TWM549701U - Metal textile yarn with metal oxide ceramic coating layer - Google Patents
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本創作為有關於一種披覆金屬氧化物陶瓷鍍層之金屬紡絲，特別是全金屬或有電鍍金屬層的紡絲基材上披覆著一層金屬氧化物陶瓷鍍層，構成新型紡織材料以應用於紡織品。 The present invention relates to a metal-spun yarn coated with a metal oxide ceramic coating, in particular, a metal-coated ceramic substrate coated with a metal oxide ceramic coating to form a new textile material for application. textile.
金屬纖維或金屬紡織絲具有導熱、導電、耐蝕、耐高溫等特性，可應用於紡織品，常見防輻射服、襪子、面罩、口罩等等產品，或可透過金屬紡絲導電製成加熱防寒衣，甚至連接電子裝置與生物晶片達到運動、疾病監控等目的。主要原因為金屬紡絲可直接與棉、腈綸、粘膠、滌綸等原料按照不同比例混紡，混紡入紡織品或製成金屬布料，其具有下列優點：金屬紡絲紡織品能夠防輻射、能夠抗靜電、可以導電與傳輸電子訊號、強力除臭、若含有光觸媒或某些金屬可以強力殺菌等。 Metal fiber or metal textile wire has the characteristics of heat conduction, electrical conductivity, corrosion resistance, high temperature resistance, etc. It can be applied to textiles, common radiation protection suits, socks, masks, masks, etc., or can be made of heat-resistant winter clothes through metal spinning. Even connecting electronic devices and bio-chips for sports, disease monitoring, etc. The main reason is that metal spinning can be directly blended with cotton, acrylic, viscose, polyester and other raw materials in different proportions, blended into textiles or made into metal fabrics. It has the following advantages: metal-spun textiles can prevent radiation and antistatic, It can conduct electricity and transmit electronic signals, strong deodorization, and can be strongly sterilized if it contains photocatalyst or some metals.
目前金屬紡織以銅紡絲、鎳紡絲、銅鍍鎳紡絲、銀紡絲與不鏽鋼紡絲為主，其中，銀紡絲常以尼龍6絲為紡絲基材，採用化學鍍銀技術在紡絲基材的表面形成一層銀的電鍍層，銀紡絲具有良好的延展性、電阻低，保持了尼龍纖維的可紡性。銅紡絲也使用類似的方法製成，而銅紡絲的價格較便宜，但耐蝕性不佳。又不鏽鋼紡絲以其容易製造的特性，在金屬紡織中也廣泛被利用。不鏽鋼紡絲主要缺點為不鏽鋼紡絲密度相當于普通紡織纖維的5-8倍，做成織品穿戴起起來較重。但不鏽鋼紡絲是純金屬，導電性能好、耐蝕性尚佳、電阻低、防靜電、遮罩電磁波等。不鏽鋼紡絲混紡的紡織物可製作抗靜電工作服，具有可靠的防燃、防爆作用、防止電 磁波幹擾導致電子計算機、電子儀器誤動作所造成的危害等。 At present, metal textile is mainly made of copper spinning, nickel spinning, copper nickel plating, silver spinning and stainless steel spinning. Among them, silver spinning is often made of nylon 6 silk as a spinning substrate, using electroless silver plating technology. The surface of the spun substrate forms a layer of silver plating. The silver spun yarn has good ductility and low electrical resistance, and maintains the spinnability of the nylon fiber. Copper spinning is also made using a similar method, while copper spinning is cheaper but has poor corrosion resistance. Stainless steel spinning is also widely used in metal textiles because of its easy-to-manufacture properties. The main disadvantage of stainless steel spinning is that the stainless steel spinning density is 5-8 times that of ordinary textile fibers, and the fabric is heavier to wear. However, stainless steel spinning is a pure metal, which has good electrical conductivity, good corrosion resistance, low electrical resistance, anti-static, and electromagnetic waves. Stainless steel spun blended fabric can be made of antistatic overalls, with reliable flameproof, explosion-proof and anti-electricity Magnetic wave interference causes damage caused by malfunction of electronic computers and electronic instruments.
歐盟於1994年通過了94/27/EC指令(Nickel Release Directive)，該指示是用以管制鎳Ni在與皮膚有直接及長期接觸的產品上的使用量，理由是鎳可能令皮膚引致過敏反應。規定和人體皮膚長期直接接觸的產品中鎳的釋放量不得超過0.5μg/cm2/week，這些產品包括：耳環，項鍊，手鐲和手鏈，腳鐲，指環，錶鏈，錶帶，以及服裝中的紐扣、緊固件、鉚釘、拉鍊及其它金屬標誌。因此對於穿戴含有鎳成分的金屬紡絲製成的紡織品，更是難通過94/27/EC指令。 The European Union adopted the Directive 94/27/EC (Nickel Release Directive) in 1994 to regulate the use of nickel Ni in products that have direct and prolonged contact with the skin on the grounds that nickel may cause skin allergic reactions. . The release of nickel from products that have long-term direct contact with human skin must not exceed 0.5 μg/cm 2 /week. These products include: earrings, necklaces, bracelets and bracelets, anklets, rings, bracelets, straps, and clothing. Buttons, fasteners, rivets, zippers and other metal signs. Therefore, it is more difficult to pass the 94/27/EC directive for textiles made of metal-spun yarns containing nickel.
然而，雖然不鏽鋼對酸、堿及有機溶劑的腐蝕比銅紡絲、鎳紡絲、銅鍍鎳紡絲優良，但整體上金屬紡絲的耐腐蝕性、耐撓折、耐洗程度較差，甚至金屬紡絲容易對人體產生過敏(如鎳的溶出量)，不具有生物相容性(ISO10993)。若金屬紡絲能克服前述的缺點，更可被廣泛用於航太、航空、汽車工業、化工、化纖、紡織、醫藥、食品等領域。 However, although the corrosion of stainless steel on acid, bismuth and organic solvent is better than that of copper spinning, nickel spinning and copper nickel plating, the overall corrosion resistance, scratch resistance and washing resistance of metal spinning are poor, even Metal spinning is prone to allergies to the human body (such as the amount of nickel dissolved) and is not biocompatible (ISO 10993). If metal spinning can overcome the aforementioned shortcomings, it can be widely used in aerospace, aviation, automotive, chemical, chemical fiber, textile, pharmaceutical, food and other fields.
