KR960000423B1 - Conductive polymer composition - Google Patents

Abstract

No content.

Description

Conductive Polymer Compositions and Their Electrical Apparatus

1 is a cross-sectional view of an electrical device according to the invention.

2 is a cross-sectional view of an electrical device according to the invention with a plurality of electrode layers.

3 is a circuit diagram with an electrical device according to the invention.

4 is a circuit diagram with an electrical device according to the invention.

5 is a circuit diagram with an electrical device according to the invention.

6 is a resistance-temperature characteristic graph of an electrical device illustrating the PTC action of a composition according to the present invention.

7 is a graph showing the current-voltage characteristics of the electric apparatus according to the present invention.

The present invention relates to a constant temperature coefficient polymer composition, and to an electrical device composed of the composition having a high breakdown voltage.

Conductive polymer compositions exhibiting a positive temperature coefficient (PTC) action and electrical devices composed of these compositions are well known by the following patents.

See, eg, US Pat. No. 2,952,761; 2,978,665; 3,243,753; 3,351,882; 3,571,777; 3,697,450; 3,757,086; 3,760,495; 3,793,716; 3,823,217; 3,858,144; 3,861,029; 3,950,604; 4,017,715; 4,072,848; 4,085,286; 4,117,312; 4,124,747; 4,177,376; 4,177,446; 4,188,276; 4,237,441; 4,238,812; 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; 4,309,597; 4,314,230; 4,314,231; 4,315,237; 4,317,027; 4,318,881; 4,318,220; 4,327,351; 4,329,726; 4,330,704; 4,334,148; 4,334,351; 4,352,083; 4,361,799; 4,388,607; 4,398,084; 4,400,614; 4,413,301; 4,425,397; 4,426,339; 4,426,633; 4,427,877; 4,435,639; 4,429,216; 4,442,139; 4,459,473; 4,481,498; 4,476,450; 4,502,929; 4,514,620; 4,517,449; 4,534,889; 4,545,926; 4,951,700; 4,724,417; 4,743,321; 4,764,664; 4,848,838; 4,857,880; German OLS No. 1,634,999; German Patent Publication No. 2,746,602; German Patent Publication No. 2,821,799; EP application 38,718; EP application 38,713; EP application 38,714; British Patent Application No. 2,076,106A; EP application 63,440; EP application 74,281; EP application 92,406; EP application 119,807; EP application 84,304; 505.2; EP application 84,305,584.7; EP application number 84,307,984.9; British Patents 1,470,502 and 1,470,503; Klason and kubat, J. Applied Polymer Science 19, 831-845 (1975); J. Meyer, Polymer Engineering and Science, Vol. 13. No. 6, 462-468 (1973); J. Meyer, Polymer Engineering and Science, Vol. 14, No. 10, 706-716 (1974); M.Narkis, Polymer Engineering and Science, Vol. 18, No. 8, 649-653 (1978); M.Narkis, J. Applied Polymer Science, Vol. 25, 1515-1518 (1980).

The disclosure of each patent publication and application is outlined by reference. In particular, J. Meyer, M. Naris, and U.S. Patent No. 4,237,441 disclose conductive polymers of various conventional carbon blacks and their PTC action.

It is well known that polymers, which are polymer crystals, are electrically conductive because they disperse an appropriate amount of highly purified conductive starting material therein.

Some conductive polymers are known to act as PTC (positive temperature coefficient; hereafter PTC).

As used herein, the terms "PTC polymer", "composition exhibiting PTC action" and PTC composition refer to compositions having at least 2.5 phases of R14 values and a value of R100 of at least 10, preferably with a value of R30 of 6 or more. It is good to have. In this case, R14 is the resistivity ratio at the initial and final values in the range of 14 degrees Celsius, R100 is the resistivity ratio at the initial and final values in the range of 10 degrees Celsius, and R30 is the resistivity at initial and final values in the range of 30 degrees Celsius. It is rain.

The logarithmic (10 g) plot of the resistance of a PTC device (referring to a device made of a PTC composition) to temperature shows a sharp gradient change on any part of the predetermined temperature range in a composition having an R100 value of 100 or more.

The term "switching temperature" (Ts fluctuating) means the temperature at the point of intersection of the extension which becomes a substantially straight part of the figure on either side of the part exhibiting a sharp change in slope.

The term "peak resistance" means the maximum resistance at which the composition exhibits approximately Ts. The term "peak temperature" means the temperature at which the composition has its peak resistance. These relationships are shown in FIG. Where A is the resistance at 25 ° C, B is the average slope of the curve, and C is the maximum resistance.

It is known that the PTC action of the conductive polymer composition depends on the physical and chemical properties of the mixed and dispersed polymer and carbon black.

In recent years, there has been an increasing demand for circuit protection devices having high breakdown voltages for use in electrical devices that consume a considerable amount of power. In many applications, circuit protection devices must withstand high supply voltages in the event of a fault, ie their high resistance. It is known that the composition becomes an insulator at a temperature of high resistance state and the conductive polymer composition exhibits PTC action.

Circuit protection devices have a relatively low resistance under normal conditions, but should be high resistance under fault conditions.

That is, above the switching temperature of the PTC polymer, it "trips" and reduces the current flow through the electrical device, thereby protecting the circuit. Modern electrical or electronic devices and devices that are powered by batteries that supply large amounts of power have relatively low resistance, and often their resistance may be very low.

In particular, the use of devices with very low resistance has been increasing with the development of electrical and electronic technology, and protection circuits capable of withstanding high supply voltages with very low resistance, for example at most about 500 milliohms. The demand for devices has increased significantly.

To achieve a very low resistance state during normal operation in a circuit protection device, the contact resistance between the electrodes of the circuit protection device and the PTC polymer in contact with the electrode must be reduced, and the PTC polymer layer between the electrodes must be as thin as possible. However, very thin conventional PTC polymer elements with low resistance can only be used at relatively low supply voltages.

This is because the breakdown voltage of the device decreases as the thickness of the polymer layer decreases or the resistance of the polymer material (here the resistance of this device) decreases. As described herein, the term "breakdown voltage" is a maximum power supply voltage that increases at a normal rate of 60 volts per minute and can be applied across the PTC polymer element without causing breakdown of the PTC polymer composition.

High breakdown voltages can often be used because unprecedented high supply voltages are required to drive devices such as motors. However, although conventional circuit protection devices with low resistance conductive polymer compositions allow more current to flow through them, these devices often could not withstand high voltages.

Irradiation crosslinking and heating in two steps between crosslinking steps is described in US Pat. Nos. 4,857,880 and 4,724,417 as techniques to maintain PTC action after tripping to high resistance or prolonged high resistance and application of high voltage. have. However, this requires at least three or more processes and is complicated and expensive.

Conventional PTC conductive polymer compositions containing several types of carbon black do not have significantly higher breakdown voltages. However, it has been found that compositions containing certain carbon blacks have significantly higher breakdown voltages and excellent PTC operation, despite having very low resistance.

It is an object of the present invention to provide a PTC polymer composition having both low capacity resistance and high breakdown voltage.

Another object of the present invention is to provide a circuit protection device having a high breakdown voltage.

Another object of the present invention is to provide a circuit protection device having a high breakdown voltage and a low resistance.

It is still another object of the present invention to provide a novel circuit protection device which is made of a device made of PTC material and which can flow a relatively high current even in a small size.

