TW469448B - Conductive fiber, a process and an apparatus for preparing the same and their usage - Google Patents
Conductive fiber, a process and an apparatus for preparing the same and their usage Download PDFInfo
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469448 Α7 Β7 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 五、發明說明G ) 本發明乃白色度高而導電性優異之白色導電性纖維有 關’也跟對於纖維體具有優異的金屬被膜黏附性的導電性 纖維有關者。更詳言之，係有關由尼龍纖維或聚酯纖維等 高分子材料所構成纖維體表面上塗布有金屬被膜而成之導 電性纖維_，金屬被瞑具有優異的黏附強度和導電性，而 白色度高之導電性纖維。本發明之導電性纖維可提供各種 布質材料或衣料品之材料使用，或提供電磁波屏蔽材料， 防止靜電材料’電極以及電線之代替材料等產業材料用途 使用〇 以往已知存在有由尼龍纖維或聚酯纖維等高分子材料 所構成之纖維表面上塗布有金屬薄膜而成導電性纖維，並 為提高金屬被膜之黏附性也嚐試各種方法^例如塗布硫化 鋼時’以具有鋼離子捕捉基之染料對於高分子材料施與前 處理，然後結合以銅離子後，再行硫處理之方法（參考特公 平01-37513號）’或經鹼處理而使纖維表面粗糙化之後， 附著以鋼離子捕捉基，然後結合以硫化銅之方法·（參考特開 平06-298973號）等皆屬周知方法。另外，對於芳基醯胺纖 維等很難施與金屬鑛飾者’也已知可利用聚乙烯吡咯烷酮 (簡稱PVP)而附著以金屬離子’再加以還原而形成金屬鍍 飾之方法（參考特表平06-506267號）。 然而，上述利用PW之鍍飾方法所能應用之纖維種類 有限’缺乏沉用性。另外，利用導入銅離子捕捉基之塗布 方法’該金屬被膜也限定在銅或其化合物，而且金屬被膜 之黏附強度也不見得充分等缺點存在β ^ ^ ^ ^ ______ 又，利用鹼處理· 本紙張尺度適用中國國家標準（CNS)A4規格（210χ 297公釐） 1 311634 (請先閲讀背面之注項再填窝本頁) 0 n .^1-^BJf n n469448 Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention G) The present invention is related to white conductive fibers with high whiteness and excellent electrical conductivity. It is also related to electrical conductivity with excellent metal film adhesion to fibrous bodies. Sexual fiber related. More specifically, it refers to conductive fibers made of polymer materials such as nylon fibers or polyester fibers coated with a metal coating on the surface of a fiber body. Metal quilts have excellent adhesion strength and conductivity, while white High degree of conductive fiber. The conductive fiber of the present invention can be used for various cloth materials or clothing materials, or can be used for industrial materials such as electromagnetic wave shielding materials, anti-static materials, electrodes, and alternative materials for electric wires. It has been known that nylon fibers or Conductive fibers are coated with a metal film on the surface of a fiber composed of polymer materials such as polyester fibers, and various methods have been tried to improve the adhesion of metal coatings. Pre-treatment of polymer materials, then combined with copper ions, and then sulfur treatment (refer to Japanese Patent No. 01-37513) or alkali treatment to roughen the fiber surface, and then attach the steel ion capture base , And then combined with copper sulfide method (refer to JP 06-298973) and other methods are well known. In addition, for those who are difficult to apply metal ore decoration such as arylamine fibers, it is also known to use polyvinylpyrrolidone (abbreviated as PVP) to attach metal ions and then reduce to form metal plating (refer to the special table) Hei 06-506267). However, the above-mentioned plating method using PW has limited types of fibers' and lacks sinkability. In addition, a coating method using a copper ion-capturing group is introduced. The metal film is also limited to copper or its compounds, and the adhesive strength of the metal film is not sufficient. There are also shortcomings such as β ^ ^ ^ ^ ______, and alkali treatment. · This paper Standards are applicable to China National Standard (CNS) A4 specifications (210 x 297 mm) 1 311634 (please read the notes on the back before filling in this page) 0 n. ^ 1- ^ BJf nn
I I 線、 469448 經 濟 部 智 慧 財 產 局 員 X 消 費 合 作 社 印 製 A7 B7 五、發明說明6 ) 纖維表面粗糙化’雖然能提高金屬被膜之黏附強度，但是 粗糖化程度和金屬被膜狀況要適妥始能獲得充分的效果。 另外’以往製造白色導電性纖維之方法，已知有（i )， 絲線原料中混入導電性白色成分，然後嫁融紡紗之方法； (2)’使纖維體含有碳成分，然後其表面塗布白色成分之方 法[參考特開平04-2808號、特開平02-169715號、特開平 04-361613、特開昭60_126321號〗，（3)，以各種方法在原 料纖維上塗布金屬之方法[參考特開平〇7_179769號、特開 平04-263667號]等。然而，這些方法有下述問題存在。直 言之’上述（1)、（2)兩項方法所製成之導電性纖維，其體積 電阻係數在1 〇5至1 〇6 Q · cm以上，因此，做為電磁波屏 蔽用途’其導電性不足，僅限於防止帶電或防止靜電用途 上利用。又’按照上述（3)項之方法，為提高要塗布之金屬 和纖維間之黏附性，在塗布金屬之前，先施與染料之前處 理’因此’塗布之絲線受染而失去原料纖維之白色度，大 多數帶有藍色、綠色、灰色、黑色系統之顏色，所以做為 纖物或布料等用途時造成問題。 其他，尚已知有在有機纖維上鍍銀而做為導電性填充 材料或電磁波屏蔽材料用之銀被覆纖維，然而該纖維最長 也不過20cm左右，並非具有汎用性質之連續性絲線。藉 妨紗工程捲裝在軸上狀態的連續性絲線上施與锻金屬外， 捲綑的連續性絲線的内部鍍液無法充分滲透進去，大部分 成為鍍斑顯著之不良品，很難獲得連續性絲線之整體表面 上施有均勻之金屬鍍飾的製品。 本紐尺度適用%國家標準（CNS)A4規格⑽X 297公釐)------- 2 311634 Γ晴先閱讀背面之注意事項再壤寫本買> 訂---------尊 469448 A7 __________B7__ 五、發明說明（3 ) 本發明乃解決已往之白色導電性纖維上之上述問題， 在捲裝之連續性絲線之狀態下，也能提供在整體表面上具 有均勻的金屬鍍飾、白色度高且導電性優異之白色導電性 纖維，以及其製造方法。本發明更進而提供具有黏附強度 優異的金屬被膜，具有高導電性和金屬被覆強度優異之導 電性金屬被覆纖維。另外，本發明也提供上述導電性纖維 之製造方法以及其設備。 導電性緻錐 本發明乃有關纖維體上設置金屬被膜而成導電性纖 維’其特徵為具有50以上之白色度（利用Lab法之L值表 示者）和100Ω . cm以下之體積電阻係數之導電性纖維β 本發明更進而有關於纖維體上設置金屬被膜而成之導電性 纖維中’具有掛桔表皮狀之金屬被膜表面為特徵之導電性 纖維者。 本發明之導電性纖維以具有50以上之白色度值） 和100Ω· cm以下之體積電阻係數，並且具有柑桔表皮狀 之金屬被覆膜表面為特徵之導電性纖維為宜。纖維體可使 用聚酯纖維、尼龍纖維或丙烯酸系纖維。又，金屬被膜可 使用銀、金、白金、鎳、錫、鋅、la或其合金。又以白色 度（L值）在55以上，體積電阻係數在0.1 Ω · cm以下，金 屬被覆膜係表面粗糙度為〇.〇1至Ιμιη之柑祜表皮狀之導 電性纖維為更佳 本發明有關之上述導電性纖維以連續性之長絲線狀態 而獲得，因此’便於提供織布等用途，可廣泛應用在衣料 (請先閱讀背面之注意事項再填寫本頁} "裝--------訂！！線、 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 3 311634 46 944 8 A7 經 濟 部 智 慧 財 產 局 員 X 消 費 合 作 社 印 製 五、發明說明ς ) 品或各種布料用途。又，由於具備高導電性，因此.藉少量 織在基材中就能發揮優異之導電性，並且不影響基材之色 調和風格。更可以廣泛地利用在電磁波屏蔽材料等各種導 電性材枓方面。又，具有優美的白色性質，所以混妨在白 色度高之衣服或基材中也能製得不影響原有色調之製品。 同時，所使用之纖維種類屬於廣泛性高之尼龍、聚酯、丙 烯酸系纖維之連續性絲線，所以可提供廣泛用途上利用。 又’本發明之導電性纖維具有柑桔表皮狀（香橙皮或粗 果皮狀），因此具有高黏附性’具體言之，據剝離強度試驗， 金屬被膜具有3級以上之基準強度。另外，使用銀做為金 屬被膜者具有銀離子所帶來的抗菌性，因此，可提供抗菌 材料用途。其他，在設置於纖維體之金屬被覆上再施與表 面處理，例如施與防銹處理或油處理等而抑制白色性劣化 或黏附性降低，油處理可以改善纖維之滑潤性。 上述本發明之導電性纖維適用於織布或不織布、編織 品、抗菌衣料、電磁波屏蔽材料、靜電防止材料、電極或 電線之替代材料，或纖維強化塑膠之導電性增強材料用 途。 導電性鏃維之製造方法 本發明乃鍍液槽中設置具有多數導液孔之管狀固定 軸，將捲裝有原絲線之捲裝絲線體裝設在上述固定輛，經 由上述固定軸將鍍液滲透在捲裝絲線體形成經固定軸到捲 裝絲線體而流到鍍液槽的液流，在上述液流中對於原絲線 施與非電解性鍍飾為其特徵之導電性纖維之製造方法有關 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 311634 (請先閲讀背面之注意事項再填寫本頁)Line II, 469448 Member of the Intellectual Property Bureau of the Ministry of Economic Affairs X Printed by the Consumer Cooperative A7 B7 V. Description of the invention 6) Although the surface of the fiber is roughened, although it can improve the adhesion strength of the metal coating, the degree of coarse saccharification and the condition of the metal coating can be obtained only after proper Full effect. In addition, 'the conventional method of manufacturing white conductive fibers is known as (i), a method in which a conductive white component is mixed in a silk material and then spun into a yarn; (2)' the fiber body contains a carbon component, and the surface is coated Method of white component [Refer to JP 04-2808, JP 02-169715, JP 04-361613, JP 60_126321] (3), the method of coating metal on raw fiber by various methods [Reference Japanese Patent Application No. 07_179769, Japanese Patent Application No. 04-263667]. However, these methods have the following problems. To put it bluntly, "the conductive fiber made by the above two methods (1) and (2) has a volume resistivity of 105 to 1.06 cm · cm. Therefore, it is used for electromagnetic wave shielding" and its conductivity is Insufficient use is limited to prevent electrification or prevent static electricity. Also 'according to the method of item (3) above, in order to improve the adhesion between the metal to be coated and the fiber, before coating the metal, first apply a dye before treatment'. Therefore, the coated yarn is dyed and the whiteness of the raw fiber is lost. , Most with blue, green, gray, black system colors, so when used as fiber or cloth and other purposes cause problems. Others are also known as silver-coated fibers that are plated with silver on organic fibers as a conductive filler or electromagnetic wave shielding material. However, the longest fibers are only about 20 cm long and are not continuous filaments with general properties. With the help of yarn engineering, the continuous wire on the shaft is applied with wrought metal, and the inner plating solution of the continuous wire of the bundle cannot be fully penetrated, and most of it becomes a defective product with significant plating spots. It is difficult to obtain continuous The entire surface of the sexual thread is coated with a uniform metal plating article. This New Zealand standard applies to the National Standard (CNS) A4 specification (X 297 mm) ------- 2 311634 Γ Read the notes on the back first and then buy the manuscript > Order --------- Respect 469448 A7 __________B7__ V. Description of the invention (3) The present invention solves the above problems on the past white conductive fibers. Under the condition of continuous filaments in the package, it can also provide uniform metal plating on the entire surface. , White conductive fibers with high whiteness and excellent conductivity, and a method for manufacturing the same. The present invention further provides a conductive metal-coated fiber having a metal coating film having excellent adhesion strength, high electrical conductivity, and excellent metal coating strength. The present invention also provides a method for producing the above-mentioned conductive fiber and an apparatus therefor. The present invention relates to a conductive fiber formed by providing a metal coating on a fibrous body, and is characterized in that it has a whiteness of 50 or more (expressed by the L value of the Lab method) and a volume resistivity of 100 Ω. Cm or less. Sexual fiber β The present invention further relates to a conductive fiber characterized by having a surface of a metal coating with an orange skin-like shape among conductive fibers formed by providing a metal coating on a fibrous body. The conductive fiber of the present invention is preferably a conductive fiber having a volume resistivity of at least 50) and a volume resistivity of 100 Ω · cm or less, and having a citrus skin-like metal coating film surface. As the fiber body, polyester fiber, nylon fiber, or acrylic fiber can be used. As the metal film, silver, gold, platinum, nickel, tin, zinc, la, or an alloy thereof can be used. The whiteness (L value) is more than 55, the volume resistivity is less than 0.1 Ω · cm, and the metal-coated film has a citrus skin-like conductive fiber with a surface roughness of 0.01 to 1 μm, which is more preferable. The above-mentioned conductive fibers related to the invention are obtained in a continuous filament