金屬化陶瓷(metallic ceramic)係為非金屬元素參雜有金屬元素共同形成的一種類似陶瓷結構的共構物，使其兼具有金屬特性與陶瓷特性，例如，有些共構物具有一般陶瓷的硬度與甚佳耐腐蝕性、或兼具有金屬光澤性與導電性、或兼具有陶瓷的色澤等；可應用在耐磨元件、車削刀具、熱交換器、引擎元件、生醫、軍事及太空上。 A metallic ceramic is a ceramic-like constitutive structure formed by a non-metallic element mixed with a metal element, which has both metal characteristics and ceramic characteristics. For example, some eutectics have general ceramics. Hardness and very good corrosion resistance, or both metallic luster and electrical conductivity, or the color of ceramics; can be applied to wear-resistant components, turning tools, heat exchangers, engine components, biomedical, military and In space.
台灣專利I456093公開了一種形成黑色三價氧化鉻鍍層之電化學方法，係以電鍍的方法形成黑色三價氧化鉻電鍍層，該黑色三價氧化鉻電鍍層可達到耐腐蝕、表面硬度高與耐磨性佳的需求；台灣專利M490197、M501441則公開了在滑軌表面利用電鍍方法形成由鉻元素、氧元素、氫元素、鈷元素與磷元素所組成的鉻鈷基金屬氧化物陶瓷鍍層；更進一步台灣專利M487936則將此技術應用於消光元件上、台灣專利M498114則將此技術應用於醫療器材上。然而前述的技術主要在於產生黑色的三價氧化鉻電鍍層或鉻鈷基金屬氧化物陶瓷鍍層電鍍層，而應用在傳動元件、消光元件或醫療器材上，但對於金屬氧化物陶瓷鍍層應用在金屬紡紗提高金屬紡紗的耐用性、且符合生物相容性(biocompatibility)，係為紡織材料急迫需要的課題。 Taiwan Patent I456093 discloses an electrochemical method for forming a black trivalent chromium oxide plating layer, which is formed by electroplating to form a black trivalent chromium oxide plating layer which can achieve corrosion resistance, high surface hardness and resistance. The demand for good wearability; Taiwanese patents M490197 and M501441 disclose the formation of chromium-cobalt-based metal oxide ceramic coatings composed of chromium, oxygen, hydrogen, cobalt and phosphorus on the surface of the rail by electroplating; Further Taiwan patent M487936 applies this technology to extinction components, and Taiwan patent M498114 applies this technology to medical equipment. However, the foregoing technology mainly produces a black trivalent chromium oxide plating layer or a chrome-cobalt-based metal oxide ceramic plating plating layer, which is applied to a transmission element, a matting element or a medical device, but is applied to a metal oxide ceramic coating layer. Spinning improves the durability of metal spinning and is biocompatibility, which is an urgent need for textile materials.
有鑑於上述習知技藝之問題，本創作主要目的之一為提出一種披覆金屬氧化物陶瓷鍍層之金屬紡絲，該金屬紡絲由一紡絲基材所製成，並在紡絲基材上以電鍍的方法，電鍍一層的金屬氧化物陶瓷鍍層。該紡絲基材可為不鏽鋼、鐵、鎳、銅、銀、金或其合金，或者，紡絲基材為棉、麻、玻璃纖維、錦綸、滌綸、腈綸、氨綸、維綸、丙綸、氯綸等之一或其組合，而在表面以無電鍍、電鍍、無電鍍、蒸鍍、氣相沉積、物理沉積等形成一金屬鍍層，其中該金屬鍍層為鎳、鐵、銅、銀、金之一金屬或其合金。當應用於紡織品，該紡絲基材為長纖維狀，最佳的長度為120mm以上、直徑為5~300μm。 In view of the above-mentioned problems of the prior art, one of the main purposes of the present invention is to propose a metal spinning coating of a metal oxide ceramic coating which is made of a spinning substrate and is used in a spinning substrate. A layer of metal oxide ceramic coating is electroplated by electroplating. The spinning substrate may be stainless steel, iron, nickel, copper, silver, gold or alloys thereof, or the spinning substrate is cotton, hemp, glass fiber, nylon, polyester, acrylic, spandex, vinylon, polypropylene, polyvinyl chloride. Or one or a combination thereof, and forming a metal plating layer on the surface by electroless plating, electroplating, electroless plating, evaporation, vapor deposition, physical deposition, etc., wherein the metal plating layer is one of nickel, iron, copper, silver, gold Metal or its alloy. When applied to textiles, the spinning substrate is long-fiber-shaped, and the optimum length is 120 mm or more and the diameter is 5 to 300 μm.
其中，該金屬氧化物陶瓷鍍層係以電鍍方法在該紡絲基材上形成，係由鉻元素、氧元素、氫元素、鈷元素與磷元素所組成，係為非晶相結構；該金屬氧化物陶瓷鍍層之厚度為5μm以下。 Wherein, the metal oxide ceramic plating layer is formed on the spinning substrate by an electroplating method, and is composed of chromium element, oxygen element, hydrogen element, cobalt element and phosphorus element, and is an amorphous phase structure; the metal oxide is oxidized The thickness of the ceramic coating is 5 μm or less.
其中，金屬氧化物陶瓷鍍層至少包含下列群組：(1)第一群組為：鉻(Cr)與氧化鉻(Cr2O3)、(2)第二群組為：氫氧化鉻(為三價鉻之氫氧化物Cr(OH)3)與磷化鉻(CrP)之一或其組合)；(3)第三群組為：鈷(Co)與氧化鈷(為二價鈷或三價鈷之氧化物Co3O4、Co2O3)之一或其組合)；(4)第三群組為：氫氧化鈷(為二價鈷或三價鈷之氫氧化物Co(OH)2、Co(OH)3)與磷化鈷(為二價鈷或三價鈷之磷化物CoP、Co2P3)之一或其組合)；又本創作提出的披覆金屬氧化物陶瓷鍍層之金屬紡絲，符合ISO 10993中第二種類之接觸體表之醫療器材之生物相容性，包含皮膚、黏膜與受傷體表。本創作金屬紡絲之金屬氧化物陶瓷鍍層具有生物相容性，生物相容性係皮內刺激試驗沒有皮膚病變及症狀產生、溶血性試驗不會造成溶血現象、皮膚刺激性試驗未對皮膚產生刺激性、細胞毒性試驗無造成細胞死亡或抑制細胞生長。 Wherein, the metal oxide ceramic plating layer comprises at least the following groups: (1) the first group is: chromium (Cr) and chromium oxide (Cr 2 O 3 ), and (2) the second group is: chromium hydroxide (for a trivalent chromium hydroxide Cr(OH) 3 ) and one or a combination of chromium phosphide (CrP); (3) the third group is: cobalt (Co) and cobalt oxide (for divalent cobalt or three) a covalent cobalt oxide of one of Co 3 O 4 , Co 2 O 3 ) or a combination thereof; (4) The third group is: cobalt hydroxide (cobalt of divalent cobalt or trivalent cobalt Co(OH) 2 ) Co(OH) 3 ) and cobalt phosphide (either one of divalent cobalt or trivalent cobalt phosphide CoP, Co 2 P 3 ) or a combination thereof; and the coated metal oxide ceramic proposed by the present invention The metallization of the coating conforms to the biocompatibility of the medical device of the second type of contact surface in ISO 10993, including the skin, mucous membrane and wounded body surface. The metal oxide ceramic coating of the present metal spinning has biocompatibility, the biocompatibility intradermal stimulation test has no skin lesions and symptoms, the hemolytic test does not cause hemolysis, and the skin irritation test does not produce skin. Irritant, cytotoxicity tests did not cause cell death or inhibited cell growth.
