573026 A7 B7 五、發明説明（1 ) 1. 發明範圍 (請先閱讀背面之注意事項再填寫本頁) 本發明係關於無鎳白銅合金，其合適例如用於元件、 滑座、制動器以及滑座扣件，或用於零件例如金屬鈕扣、 衣服扣件等，其具有極佳的強度、硬度、加工性及耐腐鈾 性，不會造成鎳過敏，且不會造成針偵測器故障，以及製 備此無鎳白銅合金的方法。 2. 先前技藝之說明 迄今，銅-鎳-鋅合金例如具有白合金色調之鎳銀、紅黃 銅及黃銅代表之銅鋅合金等曾經使用例如作爲銅合金用於 上述之滑座扣件，但是鎳銀含鎳作爲合金元素，且因此具 有極佳的耐腐飩性，但是如果用於滑座扣件等時，因爲扣 件經常與皮膚接觸，會產生鎳過敏的問題。而且，紅黃銅 及黃銅代表之銅-鋅合金不含鎳且因此不會發生鎳過敏的問 題，但是其色調是黃色，因此無法得到白色合金。 經濟部智慧財產局員工消費合作社印製 本發明者因此硏發且公告無鎳白銅合金之專利申請例 如揭示在日本專利申請公告1 1 -1 24644號、日本專利申請 公告2000-303129號、日本專利申請公告2000-303130號及 日本專利申請公告200 1 -3 1 25號，揭示在日本專利申請公 告1 1 - 1 24644號、日本專利申請公告2000-3 03 1 29號、曰本 專利申請公告2000-3 03 1 3 0號及日本專利申請公告2001 -3 125號之無鎳白銅合金具有極佳的強度、硬度、加工性及 耐腐蝕性，且不含鎳因此不會發生鎳過敏的問題，而且這 些合金因爲可以保持引人程度之白色而具有高裝飾價値。 本紙張尺度適用中國國家標隼（CNS ) A4規格（210X297公釐） ， -4 - 573026 A7 B7 五、發明説明（2 ) 但是，因爲在上述合金中所含的猛是磁性物質，上述 (請先閲讀背面之注意事項再填寫本頁) 合金具有磁性本質，且因此具有的問題是當進行調查使用 針偵測器在縫製物件例如衣服尋找扣針時，造成針偵測器 故障，且因此無法鑑定扣針，在Cu-Mn銅合金其中Μη是 少量添加之情形下，磁性作用小且因此合金不易造成針偵 測器故障，但是一個問題是合金之色調傾向於不是白色， 因此無法得到高品質之印象。 對於上述合金不利於針偵測器之問題，可以想到的辦 法是經由電鍍等進行表面處理，使得不會造成針偵測器故 障，但是在合金表面形成的電鍍膜等因爲隨時間變化、與 其他物質接觸等而可能剝落，在此情形下將會發生問題， 如果經電鍍之基質合金含上述之磁性元素，則將造成針偵 測器故障且因此如上述無法區分扣件，而且將破壞其裝飾 性，另外，雖然不會造成針偵測器故障之銅合金也存在例 如合金之色S周不是白色，或含錬合金其造成錬過敏之問題 ，至今沒有合金可以滿足全部上述要求。 發明槪述 經濟部智慧財產局員工消費合作社印製 因此本發明之目的是提供一種無鎳白銅合金，其具有 相當於鎳銀之強度及極佳的硬度，以及有極佳的加工性、 耐腐蝕性與白色以及延性，且因爲無鎳而沒有鎳過敏問題 ，而且當進行調查使用針偵測器在縫製物件例如衣服尋找 扣針時，不易造成針偵測器故障，本發明之另一個目的是 提供製備此無鎳白銅合金的方法。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 573026 A7 B7 五、發明説明（3 ) 本發明是由下列組成。 (請先閲讀背面之注意事項再填寫本頁) (1) 通式CuaZnbTic代表之無鎳白銅合金，其中b及C 以質量％表示爲0.5SbS30且l^c<7，且a是剩餘部分，也 可能含其他不能避免的元素。 (2) 通式CuaZnbTicXd代表之無鎳白銅合金，其中X是 至少一種選自包括Al、Sn、Ag及Μη之元素，b、c及d以 質量％表示爲0.5SbS30，Kc<7且0.1<d<4，且a是剩餘部 分，也可能含其他不能避免的元素。 (3) 根據上述（1)或（2)之無鎳白銅合金，其在室溫是由單 一 α _相組成。 (4) 根據上述（1)至（3)之無鎳白銅合金，其在18 KOe磁 場中的磁化強度是80 memu/克或更低。 (5) 根據上述（1)至（4)之無鎳白銅合金，其導電度是20 % IACS (International Annealed Copper Standard)或更低 ο (6) 根據上述（1)至（5)之無鎳白銅合金，其中b及c以質 量％表示爲2幺bSl3且3Sc<6。 經濟部智慧財產局員工消費合作社印製 (7) 製備無鎳白銅合金的方法，其包括：製備通式 CUaZnbTie代表之合金，其中 b及 c以質量％表示爲 0.5:ibS30且1么<7,且a是剩餘部分，也可能含其他不能 避免的元素；加熱合金到700至8 8 5 °C ;並冷卻合金。 (8) 製備無鎳白銅合金的方法，其包括：製備通式 CuaZnbTieXd代表之合金，其中X是至少一種選自包括A1 、Sn、Ag及 Μη之元素，b、c及d以質量％表示爲 -6 - 本紙張尺度適用中國國家標隼（CNS ) A4規格（210X297公釐） 573026 A7 B7 五、發明説明（4 ) 0.5AS30，1以<7且〇.1<d<4，且a是剩餘部分，也可能含 其他不能避免的元素；加熱合金到700至8 8 5 °C ;並冷卻合 金。 (請先閲讀背面之注意事項再填寫本頁) (9)製備根據上述（7)或（8)之無鎳白銅合金的方法，其中 該無鎳白銅合金在室溫是由單一 α-相組成。 (1 0)製備根據任何上述（7)至（9)之無鎳白銅合金的方法 ，其中該無鎳白銅合金在18 KOe磁場中的磁化強度是80 memu/克或更低。 (1 1)製備根據任何上述（7)至（10)之無鎳白銅合金的方法 ，其中該無鎳白銅合金之導電度是20% IACS或更低。 較佳具體實施例之詳細說明 以下是本發明無鎳白銅合金的組成物之說明。 本發明之目的可經由上述之組成物達成。 經濟部智慧財產局員工消費合作社印製573026 A7 B7 V. Description of the invention (1) 1. Scope of the invention (please read the notes on the back before filling out this page) The invention is about nickel-free white copper alloy, which is suitable for components, slides, brakes and slides, for example Fasteners, or parts such as metal buttons, clothing fasteners, etc., which have excellent strength, hardness, processability, and corrosion-resistant uranium, will not cause allergy to nickel, and will not cause needle detector failure, and Method for preparing this nickel-free white copper alloy. 