than

The stress required to stretch (or break) a sample 100% in a usage test The modinilus (i.e., M,... value) is alternatively determined when the sample is 100% elongated. If the rupture occurs before the break, it is calculated from .

The hot modulus of composite fillers cannot be measured directly from the compositions of the present invention.

However, crosslinking the composition after mixing the matrix polymer and composite filler Cross-link the composite filler before milling under the condition that it is not present and if it is cross-linked. Under these conditions, the hot modulus value can be determined directly from the starting material. hotmo This is because the durus value does not change due to mixing and molding processes. In other cases i.e., when no starting material is available, the hot modulus value is one or more products having a composition substantially similar to the testable article. Design test methods and measure the hot modulus values of the products of these test methods. This can be indirectly confirmed by

The filling curves described herein are the logarithm of resistivity on the vertical axis and the filler volume on the horizontal axis. Draw in the usual way, which is amount %. As used herein, logarithms are common logarithms.

Unless otherwise specified, in this specification (whether related to filling curves or otherwise) All resistivities were measured with a pulse time of 100 μs and a repetition rate of 1/s. Measurements are made using the pulse method at 23° C. and an electric field strength of 100 V/c+n. one When expressing the resistivity of a composition in comparison with the resistivity of other compositions, i.e. When comparing the resistivity of both compositions? all) resistivities to similar electric field strengths Measurement shall be made at the same time. The results of comparing resistivity are lV/am and / It is also preferable that the electric field strength is accurate even in IOV/am.

As described in the various aspects of the invention, the first filler is present in the matrix. Although there are many different ways to ensure that uniqueness is retained, in many situations A preferred method is to crosslink the second conductive filler. In this way, Matrix polymer and filler are mutually compatible if the bridge level is high enough Polymers, especially matrix polymers and filler polymers containing the same a method in which the molten composition is subjected to shear forces; For example, by any method including melt extrusion, injection molding and flow molding. It becomes possible to mold the composition. Therefore, the composite filling used in the present invention The filler comprises a second polymer and at least one homogeneous conductive particulate filler; one or more components present if required (e.g., non-conductive fillers, oxidized inhibitor, chemical crosslinker, radiation crosslinker, etc.), and Cross-linking (increasing the phototomodinirus) and grinding or otherwise pulverizing the mixture Preferably, it is produced by crushing. A suitable mixture can be used as a reference. It includes what is described in the literature described in . In one aspect of the invention , one or both of the first polymer and the second polymer may be, for example, poly(aryline). ) etherketone or polyetheretherketone or other polyaryle It has a melting point of at least 250°C. Such polyarylene is , can be crosslinked with the aid of sulfur (e.g., U.S. Pat. No. 4, No. 616.056, the disclosure of which is incorporated by reference. ). Mixing melt extruder or by mixing the homogeneous filler with hot filler polymer, such as in a mill. This can be done by a method comprising: Fine pulverization of the mixture is preferably carried out after crosslinking. stomach. Crosslinking can be done by chemical crosslinking, by electron beam or by gamma radiation, depending on the polymer used. This can be done by irradiation with radiation or by other methods. Cross-linked, cross-linked composite filling at least 250 psi (17,5 kg/am), especially at least 350 psi (17,5 kg/am) psi (24,5 kg/cm, especially at least 450 psi (31, 5 kg/cm'). Delicious. Preferably, the crosslinking is substantially uniform throughout the filler. light When using thermoplastic polymers such as polyethylene, which are easily crosslinked by , good results were obtained using doses of at least 40 Mrad, and doses of at least 60 Mrad Even better results are obtained using doses of Mrad, e.g. 60-90 Mrad. Ru. In the melt-molded compositions tested, other things being similar, the composite The greater the degree of crosslinking of the filler, the lower the resistivity of the final composition, the degree of change gradually decreases with increasing crosslinking. Crosslinking level is the logarithm of resistivity vs. Is it in a fairly flat part of the graph for hot modulus and/or resistivity? is preferably such that it lies on a fairly flat part of the logarithm of the cross-linking level vs. . (The crosslinking level is expressed in Mrad when crosslinking is carried out by ionizing radiation. , expressed in weight percent of crosslinking agent when crosslinking is carried out by a chemical crosslinking agent. ) Such a fairly flat part is greater than -0,5, e.g. -0,5 to 0 1 especially has a slope greater than -0,25, especially greater than -0,15 It is preferable.

