TW408343B - Electrical device comprising a conductive polymer and method for making the same - Google Patents

Abstract

An electrical device (1) containing a resistive element (9) composed of a conductive polymer composition which exhibits PTC behavior which is attached to two metal foil electrodes (11, 13). The device is prepared by a method which includes the steps of (a) cutting the device from a laminate containing the conductive polymer composition positioned between two metal foils; (b) exposing the device after the cutting step to at least one thermal excursion from a first temperature which is at most (Tm-100) DEG C to a second temperature which is at most (Tm-25) DEG C; and (c) crosslinking the conductive polymer composition after the thermal excursion. The devices of the invention have low resistance and are useful as circuit protection devices.

Description

About 4 ~ month

Case No. 87120621 6. Application Patent Scope 1. An electrical device including a conductive polymer, including (A) a resistive element composed of a conductive polymer composition and displaying a PTC reaction and including, (1) A polymerized part having at least 20% crystallinity and a melting point Tm, (2) dispersed in the polymerized part, a special conductive filter, and (B) two electrode systems (i) bonding Resistive element: (ii) contains metal foil, and (iii) can be connected to a power source of electrical power. The device is prepared by a method, which includes the steps of: (a) cutting and positioning on two metals Plywood device with conductive polymer composition wrapped between foils; (b) After the device cutting step, it is exposed to at least a first temperature of at most (Tn- 1 0 0) ° C and at most (T „-25) ° C A thermal history of the second temperature; and (c) cross-linking after the thermal history of the conductive polymer composition. 2. If the device of the scope of patent application is No. 1, wherein the method is after step (a) and Before step (b), the method further includes at least one conductive lead connected to the metal foil and an electrode. 3. If the device in the scope of patent application 1 or 2 has a resistance value of at most 0.1 100 ohms ... 4. If the device in the scope of patent application 1 or 2 is applied, it is in step (c) The completion of the cross-linking is equivalent to 1 to 20 million Rads. · 5. The device according to item 1 or 2 of the patent application scope, wherein the polymer composition comprises polyethylene, ethylene, homopolymer or fluoropolymer. 6. The device according to item 1 or 2 of the scope of patent application, wherein in step (b)

O: \ 56 \ 56290.ptc Page 1 2000.04. 26. 017 408343 V. Description of the invention (1) ^ '一'-a kind of electrical device and invention of Ming Ming Ming range which is related to the kind of polymer containing conductive Method for making this device 〆Introduction to the invention The aeration device includes a conductive polymer composition showing a ptc (positive temperature resistivity) response and is known and has been used as a circuit. Protection devices and electric heaters of this kind of circuit protection device Contains a low-resistance conductive polymer composition that reacts depending on changes in room temperature and / or current. Under normal conditions, when a load is connected in series, the circuit protection device keeps-low resistance ° 断 ί 向 #: When the current or over temperature conditions, the device will increase its resistance and effectively cut the current to two low power. In normal use, the device is best to take steps: under the rule-to reduce all resistance values on the circuit to the minimum °-to the maximum ί at a low temperature 'a low resistance allows this device to pass higher, As for the occurrence of high-resistance conditions, the installation of two ::: electrical, protective devices can be made very small by changing the distance between the body and the body. Red and blue + + ㈣Large'㈣Small device. This device takes up less space and has the required thermal characteristics. Combined with the key points of the invention:-The most commonly used technology for small devices is the use of -low thunder. The different processing steps are known. When the resistance ratio of the cracking agent is 2 or the bag is 1 or it is exposed to the ascending step, it can be used as it is. The resistivity field of the product = and the lower the resistivity when the solder flows away, the better, so that the final result is obtained.

