TWI270562B - Positive temperature coefficient polymer composition and circuit protection device made therefrom - Google Patents

Abstract

A PTC polymer composition contains: (a) a non-elastomeric polymer mixture in an amount from 20 wt% to 80 wt% based on the weight of the polymer composition; (b) a conductive particulate material in an amount from 20 wt% to 60 wt% based on the weight of the polymer composition; (c) a voltage resistance-enhancing agent that contains particulate metal oxide material in an amount from 1 wt% to 30 wt% based on the weight of the polymer composition; and (d) a polymer stabilizer that contains a thermoplastic elastomer in an amount from 1 wt% to 30 wt% based on the weight of the polymer composition.

Description

吴國專利第6,238,598號揭露一種包含U.S. Patent No. 6,238,598 discloses an inclusion

I 之7〇562 九、發明說明： 【毛明所屬之技術領域】 士本發明是有關於一種正溫度係數（PTC)聚合物組成物， 特別是指一種具有抗電壓增強劑和聚合物穩定劑的正溫度 係數聚合物組成物及由其製成的電路保護元件。 【先前技術】 —1 ^ jL· λΤΛ. 合物及—結晶性未接枝聚合物的正溫度係數聚合物組成物 5物組成物中加入該接枝聚合物能增進由其所製 成的正溫度係數元件的特性，例如拉伸強度、低接觸阻抗 、低初始阻抗、高跳脫電流，及高♦值體積阻抗等。 人吴國專利第6,359,053號揭露一種包含一結晶性接枝聚 / ° 性非接枝聚合物及一離子鍵聚體（ionomer)的 &人又系數^ °物組成物。該離子鍵聚體為結晶性未接枝 ::物與離子化的不飽和叛酸所形成的離子共聚物。該聚 二：成：中加入該離子共聚物能增進由其所製成的正溫 度係數聚合物組成物所製成的電路二且克=二 5〇〇hm-cm的體積電 /…、有低於 麼。一般而言，1所且有4〇_的工作電 操作電厂堅達到兮最大電星範圍大約為一’當 电壓時，該電路保護元件可能損壞或 5I 7 〇 562 IX. Description of the invention: [Technical field to which Mao Ming belongs] The present invention relates to a positive temperature coefficient (PTC) polymer composition, in particular to an anti-voltage enhancer and a polymer stabilizer. The positive temperature coefficient polymer composition and circuit protection components made therefrom. [Prior Art] - 1 ^ jL · λΤΛ. and the positive temperature coefficient of the crystalline non-grafted polymer. The addition of the graft polymer to the composition of the 5 composition enhances the positive Characteristics of temperature coefficient components such as tensile strength, low contact resistance, low initial impedance, high trip current, and high ♦ value volume impedance. U.S. Patent No. 6,359,053 discloses a <RTI ID=0.0>>>>> The ionic bond is an ionic copolymer formed by crystalline ungrafted::immediate and ionized unsaturated oxonic acid. The poly 2: into: the addition of the ionic copolymer can enhance the circuit made of the positive temperature coefficient polymer composition made of the second and the gram = 2 〇〇 hm-cm volume of electricity / ..., there Less than that. In general, a working electrical power plant with 1 且 坚 兮 兮 兮 兮 兮 兮 兮 兮 兮 兮 兮 兮 兮 兮 兮 兮 兮 兮 兮 兮 兮 兮 兮 兮 兮 兮 兮 兮 兮 兮 兮 兮

