472499 A7 經濟部智慧财產局貝.工消费合作社印製 ____B7___五、發明說明（1 ) 技術領域 本發明爲關於使用在到達指定溫度（以下，稱爲開關 溫度）區域時，顯示出電阻値爲急速上升之正溫度特性， 所謂 P T C ( Positive Temperature Coefficient )特性之導 電性組成物（以下，稱爲「P T C組成物」）所構成之 P T C元件及其製造方法。 背景技術 以往，PTC元件已被使用於蓄電池爲首之電器機器 、電子機器，並且於此些機器中做爲異常發生時防止流經 過電流之電路保護元件等。 一般，P T C元件爲由結晶性聚合物中混練導電性粉 .末所得之P T C組成物，與該P T C組成物中所形成之電 極所構成，若到達開關溫度則顯示出電阻値急速上升。即 ，P T C組成物爲經由材料固有之電阻値R，和透過上述 電極流至元件的電流値I所發生之焦耳熱（I 2 R熱）而發 熱。如此，若於P T C組成物中流過較大之電流則引起發 熱，且其電阻値上升。一般而言，PTC元件爲被使用做 爲利用上述焦耳熱發生的面狀發熱體，和利用電阻値上升 之過電流保護元件等。 ^ 二先前的P T C元件，特別由其電極形成方法之觀點而 *ί _ . 言，例如已知下列三種元件。 第一爲已知令不銹鋼或鎳等金屬板之表面接合P T c 組成物之表面，並以此金屬板做爲電極。 請 先 閲 讀 背 面 之 注 項 再 填 裝 訂 本紙張尺度適用申國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局貝工消费合作社印製 4724913 A7 ________ B7 五、發明說明（2) 第二爲已知爲了提高此類電極與P T C組成物之密合 性，再將金屬板之表面予以物理性或化學性地粗面化，並 將此粗面化之面接合P T C組成物之表面做爲電極。 第三已知爲於P T C組成物直接施以金屬鍍層，並將 其做爲電極。 但是，將_金屬板之表面接合至P T C組成物之表面做 爲電極的第一先前例中，PTC組成物與電極間的接觸電 阻値變高，無法取得良好的歐姆（Ohmic )接觸。其結果 ，此第一先前例之P T C元件，於室溫下的電阻値變高， 難以利用做爲過電流保護元件等。加上，因爲P T C組成 物與電極間的密合性不夠充分，故令P T C元件重覆操作 (通電）時，則使得電阻値大幅增加。 又，將物理性或化學性地粗面化之金屬板表面，接合 p T c組成物表面做爲電極之第二先前例，比上述之第一 先前例，令P T C組成物與電極間之接觸電阻値變低，且 兩者間的密合性亦更加良好，但並未到達取得良好之歐姆 接觸。關連於此第二先前例已提案爲了令P T C元件的室 溫電阻値降低並且對於重覆操作之安定性提高，故將 PTC組成物中分散的導電性粉末量增加至45VO 1% 以上左右。但是’此情況不僅難令室溫下的電阻値爲一定 値以孑：，且於重覆操作時，完全無法抑制每次操作的電阻 値上升。 更且，對P T C組成物直接施以金屬鍍層做爲電極之 第三先前例中，PTC組成物與鍍層被膜間的密合性並不 — — — — — — I — — — — — — * — — — 111— -1^ · I I ^1 1_· 1> n I 線 (請先閲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） - 經濟部智慧財產局貝工消费合作社印製472499 A7 Printed by the Bureau of Intellectual Property, Ministry of Economic Affairs, Industrial and Consumer Cooperatives ____B7___ V. Description of the Invention (1) Technical Field The present invention relates to the use of resistance when it reaches a specified temperature (hereinafter, referred to as the switching temperature) area.値 is a rapidly rising positive temperature characteristic, a PTC element composed of a conductive composition (hereinafter, referred to as a "PTC composition") with a so-called PTC (Positive Temperature Coefficient) characteristic, and a manufacturing method thereof. BACKGROUND ART Conventionally, PTC elements have been used in electrical appliances and electronic appliances such as storage batteries, and these devices have been used as circuit protection elements that prevent an overcurrent from flowing when an abnormality occurs. Generally, a P T C element is composed of a P T C composition obtained by kneading conductive powder in a crystalline polymer and an electrode formed in the P T C composition. When the switching temperature is reached, the resistance increases rapidly. That is, the P T C composition generates heat by the Joule heat (I 2 R heat) generated by the material's inherent resistance 値 R and the current 値 I flowing through the electrode to the device. In this way, if a large current flows in the P T C composition, heat is generated, and its resistance 値 increases. Generally, PTC elements are used as planar heating elements that generate Joule heat as described above, and as overcurrent protection elements that increase resistance 値. ^ Two previous P T C elements, particularly from the standpoint of their electrode formation methods * ί _. For example, the following three elements are known. First, it is known that the surface of a metal plate such as stainless steel or nickel is bonded to the surface of the P T c composition, and the metal plate is used as an electrode. Please read the note on the back before filling and binding. The paper size is applicable to the National Standard of China (CNS) A4 (210 X 297 mm). Printed by Shellfish Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 4724913 A7 ________ B7 V. Description of the invention ( 2) Secondly, in order to improve the adhesion between such electrodes and the PTC composition, the surface of the metal plate is physically or chemically roughened, and the roughened surface is joined to the PTC composition. The surface is used as an electrode. The third is known as applying a metal plating layer directly to the P T C composition and using it as an electrode. However, in the first previous example in which the surface of the metal plate was bonded to the surface of the PTC composition as the electrode, the contact resistance between the PTC composition and the electrode became high, and good Ohmic contact could not be obtained. As a result, the P T C element of the first previous example has a high resistance 値 at room temperature, and it is difficult to use it as an overcurrent protection element. In addition, since the adhesion between the P T C composition and the electrode is not sufficient, the repeated operation (power-on) of the P T C element causes the resistance to increase significantly. In addition, the second prior example of using the surface of a physically or chemically roughened metal plate and joining the surface of the p T c composition as an electrode makes the contact between the PTC composition and the electrode more than the first prior example described above. The resistance 値 becomes lower and the adhesion between the two is better, but it does not reach to obtain a good ohmic contact. In relation to this second previous example, it has been proposed to increase the amount of conductive powder dispersed in the PTC composition to about 45 VO 1% or more in order to reduce the room temperature resistance P of the P T C element and improve the stability for repeated operations. However, in this case, it is not only difficult to make the resistance 室温 constant at room temperature 値: 且, but also it is impossible to suppress the increase in resistance 每次 per operation at the time of repeated operations. Furthermore, in the third previous example in which a metal plating layer was directly applied to the PTC composition as an electrode, the adhesion between the PTC composition and the plating film was not — — — — — — — I — — — — — — — — — — 111— -1 ^ · II ^ 1 1_ · 1 > n I line (Please read the precautions on the back before filling this page) This paper size applies to Chinese national standard (CNS > A4 size (210 X 297 mm) -Printed by Shellfish Consumer Cooperative, Intellectual Property Bureau, Ministry of Economic Affairs