state, so 'easy to provide woven fabrics, etc., can be widely used in clothing (please read the precautions on the back before filling out this page} " equipment ----- ----- Order !!! Line, printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is printed in accordance with China National Standard (CNS) A4 (210 X 297 mm) 3 311634 46 944 8 A7 Member of the Intellectual Property Bureau of the Ministry of Economic Affairs X Printed by Consumer Cooperatives 5. Invention Descriptions) or various fabric uses. In addition, since it has high conductivity, it can exhibit excellent conductivity by weaving a small amount in the base material without affecting the color tone and style of the base material. It can be widely used in various conductive materials such as electromagnetic wave shielding materials. In addition, it has beautiful white properties, so it is possible to make products that do not affect the original color tone even in clothes or substrates with high whiteness. At the same time, the types of fibers used are continuous yarns of nylon, polyester, and acrylic fibers with high versatility, so they can be used in a wide range of applications. Furthermore, the conductive fiber of the present invention has a citrus skin (tangerine peel or coarse peel) and therefore has high adhesion '. Specifically, according to a peel strength test, the metal film has a standard strength of 3 or more. In addition, those who use silver as the metal coating have antibacterial properties due to silver ions, and therefore can be used as antibacterial materials. In addition, the metal coating provided on the fibrous body is subjected to a surface treatment, such as anti-rust treatment or oil treatment, to suppress whiteness deterioration or decrease in adhesion. Oil treatment can improve the smoothness of the fiber. The above-mentioned conductive fiber of the present invention is suitable for use as a woven or non-woven fabric, knitted fabric, antibacterial clothing, electromagnetic wave shielding material, antistatic material, electrode or wire substitute material, or fiber-reinforced plastic conductive material. Method for manufacturing conductive tritium. The present invention is provided with a tubular fixed shaft having a large number of liquid-conducting holes in a plating bath, and a rolled wire body wound with a raw silk thread is installed on the fixed vehicle, and the plating solution is passed through the fixed shaft. A method for producing a conductive fiber characterized by infiltrating the package thread body through a fixed shaft to the package thread body and flowing into a plating solution tank, and applying non-electrolytic plating to the original thread in the liquid flow. Regarding the paper size, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applicable. 311634 (Please read the precautions on the back before filling this page)
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Mff $ &M [F OHO · o 3 δ· JM , ^$r Ά s 於爹卡1迴辦翁咖(ozs»4弟孩¢210 X 297中喊> ^ ins 469448 A7 B7 五、發明說明$ ) 白色度和高導電性之白色導電性纖維。 原料絲線可使用聚酯、尼龍、丙烯腈等之連續性絲線。 已往’上述連續性絲線在固定軸上以上下相同粗細情況下 捲裝時，要在整體絲線上均勻地施與金屬被覆膜甚為困 難’因此，這種連續性絲線無法製成像本發明一樣兼具有 白色度和導電性皆高之白色導電性纖維。已往之導電性纖 維雖然有白色度在55左右者，但其導電性低，達不到電磁 波屏蔽之水準’另一方面，能滿足電磁波屏蔽水準的，其 白色度在40左右，並且還帶有各種色調，因此，其用途有 限0 本發明之導電性纖維乃係連續性絲線捲裝在固定軸之 狀態下，在連續性絲線之整體表面上施與均勻地鍍銀處 理’其中較佳的是將鍍銀等保持在0.2至Ι.Ομηι厚度下施 與均勻被覆處理，藉此獲得白色度為50以上，其中較佳的 是白色度55以上，同時體積電阻係數在ι〇〇Ω · cm以下， 其中較佳為0.1Ω .cm以下’具有美麗白色而導電性高的 由連續性絲線所構成之白色導電性纖維。 另外，本發明之導電性金屬被覆纖維之特徵為被覆在 纖維體之金屬被覆臈之表面呈現柑桔表皮狀。所謂柑桔表 皮狀（orange peel)乃指呈顯柑桔表皮狀之粗糙表面狀態， 在曰本另稱為香橙皮狀或粗梨皮狀等狀態者《金屬被覆膜 表面呈現柑桔表皮狀乃係指該金屬被覆膜表面之狀態如同 掛桔表皮狀之粗糙表面狀態。當金屬被覆膜表面具有措插 表皮狀時，其中最好是由下述適當粒徑之金屬粒狀物所形 C請先閱讀背面之注^^^wκ項再填寫本頁) ! I!— 訂----— II--線、 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 7 311634 46 944 8 A7 ______B7___ _ 五、發明說明（8) 成時，該金屬被覆膜具有高黏附強度，因此，其耐久性優 異。 (請先閱讀背面之注意事項再填寫本頁) 該柑桔表皮狀物由金屬被覆膜表面之微細金屬粒狀物 所形成。本發明有關之金屬被覆膜之掛桔表皮狀物係由粒 徑為0.01至Ιμπι之金屬粒狀物所形成，即，具有0.01至 Ιμιη之表面粗糙度為宜，其中以具有0_05至0·5μηι之表面 粗糙度為更佳。又，金屬被覆膜之表面粗链度小於Ο.ΟΙμηι 時，被覆膜表面呈現光滑外觀，且金屬被覆膜厚而容易剝 落。相反地，表面粗糙度大於Ιμιη時，金屬粒狀物容易剝 落而不佳。 經濟部智慧財產局員工消費合作社印製 當被覆在纖維體之金屬被覆膜具有Ο.ΟΙμπι至Ιμιη之 表面粗糙度的柑桔表皮狀態時，該金屬被覆膜具有高黏附 強度。具體言之，雖然隨金屬被覆膜之鍍飾方法也有所不 同，在依據日本工業標準JIS L0849所記載之剝離強度試 驗具備污染判定標準在3級以上之剝離強度（3級以上強 度）。上述標準試驗（即JIS L0 849)乃測試纖維或布之染色 堅牢度有關試驗，染色布料上重疊以白布，在所定荷重下 按照所規定次數進行摩擦，由白布上之污染情形判斷染色 之附著性者。依據污染度之高低順序（即附著性之低高順序） 訂定1至5等級，即5級之污染度最低，所以黏附性也最 高。本發明之金屬被覆纖維據試驗在3級以上，大概具備 4至5級之高黏附強度。 上述甜桔表皮狀之金屬被覆膜由調整鍍飾條件，特别 是鍍飾成長速度而形成之。金屬鍍飾在開始後於底材（纖維 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 8 311634 469448 經 濟 部 智 慧 財 k 局 員 工 消 費 合 作 社 印 製 9 A7 B7 五、發明說明（9) 表面）上產生金屬粒狀物之種核，由種核之成長而成為被覆 膜。該時，鍍飾溫度過高，觸媒量過多時，鍍飾成長速度 過快，在底材表面上同時產生多數之超微粒狀之金屬粒狀 種核（具體而言，表面呈現平坦狀），不能成為具有優異之 黏附性的緻密金屬被覆膜。相反地，以適當成長速度進行 鍍飾者’開始鍍飾後在底材表面所產生之金屬粒狀物做為 種核，保持金屬粒狀物形狀之下慢慢成長，因此，可成為 黏附性優異的緻密金屬被覆膜。又，如同前述，金屬被覆 膜表面之柑桔表皮狀態隨施工條件等而異，不能依據金屬 被覆膜之膜厚而概論之。因此，金屬被覆膜不論其膜厚以 具有柑桔表皮狀為重要。當然’金屬被覆膜過厚時還是容 易剝落這一點是不變的。但是’具有相同膜厚時，柑桔表 皮狀之被覆膜黏附強度大，較之表面平滑的被覆膜不容易 剝離。 本發明之金屬被覆纖維所使用纖維之種類，例如聚 酯、聚醯胺、丙烯酸、聚烯烴、尼龍等高分子材料為主要 成分的纖維，以及木棉或人造絲等纖維素系材料由上述 高分子材料和纖維素系材料所構成有機纖維之外，玻璃纖 維等無機纖維，或金屬纖維包含在内之材料所複合形成之 纖維等皆可使用。其中對於聚醋纖維、丙缔酸鐵維、尼龍 纖維等較為有用。特別是聚醋長纖維本來狼難被覆處理， 藉本發明方法可得黏附強度高之金屬被覆纖維。這些纖維 之單纖維粗細以0.1至15丹尼爾者為較適宜。該纖維徑小 _L ^ ^ i時’纖維強度不足而不宜，但是纖維徑大於 本紙張尺度規格(210 x 297公釐----- 311634 (請先閱讀背面之注意事項再填寫本頁) vm--------訂--------線. 4 6 944 8 A7 經濟部智慧財產局員工消費合作社印製 五、發明說明Q ) 丹尼爾時’施與金屬被覆膜處理時’纖維變硬而失去可 撓性也不佳。 被覆在纖維體表面用之I盈德艇# & 一 用之金屬種類並無特別限制。具體 而言’例如銀、金、白* 金鋼、鎳、錫、鋅、鈀以及上述 之口金等。其中’為獲得白色導電性纖維，可使用銀、白 金錫、鎳以及其合金等具有白色光澤之高導電性之金屬 類金屬可藉電鍵，化學鍵或真空蒸鑛等方法覆蓋在 、屬體表面上上述金屬被覆膜能具有上述柑桔表皮狀之 條件或方法之外，其他加工條件不再有任何限制。 依據本發明在纖維體上覆蓋以具有柑桔表皮狀之金屬 被覆膜，可得黏附強度優異之導電性纖維。具體而言，單 纖維之比電阻（體積電阻）在〇 〇1 ◦ · cm以下，其中以〇 〇〇1 Ώ . cm以下為較宜，最佳能得1〇-4至1〇.5q ·⑽左右之 導電性纖維。另外，特別是使用銀或白金、鎳、錫等白色 光澤金屬被覆者可得白色度（L值）在50以上之白色度高之 導電性纖維。又’上述白色度乃依據罕特氏之Lab值法所 測定。 已往，已知有各種白色導電性纖維之存在，但纖維材 料本身混入導電性白色成分而製造者，其比電阻（體積電阻 係數）較高在104至1〇6Ω · cm以上，做為電磁波屏蔽材料 用途而言，其導電性不足。又，使用染料前處理纖維之後， 塗有金屬被覆膜時，已知可得0.01Ω .cm左右之導電性纖 維’然而這是屬於帶藍色或綠色系統之纖維，並未得白色 度高之導電性纖維。相對地，本發明之金屬被覆纖維藉形 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 10 311634 <請先間讀背面之注意事項再填寫本頁) ，裝 • n ----訂----- 線、 d6 944 8 A7 經 濟 部 智 慧 財 k 局 員 工 消 費 合 作 社 印 製 五、發明說明L ) 成柑桔表皮狀之金屬被覆膜而提升其黏附性，因此，、、有 染料所導致著色，所以具有高白色度且由被覆膜之 度（黏附強度）大而具有優異之導電性。 又’本發明之金屬被覆纖維藉使用銀做為被覆用金 屬’可得白色性和導電性優異之外’同時藉銀離子而得抗 fe性優異之特性。本發明有關之銀被覆纖維可長時間麵常 釋放微量（例如Ippb至lppm)之銀離子，所以能長時間保 持抗菌性。 ' 本發明之金屬被覆纖維在金屬被覆之外，再施與表面 處理。上述表面處理之例舉如防銹處理或油處理等。施與 防錄處理可防止白色度之經時性劣化或黏附性（剝離強度） 之降低。又，施與油處理時，可提升纖維表面之滑性。又， 該油處理係在利用織機或編機加工纖維之際，能提升其滑 性有助於保護金屬被覆膜之黏附性。 這些表面處理和前工程所進行纖維之脫脂處理或活化 處理一樣可在第2圖所示鍍飾裝置’將處理液加壓楯環而 進行°防銹劑可使用例如銀用水溶性變色防止劑（商品名. 開士來特ACW-1，開士特公司製品），金銀變色防止劑（商 w名*預塗布-AG ’曰本高純度化學公司製品），銀變色防 止劑（商品名：EL，曰進化成公司製品）等。又，油處理劑 可使用得利汪480(商品名）和SMA-2(商品名）之混合物為 適宜。 . " 本發明之金屬被覆纖維可提供織布或不織布等布料或 編物材料等用途。該時，使用銀或錫、鎳等者具有高白色 本紙張尺"擊4規格⑵〇 χ 297公髮） 311634 讀先閲讀背面之注意事項再填寫本頁) 裝-!訂.·!t V line. a e ΰ 仁 仁 s A7 W7 .Θ 'Fortunately s purple Ba4 V price choose meal preparation.瘅 捧 捧 1¾ Potential Umbrella ss Poison Oblique Bird Net Base «4 δ- © Φ ^ ¢ 4 v ^ p ir β $. Β s' 4, ΛΓ 1 Μ, ^ Booz-Meal Solution Net * Weng Zaixuan Female Female Office-Lr β B & 4, ^ 4 $ rf ^ Jiantiao • Xu Pei's Yu Bu Po tearing ♦ Holding the net "L " Weng% Telluride Art Destruction Bu Bang 0 Branch Ϊ UM.-Β fr @ Ϊ s- $ ^ β $, β ^ $, β 4 4 ρ Μ, $ β Λ1 ¢, Λ 秦 嫜 嫜 烯 烯 ϊ ϊ ϊ.獐 獐 辩 裨 fr 暴 -s ^ ^ -s ^ $ t E ^ ts ^ r $ ^ Μ $ β 4 j S Zhi & Weng Jing I want to h $ axe speed review net 碓 吾 彦 系 翁Pure miscellaneous tears. Dare to fry though S 擗 _ material Jia 埤 Mai Bu holding 嫜 stick Xu Xu. -B 9 s ^ s ^ S ΐ Jn ^ ^ H ^ ^ s o 铖 2 迩 哥 _ 旖 黎 餐 杂 Θ 杂 旖 穿 ® Θ 契 乱 1.铖 3 迩 Speaking of squinting oblique honey: ¾ ^ Weng Jingji 3 people Huang 9 Weng Cai painting. ^ p 0 ^ r $ s nNJ ^ νβ ^ β ^ A- ^ a $ i ^ r ^ r L ^ rp ^. Mr 0rm > son Twisting s meeting y: rvId 诹 诹 姆 亦 —meal 4Γ ^ ψ S Λ1 Μ, Λ β $, Sr ΰ ΛΜ7 ^ β Μ ,, $ rs, ^ ^ 0 Μ, ϊ卷卷 5 雔 着 决 次 决--Comment on 桊 ❿ ❿ ❿ L (L at > Xu-Γ 麻) and 5 0 pr up * 祆 本 外 55 交 卜 q 杂 杂 -¾: MOOD »03 JM. Mff $ & M [F OHO · o 3 δ · JM, ^ $ r Ά s Yu Da Ka 1 back to Weng Ka (ozs» 4 younger children ¢ 210 X 297 shouting > ^ ins 469448 A7 B7 V. Description of the invention $) White conductive fiber with whiteness and high conductivity. As the raw yarn, continuous yarns such as polyester, nylon, and acrylonitrile can be used. In the past, it is difficult to uniformly apply a metal coating on the entire wire when the above-mentioned continuous wire is wound on the fixed shaft with the same thickness above and below. Therefore, such a continuous wire cannot be made like the present invention. Both white conductive fibers with high whiteness and high conductivity. In the past, although the conductive fiber has a whiteness of about 55, it has low conductivity and does not reach the level of electromagnetic wave shielding. On the other hand, those that can meet the level of electromagnetic wave shielding have a whiteness of about 40 and also have Various colors, therefore, its use is limited. 