Page 5 408343 Amendment No. 87120621 Six 'patent application scope The device is exposed to at least one of the first temperature to the second temperature and back to the first temperature thermal cycle 7. First 8. Where. (Ii) by a first 2. 9. Device 10 The conductive electrode should be installed and the device as described in item 1 or 2 of the scope of patent application, wherein the temperature L in step (b) is lower than 2 3 ° C. The method of the electrical device of item 1, (1) the resistive element (i) has a thickness of at most 0.51 cm and is crosslinked to at least an equivalent of 2 million rads: and (2) after cutting in step (b) The device is exposed to at least a thermal cycle at a first temperature of at most (Tm-100) ° C to a temperature of at most (Tn-25) ° C and returned to the first temperature. A method as claimed in item 8 of the patent application, wherein the step (b) is exposed to at least three thermal cycles. A battery pack includes (1) a battery including one of the first and second terminals and (2) the device according to item 1 of the patent application scope, and further includes (a)-the first 1 lead is connected to the An electrode, * and (b)-the second conductive lead is connected to the second _ * * is placed in contact with the first terminal of the battery so that the first conductive lead is substantially electrically connected to the terminal *.

O: \ 56 \ 56290.ptc Page 2 2000. 04. 26.018 W8343 V. Description of the Invention (2) We have found a process sequence that can particularly help to produce a device with a low resistance. In a first aspect, the invention provides an electrical device comprising (A) a resistive element composed of a conductive polymer composition and exhibiting a PTC reaction and comprising (1) having at least a 20% crystallinity and a A polymer portion of the melting point Tm, and (2) a polymer portion: dispersed in a special conductive filter, and (B) two electrodes (i) joining resistive elements, (ii) including a metal foil, and (iii) and can be connected to an electrical power source. One method of preparing the device includes the steps of (a) cutting a plywood device made of a conductive polymer composition positioned between two metal foils; (b) exposing the device completed by the cutting step to at least the (T „-100) ° C first temperature is at most one of the thermal history of (Tra-25) ° C second temperature; and (c) the conductive polymer composition is crosslinked after the thermal history. In the second aspect The invention provides a method for completing an electrical device comprising: (A) a resistive element (i) having a thickness of approximately 0.51 cm, (ii) cross-linking it to at least 2 million equivalents, and (iii) It is composed of a conductive polymer composition and contains (1) a polymer part having at least a 20% crystallinity and a melting point Tm, and (2) in the polymer part, a special conductive filter Internal division

_408C43_ 5. Description of the invention (3) The two electrodes of scattered J and (β) (i) are connected with the resistive element, (i i) includes metal foil, and (i i i) and can be connected to an electric power source. The method includes (a) cutting a plywood device made of a conductive polymer composition positioned between two metal foils. (B) exposing the device to a temperature of (Tm-1 0 0) ° C after the cutting step. The first temperature is at least one thermal cycle at a second temperature of (T, -25) 1:) C, (c) the conductive polymer is crosslinked after the thermal cycle step. According to a third aspect, the invention provides a battery pack including (I) a battery having first and second terminals; and (Π) a device according to the first aspect of the invention including (C) one of the first terminals A conductive lead, and (D) a second conductive lead connected to one of the second terminals; the device is connected to the first terminal of the battery so that the first conductive lead is substantially and electrically connected to the terminal. The drawings focus on explaining the invention in terms of drawings, in which FIG. 1 is a cross-section of a device of the invention; FIG. 2 is a top view of a device of the invention; FIG. 3 is a top view of a part of the first conductive lead in the device of the invention Figure 4 is a top view of a second conductive lead in a device of the invention; Figure 5 is a top view of an insulating layer in a device of the invention; Figure 6 is a view showing a device made by the method of the invention by an invention Method and two contrasting methods.

408343 V. Description of the invention (4) Detailed description of the invention The electrical device of the invention includes a conductive polymer composition group, a resistive element, and first and second metal foil electrodes joined and sandwiched with the resistor. Sex element. The conductive polymer composition contains a polymer portion and a special conductive filter for dispersion therein. The polymer part contains one or more more polymers, one of which is preferably a crystalline polymer and has a crystallinity of at least 20% as measured by scanning with a differential calorimeter in a non-full case. Appropriate. The crystalline polymer contains one or more thin smoke, special polyethylene such as high density polyethylene, at least one olefin homopolymer and at least one monomer can form homopolymer, and further Acrylic, ethylene / ethyl acrylic vinegar; 'ethylene / vinyl acetate and ethylene / butyl acrylic vinegar homopolymer; fused into a formable tetrafluorofluorescent polymer such as polyvinyl fluoride (PVDF) and ethylene / ra Fluorinated ethylene with polymers (ETFE includes terpolymers); and mixing two or more polymers. In some applications it may be necessary to mix a crystalline polymer with another polymer, such as an elastomer or an amorphous thermoplastic polymer, to obtain the required physical or thermal properties such as variability and maximum exposure temperature. — Sex. The polymer portion is generally included at 40% to 90% by volume. It is best to be between 45% and 80% in volume, especially in the whole composition. The volume accounts for 50% to 75%.