47249U A7 B7 五、發明說明（3) 充分，且兩者間的接觸電阻値變高。又，亦無法避免重覆 操作所大幅增加的電阻値。 以上第一〜第三先前例之共通問題點爲將P T C元件 重覆操作（通電）時，經由P. T C組成物本身惡化，亦具 有室溫下之電阻値變高之問題。其原因推測係因重覆操作 時，經由每次動作之熱震盪造成結晶性聚合物成分惡化。 另一方面，因爲P T C組成物爲有機物與無機物之複 合材料，故於保存及使用中環境濕度之影響大，於重覆進 行開關動作後，亦具有經時地電阻變化大之問題。特別， 於使用金屬系導電性充塡劑之P T C組成物中爲了取得具 有良好導電性之元件，乃必須令導電性充塡劑予以高充塡 化，但將無機物之導電性充塡劑進行高充塡化時，更易受 .到上述保存及使用中環境濕度之影響，如上述，重覆進行 開關軌作後，.元件本體經時地易由電極上剝離，故無法取 得長期使用（重覆使用）之充分的信賴性。 於是，本發明之第一目的爲在於提供對於重覆操作之 安定性優，且與P T C組成物之間的密合性充分，接觸電 阻値低之具有電極之P T C元件及其製造方法。 又，本發明之第二目的爲在於提供達成上述第一目的 之P T C元件及其製造方法中，可有效防止環境濕度影響 所成之P T C元件本體由電極上剝離，且對於重覆使用 之安定性和再現性良好之信賴性高的P T C元件及其製造 方法。 — — — — — — — — — — — — — ·1111111 ·111 — I — I (請先閲讀背面之注意事項再填寫4頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -〇 經濟部智慧財產局員工消費合作社印製 472499 A7 B7 五、發明說明（4) 發明之揭示 爲了達成上述第一目的，本發明之P T C元件及其製 造方法爲於結晶性聚合物成分中，將T i C，WC，W2C ，ZrC，VC，NbC，TaC，及M〇2C 中至少一種 所構成之導電性粉末充塡材料混練3 5〜6 Ο v ο 1 %， 形成組成物成形體，並由該組成物成形體之表面令導電體 一部分露出地將導電體予以壓黏，埋設，加上於組成物成 形體之前述表面予以鍍層處理，形成電極。 即，若根據本發明之一態樣，則爲取得具有結晶性聚 合物成分中混練3 5〜6 0 ν ο 1 %導電性粉末充塡材料 之組成物成形體，與前述組成物成形體表面令導電體一部 分露出地壓黏和埋設之導電體，與前述組成物成形體之前 .述表面經由鍍層處理所形成之電極，且使用T i C，WC ，W2C，ZrC’ VC，NbC，TaC，及 M02C 中 之至少一種做爲前述導電性粉末充塡材料爲其特徵之 P T C元件。 較佳爲前述導電體中，包含N i粉末，A 1粉末， C u粉末，F e粉末，Ag粉末，或黑鉛粉末。 又，較佳爲結晶性聚合物成分中，將前述導電性粉末47249U A7 B7 5. Description of the invention (3) Adequate, and the contact resistance 两者 between the two becomes high. Also, it is impossible to avoid a large increase in resistance 値 caused by repeated operations. The common problems of the above first to third previous examples are that when the P T C element is repeatedly operated (energized), the P. T C composition itself deteriorates and the resistance 问题 at room temperature also becomes high. The reason for this is presumably due to the deterioration of the crystalline polymer component due to thermal shock during each operation during repeated operations. On the other hand, because the P T C composition is a composite material of organic and inorganic substances, the influence of environmental humidity during storage and use is large. After repeated switching operations, the resistance also changes with time. In particular, in order to obtain a component having good conductivity in a PTC composition using a metal-based conductive filler, it is necessary to make the conductive filler highly charged, but to increase the conductivity of inorganic conductive fillers. When it is fully charged, it is more susceptible to the effects of environmental humidity during storage and use. As described above, after the switch rail is repeatedly operated, the element body is easily peeled from the electrode over time, so it cannot be used for a long time (repeat Use) for full reliability. Therefore, a first object of the present invention is to provide a PTC device having electrodes having excellent stability to repeated operations, sufficient adhesion to the PTC composition, and low contact resistance, and a method for manufacturing the same. In addition, a second object of the present invention is to provide a PTC element that achieves the above-mentioned first object and a method for manufacturing the same, which can effectively prevent the PTC element body formed by the influence of environmental humidity from peeling off from the electrode, and is stable for repeated use. A highly reliable PTC element with good reproducibility and its manufacturing method. — — — — — — — — — — — — — · 1111111 · 111 — I — I (Please read the notes on the back before filling in 4 pages) This paper size is applicable to China National Standard (CNS) A4 (210 X 297) (Mm)-0 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 472499 A7 B7 V. Description of the invention (4) Disclosure of the invention In order to achieve the above-mentioned first object, the PTC element and its manufacturing method of the present invention are crystalline polymers Among the ingredients, a conductive powder filling material composed of at least one of T i C, WC, W2C, ZrC, VC, NbC, TaC, and Mo2C is kneaded 3 5 to 6 0 v ο 1% to form a composition. The formed body is pressed against the conductive body with a part of the conductive body exposed from the surface of the formed body of the composition, buried, and plated on the aforementioned surface of the formed body of the composition to form an electrode. That is, according to one aspect of the present invention, in order to obtain a composition molded body having 3 to 5 0 ν ο 1% conductive powder filling material mixed with a crystalline polymer component, and the surface of the aforementioned molded body of the composition A part of the conductive body is exposed to the pressure-bonded and buried conductive body, and before the above-mentioned composition is formed, the electrode formed by the above-mentioned surface is treated by plating, and T i C, WC, W2C, ZrC 'VC, NbC, TaC, And at least one of M02C is a PTC element characterized by the aforementioned conductive powder filling material. It is preferable that the aforementioned conductor includes Ni powder, A1 powder, Cu powder, Fe powder, Ag powder, or black lead powder. Moreover, it is preferable that the said conductive powder is a crystalline polymer component.
V V 充塡材料4 5〜6 0 V 0丨％混練形成組成物成形體。 ---又_.，若根據本發明之其他態樣，則取得具有於結晶性 聚合物成分中，將TiC，WC，w2c，ZrC，VC， NbC，Ta C，及M〇2C中之至少一種做爲導電性粉末 充塡材料混練3 5〜6 0 v 〇 1 %取得組成物成形體之工 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） |丨| — — — — — · — — — · i I ! I I I ^^ 111 — ！！ ^^ {請先閱讀背面之注意事項再填寫彳頁) 經濟部智慧財產局員x消費合作社印製 472499 A7 __ B7 五、發明說明（5) 程，與對該組成物成形體塗佈含有導電體粉末之導電體獎 料後，進行前述導電體粉末之壓黏處理，令前述導電體粉 末之一部分由前述組成物成形體之表面露出地埋設前述導 電體粉末之工程，與對前述組成物成形體之前述表面進行 鍍層處理並形成電極之工程爲其特徵之P T C元件的製造 方法。 較隹爲使用Ni粉末，A1粉末，Cu粉末，Fe粉 末，A g粉末，或黑鉛粉末做爲前述導電體粉末。 又，較佳爲於結晶性聚合物成分中，混練4 5〜6 0 v ο 1 %前述導電性粉末充塡材料，形成組成物成形體。 爲了達成上述第二目的，本發明之PTC元件及其製 造方法爲於結晶性聚合物成分中，將T i C，WC，W2C ，ZrC，VC，NbC，TaC，及M02C 中之至少一 種所構成之導.電性粉末充塡材料混練3 5〜6 Ο v ο 1 % 形成組成物成形體，並由該組成物成形體之表面令導電體 一部分露出地將導電體予以壓黏和埋設，加上於組成物成 形體之前述表面以鎪層處理形成電極，加上於P T C元件 之前述鍍層電極以外之部分，形成水蒸氣阻擋層。 即，若根據本發明之再其他態樣，則可取得具有於結 晶性聚合物成分中，將TiC，WC，W2C，ZrC ’ V C..? :NbC，TaC，及M〇2C之至少一種之導電性粉 末充塡材料混練3 5〜6‘0 v ο 1 %之組成物成形體，與 j 由前述組成物成形體之表面令導電體一部分露出地壓黏和 埋設之導電體，與前述組成物成形體之前述表面以鍍層處 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 丨丨丨！_1!· ^^ ·!1 訂·！_ *^ (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消费合作社印製 472499 A7 __ B7 五、發明說明（6) 理所形成之電極，與前述鍍層電極以外之部分所形成之水 蒸氣阻擋層爲其特徵之P T C元件。 較佳爲前述結晶性聚合物成分爲混合至少一種熱塑性 聚合物之聚合物合金。 又，若根據本發明之另外態樣，則可取得具有於結晶 性聚合物成分中，.將Ti C，WC，W2C，ZrC，VC ，NbC，Ta C，及Mo2C中之至少一種做爲導電性粉 末充塡材料混練3 5〜6 Ο ν ο 1 %取得組成物成形體之 工程，與對該組成物成形體塗佈含有導電體粉末之導電體 漿料後，進行前述導電體粉末之壓黏處理，令前述導電體 粉末之一部分由前述組成物成形體之表面露出地埋設前述 導電體粉末之工程，與對前述組成物成形體之前述表面進 .行鍍層處理並形成電極之工程，與對前述鍍層電極以外之 部分施以水蒸氣阻擋處理之工程爲其特徵之P T C元件的 製造方法。 圖面之簡單說明 圖1爲示出本發明第一實施形態之p T C元件的截面 圖， 圖2爲用以說明本發明第一實施形態之p T C元件之 製造·_方:法之圖，（a)爲示出組成物成形體，（b)爲示 出由組成物成形體之表面令其一部分露出地將導電體予以 壓黏和埋設之狀態，（c)爲示出對組成物成形體進行鎪 層處理並且形成電極之狀態的各截面圖， 本紙張尺度適用t國國家標準（CNS)A4規格（210 X 297公釐） — 丨 — I----裝.！ ！ I 訂.！ •線 (請先閱讀背面之注意事項再填寫4頁) 47249ΰ 經濟部智慧財產局貝工消費合作社印製 Α7 Β7 五、發明說明（7) 圖3爲示出本發明之一實施例之P T C元件的溫度— 電阻率特性之圖， 圖4爲示出本發明之一實施例之P T C元件及比較例 之PTC元件中重覆外加電流1 0A ( 5 0V)後之電阻 率特性之圖， 圖5爲示出本發明第二實施形態之P T C元件的部分 截面圖， 圖6爲用以說明本發明第二實施形態之P T C元件之 製造方法之圖，（a)爲組成物成形體之截面圖，（b) 爲由組成物成形體之表面令導電體一部分露出地進行壓黏 和埋設狀態之截面圖，（c)爲對組成物成形體進行鍍層 處理並且形成電極之狀態之截面圖，（d)爲示出水蒸氣 阻擋處理之槪念圖，（e)爲施以水蒸氣阻擋處理之 P T C元件的部分截面圖。 -------------裝！ — — II訂.--------線 {請先閱讀背面之注意事項再填寫本頁) 符號說 明 1 0 P τ C元件 1 2 組 成物成形 體 1 2 A 表 面 1 3 導 電 體 ns 4 A 電 極 1 4 B 電 極 1 6 水 蒸 氣阻擋 層 1 6 a Ρ V C D 膠 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）The V V filling material 4 5 to 6 0 V 0% is kneaded to form a composition molded body. --- And _., According to another aspect of the present invention, obtain at least one of TiC, WC, w2c, ZrC, VC, NbC, Ta C, and MoC in the crystalline polymer component. As a conductive powder filling material, it is mixed with 3 5 ~ 60 v 〇1% to obtain the forming paper of the composition. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) | 丨 | — — — — — · — — — · I I! III ^^ 111 —! !! ^^ {Please read the notes on the back before filling in the title page) Member of the Intellectual Property Bureau of the Ministry of Economic Affairs x Consumption Cooperative Printed 472499 A7 __ B7 V. Description of the invention (5) Process, and coating the formed product with a conductive body After the conductive material of the powder is prized, the pressure-bonding treatment of the conductive powder is performed, and a part of the conductive powder is buried from the surface of the molded body of the composition to bury the conductive powder, and the molded body of the composition The process of plating the aforementioned surface and forming an electrode is a manufacturing method of a PTC element characterized by the process. It is preferred to use Ni powder, Al powder, Cu powder, Fe powder, Ag powder, or black lead powder as the foregoing conductor powder. In addition, it is preferable that the conductive powder filling material is kneaded in the crystalline polymer component to form a composition molded body. In order to achieve the above-mentioned second object, the PTC device and the manufacturing method thereof of the present invention are composed of at least one of T i C, WC, W2C, ZrC, VC, NbC, TaC, and M02C in a crystalline polymer component. Guide. Electric powder filling material is mixed with 3 5 ~ 6 Ο v ο 1% to form a composite molded body, and the conductive body is partially exposed and the conductive body is pressed and buried by the surface of the composite molded body. An electrode is formed on the aforementioned surface of the molded article of the composition by a slush treatment, and a portion other than the aforementioned plating electrode of the PTC element is added to form a water vapor barrier layer. That is, according to still another aspect of the present invention, it is possible to obtain at least one of TiC, WC, W2C, ZrC 'V C ..?: NbC, TaC, and Mo2C among the crystalline polymer components. 3 5 ~ 6'0 v ο 1% of the composition formed body of the conductive powder filling material, and j is a part of the conductor formed by the surface of the foregoing composition formed body, and the conductor is exposed and pressed and buried. The aforesaid surface of the formed article of the composition is in accordance with the Chinese paper standard (CNS) A4 specification (210 X 297 mm) at the paper scale. 丨 丨 丨! _1! · ^^ ·! 1 Order! _ * ^ (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed 472499 A7 __ B7 V. Description of the invention (6) The electrode formed by the principle, and the part other than the aforementioned plated electrode The formed water vapor barrier layer is a characteristic PTC element. Preferably, the crystalline polymer component is a polymer alloy in which at least one thermoplastic polymer is mixed. In addition, according to another aspect of the present invention, it is possible to obtain at least one of Ti C, WC, W2C, ZrC, VC, NbC, Ta C, and Mo2C in a crystalline polymer component. 3 5 ~ 6 Ο ν ο 1% to obtain a composite molded product, and apply the conductive paste containing the conductive powder to the molded composite, and then press the conductive powder. A process of burying the conductive powder so that a part of the conductive powder is exposed from the surface of the molded body of the composition, and a process of plating and forming an electrode on the surface of the molded body of the composition, and A method for manufacturing a PTC element characterized by a process of subjecting a part other than the aforementioned plated electrode to a water vapor barrier process is a feature. Brief Description of the Drawings FIG. 1 is a cross-sectional view showing a p TC element according to the first embodiment of the present invention, and FIG. 2 is a diagram for explaining the manufacturing method of the p TC element according to the first embodiment of the present invention. (A) shows a composition molded body, (b) shows a state in which a conductive body is pressed and buried with a part of the surface of the composition molded body exposed, and (c) shows a molding of the composition The cross-sectional views of the state where the body is subjected to a layer treatment and the electrodes are formed. This paper size is applicable to the national standard (CNS) A4 specification (210 X 297 mm) — 丨 — I ---- install.! !! I order.! • Line (please read the precautions on the back before filling in 4 pages) 47249 印 Printed by Shelley Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (7) Figure 3 shows a PTC element showing an embodiment of the present invention FIG. 4 is a graph showing resistivity characteristics of a PTC element according to an embodiment of the present invention and a comparative example of a PTC element after repeated application of a current of 10 A (50 V), FIG. 5 In order to show a partial cross-sectional view of a PTC element according to a second embodiment of the present invention, FIG. 6 is a diagram for explaining a method for manufacturing the PTC element according to the second embodiment of the present invention, and (a) is a cross-sectional view of a formed article, (B) is a cross-sectional view of a state where the conductive body is partially pressed and buried with the conductive body exposed from the surface of the formed body of the composition, (c) is a cross-sectional view of a state where the formed body of the composition is plated and an electrode is formed, (d ) Is a schematic view showing a water vapor barrier treatment, and (e) is a partial cross-sectional view of a PTC element subjected to the water vapor barrier treatment. ------------- Install! — — Order II. -------- Line {Please read the precautions on the back before filling out this page) Symbol description 1 0 P τ C element 1 2 Composition molded body 1 2 A Surface 1 3 Conductor ns 4 A electrode 1 4 B electrode 1 6 Water vapor barrier layer 1 6 a VCD VCD paper size Applicable to China National Standard (CNS) A4 specification (210 X 297 mm)