0 The conductive fiber of the present invention is a state where a continuous yarn is wound on a fixed shaft, and uniform silver plating is applied to the entire surface of the continuous yarn. The silver plating and the like are maintained at a thickness of 0.2 to 1.0 μηι and subjected to uniform coating treatment, thereby obtaining a whiteness of 50 or more, of which a whiteness of 55 or more is preferred, and a volume resistivity is less than ιωΩ · cm Among them, it is preferably 0.1 Ω.cm or less, which is a white conductive fiber composed of continuous filaments with beautiful white color and high conductivity. In addition, the conductive metal-coated fiber of the present invention is characterized in that the surface of the metal-coated fiber coated on the fibrous body is citrus-like. The so-called orange peel refers to the rough surface state of the citrus skin. In the Japanese version, it is also called orange peel or rough pear skin. The surface of the metal coating film is citrus skin. The state refers to the rough surface state of the surface of the metal coating film like the skin of a hanging orange. When the surface of the metal coating has a plug-in skin shape, it is best to be shaped by metal particles of the appropriate particle size as described below. C Please read the note on the back ^^^ wκ before filling this page)! — Order ----— II-line, printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, this paper is printed in accordance with China National Standard (CNS) A4 (210 X 297 mm) 7 311634 46 944 8 A7 ______B7___ _ 5 Explanation of the invention (8) At the time of completion, the metal coating film has high adhesion strength, and therefore has excellent durability. (Please read the precautions on the back before filling this page.) The citrus skin is formed by fine metal particles on the surface of the metal coating. The orange-coated skin of the metal-coated film according to the present invention is formed of metal particles having a particle diameter of 0.01 to 1 μm, that is, it has a surface roughness of 0.01 to 1 μm, and it is preferable to have a surface roughness of 0 to 05 to 0 ·. A surface roughness of 5 μηι is even better. In addition, when the surface coarse chain degree of the metal coating film is less than 0.01 μm, the surface of the coating film exhibits a smooth appearance, and the metal coating film is thick and easily peeled off. Conversely, when the surface roughness is larger than 1 μm, the metal particles are liable to peel off and are not good. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. When the metal coating film covering the fiber has a citrus skin state with a surface roughness of 0.001 μm to 1 μm, the metal coating film has high adhesion strength. Specifically, although the plating method varies depending on the metal coating film, the peel strength test according to the Japanese Industrial Standard JIS L0849 has a peel strength of pollution level 3 or higher (strength 3 or higher). The above standard test (ie JIS L0 849) is a test for measuring the fastness of dyeing of fiber or cloth. White cloth is superimposed on the dyed cloth, and rubbed at a specified number of times under a specified load. The contamination of the white cloth is used to judge the adhesion of the dyeing. By. According to the order of the pollution degree (that is, the order of low adhesion to high), grades 1 to 5 are set, that is, the pollution degree of grade 5 is the lowest, so the adhesion is the highest. According to the test, the metal-coated fiber of the present invention has a grade of 3 or more, and has a high adhesion strength of grades 4 to 5. The sweet orange skin-like metal coating film is formed by adjusting the plating conditions, especially the growth rate of the plating. Metal plating is printed on the substrate after the start (the size of the fiber paper is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 8 311634 469448 Printed by the staff consumer cooperative of the Bureau of Intellectual Property of the Ministry of Economic Affairs 9 A7 B7 V. Invention Explanation (9) The seed nucleus that produces metal particles on the surface) becomes a coating from the growth of the seed nucleus. At this time, when the plating temperature is too high and the amount of catalyst is too large, the growth rate of the plating is too fast, and a large number of ultra-fine particulate metal grain seed nuclei are produced on the substrate surface at the same time (specifically, the surface is flat) , Can not be a dense metal coating film with excellent adhesion. Conversely, those who are plated at a proper growth rate, 'the metal particles produced on the surface of the substrate after plating start, are used as seed nuclei, and grow slowly under the shape of the metal particles, so they can become adhesive. Excellent dense metal coating. Also, as mentioned above, the state of the citrus skin on the surface of the metal coating film varies depending on the construction conditions and the like, and cannot be generalized based on the film thickness of the metal coating film. Therefore, it is important that the metal coating has a citrus skin shape regardless of its thickness. Of course, when the metal coating is too thick, it is easy to peel off. However, with the same film thickness, the citrus skin-like coating film has a strong adhesive strength, and is not easily peeled off compared to a coating film having a smooth surface. The types of fibers used in the metal-coated fibers of the present invention, for example, fibers containing polymer materials such as polyester, polyamide, acrylic, polyolefin, and nylon as main components, and cellulose-based materials such as kapok or rayon are composed of the above polymers In addition to organic fibers composed of materials and cellulose-based materials, inorganic fibers such as glass fibers, or fibers formed by combining materials including metal fibers can be used. Among them, it is useful for polyester fiber, iron acrylate and nylon fiber. Particularly, the long polyester fiber is difficult to be coated, and the metal-coated fiber with high adhesion strength can be obtained by the method of the present invention. The single fiber thickness of these fibers is preferably from 0.1 to 15 deniers. When the fiber diameter is small _L ^ ^ i, the fiber strength is insufficient, but the fiber diameter is larger than the paper size specification (210 x 297 mm ----- 311634 (Please read the precautions on the back before filling this page) vm -------- Order -------- line. 4 6 944 8 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention Q) Daniel's application of metal coating During processing, the fibers hardened and lost flexibility. There is no particular limitation on the type of metal used for covering the surface of the fiber body. Specifically, 'e.g., silver, gold, white * gold steel, nickel, tin, zinc, palladium, and the above-mentioned gold. Among them, in order to obtain white conductive fibers, silver, platinum tin, nickel and its alloys, which have high whiteness and high conductivity, can be used to cover the surface of the metal body by electrical bonds, chemical bonds or vacuum evaporation. In addition to the above-mentioned citrus skin-like conditions or methods, the above-mentioned metal coating film is not subject to any restrictions on other processing conditions. According to the present invention, the fibrous body is covered with a metal coating film having a citrus skin shape, and conductive fibers having excellent adhesion strength can be obtained. Specifically, the specific resistance (volume resistance) of the single fiber is less than 0.001 ◦ · cm, and preferably less than 0.001 Ώ. Cm, and the best result is 10-4 to 10.5q. ⑽ Left and right conductive fibers. In addition, it is possible to obtain conductive fibers having a high whiteness (L value) of 50 or more with a white gloss metal coating such as silver or platinum, nickel, and tin. The above-mentioned whiteness was measured according to Hunt's Lab value method. In the past, various white conductive fibers are known to exist, but the fiber material itself is mixed with conductive white components and the manufacturer has a higher specific resistance (volume resistivity) of 104 to 106Ω · cm or higher, which is used as electromagnetic wave shielding. In terms of material use, its conductivity is insufficient. In addition, after pre-treatment of the fibers with dyes, it is known that conductive fibers of about 0.01 Ω.cm can be obtained when coated with a metal coating. However, this is a fiber with a blue or green system, and it does not have high whiteness. Conductive fiber. In contrast, the paper size of the metal-coated fiber borrow paper of the present invention is in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 10 311634 < Please read the precautions on the back before filling in this page). n ---- Order ----- line, d6 944 8 A7 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of invention L) Form a citrus skin-like metal coating to improve its adhesion, Therefore, because of the coloration caused by dyes, it has high whiteness, and has a high degree of adhesion (adhesion strength) of the coating film, and has excellent electrical conductivity. In addition, "the metal-coated fiber of the present invention uses silver as the coating metal" to obtain properties other than excellent whiteness and conductivity, and also uses silver ions to obtain excellent fe resistance. The silver-coated fiber of the present invention can release a small amount of silver ions (for example, Ippb to 1 ppm) over a long period of time, so it can maintain antibacterial properties for a long time. '' The metal-coated fiber of the present invention is subjected to a surface treatment in addition to the metal coating. Examples of the surface treatment include rust prevention treatment and oil treatment. The anti-recording treatment can be used to prevent deterioration of the whiteness over time or decrease in adhesion (peel strength). Moreover, when the oil treatment is applied, the slipperiness of the fiber surface can be improved. In addition, this oil treatment can improve the sliding property and protect the adhesion of the metal coating film when the fiber is processed using a loom or a knitting machine. These surface treatments can be performed in the same way as the degreasing treatment or activation treatment of the fibers used in the previous process. The plating solution shown in FIG. Product name. Cashelite ACW-1, product of Cashel Company), gold and silver discoloration preventive agent (commercial name * pre-coated-AG 'Yueben High Purity Chemical Co., Ltd.), silver discoloration preventive agent (brand name: EL , Said to evolve into company products) and so on. As the oil treatment agent, a mixture of Deliwang 480 (trade name) and SMA-2 (trade name) can be suitably used. " The metal-coated fiber of the present invention can be used for cloth or knitted materials such as woven or non-woven fabrics. At this time, use silver, tin, nickel, etc. have a high white color. This paper ruler "click 4 specifications ⑵〇 χ 297 public hair) 311634 Read the precautions on the back before filling in this page) Installation-! Order. ·!