It is another object of the present invention to provide a method for preparing a PTC polymer composition having a low resistance and a high breakdown voltage.

The objects of the present invention can be seen that the new conductive polymer composition consisting of a dispersion of carbon black having a large particle diameter and a high absorption function of Dibutyl Phthalate (Dibutyl Phthalate) in the crystalline polymer.

In particular, in one embodiment, the present invention provides an electroconductive comprising (a) a crystalline polymer dispersed therein and (b) a carbon black having an average particle diameter of at least about 60 milli microns or more and an absorbing function of at least about 800 cc / 100 g or more It relates to a polymer composition.

The present invention also relates to a process for preparing a conductive polymer composition of the desired form, which method comprises: (a) a crystalline polymer component, (b) an average particle diameter of at least about 60 milli microns or more and a DBP absorption function of at least about 800 cc / 100 g or more A first step of preparing a carbon black having a; and a second step of manufacturing a composition in which the carbon black is dispersed in the polymer is dispersed by dispersing the carbon black in the polymer component while the polymer component is melted, and the composition in the form of a sheet And a third step of melt molding, and annealing the sheet with heat under a predetermined pressure.

In another aspect, the invention relates to a PTC device of the conductive polymer composition and at least two or more electrical devices connected to a power source to allow current to flow through the PTC device.

The present invention will be described in detail with reference to the accompanying drawings.

I. Composition

A. Carbon Black

In the compositions according to the invention, certain carbon blacks with a fairly large particle diameter and high DBP absorption function are dispersed over a wide range of crystalline polymers. Carbon black used in the present invention has an average particle diameter of at least about 60 millimeters or more, preferably an average diameter of at least about 70 millimeters or more, and more preferably, an average diameter of at least about 80 millimeters or more. good. The maximum average particle diameter is at most about 500 millimeters, preferably at most about 400 millimeters, more preferably about 350 millimeters. Most preferred average particle diameter is about 80 to 110 millimeters.

The average particle diameter D of carbon black is described in detail in K. Kinoshita's "Carbon: Chemical and Physical Properties 45-48 (Wiley Inter Science 1987)" using conventional electron microscopy.

A second important property of carbon black used in the compositions according to the invention is its DBP absorption.

The DBP absorption of carbon black is at least about 80 cc / 100 g or more, preferably at least about 90 cc / 100 g or more, and more preferably at least about 100 cc / 100 g or more.

Maximum DBP absorption is at least about 500 cc / 100 g, more preferably about 200 cc / 100 g. The preferred DBP absorption range of carbon black is about 100cc / 100g to 140cc / 100g, and more preferred DBP absorption range is about 100cc / 100g. DBP absorption is measured according to the process of ASTM D-2414-79.

Conventional carbon blacks having an average particle diameter of about 60 millimeters or more are generally classified as lower carbon blacks such as ThermalBlack (a kind of carbon black) and have high electrical resistance. Thus, a conductive polymer composition composed of a mixture of polymer and such lower carbon black does not have good electrical conductivity. DBP absorption is related to the well-known structure of carbon black, which is an average particle size of carbon-carbon bond chain size. Lower carbon blacks with an average particle diameter of 60 milli microns or more generally have a DBP absorption of less than about 6 cc / 100 g. The average carbon black used in the present invention is the absorption of a typical carbon black having an average particle diameter of only 50 milli microns that is minimal DBP absorption of 80 cc / 100 g. Table 1 shows the physical properties of various carbon blacks, including the carbon blacks of the present invention, which are available from commercially available ME010 and 011 (Tokyo 107, Tokai Carbon Co., Ltd., Minato-ku Mita-Aoyama 1-2-3). Indicates. ME010 and 011 have very large average particle diameters of 90 millimicrons and have a low surface area of 21-23 m2 / g, which is either Dermal Black (ASTM-designated N907) or SRF (Semi-Reinforcing Furnace) black (ASTM-designated N762- 787). ME010 and 011, however, have DBP absorption values of 116 and 135, which are almost the same as HAF, SAF or acetylene black, which are much larger than those of the dermal or SRF black, and are conductive carbons larger than the dermal or SRF black.

Rubber grade carbon blacks are classified into grades according to standard ASTM designation according to ASTM D1765-88b based on the average particle size of carbon black determined by electron microscopy.

ASTM D1765-88b represents the typical physical properties of each standard grade carbon black. ME010 and 011, however, differ from standard grade carbon black. This is because they have a high DBP absorption despite having a very large particle size.

TABLE 1

1) ASTM D3037

2) ASTM D2417

The values of surface area S in Table 1 are measured by the well-known citrogen absorption method, and the data described in detail by the measurement of D and S are described in Schott, Ford and Lyon et al. It is described in detail in "Analysis of Carbon Black".

B. Polymer

The polymer component may consist of one or more crystalline polymers or may consist of at least about 75% of an amorphous polymer by weight. The crystalline polymer consists of at least about 10% crystals, preferably at least about 20% and up to 98% crystals. The polymer crystal is preferably in the range of 20% -40% although it depends on the amount of carbon black in the composition.

Crystals are measured by X-ray crystallography (Crystallography), and a representative polymer of the present invention is described in "Encyclopedia of Polymer Science and Technology", pages 449-529 (John Wiley & Son, New York 1972).

Most suitable polymers are polyolefins, in particular polymers of one or more alpha-olefins, for example polyethylene, polypropylene and ethylene / propylene copolymers, and copolymers of one or more alpha-olefins, for example one or More comonomers (comonomers), ie vinyl acetate, acrylic acid, ethyl acrylic acid (and its salts), ethyl acrylate and methyl acrylate, poly arylene, for example polyarylene ether ketones and sulfones and polyphenyls Ethylene sulfide and polyesters composed of polylactones, ie polybutylene telephthalate, polyethylene telephthalate and polycaprolactone, polyamides, polycarbonates, fluorocarbon polymers, such as fluorine by weight ratio of at least 10%, preferably More than 20%, for example polyvinyl fluoride polytetra Copolymers of comonomo and optionally tertiary comonomones comprising fluorine such as fluoroethylene, fluorinated ethylene / propylene copolymers, ethylene, and tetrafluoroethylene, polyolefins and small amounts of maleic acid, epoxy or isocyanate Polyolefin copolymer modified with an nate group.

Preferred polymers are polyethylene, preferably high density polyethylene, ethylene copolymers and ionized copolymers, more preferably acrylic acid or vinyl acetate.

The copolymer may be modified to include ereric acid or epoxy groups. These polymers may be used alone or in combination. Preferred copolymers comprise from about 80% to 100% by weight of ethylene, such as high density polyethylene, and 0% to 25% or more by weight of comonomer.

As described in more detail below, the polymer component of the present invention is not particularly limited as long as the minimum crystallinity is satisfied, and the polymer can be freely selected over a wide range to meet the particular physical or electrical performance requirements of the PTC composition.

For example, preferred ethylene polymers are high density polyethylene (MFR (MELT FLO W RATIO): (melt flow ratio) 0.3-50), low density polyethylene (MFR 0.3-50), copolymer of ethylene and vinyl acetate (VA content 2- 46%, mp (melting point) 108-67 ° C), acrylic acid (AA content 7-20%), ethyl acrylate (9-35% EA, mp 91-65 ° C), methacrylic acid (crystal 25%, MMA Content of 9-12%, mp 80-100 ° C) and methyl methacrylate (MMA content 10-40%), ethylene, vinylacetate and a small amount of glycid methacrylate (crystal 40-50%) , VA content 8-10, GMA content 1-5%, mp 90-100 ° C.).