2. Description of previous techniques So far, copper-nickel-zinc alloys, such as nickel-silver with white alloy hue, red brass, and copper-zinc alloys represented by brass, have been used, for example, as copper alloys for the above-mentioned slide fasteners, However, nickel-silver contains nickel as an alloying element, and therefore has excellent corrosion resistance. However, if it is used in a slide fastener, etc., because the fastener often contacts the skin, nickel may cause allergy problems. In addition, copper-zinc alloys represented by red brass and brass do not contain nickel and therefore do not cause nickel allergy problems, but their hue is yellow, so white alloys cannot be obtained. The Intellectual Property Bureau of the Ministry of Economic Affairs' employee consumer cooperative printed the patent application issued by the inventor and announced nickel-free copper-nickel alloys, such as disclosed in Japanese Patent Application Publication No. 1 1 -1 24644, Japanese Patent Application Publication No. 2000-303129, Japanese Patent Application Bulletin 2000-303130 and Japanese Patent Application Bulletin 200 1 -3 1 25, disclosed in Japanese Patent Application Bulletin 1 1-1 24644, Japanese Patent Application Bulletin 2000-3 03 1 29, Japanese Patent Application Bulletin 2000 -3 03 1 3 0 and Japanese Patent Application Publication No. 2001 -3 125 The nickel-free white copper alloy has excellent strength, hardness, processability and corrosion resistance, and does not contain nickel, so it does not cause nickel allergy problems. And these alloys have a high decorative price because they can maintain an attractive white color. This paper size applies to China National Standard (CNS) A4 (210X297 mm), -4-573026 A7 B7 V. Description of the invention (2) However, because the fierce magnetic substance contained in the above alloy is the above (please Read the precautions on the back before filling this page) The alloy is magnetic in nature, and therefore has the problem that when using a needle detector to investigate a sewing object such as clothing to find a pin, it will cause the needle detector to malfunction, and therefore cannot be used. Identification of the pin, in the case of Cu-Mn copper alloy where Mn is added in a small amount, the magnetic effect is small and therefore the alloy is not easy to cause the needle detector to malfunction, but one problem is that the tint of the alloy tends not to be white, so high quality cannot be obtained Impression. For the problem that the above alloy is not conducive to the needle detector, a conceivable way is to perform surface treatment through electroplating, etc., so that the needle detector will not cause failure. However, the plating film formed on the alloy surface due to changes with time, and other It may peel off due to material contact, etc. In this case, problems will occur. If the electroplated matrix alloy contains the above-mentioned magnetic elements, it will cause the needle detector to malfunction and therefore, the fastener cannot be distinguished as described above, and its decoration will be damaged. In addition, although copper alloys that do not cause malfunction of the needle detector also have problems such as the color of the alloy is not white, or rhenium-containing alloys cause erbium allergy, so far no alloy can meet all of the above requirements. The invention is described by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economics. Therefore, the object of the present invention is to provide a nickel-free white copper alloy which has the strength and excellent hardness equivalent to nickel silver, and has excellent processability and corrosion resistance. And white and ductility, and no nickel allergy because of nickel-free, and it is not easy to cause the needle detector to malfunction when using a needle detector to search for sewing needles such as clothing, another object of the present invention is to A method of preparing this nickel-free white copper alloy is provided. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 573026 A7 B7 V. Description of the invention (3) The invention consists of the following. (Please read the precautions on the back before filling this page) (1) Nickel-free white copper alloy represented by the general formula CuaZnbTic, where b and C are expressed as 0.5% bS30 and l ^ c < 7 in mass%, and a is the remaining part, May also contain other unavoidable elements. (2) Nickel-free white copper alloy represented by the general formula CuaZnbTicXd, where X is at least one element selected from the group consisting of Al, Sn, Ag, and Mη, b, c, and d are expressed as 0.5% by mass in terms of 0.5SbS30, Kc < 7 and 0.1 <; d < 4, and a is the remainder, and may contain other unavoidable elements. (3) The nickel-free white copper alloy according to (1) or (2) above, which is composed of a single α _ phase at room temperature. (4) The nickel-free white copper alloy according to (1) to (3) above, whose magnetization in an 18 KOe magnetic field is 80 memu / g or less. (5) Nickel-free white copper alloy according to (1) to (4) above, whose conductivity is 20% IACS (International Annealed Copper Standard) or lower. (6) Nickel-free according to (1) to (5) above For a white copper alloy, b and c are expressed as 2% bSl3 and 3Sc < 6 in mass%. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (7) A method for preparing nickel-free copper alloys, including: preparing an alloy represented by the general formula CUaZnbTie, where b and c are expressed in mass% as 0.5: ibS30 and 1? <7 And a is the remainder, and may also contain other unavoidable elements; heat the alloy to 700 to 8 8 ° C; and cool the alloy. (8) A method for preparing a nickel-free white copper alloy, comprising: preparing an alloy represented by the general formula CuaZnbTieXd, wherein X is at least one element selected from the group consisting of A1, Sn, Ag, and Mn, and b, c, and d are expressed as mass% as -6-This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 573026 A7 B7 V. Description of the invention (4) 0.5AS30, 1 with < 7 and 0.1 < d < 4, and a Is the remainder and may also contain other unavoidable elements; heat the alloy to 700 to 8 8 ° C; and cool the alloy. (Please read the notes on the back before filling this page) (9) The method for preparing the nickel-free white copper alloy according to (7) or (8) above, wherein the nickel-free white copper alloy is composed of a single α-phase at room temperature . (10) A method for producing a nickel-free white copper alloy according to any of the above (7) to (9), wherein the magnetization of the nickel-free white copper alloy in a magnetic field of 18 KOe is 80 memu / g or less. (1 1) A method for producing a nickel-free white copper alloy according to any of (7) to (10) above, wherein the electrical conductivity of the nickel-free white copper alloy is 20% IACS or less. Detailed Description of the Preferred Embodiments The following is a description of the composition of the nickel-free white copper alloy of the present invention. The object of the present invention can be achieved by the aforementioned composition. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs
Zn具有經由其固體溶液強化效應改良合金機械性質之 效應、熔化物在熔化過程中的去氧化作用、以及減低合金 成本之效應，如果Zn含量低於上述0.5質量％，則合金成 本之下降將不足，且強化程度及熔化物的去氧化作用也將 不足，而且，如果Zn含量大於30質量％，則將破壞抗季 節裂化。Zn has the effect of improving the mechanical properties of the alloy through its solid solution strengthening effect, the deoxidation of the melt during the melting process, and the effect of reducing the cost of the alloy. If the Zn content is lower than the above 0.5 mass%, the reduction in alloy cost will be insufficient In addition, the degree of strengthening and deoxidation of the melt will also be insufficient, and if the Zn content is greater than 30% by mass, the resistance to seasonal cracking will be destroyed.
Ti經由其固體溶液強化效應具有改良合金機械性質之 效應、以及白化銅合金色調之效應，而且，經由添加T1代 替Zn，具有改良抗季節裂化之效應，Ti也具有降低合金導 電度之效應，因此具有防止針偵測器因爲產生渦電流而故 本紙張尺度適用中國國家標隼（CNS ) A4規格（210X297公釐） · 7 - 573026 Α7 Β7 五、發明説明（5) (請先閲讀背面之注意事項再填寫本頁) 障之效應，如果Ti含量低於1質量％，則其將不可能預期 有白化銅合金色調之效應，如果Ti含量是7質量％或更高 ，則熔化時將產生大量氧化物，因此熔化物澆鑄將變成困 難，且不再可能確保足夠的冷加工性，而且將增加原料之 成本。 X是至少一種選自包括Al、Sn、Ag及Μη之元素，經 由在0.1至4質量％ (其中不包括上限及下限）之範圍內另外 加入這些元素至上述Cu-Zn-Ti合金內，可以預期有下列效 應。 A1及Sn經由在合金表面形成安定氧化物膜而具有改良 抗季節裂化之效應，而且，經由其固體溶液強化效應也具 有改良合金機械性質之效應、以及減低合金成本之效應， 如果含量是0.1質量％或更低，則合金之抗季節裂化將不足 ，且強化效應也將不足，而且，如果含量是4質量％或更 高，則結構將形成a + yS相，且因此將不再確保足夠的冷加 工性。 經濟部智慈財產局員工消費合作社印製The strengthening effect of Ti through its solid solution has the effect of improving the mechanical properties of the alloy and the effect of whitening the tint of the copper alloy. In addition, by adding T1 instead of Zn, it has the effect of improving the resistance to seasonal cracking. Ti also has the effect of reducing the conductivity of the alloy. It has a needle detector to prevent the eddy current from being generated, so the paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) · 7-573026 Α7 Β7 V. Description of the invention (5) (Please read the note on the back first Please fill in this page again.) If the Ti content is less than 1% by mass, it will not be possible to expect the effect of the hue of the albino copper alloy. If the Ti content is 7% by mass or higher, a large amount will be generated during melting. Oxides, and therefore melt casting will become difficult, it will no longer be possible to ensure sufficient cold workability, and the cost of raw materials will be increased. X is at least one element selected from the group consisting of Al, Sn, Ag, and Mn. By additionally adding these elements to the above-mentioned Cu-Zn-Ti alloy in the range of 0.1 to 4% by mass (excluding the upper and lower limits), it is possible to The following effects are expected. A1 and Sn have the effect of improving the seasonal cracking resistance by forming a stable oxide film on the surface of the alloy, and the solid solution strengthening effect also has the effect of improving the mechanical properties of the alloy and the effect of reducing the cost of the alloy. If the content is 0.1 mass % Or lower, the alloy's resistance to seasonal cracking will be insufficient, and the strengthening effect will also be insufficient, and if the content is 4% by mass or higher, the structure will form an a + yS phase, and therefore no longer sufficient Cold workability. Printed by the Consumer Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs
Ag經由其固體溶液強化效應具有改良合金機械性質之 效應、以及白化銅合金色調之效應，而且，經由添加Ag代 替Zn，具有改良抗季節裂化之效應，如果Ag含量是0.1質 量％或更低，則白化銅合金色調之效應將消失，而且，如 果Ag含量是4質量％或更高，則其將不再確保足夠的冷加 工性，且將增加原料之成本。 Μη具有白化銅合金色調之效應，而且，經由添加Μη 代替Ζη，具有改良抗季節裂化之效應，Μη也具有降低合 -8- 本紙張尺度適用中國國家標隼（CNS ) Α4規格（BOX297公釐） 573026 A7 ___B7 五、發明説明（6 ) (請先閱讀背面之注意事項再填寫本頁) 金導電度之效應，因此可以預期具有防止針偵測器因爲產 生渦電流而故障之效應，如果Μη含量是0.1質量％或更低 ，則白化銅合金色調之效應將消失，而且，如果Μη含量是 4質量％或更高，則熔化時將產生大量氧化物，隨著產物之 性質而產生困難，且不再可能確保足夠的冷加工性，而且 將增加磁化強度，因此造成針偵測器故障。 經由合金之結構是由單一 α -相組成，可使冷加工性極 佳，且不易發生針偵測器故障。 而且，經由在1 8 Κ 0 e磁場中的磁化強度是8 0 m e m u / 克或更低，當進行調查使用針偵測器在縫製物件尋找扣針 時，不易造成針偵測器故障，也就是說製成的合金具有極 佳的能力與針偵測器對應，通常，使製成的合金具有針偵 測器對應能力可經由在1 8 KOe磁場中使磁化強度是200 memu/克或更低，但是在本發明中，此磁化強度如上述是 80 memu/克或更低，因此合金有更佳的針偵測器對應能力 〇 另外，20% IACS或更低之導電度是在用針偵測器測 量期間使渦電流不易發生之非常有效的情形。 經濟部智慧財產局員工消費合作社印製 關於上述組成物，如果Zn含量是2至13質量％且Ti 含量是3至6質量％ (其中包括上限及下限），白金之白色程 度與傳統的鎳銀或高錳Cii-Mn銅合金相當，且有更佳的加 工性。 在製造具有本發明所需的這些特徵之合金時，其可得 自經由製備具有上述特定組成物之原料合金（起始合金），加 本紙張尺度適用中國國家標季（CNS ) A4規格（210X297公釐） · Q _ 573〇26 A7 _______B7_ 五、發明説明（7 ) (請先閲讀背面之注意事項再填寫本頁) 熱合金到700至8 8 5 °C ;並隨後將其冷卻，具體地說，在製 備原料合金之階段，原料合金在1 8 KOe磁場中的磁化強度 是高於80 memu/克，但是經由加熱原料合金到700至885 °C並隨後將其冷卻，在1 8 KOe磁場中的磁化強度變成是 memu/克或更低，也就是說磁化強度下降，且因此所得 的合金可以具有較佳的針偵測器對應能力，也就是說所得 的合金將不會造成針偵測器故障，如果加熱溫度是低於上 述溫度範圍，則將存在沈澱物，且因此增加磁化強度，而 且結構不再是單一 α -相，且因此冷加工性將會不良，而且 如果加熱溫度是相反地高於上述溫度範圍，則合金將在高 於Cu-Ti之低共熔溫度加熱且造成熔化狀態（固體-液體共存 之狀態），因而造成降低產品品質。 而且，在此方法中，加熱後的冷卻很重要，快速經由 淬火等進行此冷卻很重要，對於冷卻方法，較宜使用水、 空氣或氣體或其他冷卻介質經由淬火等快速冷卻，具體地 說，在冷卻過程中較宜使冷卻速率至少是1 〇 K/s，經由此 方法進行冷卻，結構變成是單一 α -相，其可用於冷加工， 且因此可以提供從加工方有用途之合金。 經濟部智慧財產局員工消費合作社印製 經由本發明生產的合金是在-2<a*<7及-3<b*<20之範 圍內，以JIS Z 8 729規定的（L*, a*，b*)比色系統之色圖爲 基準。 在本發明中提到的’色調’是使用JIS Z 8729規定的表示 標的物顏色之方法表示且由亮度指數L* (亮度：L星號）及 色指數a* (綠至紅：a星號）及b* (藍至黃：b星號）之値代 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨〇'〆297公釐） _ 1〇 - 573026 A7 B7 五、發明説明（8 ) (請先閱讀背面之注意事項再填寫本頁) 表，具體地說，本發明的一個特性是其中色調是白色，且 因此愈接近無色愈佳，且因此色調是由上述色指數a*及b* 描述。 而且，在本發明中，因爲合金本身是不會造成針偵測 器故障之合金，在合金表面可形成塗覆層，即使塗覆層剝 落，也不會發生造成針偵測器故障且因此無法辨識扣針之' 問題，在形成塗覆層之情形下，a*及b*之範圍必須設定類 似於上述合金，且經由形成塗覆層，可以提供更白的物質 ，在此情形下，即使如果塗覆層發生剝落，因爲形成基質 之合金具有接近塗覆層之顏色，如此將沒有問題，尤其是 關於顏色。 此塗覆層之實例是Sn電鍍層、Cr電鍍層、Ag電鍍層 及Cu-Sn電鍍層，雖然只要塗覆層顯現上述之色調，可以 使用不是這些電鍍層之塗覆層，在形成塗覆層之情形下， 技術可以是濕式或乾式電鍍，例如在濕式電鍍中，可以使 用無電電鍍、熔化電鍍等，且乾式電鍍可以使用物理蒸汽 沈積法（PVD)、化學沈積法（CVD)等。 經濟部智慧財產局員工消費合作社印製 關於塗覆層之厚度，有效的範圍是0.001至10微米， 其中塗膜將預期具有效應、不會發生例如剝落之問題、並 考慮成本，而且決定於用途，此種原料可進行後加工例如 切割或彎曲，在此情形中，考慮由於此加工之剝落、磨損 等，較宜使塗覆層之厚度是在0.005至5微米之範圍。 實例 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公羡） 573026 A7 B7 五、發明説明（9) 以下是本發明經由實例之特定說明，但是本發明當然 不受限於下列實例，在下列實例中，全部百分比是以質量 %表示，除非另外說明。 (請先閲讀背面之注意事項再填寫本頁) 從本發明之合金製成的測試樣品： 如表1及2所示之從本發明之合金製成的測試樣品是 製備如下，並進行評估，實例比較之測試樣品也在相同的 方式下製備。 秤取純 Cu (99.9%)、純 Zn (99.9 至 99.99%)、純 Ti (99.9%)、純A1、純Sn、純Ag、純Μη及純Ni用於製成 200立方公分錠塊之表1及2所示的各組成物，各組成物在 Ar氣壓（1 〇公分汞柱）進行高頻熔化，放置經4分鐘後，將 熔化物倒入銅鑄模（直徑40毫米X長度28毫米），將所得的 錠塊（200立方公分）切成長度約7毫米，因而製成鐵棒用於 擠壓。 經濟部智慧財產局員工消費合作社印製 在鐵棒溫度是800 °C且容器溫度是600 °C下進行擠壓， 擠壓後的物質（直徑8毫米X長度約1 3 00毫米）進行熱處理 ，包括在800 °C加熱1小時後經由爐冷卻（以下稱爲，熱處理 ’），經此熱處理後，將擠壓後的物質（鐵線）進一步加熱至溫 度是7 0 0至8 8 5 °C，然後使用水作爲冷卻介質進行淬火，所 得的物質作爲測試樣品。 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 573026 Α7 Β7 五、發明説明（1G) 經濟部智慧財產局員工消費合作社印製 Οί) e 〇\ OO 卜 CO 1/^) 卜 τ—Η CNl 卜 a ε <υ 1 1 1 1 1 1 1 I 1 1 1 1 UO Η 撞 ε _ d + TILL Μ 鬨 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 X 〇 • 1-Η id 00 u τ~( r—H o On Ο ON On CT\ od τ—Η csi O CNl OO CO < 1—Η ¢1 疝 ¢1 ¢1 卸 ¢1 φ] ¢3 φ] φ] ¢3 φ] ΪΠ ίΠ ΪΠ ΐΠ ΐΠ ft 4Ή 舾 • r-H 1 i 1 1 1 1 1 1 1 1 1 1 寸 1 質量％ ) s 1 1 1 1 1 1 1 1 1 1 1 1 1 ο H ，i m U~) csi CO CO CNl CS1 CO 0.5 o 1 1 1 c o o cn 卜 ΐ ' i OO V Ο 1 un o 寸 u〇 N r—< r—< CNl CN CNl CN cn csi τ—Η CNl τ—( Φ Φ φ Φ Φ Φ φ φ I^L. 哨n t£2. 如 t^2. 相Π 书η 哨η b£l b£l t^L b^L 切n 切n b£l 哨Π ^Ω. 