I I 線、 46 9448 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（么 度’所以染色之際具有優異之顯色性，適用於織物或衣料 品等之布料用途。又’使用銀等塗布者可提供抗菌纖維和 抗菌衣料用途。具體之用途有抗菌性襪子、内衣、上衣、 白衣、寢具、被單、餐巾、手套、襯衫、長褲或工作衣等。 又’本發明之金屬被覆纖維不限於布料等材料，尚可利用 導電性做為電磁波屏蔽材料、無塵衣服或手套、鞋子、覆 蓋物、工作衣等靜電防止材料，或電極或電線等輕量化為 目的之替代材料用途。更可以做為纖維強化塑膠之導電性 補強材料使用。 (Π)製造方法和製递f罟 製造本發明之導電性纖維用裝置之例舉之一示於第1 圖。如第1圖所示’本發明之鍍飾裝置備有鍍液槽（10)， 鍍液貯槽（20) ’連接鍍液槽（〗〇)和鍍液貯槽（20)用之輸液管 (31和32) ’介於輸液管中之輸液泵（40)。鍍液槽（1〇)之上 方藉蓋子（13)加以封蓋。該鍍液槽（1 〇)内部設有將原料絲線 以長方形狀捲裝體（50)按裝用之固定軸（11)。該固定軸（11) 由中空之管材而形成，其管壁上設有多數之導液孔（12)。 圖示中之裝置例舉中，該固定軸（11)豎立在鍍液槽（1〇)之底 部’其頂部用栓蓋（16)封止。又，固定軸（11)為便於按裝捲 裝體（50)，另外，當捲裝體之芯部（51)之直徑不相同時也能 適應’以可以自由裝卸狀按裝在槽底。連通該固定轴（11) 以供液用之輸液管（31)連接之。經過該輸液管（31)藉輸液栗 (40)由貯槽（20)輪送鍍液到固定軸（11)，由設置在固定軸 (11)之管壁上的多數導液孔（12)供應鍍液到槽内。又，鍍液 {請先間讀背面之注意事項再填寫本頁) ，束 i !—訂-- - --- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 12 311634 ! 6 9448 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（I3 ) 槽（11)之上側和下側之側面部分分別連接有通到貯槽（20) 用之排液用輸液管（32)，藉上述輸液管（31)、（32)形成鍍液 之循環系統。輸液管（31)、（32)在適當地方設有開關閥 (33) 〇 另一方面’如第2圖所示原料絲線以上下相同粗細狀 態捲繞在透水性的中空捲芯（51)上而形成捲裝絲線體 (50)’固定軸（11)以貫串上述捲芯（5 〇狀，將捲裝絲線體（5〇) ***固定軸（11)加以安裝。必要時捲裝絲線體（5〇)可以上下 複數段狀安裝之。第2圖所示例舉中分為上下二段安裝。 安裝有捲裝絲線體（50)之固定軸（11)之頂部設置以固定板 (14)。該固定板（14)之中央部分存有螺絲孔（17)，藉這螺絲 孔（17)以螺絲固定在固定軸（11)之頂部。固定板（14)擠攏在 捲裝絲線體（50)’旋塞在固定軸（11)之軸頂而上下擠壓捲裝 絲線體（50)，使固定板（14)和捲裝絲線體（5〇)相互間不留空 隙而防止鍍液由此空隙漏溢。更進而在上下捲裝絲線體（5〇) 之間’以及下側之捲裝絲線體（5〇)和鍍液槽底部之間設有 調距板（15)而防止這部分之溢漏。 又，圖示之裝置中，固定軸（11)以豎立在槽内狀設置， 也可以將固定軸（11)橫放，能自由裝卸狀態下安裝在鍍液 槽之侧壁上。圖示例舉中將固定軸（u)以自由裝卸狀態下 豐立，乃係求其方便取出來。又，固定抽⑴）橫放而設置 時，在轴内流動的鍍液流壓能均勻而較佳。 上述裝置之構造中，將捲裝絲線體（5〇)***鍍液槽（1〇) 之固定軸（11)而安裝，在上下之捲裝絲線體（5〇)之間以及捲 私紙張尺度適用中關家標準（CNS〉A4規格咖x 2g ) 13 311634 (請先閱讀背面之注意事項再填寫本頁)Line II, 46 9448 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (Modo 'so it has excellent color rendering when dyeing, and it is suitable for the use of fabrics such as fabrics or clothing.' Applicants such as silver can provide antibacterial fibers and antibacterial clothing. Specific applications include antibacterial socks, underwear, tops, white clothes, bedding, sheets, napkins, gloves, shirts, trousers, or work clothes. Metal-coated fibers are not limited to materials such as cloth. They can also use conductivity as an electromagnetic wave shielding material, dust-free clothes or gloves, shoes, coverings, work clothes and other static prevention materials, or lightweight materials such as electrodes or wires. Uses. It can also be used as a conductive reinforcing material for fiber-reinforced plastics. (Π) Manufacturing method and manufacturing process f 制 One example of a device for manufacturing the conductive fiber of the present invention is shown in Fig. 1. As shown in Fig. 1 "The plating device of the present invention is provided with a plating solution tank (10) and a plating solution storage tank (20)", and an infusion tube (31 and 32) for connecting the plating solution tank (〖〇) and the plating solution storage tank (20) 'The infusion pump (40) is located in the infusion tube. The top of the plating bath (10) is closed by a cover (13). The plating bath (10) is provided with a raw material wire wrapped in a rectangular shape. The body (50) is according to the fixed shaft (11) for installation. The fixed shaft (11) is formed by a hollow pipe, and the pipe wall is provided with a large number of liquid guide holes (12). The device in the illustration is exemplified The fixed shaft (11) is erected on the bottom of the plating bath (10) and its top is sealed with a bolt cover (16). The fixed shaft (11) is convenient for mounting the roll body (50). In addition, When the diameter of the core (51) of the package body is different, it can also be adapted to be mounted on the bottom of the tank in a freely removable manner. The fixed shaft (11) is connected to the infusion tube (31) for liquid supply. Through the infusion tube (31), the plating solution is sent from the storage tank (20) to the fixed shaft (11) by the infusion pump (40), and is supplied by most of the liquid guide holes (12) provided on the wall of the fixed shaft (11). The plating solution enters the tank. Also, the plating solution {please read the precautions on the back before filling this page), bundle i! —Order----- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 12 311634! 6 9448 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (I3) The upper and lower side parts of the tank (11) are connected to the drain for the tank (20). The infusion tube (32) forms a circulation system of the plating solution by using the infusion tubes (31) and (32). The infusion tubes (31) and (32) are provided with an on-off valve (33) at an appropriate place. On the other hand, 'the raw material thread is wound around a water-permeable hollow core (51) in the same thickness state as shown in FIG. 2. A packaged wire body (50) 'is formed with a fixed shaft (11) in series with the winding core (50), and the packaged wire body (50) is inserted into the fixed shaft (11) for installation. If necessary, the packaged wire body ( 50) It can be installed in a plurality of upper and lower sections. The example shown in Fig. 2 is divided into two sections for installation. The top of the fixed shaft (11) on which the wire body (50) is mounted is provided with a fixed plate (14). A screw hole (17) is stored in the central part of the fixing plate (14), and the screw hole (17) is used to fix the top of the fixing shaft (11) with screws. The fixing plate (14) is squeezed into the coiled wire body (50). ) 'Cock on the top of the fixed shaft (11) and press the packaged wire body (50) up and down, so that the fixing plate (14) and the packaged wire body (50) do not leave a gap between each other, thereby preventing the plating solution The gap is leaking. Furthermore, a distance is set between the upper and lower winding wire bodies (50) and between the lower winding wire body (50) and the bottom of the plating bath. (15) to prevent this part from leaking. In the device shown in the figure, the fixed shaft (11) is erected in the groove. The fixed shaft (11) can also be placed horizontally and can be installed in a freely detached state. On the side wall of the plating bath. In the example shown in the figure, the fixed shaft (u) is plumped in a free loading and unloading state, in order to facilitate its removal. In addition, it is fixed inside the shaft when it is placed horizontally. The pressure of the flowing plating solution can be uniform and better. In the structure of the above device, the packaged wire body (50) is inserted into the fixed shaft (11) of the plating bath (10) and installed, between the upper and lower packaged wire bodies (50) and the private paper scale. Apply Zhongguanjia standard (CNS> A4 size coffee x 2g) 13 311634 (Please read the precautions on the back before filling this page)
In I 線、 469448 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（14 ) 裝絲線體（50)和槽底之間設置調距板（15)，同時將固定板 (14)旋塞在軸頂，將固定板（14)勒緊使捲裝絲線體（5〇)和調 距板（15)以及固定板（14)沒有空隙狀態下固定，防止漏液之 後，再經由輸液管（31)將鍍液導入固定軸（11)。鍍液由固定 轴（11)經過導液孔（12)流向捲裝絲線體（50)，通過透水性之 捲芯（5 1)滲透到捲裝絲線體内，部，而經由捲裝絲線體内部 流向鍍液槽（10)而形成液流。並在該液流下進行非電解鍍 飾。鍍液由鍍液槽（10)的流出量和供應到鍍液槽（10)的液量 保持平衡下使之循環流動。 具體而言，例如將聚酯長纖維等以上下相同粗細狀 捲裝而成的捲裝絲線體（50)安裝在鍍液槽（10)，使脫脂液循 環而將纖維表面進行脫脂處理後，水洗，再導入鹼液進行 蝕刻處理，然後水洗。繼之，導入濃鹽酸或硫酸溶液中和 處理之後，使用錫系或鈀系之一種或二種之混合溶液活化 處理。之後’導入銀等鍍液而進行非電解鍍飾，鍍飾後水 洗之。另外，代替鹼處理也可以使用氣化亞錫溶液處理之。 依據上述製造裝置或製造方法，鍍液經由固定轴從捲 裝絲線體内側供應而向捲裝絲線體外部流動，因此，纖維 間之孔隙被鍍液向外側推開’所以鍍液能滲透到纖維間之 細部’因此，以上下相同粗細狀捲裝狀態下，也能在纖維 表面上均勻鍍銀或鍍白金。結果，可得白色度（L值）5〇以 上’最好是55以上’而體積電阻係數在ι〇〇Ω · cni以下， 最好是0.1 Ω · cm以下之白色導電性纖維，且其造價低廉。 又，鍍飾方法上，將鍍液導入固定軸加以暫停，使貯 (請先閲讀背面之注意事項再填寫本頁) 訂---------線、 本紙張尺度適用尹國國家標準（CNSM4規格（2】0 X 297公愛 14 311634 ^ 6 9448 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（15 ) 留在锻液槽的鍵液滲透到捲裝絲線體内部，必要4，經由 固定軸將鍍液排除到系外，和上述之液流相反，由鑛液槽 經由捲裝絲線體内部流向固定軸而形成暫時性液流，藉此 可提升鍍飾金屬之均勻性。 又’具有本發明之柑桔表皮狀之金屬被覆纖維，可在 上述有機纖維等纖維體（原料絲線）表面施與電鍍或化學鍍 飾等而得柑拮表皮狀之上述金屬被覆膜。又，被覆上述金 屬被覆膜之際，可事先藉鹼等蝕刻處理纖維體表面，使表 面粗糙化之後，讓鍍飾金屬進入該粗糙面而發揮錨固效 果，因此，更為理想。 以下，藉實施例具體說明本發明，但本發明範圍不受 其偈限β 實施例1 使用第1圖所示鍍飾裝置，將聚酯多纖維（75d/36f) 5〇〇g在捲裝密度0.130g/Cm3之下輕輕捲撓成為上下相同粗 細之捲裝絲線體，然後安裝於鑛飾裝置之固定軸，按照下 列順序進行（1)脫脂處理’.（2)驗處理。中和處理.，（3)活化 處理’（4)非電解鍍飾處理。這些處理在泵壓1〇kg/cm2 ，液量1 之條件下，以加壓型藥液循環下進行。 (1) 脫脂處理：脫脂液（愛司克淋A-220，曰本奥野製 藥工業公司製品）5重量％溶液在55eC下於鍍液槽 中循環5分鐘’然後’導入離子交換水加以充分 洗淨之。 (2) 驗處理：繼之’將20重量❶/。之氫氧化鈉溶液在7〇 ^麟辟（CNS)A4 規格 〇 X 297公釐） 15 311634 (請先閲讀背面之注意事項再填寫本頁) '衮 訂---------線、. 經濟部智慧財產局員工消費合作杜印製 4 6 9 4 4 8 A7 _ B7 五、發明說明（16 ) °匸下，於鍍液槽中循環20分鐘，然後，導入離子 交換水充分洗淨之後，用5重量％之濃鹽酸溶液在 室溫下，於鍍液槽令循環2分鐘。 (3) 活化處理：將濃鹽酸溶液和氣化纪混合溶液（催化 劑C:日本奥野製藥工業公司製品）在鍍液槽中室 溫下循環3分鐘之後，導入離子交換水充分洗淨 之。繼之，用10重量％硫酸溶液在鍍液槽中45 °C 溫度下循環3分鐘而加以活化之。 (4) 鍍飾步驟：藉上述前處理，將觸媒附著在纖維表 面之後，用銀鍍液（液溫25。〇在鍍液槽中循環而 鍵銀。銀鑛液之組成分為乙二胺四乙酸四鈉 (200g/2/)，氫氧化鈉（50g/2〇，福馬林液 (l〇〇m//2/)，硝酸銀（3 6.1g)以及氨水（l〇〇m/)所構 成。又，鍍液中之銀離子全部會還原而析出，因 此，使用相當於含有被覆量之銀離子之鍍液而施 行。對於原料絲線使用20重量％(相當於125g之 銀之份量）進行鍍銀後，以水充分洗淨，在80°C下 熱風乾燥1 7小時以上。 