Milling of the mixture may be carried out by any convenient method, including cryogenic milling. E, the average particle size (more preferably maximum particle size) of the composite filler is 425 microns. It is preferable that the diameter is less than 100 μm, for example, 100 to 425 μm. . The pulverized mixture can be sieved, e.g. particles over a certain size can be excluded. In particular, chemistry When a standard crosslinking agent is used, the crosslinking and pulverization steps are carried out in one step under dynamic mixing conditions. It can be performed. Therefore, the crosslinker connects the second polymer to the second particulate conductive charge. The second polymer and the second polymer may be added during mixing with the filler or premixed with the second polymer. Mixing pellets of particulate filler with a crosslinker and then conditions that cause decomposition of the crosslinker You can mix it below. Fairly high levels of chemical crosslinkers, i.e. by weight of the total composition at least 3% by weight, preferably at least 4% by weight, especially at least At 5% by weight, the degree of crosslinking is such that the material becomes brittle. (Crosslinking agent The level of is substantially higher than the 1-2% normally used for crosslinking. ) chemical crosslinking the blend of the second polymer and the second filler to a sufficiently high level of crosslinking. When mixed at high temperatures under dynamic conditions for a sufficient period of time, the resulting mixture will break into fragments. Become. Under sufficient shear conditions, the debris is ground into a coarse powder. The powder is the first grain. May be used without further processing as a conductive filler to form finer particles. Further milled or otherwise improved to form. such as polyethylene In some preferred polymers, useful first particles include a second polymer, a second particle, Manufactured by mixing fillers and chemical crosslinkers in a Banbury mixer. However, other fairly high shear dynamic mixing devices may be used.

The amount of homogeneous conductive filler in the composite filler may vary widely, but in the fairly flat part of the filling curve for homogeneous fillers in the medium, preferably with a slope of -0 , greater than 5, especially greater than −0, 3. It is preferable to do so. Filler polymers and homogeneous fillers are listed as reference In the composite filler and in the final product, as described in the literature, selected to have a favorable temperature/resistivity relationship (e.g. PTC or ZTC). Ru. It is preferable to use carbon black as a conductive filler, In the composition, 35-50% by weight of carbon black dispersed in a crystalline polymer. Particularly good results were obtained using . When chemically crosslinking composite fillers, High loadings of carbon black, for example 40-60% by weight, are preferred.

Filler polymers and matrix polymers are manufactured products with preferred physical and electrical properties. Select to have specific and chemical properties. These are mutually compatible (i.e. Completely miscible over a wide ratio range when both polymers are not crosslinked ) is preferred. Thus, the two polymers have similar or identical substituents, For example, it may have polar groups and/or similar or identical repeating units. preferable. Each polymer contains, for example, at least 25 mol%, preferably Contains at least 50 mol%, especially at least 80 mol% of similar repeating units do. It is particularly preferred that the two polymers are chemically identical, e.g. Both the agent polymer and the matrix polymer are polyethylene. PTC group at least one of a filler polymer and a matrix polymer; Preferably each is a crystalline thermoplastic material. ZTC composition In this case, both the filler polymer and the matrix polymer are elastomers. It is preferable that there be.

A composite conductive filler is a composite conductive filler comprising a homogeneous conductive filler and obtained by milling the composition of the invention comprising a matrix filler. It may also be a filler. two or more dispersed in a matrix polymer There may be the above composite fillers. Homogeneous guide dispersed in matrix polymer There may also be electrically conductive fillers. Such homogeneous fillers are NTC or ZTC It is preferable that the carbon black or graphite exhibits a dynamic action, such as carbon black or graphite, but For example, doped barium titanate or other PTC cell It may be lamic. The average particle size of another conductive filler, if present, is It is preferably at least lnm, for example 5 to 1100n. Ease of grinding from inert fillers such as zinc oxide, titanium dioxide, glass, alumina or or other materials, organic materials, such as polymers that are incompatible with the second polymer, or Additional conductive fillers may be added to the composite conductive filler. of additional fillers The presence increases the brittleness of composite fillers, especially in soft or elastomeric polymers. - or improve the ease of grinding in polymers with low melting points. inactive Particles made from a composition comprising a filler have a uniform size when milled. Often has a law and shape.

The amount of composite filler present in the compositions of the present invention is determined in particular to ensure that the composition has a dispersed homogeneous conductivity. The fillers may vary widely. The conductive filler content is determined by the filling curve. a fairly flat section, preferably greater than -0.5, in particular greater than -0.3; Especially for graphs with slopes greater than -0.25, e.g. greater than -0.15. Preferably, it is something that applies to only one part. Shearing composite filler When used alone in a composition, the content is, for example, 40 to 80% by weight, Preferably it is 55 to 75% by weight. Composite fillers used alone in sintered compositions When used, its content is at least 20% by volume. Shear processing composition odor When both a composite filler and a homogeneous conductive filler are present, The content is, for example, 1 to 40% by volume, preferably 15 to 25% by volume, and is homogeneous. The filler content is up to 10% by volume, such as 3-5% by volume.