爷Π 切Π U <tmii <inni 雜 貔 雜 蘊 雜 雜 雜 frmT 靈 Μ 靈 藤 靈 藤 ΠτοΓ Μ ilnV 露 藤 藤 Μ y 1 C<l cn 寸 VO 〇〇 On 7—< CNl cn 寸 ---------衣-- (請先閲讀背面之注意事項再填寫本頁) 、1Τ 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） -13- 573026 A7 B7 五、發明説明（11) 經濟部智慧財產局員工消費合作社印製 磁性作用 § ε 寸 1 oo 1 CO C-p ON CN CNl «ο t " '< 1 他 α + β j Ni過敏 〇 〇 〇 〇 〇 〇 O Ο Ο 〇 〇 〇 X 導電性 IACS% \ Η On 〇 ON On On 卜 cn cn CO r- 色調 却 4Ή in ¢1 4Ή 4Ή 切 ¢1 黃色 黃色i ¢1 ΐΠ 却 4Ή 合金組成物（質量％) 1 1 1 1 1 1 1 1 1 1 1 1 s 1 CN1 1 1 1 1 1 CnI 1 1 1 ο 1 1 1 1 1 1 1 1 1 r- i 1 1 1 1 1 1 1 1 r-H 1 1 1 1 1 ι/Ί 1 1 f i 1 cn \ ' < CO 1 1 1 1 1 ， ( CO uo CN| CO esi CN CN CO υη ο CN 1 ο r—Η ο cn t—H 〇5 VD esi ι/Ί CO ί〇 τ—Η 剩餘部分 剩餘部分 剩餘部分 剩餘部分 剩餘部分 剩餘部分 剩餘部分 剩餘部分1 剩餘部分 剩餘部分 剩餘部分 剩餘部分 剩餘部分 \ < OCI CO Γ un 卜 〇〇 On τ—Η C^l cn 寸 悔粼郜W _(孽 κ蓐:Η鎰 — (請先閲讀背面之注意事項再填寫本頁)Ag has the effect of improving the mechanical properties of the alloy through its solid solution strengthening effect and the hue of the albino copper alloy, and also has the effect of improving the resistance to seasonal cracking by adding Ag instead of Zn. If the Ag content is 0.1% by mass or less, The hue effect of the albino copper alloy will disappear, and if the Ag content is 4% by mass or more, it will no longer ensure sufficient cold workability, and the cost of raw materials will be increased. Mn has the effect of hue of albino copper alloy, and by adding Mn instead of Zn, it has the effect of improving the anti-seasonal cracking. Mn also has the effect of reducing the -8- This paper size is applicable to China National Standard (CNS) A4 specification (BOX297 mm ) 573026 A7 ___B7 V. Description of the invention (6) (Please read the precautions on the back before filling out this page) The effect of gold conductivity, so it can be expected to have the effect of preventing the needle detector from malfunctioning due to eddy current. If Μη If the content is 0.1% by mass or less, the hue effect of the albino copper alloy will disappear, and if the Mη content is 4% by mass or more, a large amount of oxides will be generated during melting, which will cause difficulties depending on the nature of the product. It is no longer possible to ensure sufficient cold workability, and the magnetization will increase, thus causing the needle detector to malfunction. The structure of the alloy is composed of a single α-phase, which can provide excellent cold workability and is less prone to needle detector failure. In addition, the magnetization in a magnetic field of 1 8 Κ 0 e is 80 memu / g or lower. When a survey is performed using a needle detector to find a needle in a sewing object, it is not easy to cause the needle detector to malfunction, that is, It is said that the made alloy has excellent ability to correspond to the needle detector. Generally, the alloy made with the needle detector can correspond to a magnetization of 200 memu / g or lower in a magnetic field of 1 8 KOe. However, in the present invention, the magnetization is 80 memu / g or lower as mentioned above, so the alloy has a better needle detector corresponding ability. In addition, the conductivity of 20% IACS or lower is detected by the needle. A very effective situation in which eddy currents are less likely to occur during the measurement of a detector. Printed on the above composition by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, if the Zn content is 2 to 13 mass% and the Ti content is 3 to 6 mass% (including the upper and lower limits), the whiteness of platinum is similar to that of traditional nickel silver Or high manganese Cii-Mn copper alloy is equivalent, and has better processability. When manufacturing an alloy with these characteristics required by the present invention, it can be obtained by preparing a raw material alloy (starting alloy) with the above-mentioned specific composition, plus the paper size applicable to the Chinese