A7 4 6 650 9 B7__ 五、發明說明（1 ) 發明背景 (請先閱讀背面之注意事項再填寫本頁) 先前技藝 本發明係關於一有機正溫度係數熱變電阻體，其係用 作爲溫度感應器或過量電流保護元件，且帶有P T C (電 阻率之正溫度係數）特色及性能，其電阻値隨溫度之升高 而增加。 技藝背景 一有機正溫度係數熱變電阻體，其具有導電性粒子分 散於結晶性聚合物中，其係此類技藝中所習知，如典型地 揭示於 United States Patent Nos. 3,243,753 及 3,35 1,882。此 電阻値之增加咸信由於結晶性聚合物在融熔時之膨脹，而 導致切斷由導電性微細粒子形成的電流運送途徑《 經濟部智慧财產局貝工消费合作社印製 一有機正溫度係數熱變電阻體可用作爲自身控制加熱 器、過量電流保護元件、及溫度感應器。這些元件之需求 在於室溫非操作狀態下充分低的電阻値、介於室溫電阻値 與操作電阻値間充分地大的變化速率、及在反覆操作下有 降低的電阻値變化。 爲滿足該需求，擬將低分子有機化合物如石蠟加入聚 合物基質中。該有機正溫度係數熱變電阻體，包括例如聚 異丁嫌 / 石撮 / 碳黑系統（F. Bueche，J . Appl . Phys ., 44,532,1 973 )，’苯乙烯一丁二烯橡膠/石蠟/碳黑系統（ F . Bueche,J . Polymer Sci . 11，1 3 19,1973 )，及低密度聚 -4- 本紙張尺度適用中困國家標準（CNS)A4規格（210 X 297公釐〉 4 6 650 9 A7 B7 五、發明說明（2 ) 乙烯 /石蠘/碳黑系統（K · Ohe et al . ,Jpn . J . Appl . Phys . iQ_,99，1971 ) »自身控制加熱器、電流限制元件等 諳 先 闓 讀 背 面 之 注 意 事 項 再 填 寫 本 頁 ，其中包含有機正溫度係數熱變電阻體其使用低分子有機 •化合物者也揭示於JP — B’ s 62-16523、7 -109786 及.7-48396，與 JP-A’ s 6 2-5 1184、62-51185 '62-51186 、62-51187、l — 231284、3-1320 01、9 — 27383 及 9-69410。這些案例中， 電阻値之增加咸信係由於低分子有機化合物之融熔所致》 經濟部兮慧財產局貝工消费合作社印製 使用低分子有機化合物的優點之一在隨溫度升高而使 電阻急劇地升高|因爲低分子有機化合物通常較聚合物有 較高的結晶度。而聚合物因爲可容易地置入過冷狀態，而 展示磁滞現象，其隨降溫而電阻降低之溫度，通常低於隨 升溫而電阻增加之溫度。當加入低分子有機化合物之後可 使磁滯減小。經由使用不同融點的低分子有機化合物，可 容易地控制此電阻升高之溫度（操作溫度）。聚合物基於 下列差異而易於發生融點變化：分子量與結晶度，及其與 共單體之共聚合，因而造成結晶狀態之變化。在此案例中 經常無法得到充分的P T C特色。 然而，上述文獻中的有機正溫度係數熱變電阻體，並 未達到在低起始（室溫）電阻與大的電阻變化速率之間明 顯的平衡。Jpn. J· Appl. ?1^5.，1〇_，99，1971展示一實 施例其中電阻率値（Ω cm)之增加因子爲1 〇8。然而， 室溫電阻率値係高達1 04Ω_ cm，且如此尤其不切實際 -5- 本纸張尺度適用中國國家標準<CNS)A4规格（210 X 297公* > Α7 4 6 6 5 Ο 9 Β7 _ 五、發明說明（3 ) 於作爲過量電流保護元件或溫度感應器。其它文獻展示了 電阻値（Ω)或電阻率値（Ω，cm)的增加，在介於1 0 倍（或更低）與1 04倍範圍，而室溫電阻未完全降低。 • 使用熱塑性聚合物作爲基質將引起一項問題，因爲在 聚合物基質之融點將融熔且流體化*尤其是當暴露於高溫 系統之分散狀態將改變，導致性能不穩定。 另方面，JP — A’ s 2-156502，2 — 230684 | 3 — 132001 及 3-205777 揭 示了一種有機正溫度係數熱變電阻體，其使用低分子量有 機化合物與熱固性聚合物作爲基質。然而，因爲使用碳黑 與石墨作爲導電性顆粒|電阻變化速率係小至十的一次方 或更低，且室溫電阻未充分地降低或大約1 Ω . c m。如 此，未能造成介於低起始電阻與大的電阻變化速率之間的 折衷。 JP-A’ s 55-68075，58-3490 1，63-170902，2-33881，9-948 2 及 10 - 4002，及 U n i t e d S t a t e s P a t e n t N 〇 · 4，9 6 6， 729提出一有機正溫度係數熱變電阻體，結構上單純由熱 固性聚合物與導電性顆粒所構成，未求助於低分子量有機 化合物。在這些熱變電阻體中，因爲將碳黑與石墨使用作 爲導電性顆粒，未在介於室溫電阻在高達〇 . 1 Ω . cm 與大的電阻變化速率在十的5次方或更高兩者之間作折衷 。一般而言，熱變電阻體系統僅由熱固性聚合物與無明顯 融點之導電性顆粒所構成，故其中許多在溫度對電阻性能 裝 SI — — I I 訂·！ •線 \ {請先Μ讀背面之注意Ϋ項再填寫本頁> 經濟部智慧財產局負工消费合作杜印製 本紙張尺度適用中國困家標準（CNS>A4規格（210 X 297公釐） -6- 經濟部智慧財產局員工消費合作社印製 4 η B 5 0 9 Α7 Β7 五、發明說明（4 ) 上展示緩慢的電阻上升，尤其是在過量電流保護元件、溫 度感應器等用途無法提供令人滿意的性能。 在許多案例中，碳黑與石墨已被用作爲導電性粒子， '在先前技藝的有機正溫度係數熱變電阻體中，包括前述者 。然而，碳黑之問題在於，當用以降低起始電阻値之碳黑 其用量增加，將不能得到充分的電阻變化速率；在低起始 電阻與大的電阻變化速率之間無法得到合理的平衡。有時 ，將一般可獲得的金屬之粒子用作爲導電性粒子。在此案 例中，也難以達到在低起始電阻與大的電阻變化速率之間 達到明顯的平衡。 爲解決此問題的硏究揭示於J P — A 5 - 4 7 5 0 3，其中提及使用具有尖的突起之導電性粒子其。更特定 地，其揭示作爲結晶性聚合物的聚氟亞乙烯，及作爲具有 尖的突起之導電性粒子的尖的鎳粉。United States Patent No. 5,378,407，也揭示一熱變電阻體其中包含具有尖的突 起之絲狀的鎳、及聚烯烴、烯烴共聚合物或氟聚合物。然 而，這些熱變電阻體分在磁滯上仍不充分，且因此不適合 如溫度感應器之用途，雖然其已改進了在低起始電阻與大 的電阻變化之間的平衡。這是因爲未使用低分子量有機化 合物作爲工作或活性物質。這些熱變電阻體另一問題在於 當它們在操作中電阻上升之後進一步加熱，它們將展示 NT C (電阻率之負溫度係數）性能，其電阻値隨溫度上 升而下降。 JP — A 5-198403 及 5— 198404 揭 本紙張尺度適用中國國家標準（CNSXA4规格（210 * 297公爱） ,1!1!裝·！ —訂·！！ ^^ fv ί«·先明讀背面之注意事項再«.寫本I) 經濟部智慧財產局具工消費合作杜印數 ，Ο 9 Α7 __Β7_ 五、發明說明（5 ) 示一有機正溫度係數熱變電阻體，其中包含熱固性樹脂與 具有尖的突起之導電性顆粒之混合物，且展示所得到電阻 變化速率爲十的9次方更高。然而，當增加塡充料之量室 ‘溫電阻値將降低，未能得到充分的電阻變化速率。如此， 難以達到在低起始電阻値與大的電阻變化之間的平衡。同 時，因爲由熱固性樹脂與導電性顆粒所構成，熱變電阻體 無法展示充分急劇的電阻上升。上述文獻也未提及關於低 分子量化合物之使用《 本發明槪要 本發明之目標在提供有機正溫度係數熱變電阻體其於 室溫具有充分地低電阻，且在介於操作狀態及非操作狀態 間具有大的電阻變化速率，且可有降低的溫度對電阻曲線 磁滞，操作溫度易於控制，且有高的性能穩定性》 該目標係由以下所述的本發明所達成。 (1 )有機正溫度係數熱變電阻體，其中包含熱固性 聚合物基質、低分子有機化合物及各自具有尖的突起之導 電性粒子。 (2)依據（1 )之有機正溫度係數熱變電阻體，其 中該低分子量有機化合物之融點在4 0至2 0 〇°C。 (3 )依據（1 )之有機正溫度係數熱變電阻體，其 中該低分子量有機化合物具有分子量4，0 0 0或更低。 (4)依據（1 )之有機正溫度係數熱變電阻體，其 中該低分子量有機化合物爲石油蟠或脂肪酸。 1IIIIIIIIIII1 * — — — — — — — ^·11111111 ί i (锖先Μ讀背面之注意事項再填窝本頁) 本紙張尺廋適用中國國家標準（CNS)A4規格（210 * 297公釐） -8- A7 ^50 9 _B7_ 五、發明說明（6 ) (5 )依據（1 )之有機正溫度係數熱變電阻體，其 中該熱固性聚合物基質爲下列中之任何一項：環氧樹脂、 不飽和聚酯樹脂、聚醯亞胺、聚胺基甲酸酯、酚樹脂、及 1聚矽氧烷樹脂" (6 )依據（1 )之有機正溫度係數熱變電阻體•其 中該低分子有機化合物之重量爲0.2至2.5倍於該熱 固性聚合物基質之重量。 (7 )依據（1 )之有機正溫度係數熱變電阻體，其 中各自具有尖的突起之該導電性粒子，係以鏈狀相連接。 作用 在本發明中，在導電性粒子上突起尖的形狀可使隧道 電流（tunnel current)立即通過熱變電阻體，使得有可能 使得到起始電阻可低於以球形導電性粒子所可能達到的起 始電阻。當熱變電阻體在操作中，可得到大的電阻變化， 因爲介於尖的導電性粒子間之空間大於那些介於球形導電 性粒子間之空間》 在本發明中，在熱變電阻體中加入低分子有機化合物 ，以使由融熔低分子有機化合物而達到隨溫度升高而電阻 値增加之PTC (電阻率之正溫度係數）性能。由此，溫 度對電阻曲線磁滯可更降至低於由將結晶性熱塑性聚合物 融熔所得者。經由使用具有改變融點等之低分子有機化合 物而控制操作溫度，較改變聚合物融點而控制操作溫度更 爲容易》不似使用熱固性聚合物作爲工作或活性物質之熱 — — — — — — — — — — —J J — — — — — —II 1111111 |> <請先閲讀背面之泫意事項再填寫本頁> 經濟部智慧財產局負工消费合作社印製 本纸張尺度遶用中國國家標準（CNS>A4规格（210 X 297公爱） -9 - 466509 A7 B7 五、發明說明（7 ) 變電阻體，本發明之熱變電阻體於操作中展現急劇的電阻 上升。A7 4 6 650 9 B7__ V. Description of the invention (1) Background of the invention (please read the notes on the back before filling out this page) Prior art The present invention relates to an organic positive temperature coefficient thermal resistor, which is used as a temperature sensor Device or overcurrent protection element, with PTC (Positive Temperature Coefficient of Resistivity) features and performance, its resistance 値 increases with temperature. Technical background: An organic positive temperature coefficient thermal resistor, which has conductive particles dispersed in a crystalline polymer, is known in this type of technology and is typically disclosed in United States Patent Nos. 3,243,753 and 3,35. 1,882. This increase in resistance is due to the expansion of the crystalline polymer during melting, which causes the current transport path formed by the conductive fine particles to be cut off. Coefficient thermal resistors can be used as self-control heaters, excess current protection elements, and temperature sensors. The requirements for these components are a sufficiently low resistance 室温 at room temperature non-operating conditions, a sufficiently large rate of change between room temperature resistance 操作 and operating resistance 、, and reduced resistance 値 changes under repeated operation. To meet this demand, it is intended to add low-molecular organic compounds such as paraffin to the polymer matrix. The organic PTC thermistor includes, for example, a polyisobutylene / stone pinch / carbon black system (F. Bueche, J. Appl. Phys., 44,532,1 973), 'styrene-butadiene rubber / Paraffin / carbon black system (F. Bueche, J. Polymer Sci. 11, 1 3 19, 1973), and low-density poly-4- This paper size is applicable to the National Standard (CNS) A4 specification (210 X 297 mm) 〉 4 6 650 9 A7 B7 V. Description of the invention (2) Ethylene / stone / carbon black system (K · Ohe et al., Jpn. J. Appl. Phys. IQ_, 99, 1971) »Self-control heater, Current limiting elements, etc. Please read the precautions on the back before filling out this page, which contains organic positive temperature coefficient thermal resistors, and those using low molecular organic compounds are also disclosed in JP — B's 62-16523, 7 -109786 And .7-48396, and JP-A's 6 2-5 1184, 62-51185, 62-51186, 62-51187, 1—231284, 3-1320 01, 9—27383, and 9-69410. In these cases, The increase in resistance is caused by the melting of low-molecular-weight organic compounds. One of the advantages of low-molecular-weight organic compounds is that the resistance increases sharply with increasing temperature | because low-molecular-weight organic compounds generally have higher crystallinity than polymers. Because polymers can be easily placed in a supercooled state, The hysteresis phenomenon is shown. The temperature at which the resistance decreases with decreasing temperature is usually lower than the temperature at which the resistance increases with increasing temperature. When low molecular organic compounds are added, the hysteresis can be reduced. By using low molecular organic compounds with different melting points The temperature (operating temperature) at which this resistance rises can be easily controlled. Polymers are susceptible to melting point changes based on the following differences: molecular weight and crystallinity, and their copolymerization with comonomers, resulting in changes in crystalline state. In this case, sufficient PTC characteristics are often not obtained. However, the organic positive temperature coefficient thermal resistor in the above literature has not reached a clear balance between a low initial (room temperature) resistance and a large resistance change rate. Jpn. J. Appl.? 1 ^ 5., 10_, 99, 1971 shows an example in which the increase factor of the resistivity 値 (Ω cm) is 108. However, the chamber The temperature resistivity is as high as 1 04 Ω_ cm, and it is so unrealistic. -5- This paper size applies to the Chinese national standard < CNS) A4 specification (210 X 297 male * > Α7 4 6 6 5 Ο 9 Β7 _ 5. Description of the invention (3) As an excessive current protection element or temperature sensor. Other literatures show that the increase in resistance 値 (Ω) or resistivity 値 (Ω, cm) is in the range of 10 times (or lower) and 104 times, while the room temperature resistance is not completely reduced. • The use of thermoplastic polymers as a matrix will cause a problem because the melting point of the polymer matrix will melt and fluidize * especially when the dispersion state of the system exposed to high temperatures will change, resulting in unstable performance. On the other hand, JP — A ’s 2-156502, 2 — 230684 | 3 — 132001 and 3-205777 disclose an organic positive temperature coefficient thermistor using a low molecular weight organic compound and a thermosetting polymer as a matrix. However, because carbon black and graphite are used as the conductive particles, the resistance change rate is as small as a tenth power or lower, and the room temperature resistance is not sufficiently reduced or approximately 1 Ω.cm. In this way, there is no compromise between a low initial resistance and a large resistance change rate. JP-A's 55-68075, 58-3490 1, 63-170902, 2-33881, 9-948 2 and 10-4002, and Unnited States P atent N 0.4, 9 6 6, 729 Organic PTC thermistors are structurally composed solely of thermosetting polymers and conductive particles, without resorting to low molecular weight organic compounds. Among these thermal resistors, because carbon black and graphite are used as conductive particles, the resistance between room temperature is as high as 0.1 Ω.cm and the large resistance change rate is ten to the fifth power or higher. Make a compromise between the two. Generally speaking, the thermo-resistor system is only composed of thermosetting polymer and conductive particles without obvious melting point, so many of them have resistance to temperature resistance. SI — — I I Order ·! • Line \ {Please read the note on the back before filling in this page> The printed paper size is applicable to Chinese standards (CNS > A4 (210 X 297 mm) ) -6- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 η B 5 0 9 Α7 Β7 V. The description of the invention (4) shows a slow rise in resistance, especially for applications such as excessive current protection elements, temperature sensors, etc. Provides satisfactory performance. In many cases, carbon black and graphite have been used as conductive particles. 'In the prior art organic positive temperature coefficient thermal resistors, including the foregoing. However, the problem with carbon black is that When the amount of carbon black used to reduce the initial resistance is increased, the sufficient resistance change rate cannot be obtained; a reasonable balance cannot be obtained between a low initial resistance and a large resistance change rate. Sometimes, it will generally be possible to The obtained metal particles are used as conductive particles. In this case, it is also difficult to achieve a clear balance between a low initial resistance and a large resistance change rate. To solve this problem Research is disclosed in JP — A 5-4 7 5 0 3, which mentions the use of conductive particles having pointed protrusions. More specifically, it discloses polyfluoroethylene as a crystalline polymer, and as Sharp nickel powder of conductive particles with protrusions. United States Patent No. 5,378,407, also discloses a thermistor body which contains filamentous nickel with sharp protrusions, and polyolefin, olefin copolymer or fluoropolymer. However, these thermistor components are still insufficient in hysteresis and are therefore unsuitable for applications such as temperature sensors, although they have improved the balance between low initial resistance and large resistance changes. This is because No low molecular weight organic compounds are used as work or active materials. Another problem with these thermorheological resistors is that when they are heated further after the resistance rises during operation, they will exhibit NT C (Negative Temperature Coefficient of Resistivity) performance, their resistance 値It decreases as the temperature rises. JP — A 5-198403 and 5 — 198404 The paper size of the paper is applicable to the Chinese national standard (CNSXA4 specification (210 * 297 public love), 1! 1! Installed ·! — ·！ ^^ fv ί «· Read the precautions on the back first and then« .Written copy I) Number of printed copies of industrial and consumer cooperation of the Intellectual Property Bureau of the Ministry of Economic Affairs, 〇 9 Α7 __Β7_ 5. Explanation of the invention (5) Temperature coefficient thermal resistor, which contains a mixture of thermosetting resin and conductive particles with pointed protrusions, and shows that the obtained resistance change rate is ten times higher than the ninth power. However, when the volume chamber of the 塡 filling is increased, The temperature resistance 値 will decrease, and a sufficient resistance change rate cannot be obtained. In this way, it is difficult to achieve a balance between a low initial resistance 値 and a large resistance change. At the same time, because it is composed of a thermosetting resin and conductive particles, the thermal change The resistor cannot exhibit a sufficiently sharp resistance rise. The above-mentioned document also does not mention the use of low-molecular-weight compounds. The present invention requires that the object of the present invention is to provide an organic positive temperature coefficient thermal resistance resistor which has sufficiently low resistance at room temperature, and is in an operating state and a non-operating state. The state has a large resistance change rate, and can have reduced temperature-to-resistance curve hysteresis, easy control of operating temperature, and high performance stability. This goal is achieved by the present invention described below. (1) An organic positive temperature coefficient thermistor, which includes a thermosetting polymer matrix, a low-molecular organic compound, and conductive particles each having a pointed protrusion. (2) The organic positive temperature coefficient thermal resistor according to (1), wherein the melting point of the low molecular weight organic compound is 40 to 200 ° C. (3) An organic positive temperature coefficient thermal resistor according to (1), wherein the low molecular weight organic compound has a molecular weight of 4, 000 or less. (4) The organic positive temperature coefficient thermal resistor according to (1), wherein the low molecular weight organic compound is petroleum rhenium or a fatty acid. 1IIIIIIIIIII1 * — — — — — — — ^ · 11111111 ί i (锖 Please read the precautions on the back before filling in this page) The size of this paper applies to China National Standard (CNS) A4 (210 * 297 mm)- 8- A7 ^ 50 9 _B7_ V. Description of the invention (6) (5) Organic positive temperature coefficient thermorheological resistor according to (1), wherein the thermosetting polymer matrix is any one of the following: epoxy resin, no Saturated polyester resin, polyimide, polyurethane, phenol resin, and 1 polysiloxane resin " (6) Organic positive temperature coefficient thermal resistor based on (1) The weight of the organic compound is 0.2 to 2.5 times the weight of the thermosetting polymer matrix. (7) The organic positive temperature coefficient thermistor according to (1), wherein the conductive particles each having a sharp protrusion are connected in a chain shape. Acting in the present invention, the shape of the protruding tip on the conductive particles allows the tunnel current to immediately pass through the thermo-resistor, making it possible to make the initial resistance lower than that achievable with spherical conductive particles Starting resistance. When the thermistor is in operation, a large resistance change can be obtained because the space between the sharp conductive particles is larger than the space between the spherical conductive particles. In the present invention, in the thermistor Add low-molecular-weight organic compounds to achieve the PTC (Positive Temperature Coefficient of Resistivity) performance by increasing the temperature and increasing the resistance 升高 by melting the low-molecular-weight organic compounds. As a result, the temperature-resistance curve hysteresis can be further reduced to a value lower than that obtained by melting a crystalline thermoplastic polymer. Controlling the operating temperature by using low-molecular organic compounds with changing melting points, etc., is easier than controlling the operating temperature by changing the melting point of the polymer. "It is not like using a thermosetting polymer as the heat of work or active substance — — — — — — — — — — —JJ — — — — — — II 1111111 | > < Please read the intent on the back before filling out this page > Chinese National Standard (CNS > A4 specification (210 X 297 public love) -9-466509 A7 B7 V. Description of the invention (7) Varistor, the thermal rheostat of the present invention exhibits a sharp resistance increase during operation.