The composition may include other ingredients dispersed in the matrix polymer, such as one or more The above non-conductive filler may also be included. For example, stress control composition When used in US Pat. No. 4,470,898, the compositions silicon carbide, iron oxide, and aluminum flakes as described in the issue. one type suitable for such compositions, such as carbon black and other fillers. or more components.

In many applications, the composite filler is dispersed into the first polymer by melt mixing. Preferably, the mixture is formed by melt molding. The composition is 1 polymer particles are completely melted by the method of the seventh aspect of the invention. When the triblend of the first polymer particles and the composite filler is Preferably, the layer is formed on a substrate that supports the layer while the polymer is molten. . The substrate is a sheet electrode, for example a metal foil. The second sheet electrode, e.g. metal foil , may be placed on top of the layer before exposing the assembly to heat and pressure. The foil is As described in U.S. Patent Application No. 787.218, conductive polyester It is preferred to have a rough surface adjacent to the mer. These processes are performed from roll to Apply triblend to one of the electrodes, then apply the layer This can be done by passing the electrode and other electrodes through heated nip rolls. electrode During manufacture or use, in order to prevent the It is preferable to include a separation member between the electrodes, for example, by applying a triblend. Place it on top of the electrode before doing so.

Improve the electrical and mechanical stability after shaping the composition, especially at high temperatures For this purpose, crosslinking is carried out, if necessary, preferably by irradiation.

This section sintered tri-blend of matrix polymer and composite filler It relates to a composition produced by. In such compositions, conductive Particles exist substantially only at grain boundaries. This means that the current flows through the composition When resistive heating occurs essentially only at the boundaries, but within the matrix grains, This means that it does not occur in the area. This improves the thermal stability of the matrix , thus improving the thermal stability of the overall composition. In conductive polymer compositions Sintered composition with filler concentrated at grain boundaries to achieve favorable conductivity levels The amount of filler required for the product is lower in non-sintered compositions where the filler is more evenly distributed. less than

The sintered composition of the present invention is (i) is electrically conductive; (ii) dispersed in the matrix but only at or with boundaries of coalesced particles; A second particulate filler is present substantially only in the vicinity.

The first particulate filler and (if present) the second particulate filler are present at the boundaries of the coalesced particles. In preferred compositions, they are present substantially only at or near the boundaries of the assembly. It is the only conductive particle in the composition.

However, the invention also encompasses compositions containing additional electrically conductive particles. for example , the sintered particles themselves are organic polymers with conductive particles uniformly dispersed within them. The conductive particles are the same as the first or second particulate filler. It may be similar or different.

where the first particulate filler changes its resistivity in response to temperature or other variables; The composition also changes its resistivity. The resistivity change of the total composition is the resistance of the first particulate filler. It may be the same as or different from the rate change. The resistivity change of the first granular filler is a variable. If the composition exhibits a sudden change in the value of the variable, the composition also exhibits a total resistance at similar values of the variable. It is preferable that the resistivity shows a rapid change.

the first particulate filler comprises a suitable material that changes its resistivity in response to changes in the variable; It may consist of In one preferred embodiment, the filler is a crystalline organic polymer. A conductive composition comprising a conductive polymer comprising dispersed conductive fillers. It consists of The conductive polymer of the filler preferably exhibits PTC behavior. stomach. Such fillers are used in compositions that change their resistivity in response to changes in temperature. It can be used as The first particulate filler is (a) PTC having a switching temperature T5. (b) at temperatures up to and above Ts; maintains its integrity within the matrix. Conductive polymer of first particulate filler The composition comprises carbon black molecules in a crystalline organic polymer. is preferred. In other preferred embodiments, the composition exhibits PTC behavior, the first filler comprises a non-polymeric material exhibiting PTC behavior, such as barium titanate.

Contains other fillers (e.g. carbon bras, silica) dispersed in organic polymers. The composition of the present invention containing a first particulate filler may itself be pulverized; It may be used as the first particulate filler in other compositions of the invention. The new composition is , which may itself be finely divided, and in still other compositions of the invention, the first filler May be used as

The first particulate filler can be obtained by any suitable route. One preferred state In the process, the first particulate filler is obtained by pulverizing the conductive polymer composition in a molten press. It can be manufactured by

The sintered matrix polymer comprises a suitable polymer. Polymers that can be used - Examples include polyethylene with a weight average molecular weight of 30,000 to 8 million. Including polyethylene.