National Standard Season (CNS) A4 specification (210X297 Mm) · Q _ 573〇26 A7 _______B7_ V. Description of the invention (7) (Please read the notes on the back before filling this page) Thermal alloy to 700 to 8 8 5 ° C; and then cool it down, specifically That is, in the stage of preparing the raw alloy, the magnetization of the raw alloy in a magnetic field of 1 8 KOe is higher than 80 memu / g, but by heating the raw alloy to 700 to 885 ° C and then cooling it, the magnetic field is in a magnetic field of 1 8 KOe The magnetization in the medium becomes memu / g or lower, which means that the magnetization decreases, and therefore the resulting alloy can have better corresponding ability of the needle detector, which means that the obtained alloy will not cause needle detection. Device failure, if the heating temperature is lower than the above temperature range, there will be precipitates, and therefore increase the magnetization, and the structure is no longer a single α-phase, and therefore the cold workability will be poor, and if The heating temperature is conversely higher than the above temperature range, then the alloy will be low in the high-Cu-Ti eutectic temperature of the heated and molten state cause (solid - liquid coexistence of the state), resulting in lower product quality. Moreover, in this method, cooling after heating is important, and it is important to quickly perform the cooling through quenching. For the cooling method, it is preferable to use water, air, or a gas or other cooling medium to rapidly cool through quenching, specifically, In the cooling process, the cooling rate is preferably at least 10 K / s. After cooling through this method, the structure becomes a single α-phase, which can be used for cold working, and therefore, it can provide an alloy useful from the processing side. The alloy produced by the present invention printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is within the range of -2 < a * < 7 and -3 < b * < 20 and is specified in JIS Z 8 729 (L *, a *, b *) The color chart of the colorimetric system is used as a reference. The “hue” mentioned in the present invention is expressed using a method for expressing the color of a target object specified by JIS Z 8729 and is represented by a brightness index L * (brightness: L asterisk) and a color index a * (green to red: a asterisk) and b * (blue to yellow: b asterisk) the paper size of this paper applies the Chinese National Standard (CNS) A4 specification (2 丨 〇'〆297 mm) _ 10- 573026 A7 B7 V. Description of the invention (8) ( Please read the notes on the back before filling in this page) table. Specifically, one characteristic of the present invention is that the hue is white, and therefore the closer it is to colorless, the better, and therefore the hue is determined by the above color indexes a * and b *. description. Moreover, in the present invention, because the alloy itself is an alloy that does not cause a malfunction of the needle detector, a coating layer can be formed on the surface of the alloy, and even if the coating layer is peeled off, the malfunction of the needle detector will not occur and therefore cannot be performed. Identify the problem of the pin. In the case of forming a coating layer, the range of a * and b * must be set similar to the above alloy, and by forming the coating layer, a whiter substance can be provided. In this case, even if If the coating is peeled off, because the matrix-forming alloy