先 閲 讀 背 面 之 注 意 事 項 再 填 窵 本 I 經濟部智慧財產局員工消f合作杜印製 再者，本發明使用熱固性聚合物作爲基質》當操作本 •發明之熱變電阻體時，係利用低分子量有機化合物其融熔 伴所隨的大的體積膨脹，而得到大的電阻變化。然而，僅 由低分子量有機化合物與導電性顆粒所構成之熱變電阻體 元件，於操作中不能保持形狀，此係由於低分子量有機化 合物低的融熔黏度。當熱變電阻體元件在操作中，爲防止 低分子量有機化合物由於其融熔所致之流化，或防止熱變 電阻體元件於操作中之變形，如此須要將低分子量有機化 合物與導電性顆粒分散於基質聚合物中。當以熱塑性聚合 物使用作爲此基質聚合物，將會發生高溫下穩定性問題， 尤其是因爲在高於其融點聚合物將融熔。依據本發明，其 中使用於作爲聚合物基質以分散低分子量有機化合物及導 電性顆粒之熱固性聚合物，係不可溶解不可融熔的三度空 間基質，相較於使用熱塑性聚合物之熱變電阻體，此熱變 電阻體在性能穩定性上已大幅地改良，故此熱變電阻體可 保持低的室溫電阻與長時間下於操作中大的電阻變化。 當使用熱塑性聚合物之熱變電阻體基質在加熱至於其 電阻已上升之後，發現NT C現象，其電阻値隨溫度上升 而下降。於冷卻中，將其中電阻自高於低分子量有機化合 物融點之溫度下降，熱變電阻體展現大的溫度對電阻曲線 之磁滯。當熱變電阻體在高於其預設溫度之溫度恢復電阻 値將變成嚴重問題，尤其當其使用作爲保護元件時。此 •10- 本紙張尺度適用中圉國家標準（CNS)A4规格<210 X 297公釐） A7 466509 _____B7___ 五、發明說明（8 ) ί請先《讀背面之注$項再填寫本頁> NTC現象也發現在使用熱塑性樹脂與導電性顆粒之系統 。電阻下降似乎是因爲導電性顆粒在融熔態基質中重新排 列（其係由於即使於電阻上升之後，電流持續流經熱變電 '阻體）。相同理由對於下列案例也成立，於冷卻中，電阻 値由高於加熱操作中之溫度下降。依據本發明，可經由使 用此不可溶解且不可融熔之熱固性聚合物基質，而實質上 消除上述問題，即NT C現象發生於電阻上升之後與溫度 對電阻曲線磁滯，。 圖示簡要敘沭 圖1爲一有機正係數熱變電阻體之斷面圖》 圖2爲在實施例1中熱變電阻體元件的溫度對電阻之 曲線。 圖3爲在實施例2中熱變電阻體元件的溫度對電阻之 曲線。 圖4爲在比較實施例1中熱變電阻體元件的溫度對電 阻之曲線。 經濟部智慧財產局員工消费合作社印製 元件對照表 11 鎳箔電極 12 熱變電阻體元件薄片 較佳體系之說明 本發明之有機正溫度係數熱變電阻體包含熱固性聚合 -11 - 本紙張尺度適用中國國家標準（CNS>A4規格（210 * 297公« ) 經濟部智慧財產局貝工消费合作社印製 4 6 65 0 9 A7 ___B7__ 五、發明說明（9 ) 物基質、低分子量有機化合物及具有尖的突起之導電性顆 粒。 較佳但不排外地，環氧樹脂、不飽和聚酯樹脂、聚醯 '亞胺，聚胺基甲酸酯、酚樹脂、及聚矽氧烷樹脂可使用作 爲熱固性聚合物基質。 環氧樹脂之製作係由使用各種硬化劑而將帶有具活性 環氧末端基團之寡聚物（其分子量數百至約1 0，0 0 0 )作硬化（交聯），且分爲環氧丙基醚型其代表爲雙酚A ，環氧丙基酯型，環氧丙基胺型、及亞克力型。在一些應 用中，也可使用三官能性或多官能性環氧樹脂。其它類型 ’宜使用環氧丙基醚型環氧樹脂，以雙酚A型環氧樹脂爲 最佳。較佳地，在此使用之環氧樹脂帶有環氧當量約 1 0 0至5 0 0。硬化劑可分類爲聚加成型、觸媒型及縮 合型，基於反應機構。聚加成型硬化劑係由本身加入環氧 或羥基基團，且包括聚胺、酸酐、聚酚、聚硫醇、異氰酸 酯等等a觸媒型硬化劑催化環氧基團之聚合，且包括三級 胺與咪唑等等。縮合型硬化劑與羥基基團縮合以硬化，且 包括酚樹脂、密胺樹脂等等。在本發明中，宜使用聚加成 型硬化劑，尤其聚胺硬化劑及酸酐硬化劑作爲對於雙酚A 型環氧樹脂之硬化劑。硬化條件可以適當地決定。 該環氧樹脂與硬化劑係商業上可購得的，例如包括 Epicoat(樹脂）及Epicure及Epomate(硬化劑），均產自Yuka Shell Epoxy Co .，Ltd .;及 Araldite，產自 Ciba-Geigy。 不飽和聚酯樹脂包含聚醅（其具有分子量約 - ------— — — — — — · I I I ---I ^ « — — In — —· ^ (請先Μ讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐〉 -12- A7 4 6 65 0 9 ___B7 _ 五、發明說明（1〇 > 1 ，000至5 ’ 〇〇〇)，其主要由下列成分所構成： 不飽和二元酸或二元酸與多元醇及交聯乙烯基單體，及溶 解在其中的聚酯。之後’使用有機過氧化物如過氧化苯甲 醯作爲聚合起始劑將溶液硬化。在硬化中’若須要可以使 用聚合促進劑。在此作爲不飽和聚酯之起始材料’馬來酸 酐及反丁烯二酸酐爲較佳之不飽和二元酸、鄰苯二甲酸酐 ，間苯二甲酸酐及對苯二甲酸酐爲較佳之二元酸，且丙二 醇及乙二醇爲較佳之多元醇。苯乙烯、二烯丙基鄰苯二甲 酸酯及乙烯基甲苯爲較佳之乙烯基單體。乙烯基單體之量 可以適當地決定。然而，通常宜採每一反丁烯二酸單元有 乙烯基單體之量約1.0至3·Omo1 。爲防止凝膠化 且控制硬化性質等等，在合成方法中’可使用已知的聚合 抑制劑如醌及氫醌。硬化條件可以適當地決定· 該不飽和聚酯樹脂係商業上可購得的，例如包括 Epolac，產自 Nippon Shokubai Co .，Ltd . ;Polyset,產自 Hitachi Kasei Co.，Ltd.;及 Polylight,產自 Dainippon Ink & Chemicals,Inc . e 聚醯亞胺通常分爲縮合型及加成型，基於製作方法。 然而，在本發明中，宜採二馬來醯亞胺型聚醯亞胺，其爲 加成聚合型聚醯亞胺。此二馬來醯亞胺型聚醯亞胺之硬化 可以經由均聚合，與其它不飽和鍵反應，與芳香族胺之麥 克（Michae丨）加成反應，與二烯之狄爾斯一阿爾德（Diels Alder)反應等等。特別宜採二馬來醯亞胺型聚醯亞胺樹脂 ，其係得自介於二馬來醯亞胺與芳香族二胺之間的加成反 !1!1!* ^^ ·! ί 1 I 訂 (請先《讀背面之注意事項再填寫本頁) 經濟部智慧財產局貝工消f合作社印製 本紙張尺度適用中國國家標準（CNS>A4規格（210 X 297公» ) •13- A7 4 6 650 9 _B7_ 五、發明說明（11 ) 應。此芳香族二胺包括二胺基二苯基甲烷等等。其合成與 硬化條件可以適當地決定* {請先Μ讀背面之注項再填寫本頁) 該聚醯亞胺係商業上可購得的，例如包括Imidaloy，產 自 Toshiba Chemical Co. Ltd.;及 Kerimide，產自 Ciba-Geigy ο 聚胺基甲酸酯係得自介於聚異氰酸酯及多元醇之間的 聚加成反應。聚異氰酸酯分爲芳香族型及脂肪族型，而以 芳香族型較佳。宜採2，4_或2，6 —伸甲苯基二異氟 酸酯，二苯基甲烷二異氰酸酯|萘二異氰酸酯等等。多元 醇包括聚醚多元醇如聚丙二醇，聚酯多元醇，丙烯醯基多 元醇等等，而以聚丙二醇爲較佳》在此使用之觸媒可以是 胺型觸媒（三級胺觸媒如三伸乙基二胺，及胺鹽觸媒）。 然而，宜使用有機金屬型觸媒如二丁基錫二月桂酸酯，及 辛酸錫。觸媒在使用上可以合併以次助劑如交聯劑，例如 多元醇及多元胺。可適當地決定合成與硬化條件》 經濟邨智慧財產局貝工消費合作社印製 該聚胺基甲酸酯樹脂係商業上可購得的，例如包括 Sumijule，產自 Sumitomo Bayer Urethane Co .，Ltd ;ΝΡ系 列，產自 Mitsui Toatsu Chemicals;Inc.，及 Colonate，產自 Nippon Polyurethane,Co., Ltd. ° 酚樹脂係得自酚與醛如甲醛之反應，且通常基於合成 條件而分爲酚醛淸漆（novolak)型及甲階酚醛樹脂型。酸 性觸媒下酚醛淸漆型酚係與交聯劑如六伸甲基四胺共同加 熱而硬化，在鹼性觸媒下形成之甲階酚醛樹脂型酚樹脂則 由本身加熱硬化或在酸性觸媒存在下硬化。此二型均可使 -14- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） A7 466509 ___Β7_ 五、發明說明（12 ) 用在本發明中。合成與硬化條件可以適當地泱定。 (請先《讀背面之注意事項再填寫本頁) 該酚樹脂係商業上可購得的，例如包括Sumicon，產自 Sumitomo Bakelite Co ·，Ltd . ;Standlite，產自 Hitachi Kasei Co .，Ltd .;及 Tecolite，產自 Toshiba Chemical Co .，Ltd . 聚矽氧烷樹脂包含重複的矽氧烷鍵•例如包括聚矽氧 烷樹脂其主要得自有機鹵矽氧烷之水解或聚縮合，或將聚 矽氧烷樹脂改良以醇酸樹脂、聚酯、亞克力、環氧樹脂、 酚、胺基甲酸酯、及密胺，以有機過氧化物交聯線型聚二 甲基矽氧烷或其共聚物而得到的聚矽氧烷橡膠等等，及室 溫硫化（RTV)縮合或加成型聚矽氧烷橡膠。 該聚矽氧烷樹脂係商業上可購得的，例如包括各種聚 矽氧烷橡膠及各種聚矽氧烷樹脂，產自The Shin-Etsu Chemical Co .，Ltd . ;Toray Dow Corning Co .，Ltd .，及 Toshiba Silicone Co .，Ltd .。 經濟部智慈財產局貝工消费合作社印製 在此使用之熱固性樹脂可作適當地選擇•基於熱變電 阻體所欲之性能及熱變電阻體之用途》特別較佳地使用環 氧樹脂與不飽和聚酯樹脂。可將二種或多種樹脂共同聚合 爲一聚合物。 即使此聚合物基質宜單獨地由該如上述熱固性聚合物 所構成，在某些案例中可在熱固性聚合物中加入彈性體及 /或熱塑性樹脂。 較佳但不排外地，在此使用低分子量有機化合物爲結 晶狀固體（於正常溫度或約2 5 °C)物質，其具有分子量 -15- 本紙張尺度適用中圉國家標準（CNS)A4規格<210 * 297公釐） 經濟部智慧財產局貝工消t合作社印製 A7 ___ B7 _._ 五、發明說明（13 ) 高達約4，〇〇〇 ’較佳爲高達約1，〇〇〇，且更佳爲 2 0 0 至 8 0 0。 該低分子有機化合物，包括例如蠟（例如石油蠟如石 邋及微結晶性蠟，及天然蠛如蔬菜蠟、動物蠟及礦物躐） ，及脂肪及油（例如脂肪，及那些稱爲固體脂肪者）。此 蠟及脂肪及油之實際成分可爲烴（例如烷型直鏈烴其具有 22或更多的碳原子），脂肪酸（例如烷型直鏈烴脂肪酸 其具有12或更多的碳原子），脂肪酯（例如飽和脂肪酸 之甲酯’其係得自具有2 0或更多的碳原子之飽和脂肪酸 與較低醇如甲醇），脂肪醯胺（例如不飽和脂肪醯胺類之 醯胺如油酸醯胺及芥酸醯胺），脂肪族胺類（例如具有 16或更多碳原子的脂肪族一級胺），及較高的醇（例如 具有16或更多碳原子的正烷醇），及氯化石蠟。然而， 這些成分其本身可使用作爲低分子有機化合物•在此使用 之低分子量有機化合物宜選擇自那些可良好地一起分散之 成分，且應考量聚合物基質之極性。就低分子量有機化合 物而言以石油孅爲較佳。 這些低分子有機化合物係商業上可獲得的，且商業上 產物可立即使用。 在本發明中之一項目標在提供熱變電阻體其可較佳地 在低於2 〇 o°c操作，且尤其較佳地在低於1 〇 o°c操作 ，所用該低分子有機化合物較佳地帶有融點’ mp ’在 40至20 ，且較佳在40至1 0 0t »該低分子有 機化合物包括例如石蠟（例如廿四烷mp 49-52°C;三 ----— — — I--- --I I I I--^ illlllf I J <请先《讀背面之注意事項再填寫本買) 本紙張尺度適用中Η國家標準（CNS>A4規格（210 X 297公釐> -16- A7 4 6 650 9 B7_ 五、發明說明（14 ) 十六院 C36H7* mp73eC;HNP-10 mp 75 °C，Nippon Seiro Co., Ltd.;及 HNP-3 mp 66 °C, Nippon Seiro Co.，Ltd.)，微結 晶性蟠（例如 Hi-Mic-1080 mp 83°C，Nippon Seiro Co.，Ltd '.;Hi-Mic-1045 mp 70°C,Nippon Seiro Co. , Ltd. ;Hi-Mi c-2045 mp 64〇C ,Nippon Seiro Co . , Ltd . ;Hi-Mic-3090 mp 89°C,Nippon Seiro Co. , Ltd. ;Seratta 104 mp 96°C, Nippon SekLyu Seisei Co . , Ltd .;及 155 Microwax mp 70 °C,Nippon Seklyu Seisei Co,，Ltd.)，脂肪酸（例如正十二 烷酸 mp 81°C，Nippon Seika Co.，Ltd.;硬脂酸 mp 72DC，Ni ppon Seika Co.，Ltd.;及十六酸 mp 64eC，Nippon Seika Co.，Ltd·)，脂肪酯（花生四烯酸甲基酯mp 48°C，Tokyo Kas ei Co . , Ltd .)，及脂肪酪胺（例如油酸醯胺mp 76°C，Nippo π Seika Co. , Ltd.)。也可使用聚乙稀蠟（例如Mitsui High -Wax 110 mp 100。0,產自 Mitsui Petrochemical Industries’Inc .)，硬脂酸醯胺（111?1〇9°(：)，正十二烷酸醯胺（ mplll°C) ，N — N，一乙烯二月桂酸醯胺（mp 1 5 7 °C ) ，N—Ν’ 一二油醯己二酸醯胺（mpll9 °C)及Ν- Ν’ —六伸甲基一二硬脂酸醯胺（mp 140 °C)。也可使用石蠟混和物其中包含石蠘及樹脂，且可另 外包含微結晶性蠟，且其融點等於或高於4 0°C且低於 2 0 0 t。 低分子有機化合物可單獨使用或使用二或更多種的組 合*但取決於操作溫度等。 在此使用的低分子量有機化合物之重量應較佳爲 本紙張尺度適用中困國家標準（CNS)A4规格<210 X 297公釐） ---I------— I— i I I I I I I ^il — 1 I 1!^ (請先《讀背面之注意事項再填寫本頁) 經濟部智慧財產局霣工消费合作社印製 -17- A7 lG 65 0 9 _B7__ 五、發明說明（15 ) 0.2至4倍’且更佳爲0.2至2.5倍於熱固性聚合 物基質（包括硬化劑等等）之總重量。當此混合比變得較 低或低分子量有機化合物之量變得較小，將不能得到充分 •的電阻變化速率。相反地，當混合比變得較高或低分子量 有機化合物之量變得較大，不僅在低分子有機化合物融熔 時不能有大的熱變電阻體元件之變形，且難以將低分子量 有機化合物與導電性顆粒混合。 在此使用之導電性粒子（其各自具有尖的突起）係各 自由一級粒子所製，該一級粒子具有尖的突起。更特定地 ，許多（通常爲1 0至50 0)圓錐形及尖的突起，其各 自高度在粒子直徑的1/3至1/5 0，存在於一個單一 粒子上。此導電性粒子宜由N. i或其類似物所製》 雖然該導電性粒子可以分離的粉末形式使用，宜將其 以鏈型約10至1 | 0 0 0相連的一級粒子形成二級粒子 而使用。鏈型相連一級粒子可局部包含一級粒子。前者之 實施例包括具有尖的突起的球形形式鎳粉，其中之一爲商 場上可由商品名I NCO型1 2 3鎳粉（INCO Co .，Ltd · )得到者。這些粉末具有平均粒子直徑約3至，表 觀密度約1 . 8至2 . 7g/cm3，且比表面面積約 0.34 至 0.44m2/g» 後者較佳之實施例爲絲狀的鎳粉，其中有些可在商場 上由下列商品名得到：INC0型255鎳粉、INC0 型270鎳粉、INC ◦型287鎳粉、及INC ◦型 2 1 0鎳粉，全由INCO Co .，Ltd ·製作，以前三項爲較 !!!J裝·！1!11 訂♦1! ! 線 <锖先《讀背面之注意事項再填寫本頁) 經濟部暫慧財產局貝工消t合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐> -18- 經濟部智慧財產局貝工消费合作社印製 4 6 650 9 A7 _B7_ 五、發明說明（16 ) 佳》—級粒子具有平均粒子直徑較佳地至少爲〇 . l//m ，及更佳地爲約0 . 5至約4 . 0#m (包含）具有平 均粒子直徑1·0至4.Ogm(包含）之一級粒子爲最 •佳，且可以50%或更低之重量比與平均粒子直徑0.1 至低於1 . 〇ym之一級粒子混和。其表觀密度約 0 . 3至1 . 〇g/cm3且比表面面積爲約〇 . 4至 2 . 5 m 2 / g。 就此而言，値得注意的是平均粒子直徑係由費雪（ Fischer)次篩方法量測，該導電性粒子首見於JP-A 5-47503及 United States Patent No. 5，378，407。 除了具有尖的突起之導電性粒子I導電性粒子也可使 用如碳黑、石墨、碳纖維、金屬化碳黑、石墨化碳黑及金 屬化碳纖維、球形、薄片化或纖維狀金屬粒子，金屬粒子 塗佈以不同的金屬（例如銀塗佈鎳粒子），陶瓷導電性粒 子如那些碳化鎢、氮化鈦、氮化锆、碳化鈦、硼化鈦及矽 化鉬、及導電性鈦酸鉀晶鬚，其揭示於JP—A· s 8 一 31554及9 — 27383。在含量上較佳地應有高 達2 5%重量比的該導電性粒子爲具有尖的突起之導電性 粒子。 接著，將解釋如何製作本發明之有機正溫度係數熱變 電阻體。 將既定量的熱固性樹脂（不作硬化）、硬化劑或其類 似者、熱塑性樹脂、低分子量有機化合物及具有尖的突起 之導電性顆粒共同混合並分散而得到塗料形式的混合物。 nlltl — ϋ - — — — III— ^ 111111 I t <請先《讀背面之注意事項再填*本頁> 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐〉 -19- A7 4 6 650 9 ___B7_ 玉、發明說明（17 ) 混合與分散之執行可以由已知方式使用各種攪拌器，分散 器，磨機、塗料滾壓機等等。若氣泡發生於混合物中，則 將在混合物則在真空下除氣泡。就黏度控制而言，可使用 _各種溶劑如芳香族碳氫化合物溶劑、酮類及醇類《將混合 物澆鑄在介於鎳、銅或其它金屬箔電極之間，或將混合物 塗覆於該電極上（藉由屏幕塗刷等等），而得到一片材》 將此片材在對於熱固性樹脂作既定熱處理之條件下硬化。 此時，熱固性樹脂可以是在相對低溫下預硬化，接著在高 溫下作硬化。供選擇地*混合物可以單獨地硬化成爲片狀 ，於之後再其上塗覆導電性膏或其類似物，以在其上形成 電極。最後將所得之片材沖壓成所欲之形狀而得到熱變電 阻體元件β 本發明之有機熱變電阻體可包含各種添加劑，只要它 們無害於本發明所欲之性能。爲防止聚合物之基質及低分 子有機化合物熱降解•可也將例如抗氧化劑加入熱變電阻 體元件中。酚，有機硫、亞磷酸鹽（基於有機磷）等等可 使用作爲抗氧化劑》 此外，本發明熱變電阻體可包含如良好導熱及導電性 添加的氮化矽、二氧化矽、氧化鋁及黏土（雲母，滑石等 )其敘述於JP — A 57 - 1 2061 ;矽、碳化矽、 氮化矽、氧化鈹及硒其敘述於JP — B 7 77161， 無機氮化物及氧化鎂其敘述於J P—A 5-21771 1，及其類似者。 就堅實之改良言，本發明熱變電阻體可包含氧化鈦、 本紙張尺度適用中國國家標準（CNS>A4規格（210 * 297公釐) ^2〇 _ — — — — — II — — — — — — - I I 11 111 — — — — — — — <請先《讀背面之注項箨填寫本頁> 經濟部智慧財產局貝工消费合作社印製 4 6 650 9 Δ7 Α7 Β7 五、發明說明（18 ) (請先閲讀背面之注意事項再填寫本I) 氧化鐵、氧化鋅、二氧化砂、氧化鎂、氧化链、氧化鉻、 硫酸鋇、碳酸鈣、氫氧化鈣及氧化鉛其敘述於J P_ A 5-226112,無機固體其具有高相對介電常數其敘 述於J P - A 6 — 68963，例如鈦酸鋇、鈦酸鋸及 鈮酸鉀，及其類似物。 