按照上述製造步驟程所製得白色導電性纖維之端子間 電阻，體積電阻係數以及白色度之測定結果示於表1中。 另外，對於耐洗滌之耐久評估試驗結果示於表2中。又， 上述耐洗滌之耐久性試驗乃利用一般家庭用洗衣機，將試 料之導電性纖維從捲裝絲線體上解開數公尺後放入洗滌 網’按照一般洗衣方法一樣放入家庭用洗衣劑和水，進行 (請先閲讀背面之注意事項再填寫本頁) /哀--------訂——----線/ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 16 311634 經濟部智慧財產局員工消費合作社印製 469448 A7 ______B7_ 五、發明說明（Θ 洗蘇—清洗—脫水步驟為一次循環而試驗。評估乃每次循 環以SEM觀察纖維表面，並於最次之5循環和其後每1〇 循環之後測定其端子間電阻值（Ω/cm)。又，依照測定試料 之形狀也求得體積電阻值（Ω .cm)。另外，體積電阻值乃 就所用聚酯纖維1丹尼爾之長度450m以下具有〇 〇5g重 量者，從端子間電阻值換算而求得。 實施例2至5 各個捲裝絲線體之捲裝密度改為〇.182g/cm3(實施例 2)，使用粗細為40丹尼爾（40d/18f)之聚酯纖維（實施例3)， 或改鍍銀量為原料絲線之5重量％(實施例4)或50重量 %(實施例5)之外，其他皆依照實施例丨所示相同方法在纖 維表面上鍍銀而製造白色導電性纖維。其結果示於表i 中。另外’對於洗滌之耐久性試驗結果示於表2中。 實施例6 將丙烯酸系多纖絲纖維（75d/36f)以捲裝密度為 0.130g/cm3輕輕捲撓成上下相同粗細狀做為捲裝絲線體使 用，前處理以脫脂液（愛司克淋A-200 :曰本奥野製藥工業 公司製品）5重量％溶液在55 °C下，於鍍液槽中循環5分 鐘’然後導入離子交換水充分洗淨之後，用1重量％之氯 化亞錫溶液和2重量％之鹽酸溶液所構成混合溶液在鍍液 槽中室溫下循環1 0分鐘，然後，導入離子交換水充分洗淨 之外’其他皆按照實施例1同樣施與非電解鍍銀處理，而 製得白色導電性纖維。該白色導電性纖維之體積電阻和白 色度之結果示於表1中，對於洗滌之耐久性試驗結果示於 -----^---------------訂---------線} c .V. (請先閱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） 17 311634 469448 A7 ----------B7___ 五、發明說明（18 ) 表2中。 如表1中所示，本發明有關之白色導電性纖維皆呈現 美麗的乳白色，其白色度（L值）皆在5〇以上，大多數屬Η 以上。又’這些白色導電性纖維之導電性高，皆在體積電 阻係數為100 Ω .cm以下，其中大多數在〇1Ω .cm以下。 又，本發明之白色導電性纖維之金屬被覆膜之黏附性甚 佳’如表2令所示使用一般洗滌方法被覆臈也不會剝離， 具有優異之耐久性。又，重複洗滌時，其體積電阻係數之 增加比率皆报小，對於洗滌之耐久性亦優異乂 比較例1 使用和實施例1相同之聚酯多纖絲（750/36£)50(^以捲 裝密度為0.130g/cm3，輕輕捲撓成為上下相同粗細之捲裝 絲線體，經前處理之後浸潰在銀鑛液中施與鍵銀。上述前 處理液使用調整纖維之表面極性用表面處理染色液（日本 化藥公司製品：卡耶諾、米琳、綠）0.6重量％溶液和5重 量％濃度之乙酸銨溶液，以及1重量％乙酸所構成混合溶 液，以液溫98至10(TC下浸潰上述捲裝絲線體45分鐘之 後，再用離子交換水充分洗淨之。繼之，在5重量％聚羥 基苯基磺酸系固定化劑溶液（8Ό至90°C)浸潰30分鐘，然 後用離子交換水充分洗淨之後，以5重量％聚乙烯亞胺溶 液（95至98°C )浸潰30分鐘而使表面極性安定化，再用離 子交換水充分洗淨之β 上述表面處理之後，使用實施例1相同銀鍍液，將捲 裝絲線體浸潰在事先貯存有銀鍍液之鍍液槽中（在捲裝絲 (請先閲讀背面之注意事項再填寫本頁) ^ · —-----tr---------線 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 18 311634 9448In I line, 469448 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention (14) A distance adjusting plate (15) is installed between the wire body (50) and the bottom of the groove, and the fixed plate (14) The cock is on the top of the shaft, and the fixing plate (14) is tightened to fix the packaged wire body (50), the distance adjusting plate (15) and the fixing plate (14) in a state without a gap, to prevent leakage, and then through the infusion tube (31) The plating solution is introduced into the fixed shaft (11). The plating solution flows from the fixed shaft (11) through the liquid guide hole (12) to the package thread body (50), penetrates into the package thread body through the water-permeable core (5 1), and passes through the package thread body The inside flows to the plating bath (10) to form a liquid flow. Electroless plating is performed under this liquid flow. The amount of the plating solution flowing from the plating solution tank (10) and the amount of the liquid supplied to the plating solution tank (10) were circulated while maintaining balance. Specifically, for example, a package thread body (50) formed by winding polyester long fibers with the same thickness as above is installed in a plating bath (10), and the degreasing liquid is circulated to degrease the fiber surface. It was washed with water, and then lye was introduced for etching treatment, and then washed with water. After that, a concentrated hydrochloric acid or sulfuric acid solution is introduced for neutralization treatment, and then a mixed solution of one or two kinds of tin or palladium is used for activation treatment. After that, a plating solution such as silver is introduced for non-electrolytic plating, and it is washed with water after plating. Alternatively, instead of alkali treatment, a gasified stannous solution may be used. According to the above manufacturing apparatus or manufacturing method, the plating solution is supplied from the inside of the package thread body through the fixed shaft and flows to the outside of the package thread body. Therefore, the pores between the fibers are pushed outward by the plating solution, so the plating solution can penetrate the fibers. As a result, the fiber surface can be uniformly plated with silver or platinum even in the same thickness as above. As a result, a white conductive fiber having a whiteness (L value) of 50 or more, preferably 55 or more, and a volume resistivity of ιω Ω · cni or less, and preferably 0.1 Ω · cm or less, can be obtained, and its cost low. In addition, in the plating method, the plating solution is introduced into the fixed shaft and suspended for storage (please read the precautions on the back before filling this page). Standard (CNSM4 Specification (2) 0 X 297 Public Love 14 311634 ^ 6 9448 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (15) The key liquid left in the forging bath penetrates the packaged wire body Internally, if necessary, 4, the plating solution is excluded from the system via the fixed shaft. Contrary to the above-mentioned liquid flow, a temporary liquid flow is formed by the mineral liquid tank flowing to the fixed shaft through the interior of the packaged wire body, thereby improving the plating metal. It also has the citrus skin-like metal-coated fiber of the present invention, and can be electroplated or electrolessly plated on the surface of the fibrous body (raw material thread) such as the organic fiber to obtain the citrus-like skin coating. Coating. When coating the above-mentioned metal coating, the surface of the fibrous body may be treated by etching in advance with alkali or the like to roughen the surface, and then the plated metal may enter the rough surface to exert the anchoring effect. Therefore, it is more preferable. The following The examples specifically illustrate the present invention, but the scope of the present invention is not limited thereto. Example 1 Using a plating device as shown in FIG. 1, 500 g of polyester multifiber (75d / 36f) was packaged at a density of 0.130 g. / Cm3 is gently rolled to form a coiled wire body of the same thickness above and below, and then installed on the fixed shaft of the mining device, and performs (1) degreasing treatment '. (2) inspection treatment. Neutralization treatment., (3) Activation treatment '(4) Non-electrolytic plating treatment. These treatments are performed under a pump pressure of 10 kg / cm2 and a liquid volume of 1 under a pressurized chemical liquid circulation. (1) Degreasing treatment: degreasing Solution (Eskolen A-220, product of Yoshimoto Okano Pharmaceutical Industry Co., Ltd.) was circulated in a plating bath for 5 minutes at 55eC, and then ion-exchanged water was introduced and washed thoroughly. (2) Inspection Treatment: Followed by 'put 20 weight ❶ /. Of sodium hydroxide solution in 7〇 ^ 辟 (CNS) A4 size 0 × 297 mm) 15 311634 (Please read the precautions on the back before filling this page)' 衮Order --------- line ,. Consumer cooperation of Intellectual Property Bureau of the Ministry of Economic Affairs, Du printed 4 6 9 4 4 8 A7 _ B7 V. Invention theory (16) ° C, circulate in the plating bath for 20 minutes, then introduce ion-exchanged water and wash thoroughly, and then use a 5% by weight concentrated hydrochloric acid solution to circulate in the plating bath for 2 minutes at room temperature. 3) Activation treatment: After concentrating the hydrochloric acid solution and the gasification period mixed solution (Catalyst C: Japan Okano Pharmaceutical Industry Co., Ltd.) circulated in the plating bath for 3 minutes at room temperature, the ion exchange water was introduced to thoroughly wash it. Then, 10% by weight sulfuric acid solution was circulated at 45 ° C in the bath for 3 minutes to activate it. (4) Plating step: After the catalyst was adhered to the surface of the fiber by the above pretreatment, the silver plating solution was used ( Liquid temperature 25. ○ Circulate in the plating bath to bond silver. The composition of the silver ore solution is divided into tetrasodium ethylenediamine tetraacetate (200g / 2 /), sodium hydroxide (50g / 20), formalin solution (100m / 2/2), and silver nitrate (3 6.1g). And ammonia water (100m /). Since all the silver ions in the plating solution are reduced and precipitated, it is performed using a plating solution that contains silver ions corresponding to the coating amount. 