47249U 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（8) 用以實施發明之最佳型態 爲了更詳細說明本發明，根據所附圖面予以說明。 首先，參照圖1〜圖4，說明本發明第一實施型態之 PTC元件及其製造方法。 如圖1所示般，本發明第一實施型態之P T C元件 1 0爲具有於結晶性聚合物成分中將導電性粉末充塡材料 (未予圖示）混練35〜60vo1%之組成物成形體 1 2，與由組成物成形體1 2之表面1 2A令導電體之一 部分露出地壓黏、埋設之導電體1 3，與組成物成形體 1 2之表面1 2A以鍍層處理所形成之電極1 4A及 14B。導電性粉末充塡材料可使用Ti C，WC，W2C ，Z rC，VC，NbC，TaC，及M02C 中之一種或 二镩以上。尙，導.電體1 3中以含有N i粉末，A 1粉末 ，Cu粉末，Fe粉末，Ag粉末，或黑鉛粉末爲佳。 製造本實施型態之P T C元件1 〇，必須具有至少如 圖2 (a)所示般，於結晶性聚合物成分中，將TiC， WC，W2C，ZrC，VC，NbC，TaC，及 Μ 〇 2 C中之至少一種做爲導電性粉末充塡材料並且混練 35〜6〇νο 1%取得組成物成形體12之工程’與於 組成物成形體1 2之表面1 2Α塗佈含有導電體粉末1 3 之導電體漿料後，進行導電體粉末1 3之壓黏處理’並如 圖2 ( b )所示般，令導電體粉末1 3之一部分由組成物 成形體1 2之表面1 2A露出地埋設導電體粉末1 3之工 本紙張尺度適甩中國國家標準（CNS)A4規格（210 X 297公釐） -TV- — — — — — - II---I — ·1111111 ·11111111 (請先閲讀背面之注意事項再填寫本頁) 472499 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（9) 程，並如圖2 (c)所示般，於組成物成形體12之表面 1 2A進行鍍層處理（鑛層）形成電極1 4A及1 4B之 工程。 首先，將做爲聚合物成分之軟化點爲約1 3 0°C之結 晶性高密度聚乙烯與粒徑1〜5 //m之導電性粉末充塡材 料，於約1 4 0〜.2 0 Ot溫度之加熱滾筒上令導電性粉 末以35〜60vo1%混練取得高分子混練物。尙，導 電性粉末可使用例如Ti C，WC，W2C，ZrC，VC ，NbC，TaC，及M〇2C中之一種或二種以上〔參照 圖 2 ( a )〕。 其次，將上述之高分子混練物予以粉末化後，以約 1 4 0〜2 0 0 °C之溫度加壓成型予以薄片化，最得高分 子混練物薄片。其後，於此高分子混練物薄片之兩面，塗 佈由N i粉末和聚乙烯丁縮醛及溶劑所構成之導電性粉末 ，並於室溫下進行5小時以上之乾燥處理，作成乾燥處理 完畢之薄片。將此乾燥處理完畢之薄片以約1 4 0〜 2 0 0°C之溫度加壓約5〜1 5分鐘，進行N i粉末之壓 黏處理。其結果，取得N i粉末大部分被埋設於薄片中， 且其一部分爲以露出薄片表面狀態之p T C組成物薄片〔 參照圖2 ( b ') 〕。 ~ 其:後，令如上述進行壓黏處理之P T C組成物薄片予 以脫脂處理後，施以N i無電解+Ν i電解鍍層處理，形 成電極〔參照圖2 (c)〕。 由上述處理所得之N i鏟層薄片中打穿面積1 c m 2之 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------裝1_!!1訂·!-線 (請先閱讀背面之注意事項再填寫才頁) 472499 經濟部智慧財產局員工消费合作社印製 A7 - _ B7 _____ 五、發明說明（1〇) 試驗片，做爲評價用試料（以下，將此評價用試料稱爲 實施例」）。尙，進行壓黏處理並埋設於薄片中之導電體 粉末除了 Ni粉末以外，亦可使用A 1粉末，Cu粉末’ Fe粉末，Ag粉末，或黑鉛粉末。 其次，爲了與實施例比較，如下處理製作比較試料1 (以下，將此比較試料稱爲「比較例1」）。 於此比較例1中，將高分子混練物予以薄片化爲止’ 可進行與上述實施例同樣之處理。其後，於約1 4 0〜 2 0 〇°C之溫度下，於混練物薄片之兩面以熱加壓接合金 屬板，形成電極。其後，由此薄片中打穿面積1 cm2之試 驗片，取得P T C元件（比較例1 )。 更且，如下處理製作比較試料2 (以下，將此比較試 .料稱爲「比較例2j)。於此比較例2中，將高分子混練 物予以薄片化爲止，可進行與上述實施例同樣之處理。其 後，於約1 4 0〜2 0 0 °C之溫度中，於混練物薄片之兩 面以熱加壓，將接觸混練物薄片側之面（單面）經由電解 粗面化之金屬板予以接合形成電極。其後，由此薄片中打 穿面積lcm2之試驗片，取得PTC元件（比較例2)。 又，如下處理製作比較試料3 (以下，將此比較試料 稱爲「比較例3」）。於此比較例3中，將高分子混練物 予以」薄片化爲止，可進行與上述實施例同樣之處理。其後 ，將混練物薄片脫脂處理後，施以N i無電解+N i電解 鍍層處理，形成電極。其後，由此薄片中打穿面積1 cm2 之試驗片，取得P T C元件（比較例3 )。 -------------裝 n II 1· _1 I 訂i n ϋ I I 線 (請先《讀背面之注意事項再填寫4,頁> 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ^Τ3Γ 經濟部智慧財產局員工消費合作社印製 A7 _____B7_ 五、發明說明（11) 更且，如下處理製作比較試料4 (以下，將此比較試 料稱爲「比較例4」）。將做爲聚合物成分之軟化點爲約 1 30 °C之結晶性高密度聚乙烯，與粒徑1〜5ym之導 電性粉末，於約1 4 0〜2 0 0 t溫度之加熱滾筒上，以 導電性粉末爲3 4 v ο 1 %進行混練取得高分子混練物。 尙，導電性粉末可使用Ti C，WC，W2C，ZrC， VC，NbC，TaC，及M〇2C。進行與上述實施例同 樣之處理》並由薄片中打穿面積1 cm2之試驗片，取得 P T C元件（比較例4 )。 對於如上述處理所得之實施例及比較例1至3，進行 特性試驗。尙，P T C元件之目標特性之電極接合強度， 爲可保持做爲電極之充分信賴性之5 0 0 g f/cm2以上 .，室溫電阻爲2 Ω · c m以下，相對於溫度之電阻値於急 速上升後（開關後）之電阻値，與室溫下之電阻値之比（ 開關後R /室溫R )爲充分做爲過電流保護元件之動作， 且爲可充分使用做爲面狀發熱體之1 〇4以上。更且’將 P T C元件重覆開關時之室溫電阻値的目標値，即使於開 關500回後亦爲2Ω. cm以下。 首先，將如上述處理所得之P T C元件（實施例及比 較例1至3 )之電極表面/以附有焊藥之導線予以連接， 再陝周圍以環氧樹脂覆被，製作電極接合強度之測定用試 料。其後，接上分別對應於實施例及比較例1至3之各測 定用試料之導線，測定電極的接合強度。測定結果示於以 下之表1。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐〉 — — — — — — — — — — — — — ·1111111 ·1111111 (請先閲讀背面之注意事項再填寫4貝) 472499 A7 B7 -、發日戶銳明（12) 樣品 接合強度（gf/cm2) 實施例 800-2300 比較例1(金屬板） 25-150 比較例2(粗面化金屬板） 850-2400 比較例3(僅鍍層） 30-170 表1 .電極之接合強度 如表1所闡明般，實施例之電極的接合強度，比使用 未粗面化金屬板之電極之比較例1’和僅進行鍍層處理形 成電極之比較例3大’並且取得與電極中使用粗面化金屬 板之比較例2大約同等之數値。由此確認實施例之電極的 接合強度，可保持於做爲電極之充分信賴性的5 0 0 g f / c m 2以上。 .其次，對於實施例及比較例1至3 ，測定5 Ο 0回開 關後於室溫之電阻値。測定結果示於以下之表2。尙，於 室溫電阻率之測定中，使用直流4短針數位式Multimeter --— — — — —-----I ^ i — — —— —— ------— 1^ (請先閲讀背面之注意事項再填窝4頁) 經濟部智慧財產局員工消费合作社印製 -16 - 本紙張尺度適用中國國家標準（CNS)A4規格<210 X 297公釐） 472499 A7 _____ B7 五、發明說明（13) 樣品 室溫電阻率（Ω . cm) 實施例（Tie) 0.4 實施例（WC) 0.5 實施例（W2c) 0.4 實施例（ZrC) 0.4 實施例（VC) 0.6 實施例（NbC) 0.5 實施例（TaC) 0.4 實施例（M〇2C) 0.5 比較例1(金屬板） 110.0 比較例2(粗面化金屬板） 1.3 比較例3(僅鍍層） 320.0 表2 ·室溫電阻率 --------------裝 (請先閲讀背面之注意事巩再填寫. --線· 經濟部智慧財產局貝工消費合作社印製 如表2所闡明般，實施例中使用T i C，WC，W2C ，ZrC，VC，NbC，TaC，及M02C 中之任何一 種做爲導電性粉末時，均可確認室溫電阻率爲目標値之 2 Ω . c m以下。47249U Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (8) Best Mode for Implementing the Invention In order to explain the present invention in more detail, it will be explained according to the attached drawings. First, a PTC device and a manufacturing method thereof according to a first embodiment of the present invention will be described with reference to FIGS. 1 to 4. As shown in FIG. 1, the PTC element 10 according to the first embodiment of the present invention is formed by compounding a conductive powder filling material (not shown) with 35 to 60 vo1% in a crystalline polymer component. The body 12 is formed by pressing and embedding a part of the conductive body 13 with the surface 1 2A of the molded body 12 of the composition exposed, and the surface 1 2A of the molded body 12 is formed by plating. Electrodes 1 4A and 14B. As the conductive powder filling material, one of Ti C, WC, W2C, Z rC, VC, NbC, TaC, and M02C, or two or more fluorene can be used. Alas, the conductor 1 3 preferably contains Ni powder, A1 powder, Cu powder, Fe powder, Ag powder, or black lead powder. To manufacture the PTC element 10 of this embodiment, at least as shown in FIG. 2 (a), among the crystalline polymer components, TiC, WC, W2C, ZrC, VC, NbC, TaC, and M0 are required. At least one of 2C is used as a conductive powder filling material and kneaded 35 to 60%. 