就電壓電阻改良而言*本發明熱變電阻體可包含敘述 於JP—A 474383之硼碳化物等。 就強度改良而言，本發明熱變電阻體可能包含敘述於 J P — A 5 — 74603水合的鹼性鈦酸鹽，敘述於 J P - A 8 — 1 7563的氧化鈦、氧化鐵、鋅氧化物 及二氧化矽等。 經濟部智慧財產局工消费合作社印製 作爲結晶晶核，本發明熱變電阻體可包含敘述於J P -B 59-10553之鹼性鹵化物及密胺樹脂，敘述 於J P — A 6 - 765 1 1之苯甲酸，二亞苄基山梨醇 及金屬苯甲酸酯，敘述於J P_A 7 — 6 8 6 4之滑石 、沸石及二亞苄基山梨醇，敘述於J P_ A 7-263 127之山梨醇衍生物（膠化劑）、瀝青及二（4—三級 -丁基苯基）磷酸鈉等。 作爲電弧控制劑，本發明熱變電阻體可包含敘述於J Ρ — Β 4 - 28744的氧化鋁及氧化鎂水合物，及敘 述於J Ρ-Α 6 1 - 250058之金屬水合物及碳化 矽等。 作爲預防金屬的有害效應，本發明熱變電阻體可包含 Irganox MD 1024(Ciba-Geigy)其欽述於 J Ρ — A 7 — -21 - 本紙張尺度適用中Η國家標準（CNSU4規格（210 X 297公釐） 4 6 650 9 A7 B7 五、發明說明（19 ) 6 8 6 4 〇 作爲阻焰劑，本發明熱變電阻體可包敘述於J P - A 6 1 — 2 3 9 5 8 1之含三氧化二銻及氫氧化鋁；敘述 ’於JP—A 5-74603之氫氧化鎂：含鹵素之有機 化合物（包括聚合物）如2，2 —二（4 一羥基_3，5-一二溴苯基）丙烷及聚氟亞乙烯（PVDF):磷化合物 如磷酸銨等。 除了這些添加劑，本發明熱變電阻體可包含硫化鋅、 鹼性碳酸鎂、氧化鋁、矽酸鈣、矽酸鎂、鋁矽酸鹽黏土（ 雲母、滑石、高嶺石、蒙脫石等）、玻璃粉末、玻璃薄片 、玻璃纖維、鈣硫酸鹽等。 上述添加劑使用量應高達聚合物基質、低分子有機化 合物及導電性粒子總重量之2 5%重量比* 依據本發明之有機正溫度係數熱變電阻體，在其非操 作狀態具有低起始電阻或室溫電阻率値約102至10°Ω c m，在操作中具有急速的電阻上升，且在由非操作狀態 轉變爲操作狀態時電阻變化速率爲高於十的6次方》 請 先 讀 背 面 之 注 項I裝 頁 訂 經濟部智慧財產局貴x消费合作社印製 實施例 本發明現在將更特定地以實施例及比較實施例說明。 實施例1 將雙酚A型環氧樹脂（Epicoat 801，產自Yuka Shell Epoxy Co .，Ltd ·)及改良胺硬化劑（Epomate B002,產自 本紙張尺度適用4»困國家標準（CNS>A4規格（210 X 297公釐〉 -22- 經濟部智慧財產局員工消費合作社印數 4 6 6 5 0 9 A7 _B7 五、發明說明（20 )Read the precautions on the back before filling in this document. The cooperation with the staff of the Intellectual Property Bureau of the Ministry of Economic Affairs and the printed matter is further printed. Furthermore, the present invention uses a thermosetting polymer as the substrate. The molecular weight organic compound melts with a large volume expansion, resulting in a large change in resistance. However, a thermal resistor element composed of only a low-molecular-weight organic compound and conductive particles cannot maintain a shape during operation because of the low melt viscosity of the low-molecular-weight organic compound. In order to prevent the low-molecular-weight organic compound from fluidizing due to melting when the thermo-resistive element is in operation, or to prevent the thermo-rheological element from being deformed during the operation, the low-molecular-weight organic compound and conductive particles are required. Dispersed in the matrix polymer. When a thermoplastic polymer is used as this matrix polymer, stability problems at high temperatures will occur, especially because the polymer will melt above its melting point. According to the present invention, a thermosetting polymer used as a polymer matrix to disperse low-molecular weight organic compounds and conductive particles is a three-dimensional matrix that is insoluble and infusible, compared to a thermo-resistor using a thermoplastic polymer. The thermal resistance resistor has been greatly improved in performance stability, so the thermal resistance resistor can maintain low room temperature resistance and large resistance change during operation for a long time. When the thermistor matrix using a thermoplastic polymer is heated so that its resistance has increased, the NT C phenomenon is found, and its resistance 値 decreases with increasing temperature. During the cooling, the resistance is decreased from a temperature higher than the melting point of the low-molecular-weight organic compound, and the thermal variable resistor exhibits a large temperature-resistance curve hysteresis. The resistance 变 becomes a serious problem when the thermistor returns to a temperature higher than its preset temperature, especially when it is used as a protection element. This • 10- The paper size is applicable to the China National Standard (CNS) A4 Specification < 210 X 297 mm) A7 466509 _____B7___ V. Description of the Invention (8) ί Please read the “$” on the back side before filling in this page & gt The NTC phenomenon is also found in systems using thermoplastic resins and conductive particles. The decrease in resistance appears to be due to the rearrangement of the conductive particles in the molten matrix (this is due to the fact that current continues to flow through the thermoelectric resistors even after the resistance has increased). The same reason is true for the following case, in which the resistance 値 decreases from a temperature higher than that during the heating operation during cooling. According to the present invention, the above problem can be substantially eliminated by using this insoluble and infusible thermosetting polymer matrix, that is, the NT C phenomenon occurs after the resistance rises and the temperature versus the resistance curve hysteresis. Brief description of the figure: Figure 1 is a cross-sectional view of an organic positive coefficient thermal resistance resistor. Figure 2 is a temperature vs. resistance curve of the thermal resistance resistor element in Example 1. Fig. 3 is a temperature vs. resistance curve of a thermistor element in Example 2. Fig. 4 is a temperature-resistance curve of a thermistor element in Comparative Example 1. Figs. Comparison Table of Printed Components for Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 11 Nickel foil electrodes 12 Description of the preferred system of the thermoelectric resistor element sheet The organic positive temperature coefficient thermoelectric resistor of the present invention includes thermosetting polymer-11-This paper applies Chinese National Standard (CNS > A4 Specification (210 * 297) «) Printed by Shelley Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 4 6 65 0 9 A7 ___B7__ 5. Description of the invention (9) Substance matrix, low molecular weight organic compounds and Protruded conductive particles. Preferred, but not exclusive, epoxy resins, unsaturated polyester resins, polyimide, polyurethanes, phenol resins, and polysiloxane resins can be used as thermosetting Polymer matrix. Epoxy resin is made by using various hardeners to harden (crosslink) oligomers with active epoxy end groups (whose molecular weight is in the range of several hundred to about 10,000). It is divided into glycidyl ether type which is represented by bisphenol A, glycidyl ester type, glycidyl amine type, and acrylic type. In some applications, trifunctional or polyfunctionality can also be used Epoxy. Other types' should use epoxy propyl ether type epoxy resin, bisphenol A type epoxy resin is the best. Preferably, the epoxy resin used here has an epoxy equivalent of about 100 to 50. 0. Hardeners can be classified as polyaddition, catalyst and condensation based on the reaction mechanism. Polyaddition hardeners are epoxy or hydroxyl groups added by themselves, and include polyamines, anhydrides, polyphenols, polysulfides Alcohol, isocyanate, etc. a catalyst-type hardener catalyzes the polymerization of epoxy groups, and includes tertiary amines and imidazoles, etc. Condensation-type hardeners condense with hydroxyl groups to harden, and include phenol resins, melamine resins, etc. Etc. In the present invention, it is preferable to use a polyaddition hardener, especially a polyamine hardener and an acid anhydride hardener as the hardener for the bisphenol A type epoxy resin. The hardening conditions can be appropriately determined. The epoxy resin and hardening Agents are commercially available and include, for example, Epicoat (resin) and Epicure and Epomate (hardeners), both of which are produced by Yuka Shell Epoxy Co., Ltd .; and Araldite, which are produced by Ciba-Geigy. Unsaturated polyester resins Contains polyfluorene (which has a molecular weight of about-- -----— — — — — — · III --- I ^ «— — In — — · ^ (Please read the notes on the back before filling out this page) The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm> -12- A7 4 6 65 0 9 _B7 _ V. Description of the invention (1〇 > 1,000 to 5 '〇〇〇), which is mainly composed of the following components: Unsaturated Dibasic acids or dibasic acids with polyols and crosslinked vinyl monomers, and polyesters dissolved therein. Afterwards, the solution is hardened using an organic peroxide such as benzamidine peroxide as a polymerization initiator. In hardening ', a polymerization accelerator can be used if necessary. Here, as the starting materials of unsaturated polyesters, maleic anhydride and fumaric anhydride are preferred unsaturated dibasic acids, phthalic anhydride, and isophthalic anhydride and terephthalic anhydride are preferred. Dibasic acids, and propylene glycol and ethylene glycol are preferred polyols. Styrene, diallyl phthalate and vinyltoluene are preferred vinyl monomers. The amount of the vinyl monomer can be appropriately determined. However, it is generally preferred to have an amount of vinyl monomer per fumaric acid unit of about 1.0 to 3.0 mol. In order to prevent gelation and control hardening properties and the like, known polymerization inhibitors such as quinone and hydroquinone can be used in the synthesis method. The hardening conditions can be appropriately determined. The unsaturated polyester resin is commercially available, and includes, for example, Epola, produced by Nippon Shokubai Co., Ltd .; Polyset, produced by Hitachi Kasei Co., Ltd .; and Polylight, The polyimide produced by Dainippon Ink & Chemicals, Inc. e is generally divided into condensation type and addition molding, based on the production method. However, in the present invention, it is preferable to use a dimaleimide-type polyfluorene imine, which is an addition polymerization-type polyfluorene. The hardening of this dimaleimide-type polyfluorene imine can be through homopolymerization, reaction with other unsaturated bonds, Mike addition reaction with aromatic amines, and Diers-Alder of diene. (Diels Alder) reaction and so on. It is particularly suitable to use dimaleimide imide type polyimide resin, which is derived from the addition reaction between dimaleimide and aromatic diamine! 