Preferred polymers for use are crosslinked polyesters having a molecular weight of about 100,000. tyrene, or crosslinked or uncrosslinked polyethylene with a molecular weight in the range of 3 to 6 million It's Ren. Other examples of polymers that may be used include fluoropolymers, e.g. , polytetrafluoroethylene, polyvinylidene fluoride [Kynar (K) polyphenylene sulfide, polyether ether ketone (PE EK), polyarylene ether ketones and polyimides.

When the first particulate filler comprises a conductive polymer composition, the filler polymer and The polymer in which it is called can be a single polymer or a mixture of polymers; The particulate conductive filler in the particulate conductive filler may be a single filler or a mixture of fillers.

Suitable conductive polymers are described in the literature cited herein by reference. There is. The sintered matrix polymer and filler polymer are preferably compatible. Yes. The greater the compatibility, the more the change in resistivity of the composition as a whole is the resistance of the filler. Follow rate changes more closely. a second filler, e.g. carbon black, is present; This is especially the case when the filler polymer wets the second filler. filler polymer and Compatibility between matrix polymers is determined by the presence of similar or identical substituents, e.g. polar groups. , and/or the use of polymers comprising repeating units. This can be achieved by a method. Therefore, filler polymers and matrices Each of the may also have 50%, especially at least 80%, of similar repeating units. Especially preferred The new composition is such that the filler polymer and the matrix polymer are chemically substantially The same is true, for example both are polyethylene. In this case, filler and and matrix polymers may have similar or different molecular weights; Both or one may be crosslinked. In any case, the first filler is Retains its physical identity during manufacture or use, and maintains the electrical properties of the composition when used. filler polymer and matrix polymer to ensure that they are qualitatively unchanged. Preferably, a reamer is selected. Examples of combinations using different polymers is a polyvinylidene fluoride contained in a polytetrafluoroethylene matrix. Ride particles, polyphenyls contained in polyetheretherketone matrix Rensulfide particles and polyimide contained in the high molecular weight polyimide matrix These are ether ether ketone particles.

Since the sintering process is a non-shearing process, the first particulate filler is Even when the matrix contains conductive polymers that are similar to can maintain its integrity. In short, the integrity of each of the polymer components is This can be improved by controlling the viscosity of each of the remers. this may be achieved, for example, by crosslinking one or both of the polymers.

When the first particulate filler comprises a polymeric material, the material It may have a higher viscosity than the polymer and vice versa.

The respective dimensions and amounts of conductive fillers are selected depending on the desired resistivity.

The particle size of the second filler (if present) is at least 1 nm, in particular from 5 to 11 00n, the first filler preferably has an average size of at least lnm, It is particularly preferred to have an average size of at least 20 microns. First granular filling The average size of the agent is preferably no larger than half of the sintered matrix particles. . Typically, the average size of the sintered matrix particles is between 200 and 500 microns. be. The second filler (if present) accounts for no more than 10% by volume of the composition. It is preferable that the The first filler may account for 1 to 40% by volume of the composition. preferable. If a second filler is present, the first particulate filler is preferably occupies 15 to 25% by volume, in particular about 20% by volume. When the second filler is not present Preferably, the first particulate filler occupies more than 30% by volume of the composition. - The first filler may be present more than the second filler, or vice versa. Good too. In one embodiment, the composition comprises about 20% by volume of a first particulate filler; and about 3-5% by volume of a second particulate filler.

If the first particulate filler is not a polymer, for example a ceramic, the first particulate filler The filler wets the surface of the second filler (if present) to interrupt the conductive path. I can't moisturize. In these cases, the particle size of each of the first and second fillers are preferably substantially the same. This will cause the second filling to interrupt the current path. allowing the agent to mix with the first filler.

The second particulate filler changes its resistivity in response to changes in variables. In short, The composition contains one or more fillers that change its resistivity in response to changes in variables. It's good that it has been done. If more than one such filler is included, the filler is Varies its resistivity in response to changes in similar variables or in response to changes in different variables let

Reference is made to FIG. 5, which shows a schematic cross-sectional view of the composition of the present invention. matric The sppolymer comprises sintered ultra-high molecular weight polyethylene particles 2. 2 types A filler is dispersed in the matrix along the interface of the particles 2. 1st filling The filler 4 comprises carbon black, and the second filler 6 (formed by melt extrusion) PTC conductive material comprising carbon black dispersed in polyethylene comprising a polymer composition. Polymer 2 and the polymer of Composition 6 are compatible.