1% of the process of obtaining the composition molded body 12 and coating the surface of the composition molded body 12 with the conductive powder 1 2A After the conductive paste of 1 3, the pressure-bonding treatment of the conductive powder 13 is performed, and as shown in FIG. 2 (b), a part of the conductive powder 13 is formed from the surface 1 2A of the molded body 12 of the composition. The paper size of the conductor powder 1 3 exposed in the ground is suitable for Chinese National Standard (CNS) A4 specifications (210 X 297 mm) -TV- — — — — — — II --- I — · 1111111 · 11111111 (Please (Please read the notes on the back before filling this page) 472499 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. The description of the invention (9), and as shown in Figure 2 (c), The surface 1 2A is subjected to plating treatment (mineral layer) to form electrodes 1 4A and 1 4B. First, a crystalline high-density polyethylene with a softening point of about 130 ° C as a polymer component and a conductive powder-filled material with a particle size of 1 to 5 // m are formed at about 1 4 to 2 The conductive powder was kneaded at 35 ~ 60vo1% on a heating roller at a temperature of 0 Ot to obtain a polymer kneaded product. In other words, one or two or more of Ti C, WC, W2C, ZrC, VC, NbC, TaC, and MoC can be used as the conductive powder [see FIG. 2 (a)]. Next, after the above-mentioned polymer kneaded material is powdered, it is pressure-molded at a temperature of about 140 to 200 ° C to be thinned to obtain a high-molecular kneaded material sheet. Thereafter, on both sides of the polymer kneaded material sheet, a conductive powder composed of Ni powder, polyvinyl butyral, and a solvent was applied, and a drying treatment was performed at room temperature for more than 5 hours to prepare a drying treatment. Finished flakes. The dried sheet was pressurized at a temperature of about 140 to 200 ° C for about 5 to 15 minutes, and then a N i powder was pressure-bonded. As a result, most of the Ni powder was buried in the sheet, and a part of the Ni powder was a p T C composition sheet in a state where the surface of the sheet was exposed [see FIG. 2 (b ′)]. ~ After that, the P T C composition sheet subjected to the pressure-bonding treatment as described above is subjected to a degreasing treatment, and then subjected to an Ni electroless + Ni electrolytic plating treatment to form an electrode [see FIG. 2 (c)]. The paper size of 1 cm 2 of the Ni sheet layer obtained from the above treatment is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ----------- Packing 1_ !! 1 order !!-line (please read the precautions on the back before filling in the page) 472499 A7-_ B7 _____ printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (1) Test piece as Samples for evaluation (hereinafter, this sample for evaluation is referred to as Example). That is, in addition to the Ni powder, the conductor powder that has been pressure-bonded and buried in the sheet may be A 1 powder, Cu powder 'Fe powder, Ag powder, or black lead powder. Next, in order to compare with the examples, a comparative sample 1 was prepared as follows (hereinafter, this comparative sample is referred to as "comparative example 1"). In this Comparative Example 1, the same process as in the above-mentioned Example can be performed until the polymer kneaded product is thinned. Thereafter, a metal plate was bonded to both sides of the kneaded material sheet by hot pressing at a temperature of about 140 to 200 ° C to form an electrode. Thereafter, a test piece having an area of 1 cm2 was punched through the sheet to obtain a P T C element (Comparative Example 1). Furthermore, comparative sample 2 was prepared as follows (hereinafter, this comparative sample is referred to as "comparative example 2j". In this comparative example 2, the polymer kneaded product was thinned, and the same procedure as in the above-mentioned embodiment can be performed. After that, at a temperature of about 140 to 200 ° C, heat-pressurize both sides of the kneaded material sheet, and the surface (single side) contacting the side of the kneaded product sheet is electrolytically roughened. Metal plates were joined to form electrodes. Thereafter, a test piece having an area of 1 cm2 was punched through the sheet to obtain a PTC element (Comparative Example 2). Comparative Sample 3 was prepared as follows (hereinafter, this comparative sample is referred to as "comparison" Example 3 "). In this Comparative Example 3, the same treatment as in the above-mentioned Example can be performed until the polymer kneaded product is thinned. Thereafter, the kneaded material sheet was degreased, and then subjected to Ni electroless plating and Ni electrolytic plating treatment to form an electrode. Thereafter, a test piece having an area of 1 cm 2 was punched through the sheet to obtain a P T C element (Comparative Example 3). ------------- Install n II 1 · _1 I order in ϋ II line (please read "Notes on the back side and then fill in 4, page > This paper size applies to Chinese national standard (CNS ) A4 specification (210 X 297 mm) ^ Τ3Γ Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _____B7_ V. Description of the invention (11) In addition, the following process is used to make a comparative sample 4 (hereinafter, this comparative sample is referred to as" Comparative Example 4 "). A crystalline high-density polyethylene having a softening point of about 1 30 ° C as a polymer component and a conductive powder having a particle size of 1 to 5 μm were used at about 1 40 to 2 0 0 t. On a heating roller at a temperature, the conductive powder is kneaded at 3 4 v ο 1% to obtain a polymer kneaded product. 尙, the conductive powder can be Ti C, WC, W2C, ZrC, VC, NbC, TaC, and M. 2C. Perform the same treatment as in the above-mentioned Example "and pierce a test piece with an area of 1 cm2 from the sheet to obtain a PTC element (Comparative Example 4). For the Examples and Comparative Examples 1 to 3 obtained as described above, the characteristics were performed Tests: 尙, the target joint strength of the PTC element is sufficient to maintain sufficient electrode performance. Dependence is more than 5 0 0 gf / cm2. Room temperature resistance is 2 Ω · cm or less. The resistance relative to temperature (resistance 后 after rapid rise (after switching)) and the resistance 室温 at room temperature ( After switching, R / room temperature R) is sufficient to act as an overcurrent protection element, and it can be used as a surface heating element more than 1.04. Furthermore, the room temperature resistance when the PTC element is repeatedly switched The target 値 of 即使 is less than 2 Ω · cm even after 500 times of switching. First, the electrode surface of the PTC element (Examples and Comparative Examples 1 to 3) obtained as described above is provided with a wire with solder Connected, and then coated with epoxy resin around Shaanxi to prepare a test sample for measuring the electrode joint strength. Then, a lead wire corresponding to each of the measurement samples of the Examples and Comparative Examples 1 to 3 was connected to measure the electrode joint strength. The measurement results are shown in Table 1. The paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) — — — — — — — — — — — — — 1111111 (Please read first (Notes on the back are filled in 4 shells) 472499 A7 B7-, Hiroshi Tori (12) Sample joint strength (gf / cm2) Example 800-2300 Comparative example 1 (metal plate) 25-150 Comparative example 2 (roughened metal plate) 850-2400 Compare Example 3 (plating only) 30-170 Table 1. The joint strength of the electrode is as explained in Table 1. The joint strength of the electrode of the example is better than that of Comparative Example 1 ′ using an electrode without a roughened metal plate and only plating. The comparative example 3 was processed to form an electrode, and was approximately the same number as the comparative example 2 using a roughened metal plate for the electrode. From this, it was confirmed that the joint strength of the electrode of the example can be maintained at 50 gf / cm2 or more, which is sufficient reliability of the electrode. Secondly, for the examples and comparative examples 1 to 3, the resistance 室温 at room temperature after 500 switching cycles was measured. The measurement results are shown in Table 2 below.尙, in the measurement of room temperature resistivity, use a DC 4 short pin digital Multimeter --- — — — —----- I ^ i — — —— —— ------— 1 ^ (Please Please read the notes on the back before filling in the page 4) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -16-This paper size applies to China National Standard (CNS) A4 specifications < 210 X 297 mm) 472499 A7 _____ B7 5 Description of the invention (13) Sample room temperature resistivity (Ω.cm) Example (Tie) 0.4 Example (WC) 0.5 Example (W2c) 0.4 Example (ZrC) 0.4 Example (VC) 0.6 Example (NbC ) 0.5 Example (TaC) 0.4 Example (M0C) 0.5 Comparative Example 1 (Metal Plate) 110.0 Comparative Example 2 (Roughened Metal Plate) 1.3 Comparative Example 3 (Plating only) 320.0 Table 2 · Room Temperature Resistivity -------------- Installation (Please read the notes on the back before filling it out. --Line · Printed by the Shellfish Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs as explained in Table 2 and implemented When using any of T i C, WC, W2C, ZrC, VC, NbC, TaC, and M02C as conductive powder, the room temperature resistivity can be confirmed. Zhi standard of 2 Ω. C m or less.
V V 相對地，於電極使用未粗面化之金屬板之比較例1， 和行鍍層處理形成電極之比較例3中，可知室溫電阻 率高，根本無法取得目標値之2Ω· cm以下之數値。其 可理解係因電極與混練物薄片間的接觸電阻高。.另一方面 ，於電極使用粗面化金屬板之比較例2中，雖爲目標値之 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 9 4 CNi 7 4 經濟部智慧財產局員工消費合作社印製 A7 __B7___ 五、發明說明（14) 2 Ω · cm以下，但可知室溫電阻率比實施例高。其可理 解係因爲電極與混練物薄片間無法取得如實施例般良好的 歐姆接觸。 其次，關於實施例測定溫度和電阻率之關係。測定結 果示於圖3。尙，測定時，於油浴中使用4短針法進行， 於電阻率之測+定中，使用數位式Multimeter。 如圖3所閫明般，實施例中，室溫中之電阻率爲目標 値之2Ω· cm以下，且溫度—電阻率曲線爲在大略對應 於本實施例所用樹脂之結晶性高密度聚乙烯之軟化點（約 1 3 0°C)溫度開始。又，相對於溫度之電阻値急速上升 後（開關後）之電阻値與室溫下之電阻値之比（開關後R /室溫R)爲大於1 08，且可充分做爲過電流保護元件之 _動作，且大幅提高可充分使用做爲面狀發熱體之1 04目標 値。 更且，對前述所得之P T C元件（實施例及比較例1 至4 )分別重覆通電1 0 A ( 5 Ο V )之電流，並且測定 動作後之電阻率變化。測定結果示於圖4。 如圖4所闡明般，實施例中，初期室溫電阻率爲目標 値之2Ω· cm以下，且即使重覆通電後，亦繼續維持目 標値之2 Ω:'cm以下。又 '，於重覆通電數回後，可知室 溫電+阻率之增加爲略呈飽和。 相對地，於電極使用未粗面化之金屬板之比較例1， 和僅進行鍍層處理形成電極之比較例3中，可知初期室溫 電阻率爲大幅超過目標値之2Ω· cm，更且，室溫電阻 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） — — — — — — — — — — — — — — — — — — — I— 11111!1 I (請先閱讀背面之注意事項再填寫4¾)In contrast, in Comparative Example 1 in which an electrode was used with a non-roughened metal plate, and Comparative Example 3 in which an electrode was plated, it can be seen that the resistivity at room temperature is high, and it is impossible to obtain the target 値 2Ω · cm or less. value. It can be understood that the contact resistance between the electrode and the kneaded material sheet is high. On the other hand, in Comparative Example 2 in which a roughened metal plate is used for the electrode, although the target paper size is China Paper Standard (CNS) A4 (210 X 297 mm) 9 4 CNi 7 4 Ministry of Economic Affairs Printed by A7 __B7___ of the Intellectual Property Bureau's Consumer Cooperative Fifth, the description of the invention (14) 2 Ω · cm or less, but it can be seen that the room temperature resistivity is higher than the example. This is understandable because the ohmic contact between the electrode and the kneaded material sheet cannot be as good as in the embodiment. Next, the relationship between temperature and resistivity was measured in the examples. The measurement results are shown in FIG. 3. Alas, the measurement was performed in an oil bath using the 4-short needle method. For the measurement and centering of resistivity, a digital Multimeter was used. As shown in Fig. 3, in the embodiment, the resistivity at room temperature is less than 2Ω · cm of the target, and the temperature-resistivity curve is a crystalline high-density polyethylene that roughly corresponds to the resin used in this embodiment. The softening point (about 130 ° C) of the temperature starts. In addition, the ratio of the resistance 温度 to the temperature 値 after a rapid rise (after switching) to the resistance 室温 at room temperature (after switching R / room temperature R) is greater than 108, and can be fully used as an overcurrent protection element The _ action, and greatly improved, can be fully used as the 04 04 target 发热 as a planar heating element. Furthermore, the P T C elements obtained in the foregoing (Examples and Comparative Examples 1 to 4) were repeatedly charged with a current of 10 A (50 V), and the resistivity change after the operation was measured. The measurement results are shown in FIG. 4. As illustrated in Fig. 4, in the embodiment, the initial room temperature resistivity is 2 Ω · cm or less of the target 値, and the target 値 2 Ω: 'cm or less is maintained even after repeated power-on. Also, after several times of repeated energization, it can be seen that the increase in room temperature electricity + resistivity is slightly saturated. On the other hand, in Comparative Example 1 in which an unroughened metal plate was used for the electrode, and Comparative Example 3 in which the electrode was formed only by plating treatment, it was found that the initial room temperature resistivity significantly exceeded the target 値 by 2Ω · cm, and, Room temperature resistance This paper is sized according to Chinese National Standard (CNS) A4 (210 X 297 mm) — — — — — — — — — — — — — — — — — — — — — 11111! 1 I (please first Read the notes on the back and fill in 4¾)