In addition, as the modified copolymer, a copolymer of ethylene and vinyl acetate modified with a small amount of maleic acid (m. P. 80-90 ° C.) may be used.

If there is no need to limit the trip temperature, high density polyethylene is preferred, for example Hizex 220J (manufactured by Mitsui). If it is necessary to limit the trip temperature to 100 ° C. or lower, copolymers of ethylene and methacrylic acid and their metatic salts, for example ionomers such as Hi-Milan 1650 (manufactured by Dupont Mitsui) or Bondfast 7B It is preferable to use terpolymers of ethylene, vinyl acetate and glycine methacrylate such as (Sumitomo Chemical Co., Ltd. product). Conventional devices containing these copolymers have a trip temperature of 70-75 ° C.

The choice of polymer depends on the desired properties of the PTC composition. One of these remarkable characteristics can be the maximum temperature of the trip protection circuit made of the conductive polymer composition. For example, fluoropolymers are suitable at high temperatures, but copolymers of polyolefins are suitable at temperatures below 100 ° C.

Another important condition is electrical resistance.

Low resistance is usually desirable for use in circuit protection devices because it is desirable that the power loss of the circuit protection device be as small as possible in steady state. The resistance of this device is determined by the electrical resistance of the conductive polymer composition and the contact resistance between the electrode and the composition. The electrical resistance is determined by the combination of the composition, for example the polymer, carbon black and its contents.

Contact resistance is determined by the bond between the electrode and the polymer composition. Copolymers of polyolefins, such as copolymers of ethylene and one or more carboxyl or ester group-containing monomers, are preferably olefin copolymers modified to include functional groups such as epoxy or isocyanate groups.

C. Composition

The predetermined amount of carbon black in the composition should have a composition resistance of at most about 100Ω-cm, preferably at most about 50Ω-cm, especially at most about 20Ω-cm and more particularly at most about 10Ω-cm, and these resistances are -40 It is preferred to be kept at a temperature between < RTI ID = 0.0 > Desirably, the resistance should be significantly reduced, preferably about 7 Ω-cm or less, or preferably about 5 Ω-cm, in particular about 3 Ω-cm, more preferably about 1 Ω-cm.

The amount of carbon black required to have a low resistance combined with a given PTC action depends on the polymer component, carbon black and other particulate fillers present and the methods used to prepare and form the composition.

The weight ratio of carbon black and other particulate filler to polymer in the composition has a significant effect on the electrical properties of the composition.

The determination of polymers is well known to those skilled in the art, and the amount of carbon black is typically about 50 to 150 PHR (which is what part per 100 parts by weight) for the composition containing the copolymer. do.

The amount of carbon black is usually about 40 to 120 PHR for polymers such as polyethylene. It has been found that other compositions are effective in preparing other PTC compositions in the present invention without limiting the scope of the invention. For high density polyethylene the carbon black ranges from about 50 to 100 PHR, preferably from about 65 to 85 PHR.

Terpolymers of ethylene, vinyl acetate and glycine methacrylate are preferably about 60 to 120 PHR, more preferably about 70 to 100 PHR.

The amount of carbon black is about 60 to 120 PHR, and preferably about 70 to 100 PHR, for inomeric copolymers of ethylene and methylcrylic acid and metallic salts. Compositions having a relatively small amount of carbon black have values of relatively high dielectric breakdown strength and relatively low conductivity, for example, 100 V / m or more and 100 Ω-cm or less, respectively.

Compositions having a relatively high amount of carbon black have relatively high conductivity and relatively low dielectric breakdown strength, for example, 10 Ω-cm or less and 50 V / mm or more, respectively.

The volume ratio of carbon black to polymer component can be calculated for a given polymer based on the weight range, preferably in the range of about 0.15 to 0.65.

The method used to disperse the carbon black in the polymer and make the compositional radish and in particular the power consumed in this method has a significant effect on the electrical properties of the composition. If the power consumption is high, the composition tends to have a very high resistance at temperatures below Ts and unsatisfactory electrical stability against aging at elevated temperatures. On the other hand, when the power consumption is very low, this also results in a composition exhibiting unsatisfactory PTC action. A process for the dispersion of carbon black in crystalline polymers is described in US Pat. No. 4,237,441, which is suitable for the preparation of new dispersions according to the invention. Regardless of which method of dispersing the filler component in the polymer component is used, the most practically advantageous method is a mechanical shearing process of a solid polymer and filler component (and optionally an external heating process) to melt the polymer and disperse the filler in the molten polymer. Should be included). This dispersing process can be carried out, for example, in a Banbury mixer, roller mill or single screw or twin screw. The dispersion is either directly extruded into the desired final molded body or recovered from the mixer in a convenient manner, scraped off and subsequently melt molded, for example by compression, molding or sintering.

Typically, the composition is extruded into a rod, cooled with water and then pelletized. The pellet is extruded at a temperature above the melting point of the composition to form a film.

This film is sandwiched between two thin metal foils and pressed at a temperature above the melting point of the composite to form a thin film sheet. In order to reduce the contact resistance and to provide stable conductivity, heat treatment or hot rock should be performed before crosslinking at a temperature above the melting point of the polymer composition.

In this annealing step, the temperature is usually in the range of about 300 ° C. from the melting point, and the preferred temperature is about 30 ° C. or more to 280 ° C. than the melting point, and more preferably about 50 ° C. or more than the melting point. The raw material should preferably be annealed at this temperature for at least about 5 minutes or more, more preferably for about 10 minutes, most preferably at least 60 minutes at a pressure of at least about 1 kg / cm &lt; 2 &gt; In about 30 gk / cm <2> is preferable. It is then cooled to room temperature while maintaining the same pressure.

The thin film sheet is preferably bonded by, for example, an accelerated electron beam, or by chemical or silane (crosslink) crosslinking to form a crosslinked PTC polymer sheet.

This thin sheet is then cut into small pieces of square or other shape. The metal conductor is fixed to the metal foil by conventional processes such as welding to provide electrical conductors. Typically the device is installed in an electrically insulated housing, which is either thermally conductive or thermally insulated as required. Suitable housings include an antioxidant layer, as disclosed in US Pat. No. 4,315,237, which is incorporated herein by reference.

In addition to the above annealing treatment before crosslinking, it is also a good idea to heat treat the electrical device again after the crosslinking and finishing process steps. That is, the thin film composition is heat-treated by external heating for at least one minute at a temperature such that its resistance is between 100 Ω-cm and peak resistance while its composition is maintained, thereby at least one or more between -40 ° C and Ts. It provides a heat treatment composition having a resistance of 0.5 to 2.0 times the composition resistance at the same temperature before heat treatment at the temperature.

The thin film conductive PTC polymer composition is also heat treated by electrical resistance heating to allow the composition to pass through the composition for at least one minute or longer to provide sufficient current to maintain the composition at temperatures between Ts and (Ts + 50) ° C. And between 0.5 and 20 times the resistance of the composition at the same temperature, heat treated at least one temperature between Ts.

The carbon black must be sufficiently irradiated to form a composition having substantially uniform electrical properties, and to some point the increase in power consumption in this process results in a composition that exhibits a very large PTC effect.