更進一步，本創作提出的披覆金屬氧化物陶瓷鍍層之金屬紡絲，其金屬氧化物陶瓷鍍層具有良好的耐蝕性，其耐候性依據ASTM B-117 5%鹽霧試驗標準至少72小時以上。 Furthermore, the metal-spun ceramic coating of the metal oxide ceramic coating proposed by the present invention has good corrosion resistance, and the weather resistance is at least 72 hours according to the ASTM B-117 5% salt spray test standard.
又進一步，本創作提出的披覆金屬氧化物陶瓷鍍層之金屬紡絲，該披覆金屬氧化物陶瓷鍍層之金屬紡絲之構造進一步包含一樹脂的保護層，該保護層係附著於該金屬氧化物陶瓷鍍層之全部或一部份；保護層可為二氧化矽(SiO2)、二氧化鈦(TiO2)、聚矽氧烷化合物(polysiloxane)、全氟碳化物(Perfluorinated chemicals,PFCs)、全氟樹脂(fluororesin)、酚醛樹脂(phenolic resins)、丙烯酸樹脂(或稱為聚羰基乙烯樹脂polycarboxyethylene resin)、丙烯酸矽改質樹脂(或稱為聚羰基乙烯變性矽樹脂polycarboxyethylene silicon modified resin)之一或其組合，不為所限。較佳的，該保護層之厚度為15μm以下。本創作提出的披覆金屬氧化物陶瓷鍍層之金屬紡絲，若披覆有保護層，耐蝕性更提升，其耐候性依據ASTM B-117 5%鹽霧試驗標準至少96小時以上。 Further, in the metal spinning of the coated metal oxide ceramic coating proposed by the present invention, the metal-spun structure of the metal oxide ceramic coating further comprises a protective layer of a resin attached to the metal oxide. All or part of the ceramic coating; the protective layer may be cerium oxide (SiO 2 ), titanium dioxide (TiO 2 ), polysiloxane, perfluorinated chemicals (PFCs), perfluoro One of fluororesin, phenolic resins, acrylic resin (or polycarboxyethylene resin), or fluorene acrylate modified resin (or polycarboxyethylene silicon modified resin) Combination, not limited. Preferably, the protective layer has a thickness of 15 μm or less. The metal spinning of the coated metal oxide ceramic coating proposed by the present invention is improved in corrosion resistance if it is covered with a protective layer, and the weather resistance is at least 96 hours according to the ASTM B-117 5% salt spray test standard.
對於不同紡織織品的應用，可依據需求，在前述的樹脂中添加各種顏色的顏料，以呈現不同色澤或無光(消光)的顏色，不為所限。 For the application of different textile fabrics, pigments of various colors may be added to the aforementioned resins according to requirements, in order to present different colors or matt (extinction) colors, which are not limited.
承上所述，依本創作之一種披覆金屬氧化物陶瓷鍍層之金屬紡絲，其可具有一或多個下述優點： As described above, a metal-spun metal coated ceramic oxide coating can have one or more of the following advantages:
(1)本創作紡絲基材可選用金屬紡絲如不鏽鋼、鎳、銅、銀、金，在金屬的紡絲基材上以濕式法電鍍形成金屬氧化物陶瓷鍍層，改善了習知技術以高溫滲透法、氣相沉積法(CVD)或物理氣相沉積法(PVD)等其他乾式法披覆金屬化陶瓷的技術，可大幅降低成本、披覆層均勻外，更可免於使用高溫的披覆環境使金屬的紡絲基材斷裂的缺點。 (1) The spinning substrate can be made of metal spinning such as stainless steel, nickel, copper, silver or gold, and the metal oxide ceramic coating is formed by wet plating on the metal spinning substrate, thereby improving the conventional technology. The technique of coating metallized ceramics by other dry methods such as high temperature permeation, vapor deposition (CVD) or physical vapor deposition (PVD) can greatly reduce the cost, uniform coating layer, and avoid high temperature. The covering environment has the disadvantage of breaking the metal spun substrate.
(2)本創作紡絲基材又可選用在有機纖維(如棉、麻)或化學纖維(如錦綸、滌綸、腈綸、氨綸、維綸、丙綸、氯綸等)的金屬鍍層上以電鍍形成金屬氧化物陶瓷鍍層，更具有實用性。 (2) The spinning substrate can be selected from metal plating on organic fiber (such as cotton, hemp) or chemical fiber (such as nylon, polyester, acrylic, spandex, vinylon, polypropylene, chlorin, etc.) to form metal. Oxide ceramic coatings are more practical.
(3)由於本創作在紡絲基材形成了金屬氧化物陶瓷鍍層，金屬氧化物陶瓷鍍層有很好的耐腐蝕能力，可以防止紡絲基材的受環境中化學溶劑、水分、酸、鹼等的腐蝕，使金屬紡絲可經久耐用。更由於鍍有金屬氧化物陶瓷鍍層的金屬紡絲耐蝕性佳，可選用直徑較小的紡絲基材，使兼顧柔軟、耐撓折、耐機器洗滌與耐腐蝕的特性。 (3) Due to the formation of metal oxide ceramic coating on the spinning substrate, the metal oxide ceramic coating has good corrosion resistance, which can prevent the chemical substrate, chemical, solvent, moisture, acid and alkali of the spinning substrate. Corrosion of the metal makes the metal spinning durable. Moreover, due to the excellent corrosion resistance of the metal-plated metal-plated ceramic coating, a spinning substrate having a small diameter can be selected to achieve both softness, flexing resistance, machine washing resistance and corrosion resistance.