1270562 因此，有需要增加前述傳統的正溫度係數聚合物組 成物的耐電壓，但卻不犧牲該電路保護元件的其他特性。 商業的聚合物正溫度係數加熱元件是由體積電阻值大 於5〇〇hm_cm且通常介於鹰_1〇〇〇〇hm cm之間的聚合物 組成物所製成。此加熱元件一般使用於高電壓狀況下，例 如⑽侧⑽或更高（大於 組成物具有相對較高的耐„，並不f要如電路保護元件 增強其耐電壓以滿足要求。 在-與本發明相關且於鳩3年5月8日在美國提出申 申請案號f 1〇/435,065號，尚在審查中的專利案中揭 路：種正溫度係數聚合物組成物，其包含一聚合混合物' :導電性顆粒材料及一含有顆粒金屬氧化物材料的抗電壓 增強劑。雖然藉由該抗電壓增強劑可以增加該正溫度係數 聚合物組成物的耐電壓’但是仍有需要增加其使用壽命 (Life Cycle)以供高電壓的應用。 上述專利案所揭露的全部内容在此一併列為參考。 【發明内容】 人因此，本發明之目的，即在提供一種可以增進使用壽 命亚含有聚合物穩定劑的正溫度係數聚合物組成物。 本發明的另一目的，即在提供一種由本發明之聚合物 組成物所製成的電路保護元件。 本發明所提供的一種正溫度係數聚合物組成物包含： ⑷-佔該聚合物組成物2()至⑽重量百分比㈣％)的非彈性 聚合物混合物、（b)一佔該聚合物組成物20至60重量百分 1270562 比（wt%)的導電性顆粒材料、（C)一佔該聚合物組成物1至30 重量百分比（wt%)的含有顆粒金屬氧化物材料之抗電壓增強 劑，及（d) —佔該聚合物組成物1至30重量百分比（wt%)的 含有熱塑性彈性體之聚合物穩定劑。 【實施方式】1270562 Therefore, there is a need to increase the withstand voltage of the aforementioned conventional positive temperature coefficient polymer composition without sacrificing other characteristics of the circuit protection component. Commercial polymer PTC heating elements are made of a polymer composition having a volume resistance greater than 5 〇〇 hm cm and typically between eagle and 〇〇〇〇 〇〇〇〇 cm cm. This heating element is generally used under high voltage conditions, such as (10) side (10) or higher (greater than the composition has relatively high resistance), and does not have to withstand the voltage as the circuit protection component meets the requirements. In connection with the invention and filed in the United States on May 8th, 3rd, the application number of the application number f 1〇/435,065, which is still under review, reveals a positive temperature coefficient polymer composition comprising a polymerization mixture. ' : Conductive particulate material and a voltage-resistant enhancer containing particulate metal oxide material. Although the withstand voltage enhancer can increase the withstand voltage of the positive temperature coefficient polymer composition, there is still a need to increase its service life. (Life Cycle) for high voltage applications. The entire contents of the above-mentioned patents are hereby incorporated by reference herein. Positive Temperature Coefficient Polymer Composition of Stabilizer Another object of the present invention is to provide a circuit protection component made from the polymer composition of the present invention. A positive temperature coefficient polymer composition provided by the present invention comprises: (4) - a non-elastic polymer mixture constituting 2 to 8% by weight of the polymer composition, and (b) a polymer composition 20 to 60 weight percent of 1,270,562 to (wt%) conductive particulate material, (C) one to 30 weight percent (wt%) of the polymer composition, and an anti-voltage enhancer comprising a particulate metal oxide material, And (d) - a polymer stabilizer containing a thermoplastic elastomer in an amount of from 1 to 30% by weight (wt%) based on the polymer composition.

本發明正溫度係數聚合物組成物，特別地適用於製造 正溫度係數電路保護元件，例如在23°C具有體積電阻值低 於50 ohm-cm的正溫度係數保護元件。該正溫度係數聚合 物組成物包含：（a)—佔該聚合物組成物20至80重量百分 比（wt%)的非彈性聚合物混合物（non-elastomeric polymer mixture)、（b) —佔該聚合物組成物20至60重量百分比 (wt%)的導電性顆粒材料（conductive particulate material)、 (c)一佔該聚合物組成物1至30重量百分比（wt%)的含有顆 粒金屬氧化物材料（particulate metal oxide material)之抗電壓 增強劑（voltage resistance-enhancing agent)，及（d) — 佔該聚 合物組成物1至30重量百分比（wt%)的含有熱塑性彈性體 (thermoplastic elastomer)之聚合物穩定劑（polymer stabilizer) 較佳地，該非彈性聚合物混合物含有⑴一結晶性接枝 聚合物（crystalline grafted polymer)、（ii)一結晶性未接枝聚 合物（crystalline non-grafted polymer)，及可選擇地（iii) 一由 該結晶性未接枝聚合物與離子化的不飽和緩酸（ionized unsaturated carboxylic acid)所形成的離子共聚物（ionic copolymer)。值得注意的是，在本發明的聚合物組成物中該 1270562 聚合混合物與該聚合物穩定劑的結合意外地提供綜合的效 應，使得由該聚合物組成物所製成的正溫度係數電路保護 元件與由包含聚合物穩定劑及僅具非接枝聚合物的聚合物 之組成物所製成的電路保護元件相比較有較佳的使用壽命The positive temperature coefficient polymer composition of the present invention is particularly suitable for use in the manufacture of positive temperature coefficient circuit protection elements, such as positive temperature coefficient protection elements having a volume resistance value of less than 50 ohm-cm at 23 °C. The positive temperature coefficient polymer composition comprises: (a) - 20 to 80 weight percent (wt%) of the polymer composition of a non-elastomeric polymer mixture, (b) - accounting for the polymerization 20 to 60 weight percent (wt%) of conductive particulate material, (c) 1 to 30 weight percent (wt%) of the polymer composition containing particulate metal oxide material ( a particulate resistance-enhancing agent, and (d) - a polymer containing a thermoplastic elastomer in an amount of 1 to 30% by weight (wt%) based on the polymer composition Preferably, the non-elastic polymer mixture comprises (1) a crystalline grafted polymer, (ii) a crystalline non-grafted polymer, and Alternatively (iii) an ionic copolymerization of the crystalline ungrafted polymer with ionized unsaturated carboxylic acid (Ionic copolymer). It is noted that the combination of the 1270562 polymeric mixture with the polymeric stabilizer in the polymer composition of the present invention unexpectedly provides a combined effect that the positive temperature coefficient circuit protection component made from the polymer composition Better service life than circuit protection components made of a polymer containing a polymer stabilizer and a polymer having only a non-graft polymer