On the other hand, if the power consumption is too high in this process, the composition may become electrically unstable when aged at elevated temperatures and may have a very high resistance at temperatures below Ts. Advantageously the total energy used to prepare the composition and melt molding is 1 to 300 hp · hr · ft −3 (hours per cubic foot of the composition), preferably 1 to 50 hp, especially 1 to 25 hp · hr · ft ± 3.

According to the present invention it is possible to prepare a conductive polymer composition exhibiting a PTC action with a temperature of Ts of 6 ° C. or higher, which has a resistance of at least 7Ω-cm at at least one temperature between Ts and −40 ° C. It has satisfactory electrical stability while having a peak resistance of about 1000Ω-cm or more during aging at.

The peak resistance of the composition of the present invention is preferably at least 1,000 Ω-cm or more, more preferably at least 5,000 Ω-cm or more, particularly preferably at least 10,000 Ω-cm. Typical compositions according to the invention have a resistance of 5 Ω-cm at 20 ° C. and a peak resistance of 1 × 10 = Ω-cm.

D. Additive

The composition also has a non-conductive filler, which consists of arc inhibitors, antioxidants and crosslinkers, antioxidants and other auxiliaries.

The composition preferably consists of antioxidants or other additives, such as heat-oxidizing agents, which stabilize the composition against degradation, where the amount of such additives is usually 0.005 to 10% by weight based on the weight of the polymer. do.

Conventional antioxidants, for example 4,4'-thiobis-6-tert-butyl-3-methylphenol or tetrakis- [methylene] 3 (3 ', 5'-di-tert-butyl-4'- Hydroxyphenyl) propionate] methane is preferably used in an amount of 0.05 PHR to 05 PHR.

The additive consists of sintered phenol, as known from US Pat. No. 3,986,981 (Leon) and "Irganox" manufactured by Ciba Geigy. The choice of antioxidant depends, of course, on the polymer, and it should also be noted that several materials useful as antioxidants cause the electrical properties of the composition to lose stability upon exposure to elevated temperatures.

Synthetic fillers may also be added to the PTC composition according to the present invention, consisting of alumina hydroxide, magnesium hydroxide and talc in amounts of about 5 to 150 PHR. The crude Seoul contains other particulate fillers and consists of zinc oxide, antimony oxide or clay, for example as non-conductive inorganic or organic fillers. The term “filler component” is used herein to refer to all particulate fillers in the composition.

Value of the amount of the composition to obtain a composition having the desired electrical properties

Is at most about 1.0, preferably 0.5 or less, more preferably 0.4 or less, and particularly preferably 0.1 or less.

Compounds that can be thermally degraded to initiate crosslinking when the composition is intended to be crosslinked or compounds that enhance crosslinking when the composition is irradiated are included. Conventional crosslinking methods can be used here.

The irradiation of the electron beam is at least about 3 Mrad or more in an applied amount, preferably 5 Mrad or more, more preferably at least about 10 Mrad or more. This is the radiation crosslinking method disclosed in US Pat. Nos. 4,845,838, 4,857,880 and 4,907,340 described herein.

For chemical crosslinking, the PTC polymer composition includes a crosslinking agent such as dicumyl peroxide in an amount of about 2% by weight.

Other peroxides (peroxides), ie 2,5-dimethyl-2, 5-di-benzolperoxyrexane and thi-butyl peroxybenzone can also be used. Triarylcyanic acid or trimethylolpropane trimethacrylates can be used as chemical crosslinking accelerators.

Conventional silane crosslinking processes described in US Pat. No. 4,277,155 can be used.

Whichever crosslinking method is used, the gel content of the cured polymer should be at least about 20% or greater, preferably at least about 40% or greater.

II. Electrical equipment

The electrical device according to the invention consists, for example, of a circuit protection device, a thermal sensor and a thermal current limiting device.

Devices particularly useful for circuits carrying a steady current of 0.1 amps or more may protect the circuit against either or both against overcurrent or excessive temperature resulting from short circuits or voltage surges. The circuit protection device acts to increase its resistance when the current flowing through it exceeds the trip current or when the temperature of the circuit protection device exceeds the trip temperature.

The circuit protection device has a low resistance and operates normally in a stable thermal equilibrium with its surroundings, but when an overcurrent fault condition occurs, the device generates heat of I2R at a rate faster than the heat loss from it. Raise the temperature above the trip temperature.

The resistance of the device then rises rapidly until it reaches a stable thermal equilibrium at very high temperatures.

The ratio of the circuit current (a) in the steady state to the circuit current (b) in the high temperature equilibrium state is at least 2 or more, preferably at least 10 or more, so as to surely reduce the circuit current to a sufficiently low level. At least 20 or more is good.

Most of the devices of the present invention can be used to protect circuits against both very high ambient temperatures and excessive current. On the other hand, for optimum performance, the details of the device and its thermal conditions should be selected in light of the failure conditions of the dog, in which case they respond to an excessive increase in current but an undesired increase in ambient temperature or vice versa. There may be several circuits and thermal conditions that function according to the invention. This device is particularly useful in circuits that allow a 15 amp or more steady state current to pass at 20 ° C. with a current of at least 0.1 amps, ie 0.1 to 20 amps, preferably 0.1 to 10 amps, in normal operation. .

The way this device works depends in part on the rate at which heat can be removed therefrom. This rate depends on the heat transfer coefficient of the device, and in general the device should have a heat transfer coefficient of 2.5-5 milliwatts / ° C.-cm 2 measured in the air and averaged over its entire surface area. The optimal thermal design of the device depends on the fault condition that provides protection against it.

In most cases, the device reacts as quickly as possible to a fault condition. The circuit protection device of this invention consists of an electrical insulation jacket which surrounds an PTC element and an electrode, and connects a lead wire to an electrode in this insulation jacket.

This jacket also affects the thermal properties of the device, the thickness of which is chosen accordingly. Preferably the device comprises an antioxidant layer such as described in US Pat. No. 4,315-237.

A. Resistance

The electrical device consisting of the electrode is in intimate contact with the conductive polymer composition, which is a mixture of the polymer and the carbon black, wherein the amount of carbon black is suitable to provide a low resistance (at most about 30 Ω-cm) to the composition, and It should have a low resistance, at most about 500mΩ, and an unexpected high breakdown strength, ie about 600v / mm.

During normal operation of the circuit, the resistance Rdn of the device is determined by the resistance of the PTC device in the case of a device consisting of two metal electrodes in contact with the PTC device, which is usually in the range of 1.0 to 5000 mΩ, preferably 5.0 to 100 mΩ. More preferably about 10 to 500 mΩ.

To provide a device with such a low resistance, the PTC polymer composition typically has a resistance of at most 1000 Ω-cm, preferably at most 500 Ω-cm, particularly preferably at most 100 Ω-cm.

In order to have such a low resistance the PTC layer should be as thin as possible, for example about 100 μm to 1 mm thick, preferably 100 μm to 500 μm. The nominal diameter of this device is preferably in the range of 3 to 80 mm, preferably in the range of 5 to 50 mm, although a substantially larger thickness or nominal diameter may be used.

In addition, in the circuit used in this apparatus, Rdn needs to be 0.1 × RL or less. In this case RL holds the resistance of the rest of the circuit in series. Rdn is preferably 0.04 × RL or less, more preferably 0.001 × RL or less. The RL should preferably be a practical constant, which does not change by more than ± 25% over the operating temperature range of the circuit. The RL is generally a resistive load, wholly or partially capacitive, or may be an inductive element.