47249U 經濟部智慧財產局貝工消費合作社印製 A7 B7 五、發明說明（15) 率爲大略比例於重覆通電地大爲上升。另一方面，於電極 使用粗面化金屬板之比較例2中，雖然初期室溫電阻率爲 目標値之2Ω· cm以下，但重覆通電則令室溫電阻率超 過目標値之2Ω. cm，且室溫電阻率之增加並未察見飽 和。 又，導電性粉末爲34vo 1%之比較例4，雖然初 期室溫電阻率亦爲目標値之2Ω· cm以下，但經由重覆 通電令室溫電阻率超過目標値2Ω· cm，可知對於重覆 通電並無法取得安定性。 然而，於導電性粉末使用金屬粉末之情形中，粉末本 身發生凝集且部分形成導電路徑，因而令耐電壓特性降低 。又，以碳黑、黑鉛等之碳系粉末做爲導電性粉末時，因 _爲粉末體之導電率爲比金屬碳化物粉末高，故室溫電阻率 爲超過..目.標値.·2 Ω ·, c m。 更且，導電性粉末之充塡量低於35vo 1%時，如 上述，對於重覆通電之安定性降低，且隨著動作次數，而 令室溫電阻率超過目標値2Ω· cm。另一方面，於導電 性粉末之充塡量爲超過6 0 v ο 1 %時，令元件製作的作 業性降低，且實質上，令元件製作困難。 加上，以如實施例般埋入導電性粉末及以金屬鍍層以 外之_方:法形成電極之情形中，如前述，對於重覆通電之安 定性降低，且隨著動作次數，令室溫電阻率超過目標値2 Ω· cm。尙，導電性粉末之充塡量若爲45vol%以 上，則可知對於重覆通電之安定性更加提高》 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱) · 1!1 — 11!1! ^^ · ! I I ! I β 1! (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 47249ΰ Α7 Β7 五、發明說明（16) 如上述說明般，本發明之第一實施型態爲於結晶性聚 合物成分中，將導電性粉末充塡材料混練混練3 5〜6 0 v ο 1 %之組成物成形體表面中，令導電體之一部分露出 地壓黏並埋設，並在此露出一部分導電體之組成物成形體 表面經由鍍層處理形成電極，並且因爲使用T i C，WC ，W2C，ZrC，VC，NbC，TaC，及 M02C 中 之至少一種做爲導電性粉末充塡材料，故P T C組成物與 電極之間的密合性良好，且可令兩者間的接觸電阻値降低 。又，可取得對於重覆通電之安定性優良之P T C元件。 其次，關於本發明之第二實施型態，參照圖面予以詳 細說明。 圖5爲示出本發明第二實施型態之P T C元件的部分 .截面圖。如圖5所示般，本實施型態之PTC元件10， 爲具有組成物成形體1 2，與組成物成形體1 2之表面 1 2A中令導電體1 3 —部分露出地壓黏和埋設之導電體 1 3，與組成物成形體1 2之表面1 2A以鍍層處理所形 成之電極1 4A及1 4B，且於（鍍層）電極1 4A及 1 4 B以外之組成物成形體1 2露出之部分，被水蒸氣阻 擋層1 6所覆蓋。 組成物成形體12爲與上述第一實施型態者完全相同 ，鼠於:結晶性聚合物成分中，將使用T i C，WC，W2C ，Z r C，VC，NbC，TaC，及M02C 中之至少一 種之導電性粉末充塡材料以混練3 5〜6 0 v ο 1 %混練 所形成者。組成物成形體1 2中之結晶性聚合物成分例如 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） — — — — — — — — — — — — — — — — — — — I— — — — — — — — (請先閲讀背面之注意事項再填寫4頁) 經濟部智慧財產局員工消費合作社印製 472499 A7 — B7 五、發明說明（17) 可爲改質聚乙烯和改質聚丙烯般之熱塑性聚合物之一種或 二種以上混合之聚合物合金所構成。 於鍍層電極1 4A及1 4B分別使用鎳（N i )箔。 水蒸氣阻擋層1 6例如後述般，可施以覆蓋P V C D膠乳 等之水蒸氣阻擋處理而形成。 以下，參照圖6，具體說明上述實施型態之PTC元 件1 0之製造方法的一實施例。圖6爲用以說明本實施例 之PTC元件的製造方法之圖，（a)爲示出組成物成形 體，（b)爲示出由組成物成形體之表面令導電體一部分 露出地壓黏和埋設之狀態，（c)爲示出對組成物成形體 進行鎪層處理形成電極之狀態，（d)爲示出水蒸氣阻擋 處理，（e)爲示出施以水蒸氣阻擋處理之PTC元件之 圖。 於圖6中，（a ) ，（ b )及（c )之各工程爲與圖 2所示狀態中之（a) ，（b)及（c)各工程完全同樣 〇 本實施例爲將組成物成形體1 2中之鍍層電極（鎳箔 )14A及14B以外之部分’即’組成物成形體12之 表面露出之部分1 2 C ’如圖6 ( d )所示般’形成以 P V C D膠乳> 1 6 a所覆羞之水蒸氣阻擋層1 6 ，製作出 圖e )所示之本實施例之PTC (電阻）元件1 0 ° 如此，於鍍層電極（鎳箔）14A及14B以外之部 分，形成以P V C D膠乳覆蓋之水蒸氣阻擋層之本實施例 的P T C元件，例如於恆溫槽下8 5 °C X 9 0 % R Η下 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公« ) !11!!1! _ 11 I I II e 111! ^^ {請先Μ讀背面之注意事項再填寫才頁) 經濟部智慧財產局貝工消费合作社印製 472499 A7 B7 五、發明說明（18) 經過5 0 0小時後亦爲開關後之電阻率安全，比未形成水 蒸氣阻擋層之元件，增加8倍以上之信賴性，確認可達成 更安定之重覆電流阻斷。因此，於保存及使用之環境濕度 高之狀態下重覆進行開關動作，亦可取得安定的電阻。 以上，雖以特定之實施型態敘述本發明，但本發明並 非限定於此，且在申請專利範圍所記載之發明範圍內，亦 可應用於其他的實施型態。 例如，上述之第一及第二實施型態中，雖使用高密度 聚乙烯樹脂做爲組成物成形體之主成分，但並非特別限定 於此。組成物成形體之主成分除了高密度聚乙烯樹脂以外 ，亦可使用聚丙烯型和低密度聚乙烯型等樹脂。 更且，於上述之第二實施型態中，雖形成以PVCD .膠乳所覆蓋之水蒸氣阻擋層，但除此以外亦可考慮例如使 用偏氯乙烯等水蒸氣穿透率低之物質之水蒸氣阻擋處理之 方法。 產業上之可利用性 如上述說明般，本發明之第一實施型態爲於結晶性聚 合物成分中，將導電性粉末充塡材料混練3 5〜47249U Printed by Shelley Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of invention (15) The ratio is roughly the same as that of repeated power-on. On the other hand, in Comparative Example 2 in which a roughened metal plate was used for the electrode, although the initial room temperature resistivity was below 2Ω · cm of the target 値, repeated application of electricity caused the room temperature resistivity to exceed the target 値 of 2Ω · cm. , And the increase in room temperature resistivity did not see saturation. In Comparative Example 4 where the conductive powder was 34 vo 1%, although the initial room temperature resistivity was 2 Ω · cm or less of the target ，, the room temperature resistivity exceeded the target 値 2 Ω · cm by repeated application of electricity. Overheating does not provide stability. However, in the case where a metal powder is used as the conductive powder, the powder itself agglomerates and a conductive path is partially formed, thereby reducing the withstand voltage characteristics. In addition, when carbon-based powders such as carbon black and black lead are used as conductive powders, since the conductivity of the powder body is higher than that of metal carbide powders, the room temperature resistivity exceeds ... · 2 Ω ·, cm. In addition, when the filling amount of the conductive powder is less than 1% of 35vo, as mentioned above, the stability to repeated current application is reduced, and the room temperature resistivity exceeds the target 値 2Ω · cm with the number of operations. On the other hand, when the filling amount of the conductive powder is more than 60 v ο 1%, the workability of device manufacturing is reduced, and in fact, the device manufacturing is difficult. In addition, in the case where the conductive powder is embedded as in the embodiment and the electrode is formed by a method other than metal plating, as described above, the stability for repeated current application is reduced, and the room temperature is increased with the number of operations. The resistivity exceeds the target 値 2 Ω · cm. Alas, if the charged amount of conductive powder is more than 45vol%, it can be known that the stability of repeated power is further improved. ”This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love) · 1! 1 — 11! 1! ^^ ·! II! I β 1! (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 47249ΰ Α7 Β7 5. Description of the invention (16) As above In general, the first embodiment of the present invention is a method in which a conductive powder filling material is kneaded and kneaded in a crystalline polymer component, and the composition is formed on the surface of a formed body of 3 5 to 6 0 v ο, so that Part of the surface is pressed and buried, and the surface of the formed part of the conductive body composition is exposed to form an electrode through plating treatment, and because T i C, WC, W2C, ZrC, VC, NbC, TaC, and M02C are used. At least one is used as the conductive powder filling material, so the adhesion between the PTC composition and the electrode is good, and the contact resistance between the two can be reduced. In addition, a P T C element excellent in stability against repeated current application can be obtained. Next, the second embodiment of the present invention will be described in detail with reference to the drawings. Fig. 5 is a partial cross-sectional view showing a P T C element according to a second embodiment of the present invention. As shown in FIG. 5, the PTC element 10 according to this embodiment has a composition molded body 12 and a conductive body 1 3-partially exposed and pressed and buried in a surface 12A of the composition molded body 12. Conductive body 1 3, electrode 1 4A and 1 4B formed by plating treatment on the surface 1 2A of the formed body 12 of the composition, and formed body 1 2 of the composition other than (plating) electrodes 1 4A and 1 4 B The exposed portion is covered with a water