該結晶性接枝聚合物是選自於接枝聚烯烴（grafted polyolefin)、接枝聚稀烴衍生物（grafted polyolefin derivatives)及聚稀烴與聚烯烴衍生物之接枝共聚物（grafted copolymer)所組成之群組。該接枝聚合物是經由一極性基圑 接枝，該極性基團是選自於叛酸（carboxylic acids)及其衍生 物所組成之群組。 該結晶性未接枝聚合物是選自於未接枝聚烯烴（non-grafted polyolefin)、未接枝聚烯烴衍生物（non-grafted polyolefin derivatives)及聚稀烴與聚烯烴衍生物之未接枝共 聚物（non-grafted copolymer)所組成之群組。該未接枝聚合 物的熔點大致與該接枝聚合物的熔點相同。 該抗電壓增強劑包含一散佈於該聚合物混合物中的顆 粒金屬氧化物材料，藉以增加該聚合物組成物之而ί電壓性（ 即毁損導因於施加的電壓）。更明白的說，該電路保護元件 的最大電壓阻抗定義為在此電壓值該電路保護元件將彳貝壞 或燒毀。 較佳地，該接枝聚烯烴是選自於接枝高密度聚乙烯 (HDPE)、接枝低密度聚乙烯（LDPE)、接枝線形低密度聚乙 烯（LLDPE)、接枝中密度聚乙烯（MDPE)，及接枝聚丙烯（ΡΡ) 8 1270562 所組成之群組。更佳地，該接枝聚烯烴為接枝高密度聚乙 烯（HDPE)。較佳地，該聚烯烴及聚烯烴衍生物之接枝共聚 物是選自於接枝乙烯-乙酸乙烯（EVA)共聚物、接枝乙烯-丙 烯酸丁酯（EBA)共聚物、接枝乙烯-丙烯酸（EAA)共聚物、接 枝乙烯-甲基丙烯酸（EMAA)共聚物及接枝乙烯-丙烯酸甲酯 (EMA)共聚物所組成之群組。The crystalline graft polymer is selected from the group consisting of grafted polyolefins, grafted polyolefin derivatives, and grafted copolymers of polyolefins and polyolefin derivatives. The group formed. The graft polymer is grafted via a polar group selected from the group consisting of carboxylic acids and derivatives thereof. The crystalline ungrafted polymer is selected from the group consisting of non-grafted polyolefins, non-grafted polyolefin derivatives, and non-grafted polyolefin derivatives. A group consisting of non-grafted copolymers. The ungrafted polymer has a melting point substantially the same as the melting point of the graft polymer. The anti-voltage enhancer comprises a particulate metal oxide material dispersed in the polymer mixture to increase the voltage of the polymer composition (i.e., the damage is due to the applied voltage). More specifically, the maximum voltage impedance of the circuit protection component is defined as the voltage protection value of the circuit protection component that will destroy or burn the mussel. Preferably, the grafted polyolefin is selected from the group consisting of grafted high density polyethylene (HDPE), grafted low density polyethylene (LDPE), grafted linear low density polyethylene (LLDPE), and grafted medium density polyethylene. (MDPE), and a group of grafted polypropylene (ΡΡ) 8 1270562. More preferably, the grafted polyolefin is grafted high density polyethylene (HDPE). Preferably, the graft copolymer of the polyolefin and the polyolefin derivative is selected from the group consisting of grafted ethylene-vinyl acetate (EVA) copolymer, grafted ethylene-butyl acrylate (EBA) copolymer, grafted ethylene- A group consisting of an acrylic acid (EAA) copolymer, a grafted ethylene-methacrylic acid (EMAA) copolymer, and a grafted ethylene-methyl acrylate (EMA) copolymer.