However, if the RL changes substantially over the operating temperature range, the device is protected against excessive current resulting from a decrease in the RL, thus protecting the circuit against excessive changes in the RL.

As can be seen from the above, in the normal operation of this circuit, the power of the device is very low and it is easily dissipated to the surroundings. On the other hand, when a fault condition occurs, the power of this device increases rapidly and cannot be lost to the surroundings, and then a stable point of high temperature loses power and reaches a point where the resistance of the device is high enough to ensure circuit "break". Until the power of this device is reduced. That is, the current in the circuit is reduced to a reasonably low level. Since the power dissipated in this device depends on the resistance (depending on temperature) and the current through it, the device breaks the circuit in response to excessive temperature or excessive current in its surroundings. In order to reduce the current to the level required in the practical application, the switching ratio, i.e. the current ratio of the circuit in the circuit to the disconnection state in the normal operating state, should be at least 2 or higher, preferably higher than 10 or more preferably at least 20 Should be

Such electrical devices have an operating voltage of about 1 to 50V in the circuit and typically have an operating voltage of about 1.25 to 40V. Above about 5V, the breakdown voltage of this device is the critical rate, the maximum operating voltage of this device is desirable, about 30-35V. Current limiting devices shall be able to withstand this voltage in the event of a circuit breakdown.

A typical circuit protection device according to the invention is shown in FIG. 1, in which the metal foil 1 is formed of a thin film of a sheet 2 of PTC material of diameter d and thickness t. A lead conductor 3 is connected to each foil electrode layer 1, providing a suitable electrode for connection in this circuit. A second circuit protection device in which three electrodes 1 are coupled to two sheets 2 of PTC material is shown in FIG.

The invention is not limited to thin sheet PTC samples, but is in the form of wires or columns, unlike various PTC materials such as those described in US Pat. Nos. 4,724,417 and 4,857,880. Such devices can basically function as current limiting devices or temperature detection devices or as coupling devices thereof.

B. Other Electrical Characteristics

When the electric device is unable to limit the current, breakage of the PTC element occurs in the electric device, and the resistance of the trip device drops sharply at a temperature above the switching temperature of the PTC composition. Destruction is a short term phenomenon.

It can be seen that in the electrical device according to the invention the breakdown voltage is very closely related to the operating voltage in the circuit comprising this circuit protection device since the PTC layer has a very low resistance at normal operating temperatures and is usually very thin. The breakdown voltage depends on the speed at which the voltage of the circuit is increased, and the increase rate is suddenly changed in a circuit in a fault state of a short circuit.

In this case, the device would ideally operate instantaneously to limit the current.

Devices with low resistance generally have a relatively high current, and as will be apparent the design of the device changes the device area and thickness of the PTC device and can be easily modified to provide a trip current capacity suitable for a given application. Typically for a device according to the invention the maximum current which can pass through it without tripping is about 15 amps.

For example, when the size of the PTC layer between the two metal foil electrodes is 10 mm × 10 mm × 150 μ, the trip current is about 3 amps. If the device has a relatively large area or a relatively thin PTC element, the trip current is high.

In electrical circuits, the operating current of the device is about one third or one half of the trip current and can be appropriately selected according to already approved electrical design criteria.

The PTC composition should have a breakdown strength of at least about 100 V / mm or higher, preferably at least 200 V / mm and particularly preferably at least 400 V / mm, at high temperature and stable parallelism. in this case

The current flowing through the circuit to be protected, here the current through the protective device, increases above a certain limit, i.e. when a short circuit or surge voltage occurs at the load, the circuit protection device reaches its trip temperature. In this case, the trip temperature of the circuit protection device increases rapidly until the current is limited.

The equilibrium temperature at which the heat loss from the device is balanced by the heat generated by the current flowing through the device is the "trip temperature". In comparison, the switching temperature is not the maximum temperature at which the resistance of the device does not change or the temperature at which the resistance starts to rise.

The trip temperature, which is almost equal to the switching temperature, is the temperature at which RL = Rdn in the circuit and is different from the trip temperature of the circuit protection device. The conductive polymer composition preferably has a switching temperature of at most about 180 ° C, preferably at most about 130 ° C and more preferably at most about 100 ° C.

The “trip temperature” of equilibrium depends on a number of factors including the operating voltage of the circuit and the power that the device can lose due to heat loss under different conditions. The power that can be dissipated by the device depends on the thermal conductivity of the medium surrounding the device, the movement in any case of the medium and the surface area of the device and the temperature of the medium surrounding the device.

The circuit protection device of the present invention is generally coupled in series between a device or a system to be protected, and this series coupling is achieved by directly connecting the power supply without using another series resistor or other element in the circuit.

FIG. 7 is a graph showing the current passing through the circuit protection device by applying a voltage across the device in this circuit configuration.

Figure 6 shows the resistance of this device as a function of temperature. As shown in FIG. 7, when the protective device is normally operated, most of the power supply voltage is applied across the protection device, and only a small voltage Vn is then applied across the circuit protection device. The temperature of the circuit protection device at this time is a relatively low temperature Tn.

If the protective device is short-circuited for some reason, the voltage across the circuit protection device is raised, increasing by the corresponding amount lost in the circuit protection device and raising the temperature of the device. When the switching voltage Vs is reached (switching temperature Ts), the resistance of the circuit protection device increases rapidly. When the voltage across the circuit protection device reaches Vtrip, which is essentially the total supply voltage, the circuit protection device becomes high resistance at the trip-on Ttrip. The value of Ttrip depends on the supply voltage and the rate at which the circuit protection device dissipates heat in the medium in thermal contact.

As is clear from the above, the trip temperature in the circuit depends on the applied voltage that the circuit protection device must withstand. The trip temperature is determined for a specific voltage, and as used herein, the trip temperature is determined to be measured at an applied voltage of 5 volts.

As can be appreciated, however, in certain applications, the applied voltage should be able to vary in a significant range, and in applications it is desirable to limit the trip temperature to avoid damage to other circuitry.

In general, in many applications the trip equilibrium temperature should be below 100 ° C., preferably at most about 80 ° C., more preferably at most about 60 ° C.

C. Physical Characteristics

The electrical device according to the invention usually consists of two electrodes electrically connected to and separated by a conductive PTC polymer body, and the invention is directed to a PTC polymer body of a specific structure, ie a film, cylinder, strip or irregular solid body. It is not limited and is not limited to the atmosphere specific electrode shape, material or arrangement. That is, the electrode may be a foil, mesh, plate, perforated plate or foil, pillar, wire, cable or other shape, and may include a shape as described in US Pat. No. 4,352,083.

Preferably, the electrical device is thinned into a film or sheet of PTC material having metal foil electrodes on both sides thereof and is circular or longitudinal. Electrical devices usually have other conventional devices, such as one anti-oxidation layer or multiple anti-oxidation layers, waterproof housings and the like. The present invention comprises an electrical device having a single type of PTC polymer layer and at the same time a plurality of PTC polymer layers having different resistances or different degrees of crosslinking as described in US Pat. No. 4,907,340.

The type of electrode is not limited and is freely selected from the electrodes typically bonded to the PTC polymer material.

Conductive metal electrodes are used wherever possible, and preferably copper, tin coated or plated copper, or nickel foil electrodes having a fine roughened surface (rough surface) as described in US Pat. No. 4,689,475.