The invention is further illustrated by the following examples.

Kansenka 1 The material of the present invention was prepared by the following method.

High-density polyethylene [Marlex 50] in a Banbury mixer 100, Phillips P etroleus ) 156% by weight of the commercial product was added to carbon black [Statex G , ) a Columbian Chemicals ) A composite filler was prepared by melt-mixing 343% by weight of a commercially available product and 1% by weight of an antioxidant. Manufactured. The formulation was extruded into strands with a die and 10~ Irradiation was carried out at doses in the range of 80 Mrad. Then all particles are smaller than 250 microns. The strands were micropulverized at low temperatures until they were fine.

For each different irradiation dose, 67.5% by weight of composite filler was added to high density polyethylene powder f FA750, U, s,! , Chemicals (U, S, I.

Chemicals) Commercial product, particle size = 20 microns, melt index :229/10 minutes] and tumble blended with 32.5% by weight. Next, the compound Extruded onto 0.030 x 3.0 inch (0.076 x 7.62C tape) Ta. Electrodeposited copper foil electrodes with a thickness of 1 mil (0, OO25C2) were laminated on both sides of the tape. The resistance in the thickness direction of the sample was measured at 100 V DC.

The switching temperature, Ts, was 120°C.

The test was conducted in a two-step process. PTC particles are compacted by irradiating the particles with different doses. Modillas of shaped slabs [M,,. , i.e. at 150°C, the sample was The value required to pull 100% of the length (psi)] was measured. Ml. . The value of the (psi) is plotted as a function of particle irradiation level and is shown in FIG.

The second test was to determine the presence of carcinogens in the matrix-7x phase of the blended formulation. The amount of bomb black was measured. Cool the extruded tape sections in liquid nitrogen and microplate them. Samples with a thickness of less than 1000 angstroms were obtained by cutting at cryogenic temperatures using a tome. Ta. Using a transmission electron microscope (TEM), examine the polymer matrix at a magnification of 5000. The number of carbon black particles (sunspots) inside was counted. polymer matrix 100 Number of carbon particles per square micron plotted as a function of PTC particle dose This is shown in Figure 4.

Example 2 Instead of high-density polyethylene, use ethylene vinyl acetate [Lpax (E 1va)] x) 4260, copolymer with 28% vinyl acetate content, DuPont A composite filler was obtained according to the procedure shown in Example 1 except that a commercially available product was used. 6 After irradiation with a dose of 0 Mrad, the particle size is less than 250 microns. The particles were crushed and blended with high density polyethylene. Switching of the obtained formulation The temperature, T, was 75°C.

Example Low density Botethylene [Petrothene NA 140, U.

S, 1. The procedure described in Example 1 was followed except that commercially available chemicals were used. A composite filler was prepared. The formulation was irradiated with a dose of 60 Mrad to reduce the particle size to 2. Grinded to less than 50 microns and then blended with high density polyethylene . The switching temperature, Ts, of the resulting formulation was 90°C.

Example 4 The composite filler of Example 1 was irradiated with a 6Q MradO dose to crosslink it, resulting in a low melt index. high-density polyethylene: / (FA 113, T;, S, ].

Chemical commercial product, particle size: 20 microns, melt indenox 259/10 minutes) and blended.

Example 5 Polyetheretherketone powder (ICI commercial product) was mixed with carbon black (stated). 40% by weight and 0.25% by weight of sulfur % to obtain a composite filler. Add the mixture to 33 ■Leishudritsu (Le istritz) mixed in a counter-rotating twin screw extruder and using a pelletizing die. I pushed it out. The pellet was heat-treated at 300°C for 4 days to complete the crosslinking reaction, and then The powder was ground to a fine powder with a particle size of less than 250 microns. Composite charge 70% by weight filler was triblended with 30% by weight PEEK powder and the formulation was divided into two Black was produced by compression molding between two electrodeposited Sokel foil electrodes. The obtained heat Connect a 400 volt AC power supply to the converter and set the switching temperature, Ts, to approximately 335°C. heated with.

twist twist A composite filler was prepared according to the procedure shown in Example 1 and treated with a 3.5 MeV electron beam. irradiated with a dose of 80 Mrad and then reduced the particle size to less than 250 microns. It was crushed into pieces. Using a sigma mixer at 175°C for approximately 20 minutes, Sobutylene, amorphous polypropylene, hydrocarbon tackifier, antioxidant and Approximately 35% by weight of this composite filler is added to a black mastic made of carbon black. Blended. The mixture can be suspended in a solvent or melted to create a stress gradient. It was applied to the inner surface of the coating tube.