408343 V. Description of the invention 之 The amount of the filter t is required for most of the synthetic materials. The conductive filter contains 10% to 60% by volume, and preferably 20% to 55% by volume. Resistive composites are used in low-resistance protective devices, in particular between 25 and 50% of the total volume by volume. The conductive polymer composition may contain additional components, such as non-oxides, non-conductive filters, non-conductive filters, radiation cross-linking agents (mostly prorads or parent-linked multipliers such as trimeric isocyanide, stable) Agents, dispersants, coupling agents, acid scavengers (such as CaCO3), or other ingredients. These parts generally contain 20% of the total volume of the composition. Dispersed to a conductive filter and other The polymerization part can be achieved by a suitable mixing device such as a dissolving process or a dissolving compound. The mixed composition can be dissolved by any suitable method, such as dissolving and extruding, injection molding, compression molding, or other processes. Resistive element, this element is preferably a thin sheet or 1 ο ?; I rectangular, square or annual ring shape. Most of the resistance element is 0 5 1 factory = (〇, 〇4 inches) thick 'and in many applications The system is thinner, and the buckle is at most • = meters (0_—02 inches) thick, preferably 038 cm (0015 inches). Right; to the composite of several oblique resistors shows a positive temperature coefficient (PTC) Reaction, ie "head": a very high increase in less temperature range The resistance value here has Γ i ', using this so-called "PTc" can be made into a composite. The product or device or device 4 if ^, 5 and / ❹100 have a value of at least 10, and the best combination Η ^ Η ⑽ should have a value of at least 6, where Rl4 is the comparison between the termination in 14 ° C and the resistivity of Khan. R_ is the termination in the range of ~ 100 ° C and the electrical resistance 1 ^ resistivity The ratio of ^ and ^ is the ratio of the end and start of the cattle in a range of 30. Using the composition of the present invention-generally presented and the lower value

Page 9 V. Description of the invention (6) The increased resistivity is larger. Appropriate conductive 1-synthetic composites are disclosed in U.S. Patent No. 4,237,44 1 (Wen 'Kenjinbo and others), 4,545,926 (Foz and others), 4,724,41 7 (Australia and others), 4,774, 〇 24 (Emperor Popular), 4,935,156 (Shen Deze and others), 5, 〇49,85 (] (Evans and others), 5,250,228 (Bagueri and others), 5, 3 78, 407 (Shenzhen) Germany and others), 5,451,919 (Zhou and others) 'and General Assigned International Publication No. 9 6/29711 (Ruiqi Company published on September 26, 1997). The 7G resistor is joined to the first and the first On two thin plate electrodes, the electrode is connected to the resistance element, corresponding to the first and second surfaces. The conductive polymer composition is preferably extruded or otherwise formed into a plate shape, and it is conductive if it is connected to the electrode. The polymer is formed between two metal foils and is a plywood. The first and second electrodes are a conductive material and preferably a metal formed foil, such as nickel, steel, brass, stainless steel or one or more of the above One of the above metals, one or two electrodes may include a conductive lacquer or graphite layer. A connecting layer such as a conductive adhesive Materials can be used to bond the electrode to the resistance element. The first and second electrodes are particularly selected here-electrolytically deposited metal boxes such as nickel, steel, or copper coated with nickel? Suitable electrodes are disclosed in US Patent No. 4,689 , 475 (¾ * even), and 4, 800 '253 (Kelly Case and others) and international publication 9 5/340 81 (published by Lei Kai Company on December 14, 1 95). · The installation also includes a The insulating layer is used as the interface between the device's electrical and the outside world. The insulating layer generally covers any exposed surface of the resistance element and the metal foil electrode ^ two or all of it. Appropriate insulating materials include polyamines, polybutene , For the second diacid, a poly vinegar 'polyethylene ^ [