較佳地，該未接枝聚烯烴是選自於未接枝高密度聚乙 烯（HDPE)、未接枝低密度聚乙烯（LDPE)、未接枝線形低密 度聚乙烯（LLDPE)、未接枝中密度聚乙烯（MDPE)，以及未 接枝聚丙烯（PP)所組成之群組。更佳地，該未接枝聚烯烴為 未接枝高密度聚乙烯（HDPE)。較佳地，該聚烯烴及聚烯烴 衍生物之未接枝共聚物是選自於未接枝乙烯-乙酸乙烯（EVA) 、未接枝乙稀-丙稀酸丁 SI (EBA)、未接枝乙稀-丙稀酸 (EAA)、未接枝乙烯-甲基丙烯酸（EMAA)及未接枝乙烯-丙烯 酸曱酯（EMA)所組成之群組。 該導電性顆粒材料是選於碳黑（carbon black)、石墨 、碳纖維及金屬粉末顆粒所組成之群組。 該包含於離子鍵聚體中之不飽和羧酸是選自於順丁烯 二酸酐（maleic anhydride)、丙稀酸（acrylic acid)，以及乙酸 (acetic acid)所組成之群組。較佳地，該不飽和羧酸為丙烯 酸。 該抗電壓增強劑之金屬氧化物材料較佳地是選自於氧 化鋅、氧化鋁，以及氧化鎂所組成之群組。 本發明的聚合物組成物較佳地包含0.5至10重量百分 9 1270562 比（wt%)的接枝聚合物、30至60重量百分比（wt%)的非接枝 聚合物、5至30重量百分比（wt%)的抗電壓增強劑，及2至 10重量百分比的熱塑性彈性體；且更佳地包含3至5重量 百分比(wt%)的接枝聚合物、35至50重量百分比（wt%)的非 接枝聚合物、10至20重量百分比（wt%)的抗電壓增強劑， 及3至5重量百分比（wt%)的熱塑性彈性體。Preferably, the ungrafted polyolefin is selected from the group consisting of ungrafted high density polyethylene (HDPE), ungrafted low density polyethylene (LDPE), ungrafted linear low density polyethylene (LLDPE), and missed A group of medium density polyethylene (MDPE) and ungrafted polypropylene (PP). More preferably, the ungrafted polyolefin is ungrafted high density polyethylene (HDPE). Preferably, the ungrafted copolymer of the polyolefin and the polyolefin derivative is selected from the group consisting of ungrafted ethylene-vinyl acetate (EVA), ungrafted ethylene-acrylic acid butyl SI (EBA), and missed A group consisting of ethylene-acrylic acid (EAA), ungrafted ethylene-methacrylic acid (EMAA), and ungrafted ethylene-decyl acrylate (EMA). The conductive particulate material is selected from the group consisting of carbon black, graphite, carbon fibers, and metal powder particles. The unsaturated carboxylic acid contained in the ionic polymer is selected from the group consisting of maleic anhydride, acrylic acid, and acetic acid. Preferably, the unsaturated carboxylic acid is acrylic acid. The metal oxide material of the anti-voltage enhancer is preferably selected from the group consisting of zinc oxide, aluminum oxide, and magnesium oxide. The polymer composition of the present invention preferably comprises from 0.5 to 10 weight percent of 9 1270562 ratio (wt%) of graft polymer, from 30 to 60 weight percent (wt%) of non-graft polymer, from 5 to 30 weight. Percent (wt%) of anti-voltage enhancer, and 2 to 10 weight percent of thermoplastic elastomer; and more preferably 3 to 5 weight percent (wt%) of graft polymer, 35 to 50 weight percent (wt% The non-grafted polymer, 10 to 20 weight percent (wt%) of the anti-voltage enhancer, and 3 to 5 weight percent (wt%) of the thermoplastic elastomer.

該熱塑性彈性體較佳地是選自於含氟高分子 (fluoropolymer)彈性體、烯烴（oleHnic)彈性體、聚酸胺 (polyamide)彈性體、聚酯（polyester)彈性體、聚氨酯 (polyurethane)彈性體、聚氨酯/聚碳酸酯（polyurethane/ polycarbonate)彈性體、苯乙稀類（styrenic)彈性體，及乙 烯基（vinyl)彈性體所組成之群組；且更佳地是選自於烯烴 彈性體。 該烯烴彈性體可包括硬段及軟段（hard and soft segments)，且該烯烴彈性體的硬段是選自於聚丙稀（PP)、聚 乙烯（PE)及其類似物所組成之群組，而該烯烴彈性體的軟段 是選自於聚丁二烯（polybutadiene)、聚異戊二浠 (polyisoprene)、聚辛烯（polyoctene)、氫化（hydrogenated)聚 丁二烯、氫化聚異戊二稀、氫化聚辛烯、乙稀丙稀二浠單 體（EPDM)及其類似物所組成之群組。 在一較佳具體例中，該烯烴彈性體是乙烯-辛烯共聚物 本發明的聚合物之組成物的優點將能藉由參考下述實 例更加清楚明白。 10 1270562 <實施例1-7及比較例1>The thermoplastic elastomer is preferably selected from the group consisting of a fluoropolymer elastomer, an olefin (oleHnic) elastomer, a polyamide elastomer, a polyester elastomer, and a polyurethane elastomer. a group of a body, a polyurethane/polycarbonate elastomer, a styrenic elastomer, and a vinyl elastomer; and more preferably an olefin elastomer . The olefin elastomer may include hard and soft segments, and the hard segment of the olefin elastomer is selected from the group consisting of polypropylene (PP), polyethylene (PE), and the like. And the soft segment of the olefin elastomer is selected from the group consisting of polybutadiene, polyisoprene, polyoctene, hydrogenated polybutadiene, hydrogenated polyisoprene A group consisting of dilute, hydrogenated polyoctene, ethylene propylene dimer monomer (EPDM) and the like. In a preferred embodiment, the olefin elastomer is an ethylene-octene copolymer. The advantages of the composition of the polymer of the present invention will be more apparent by reference to the following examples. 10 1270562 <Examples 1-7 and Comparative Example 1>