Example 7 Tri-blend the composite filler and polyethylene powder according to the procedure shown in Example 1. did. Next, a layer of 0.030 inch thick (0.076 cm) located on top of the electrodeposited copper foil is applied. ), open mesh [0,25 square inches (0,635 square inches)] The formulation was sprayed onto electrically insulating crosslinked polyethylene or glass fiber cloth. Po Heat to 232°C, a temperature sufficient to melt and fuse the polyethylene powder. A second copper foil was laminated on top of the assembly through the two rolls. Obtained The cross section of the polymer is 0.040 inches (0.102 CjI )Met.

Charmman Melt-mix high-density polyethylene with carbon black and Statex 6140% by volume A composite filler was prepared. More than 90% of the particles have a size of 140 to 325 meshes. The mixture was pulverized to within the size range. Next, a 6M electron beam was applied to the composite filler. irradiation at a dose of rad.

Ultra High Molecular Weight Polyethylene (UHMWPE Hostalen) Gv R-212, manufactured by Hoechst] 77% by volume was added to Statex G. 1 flf. 3 volume % PTC powder and 2 flasks of PTC powder were blended. Cold mix It was compacted, sintered at 200° C. for 20 minutes and finally cooled under pressure. 10Mr product The fart was exposed to a high-energy electron beam.

The resistivity of the product is approximately 100 ohm cm at 23°C and approximately 1 at 112°C.

OOO ohm” C111, and 100,000 ohm” cm at approximately 120°C. It was.

Implementation type 1 The volume ratio of each component is t,’HMWPE 93.8% composite filler 4.2% Statex 6 Other than 2.0%, the actual Example 20 procedure was repeated.

The resistivity of the product is approximately 1.300 ohm/fJ% at 23°C and approximately 10 at 112°C. ,000 ohm Cl, about 1,000,0OO1-muC at 120'C. Ta.

Toru Oarashi 1st time The volume ratio of each component is UHMWPE 6,)% composite filler 3 5% Statex G Repeat the procedure of Example 2 except for using 0%. I went back.

The resistivity of the product is approximately 400 ohm cm at 23°C and approximately 1 at 112°C.

It was 300 ohm・C, and about 9,000 ohm・Cl at 120°C.

Example 11 Marex 50100, 56% by weight, Statex G in Brabender mixer 43% by weight of H (Columbian Chemicals commercially available Carbon Bra Tsuk) and acid. 1% by weight of anti-oxidation inhibitor and 5% by weight of the total amount of polymer/carbon black. (L upperco) 1 3 0 X L E Penwal containing peroxide Commercialization of Pennwalt Corporation A composite filler was prepared by melt-mixing with a chemical crosslinking agent]. Heat the mixture at 200°C for 30 minutes. It was heated to crosslink and then milled to obtain particles smaller than 250 microns.

Three formulations A, B and C were made with different particles and betrocene. Each formulation, Inner diameter 0.59 inches (1, 5 cx), wall thickness 0.10 inches (0.25 cx) was extruded into a tube shape. Ml. . Set each tube so that the pressure is 25 psi. After irradiation, each tube was expanded with air at various rates up to 3 times. 1 For testing with 5KV cables, each inflated tube is temporarily rated at 110KV. It has been shown that it can withstand impulses. Nonlinear as a function of increasing electrical stress The data below shows that it takes a morphological behavior.

Compound ABC particle blending amount, weight % 28 30 32 Ratio impedance (2Kv, ohm C11) Expansion: 1.00 times 1.82E=9 1.08E+9 2.09E+ 91, 29 times 2.97E+9 2.59E-9 2.61E=9 1, 4 1x 2.72E-9 2.71E= 9 1.74E↑91, 61 times 1.96E=9 1.62E◆ 9 1.7i! IE-9 specific impedance (ohm cm) Electrical stress (KV/■) 0,034g 111.17E+8 1.03Efu9 1.06E-90, 0696 6.9OE book 8 1.03E+9 9.75E↑80, 1043 5. 30E-8 1.03E-9 9.40E-80, 1217 4.64E+llll 9.17E +8 8.70E+80, 1391 2.37E+8 7.77E+8 8.0OE-80 , 16 1.44E+8 5.61E+87.36 E+8 Example 12 Marlex 50100, 50wt 1%, Statex GH in Banbury mixer The formulation was pelletized by mixing 49% by weight and 1% by weight of antioxidant, and the composite filling A filler was prepared. Tri-blend the pellets with Luperco 130XL, 5% by weight. Then, the mixture was melt-mixed at high speed using a Banbury mixer. After 1o minutes, mixer The motor current has dropped significantly. At this point mix the mixture into small pieces. I took it out. (The fragments were tested and found to be cross-linked: The reaction is complete. ) The fragments are ground to particles smaller than 250 microns. Ta. Various formulations containing 30-70% by weight of particles in Marex 50100 was prepared. At 36% by weight particles, the resistivity of the formulation is approximately 150. OOO ohm ・It was CX.