1! 1! * ^^ ·! Ί Order 1 I (please read the “Notes on the back side before filling out this page”) The paper size printed by the Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the cooperative is applicable to Chinese national standards (CNS > A4 size (210 X 297) ») • 13 -A7 4 6 650 9 _B7_ V. Description of the invention (11). This aromatic diamine includes diaminodiphenylmethane, etc. The conditions for its synthesis and hardening can be determined appropriately. {Please read the note on the back first Please fill in this page again.) The polyimide is commercially available, including, for example, Imidaloy, produced by Toshiba Chemical Co. Ltd .; and Kerimide, produced by Ciba-Geigy. Polyurethane is obtained from Polyaddition reaction between polyisocyanate and polyol. Polyisocyanates are classified into aromatic types and aliphatic types, and aromatic types are preferred. It is preferable to use 2,4_ or 2,6-tolyl diisofluoroate, diphenylmethane diisocyanate | naphthalene diisocyanate and so on. Polyols include polyether polyols such as polypropylene glycol, polyester polyols, propylene glycol polyols, etc., and polypropylene glycol is preferred. The catalyst used here may be an amine catalyst (tertiary amine catalyst (Such as triethylene diamine, and amine salt catalyst). However, organometallic catalysts such as dibutyltin dilaurate, and tin octoate are preferred. The catalyst can be used in combination with secondary auxiliaries such as cross-linking agents, such as polyols and polyamines. The conditions for synthesis and hardening can be appropriately determined. ”The Polyurethane resin printed by Economic Village Intellectual Property Bureau Shellfish Consumer Cooperative is commercially available, including, for example, Sumijule, produced by Sumitomo Bayer Urethane Co., Ltd; NP series, produced by Mitsui Toatsu Chemicals; Inc., and Colonate, produced by Nippon Polyurethane, Co., Ltd. ° Phenol resins are derived from the reaction of phenol with aldehydes such as formaldehyde, and are usually classified as phenolic lacquers based on synthetic conditions (Novolak) type and resole phenolic resin type. Under acidic catalysts, phenolic lacquer-type phenols are heated together with a cross-linking agent such as hexamethylene tetramine to harden them. Resol-type phenolic resins formed under basic catalysts are hardened by heating or in acid catalysts. Hardened in the presence of a medium. Both types can be used. -14- This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) A7 466509 ___ Β7_ 5. Description of the invention (12) is used in the present invention. The synthesis and hardening conditions can be appropriately determined. (Please read "Notes on the back side before filling out this page.") This phenol resin is commercially available, including, for example, Sumicon, produced by Sumitomo Bakelite Co., Ltd .; Standlite, produced by Hitachi Kasei Co., Ltd. And Tecolite, produced by Toshiba Chemical Co., Ltd. Polysiloxane resins contain repeated siloxane bonds, for example, including polysiloxane resins which are mainly derived from the hydrolysis or polycondensation of organohalosiloxanes, or Polysiloxane resin modified with alkyd resin, polyester, acrylic, epoxy resin, phenol, urethane, and melamine, crosslinked with linear polydimethylsiloxane or copolymerized with organic peroxide Polysiloxane rubber, etc., and room temperature vulcanization (RTV) condensation or addition molding polysiloxane rubber. The polysiloxane resin is commercially available, and includes, for example, various polysiloxane rubbers and various polysiloxane resins produced by The Shin-Etsu Chemical Co., Ltd .; Toray Dow Corning Co., Ltd. ., And Toshiba Silicone Co., Ltd. The thermosetting resin printed by the Sheller Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs can be appropriately selected. • Based on the desired performance of the thermo-resistor and the use of the thermo-resistor, it is particularly preferred to use epoxy resin and Unsaturated polyester resin. Two or more resins can be polymerized together into one polymer. Even if the polymer matrix is preferably composed of the thermosetting polymer as described above, in some cases, an elastomer and / or a thermoplastic resin may be added to the thermosetting polymer. Preferably, but not exclusively, a low-molecular-weight organic compound is used here as a crystalline solid (at normal temperature or about 25 ° C), which has a molecular weight of -15. This paper is applicable to the China National Standard (CNS) A4 specification < 210 * 297 mm) A7 ___ B7 _._ printed by the Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention description (13) Up to about 4,000,000 ', preferably up to about 1,000,000. 〇, and more preferably 2000 to 800. The low-molecular organic compounds include, for example, waxes (such as petroleum waxes such as stone wax and microcrystalline waxes, and natural waxes such as vegetable waxes, animal waxes, and mineral waxes), and fats and oils (such as fats, and those called solid fats). By). The actual composition of this wax and fats and oils can be hydrocarbons (e.g. alkane linear hydrocarbons having 22 or more carbon atoms), fatty acids (e.g. alkane linear hydrocarbon fatty acids having 12 or more carbon atoms), Fatty esters (e.g. methyl esters of saturated fatty acids, which are derived from saturated fatty acids with 20 or more carbon atoms and lower alcohols such as methanol), fatty amidamines (e.g., unsaturated fatty acids, such as amines such as oil Acid amine and erucamide), aliphatic amines (such as aliphatic primary amines having 16 or more carbon atoms), and higher alcohols (such as n-alkanols having 16 or more carbon atoms), And chlorinated paraffin. However, these components can be used as low-molecular-weight organic compounds per se. The low-molecular-weight organic compounds used here should be selected from those that can be dispersed well together, and the polarity of the polymer matrix should be considered. For low molecular weight organic compounds, petroleum rhenium is preferred. These low-molecular organic compounds are commercially available, and commercial products are ready for immediate use. An object in the present invention is to provide a thermorheological resistor which can be preferably operated below 200 ° C, and particularly preferably below 100 ° C, the low-molecular organic compound used It preferably has a melting point 'mp' of 40 to 20, and preferably 40 to 100 t. The low-molecular organic compound includes, for example, paraffin (e.g., tetramethylene mp 49-52 ° C; three ----- — — I --- --III I-^ illlllf IJ < Please read the precautions on the reverse side before filling in this purchase) This paper size applies to the China National Standard (CNS > A4 size (210 X 297 mm & gt) -16- A7 4 6 650 9 B7_ V. Description of the Invention (14) Sixteen House C36H7 * mp73eC; HNP-10 mp 75 ° C, Nippon Seiro Co., Ltd .; and HNP-3 mp 66 ° C, Nippon Seiro Co., Ltd.), microcrystalline rhenium (for example, Hi-Mic-1080 mp 83 ° C, Nippon Seiro Co., Ltd '.; Hi-Mic-1045 mp 70 ° C, Nippon Seiro Co., Ltd. ; Hi-Mi c-2045 mp 64〇C, Nippon Seiro Co., Ltd .; Hi-Mic-3090 mp 89 ° C, Nippon Seiro Co., Ltd .; Seratta 104 mp 96 ° C, Nippon SekLyu Seisei Co. , Ltd .; and 155 Microwax mp 70 ° C, Nippon Seklyu Seisei Co ,, L td.), fatty acids (eg n-dodecanoic acid mp 81 ° C, Nippon Seika Co., Ltd .; stearic acid mp 72DC, Ni ppon Seika Co., Ltd .; and hexadecanoic acid mp 64eC, Nippon