表1顯示實施例1-7(具有熱塑性彈性體）及比較例1(沒 有熱塑性彈性體）之不同聚合物組成物及使用壽命測試結果 。測試樣本是由列於表1中的聚合物組成物所製備，以供 使用壽命的測試，且藉由在高電壓下於該等樣本通過電流 來測試使用壽命。每一測試樣本藉由加壓與熱塑該聚合物 組成物以製備形成一正溫度係數片狀元件，隨後使該正溫 度係數片狀元件兩相反側邊與二銅结連接，藉以於該正溫 度係數片狀元件上形成電極。 表1 聚合物組成物 電阻 ohm 使 用 壽 命 測試條件 高密度 聚乙婦 wt% 接枝聚 乙烯 wt% 山 石厌黑 Wt% 氧化 is wt % 彈性 體# wt% 實施例1 42 4 35 17 2 3.93 3.4 3A/600Vac 實施例2 40 4 35 17 4 3.47 7.8 3A/600Vac 實施例3 38 4 35 17 6 3.94 6.6 3A/600Vac 實施例4 36 4 35 17 8 4.32 6.0 3A/600Vac 實施例5 34 4 35 17 10 4.91 6.4 3A/600Vac 實施例6 43 1 33 17 4 3.65 4 3A/600Vac 實施例7 33.5 10 35.5 17 4 4.24 2 3A/600Vac 比較例1 44 4 35 17 0 5.44 1.4 3A/600Vac #在每一實施例及比較例中所使用的彈性體是Engage®，此 為DuPont Dow Elastomers之產品，主要包含乙稀-辛稀共聚 11 1270562 物。 測試結果顯示當彈性體與聚合物混合物混合後能顯著 改善正溫度係數片狀元件的使用壽命。 <實施例8·12及比較例2>Table 1 shows the different polymer compositions and life test results of Examples 1-7 (with thermoplastic elastomer) and Comparative Example 1 (without thermoplastic elastomer). The test samples were prepared from the polymer compositions listed in Table 1 for testing the service life and testing the service life by passing current through the samples at high voltages. Each test sample is prepared by pressing and thermoplasticizing the polymer composition to form a positive temperature coefficient chip element, and then connecting the opposite sides of the positive temperature coefficient chip element to the two copper bonds, thereby An electrode is formed on the temperature coefficient sheet member. Table 1 Polymer composition resistance ohm Life test conditions High density polyethylene wt% Graft polyethylene wt% Rock black Wt% Oxidation is wt % Elastomer # wt% Example 1 42 4 35 17 2 3.93 3.4 3A /600Vac Example 2 40 4 35 17 4 3.47 7.8 3A/600Vac Example 3 38 4 35 17 6 3.94 6.6 3A/600Vac Example 4 36 4 35 17 8 4.32 6.0 3A/600Vac Example 5 34 4 35 17 10 4.91 6.4 3A/600Vac Example 6 43 1 33 17 4 3.65 4 3A/600Vac Example 7 33.5 10 35.5 17 4 4.24 2 3A/600Vac Comparative Example 1 44 4 35 17 0 5.44 1.4 3A/600Vac #In each embodiment and The elastomer used in the comparative example was Engage®, a product of DuPont Dow Elastomers, which mainly contained ethylene-octane copolymer 11 1270562. The test results show that when the elastomer is mixed with the polymer mixture, the service life of the positive temperature coefficient chip element can be significantly improved. <Examples 8·12 and Comparative Example 2>

表2顯示實施例8-12(具有彈性體及顆粒金屬氧化物材 料）及比較例2(具有彈性體但是沒有顆粒金屬氧化物材料）之 不同聚合物組成物及使用壽命測試結果。測試樣本是由列 於表2中的聚合物組成物所製備，以供使用壽命的測試， 且藉由在高電壓下於該等樣本通過電流來測試使用壽命。 每一測試樣本藉由加壓與熱塑該聚合物組成物以製備形成 一正溫度係數片狀元件，隨後使該正溫度係數片狀元件兩 相反側邊與二銅箔連接，藉以於該正溫度係數片狀元件上 形成電極。 表2 聚合物組成物 電阻 ohm 使 用 壽 命 測試條件 高密度 聚乙烯 wt% 接枝聚 乙婦 wt% 碳黑 wt% 氧化 鋁 wt% 彈性 體# wt% 實施例8 47 4 40 5 4 5.48 1.6 3A/600Vac 實施例9 45 4 37 10 4 4.87 3.8 3A/600Vac 實施例10 42 4 35 15 4 5.05 7.0 3A/600Vac 實施例11 39 4 33 20 4 5.27 5.8 3A/600Vac 實施例12 31 4 31 30 4 4.85 3.0 3A/600Vac 比較例2 50 4 42 0 4 3.07 0 3A/600Vac 12 1270562 #在每一實施例及比較例中所使用的彈性體是Engage®。 測試結果顯示當顆粒金屬氧化物材料與聚合物混合物 及彈性體混合後能顯著改善正溫度係數片狀元件的使用壽 命。 <比較例3·5>Table 2 shows the different polymer compositions and service life test results of Examples 8-12 (with elastomer and particulate metal oxide materials) and Comparative Example 2 (with elastomers but no particulate metal oxide materials). Test samples were prepared from the polymer compositions listed in Table 2 for testing the service life and testing the service life by passing current through the samples at high voltages. Each test sample is prepared by pressing and thermoplasticizing the polymer composition to form a positive temperature coefficient chip element, and then connecting the opposite sides of the positive temperature coefficient chip element to the two copper foil, thereby An electrode is formed on the temperature coefficient sheet member. Table 2 Polymer composition resistance ohm Life test conditions High density polyethylene wt% Grafted polyethylene wt% Carbon black wt% Alumina wt% Elastomer # wt% Example 8 47 4 40 5 4 5.48 1.6 3A/ 600Vac Example 9 45 4 37 10 4 4.87 3.8 3A/600Vac Example 10 42 4 35 15 4 5.05 7.0 3A/600Vac Example 11 39 4 33 20 4 5.27 5.8 3A/600Vac Example 12 31 4 31 30 4 4.85 3.0 3A/600Vac Comparative Example 2 50 4 42 0 4 3.07 0 3A/600Vac 12 1270562 # The elastomer used in each of the examples and comparative examples was Engage®. The test results show that when the particulate metal oxide material is mixed with the polymer mixture and the elastomer, the life of the positive temperature coefficient chip element can be significantly improved. <Comparative Example 3·5>