Example 13 Marex 50100.46f with Banbury mixer! ji%, Statex GH43% by weight, Tipure [New England Register] New England Resins and Pigments 110% by weight of commercially available titanium dioxide pigment from Pigments), and acid A composite filler was prepared by mixing 1% by weight of an inhibitor.

The mixture was pelletized and the pellet was irradiated with a dose of 80 Mrad to 250 microns. It was ground into particles smaller than the Mixed by adding titanium dioxide It could easily crush objects.

Filler amount (%) Dose (N/AND) Dose (4 rad) international search report Lmye-Kan1・-ml^-Gang1-1-Taste PCT/LIEε8102muε1i

Claims (1)

[Claims] 1. (a) a continuous matrix comprising a first organic polymer; and (b) a second particulate conductive particle in which each particle is dispersed in a second organic polymer and a second polymer; The matrix contains fillers that are dispersed in the matrix and maintain its identity. A composition comprising a first particulate conductive filler comprising: The following conditions (1) The composition has a resistivity that is at least 100 times the resistivity of the first filler. , (2) the first particulate filler has a hot modulus of at least 250 psi; and, (3) At a temperature exceeding the melting point or softening point of the first polymer, the first polymer at the same temperature having a viscosity not exceeding 0.2 times the viscosity of the filler; (4) the second polymer has a melting point or softening point of at least 30 (5) particles of the second filler in the matrix have a high melting point or softening point; (6) the composition has fewer than 400 particles per 100 square microns; comprises a third particulate filler dispersed in the matrix; (7) The matrix was sintered together without completely losing its identity. (8) the first particulate filler comprises particles of a first organic polymer; exhibits NTC behavior; (9) the composition is in the form of a heat recoverable article; (1) 0) the composition is in the form of a flexible tape or sheet without electrodes; (11) The composition is fixed to a base material that is deformable from the first shape to the second shape; is included in the substrate, thereby allowing the conductive composition to be applied to the second substrate; (12) The composition is connected to a high voltage device and subjected to electrical stress in a region of high electric field force. be able to limit A composition that satisfies at least one of the following. 2. (a) a continuous matrix of a first organic polymer; and (b) a matrix of The first granular conductive filler is dispersed in the bulk material and retains its uniqueness. A composition comprising: The composition has a resistivity that is less than 0.1 times the resistivity of the first polymer and a resistivity of the first filler. and a method of preparing a composition having a resistivity that is at least 100 times that of the resistivity. The components in the composition include (i) a slightly larger or slightly smaller volume % of the first filler; Many other compositions by similar methods using similar ingredients except for Prepare, (ii) measuring the resistivity of said composition and other compositions; and (iii) said set of logarithm of resistivity on the vertical axis and capacity of the first conductive filler on the horizontal axis for compositions and other compositions. %, the slope of the graph depends on the filler volume % of the composition. The composition is such that -0.25 to 0. 3. having a resistivity of at least 1,000 Ω·cm and comprising (a) a first organic polymer; (b) a continuous matrix comprising First particulate conductive filler that maintains properties A composition comprising: The orientation in which the composition was prepared and the components of the composition include (i) the volume of conductive filler; except that the % varies from a very small amount to the maximum amount that can be dispersed in the matrix. Many other compositions have been prepared by similar methods using similar ingredients and (ii ) measuring the resistivity of the composition and other compositions; and (iii) measuring the resistivity of the composition and other compositions. and other compositions, the vertical axis is the logarithm of the resistivity, and the horizontal axis is the volume % of the first conductive filler. When creating a graph, the resistivity is less than 0.1 times the resistivity of the first polymer. There are two distinct regions of the graph where the slope of the graph is between -0.25 and 0, The distinct region has a slope of the graph less than -0.5 and a resistivity below the third region. The resistivity varies by the smaller of 100 times the resistivity of the A composition separated by three regions. 4. Each particle has a size smaller than 10 mesh and contains organic polymers and organic polymers. A composite particulate conductive filler comprising a second particulate conductive filler dispersed in a reamer. So, The composite filler has the following properties (1) have a hot modulus of at least 250 psi; (2) the polymer - is melt processable and has a melting or softening point of at least 250°C; (3) the polymer is amorphous; and (4) it exhibits ZTC or NTC behavior. A composite particulate conductive filler having at least one of the following. 