(4)由於金屬氧化物陶瓷鍍層的非晶相結構，可以使塗料 樹酯或凝膠有良好附著性，當用二氧化矽凝膠、二氧化鈦凝膠包覆鍍有金屬氧化物陶瓷鍍層的金屬紡絲時，或在金屬氧化物陶瓷鍍層的金屬紡絲上浸塗樹酯時，可達到良好的保護目的。又，藉由金屬氧化物陶瓷鍍層的良好附著性，可提供塗料樹酯或凝膠的附著面，提高附著力與耐蝕特性。 (4) Due to the amorphous phase structure of the metal oxide ceramic coating, the coating can be made The resin or gel has good adhesion when it is coated with a metal oxide ceramic coating with a cerium oxide gel or a titanium dioxide gel, or dip coated on a metal-spun metal oxide coating. When the resin is used, good protection can be achieved. Moreover, by the good adhesion of the metal oxide ceramic plating layer, the adhesion surface of the coating resin or gel can be provided, and the adhesion and corrosion resistance can be improved.
(5)本創作提出的披覆金屬氧化物陶瓷鍍層之金屬紡絲，可將金屬紡絲再進行撚絲(包芯紗)或在後續撚絲、織布或浸染使用各種浸料，由於本創作的金屬紡絲具有耐蝕性，後續紡織的各種浸料不易侵蝕金屬紡絲造成電阻上升或不耐機洗試驗。 (5) The metal spinning of the coated metal oxide ceramic coating proposed in the present invention can be used for spinning the metal wire (core yarn) or using various dipping materials for subsequent twisting, weaving or dip dyeing. The created metal spinning has corrosion resistance, and various dipping materials of subsequent textiles are not easy to erode metal spinning to cause an increase in resistance or an inability to perform machine washing test.
(6)更進一步，本創作提出的披覆金屬氧化物陶瓷鍍層之金屬紡絲，其金屬氧化物陶瓷鍍層具有生物相容性，可包覆含有鎳或銅成分的紡絲基材，由於含有鎳或銅成分的紡絲接觸人體後，有些人會產生過敏反應，在某些產品規範中，金屬紡絲要通過人工汗液的鎳溶出試驗。本創作之金屬紡絲，其金屬氧化物陶瓷鍍層不但防止鎳或銅成分的溶出，更因具有生物相容性，可安全的使用於航太、航空、汽車工業、化工、化纖、紡織、醫藥、食品等領域。 (6) Further, the metal-spun metal coating of the metal oxide ceramic coating proposed by the present invention has a biocompatible ceramic coating, and can be coated with a spinning substrate containing a nickel or copper component. Some people develop an allergic reaction when the nickel or copper component is contacted with the human body. In some product specifications, the metal spinning is tested by the nickel dissolution of artificial sweat. The metal-spun ceramic coating of this creation not only prevents the dissolution of nickel or copper components, but also is biocompatible, and can be safely used in aerospace, aviation, automobile industry, chemical industry, chemical fiber, textile, medicine. , food and other fields.
為使能更進一步瞭解本創作的特徵及技術內容，請參閱以下有關本創作的詳細說明與附圖，然而所附圖式僅提供參考與說明用，並非用來對本創作加以限制者。 In order to further understand the features and technical contents of the present invention, please refer to the following detailed description and drawings of the present invention. However, the drawings are only for reference and description, and are not intended to limit the creation.
1‧‧‧紡絲基材(textile yarn substrate) 1‧‧‧Textile yarn substrate
11‧‧‧金屬鍍層(metal coated layer) 11‧‧‧metal coated layer
2‧‧‧金屬紡絲(metal textile yarn) 2‧‧‧metal textile yarn
3‧‧‧金屬氧化物陶瓷鍍層(metal oxide ceramic coating layer) 3‧‧‧metal oxide ceramic coating layer
31‧‧‧保護層(protection layer) 31‧‧‧protection layer
4‧‧‧三價鉻電鍍液(trivalent chromate electroplating solution) 4‧‧‧trivalent chromate electroplating solution
5‧‧‧鉻元素(chromium element) 5‧‧‧chromium element
6‧‧‧鈷元素(cobalt element) 6‧‧‧cobalt element
7‧‧‧氧元素(oxygen element) 7‧‧‧Oxygen element
第1圖為形成披覆金屬氧化物陶瓷鍍層之金屬紡絲方法的示意圖；第2圖為本創作之電鍍金屬氧化物陶瓷鍍層之第一實施例示意圖；第3圖為本創作之電鍍金屬氧化物陶瓷鍍層之第二實施例示意圖；第4圖為本創作之電鍍金屬氧化物陶瓷鍍層之第三實施例示意圖；以及 第5圖為本創作之電鍍金屬氧化物陶瓷鍍層之第四實施例示意圖。 Fig. 1 is a schematic view showing a metal spinning method for forming a coated metal oxide ceramic coating layer; Fig. 2 is a schematic view showing a first embodiment of the electroplated metal oxide ceramic plating layer; and Fig. 3 is a plating metal oxidation of the present invention. A schematic view of a second embodiment of a ceramic coating; FIG. 4 is a schematic view of a third embodiment of the electroplated metal oxide ceramic coating of the present invention; Figure 5 is a schematic view of a fourth embodiment of the electroplated metal oxide ceramic coating of the present invention.
有關本創作之前述及其他技術內容、特點與功效，在以下配合參考圖式及實施例的詳細說明中，將可清楚的呈現。 The foregoing and other technical contents, features and advantages of the present invention will be apparent from the following description of the drawings and the detailed description.
請參見第1圖，第1圖為本創作採用電鍍形成披覆金屬氧化物陶瓷鍍層之金屬紡絲方法之示意圖，在圖中，於三價鉻電鍍液4中，溶解有三價鉻鹽、錯合劑、黑化劑(blackening additive)與共沉積劑；當金屬紡絲的紡絲基材1開始電鍍時，會使金屬鉻還原而使鉻氧化與磷化、使金屬鈷還原而使鈷氧化或磷化，共同沉積形成金屬氧化物陶瓷鍍層3。金屬氧化物陶瓷鍍層3係由鉻元素5、氧元素7、鈷元素6、氫元素(未標示於圖中)、與磷元素(未標示於圖中)所組成。 Please refer to FIG. 1 , which is a schematic view of a metal spinning method for forming a coated metal oxide ceramic coating by electroplating. In the figure, in the trivalent chromium plating solution 4 , a trivalent chromium salt is dissolved, which is wrong. a mixture, a blackening additive and a co-deposition agent; when the metal-spun spinning substrate 1 starts to be plated, the metal chromium is reduced to oxidize and phosphate the chromium, the metal cobalt is reduced, and the cobalt is oxidized or Phosphating, co-deposition to form a metal oxide ceramic coating 3. The metal oxide ceramic plating layer 3 is composed of chromium element 5, oxygen element 7, cobalt element 6, hydrogen element (not shown in the figure), and phosphorus element (not shown in the figure).