vapor barrier layer 16. The composition molded body 12 is exactly the same as that of the first embodiment described above. Among the crystalline polymer components, T i C, WC, W2C, Z r C, VC, NbC, TaC, and M02C are used. At least one of the conductive powder filling materials is formed by kneading 35 to 60 v ο 1%. For example, the crystalline polymer component in the composition formed body 12 is compliant with the Chinese National Standard (CNS) A4 specification (210 X 297 mm) for this paper size. — — — — — — — — — — — — — — — — — — I — — — — — — — — (Please read the precautions on the back before filling in 4 pages) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 472499 A7 — B7 V. Description of the invention (17) Can be used for upgrading A polymer alloy composed of one or two or more thermoplastic polymers such as ethylene and modified polypropylene. Nickel (N i) foils were used for the plated electrodes 14A and 14B, respectively. The water vapor barrier layer 16 may be formed by applying a water vapor barrier treatment covering a P V C D latex or the like, as described later. Hereinafter, an embodiment of a method for manufacturing the PTC element 10 according to the above embodiment will be described in detail with reference to FIG. 6. FIG. 6 is a diagram for explaining a method of manufacturing the PTC element of this embodiment, (a) shows a composition molded body, and (b) shows a part of the conductive body exposed to the surface of the composition molded body and pressed and bonded. And buried state, (c) shows the state in which the composition formed body is subjected to a lamination process to form an electrode, (d) shows the water vapor barrier process, and (e) shows the PTC element subjected to the water vapor barrier process. Figure. In FIG. 6, the processes of (a), (b), and (c) are exactly the same as the processes of (a), (b), and (c) in the state shown in FIG. 2. This embodiment is composed of The parts other than the plated electrodes (nickel foils) 14A and 14B in the molded body 12 are the exposed portions 1 2 C of the formed body 12 as shown in FIG. 6 (d). A PVCD latex is formed. > The water vapor barrier layer 1 6 covered by 16 a is used to produce the PTC (resistance) element of this embodiment shown in FIG. 10) In this way, the plating electrode (nickel foil) other than 14A and 14B In part, the PTC element of this embodiment is formed with a water vapor barrier layer covered with PVCD latex, for example, 85 ° CX 90% R under a constant temperature bath. This paper size is applicable to Chinese National Standard (CNS) A4 specifications (210 X 297 public «)! 11 !! 1! _ 11 II II e 111! ^^ {Please read the notes on the back before filling in the page) Printed by the Shelley Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 472499 A7 B7 V. Invention Note (18) The resistivity after switching is also safe after 500 hours, which is 8 times more than that of components without a water vapor barrier. Reliability is confirmed to achieve more stable repeated current blocking. Therefore, it is possible to obtain stable resistance even if the switching operation is repeated under the condition of high humidity in storage and use. Although the present invention has been described in terms of a specific embodiment, the present invention is not limited to this, and can be applied to other embodiments within the scope of the invention described in the scope of the patent application. For example, in the above-mentioned first and second embodiments, although a high-density polyethylene resin is used as the main component of the molded article of the composition, it is not particularly limited thereto. In addition to the high-density polyethylene resin as the main component of the molded article of the composition, resins such as polypropylene type and low-density polyethylene type can also be used. Furthermore, in the second embodiment described above, although a water vapor barrier layer covered with PVCD. Latex is formed, in addition to this, it is also possible to consider using, for example, water having a low water vapor transmission rate such as vinylidene chloride. Method of vapor barrier treatment. Industrial Applicability As described above, the first embodiment of the present invention is a kneaded conductive powder filling material in a crystalline polymer component. 3 5 ~
6 0 v ο 1 %之組成物成形-表面中，令導電體之一部分 露壯地壓黏並埋設，並在此露出一部分導電體之組成物成 形體表面經由鍍層處理形成電極，並且因爲使用T i C ’ WC，W2C，ZrC，VC，NbC，TaC’ 及 M〇2C中之至少一種做爲導電性粉末充塡材料，故P T C 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） !!11· ·!1 訂·！ * (請先閱讀背面之注意事項再填寫才頁) 472499 A7 __B7 五、發明說明（19 ) 組成物與電極之間的密合性良好，且可令兩者間的接觸電 阻値降低。又，可取得對於重覆通電之安定性優良之 P T C元件及其製造方法。 又，若根據本發明之第二實施型態，則可令上述第一 實施型態之P T C元件及其製造方法中，更可有效防止環 境濕度之影響造成PTC元件本身由電極剝離’並且提供 對於重覆使用之安定性和再現性爲良好，信賴性高之 P T C元件及其製造方法。 ---II--------裝！----訂------ 線 (請先Μ讀背面之注項再填寫彳頁) 經濟部智慧財產局員..K消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐〉6 0 v ο 1% of the composition forming-In the surface, a part of the conductive body is exposed to pressure and buried, and a part of the surface of the conductive composition forming body is exposed to form an electrode through plating treatment, and because T is used, At least one of i C 'WC, W2C, ZrC, VC, NbC, TaC' and M0C is used as the conductive powder filling material. Therefore, the PTC paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297). Mm) !! 11 · ·! 1 Order ·! * (Please read the precautions on the back before filling out the page) 472499 A7 __B7 V. Description of the invention (19) The adhesion between the composition and the electrode is good, and the contact resistance between the two can be reduced. In addition, a P T C element which is excellent in the stability against repeated current application and a manufacturing method thereof can be obtained. In addition, according to the second embodiment of the present invention, the PTC element and the manufacturing method of the first embodiment can effectively prevent the PTC element itself from being peeled off by the electrode due to the influence of environmental humidity. PTC device with good stability and reproducibility after repeated use and high reliability and its manufacturing method. --- II -------- install! ---- Order ------ Line (please read the note on the back before filling in the title page) Member of the Intellectual Property Bureau of the Ministry of Economic Affairs: K Consumer Cooperative Co., Ltd. This paper is printed in accordance with China National Standard (CNS) A4 (210 X 297 mm>