20% by weight of the raw material yarn (Equivalent to 125g of silver) After silver plating, wash thoroughly with water, and dry with hot air at 80 ° C for more than 17 hours. The inter-terminal resistance and volume of the white conductive fiber obtained according to the above manufacturing steps The measurement results of electrical resistivity and whiteness are shown in Table 1. In addition, the results of the durability evaluation test for washing resistance are shown in Table 2. In addition, the above-mentioned durability test for washing resistance is conducted by using a general household washing machine to conduct the electrical conductivity of the sample. Unfasten the fiber from the packaged silk thread for several meters, and then put it into the washing net. Put the household detergent and water in the same way as normal washing methods (please read the precautions on the back before filling this page) / wai- ------- Order ——---- Line / This paper size is applicable National Standard (CNS) A4 (210 X 297 mm) 16 311634 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 469448 A7 ______B7_ V. Description of the invention (Θ Washing-washing-dehydration step is tested for one cycle. Evaluation The fiber surface is observed by SEM every cycle, and the resistance value between the terminals (Ω / cm) is measured after the last 5 cycles and every 10 cycles thereafter. The volume resistance value is also obtained according to the shape of the test sample. (Ω .cm). In addition, the volume resistance value is obtained by converting the resistance value between the terminals based on the polyester fiber used, which has a length of 450 m or less and has a weight of 0.05 g. Examples 2 to 5 Each packaged wire body The package density was changed to 0.282 g / cm3 (Example 2), using a polyester fiber with a thickness of 40 denier (40d / 18f) (Example 3), or the silver plating amount was changed to 5% by weight of the raw silk ( Except for Example 4) or 50% by weight (Example 5), the white conductive fiber was produced by plating silver on the surface of the fiber according to the same method as in Example 丨. The results are shown in Table i. Washing durability test results are shown in Table 2. Example 6 The acrylic multifilament fiber (75d / 36f) was lightly wound at a package density of 0.130 g / cm3 into the same thickness as the upper and lower threads, and the pre-treatment was performed with a degreasing solution (Aix Kelin A-200: product of Ben Okuno Pharmaceutical Co., Ltd.) 5% by weight solution was circulated in the plating bath for 5 minutes at 55 ° C, and then ion-exchanged water was introduced to thoroughly wash it, and then chlorinated by 1% by weight. The mixed solution consisting of a stannous solution and a 2% by weight hydrochloric acid solution was circulated in a plating bath at room temperature for 10 minutes, and then ion-exchanged water was introduced and washed thoroughly. The rest were applied to non-electrolysis in the same manner as in Example 1. Silver plating was performed to obtain white conductive fibers. The results of the volume resistance and whiteness of the white conductive fiber are shown in Table 1, and the results of the durability test for washing are shown. --------- line} c.V. (Please read the notes on the back before filling this page) This paper size applies to China National Standard (CNS) A4 specifications < 210 X 297 mm) 17 311634 469448 A7 ---------- B7___ 5. Description of the invention (18) Table 2. As shown in Table 1, all the white conductive fibers related to the present invention have a beautiful milky white color, and their whiteness (L value) are all 50 or more, and most of them are Η or more. These white conductive fibers are highly conductive, and all have a volume resistivity of 100 Ω.cm or less, and most of them have a ohmic value of 0 Ω.cm or less. In addition, the metal coating film of the white conductive fiber of the present invention has very good adhesion. As shown in Table 2, the coating film is not peeled off by ordinary washing methods, and has excellent durability. In addition, when repeated washing, the increase rate of volume resistivity is reported to be small, and the durability to washing is also excellent. Comparative Example 1 The same polyester multifilament (750/36 £) 50 (^ to 1500) was used as in Example 1. The package density is 0.130g / cm3, and it is gently rolled into a package wire with the same thickness as the top and bottom. After pretreatment, it is immersed in silver ore solution to apply bond silver. The pretreatment solution is used to adjust the surface polarity of the fiber. Surface treatment dyeing solution (product of Nippon Kayaku Co., Ltd .: Cayenne, Milin, Green) 0.6% by weight solution, 5% by weight ammonium acetate solution, and a mixed solution composed of 1% by weight acetic acid at a liquid temperature of 98 to 10 (After immersing the above-mentioned packaged thread body in TC for 45 minutes, wash it thoroughly with ion-exchanged water. Then, immerse it in a 5% by weight polyhydroxyphenylsulfonic acid-based fixing agent solution (8 ° to 90 ° C) After being crushed for 30 minutes, and then sufficiently washed with ion-exchanged water, immersed in a 5% by weight polyethyleneimine solution (95 to 98 ° C) for 30 minutes to stabilize the surface polarity, and then thoroughly washed with ion-exchanged water. β After the above surface treatment, the same silver as in Example 1 was used Liquid, immerse the packaged wire body in the plating solution tank in which the silver plating solution is stored in advance (in the packaged wire (please read the precautions on the back before filling this page) ^ · —----- tr-- ------- Printed by the Consumer Property Cooperative of the Bureau of Intellectual Property of the Ministry of Economic Affairs. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 18 311634 9448
五、發明說明（19 ) 線體内部流動之液流不像本發明之有所控制），其他皆按照 實施例1所示相同條件下施與鍍銀。由上述方法所製成之 導電性纖維如表1中所示，由於前處理之結果，其白色度 大幅度降低’白色度（L值）為4〇 »又，由於鐘銀不均勻， 所以電阻值變化很大，大多數較本發明實施例者，其體積 電阻係數大幅度增高。又，鍍銀之被覆強度小，其耐久性 亦低。 比較例2 比較例1 t ’不使用表面處理染色液進行前處理，而 進行表面之安定化處理和離子交換水之洗滌後，使用實施 例1所示相同銀鑛液，浸潰捲裝絲線體於事先貯存有銀鍍 液之鑛液槽中（捲裝絲線體内部流動之液流不像本發明有 所控制），其他皆按照實施例1所示相同條件下進行鍍銀。 依照這種製造方法所得導電性纖維，由於不使用表面處理 染色液做前處理’因此’其白色度（L值）較之比較例！者 稱高，但達不到50’又，其鍍銀情形較之比較例1者為不 均勻’因此，白色度和體積電阻係數之變動很大，體積電 阻係數在105 Ω · cm以上而格外高，較之本發明之實施例 其導電性大幅降低。又’鍍銀之耐久性亦低劣。 本紙張尺度適用中國國家標準（CNS>A4規格（210 X 297公釐) 19 311634 (請先閲讀背面之注意事項再填窝本頁) .'^.!!--訂 ------線( 經濟部智慧財產局員工消費合作社印製 46 9448 A7 B7 五、發明說明（20 ) 表1 原料絲 (連續性凝 線 線） 金屬 被覆 端子間 電阻值 (Ω /cm) 體積電 阻係數 (Ω . cm) 白色度 (L值） 評 估 種 類 粗細 捲裝 密度 成 分 被 覆 量 實1 75d/36f 0.130 Ag 20% 5.80 0.026 62 〇 實2 职 75d/36f 0.182 Ag 20% 270 1.2 55 〇 實3 取 40d/18f 0.130 Ag 20% 6.46 0.015 58 〇 實4 Θ曰 75d/36f 0.130 Ag 5% 4300 19 52 〇 實5 75d/36f 0.130 Ag 50% 0.75 0.0033 65 〇 丙 〇 實6 烯 酸 75d/36f 0.130 Ag 20% 2.4 0.011 53 系 比1 75d/36f 0.13 Ag 20% 10至 1 K 40 X 聚 5.〇χ 106 1主 5.〇χ104 X 比2 酯 75d/36f 0.13 Ag 20% 107以 105以上 47 上 (註）原料絲線之使用量皆為500g。 捲裝密度之單位為g/cm3，金屬被覆量以對於原料之重 量％表示之。評估乃係洗滌耐久性評估結果，實1至6示 實施例1至實施例6，比1示比較例1，比2示比較例2。 -----.-------Τ'裝--------訂---------線 '(_ , / <請先閲讀背面之生意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 20 311634 46 9448 A7V. Description of the invention (19) The fluid flow inside the thread body is not controlled as in the present invention), and the others are applied with silver plating under the same conditions as shown in Example 1. The conductive fiber made by the above method is shown in Table 1. As a result of the pretreatment, the whiteness is greatly reduced. The whiteness (L value) is 40%. Also, because the silver is not uniform, the resistance is The value varies greatly, and most of them have a significantly larger volume resistivity than those of the embodiments of the present invention. In addition, the silver-plated coating has low strength and low durability. Comparative example 2 Comparative example 1 t 'Without pretreatment using a surface treatment dyeing solution, after surface stabilization treatment and ion-exchange water washing, the same silver ore solution as shown in Example 1 was used to immerse the packaged wire body In a mineral liquid tank in which a silver plating solution is stored in advance (the liquid flow flowing inside the packaged wire body is not controlled as in the present invention), the others are plated under the same conditions as shown in Example 1. The conductive fiber obtained according to this manufacturing method has no whiteness (L value) compared to the comparative example because it does not use a surface treatment dyeing liquid for pretreatment. It is said to be high, but it does not reach 50 ', and its silver plating is not uniform compared to that of Comparative Example 1. Therefore, the whiteness and volume resistivity vary greatly, and the volume resistivity is particularly above 105 Ω · cm. Compared with the embodiment of the present invention, the conductivity is greatly reduced. Also, the durability of silver plating is inferior. This paper size applies to Chinese national standards (CNS > A4 size (210 X 297 mm) 19 311634 (Please read the precautions on the back before filling in this page). '^. !!-Order ------ (Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 46 9448 A7 B7 V. Description of the invention (20) Table 1 Raw wire (continuous condensed wire) Resistance value between the metal-coated terminals (Ω / cm) Volume resistivity (Ω cm) Whiteness (L value) Evaluation type Thickness package density component coating amount 1 75d / 36f 0.130 Ag 20% 5.80 0.026 62 〇 2 jobs 75d / 36f 0.182 Ag 20% 270 1.2 55 〇 3 3 40d / 18f 0.130 Ag 20% 6.46 0.015 58 〇4 4 Θ said 75d / 36f 0.130 Ag 5% 4300 19 52 〇5 5d / 36f 0.130 Ag 50% 0.75 0.0033 65 〇proper 6 enoic acid 75d / 36f 0.130 Ag 20% 2.4 0.011 53 series ratio 1 75d / 36f 0.13 Ag 20% 10 to 1 K 40 X poly 5.0 × 106 106 main 5.0 × 104 X 2 ester 75d / 36f 0.13 Ag 20% 107 above 105 47 (Note The amount of raw silk used is 500g. The unit of package density is g / cm3, and the amount of metal coating is The weight percent of the raw material is expressed. The evaluation is the result of the evaluation of the durability of the washing. Examples 1 to 6 show Example 1 to Example 6, ratio 1 shows Comparative Example 1, and ratio 2 shows Comparative Example 2. -----. ------- Τ'installation -------- order --------- line '(_, / < please read the business matters on the back before filling this page) Ministry of Economy Printed by the Intellectual Property Bureau Staff Consumer Cooperatives This paper is sized for the Chinese National Standard (CNS) A4 (210 X 297 mm) 20 311634 46 9448 A7