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408343 V. Description of the invention (7) Ethylene, liquid crystalline polymer or epoxy resin. In the method of the invention, in the cutting step, the device is cut from one of the plywood plates including a conductive polymer composition positioned between two metal foils. In this application, "cutting" may include any method of separating or separating the resistive elements of the device by a plywood shape, such as dicing, cutting, printing, cutting, etching, and / or as stated in international Separate way of publishing NO, W0 95/34084 (published December 4, 1995). The device was then subjected to a heat treatment step. The heat treatment step includes at least one process from the first temperature A to the second temperature T2. Preferably, this heat treatment step includes returning to the first temperature to complete the cycle from 1 \ to T2 to 1 \ after being exposed to the second temperature. [The first temperature is mostly (Tm-100) ° C and most preferably (Tm -120) ° C is especially (Tm-150) ° C. In addition, T „is the melting point temperature of the polymer composition, which is obtained by the honeycomb value of the endotherm measured by a differential scanning calorimeter. If there is a The above peaks * For example, when the polymer composition is a mixed crystalline polymer, the Tm temperature is set to the highest temperature peak among them. The second temperature is mostly (Tn-25) ° C, and most preferably ( Tm-35) ° C, especially (T, 50) ° C. It is most important that the first temperature should reach above the instant Tg of the polymer composition. It is usually lower than room temperature and less than 20 ° C temperature * In the method of the selected embodiment, the device is exposed to at least two thermal cycles, preferably at least three thermal cycles. For some applications, the device may be exposed to more thermal cycles , Such as six thermal cycles. In the heat treatment step, the thermal history or each thermal cycle, the device should be at the first and second temperatures Enough time to determine the total sum of the specified device temperature. During the instant device 2 which may be the same of may be different also in Ί \ and D, but a

408343 Five 'invention description (8)' --------- Second, more preferably at least 3 minutes, more preferably at least 5 minutes, special minutes at least 30 minutes 1 such as 30 knife clock / this The instantaneous measurement is based on the device reaching the fingertips, and any suitable heat source can be used as a heat treatment step. The second and second are not a single-drum oven) or other externally-managed boats. 1 J can be used as a hot sergeant step or a heated lamp. The temperature is increased from eight to 耒, and the rate of 回 (such as right back to 回 \) can be any convenient rate such as 2 to 32. As if the thermal process is a thermal cycle, the mysterious sounds of 'to eight and! ^ To eight are. different. The same can also be done after the heat treatment step. The conductive polymer composition can be delivered to the parent company — it can be achieved by chemical borrowing or radiation. For example, the use of electrical connection elements into δα alpha radioactive sources. The degree of cross-linking depends on the composition of the composite beam or channel, but is generally lower than the equivalent of 200 million rai. And can choose phase / use up to 20 million rads, preferably 1 to 15 million rads, especially for low ^ low that is 1 use (ie less than 60 volts) is 2 to 10 million rads . Circuit protection devices that are used at voltages below 30 volts should be treated with radiation to a minimum of 2 million ray = 10 million ray is applied. For some applications, it is necessary to have at least one conductive lead which is a first conductive lead which is one of the metal foil electrodes. Usually, the first and second wires are connected to the corresponding first and second electrodes. The conductive lead is used to connect the electrode to an electric power source such as a battery, a power source, or an easy-to-use method that can be used to control the heat output of the device. Conductive circuit is often a part of the lead frame. It ’s better to make it easier to make it easier to connect with the electrode, such as soldering or one-touch bonding.