Fine roughening may be produced by roaring, mechanical roughening or chemical roughening. In particular, as described in US Pat. Nos. 4,800,253 and 4,689,475, a surface electrode foil prepared by electrolytic deposition of a copper electrode or nickel layer composed of micron-odules and micro-odules is used.

The electrode thickness is not critical, and when the foil electrode is used, each electrode is usually about 20 μm to 100 μm thick, preferably about 30 μm to 70 μm thick.

Polymers used in the present invention are commonly crystalline polymers. Relatively high crystalline polymers tend to provide high breakdown voltages. However, the contact resistance between the composition and the electrode is very important so that polymers with few crystals are often used in consideration of the balance between resistance and breakdown voltage.

Protective circuit devices using the present compositions are also used when installed in less housings.

Thus, if the device trips and the temperature of the changeover is approximately equal to the melting temperature of the polymer, the neighbor will damage the device or plastic housing. It is therefore very desirable that the maximum trip temperature of the protective circuit device not exceed about 100 ° C. It is also an important criterion for polymer selection.

Such devices generally have a resistance of at most about 100 mΩ, preferably at most about 500 mΩ at room temperature. In addition, the device uses a PTC conductive polymer composition having a volume resistance of at most about 100Ω-cm and preferably having a resistance of at most 50Ω-cm.

Preferred circuit protection devices of the present invention are in direct physical and electrical contact with the PTC conductive composition and are optionally chemically bonded. The electrode and the PTC composition have a path length t and an area of d, so that the current flows through the PTC composition having a d / t of at least about 2 or more, preferably at least about 10 or more, and particularly at least about 20 or more. Arranged to flow.

The thickness of the device, i.e. the device comprising the PTC polymer layer, the electrode antioxidant layer and the housing should be as thin as possible, the thickness being in the range of 0.020 to 3,0 mm, preferably in the range of 0.03 to 1.0 mm. The nominal diameter of the device is in the range of 3 to 80 mm and preferably in the range of 5 to 50 mm.

The term “nominal diameter” means the diameter of a circle having the same area as the current flows through. This area may be of a particular shape, but for the sake of manufacture of the device it is generally circular or longitudinal.

In general, it is preferable to use two planar electrodes of the same area located opposite to each other on both sides of a flat PTC element having a certain thickness in this apparatus. However, other arrangements are possible to meet specific sizes or electrical requirements, for example, two or more electrodes or one or more PTC elements can be arranged, and a wedge-shaped device or a curved thin film PTC element of a certain thickness between each other may be used. Branches can bend curved thin film electrodes. It is clear to those skilled in the art how the d / t ratio is calculated in such other arrangements.

The composition of the present invention is preferably in the form of a molded article to be produced by a method consisting of melt molding, for example, compression or molding.

PTC devices are generally made of a uniform composition or for example two or more layers having different resistances and different switching temperatures. The electrode may be in direct contact with the PTC device or one or more of them may be electrically connected to it by another conductive material, such as a conductive polymer composition of relatively constant resistance.

The circuit protection device must withstand the supply voltage after tripping in order to successfully limit the current flow through the circuit in the event of a fault. Modern electric devices, for example wireless electric drills or automobiles, are often driven by large batteries having voltages above 20V, sometimes above 25V.

The thickness of the device should generally be thin enough to withstand high voltage stresses. For example, the PTC composition should have a voltage stress of 100V / mm when the thickness of the PTC composition is 0.25 mm and the supply voltage is 25V. Widely used conventional PTC polymer compositions must withstand voltage stresses of about 80 V / mm or more. In other words, the composition has a dielectric breakdown strength of 80 V / mm. In order to ensure safety, the circuit protection device according to the present invention has an insulation breakdown strength of at least about 200 V / mm or more when measured according to a reference voltage increase at a trip temperature, preferably at least about 400 V / mm or more, and more preferably. At least about 600V / mm or more is preferable.

Preferably, the dielectric breakdown strength is determined at about 600 to 800 V / mm.

The parameters of the circuit protection device in the circuit are for reference only limited to other circuit elements, the medium around the device and the rate at which heat loss is caused by the device and the medium therefrom. However, the parameters of the protective guards useful for various purposes are limited to the way they function when placed within the standard circuits and the harmonization of the standard. Accordingly, the present invention provides a circuit protection device comprising a PTC element of a PTC composition having a switching temperature Ts and at least two electrodes connected to a power supply and flowing current through the PTC element when the power supply is connected. The device is connected in series with a power supply having at most about 50V voltage as part of its test circuit, and the device is placed in a stil sir.

At 25 ° C, there is an unstable balance between the rate at which the device generates heat of I2R and the rate of heat loss from the device. A stable operating state is achieved next.

A) A current flows through a PTC element with an area of nominal diameter d and an average path length of t with at least d / t.

B) The device shall have a resistance Rdn of 1 ohm or less at a temperature Tdn and a resistance of the PTC composition of 10 Ω-cm or less.

C) Air and atmosphere must be at temperatures Tn below 25 ° C.

D) There must be a stable equilibrium between the rate at which this device generates heat of I2R and the rate of heat loss therefrom.

An exemplary circuit according to the invention is shown in FIG. In this case, the circuit protection device according to the present invention is connected in series with a load 4 and a power supply 5 such as a battery. The second circuit according to the invention is shown in FIG.

The power source of this circuit, which consists of a circuit protection device 3 and a load 4, consists of a transformer 6. Another circuit according to the invention in which the current limiting function of the electrical device is combined with the thermal sensing function is shown in FIG. 5, where the electrical device 3 is in thermal contact with the load 4.

Although the present invention is described herein with reference to a circuit consisting of only one PTC circuit protection device, the invention is a circuit consisting of two or more devices that can be tripped by different failures and the circuit protection device has a certain protective effect. It can be understood that two or more electrical devices connected in parallel and / or in series can be used and provided simultaneously.

As described in connection with FIG. 3, the PTC electrical apparatus of the present invention is generally connected in series with a load RL (device to be protected) and a power supply, and this series circuit has no current limiting resistor.

With this arrangement the voltage VPTC across the PTC device under steady state is represented by the following equation.

Where VPS is the power supply voltage stage. In normal operation before tripping, almost all of the supply voltage VPS is applied across the load because the RPTC is significantly less than RL.

However, if the load is shorted, the supply voltage VPS is applied immediately across the PTC device. At this time, since the PTC element is in a low resistance state, a high current flows through it and is heated by an internal resistance.

When the temperature of the PTC element reaches the switching temperature TS, as shown in FIG. 6, the resistance of this apparatus is rapidly increased, and as a result, the current passing through the series circuit is reduced to a small value. However, since the resistance of the PTC device is greater than the resistance of the load and there is no other series-connected resistor that absorbs any supply voltage, substantially all of the supply voltage is applied across the PTC device. In order to operate successfully, the breakdown voltage of the PTC element is larger than the power supply voltage (security lead). In other words, the current through the series circuit increases again.

Thus, the low breakdown voltages of conventional PTC devices severely limit their application, but only to low power supply applications. The device of the present invention, on the other hand, can be used in applications requiring significantly higher supply voltages because of their very high breakdown voltages.

Some of the representative applications of the present invention are described below.

Laptops have been developed to have a printing function in recent years and to operate for a long time with a single battery charge.

For this purpose, the computer is equipped with a battery of a large power supply. For example, a 15Ni-Cd (nickel-cadmium) cell has a total voltage of 38 V and a large internal current of 750 ohm (mΩ) can supply a large current. .