Seika Co ., Ltd.), fatty esters (arachidonic acid methyl ester mp 48 ° C, Tokyo Kas ei Co., Ltd.), and fatty tyramines (such as ammonium oleate mp 76 ° C, Nippo π Seika Co ., Ltd.). Polyethylene wax (such as Mitsui High-Wax 110 mp 100.0, produced by Mitsui Petrochemical Industries' Inc.), ammonium stearate (111-1009 ° (:)) can also be used. , Ammonium dodecanoate (mplll ° C), N-N, ammonium diethylene dilaurate (mp 1 5 7 ° C), N-N'-dioleylamine adipate (mpll9 ° C) and N-N '-hexamethylene methyl distearate (mp 140 ° C). It is also possible to use paraffin mixtures which contain osmium and resin, and may additionally contain microcrystalline waxes, whose melting point is equal to or higher than 40 ° C and lower than 200 t. The low-molecular-weight organic compound may be used alone or in a combination of two or more * but depends on the operating temperature and the like. The weight of the low-molecular-weight organic compound used here should preferably be the paper size applicable to the National Standard (CNS) A4 Specification < 210 X 297 mm) --- I ------- I--i IIIIII ^ il — 1 I 1! ^ (Please read the “Notes on the back side before filling out this page”) Printed by the Industrial and Commercial Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -17- A7 lG 65 0 9 _B7__ V. Description of Invention (15) 0.2 To 4 times' and more preferably 0.2 to 2.5 times the total weight of the thermosetting polymer matrix (including hardeners, etc.). When this mixing ratio becomes lower or the amount of low-molecular-weight organic compounds becomes smaller, a sufficient resistance change rate cannot be obtained. On the contrary, when the mixing ratio becomes higher or the amount of the low-molecular-weight organic compound becomes larger, not only cannot the large thermo-rheological element be deformed when the low-molecular-weight organic compound is melted, but it is difficult to combine the low-molecular-weight organic compound with the low-molecular-weight organic compound. The conductive particles are mixed. The conductive particles (each having a sharp protrusion) used here are made of free primary particles, and the first-order particles have sharp protrusions. More specifically, many (usually 10 to 50) conical and pointed protrusions, each having a height of 1/3 to 1/5 0 of the particle diameter, exist on a single particle. The conductive particles should be made of N.i or the like. Although the conductive particles can be used in the form of separated powders, they should be formed into secondary particles in the form of primary particles with a chain of about 10 to 1 | 0 0 0 While using. The chain-connected first-order particles may partially include first-order particles. Examples of the former include nickel powder in a spherical form with pointed protrusions, one of which is commercially available from the trade name I NCO type 1 2 3 nickel powder (INCO Co., Ltd.). These powders have an average particle diameter of about 3 to, an apparent density of about 1.8 to 2.7 g / cm3, and a specific surface area of about 0.34 to 0.44 m2 / g. The latter preferred embodiment is a filamentous nickel powder, some of which are Available in the mall under the following trade names: INC0 type 255 nickel powder, INC0 type 270 nickel powder, INC ◦ type 287 nickel powder, and INC ◦ type 2 10 nickel powder, all made by INCO Co., Ltd., previously Three items are more !!! J equipment! 1! 11 Order ♦ 1!! & 《"Read the precautions on the back before filling out this page) Printed on paper sizes of the China National Standards (CNS) A4 specification (printed on the paper) 210 X 297 mm > -18- Printed by the Shelley Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 6 650 9 A7 _B7_ V. Description of the Invention (16) Good "-Grade particles have an average particle diameter of preferably at least 0. l // m, and more preferably from about 0.5 to about 4.0 # m (inclusive). First-order particles having an average particle diameter of 1.0 to 4.0gm (inclusive) are the best, and can be 50% A weight ratio of or lower is mixed with first-order particles having an average particle diameter of 0.1 to less than 1.0 μm. Its apparent density is about 0.3 to 1.0 g / cm3 and the specific surface area is about 0.4 to 2. 5 m 2 / g. In this regard, it should be noted that the average particle diameter is measured by the Fischer sieving method. The conductive particles were first seen in JP-A 5-47503 and United States Patent No. 5 , 378, 407. In addition to the conductive particles having pointed protrusions, I can also use conductive particles such as carbon black, graphite, carbon fiber, metalized carbon black, and stone. Carbon black and metallized carbon fiber, spherical, flake or fibrous metal particles, metal particles coated with different metals (such as silver coated nickel particles), ceramic conductive particles such as those of tungsten carbide, titanium nitride, nitride Zirconium, titanium carbide, titanium boride and molybdenum silicide, and conductive potassium titanate whiskers are disclosed in JP-A · s 8-31554 and 9-27383. The content should preferably be up to 25% by weight This conductive particle is a conductive particle having sharp protrusions. Next, how to make the organic positive temperature coefficient thermistor of the present invention will be explained. A given amount of thermosetting resin (not hardened), hardener or the like It is a mixture of thermoplastic resin, low molecular weight organic compound, and conductive particles with sharp protrusions, which are mixed and dispersed to obtain a mixture in the form of a coating. Nlltl — ϋ-— — — III — ^ 111111 I t < Note for refilling * This page > This paper size applies to China National Standard (CNS) A4 (210 X 297 mm> -19- A7 4 6 650 9 _B7_ Jade and invention description (17) Execution can be performed in a known manner using various stirrers, dispersers, mills, paint rollers, etc. If bubbles occur in the mixture, the bubbles will be removed under vacuum in the mixture. For viscosity control, use _Various solvents such as aromatic hydrocarbon solvents, ketones, and alcohols. Cast the mixture between nickel, copper, or other metal foil electrodes, or apply the mixture to the electrode (by screen painting, etc.) Etc.) to obtain a sheet "This sheet is hardened under a predetermined heat treatment condition for a thermosetting resin. At this time, the thermosetting resin may be pre-cured at a relatively low temperature and then cured at a high temperature. Alternatively, the mixture may be individually hardened into a sheet shape, and thereafter a conductive paste or the like may be coated thereon to form an electrode thereon. Finally, the obtained sheet is punched into a desired shape to obtain a thermo-varistor element β. The organic thermo-resistor of the present invention may contain various additives as long as they do not harm the desired performance of the present invention. To prevent thermal degradation of the polymer matrix and low molecular organic compounds • Antioxidants can also be added to the thermistor elements, for example. Phenol, organic sulfur, phosphite (based on organic phosphorus), etc. can be used as antioxidants. In addition, the thermal resistor according to the present invention may include silicon nitride, silicon dioxide, aluminum oxide, and Clay (mica, talc, etc.) is described in JP — A 57-1 2061; silicon, silicon carbide, silicon nitride, beryllium oxide, and selenium are described in JP — B 7 77161, and inorganic nitrides and magnesium oxide are described in JP —A 5-21771 1, and the like. In terms of solid improvement, the thermal resistor of the present invention may include titanium oxide, and the paper size is applicable to the Chinese national standard (CNS > A4 specification (210 * 297 mm)) ^ 2〇_ — — — — — II — — — — — —-II 11 111 — — — — — — — < Please read the note on the back 箨 Fill this page > Printed by Shelley Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 4 6 650 9 Δ7 Α7 Β7 V. Invention Note (18) (Please read the notes on the back before filling in this I) Iron oxide, zinc oxide, sand dioxide, magnesium oxide, oxide chain, chromium oxide, barium sulfate, calcium carbonate, calcium hydroxide and lead oxide In J P_ A 5-226112, inorganic solids with high relative dielectric constants are described in JP-A 6-68963, such as barium titanate, titanate saw, potassium niobate, and the like. * The thermal resistor of the present invention may include boron carbides described in JP-A 474383, etc. In terms of strength improvement, the thermal resistor of the present invention may include basic titanic acid described in JP-A 5-74603 