特別說明，在第1圖僅繪示電鍍溶液中，鉻離子與水分子或-HCO2經電鍍形成鉻原子，而鈷離子經電鍍形成鈷原子、鉻原子與氧結合成氧化鉻、鈷原子與氧結合成氧化鈷、其他的氫氧化物或磷化物等，則未繪示於第1圖中。 In particular, in Figure 1, only the plating solution is shown, chromium ions and water molecules or -HCO 2 are electroplated to form chromium atoms, and cobalt ions are electroplated to form cobalt atoms, chromium atoms and oxygen are combined to form chromium oxide, cobalt atoms and The combination of oxygen into cobalt oxide, other hydroxides or phosphides, etc., is not shown in Fig. 1.
紡絲基材1可為金屬或非金屬，當紡絲基材1為金屬時，如不鏽鋼、鐵、鎳、銅、銀、金之一金屬或其合金時，可在紡絲基材1上直接進行電鍍形成金屬氧化物陶瓷鍍層3。另外，當紡絲基材1為棉、麻、玻璃纖維、錦綸、滌綸、腈綸、氨綸、維綸、丙綸、氯綸之一或其組合時，可在紡絲基材1上先以電鍍、無電鍍、蒸鍍、氣相沉積、物理沉積等方法形成金屬鍍層11再採用如上的方法形成金屬氧化物陶瓷鍍層3。 The spinning substrate 1 may be a metal or a non-metal. When the spinning substrate 1 is a metal, such as stainless steel, iron, nickel, copper, silver, gold, or a metal thereof, it may be on the spinning substrate 1. Direct plating is performed to form a metal oxide ceramic plating layer 3. In addition, when the spinning substrate 1 is one of cotton, hemp, glass fiber, nylon, polyester, acrylic, spandex, vinylon, polypropylene, or chloroprene or a combination thereof, the spinning substrate 1 can be electroplated first. The metal plating layer 11 is formed by plating, vapor deposition, vapor deposition, physical deposition, or the like, and the metal oxide ceramic plating layer 3 is formed by the above method.
在台灣專利I456093所揭露使用的三價鉻電鍍方法，其三價鉻電鍍液經創作人長期研究後，為使紡絲基材1(金屬材質或有金屬鍍層11)能減少推拉式電鍍(Roll-to-Roll electroplating method)或浸鍍(dipping electroplating method)對紡絲基材1拉力造成斷裂或延伸，台灣專利I456093所揭露使用的三價鉻電鍍方法已無法應用於細如絲狀的物件電鍍，電鍍方法必須改變，尤其電鍍金屬氧化物陶瓷鍍層3的速度要增加，經本創作人 團隊潛心研究後，三價鉻電鍍液組成如表一或可使用表二。 The trivalent chromium plating method disclosed in Taiwan Patent No. I456093, after the long-term study by the creator of the trivalent chromium plating solution, can reduce the push-pull plating (Roll) for the spinning substrate 1 (metal material or metal plating layer 11) -to-Roll electroplating method or dipping electroplating method causes breakage or elongation of the spinning substrate 1 tensile force. The trivalent chromium plating method disclosed in Taiwan Patent No. I456093 cannot be applied to fine wire-like object plating. , the plating method must be changed, especially the speed of plating the metal oxide ceramic coating 3, the creator After the team devoted research, the composition of the trivalent chromium plating solution is shown in Table 1 or Table 2 can be used.
經三價鉻電鍍液使用表一或表二電鍍形成的金屬氧化物陶瓷鍍層3的組成為：(1)鉻金屬(Cr)與氧化鉻(Cr2O3)，及少量的不同組成的氧與鉻的化合物；(2)三價鉻之氫氧化物(Cr(OH)3)與磷化鉻(CrP)，及少量的不同組成的氫氧根與鉻的化合物、磷與鉻的化合物；(3)鈷(Co)與氧化鈷(Co3O4)，及少量的不同組成的氧與鈷的化合物，如二價鈷或三價鈷之氧化物(三氧化二鈷Co2O3、氧化亞鈷CoO)等；(4)氫氧化鈷(Co(OH)3)與磷化鈷(CoP)，及二價鈷或三價鈷之氫氧化物(如Co(OH)2)、二價鈷或三價鈷之磷化物(如Co3P2)等。 The composition of the metal oxide ceramic coating 3 formed by electroplating of the trivalent chromium plating solution using Table 1 or Table 2 is: (1) chromium metal (Cr) and chromium oxide (Cr 2 O 3 ), and a small amount of oxygen of different composition. a compound with chromium; (2) a hydroxide of trivalent chromium (Cr(OH) 3 ) and chromium phosphide (CrP), and a small amount of a compound of a different composition of hydroxide and chromium, a compound of phosphorus and chromium; (3) Cobalt (Co) and cobalt oxide (Co 3 O 4 ), and a small amount of a compound of oxygen and cobalt of different composition, such as an oxide of divalent cobalt or trivalent cobalt (cobalt trioxide Co 2 O 3 , Cobalt oxide CoO), etc.; (4) Cobalt hydroxide (Co(OH) 3 ) and cobalt phosphide (CoP), and hydroxide of divalent cobalt or trivalent cobalt (such as Co(OH) 2 ), a valence cobalt or a trivalent cobalt phosphide (such as Co 3 P 2 ).
金屬氧化物陶瓷鍍層3的厚度(膜厚)可依據電鍍的條件進行調整，為使該披覆金屬氧化物陶瓷鍍層之金屬紡絲2在電鍍前後的變化尺寸不致影響其紡織時的精度與丹尼數，金屬氧化物陶瓷鍍層3之膜厚較佳為0.5~3μm；對於不同應用時，可延長電鍍的時間與降低電鍍溫度，使厚度可增加至5μm以下，若電鍍的時間再增加則可超過5μm以上，雖其技術可容易達成，但不符實際生產效益。 The thickness (film thickness) of the metal oxide ceramic plating layer 3 can be adjusted according to the plating conditions, so that the variation of the metal spinning 2 of the metal oxide ceramic coating layer before and after electroplating does not affect the precision of the textile and the Dan The film thickness of the metal oxide ceramic plating layer 3 is preferably 0.5 to 3 μm; for different applications, the plating time can be extended and the plating temperature can be lowered, so that the thickness can be increased to less than 5 μm, and if the plating time is increased, More than 5μm, although its technology can be easily achieved, it does not meet the actual production efficiency.