If a disk drive or printer motor of such a computer, which typically has a resistance of about 10 ohms, is shorted, there is a risk of destruction of the computer due to overheating or burning when about 50 amps of current flow through the short circuit. However, this risk can be avoided by using the circuit protection device of the present invention connected in series with the battery.

The circuit protection device is 400 microns thick, with 10 mm on each side and 50 milliohms of normal resistance.

These devices can limit the current to about 0.1 amps to prevent serious damage to the computer. Conventional circuit protection devices cannot be used in high current / high voltage applications due to their low breakdown voltage.

As another example, the circuit protection device of the present invention can be used to protect a motor of a wireless electric screwdriver, etc., which must be compact and light for easy handling. Such applications typically require a high capacity battery, for example 10 lithium cells have a total output voltage of 30V.

The circuit protection device of the present invention can be connected in series with a battery to protect the motor against a short circuit.

The invention will be described in detail hereinafter with reference to the following examples, which are not intended to limit the scope of the invention in any way.

On the other hand, all parts by weight, percentages and ratios are by weight unless otherwise indicated here.

Example 1

The ingredients listed in Table 2 were mixed at 150 ° C. for 10 minutes in a Banbury mixer and discharged onto a roll, after which the sheets of mixed compound were pelleted.

The mixed composition is melt extruded into a thin film of about 0.2 mm thickness. The sheet is sandwiched between two sheets of electrolytically amplified nickel foil of 0.05 mm thickness, each sheet having a microrough surface in contact with the PTC polymer.

The micro roughness here is composed of about 5 microns of micron modules.

The insert is pressed together for 30 minutes under pressure 50Kg / cm2 at a temperature of 80 ° C to form a sheet of thin film PTC composition having a thickness of 0.10 mm of the thin film PTC composition, and then cooled to room temperature under the same pressure, The thin film polymer is crosslinked by electron beam irradiation of 8Mrad intensity.

The PTC thin film, which becomes a square piece, is cut into a size of 10 mm x 10 mm from the PTC composition sheet of the thin film, and nickel foil lead conductors are connected to each electrode.

The physical properties of the PTC device consisting of the compositions described in Table 2 are also shown in Table 2.

The polymer used in this example is a copolymer of ethylene and methacrylic acid and its zinc salt, having a crystal of about 25%, a melting point of about 98 ° C., and Hi-Milan 1650 [Dupont Mitsui: Polychemical Co., Ltd.]. It is marketed as product of.

The antioxidant used in each example is 4,4′-thiobis-6-tert-butyl-3-methylphenol (Santonox R). In this example, the PTC polymer layer is crosslinked up to about 60% gel.

As shown in the table, the amount of each carbon black used is the most suitable amount providing the best PTC action and breakdown voltage. The samples thus prepared are individually tested by the following method.

The AC breakdown voltage of each device is measured by using a single winding transformer, increasing the voltage at a constant rate of 60V / m at room temperature until the specimen is burned or ignited until breakdown appears. The resistance of this device is measured using a Wheatstone bridge at room temperature. Trip current is measured by using a constant voltage DC generator to increase the voltage by 50mV at the stand-by temperature of the stand-by, and for 2 minutes each time. The trip current is calculated by the curves relating to voltage and current. The trip temperature is measured by thermocouples on the electrode surface of the device when a 5V voltage is applied to the device in the trip state.

No composition containing Asahi FT carbon black provides a resistance of less than 100 mΩ.

Devices composed of PTC layers containing ME 010 and 110 show good breakdown voltage and low resistance.

It shows poor results on breakdown voltage compared to carbon black ME 010 and 110 such as Vulcan XC-72 and DENKA acetylene black.

TABLE 2

1) Measure at 5V

Example 2

The components shown in Table 3 are mixed and the PTC device is manufactured in the same process as in Example 1. Test results for these samples are shown in Table 3.

PTC compositions containing Ketjenblack have very low resistance and also very low breakdown voltage, while DIA black H has both median resistance and breakdown voltage, which are all unsuitable. The polymer used in this example is a copolymer of ethylene and vinyl acetate, where a small amount of epoxy groups are bonded by polymer recognition (Bondf ast7B, manufactured by Sumitomo Chemicals).

The polymer has about 20% crystallization, and in electrical devices the PTC layer crosslinks up to about 60%. The same antioxidant is used as in Example 1.

The trip temperature of each device is about 70 ° C.

Compositions containing polymers have very low resistance and relatively low trip temperatures, which prevent thermal damage to neighboring thermal sensing elements.

TABLE 3

1) Measure at 5V

Example 3

The components shown in Table 4 are mixed and the PTC device is manufactured in the same process as in Example 1.

The polymer used in this chamber is high-density polymer ethylene, a high crystalline polymer (90%) having a melting point of 120 ° C (HIZEX 2200J, manufactured by MITSUT Petrochemical Industries, Ltd.).

Antioxidant is [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxy-phenyl) propionate] methane (Irganox1010).

The test results in Table 4 show relatively high breakdown voltages compared to Examples 1 and 2 due to the polymer's crystallization, but this PTC composition has a relatively high trip temperature to damage neighboring thermal sensing elements in electrical applications or devices. . Clearly, even when used in crystalline polymer PTC compositions, ME 010 and 110 have higher breakdown voltages than other carbon blacks.

These results show that the PTC composition according to the present invention, containing certain carbons with a range of crystalline polymers, has a higher breakdown voltage and withstands higher voltage stress than conventional PTC compositions when used in a circuit protection device for overcurrent protection. Indicates that it can.

TABLE 4

1) Measure at 5V

Although the present invention has been described in detail with reference to specific embodiments thereof, it is evident that various changes and modifications may not be made to the person skilled in the art without departing from the spirit and scope of the present application.

Claims (54)