Page 12 _____ 1 ^ 8343 V. Description of the invention ^ _ _ __ Heat treatment after the cutting step Perform an epoxy resin or other polymer before step 1. The congruent combination step is, for example, implemented when the combination step is used as an electrical insulation layer. The most common method is to implement the lead connection step before the heat treatment step and the method invented after the cutting step can make the device low. At 100 ohms, it is best that the " electrical polymer " has a low resistivity, i.e., less than 10 ohms per minute, more specifically, less than 20 ohms per ^ A, and particularly less than 2 ohms per centimeter, for example . It is less than 5 ohms per centimeter. It is particularly special. Generally, the device can be adjusted to less than 1 ohm per centimeter at 20 ° C. For the value, it is preferably lower than 0.5 ohms / s—2, which generally has a resistance lower than 1 ohm to 0,150 ohms. , Lower than 0.25 ohms, for example, 0.050 The device of the present invention is particularly suitable-Gong, and also one of the & D for-the battery pack, so that the device is connected to a general one- Rui μ ^ L Μ wire bonding can be directly connected between the battery and the first or the first pole, or between the battery and the battery electrical lead connected to the first electrode ... In some applications, the first and / or the second terminal can be Di Yi ¥ "Snap" type allows the device to be physically or electrically connected to a "Snap," type terminal. The device can be connected to any positive and negative terminals of the battery. The battery can be used to record and record metal Hybrid 'alkali' or bell batteries. General battery packs include two or more batteries, such battery packs are shown in International Publication No. W () 97/06538 (K. K 雷 陈 February 20 ' Published in 1997) and WO98 / 20567 (published by Lei Chen Company on May 14, 1998). The invention is shown in the drawing of Figure 1. A cross-sectional view of the device of the present invention, including PTC section 3, first Conductive lead 15 ', second conductive lead 18, and insulating material 23. The PTC section 3 includes a first electrode 1, a second electrode 13 and a lead

408343 V. Description of the invention (10) Resistive element 9 in which the polymer composition of electricity is sandwiched. The two electrodes shown in the PTC section 3 of FIG. 1 and the first surface 43 and the second surface 41 are opposite to each other. -The PTC portion of the top view is shown in FIG. 2. The PTC portion includes surfaces 41 and 43. It is formed by the outer periphery 5 and the inner periphery 7-the disc and has an opening 27 in the middle. This opening 2? Is defined by the inner periphery 7. FIG. 3 is a top view of the first conductive lead 15 including the first portion 16 connected to the first electrode u, and the second portion 17 extending to the opening u of the pTc portion 3. A part 16 covers all the first electrodes 丨 丨. The second portion of the first lead 15 covers at least a portion of the opening 27 for soldering, crimping or welding to a button terminal of a battery for direct electrical bonding. The second part π shows at least a part of the opening 27—a part of the cover, 4 as a top view of the second conductive lead 18, including the first part ig and the second part 21. The first part 19 is connected to the second electrode 13 and covers at least the second part. The second part 21 is extended outward from the periphery 5 if it can be connected immediately so as to reach the first and second conductive leads 15 and 18 which are connected to the second battery or other electrical parts, and can be made of suitable materials: In systems such as nickel: stainless steel 'copper' or alloys such as bronze or brass. Is usually a part of the lead frame. Lei ^ Out of the mountain is a top view of the device 1 covered with an electrical insulation layer 2 3. When-because the insulating layer is inside! &Quot; opening 27 " ^ Because of the electrical contact between the terminal and the PTC part 3, it will not cause a short circuit. For example, each π M T t ί is explained, and its example 1 and example 2 are for comparison. J is stated in the following steps:

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The first mixture was prepared by 54% by weight of black carbon (trademark "... one" 43 ° C available from Columbia Chemical) and 46% high-density polyethylene (PetrotheneTM, a petroleum preparation trademark available from Miluno "HDPE," ) Pre-mix in a Henschel mixer, mix the mixture in a Buss kneader and squeeze into pellets. The preparation number is 51.4% of black carbon and 4% by weight. The pellets of the first and second mixtures were pre-mixed to obtain a final mixture with 52.7% black carbon and 47.3% HDPE by weight, and then the mixture was extruded through a plate stamp using an Egan extruder. Form a sheet with a thickness of 0 & centimeters (0.010 inches). The pressed sheet was sandwiched between two electrolytically deposited nickel boxes and the pressing set was set at 200. The bottom press has a plywood having a thickness of about 0.033 cm = 0013 inches (available from Fukuda). The plywood is soldered to a temperature of 230 ° C, one of which contains 63% lead and 37% tin, and the plywood is punched as shown in Figure 2. Device assembly The PTC device was soldered to 6 3/37 lead / tin-tin solder as shown in Figures 3 and 4 on the first and second conductive leads. The temperature in a high-temperature furnace was 30 ° C. 〇 Increase the temperature to 230 ° C for about two minutes and let the excess solder flow out. A liquid crystalline polymer insulating layer is applied in a transfer or plastic manner. Machida Radiation 3 Use a cobalt 60 alpha radiation source to radiate the device to all places. For 14 hundred temperature cycles