金屬氧化物陶瓷鍍層3之耐候性，鹽霧試驗係依據ASTM B-117於5%氯化鈉霧滴之耐候性試驗至少可通過72小時，可依據電鍍的條件進行調整，對於不同應用可達108小時以上。 Weather resistance of metal oxide ceramic coating 3, salt spray test according to ASTM B-117 in 5% sodium chloride spray weather resistance test for at least 72 hours, can be adjusted according to plating conditions, for different applications More than 108 hours.
本創作提出的披覆金屬氧化物陶瓷鍍層之金屬紡絲2，其金屬氧化物陶瓷鍍層3具有生物相容性(ISO10993)，可包覆含有鎳或銅成分的紡絲基材1，防止鎳或銅成分的溶出，以符合人工汗液的鎳溶出試驗規範，更因具有生物相容性，可安全的使用於各種領域。 The metal-spun 2 coated metal oxide ceramic coating proposed by the present invention has a biocompatible ceramic coating (ISO10993), which can coat a spinning substrate 1 containing a nickel or copper component to prevent nickel. Or the dissolution of the copper component to meet the nickel dissolution test specification of artificial sweat, and more biocompatible, can be safely used in various fields.
生物相容性試驗主要依據之法規為ISO 10993：2003，對於接觸體表之器材，主要試驗項目為1.皮內刺激試驗、2.溶血性試驗、3.皮膚刺激性試驗、4.細胞毒性試驗、5.致敏性試驗。一般要求為：皮內刺激試驗，經24、48、72小時沒有皮膚病變及症狀產生；溶血性試驗，材料應為非溶血性材料，不會造成溶血現象；皮膚刺激性試驗，金屬陶瓷鍍層的PII值落於0~0.4範圍，且萃取液也未對皮膚產生刺激性；細胞毒性試驗，無造成細胞死亡或抑制細胞生長，不具細胞毒性造成溶血現象；致敏性試驗，在過敏攻擊投予後第24、48小時，在皮膚敷料覆蓋區域無可觀察的皮膚反應，不引發延遲性過敏反應。 The biocompatibility test is mainly based on ISO 10993:2003. For equipment that comes into contact with body surface, the main test items are 1. intradermal stimulation test, 2. hemolytic test, 3. skin irritation test, 4. cytotoxicity. Test, 5. Sensitization test. The general requirements are: intradermal stimulation test, no skin lesions and symptoms after 24, 48, 72 hours; hemolytic test, the material should be non-hemolytic material, will not cause hemolysis; skin irritation test, cermet coating The PII value falls within the range of 0 to 0.4, and the extract is not irritating to the skin; the cytotoxicity test does not cause cell death or inhibit cell growth, and does not cause cytotoxic hemolysis; sensitization test, after allergy attack At 24 and 48 hours, there was no observable skin reaction in the area covered by the skin dressing, and no delayed allergic reaction was induced.
若要增加更好的耐候性或增加色澤，可在金屬氧化物陶瓷鍍層3以噴塗或浸塗的方法披覆一樹脂或凝膠的保護層31，該保護層31係附著於該金屬氧化物陶瓷鍍層3之全部或一部份；保護層可為噴浸二氧化矽(SiO2)凝膠形成的二氧化矽(SiO2)包覆層、噴浸二氧化鈦(TiO2)凝膠形成的二氧化鈦(TiO2)包覆層，或噴浸聚矽氧烷化合物、全氟碳化物、全氟樹脂、酚醛樹脂、丙烯酸樹脂、丙烯酸矽改質樹脂的塗料所形成的樹酯包覆層，不為所限。較佳的，該保護層31之厚度為15μm以下。本創作提出的披覆金 屬氧化物陶瓷鍍層之金屬紡絲2，若披覆有保護層31，耐蝕性更提升，其耐候性依據ASTM B-117 5%鹽霧試驗標準至少96小時以上，在生產條件控制良好下鹽霧試驗至少可達128小時以上。對於紡織品色澤的要求，可在保護層31內添加所需要色澤的染料。 In order to increase the weather resistance or increase the color, a protective layer 31 of a resin or gel may be coated on the metal oxide ceramic plating layer 3 by spraying or dip coating, and the protective layer 31 is attached to the metal oxide. all of the plating layer 3 or the ceramic part; protective layer as silicon dioxide can be immersed spray (SiO 2) is formed of silicon dioxide gel (SiO 2) cladding layer, of titanium dioxide are sprayed with titanium oxide (TiO 2) gel formation a (TiO 2 ) coating layer, or a resin coating layer formed by spraying a coating of a polyoxyalkylene compound, a perfluorocarbon, a perfluoro resin, a phenol resin, an acrylic resin, or an acrylic acid modified resin, Limited. Preferably, the protective layer 31 has a thickness of 15 μm or less. The metal spinning 2 coated with the metal oxide ceramic coating proposed by the present invention is more resistant to corrosion if it is covered with the protective layer 31, and its weather resistance is at least 96 hours according to the ASTM B-117 5% salt spray test standard. The salt spray test can be controlled for at least 128 hours under good production conditions. For the requirements of textile color, a dye of a desired color can be added to the protective layer 31.
對於某些應用，可將金屬紡絲2再進行撚絲，例如將天然纖維或化學纖維包覆在金屬紡絲2的外層。另外，金屬紡絲2可在後續撚絲、織布或浸染使用各種浸料，由於本創作的金屬紡絲2具有耐蝕性，後續紡織的各種浸料不易侵蝕金屬紡絲2造成電阻上升或不耐機洗試驗。 For some applications, the metal spun 2 can be re-twisted, for example by coating natural or chemical fibers on the outer layer of the metal spun 2. In addition, the metal spinning 2 can use various dipping materials in the subsequent twisting, weaving or dip dyeing. Since the metal spinning 2 of the present invention has corrosion resistance, various dipping materials of the subsequent textile are not easy to attack the metal spinning 2, causing the resistance to rise or not. Machine wash resistance test.