B7I 明說 明發 經濟部智慧財產局員工消費合作社印製 i a 8 Ξ 0Λ a I 〇> I g cn I S 雲 i 〇v 雲 s ? 3 pa 雪 馨 S 隱 ot αα S s CTV 1 Q 蒺 s _ ^ 53 Q游 ""词 命 Ϊ ΟΛ g 1 oa 讀 » I s Μ to A 1 g Ψ B i s ce pa 證 i s g g g 1 牌弹 s* hJ-Λ, ® 'O P3 B I Bb g§ s ΙΟ i cn i g r 震 fra ♦ 雲 i g 畕 I bo S I »9 I t9 | S| §轉 C- 3 宙 >4 to 1 s i 8 i 1 1 I 證 雲 Ϊ 3 i S 茔 S 5： s 8 *—* i i 梦a s# O t® e奐 歷 1 雲 I i i 1 S5 1 置 i 5*> 歷 ύΑ <r* ? s s 荦 S a i <3 s ^ g A Η CO £ i 畢 i 贫 r- i 65 1 14 s BO 卜> i 華 苕 議 S to i BO I i bn 1 CO 侓雜 亍唸 Ω诗 pe 馨 謹 1 ϊ» § 雲 I i I s f 沄 麗丨 CD I on I Cl3 i i i 異 〇 s .θ' 5铒 Pfe ί» 藝 i 謹 ΰ〇 I 謹 | i i 1 I 1 S g S r* 1 I 掸》 a也 Λ Ρ Η-· 1 aa Is g C0 1 — 圓 〇b i 1 s % 層 ^―· 1 — po s 1 1 i S 赛 s t 、· s w P 莽 ςτι I 1 蠢 1 S 09 I 1 i § I I CO i S s 甲 s GO i 由 i»» s雄 n词 證 1 雲 I Β 窗 I 9V i I 1 03 雪 pa 1 1 a I ca s i 雲 2搏 c词 宙 CTJ _ s s 1 S Μ i 震 s i S i Ϊ"* 1 i S 議 S i 歷 ς* 〇Ρ 5矣 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） ----------------^ --------訂---------線- (請先閱讀背面之注意事項再填寫本頁) 21 311634 46 9448 A7 B7 五、發明說明（22 ) (註）E+ 00等為10之次方指數 實施你丨7 使用第1圖所示鍍飾裝置，由表3中所示高分子材料 所構成纖維體以上下相同粗細狀捲裝在軸上成為捲裝絲線 體’放入鍍液槽中，按照下列之（1)脫脂處理（2)鹼處理，中 和處理，以及（3)活化處理之後，使用表1之金屬進行（4) 非電解鍍飾處理，再施與（5)表面處理（防銹處理）。又，上 述各處理乃將藥液加壓循環而進行。 (1) 脫脂處理：將脫脂液（愛司克淋A-200，曰本奥野製 藥工業公司製品）之5重量％溶液在55 °C下鍍液槽中循 環5分鐘之後，導入離子交換水充分洗淨之。 (2) 鹼處理：脫脂處理後以20重量％之氫氧化鈉溶液在 70°C下，於鍍液槽中循環20分鐘，再導入離子交換水 充分洗淨之後，用5重量％之濃鹽酸溶液在室溫下， 於鍍液槽中循環2分鐘。 (3) 活化處理：鹼處理後，使用濃鹽酸溶液和氯化鈀混 合溶液（催化劑C :日本奥野製藥工業公司製品）在鍍 液槽中室溫下循環3分鐘之後，導入離子交換水充分 洗淨之。再用10重量％硫酸溶液於鍍液槽中45°C下循 環3分鐘而加以活化之。 (4) 鍍飾步驟：依照上述前處理將觸媒附著於纖維表面 之 後，就表1中所示白金、銀和鎳之各種鐘液在鑛 液槽中循環而形成具有柑桔表皮狀之金屬被覆膜。另 外，就各種金屬形成不具柑桔表皮狀之外，其他皆和 (請先閲讀背面之注意事項再填寫本頁) --------訂---------線' 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 22 311634 A7B7I Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ia 8 Ξ 0Λ a I 〇 > I g cn IS Cloud i 〇v Cloud s? 3 pa Xuexin S Hidden αα S s CTV 1 Q 蒺 s _ ^ 53 Q 游 " " Word life Ϊ ΟΛ g 1 oa read »I s Μ to A 1 g Ψ B is ce pa card isggg 1 card s * hJ-Λ, ® 'O P3 BI Bb g§ s ΙΟ i cn igr Earthquake fra ♦ Cloud ig 畕 I bo SI »9 I t9 | S | § Turn to C- 3 Zhou > 4 to 1 si 8 i 1 1 I Proof cloud Ϊ 3 i S Tomb S 5: s 8 * — * ii dream as # O t® e 奂 Calendar 1 Cloud I ii 1 S5 1 Set i 5 * > ύύΑ < r *? ss 荦 S ai < 3 s ^ g A Η CO £ i 毕 i rr -i 65 1 14 s BO > i Hua Yiyi S to i BO I i bn 1 CO 侓 杂 亍 念 Ω 亍 pe 谨 馨 1 ϊ »§ Yun I i I sf 沄 丽 丨 CD I on I Cl3 iii异 〇s .θ '5 铒 Pfe ί »艺 i ΰ ΰI || ii 1 I 1 S g S r * 1 I 掸 a also Λ Ρ Η- · 1 aa Is g C0 1 — circle 〇bi 1 s% layer ^-· 1 — po s 1 1 i S match st, · sw P Mang τι I 1 stupid 1 S 09 I 1 i § II CO i S s A s GO i by i »» s male n testimony 1 cloud I Β window I 9V i I 1 03 snow pa 1 1 a I ca si cloud 2 word c CTJ _ ss 1 S Μ i earthquake si S i Ϊ " * 1 i S iS i Calendar * 〇Ρ 5 矣 This paper size is applicable to Chinese National Standard (CNS) A4 (210 χ 297 mm) ---------------- ^ ------- -Order --------- Line- (Please read the precautions on the back before filling out this page) 21 311634 46 9448 A7 B7 V. Description of the invention (22) (Note) E + 00 etc. is the power of ten Use the plating equipment shown in Figure 1 and use the plating device shown in Figure 1. The fibrous body composed of the polymer material shown in Table 3 is wound on the shaft to become a rolled wire body. According to the following (1) degreasing treatment (2) alkali treatment, neutralization treatment, and (3) activation treatment, use the metal of Table 1 to perform (4) non-electrolytic plating treatment, and then apply (5) surface treatment (Anti-rust treatment). In addition, each of the above-mentioned processes is performed by pressurizing a chemical liquid. (1) Degreasing treatment: After circulating a 5% by weight solution of the degreasing solution (Eskelene A-200, manufactured by Okuno Pharmaceutical Co., Ltd.) in a plating bath at 55 ° C for 5 minutes, introduce ion-exchanged water sufficiently. Wash it. (2) Alkali treatment: After degreasing treatment, circulate in a 20% by weight sodium hydroxide solution at 70 ° C for 20 minutes in a plating bath, and then introduce ion-exchanged water to fully wash, and then use 5% by weight concentrated hydrochloric acid. The solution was circulated in the bath for 2 minutes at room temperature. (3) Activation treatment: After alkali treatment, use a mixed solution of concentrated hydrochloric acid solution and palladium chloride (Catalyst C: product of Japan Okano Pharmaceutical Industry Co., Ltd.) after circulating at room temperature for 3 minutes in a plating bath, and then wash thoroughly with ion-exchange water. Just clean it. It was further activated by cycling a 10% by weight sulfuric acid solution at 45 ° C for 3 minutes in a plating bath. (4) Plating step: After attaching the catalyst to the fiber surface according to the above pretreatment, the various bell liquids of platinum, silver and nickel shown in Table 1 are circulated in the mineral liquid tank to form a metal with a citrus skin shape. Cover film. In addition, all kinds of metals are not citrus-like, but everything is compatible (please read the precautions on the back before filling this page) -------- Order --------- Line ' Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 22 311634 A7
經濟部智慧財產局員工消費合作杜印製 469448 五、發明說明（23 ) 上述大約相同條件下形成金屬被覆膜做為此較例。 (5)表面處理（防銹處理）：將防銹劑（開吉來特八匸冒“， 開士特公司製品）以水稀釋3倍之後放入鍍液槽中，再 將依照上述處理工程而施有金屬被覆膜之纖維θ浸潰其 中施與表面處理 就上述金屬被覆纖維測定其被覆膜之黏附（剝離）強 度’導電性和白色度，其結果示於表丨中β另外，以市販 品充當比較例而示之。又，就本發明有關之實施試料Ν〇 Α1 之金屬被覆膜（銀），將呈現柑桔表皮狀之被覆膜表面之狀 況示第4圖之顯微鏡照片。 黏附強度以測試纖維或布料之染色堅牢度之標準試驗 方法（JIS L0849)相似之剝離強度試驗測定之。具體而言， 在試驗用試料之金屬被覆纖維末上重疊以白布，加上2〇〇g 重量，以每分鐘30次之來回速度進行丨00次來回摩擦，再 依據附著於白布之污染情形，由污染度高到低依序自1級 到5級分類’籍此標準判斷剝離強度（黏附強度）β導電性 乃在10cm長之金屬被覆纖維的兩端連接電極，用數位多 功能儀測定端子間電阻（Ω )，由纖維長度（cm)和剖面面積 (cm2)求得比電阻（體積電阻係數，〇 · cm)。白色度依據罕 特氏式由Lab法測定L值。L值愈大白色度愈高。 如第4圖之顯微鏡照片所示，本發明有關之金屬被覆 膜表面通常具有粒徑為0.05至Ιμιη之金屬粒狀物所形成 之柑桔表皮狀物。該柑桔表皮狀之金屬被覆膜如表1所 示，其剝離強度在3級以上，大多數在4級、5級範圍， (請先閱讀背面之注意事項再填寫本頁) -k^--------訂----I----線' 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 23 311634 469448 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明（24 較已往者具有格外高之黏附性。特別是其比電阻（體積電阻 係數在5x 10-5至10-3Ω · cm而具有優異之導電性又， 其白色度在60以上，有一部分高達白色度65至7〇而具有 優美之白色性。另一方面’市販品和金屬被覆膜表面平滑 之比較例（B1至B3)其剝離強度皆在1至2級，黏附性不良 而白色度也低劣。 表3 编號 纖維 金屬種類 表面狀態 !離 ，度 體積電 阻係數 (Ω · cm) 白色度 (L值） A1 Ni 5 級 5x l〇-s 60 PET Ag 柑桔表皮狀 5 級 5x 10·5 70 An 4 級 5x i〇-5 A2 尼龍 Ni 4 級 0. 001 60 Ag 柑桔表皮狀 4 級 0. 001 65 Au 4 級 0. 001 - A3 丙烯 Ni 5 級 5x 10·5 65 酸系 Ag 柑桔表皮狀 5 級 5x i〇-5 70 An 4 級 5x l〇-5 B1 Ni 2 級 0. 001 60 PET Ag 平滑 1 級 0. 001 65 Au 1 級 0. 001 - B2 Ni 2 級 5x 10-5 55 尼龍 Ag 平滑 2 級 0. 001 60 Au 2 級 0. 001 B3 丙烯 Ni 2 級 5x l〇-5 60 酸系 Ag 平滑 1 級 0. 001 65 Au 1 級 0. 