A conductive polymer composition exhibiting a positive temperature counting action and excellent breakdown voltage characteristics, comprising: a) a crystal polymer dispersed therein and consisting of 10 to 98% of crystals; b) an average particle diameter of 80 to 110 millimeters and 110; A conductive polymer composition composed of carbon black and the like having a DBP absorption function of 140cc / 100g, and comprising the crystalline polymer of 100 parts by weight and the carbon black of 40 to 150 parts by weight. The conductive polymer composition of claim 1 wherein the crystalline polymer has at least 20% crystals. The conductive polymer composition of claim 2 wherein the crystalline polymer has 20 to 40% crystals. The conductive polymer composition of claim 1, wherein the crystalline polymer is made of a polyolefin composed of at least one α-olefin. The conductive polymer composition of claim 4 wherein the crystalline polymer is selected from polyethylene, polypropylene and copolymers of ethylene and propylene. 6. The conductive polymer composition of claim 5, wherein the crystalline polymer is modified to contain at least one maleic acid, epoxy or isocyanate group. The conductive polymer composition of claim 4, wherein the crystalline polymer consists of a copolymer of one α-olefin and at least one ionizing comonomer. 8. The conductive polymer composition of claim 7, wherein the ionization comonomer is selected from vinyl acetate, acrylic acid, acrylate, methacrylic acid, methacrylate, ethyl acrylic acid, ethyl acrylate, ethyl acrylate and methacrylates. The conductive polymer composition of claim 8, wherein the crystalline polymer is modified to include at least one maleic acid, epoxy group or isocyanate group. The conductive polymer composition of claim 1, wherein the crystalline polymer is made of polyester. The conductive polymer composition of claim 10, wherein the polyester is selected from polybutylene terephthalate, polyethylene terephthalate and polycaprolactone. The conductive polymer composition of claim 1, wherein the crystalline polymer consists of at least one of polyarylene, polyamide, and polycarbonate. The conductive polymer composition of claim 1, wherein the crystalline polymer is made of a fluorocarbon polymer. The conductive polymer composition of claim 13, wherein the fluorocarbon polymer is selected from polyvinylidene fluoride, polytetra fluorethylene, ethylene and propylene, fluorinated copolymers and copolymers of ethylene and fluorine-containing comonomers. The conductive polymer composition of claim 4, wherein the crystalline polymer is composed of copolymer of ethylene and at least one copolymerizable monomer including an ester group or a carboxyl group. 16. The conductive polymer composition of claim 15, wherein the copolymer consists of at least one epoxy group or isocyanate group. The conductive polymer composition of claim 8, wherein the crystalline polymer is a copolymer of ethylene and at least one copolymerizable monomer selected from acrylic acid, vinyl acetate and methacrylic acid. 18. The conductive polymer composition of claim 17, wherein the copolymer is comprised of 80% to 100% ethylene and at least 0% to 25% copolymerizable monomers. The conductive polymer composition according to claim 5, wherein the crystalline polymer is made of polyethylene. 20. The conductive polymer composition of claim 19, wherein the crystalline polymer is made of high density polyethylene. The conductive polymer composition according to claim 7, wherein the crystalline polymer is an ionomer copolymer of ethylene, methacrylic acid and methacrylic acid salt. The conductive polymer composition according to claim 7, wherein the crystalline polymer is a terpolymer of ethylene, vinyl acetate and glycidyl methacrylate. The conductive polymer composition of claim 7, wherein the conductive polymer composition comprises 100 parts by weight of a crystalline polymer and 50 parts by weight to 150 parts of carbon black. The conductive polymer composition of claim 1, wherein the conductive polymer composition comprises 100 parts by weight of crystalline polymer and 50 parts by weight of carbon black. The conductive polymer composition according to claim 19, wherein the conductive polymer composition is composed of 100 parts by weight of crystalline polymer and 120 parts by weight of carbon black. The conductive polymer composition of claim 20, wherein the conductive polymer composition comprises 100 parts by weight of crystalline polymer and 40 to 110 parts by weight of carbon black. 27. The conductive polymer composition according to claim 26, wherein the conductive polymer composition comprises 100 parts by weight of crystalline polymer and 65 to 85 parts by weight of carbon black. 22. The conductive polymer composition according to claim 21, wherein the conductive polymer composition comprises 100 parts by weight of crystalline polymer and 60 parts by weight of carbon black. 29. The conductive polymer composition according to claim 28, wherein the conductive polymer composition comprises 100 parts by weight of crystalline polymer and 70 parts by weight of carbon black. The conductive polymer composition of claim 22, wherein the conductive polymer composition is composed of 100 parts by weight of crystalline polymer and 60 to 120 parts by weight of carbon black. 31. The conductive polymer composition according to claim 30, wherein the conductive polymer composition comprises 100 parts by weight of a crystalline polymer and 70 parts by weight of carbon black. The conductive polymer composition of claim 1 having a volume resistivity of at most 100 Ω-cm at a temperature between the composition -40 ° C and the bonding temperature Ts. 33. The conductive polymer composition of claim 32 having a volume resistivity of at most 50Ω-cm at a temperature between the composition -40 deg. The conductive polymer composition of claim 33 having a volume resistivity of at most 20Ω-cm at a temperature between the composition -40 ° C and the bonding temperature Ts. The conductive polymer composition of claim 34, having a volume resistivity of at most 10 Ω-cm at a temperature between the composition -40 ° C. and the bonding temperature Ts. 33. The conductive polymer composition of claim 32, wherein the composition has a peak resistance of at least 1000? -Cm. 37. The conductive polymer composition of claim 36, wherein the composition has a peak resistance of 5000? -Cm or more. The conductive polymer composition of claim 37 wherein the composition has a peak resistance of at least 10,000 Ω-cm or greater. The conductive polymer composition of claim 38 wherein the composition has a peak resistance of at least 50,000 Ω-cm. The conductive polymer according to claim 1, wherein the volume ratio of carbon black to crystalline polymer is 0.15 to 0.65. The conductive polymer composition according to claim 1, wherein the relationship between the surface area S of carbon black and the average particle diameter D of carbon black at m ² / g is at most 10. 42. The conductive polymer composition according to claim 41, wherein the volume of the S / D x carbon black is at most 1. The conductive polymer composition of claim 1 having a switching temperature Ts of at most about 180 ° C. 44. The conductive polymer composition of claim 43 having a switching temperature Ts of at most about 130 ° C. 45. The conductive polymer composition of claim 44 having a switching temperature Ts of at most about 100 &lt; 0 &gt; C. The conductive polymer composition of claim 1, wherein the conductive polymer is crosslinkable. A process for preparing a conductive polymer composition, comprising: 1) a polymer having a crystal of 10 to 98%, b) an average particle size D of 80 to 110 milli microns and a DBP absorption of 110 to 1400 cc / 100 g. Preparing carbon black; and 2) preparing a method of dispersing the carbon black in the polymer device into the composition device and simultaneously melting the polymer device; and 3) melt molding the composition. And 4) a step of crosslinking the melt-molded composition. A method of preparing a conductive polymer composition, comprising: 1) a) a polymer element having a crystal of 10 to 98%, b) an average particle size D of 80 to 110 milli microns and a DBP absorption function of 110 to 140 cc / 100 g. Step of preparing carbon black, 2) making a composition in which the carbon black dispersed in the polymer device is melted, 3) melt molding the composition, 4) heat-treating the composition A method of making a conductive polymer composition. The method of claim 48, wherein the melt-molded composition is crosslinked by irradiation after heat treatment. The method of claim 48, wherein the melt-molded composition is allowed to chemically crosslink using at least one peroxide initiator. The method of claim 48, wherein the melt-molded composition is crosslinked by silane crosslinking. 49. The method of claim 48, wherein the melt-molded composition is heat treated to maintain the composition by external heating at a temperature such that its resistance is between 100 Ω-cm and peak resistance for at least one hour, between -40 ° C and Ts. A method of making a conductive polymer composition that provides a heat treatment composition wherein the resistance at least one or more temperatures is 0.5 to 2.0 times greater than the composition resistance at the same temperature that was heat treated. 49. The electrical resistance heating of claim 48, wherein the melt-molded composition is allowed to flow through it sufficient current for at least one minute to maintain the composition at a temperature between Ts and (Ts + 50) ° C. Heat-treated to provide a heat-treatment composition such that at a temperature of at least one temperature between -40 ° C. and Ts, the resistance is 0.5 to 2.0 times greater than the composition resistance at the same temperature that was heat-treated. A method of preparing a conductive polymer composition, comprising: 1) a) a polymer having a crystal of 10 to 98%, b) an average particle plus size D of 80 to 110 milli microns and a DBP absorption of 110 to 140 cc / 100 g. (B) preparing carbon black having a carbon black, 2) dispersing the carbon black in the polymer device and dissolving the carbon black in the polymer device, and melting the polymer device; and 3) melt molding the composition. A process for producing a conductive polymer composition consisting of steps and wherein the total energy used in steps (2) and (3) is from 1 to 300 hp · hr · ft −2.

Images