在下列實施例係為本創作之披覆金屬氧化物陶瓷鍍層之金屬紡絲2之各種實施例，但實際上的態樣不以此為限。 The following examples are various embodiments of the metal-spun 2 of the metal-coated ceramic coating of the present invention, but the actual aspects are not limited thereto.
請參見第2圖，第2圖為本創作之披覆金屬氧化物陶瓷鍍層之金屬紡絲2第一實施例示意圖，金屬紡絲2之紡絲基材1為SUS304不鏽鋼，直徑為50~74μm，容許差±2μm，直徑最大偏差2μm。常見的不鏽鋼絲材質為SUS304、SUS316、SUS317等，不銹鋼金屬紡絲2原材常使用絲拉拔(stainless steel wire drawing)技術所製成，拉出的絲，尺寸精確，表面光潔，且所用拉拔設備和模具簡單，製造容易。絲拉拔技術係在拉拔力的作用下將盤條或線坯從拉絲模的模孔拉出，以生產小斷面的不鏽鋼紡絲基材1，絲拉拔技術也可應用在各種金屬及合金的不同斷面形狀和尺寸的金屬絲。本實施例之不鏽鋼紡絲基材1係使用絲拉拔技術所製成，但不以此為限。 Please refer to FIG. 2, FIG. 2 is a schematic view showing the first embodiment of the metal-spun 2 coated metal oxide ceramic coating. The spinning substrate 1 of the metal-spun 2 is SUS304 stainless steel with a diameter of 50-74 μm. The tolerance is ±2 μm and the maximum deviation of the diameter is 2 μm. Common stainless steel wire materials are SUS304, SUS316, SUS317, etc. Stainless steel metal spinning 2 raw materials are often made by stainless steel wire drawing technology. The drawn wire is accurate in size, smooth in surface, and used in pulling. Pulling equipment and molds is simple and easy to manufacture. The wire drawing technology pulls the wire rod or the wire blank from the die hole of the drawing die under the action of drawing force to produce a stainless steel spinning substrate 1 with a small cross section, and the wire drawing technology can also be applied to various metals. And wires of different cross-sectional shapes and sizes of alloys. The stainless steel spinning substrate 1 of the present embodiment is made by using a wire drawing technique, but is not limited thereto.
本實施例之紡絲基材1上以電鍍形成金屬氧化物陶瓷鍍層3，金屬氧化物陶瓷鍍層3係由鉻元素5、氧元素7、鈷元素6、氫元素(未標示於圖中)、與磷元素(未標示於圖中)所組成，其特性如表三。 On the spinning substrate 1 of the present embodiment, a metal oxide ceramic plating layer 3 is formed by electroplating, and the metal oxide ceramic plating layer 3 is composed of a chromium element 5, an oxygen element 7, a cobalt element 6, a hydrogen element (not shown in the figure), It is composed of phosphorus element (not shown in the figure) and its characteristics are shown in Table 3.
其中，耐蝕性測試評比係以AutoLAB阻抗頻譜分析線性極化試驗，其評比標準如下：1級，線性極化腐蝕電流(安培)小於1×10-7以下、2級，1×10-6以下、3級，1×10-5以下、4級，1×10-4以上；鹽霧試驗係依據ASTM B-117於5%氯化鈉霧滴之耐候性試驗；生物相容試驗係依據ISO10993規範。 Among them, the corrosion resistance test is based on AutoLAB impedance spectrum analysis linear polarization test, the evaluation criteria are as follows: Level 1, linear polarization corrosion current (amperes) less than 1 × 10 -7 below, level 2, 1 × 10 -6 or less , grade 3, 1×10 -5 or less, grade 4, 1×10 -4 or more; salt spray test is based on ASTM B-117 weatherability test of 5% sodium chloride droplets; biocompatibility test is based on ISO10993 specification.
在本實施例之金屬氧化物陶瓷鍍層3厚度薄、耐蝕性佳，符合使用需求。又生物相容性試驗為皮內刺激試驗、溶血性試驗、皮膚刺激性試驗、細胞毒性試驗；本創作之金屬氧化物陶瓷鍍層3經試驗，於皮內刺激試驗經24、48、72小時沒有皮膚病變及症狀產生；於溶血性試驗結果金屬氧化物陶瓷鍍層3非溶血性材料不會造成溶血現象；於皮膚刺激性試驗結果金屬氧化物陶瓷鍍層3的PII值落於0~0.4範圍且以萃取液也未對皮膚產生刺激性；於細胞毒性試驗結果金屬氧化物陶瓷鍍層3並無造成細胞死亡或抑制細胞生長不具細胞毒性造成溶血現象；於致敏性試驗結果金屬氧化物陶瓷鍍層3於24及48小時無引發延遲性過敏反應。 The metal oxide ceramic plating layer 3 of the present embodiment has a small thickness and good corrosion resistance, and meets the requirements for use. The biocompatibility test is an intradermal stimulation test, a hemolysis test, a skin irritation test, and a cytotoxicity test; the metal oxide ceramic coating 3 of the present invention was tested, and the intradermal stimulation test was not performed for 24, 48, and 72 hours. Skin lesions and symptoms are produced; in the hemolytic test results, the metal oxide ceramic coating 3 non-hemolytic material does not cause hemolysis; in the skin irritation test results, the PII value of the metal oxide ceramic coating 3 falls within the range of 0 to 0.4 and The extract also did not cause irritation to the skin; in the cytotoxicity test results, the metal oxide ceramic coating 3 did not cause cell death or inhibited cell growth without cytotoxicity resulting in hemolysis; in the sensitization test results, the metal oxide ceramic coating 3 There was no delayed allergic reaction at 24 and 48 hours.
請參見第3圖，第3圖為本創作之披覆金屬氧化物陶瓷鍍層之金屬紡絲2第二實施例示意圖，金屬紡絲2之紡絲基材1為蒙耐爾合金，直徑為170~184μm，許容差±4μm，最大偏徑差4μm。蒙耐爾合金為以鎳為基礎，添加銅、鐵、錳等金屬，延展性及耐蝕性佳，因蒙耐爾合金的鎳含量很高，蒙耐爾合金製成的金屬紡絲難通過人工汗液的鎳溶出試驗。 Please refer to FIG. 3, FIG. 3 is a schematic view showing a second embodiment of the metal-spun 2 metal-coated ceramic coating of the present invention. The spinning substrate 1 of the metal-spun 2 is a Monel alloy with a diameter of 170. ~184μm, the tolerance is ±4μm, and the maximum deviation is 4μm. Monel alloy is based on nickel and is added with metals such as copper, iron and manganese. It has good ductility and corrosion resistance. Because of the high nickel content of Monel alloy, metal spinning made of Monel alloy is difficult to pass artificial. Nickel dissolution test of sweat.