001 市販品 Ag 平滑 2 級 100 65 (註）A1至A3為實施例 B1至B3和市販品為比較例 _^據本發明，捲裝在軸上狀態之連續性絲線也能製得 私紙張尺度適用中國國家標準（CNS>A4規格（21〇 X 2耵公釐） 24 311634 (請先閲讀背面之注$項再填寫本頁)Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs on employee consumption cooperation 469448 V. Description of Invention (23) A metal coating film was formed under the same conditions as the above example. (5) Surface treatment (anti-rust treatment): Dilute the anti-rust agent (Kagilite Hachimanta ", manufactured by Kaisite Co., Ltd.) with water three times, and then put it into the plating bath. The fiber θ impregnated with the metal coating film was subjected to surface treatment. The adhesion (peeling) strength of the coating film, the conductivity and the whiteness were measured for the above metal coating fiber, and the results are shown in Table 丨 In addition, A commercially available product is shown as a comparative example. In addition, regarding the metal coating film (silver) of the implementation sample No.A1 related to the present invention, the state of the coating film surface showing the appearance of a citrus skin is shown in the microscope of FIG. 4 Photo. Adhesion strength is measured by a peel strength test similar to the standard test method (JIS L0849) for dyeing fastness of fibers or cloths. Specifically, a white cloth is superimposed on the metal coated fiber end of the test sample, plus 2 〇〇g weight, rubbing back and forth at a speed of 30 times per minute 丨 00 times of back and forth friction, and then according to the pollution situation attached to the white cloth, from high to low pollution in order from level 1 to level 5 'classify according to this standard strength Adhesion strength) β conductivity is connected to electrodes at both ends of a 10cm-long metal-coated fiber. The resistance between the terminals (Ω) is measured with a digital multimeter. The specific resistance is obtained from the fiber length (cm) and the cross-sectional area (cm2). Volume resistivity, 0 · cm). The whiteness is measured by the Lab method according to the Hunt's formula. The L value is greater. The larger the L value is, the higher the whiteness is. As shown in the micrograph of FIG. 4, the metal coating film according to the present invention The surface usually has a citrus skin formed by metal particles having a particle diameter of 0.05 to 1 μm. The citrus skin-like metal coating film is shown in Table 1, and its peel strength is above grade 3, and most of them are Level 4 and 5 range, (Please read the precautions on the back before filling this page) -k ^ -------- Order ---- I ---- Line 'This paper size applies to Chinese national standards (CNS) A4 specification (210 X 297 mm) 23 311634 469448 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 Printed on A7 V. Invention description (24 It has a particularly high adhesion compared to the past. Especially its specific resistance (volume resistance Coefficient is 5x 10-5 to 10-3Ω · cm and has excellent conductivity. Its white color Above 60, some have a high whiteness of 65 to 70 and have beautiful whiteness. On the other hand, the comparative examples (B1 to B3) of smooth surface of commercial products and metal coatings have peel strengths of 1 to 2 , Poor adhesion and low whiteness. Table 3 Surface condition of fiber metal types! Isolation, volume resistivity (Ω · cm) Whiteness (L value) A1 Ni 5 grade 5x l0-s 60 PET Ag Orange skin 5 grades 5x 10 · 5 70 An 4 grades 5x i〇-5 A2 nylon Ni 4 grades 0.001 60 Ag Citrus skin like 4 grades 0.001 65 Au 4 grades 0.00 to A3 acrylic Ni 5 grades 5x 10.65 65 Acid Ag Citrus Epidermis 5 grade 5x i〇-5 70 An 4 grade 5x l0-5 B1 Ni 2 grade 001 60 PET Ag smooth 1 grade 001 65 Au 1 grade 0. 001-B2 Ni 2 grade 5x 10-5 55 Nylon Ag smooth 2 grade 0. 001 60 Au 2 grade 0. 001 B3 Acrylic Ni 2 grade 5x l0-5 60 Acid Ag smooth 1 grade 001 65 Au 1 grade 0. 001 Ag smooth 2 grade 100 65 for commercial products (Note) A1 to A3 are examples B1 to B3 and commercial products are comparative examples _ ^ According to the present invention, the roll is wound on a shaft Continuity silk thread can also be made. Private paper size is applicable to Chinese national standard (CNS > A4 specification (21 × 2 耵 mm) 24 311634 (Please read the note on the back before filling this page)
4 6 9448 A7 ____B7__ 五、發明說明（25 ) 具有適於電磁波屏蔽用途之高導電性，更具體言之，體積 電阻係數在100Ω ·ί；ηι以下，最好在〇iq .cm以下，而 白色度在50以上’最好在55以上之白色導電性纖維。本 發明之白色導電性纖維具有美麗的白色，因此，適合於白 色度高之衣服或混紡在底材也不會影響到原有色調之製品 之製造用途。又，具有高導電性，因此，可以藉少量混織 在各種色調之底材而發揮優異之導電性且不影響底材原有 色調或風格。又’能以上下相同粗細之捲裝在軸上的狀態 下，從前處理到鍍飾處理施工，所以能廉價的製成高導電 性能的導電性纖維。另外，可以使用汎用性高之尼龍，聚 酯、丙烯酸系纖維之連續性絲線做為製造原料種類，所以 可供廣泛用途。又，本發明之金屬被覆纖維之被覆在纖維 表面之金屬被覆膜具有優異之黏附性，因此，耐久性高， 能長時間維持優異之導電性，所以可適用各種導電性材料 用途。另外’使用銀為金屬被覆膜者，藉銀離子能表現優 異之抗菌性，所以也可提供抗菌材料用途。 [元件符號簡單說明] (請先閱讀背面之注$項再填寫本頁) --------訂---------線·' 經濟部智慧財產局員工消費合作社印製 10 鍍液槽 11 固定軸 12 導液孔 13 蓋子 14 固定板 15 調距板 16 栓蓋 20 鍍液貯槽 31 ' 32 輸液管 33 開關閥 40 輸液泵 50 捲裝絲線體 51 芯部 本紙張尺度適用中國國家標準（CNS>A4規格（210 X 297公釐） 25 3116344 6 9448 A7 ____B7__ V. Description of the invention (25) It has high conductivity suitable for electromagnetic wave shielding applications, more specifically, the volume resistivity is 100Ω · ί; ηι, preferably below 〇iq.cm, and white White conductive fibers having a degree of 50 or more ', preferably 55 or more. The white conductive fiber of the present invention has a beautiful white color. Therefore, it is suitable for clothes with high whiteness or blended on the substrate without affecting the production of products with original color. In addition, it has high electrical conductivity, so it can exhibit excellent electrical conductivity by mixing a small amount of a substrate with various colors without affecting the original color or style of the substrate. In addition, since it can be wound on the shaft in the same thickness as the previous one, it can be constructed from pretreatment to plating treatment, so it is possible to produce conductive fibers with high conductivity at low cost. In addition, nylon, polyester, and acrylic fiber continuous filaments can be used as the raw material type, so they can be used in a wide range of applications. In addition, the metal coating film on the surface of the metal-coated fiber of the present invention has excellent adhesion, so it has high durability and can maintain excellent conductivity for a long time, so it can be used for various conductive material applications. In addition, the use of silver as a metal coating film can exhibit excellent antibacterial properties by virtue of silver ions, so it can also be used as an antibacterial material. [Simple description of component symbols] (Please read the note on the back before filling in this page) -------- Order --------- line · 'Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 10 plating bath 11 fixed shaft 12 guide hole 13 cover 14 fixing plate 15 adjusting plate 16 bolt cover 20 plating storage tank 31 '32 infusion tube 33 on-off valve 40 infusion pump 50 coiled wire body 51 core paper size Applicable to Chinese national standard (CNS > A4 specification (210 X 297 mm) 25 311634
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000040879A JP4560750B2 (en) | 2000-02-18 | 2000-02-18 | Metal-coated fibers and their applications |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW469448B true TW469448B (en) | 2001-12-21 |
Family
ID=18564196
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW89114237A TW469448B (en) | 2000-02-18 | 2000-07-17 | Conductive fiber, a process and an apparatus for preparing the same and their usage |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4560750B2 (en) |
| TW (1) | TW469448B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006008802A (en) * | 2004-06-24 | 2006-01-12 | Masahiro Matsumura | Antibacterial foam |
| JP2007220616A (en) * | 2006-02-20 | 2007-08-30 | Gunze Ltd | Surface heating element and clothing using this |
| CN103370430B (en) | 2011-02-18 | 2015-07-15 | 三井化学株式会社 | Antimicrobial substance, method for producing same, and antimicrobial material |
| JP6295821B2 (en) * | 2013-05-21 | 2018-03-20 | 王子ホールディングス株式会社 | Nonwoven sheet |
| JP7192539B2 (en) * | 2019-02-01 | 2022-12-20 | 日立金属株式会社 | Conductive fiber, cable, and method for producing conductive fiber |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3024888A1 (en) * | 1980-07-01 | 1982-02-04 | Bayer Ag, 5090 Leverkusen | COMPOSITE MATERIAL FOR SHIELDING ELECTROMAGNETIC RADIATION |
| JPS6155263A (en) * | 1984-08-20 | 1986-03-19 | 株式会社 高瀬染工場 | Improved metallization of polyester fiber-containing fiber material |
| JPS6190500A (en) * | 1984-10-09 | 1986-05-08 | 株式会社クラレ | Electromagnetic wave shielding/transmitting filter and manufacture thereof |
| JPS6197469A (en) * | 1984-10-18 | 1986-05-15 | 日本エステル株式会社 | Production of conductive polyester fiber |
| JPS62170581A (en) * | 1986-01-23 | 1987-07-27 | セ−レン株式会社 | Production of organometal composite fiber |
| JP2647466B2 (en) * | 1988-11-08 | 1997-08-27 | 龍徳 四十宮 | Method for producing surface metallized fiber |
| JPH07102476A (en) * | 1993-09-30 | 1995-04-18 | Nisshinbo Ind Inc | Production of metallized polyester fiber |
| JPH08176962A (en) * | 1994-12-20 | 1996-07-09 | Nagano Pref Gov | Antimicrobial/electromagntic wave-shielding knitted product |
| JPH1072704A (en) * | 1996-08-27 | 1998-03-17 | Tec:Kk | Clothing by using silver plated fiber |
| JP2001040578A (en) * | 1999-05-25 | 2001-02-13 | Mitsubishi Materials Corp | White electroconductive fiber, its production and device therefor |
-
2000
- 2000-02-18 JP JP2000040879A patent/JP4560750B2/en not_active Expired - Fee Related
- 2000-07-17 TW TW89114237A patent/TW469448B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001234468A (en) | 2001-08-31 |
| JP4560750B2 (en) | 2010-10-13 |
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