hydration. Salt, described in JP-A 8 — 1 7563 , Iron oxide, zinc oxide, silicon dioxide, etc. Printed as a crystalline nucleus by the Industrial and Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the thermal variable resistor of the present invention may include an alkaline halide described in JP-B 59-10553 Melamine resin, described in JP — A 6-765 1 1 benzoic acid, dibenzylidene sorbitol and metal benzoate, described in J P_A 7 — 6 8 6 4 talc, zeolite and dibenzylidene Sorbitol, described in J P_A 7-263 127, sorbitol derivatives (gelatinizers), bitumen, and sodium di (4-tertiary-butylphenyl) phosphate, etc. As arc control agents, the present invention The resistor may include alumina and magnesium oxide hydrate described in JP-B 4-28744, and metal hydrate and silicon carbide described in JP-A 6 1-250058. As a preventive effect of metals, the present The invented thermal resistor may include Irganox MD 1024 (Ciba-Geigy), which is described in J P — A 7 — -21-This paper is applicable to the China National Standard (CNSU4 specification (210 X 297 mm) 4 6 650 9 A7 B7 V. Description of the invention (19) 6 8 6 4 〇 As a flame retarder, the thermal resistor of the present invention Packages described in JP-A 6 1 — 2 3 9 5 8 1 containing antimony trioxide and aluminum hydroxide; described in JP-A 5-74603 Magnesium hydroxide: organic compounds containing halogens (including polymers) Such as 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane and polyfluoroethylene (PVDF): phosphorus compounds such as ammonium phosphate. In addition to these additives, the thermal resistor of the present invention may include zinc sulfide, basic magnesium carbonate, aluminum oxide, calcium silicate, magnesium silicate, aluminosilicate clay (mica, talc, kaolinite, montmorillonite, etc.), Glass powder, glass flakes, glass fibers, calcium sulfate, etc. The above additives should be used in an amount up to 2 5% by weight of the total weight of the polymer matrix, the low molecular organic compound and the conductive particles. * The organic positive temperature coefficient thermal resistor according to the present invention has a low initial resistance in its non-operating state. Or the room temperature resistivity 値 about 102 to 10 ° Ω cm, which has a rapid rise in resistance during operation, and the resistance change rate is higher than ten to the sixth power when the non-operating state is changed to the operating state. Note I: Bookbinding, Intellectual Property Bureau, Ministry of Economic Affairs, Guix, Consumer Cooperatives, Printing Examples The present invention will now be described more specifically with examples and comparative examples. Example 1 A bisphenol A epoxy resin (Epicoat 801, produced by Yuka Shell Epoxy Co., Ltd.) and an improved amine hardener (Epomate B002, produced from this paper are applicable to the national standard (CNS > A4) Specifications (210 X 297 mm) -22- The number of employees' cooperatives in the Intellectual Property Bureau of the Ministry of Economy 4 6 6 5 0 9 A7 _B7 V. Description of the invention (20)
Yuka Shell Epoxy Co .，Ltd _)使用作爲熱固性聚合物基質 。石蟣（HNP10,產自 Nippon Seiro Co.，Ltd.，融點在 7 5 °C)作爲低分子量有機化合物，及絲狀鎳粉末（型2 5 5 • 鎳粉末，產自INCO Co ·，Ltd .)作爲導電性顆粒》導電 性顆粒具有平均顆粒尺寸2 . 2至2 . 8；um，表觀密度 0.5至◦.65g/cm3及比表面積〇.68m2/g 〇 取二十（20)克的雙酚A型環氧樹脂I 10克的改 良胺硬化劑，15克的石蟠（0.5倍於環氧樹脂與硬化 劑之總重量），180克的鎳粉末（4倍於有機成分之總 重量）及2 〇m 1的甲苯，於離心分散器中共同混合約 1 0分鐘。將所得之塗料狀混合物塗覆於一3 0 厚 N i箔電極之一邊上，且在另一 N i箔電極上施以塗覆混 合物。將此片狀組合夾於銅板之間，使用墊片使總厚度達 1mm。於熱壓機中將其在80 °C熱硬化3小時。將此組 合以電極且作熱壓之硬化片槌成1 cm直徑之光碟形式而 得到熱變電阻體元件。由圖1可看出熱變電阻體元件之斷 面圖，熱變電阻體元件片1 2爲一硬化片（其中含有低分 子有機化合物、聚合物基質及導電性顆粒）係夾於N i箔 電極1 1之間。 在一恆溫器中將此元件加熱自室溫（2 5°C)至 1 20 °C，並自1 20 °C冷卻至室溫，其升降溫速率爲2 t/min.，之後由四端法量測某溫度下之電阻値而得 到溫度對電阻曲線。結果繪圖如圖2。 !1!· ^^一！ — I! A ' > (請先《讀背面之注意事項再瑱寫本頁) 本紙張尺度適用中0國家標準（CNS)A4規格（210 X 297公釐） -23- 經濟部智慧财產局貝工消费合作社印髮 46 650 9 A7 ___B7____ 五、發明說明（21 > 此元件具有起始室溫（25 °C)電阻爲8 . 2x 10 3 Ω (6 . 4χ1〇ζΩ οπι)，並在 75 °C 附近或 在蠟融點附近展示急劇的電阻値上升，其電阻變化速率爲 •十的10次方更高。即使當於電阻上升之後於12 0°C持 續對元件加熱，未發現電阻下降（NTC現象）。於冷卻 中發現其溫度對電阻曲線在實質上相似於加熱中之結果； 磁滯係充分地降低。 實施例2 將不飽和聚醋樹脂（G — 1 1 〇AL，產自Nippon Shokubai Co.，Ltd.)使用作爲熱固性聚合物基質，過氧 化苯甲醯（Kadox B-75W，產自.Kayaku Akuzo Co.，Ltd.) 作爲有機過氧化物，正十二烷酸（，產自Nippon Seika Co .，Ltd .，融點在8 1 t：)作爲低分子量有機化合物，及 如實施例1相同絲狀鎳粉末（型2 5 5鎳粉末，產自 INCO Co . , Ud .)作爲導電性顆粒。 取三十（30)克的不飽和聚酯樹脂| 0 . 3克的過 氧化苯甲醯，1 5克的正十二烷酸，1 8 0克的鎳粉末及 2 0 m 1的甲苯在離心分散器中共同混合約1 ◦分鐘。將 所得之塗料狀混合物塗覆於一 3 0 厚N i箔電極之一 邊上，且在另一N i箔電極上施以塗覆混合物》將此片狀 組合夾於銅板之間，使用墊片使總厚度達1 mm。於熱壓 機中將其在8 0°C熱硬化3小時。將此組合以電極且作熱 壓之硬化片槌成1 cm直徑之光碟形式而得到熱變電阻體 本紙張尺度適用令國a家標準（CNS>A4蜣格（210 X 297公爱） 24 - ϊιιι — llllli— — ·1111111 _ I I I I I I 鴨 j {請先《讀背面之注意事項再填寫本頁) A7 466509 ___B7_ 五、發明說明（22 ) 元件。之後，如實施例1得到溫度對此元件電阻之曲線。 其結果繪圖於圖3中。 此元件具有起始室溫（25eC)電阻爲5 . 〇xl(T: 'Ω(3·9χ10‘2Ω_(：ιη)，並在81 °C附近或在正十 二烷酸融點附近展示急劇的電阻値上升，其電阻變化速率 爲十的8次方更高》即使於電阻上升之後在1 2 0°C持續 對元件加熱，發現極少或沒有電阻下降（NTC現象）。 於冷卻中發現其溫度對電阻曲線在實質上相似於加熱中之 結果；磁滯在約1Ot充分地降低。由定義，磁滯度爲介 於操作之前與於操作之後兩者之間的操作溫度（定義爲溫 度對電阻曲線之正切交點）差異（絕對値），且發現於冷 卻中溫度對電阻曲線上有相似的操作溫度。 實施例3 如得自實施例1之熱變電阻體元件，除了硬化係在 1 50 t執行1小時且在1 80 °C執行3小時，而且使用 2 0克的聚胺基二馬來醯亞胺預聚物（Kerimide B601，產自Yuka Shell Epoxy Co., Ltd.) is used as a thermosetting polymer matrix. Shi Yan (HNP10, produced by Nippon Seiro Co., Ltd., melting point at 7 5 ° C) as a low molecular weight organic compound, and filamentous nickel powder (type 2 5 5 • nickel powder, produced by INCO Co., Ltd. .) As conductive particles "conductive particles have an average particle size of 2.2 to 2.8; um, an apparent density of 0.5 to ◦ 65 g / cm3 and a specific surface area of 0.68 m2 / g. Take twenty (20) grams 10 grams of improved amine hardener for bisphenol A epoxy resin I, 15 grams of stone ballast (0.5 times the total weight of epoxy resin and hardener), 180 grams of nickel powder (4 times the total amount of organic ingredients Weight) and 200 ml of toluene were mixed together in a centrifugal disperser for about 10 minutes. The resulting paint-like mixture was applied to one side of a 30-thick Ni foil electrode, and a coating mixture was applied to the other Ni foil electrode. This sheet-shaped combination is sandwiched between copper plates, and the total thickness is 1 mm using a spacer. It was heat-hardened in a hot press at 80 ° C for 3 hours. This combination was made into a 1 cm diameter disc with electrodes and hot-pressed hardened mallets to obtain a thermistor element. The cross-sectional view of the thermistor element can be seen from FIG. 1. The thermistor element sheet 12 is a hardened sheet (containing a low-molecular organic compound, a polymer matrix and conductive particles) sandwiched between Ni foils. Between electrodes 1 1. The element was heated in a thermostat from room temperature (25 ° C) to 120 ° C, and cooled from 120 ° C to room temperature with a temperature rise and fall rate of 2 t / min. Measure the resistance at a certain temperature to get the temperature versus resistance curve. The results are plotted in Figure 2. ! 1! · ^^ One! — I! A '> (Please read the “Notes on the back side before copying this page”) This paper size is applicable to 0 National Standard (CNS) A4 specifications (210 X 297 mm) -23- Intellectual Property of the Ministry of Economic Affairs Published by the local shellfish consumer cooperative 46 650 9 A7 ___B7____ 5. Description of the invention (21 > This element has an initial room temperature (25 ° C) resistance of 8.2x10 3 Ω (6.4x1〇ζΩ οπι), and Near 75 ° C or near the melting point of the wax shows a sharp rise in resistance, the rate of change in resistance is higher than the tenth power of ten. Even when the component is continuously heated at 120 ° C after the resistance rises, no component is found Resistance decreases (NTC phenomenon). It is found that the temperature vs. resistance curve in cooling is substantially similar to that in heating; the hysteresis system is sufficiently reduced. Example 2 Unsaturated polyacetal resin (G — 1 1 0AL, (Produced from Nippon Shokubai Co., Ltd.) used as a thermosetting polymer matrix, Benzamidine Peroxide (Kadox B-75W, produced by Kayaku Akuzo Co., Ltd.) as an organic peroxide, n-dodecanoic acid (From Nippon Seika Co., Ltd., melting point at 8 1 t :) Compound, and the same filamentous nickel powder (type 2 5 5 nickel powder, produced by INCO Co., Ud.) As in Example 1 as conductive particles. Thirty (30) grams of unsaturated polyester resin | 0. 