人工汗液的鎳溶出試驗係依據EN12472：2005(適用于有塗層之產品與皮膚有直接及長期接觸的產品)規定，鎳釋出量不能超出0.5微克/平方釐米/每星期。人工汗液可分為酸性與鹼性，酸性人工汗的配方為L- 組氨酸一鹽酸鹽(C6H10ClN3O2)0.45g、氯化鈉(NaCl)5g/L、磷酸氫二鈉二水合物(Na2HPO4．2H2O)2.2g/L、乳酸(C3H6O3)1.0g/L，使用氫氧化鈉(NaOH)調整溶液PH=4.7。而鹼性人工汗液則為L-組氨酸一鹽酸鹽(C6H10ClN3O2)0.45g/L、氯化鈉(NaCl)5g/L、磷酸氫二鈉二水合物(Na2HPO4．2H2O)5.0g/L、乳酸(C3H6O3)1.0g/L，使用氫氧化鈉(NaOH)調整溶液PH=8.0。 The nickel dissolution test for artificial sweat is based on EN 12472:2005 (for applications where the coated product has direct and prolonged contact with the skin) and the release of nickel must not exceed 0.5 μg/cm 2 /week. Artificial sweat can be divided into acidic and alkaline, and the formula of acidic artificial sweat is L-histidine monohydrochloride (C 6 H 10 ClN 3 O 2 ) 0.45g, sodium chloride (NaCl) 5g / L, hydrogen phosphate Disodium dihydrate (Na 2 HPO 4 .2H 2 O) 2.2 g/L, lactic acid (C 3 H 6 O 3 ) 1.0 g/L, and the solution was adjusted to pH 4.7 using sodium hydroxide (NaOH). The alkaline artificial sweat is L-histidine monohydrochloride (C 6 H 10 ClN 3 O 2 ) 0.45 g / L, sodium chloride (NaCl) 5 g / L, disodium hydrogen phosphate dihydrate (Na 2 HPO 4 .2H 2 O) 5.0 g/L, lactic acid (C 3 H 6 O 3 ) 1.0 g/L, and the solution was adjusted to pH 8.0 using sodium hydroxide (NaOH).
本實施例之紡絲基材1先以電鍍形成金屬氧化物陶瓷鍍層3，再於金屬氧化物陶瓷鍍層3上塗佈二氧化鈦(TiO2)凝膠(so-gel)經固化後形成保護層31，其特性如表四。 The spinning substrate 1 of the present embodiment is first formed by electroplating to form a metal oxide ceramic plating layer 3, and then coated with a titanium oxide (TiO 2 ) gel (so-gel) on the metal oxide ceramic plating layer 3 to form a protective layer 31. Its characteristics are shown in Table 4.
請參見第4圖，第4圖為本創作之披覆金屬氧化物陶瓷鍍層之金屬紡絲2第三實施例示意圖，金屬紡絲2之紡絲基材1為聚對苯二甲酸乙二酯(PET)滌綸，為10丹尼即直徑為30~50μm。本實施例之紡絲基材1先以無電鍍方法在PET紡絲基材1上形成厚度為5μm的銅之金屬鍍層11，再經由電鍍形成金屬氧化物陶瓷鍍層3，再於金屬氧化物陶瓷鍍層3上塗佈二氧化鈦(TiO2)凝膠(so-gel)經固化後形成保護層31，其特性如表五。 Please refer to FIG. 4, FIG. 4 is a schematic view showing a third embodiment of the metal-spun 2 metal-coated ceramic coating of the present invention. The spinning substrate 1 of the metal-spun 2 is polyethylene terephthalate. (PET) polyester, 10 denier, which is 30~50μm in diameter. The spinning substrate 1 of the present embodiment first forms a metal plating layer 11 of copper having a thickness of 5 μm on the PET spinning substrate 1 by electroless plating, and then forms a metal oxide ceramic plating layer 3 by electroplating, and then a metal oxide ceramic. The coating layer 3 is coated with a titanium oxide (TiO 2 ) gel (so-gel) to form a protective layer 31, and its characteristics are shown in Table 5.
請參見第5圖，第5圖為本創作之披覆金屬氧化物陶瓷鍍層之金屬紡絲2第四實施例示意圖，相同於第三實施例，金屬紡絲2之紡絲基材1為聚對苯二甲酸乙二酯(PET)滌綸，本實施例之紡絲基材1先以無電鍍方法在PET紡絲基材1上形成厚度為5μm的銅金屬層，再經由電鍍披覆1μm的銀金屬層，由銅金屬層與銀金屬層構成金屬鍍層11，再經由電鍍形成金屬氧化物陶瓷鍍層3，利用銀金屬層為抗菌功能以應用於醫療之導電與導熱敷料，其特性如表六。 Referring to FIG. 5, FIG. 5 is a schematic view showing a fourth embodiment of the metal spun wire 2 coated with a metal oxide ceramic coating. The spinning substrate 1 of the metal spinning 2 is the same as the third embodiment. For the polyethylene terephthalate (PET) polyester, the spun substrate 1 of the present embodiment first forms a copper metal layer having a thickness of 5 μm on the PET spun substrate 1 by electroless plating, and then coats 1 μm via electroplating. The silver metal layer is composed of a copper metal layer and a silver metal layer to form a metal plating layer 11, and then a metal oxide ceramic plating layer 3 is formed by electroplating, and the silver metal layer is used as an antibacterial function for medical conductive and heat conductive dressings, and its characteristics are as shown in Table 6. .
以上所述僅為舉例性，而非為限制性者。任何未脫離本創作之精神與範疇，而對其進行之等效修改或變更，均應包含於後附之申請專利範圍中。 The above is intended to be illustrative only and not limiting. Any equivalent modifications or alterations to the spirit and scope of this creation shall be included in the scope of the appended patent application.
1‧‧‧紡絲基材(textile yarn substrate) 1‧‧‧Textile yarn substrate
2‧‧‧金屬紡絲(metal textile yarn) 2‧‧‧metal textile yarn
3‧‧‧金屬氧化物陶瓷鍍層(metal oxide ceramic coating layer) 3‧‧‧metal oxide ceramic coating layer
5‧‧‧鉻元素(chromium element) 5‧‧‧chromium element
6‧‧‧鈷元素(cobalt element) 6‧‧‧cobalt element
7‧‧‧氧元素(oxygen element) 7‧‧‧Oxygen element
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