表3顯示比較例3-5(在聚合物混合物中沒有接枝聚合物 )之不同聚合物組成物及使用壽命測試結果。測試樣本是由 列於表3中的聚合物組成物所製備，以供使用壽命的測試 ，且藉由在高電壓下於該等樣本通過電流來測試使用壽命 。每一測試樣本藉由加壓與熱塑該聚合物組成物以製備形 成一正溫度係數片狀元件，隨後使該正溫度係數片狀元件 兩相反側邊與二銅羯連接，藉以於該正溫度係數片狀元件 上形成電極。 表3 聚合物組成物 電阻 使 測試條件 南密度 接枝聚 碳黑 氧化 彈性 ohm 用 聚乙烯 乙烯 wt% 鋁 體# 壽 wt% wt% wt% wt% 命 比較例3 46 0 33 17 4 3.52 0 1.5A/600Vac 比較例4 38 0 28 30 4 3.73 0 1.5A/600Vac 比較例5 58 0 33 5 4 5.45 0 1.5A/600Vac 在每一實施例及比較例中所使用的彈性體是Engage®。 依所述之發明，其顯然能在不脫離本發明精神下，進 行各種修飾與變化。因此，本發明能以如後詳述之申請專 13 1270562 利範圍進行界定。 【圖式簡單說明】 無 【主要元件符號說明】Table 3 shows the different polymer compositions and service life test results for Comparative Examples 3-5 (no graft polymer in the polymer mixture). Test samples were prepared from the polymer compositions listed in Table 3 for life testing and tested for service life by passing current through the samples at high voltages. Each test sample is prepared by pressurizing and thermoplasticizing the polymer composition to form a positive temperature coefficient chip element, and then connecting the opposite sides of the positive temperature coefficient chip element to the two copper ruthenium, thereby An electrode is formed on the temperature coefficient sheet member. Table 3 Polymer Composition Resistance Test Conditions Southern Density Grafting Polycarbon Black Oxidation Elasticity ohm Polyethylene Ethylene wt% Aluminum Body #寿wt% wt% wt% wt% Life Comparison Example 3 46 0 33 17 4 3.52 0 1.5 A/600 Vac Comparative Example 4 38 0 28 30 4 3.73 0 1.5A/600Vac Comparative Example 5 58 0 33 5 4 5.45 0 1.5A/600Vac The elastomer used in each of the examples and comparative examples was Engage®. According to the invention, it is apparent that various modifications and changes can be made without departing from the spirit of the invention. Accordingly, the present invention can be defined by the scope of the application specification 13 1270562, which is described in detail below. [Simple description of the diagram] None [Main component symbol description]

Claims (1)