3 g of benzamidine peroxide, 15 g of n-dodecanoic acid, 180 g of nickel powder and 20 m 1 of toluene were mixed together in a centrifugal disperser for about 1 ◦ minute. The mixture was coated on one side of a 30-thick Ni foil electrode, and a coating mixture was applied on the other Ni foil electrode. This sheet combination was sandwiched between copper plates, and the total thickness was 1 using a gasket. mm. Heat-harden it at 80 ° C for 3 hours in a hot press. Use this combination to form a 1 cm diameter disc in the form of an electrode and heat-pressed hardened mallet to obtain a thermal resistor. National Standards (CNS > A4 Grid (210 X 297 public love) 24-ϊιιι — llllli — — · · 1111111 _ IIIIII Duck j {Please read the precautions on the back before filling this page) A7 466509 ___B7_ V. Invention Explain (22) the device. After that, the temperature versus the resistance of this device is obtained as in Example 1. The results are plotted in 3. This element has an initial room temperature (25eC) resistance of 5.0 × l (T: 'Ω (3 · 9χ10'2Ω _ (: ιη)), and is near 81 ° C or at the melting point of n-dodecanoic acid. A sharp increase in resistance was shown nearby, with a resistance change rate of ten to the power of eight. Even after the resistance increased, the element was continuously heated at 120 ° C, and it was found that there was little or no resistance drop (NTC phenomenon). It was found that the temperature versus resistance curve in cooling was substantially similar to that in heating; the hysteresis was sufficiently reduced at about 10 t. By definition, the hysteresis is the difference (absolute 値) between the operating temperature (defined as the intersection of the temperature and the resistance curve) between the two before and after the operation, and it is found that there is Similar operating temperatures. Example 3 The heat resistive element obtained from Example 1 was used, except that the hardening system was performed at 150 t for 1 hour and at 1 80 ° C for 3 hours, and 20 g of poly (diamine) maleate was used. Amine prepolymer (Kerimide B601, from
Ciba-Geigy)及1 0克的二甲基甲醯胺對於熱固性聚合物基 質取代雙酚A型環氧樹脂及改良胺型硬化劑。由估計，熱 變電阻體元件發現等同於得自實施例1之熱變電阻體元件 〇 實施例4 如得自實施例1之熱變電阻體元件，除了硬化係在 本紙張尺度適用中0國家標準（CNS>A4規格<210 X 297公釐） — — — — — — — — —— — — — i I lit I I ^ --------- η. ^ (請先Μ讀背面之泫意事項再填寫本頁) 經濟部智慧財產局S工消费合作杜印製 •25- 經濟部智慧财產局貝工消费合作社印製 4 6 650 9 A7 ____B7____ 五、發明說明（23 ) 1 0 0°C執行1小時，且使用3 〇克的聚胺基甲酸酯C Colonate by Nippon PolyurethaneCo.，Ltd.)作爲熱固性 聚合物基質而取代雙酚A型環氧樹脂及改良胺型硬化劑。 由估計’熱變電阻體元件發現等同於得自實施例1之熱變 電阻體元件。 實施例5 如得自實施例1之熱變電阻體元件，除了硬化係在 1 2 0°C執行3小時且使用3 0克的酚樹脂（Sumicon PM， 產自Sumitomo Bakelite Co. , Ltd.)作爲熱固性聚合物基 質而取代雙酚A型環氧樹脂及改良胺型硬化劑。由估計， 熱變電阻體元件發現等同於得自實施例1之熱變電阻體元 件。 實施例6 如得自實施例1之熱變電阻體元件，除了硬化係在 1 0 〇°C執行1小時且使用3 0克的聚矽氧烷橡膠（ TSE3221，產自 Toshiba Silicone Co ，Ltd .)作爲 熱固性聚合物基質取代雙酚A型環氧樹脂及改良胺型硬化 劑*由估計，熱變電阻體元件發現等同於得自實施例1之 熱變電阻體元件。 比較實施例1 如得自實施例1之熱變電阻體元件，除了未使用石蠟 本纸張尺度適用中固國家標準（CNS)A4规格（210 * 297公釐） -26- — — — — — — — — — — — —— — — — — — — I— 1 — IIIIIIa I' <請先Μ讀背面之注意事項再填寫本頁) A7 466509 __B7___ 五、發明說明（24 > ，且鎳粉末用量爲4倍於環氧樹脂與硬化劑之總重量=之 後，如實施例1得到此元件溫度對電阻之曲線。其結果繪 圖於圖4中。 ‘ 此元件具有起始室溫（25 °C)電阻爲8 . 8x 10 3 Ω (6 · 9xl0'2n cm)。電阻自約 80°C 逐 步地上升而沒有明顯的轉移溫度。此外，在1 8 oec之電 阻値爲1 3Ω，且電阻變化速率低至十的3 . 2次方。 比較實施例2 如得自實施例1之熱變電阻體元件，除了對於導電性 顆粒碳黒（Toka Black #4500,產自 Tokai Carbon Co.，Ciba-Geigy) and 10 g of dimethylformamide are substituted for bisphenol A type epoxy resin and modified amine type hardener for thermosetting polymer matrix. By estimation, the thermistor element was found to be equivalent to the thermistor element obtained in Example 1. Example 4 As the thermistor element obtained in Example 1, except that the hardening system is applicable in this paper standard. Country 0 Standard (CNS > A4 Specifications < 210 X 297 mm) — — — — — — — — — — — — i I lit II ^ --------- η. ^ (Please read the back first Please fill in this page again) Printed by S Industry Consumer Cooperation of Intellectual Property Bureau of the Ministry of Economic Affairs • 25- Printed by Shellfish Consumer Cooperative of Intellectual Property Bureau of Ministry of Economic Affairs 4 6 650 9 A7 ____B7____ V. Description of Invention (23) 1 0 0 ° C for 1 hour, and using 30 grams of polyurethane (C Colonate by Nippon Polyurethane Co., Ltd.) as a thermosetting polymer matrix instead of bisphenol A-type epoxy resin and modified amine-type hardener . From the estimation of the 'thermistor element, it was found to be equivalent to the thermistor element obtained from Example 1. Example 5 The thermal resistor element obtained from Example 1 was used, except that the curing was performed at 120 ° C for 3 hours and 30 grams of a phenol resin (Sumicon PM, produced by Sumitomo Bakelite Co., Ltd.) was used. As a thermosetting polymer matrix, it replaces bisphenol A type epoxy resin and improved amine type hardener. From the estimation, the thermistor element was found to be equivalent to the thermistor element obtained from Example 1. Example 6 The thermal resistor element obtained from Example 1 was used, except that the curing was performed at 100 ° C. for 1 hour and 30 g of a polysiloxane rubber (TSE3221, produced by Toshiba Silicone Co, Ltd.) was used. ) As a thermosetting polymer matrix instead of bisphenol A-type epoxy resin and modified amine-type hardener * From the estimation, the thermo-resistor element was found to be equivalent to the thermo-resistor element obtained from Example 1. Comparative Example 1 If the thermal resistor element from Example 1 is used, except that paraffin paper is not used, the China Solid State Standard (CNS) A4 specification (210 * 297 mm) is applicable. -26- — — — — — — — — — — — — — — — — — — — I — 1 — IIIIIIa I '< Please read the notes on the back before filling this page) A7 466509 __B7___ V. Description of the invention (24 >) and nickel The amount of powder is 4 times the total weight of epoxy resin and hardener = after that, the temperature vs. resistance curve of this device is obtained as in Example 1. The results are plotted in Figure 4. 'This device has an initial room temperature (25 ° C) The resistance is 8.8x 10 3 Ω (6 · 9xl0'2n cm). The resistance gradually rises from about 80 ° C without obvious transition temperature. In addition, the resistance 1 at 1 8 oec is 1 3Ω, and the resistance The rate of change is as low as 3.2 to the third power. Comparative Example 2 The thermally variable resistor element obtained from Example 1 except for conductive particulate carbon (Toka Black # 4500, produced by Tokai Carbon Co.,
Ltd.其平均顆粒爲6 0 n m且比表面積爲6 6 m2/g) 其用量爲0.3倍於環氧樹脂、硬化劑及石蠟之總重量， 且之後如實施例1作評估。 此元件具有起始室溫（2 5°C)電阻爲7 , 2Ω ( 56 . 5Ω · cm)，並在75 °C附近或在蠟融點附近展 示電阻値上升，其電阻變化速率爲十的2 . 5次方。 由提高碳黑之量至0 . 5倍於混合物之重量，可降低 室溫電阻。然而，觀察到在電阻變化速率上進一步下降。 據此，具有尖的突起之導電性顆粒有明顯的效果》 本發明之效果 依據本發明，如此可提供有機正溫度係數熱變電阻體 ，其在室溫具有充分低的電阻，且在操作狀態與非操作狀 本紙張尺度適用中Η國家標準<CNS>A4现格（210 X 297公釐〉 !1 *!!! ί I - ， (锖先明讚背面之注$項再填寫本頁) 經濟部智慧财產局貝工消f合作社印製 -27- A7 46 650 9 B7_ 五、發明說明（25 ) 態間有大的電阻變化速率，且可以在降低溫度對電阻曲線 之磁滯下操作，於電阻上升之後無NT C性質，易於控制 操作溫度，且具有高的性能穩定性。 ---------1-_ 裝 it---II 訂--— II--- -線 J -Γ {請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局貝工消费合作社印製 -28- 本紙張尺度適用中國國家標準（CNS>A4规格<210 * 297公釐）Ltd. has an average particle size of 60 nm and a specific surface area of 66 m2 / g), and its amount is 0.3 times the total weight of the epoxy resin, hardener and paraffin, and it is evaluated as in Example 1 thereafter. This element has an initial room temperature (25 ° C) resistance of 7, 2Ω (56.5Ω · cm), and exhibits a rise in resistance near 75 ° C or near the melting point of wax with a resistance change rate of ten 2.5 power. By increasing the amount of carbon black to 0.5 times the weight of the mixture, the room temperature resistance can be reduced. However, a further decrease in the rate of change in resistance was observed. According to this, the conductive particles with sharp protrusions have a significant effect. According to the present invention, the effect of the present invention can provide an organic positive temperature coefficient thermal resistor, which has a sufficiently low resistance at room temperature and is in an operating state. The dimensions of this paper are in accordance with the China National Standard < CNS > A4 (210 X 297 mm)! 1 * !!! ί I-((Note the $ item on the back of Ming Zhan before filling out this page) ) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Bei Gong Xiao Cooperative -27- A7 46 650 9 B7_ V. Description of the Invention (25) There is a large rate of change in resistance between states, and the hysteresis of the resistance curve can be reduced under reduced temperature Operation, there is no NT C property after the resistance rises, it is easy to control the operating temperature, and it has high performance stability. --------- 1-_ Install it --- II Order --- II --- -线 J -Γ (Please read the precautions on the back before filling out this page) Printed by Shelley Consumer Cooperatives, Bureau of Intellectual Property, Ministry of Economic Affairs-28- This paper size applies to Chinese National Standards (CNS > A4 Specifications < 210 * 297) %)