408343 V. Description of the invention ¢ 12) The device is subjected to six thermal cycles, each cycle is -40 to 80 to -40 ° C, and its speed is 1 ° C per minute, at -40 ° C to 80 ° C At 60 minutes. Examples 1 and 2 (comparative) ‘The operation of the device is shown in Table 1’. The number of consecutive steps from 1 to 4 indicates the sequence of the steps of the program. The resistance value of one hundred prepared devices in each case was measured at 25 ° C. The completed device has an average resistance value that is at least 5% higher than the value of the invented device. Example 3 The operation of the device is shown in Table 1. The completed device has a lower resistance value than the conventional device. A comparison of the distribution resistance values of different devices is shown in Figure 6 '. Table 1 Example device preparation steps Resistance value thousandths of an ohm Preparation of radiative heat cycle 1 1 2 3 4 53.3 2 1 3 2 4 64.9 3 1 2 4 3 49.0 Although this patent is in the specific embodiment of the invention The description has different forms and descriptions: but can be understood; the characteristics of a special form disclosed here that do not refer to can be used to extend this feature appropriately, another form or another form of this point Merge or become an invention. It can be understood that the arrangement of the above devices and methods is only the principle or the display of the application of this invention and many other specific embodiments and modifications can be made without departing from the spirit and scope of the patent application as defined by the present invention.

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Case No. 87120621 6. Application Patent Scope 1. An electrical device including a conductive polymer, including (A) a resistive element composed of a conductive polymer composition and displaying a PTC reaction and including, (1) A polymerized part having at least 20% crystallinity and a melting point Tm, (2) dispersed in the polymerized part, a special conductive filter, and (B) two electrode systems (i) bonding Resistive element: (ii) contains metal foil, and (iii) can be connected to a power source of electrical power. The device is prepared by a method, which includes the steps of: (a) cutting and positioning on two metals Plywood device with conductive polymer composition wrapped between foils; (b) After the device cutting step, it is exposed to at least a first temperature of at most (Tn- 1 0 0) ° C and at most (T „-25) ° C A thermal history of the second temperature; and (c) cross-linking after the thermal history of the conductive polymer composition. 2. If the device of the scope of patent application is No. 1, wherein the method is after step (a) and Before step (b), the method further includes at least one conductive lead connected to the metal foil and an electrode. 3. If the device in the scope of patent application 1 or 2 has a resistance value of at most 0.1 100 ohms ... 4. If the device in the scope of patent application 1 or 2 is applied, it is in step (c) The completion of the cross-linking is equivalent to 1 to 20 million Rads. · 5. The device according to item 1 or 2 of the patent application scope, wherein the polymer composition comprises polyethylene, ethylene, homopolymer or fluoropolymer. 6. The device according to item 1 or 2 of the scope of patent application, wherein in step (b)

O: \ 56 \ 56290.ptc Page 1 2000.04. 26. 017 408343 Amendment No. 87120621 Six 'patent application scope The device is exposed to at least one of the first temperature to the second temperature and back to one of the first temperature thermal cycle 7 First 8. Among them. (Ii) A second 9. Device 10 conductive electrode should be installed and the device as in the scope of patent application item 1 or 2 ·, wherein the temperature L in step (b) is 2 3 ° C is low. "A method of making an electrical device as described in item 1 of the scope of patent application. (1) The resistive element (i) has a thickness of at most 0.51 cm and is cross-linked to at least an equivalent of 2 million mines. Obtain: and (2) in step (b) after cutting, the device is exposed to at least one thermal cycle at a first temperature of at most (Tm-100) ° C to a temperature of at most (Tn-25) ° C And back to the first temperature. A method as claimed in item 8 of the patent application, wherein the step (b) is exposed to at least three thermal cycles. A battery pack includes (1) a battery including one of the first and second terminals and (2) the device according to item 1 of the patent application scope, and further includes (a)-the first 1 lead is connected to the An electrode, * and (b)-the second conductive lead is connected to the second _ * * is placed in contact with the first terminal of the battery so that the first conductive lead is substantially electrically connected to the terminal *.

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