1270562 二0941 1 1656號專利發明申請案之申請專利範圍替換頁（95年4月修 / ---—--------i }1270562 Reissue page of patent application scope for patent application No. 2094 1 1656 (Revised in April, 1995 / ------------i } 十、申請專利範圍： 一種正溫度係數聚合物組成物，包含： (a) —佔該聚合物組成物20至8〇重量百分比（_%) 的非彈性浠聚合物混合物； (b) —佔該聚合物組成物20至6〇重量百分比（_%) 的導電性顆粒材料； (c) 一佔該聚合物組成物}至3〇重量百分比⑶㈧）的 含有顆粒金屬氧化物材料之抗電壓增強劑；及 (d) —佔該聚合物組成物！至3〇重量百分比…⑼) 的含有熱塑性烯烴彈性體之聚合物穩定劑。 2·依據中請專利範圍第1項所述之正溫度係數聚合物組成 物，其中，該非彈性聚合物混合物包含一聚合物混合物 ’該聚合物混合物含有 (i)一結晶性接枝聚合物，係為接枝聚烯烴，該接枝 聚合物是經由一羧酸的極性基團接枝，及 (11)一結晶性未接枝聚合物，係為未接枝聚烯烴，該 未接枝聚合物之熔點大致與上述接枝聚合物相同。 3·依據申請專利範圍第2項所述之正溫度係數聚合物組成 物，其中，ό亥接枝聚合物佔該聚合物組成物〇 · 5至1 〇重 量百分比（wt%)。 4·依據申請專利範圍第2項所述的正溫度係數聚合物組成 物，其中，該接枝聚烯烴是選自於接枝高密度聚乙烯、 接枝低密度聚乙烯、接枝線形低密度聚乙烯、接枝中密 度聚乙烯及接枝聚丙稀所組成之群組。 15 1270562 第〇9411i 656號專利發明申請案之申請專利範圍替換頁（95年*月修正） I依據甲請專利範圍第2項所述的正溫度係數聚合物組成 物，其中，該未接枝聚烯烴是選自於未接枝高密度聚乙 烯未接枝低密度聚乙烯、未接枝線形低密度聚乙烯、 未接枝中密度聚乙烯及未接枝聚丙烯所組成之群組。 6·依據申請專利範圍第2項所述的正溫度係數聚合物組成 物，其中，該導電性顆粒材料是選自於碳黑、石墨、碳 、截維及金屬粉末顆粒所組成之群組。 7·依據申請專利範圍第2項所述的正溫度係數聚合物組成 物，其中，該金屬氧化物材料是選自於氧化鋅、氧化鋁 及氧化鎮所組成之群組。 據申明專利範圍第3項所述的正溫度係數聚合物組成物 ，=中，該熱塑性烯烴彈性體佔該聚合物組成物2至1〇 重量百分比（wt%)。 依據申6月專利範圍第8項所述的正溫度係數聚合物組成物 ，其中，該烯烴彈性體是乙烯_辛烯共聚物。 1 〇 ·種電路保護元件，包含： 正溫度係數單元，其在23°c具有低於50 ohm-cm 之積電阻值，並具有一聚合物組成物，該聚合物組成 物包含 (a) —佔该聚合物組成物2〇至8〇重量百分比 (wt%)的非彈性烯烴聚合物混合物， (b) 一佔該聚合物組成物20至60重量百分比 (wt%)的導電性顆粒材料， (C)一佔該聚合物組成物1至30重量百分比（wt%) 16 1270562 4月修正） 第〇94n 1656料利發””之巾請w㈣頁⑼年 的含有⑽立金屬氧化物材料之抗電壓增強劑，及 邊 (d) 一佔該聚合物組成物i至3〇重量百分比 (:t%)的含有熱塑性烯烴彈性體之聚合物穩定劑；及 -電極’分別連接至該正溫度係、數單元之二相反側 11 ·依據申請專利範圍第]〇 礼图弟10項所述之電路保護元件，其中， 吞亥非？早性聚合物混人％ 4人 σ物匕έ 一聚合物混合物，該聚合物 混合物含有 ⑴、’口曰曰!·生接枝聚合物，係為接枝聚烯烴，該接枝 聚合物是經由一鲮酸的極性基團接枝，及 ()、口曰曰(生未接枝聚合物，係為未接枝聚烯烴，該 未接枝聚合物之炫點大致與上述接枝聚合物相同。 12.依據申請專利範圍帛u項所述之電路保護元件，其中， 該結晶性接枝聚合物佔該聚合物組成物0.5至1〇重量百 分比（wt%)。 13·依據申請專利範圍帛U項所述之電路保護元件，其中， 該接枝聚稀烴是選自於接枝高密度聚乙稀、接枝低密度 聚乙烯、接枝線形低密度聚乙烯、接枝中密度聚乙稀及 接枝聚丙烯所組成之群組。 14. 依據申請專利範圍帛u項所述之電路保護元件，其中， 該未接枝聚烯烴是選自於未接枝高密度聚乙稀、未接 低被度聚乙烯、未接枝線形低密度聚乙烯、未接枝中十 度？τ、乙稀及未接枝聚丙烯所組成之群組。 迷 15. 依據申請專利範圍第U項所述之電路保護元件，其中 17 1270562 之申請專利範圍替換頁（95年4月修正） 第094111656號專利發明申請案 該導電性顆粒材料是選自於碳黑、石墨、碳纖維及金屬 粉末顆粒所組成之群組。 件，其中， ，及氧化鎂 16·依據申請專利範圍第u項所述之電路保護元 該金屬氧化物材料是選自於氧化辞、氧化鋁 所組成之群組。 1 7·依據巾明專利範圍第丨2項所述之電路保護元件，其 該熱塑性稀_性體佔該聚合物組成物2至 I ’ 比（wt%)。 里百分 依據申’專利圍第1 7項所述之電路保護it件，复 該烯煙彈性體是乙烯-辛浠共聚物。 18X. Patent application scope: A polymer composition with positive temperature coefficient, comprising: (a) an inelastic bismuth polymer mixture of 20 to 8 重量% (% by weight) of the polymer composition; (b) The polymer composition is 20 to 6 weight percent (% by weight) of the conductive particulate material; (c) one of the polymer composition} to 3 weight percent (3) (eight)) of the particulate metal oxide material-containing resistance voltage enhancement And (d) - account for the polymer composition! A polymer stabilizer containing a thermoplastic olefin elastomer to a weight percentage of (3). 2. The positive temperature coefficient polymer composition of claim 1, wherein the non-elastic polymer mixture comprises a polymer mixture comprising (i) a crystalline graft polymer, The grafted polyolefin is grafted via a polar group of a monocarboxylic acid, and (11) a crystalline ungrafted polymer is a ungrafted polyolefin, the ungrafted polymerization The melting point of the substance is substantially the same as that of the above graft polymer. 3. The polymer of positive temperature coefficient according to claim 2, wherein the graft polymer accounts for 5 to 1 weight percent (wt%) of the polymer composition. 