5. (a) a first organic polymer; and (b) each particle comprising a second organic polymer and a second particulate conductive filler dispersed therein; A composition comprising mixing together a first particulate conductive filler comprising: A method of manufacturing, the method comprising: (A) heating a first polymer to a temperature above its contact point; (B) a first particulate filler; retains its uniqueness, and formula (C): γ2-(γ1-γ12) [In the formula, γ1 is the surface tension of the first polymer under mixing conditions, γ2 is the surface tension of the first filler under mixing conditions. surface tension, and γ12 is the interfacial tension between the first polymer and the first filler under mixing conditions. It is power. ] the value of is at least 0, (D) The following conditions (1) The amount of the first filler is such that the resistivity of the composition is 0.1 times the resistivity of the first polymer. the filler is at least 100 times the amount of the first filler; (2) the first particulate filler has a hot modulus of at least 250 psi; and, (3) Under mixing conditions, the viscosity of the first polymer exceeds 0.2 times the viscosity of the first filler. There is no, (4) the temperature is lower than the melting point or softening point of the second polymer; (5) the third granule (6) the method further comprises mixing the first filler with the first polymer; mixed with polymer particles, then the particles of the first polymer lose their identity completely sintering the mixture so that it is sintered together without any Beauty (7) The first particulate filler exhibits at least one of ZTC or NTC behavior. How to be satisfied. 6. (a) a continuous matrix comprising a first organic polymer; and (b) a second particulate conductive material, each particle comprising a second organic polymer and a second particulate conductive material dispersed in the second polymer; It consists of a cross-linked mixture of electrically conductive fillers, dispersed in a matrix, giving it its unique character. A method of manufacturing a composition comprising a first particulate conductive filler that retains the The method is (1) dispersing a second particulate conductive filler in a second organic polymer; (2) step (1); (3) crosslinking and pulverizing the extrudate from step (2); to form a composite granular conductive filler, (4) dispersing the composition from step (3) in a second organic polymer; , The ingredients of the composition and the conditions of the method are (i) the level of crosslinking is greater in some cases than in step (3) and in other cases In step (3), a similar but smaller (ii) preparing a number of other compositions by the method; The resistivity is measured, and the vertical axis of the composition of (iii) and other compositions is the resistance. The logarithm of the rate, the horizontal axis is the crosslinking level (crosslinking level is the crosslinking performed by ionizing radiation irradiation) expressed in M rad in case of It will be done. ), the crosslinking level in step (3) A method in which the slope of the graph is between 0.25 and 0. 7. (a) a continuous matrix comprising particles of a first organic polymer sintered together; Ricks, and (b) a second particle in which each particle is dispersed in a second organic polymer; and a second particle dispersed in the second organic polymer. It consists of a conductive filler that is dispersed in a matrix and maintains its identity. 1. A method of producing a composition comprising a first particulate conductive filler comprising: The method includes: (1) dispersing a second particulate conductive filler in a second organic polymer; (2) step (1); (3) pulverize the extrudate from step (2) to obtain a first forming a filler; (4) drying the first filler from step (3) with particles of the first polymer; Dry and mix; (5) Expose the mixture obtained in step (4) to heat and pressure to produce (a) the first polyester. the first filler particles to coalesce but not completely lose their uniqueness. The particles are sintered together such that they are present substantially only at the boundaries of the coalesced particles, and (b) causing the particles of the first polymer to completely melt. . 8. (1) The particles are sintered together so that they coalesce without completely losing their uniqueness. a matrix comprising organic polymer particles, and (2) (i) is electrically conductive; (ii) dispersed in the matrix but substantially at or at the boundaries of the coalesced particles; Exists only in the vicinity, (iii) responsive to changes in at least one of the following variables: temperature, voltage and frequency; to change the resistivity First granular filler An electrically conductive composition comprising: The conductive composition as a whole also has conductivity that changes its resistivity in response to changes in variables. Composition. 9. (a) a continuous matrix comprising a first organic polymer; and (b) a second granular form in which each particle is dispersed in a second organic polymer and a second polymer; Contains conductive fillers, dispersed in a matrix and retains its identity A composition comprising a first particulate conductive filler comprising: A composition in which the first particulate conductive filler is crosslinked under dynamic mixing conditions.