4. The positive temperature coefficient polymer composition according to claim 2, wherein the graft polyolefin is selected from the group consisting of grafted high density polyethylene, grafted low density polyethylene, and grafted linear low density. A group consisting of polyethylene, grafted medium density polyethylene, and grafted polypropylene. </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; The polyolefin is selected from the group consisting of ungrafted high density polyethylene ungrafted low density polyethylene, ungrafted linear low density polyethylene, ungrafted medium density polyethylene, and ungrafted polypropylene. The positive temperature coefficient polymer composition according to claim 2, wherein the conductive particulate material is selected from the group consisting of carbon black, graphite, carbon, cut-off and metal powder particles. The positive temperature coefficient polymer composition according to claim 2, wherein the metal oxide material is selected from the group consisting of zinc oxide, aluminum oxide and oxidized town. According to the positive temperature coefficient polymer composition of claim 3, the thermoplastic olefin elastomer accounts for 2 to 1% by weight (wt%) of the polymer composition. The positive temperature coefficient polymer composition according to the eighth aspect of the invention, wherein the olefin elastomer is an ethylene-octene copolymer. A circuit protection component comprising: a positive temperature coefficient unit having an accumulated resistance value of less than 50 ohm-cm at 23 ° C and having a polymer composition comprising (a) - a non-elastic olefin polymer mixture comprising from 2 to 8 weight percent (wt%) of the polymer composition, (b) from 20 to 60 weight percent (wt%) of the conductive particulate material of the polymer composition, (C) 1 to 30% by weight of the polymer composition (wt%) 16 1270562 April revision) 〇94n 1656料利发"" towel please w (four) page (9) years containing (10) vertical metal oxide material a voltage stabilizer, and a side (d) a polymer stabilizer containing a thermoplastic olefin elastomer in an amount of from i to 3% by weight of the polymer composition (: t%); and an electrode 'connected to the positive temperature, respectively The opposite side of the system and the number of units 11 · According to the scope of the patent application, the circuit protection components described in 10 Early polymer mixed with 4% σ 匕έ a polymer mixture containing (1), 'mouth 曰曰! · raw graft polymer, is a grafted polyolefin, the graft polymer is Grafted through a polar group of citric acid, and (), sputum (raw ungrafted polymer, which is a ungrafted polyolefin, the glare of the ungrafted polymer is substantially the same as the graft polymer described above 12. The circuit protection component according to the scope of the patent application, wherein the crystalline graft polymer comprises 0.5 to 1% by weight (wt%) of the polymer composition. The circuit protection component of item U, wherein the grafted polyhydrocarbon is selected from the group consisting of grafted high density polyethylene, grafted low density polyethylene, grafted linear low density polyethylene, grafted medium density poly A group of ethylene and grafted polypropylene. 14. The circuit protection component according to the scope of the patent application, wherein the ungrafted polyolefin is selected from the group consisting of ungrafted high density polyethylene, Unconnected low-density polyethylene, ungrafted linear low-density polyethylene, not A group consisting of ten degrees of ??, ethylene and ungrafted polypropylene. 15. Circuit protection component according to the scope of claim U, wherein the patent application range of 17 1270562 is replaced (95 Amendment of April 2004) Patent Application No. 094111656 The conductive particulate material is selected from the group consisting of carbon black, graphite, carbon fiber and metal powder particles. Parts, wherein, and magnesium oxide 16 The circuit protection element according to the scope of item [5], wherein the metal oxide material is selected from the group consisting of oxidized words and alumina. 1 7. The circuit protection element according to item 2 of the patent scope of the invention, The thermoplastic dilute body occupies 2 to I' ratio (wt%) of the polymer composition. The percentage is based on the circuit protection member described in claim 17 of the patent, and the olefinic elastomer is ethylene. - Xinyi copolymer. 18