has a color close to that of the coating, there will be no problem, especially with regard to color. Examples of this coating layer are a Sn plating layer, a Cr plating layer, an Ag plating layer, and a Cu-Sn plating layer. Although the coating layer exhibits the above-mentioned color tone, a coating layer other than these plating layers may be used to form a coating. In the case of a layer, the technology can be wet or dry plating. For example, in wet plating, electroless plating, melt plating, etc. can be used, and dry plating can use physical vapor deposition (PVD), chemical deposition (CVD), etc. . The thickness of the coating is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and the effective range is 0.001 to 10 microns, where the coating film is expected to have an effect, no problems such as peeling will occur, and cost is considered, and it depends on the use Such raw materials can be subjected to post-processing such as cutting or bending. In this case, it is preferable to make the thickness of the coating layer in the range of 0.005 to 5 microns due to peeling and abrasion of the processing. Examples This paper size applies the Chinese National Standard (CNS) A4 specification (210X297). 573026 A7 B7 V. Description of the invention (9) The following is a specific description of the invention through examples, but the invention is of course not limited to the following examples. In the following examples, all percentages are expressed as mass% unless otherwise specified. (Please read the notes on the back before filling this page) Test samples made from the alloy of the present invention: As shown in Tables 1 and 2, test samples made from the alloy of the present invention are prepared as follows and evaluated, The test samples for the comparative examples were also prepared in the same manner. Weigh pure Cu (99.9%), pure Zn (99.9 to 99.99%), pure Ti (99.9%), pure A1, pure Sn, pure Ag, pure Mη, and pure Ni to make a table of 200 cubic centimeter ingots Each composition shown in 1 and 2 is melted at a high frequency under Ar pressure (10 cm Hg). After being left for 4 minutes, the melt is poured into a copper mold (40 mm in diameter X 28 mm in length) , The obtained ingot (200 cubic centimeters) was cut into a length of about 7 mm, so an iron rod was made for extrusion. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs at an iron rod temperature of 800 ° C and a container temperature of 600 ° C. The extruded material (diameter 8 mm X length 1 300 mm) is heat treated. Including heating at 800 ° C for 1 hour via furnace cooling (hereinafter referred to as heat treatment), after this heat treatment, the extruded material (iron wire) is further heated to a temperature of 70 to 8 8 5 ° C Then, quenching is performed using water as a cooling medium, and the obtained substance is used as a test sample. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 573026 Α7 Β7 V. Description of the invention (1G) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 〇) e 〇 \ OO CO 1 / ^ ) Τ—Η CNl bu a ε < υ 1 1 1 1 1 1 1 I 1 1 1 1 UO Η collision ε _ d + TILL Μ coax 〇 〇〇〇〇〇〇〇〇〇〇〇〇〇 1 -Η id 00 u τ ~ (r—H o On Ο ON On CT \ od τ—Η csi O CNl OO CO < 1—Η ¢ 1 hernia ¢ 1 ¢ 1 unloading ¢ 1 φ] ¢ 3 φ] φ) ¢ 3 φ] ΪΠ ίΠ ΪΠ ΐΠ ΐΠ ft 4Ή 舾 • rH 1 i 1 1 1 1 1 1 1 1 1 1 inch 1 mass%) s 1 1 1 1 1 1 1 1 1 1 1 1 1 1 ο H, im U ~) csi CO CO CNl CS1 CO 0.5 o 1 1 1 coo cn ΐ 'i OO V Ο 1 un o inch u〇N r— < r— < CNl CN CNl CN cn csi τ—Η CNl τ— ( Φ Φ φ Φ Φ Φ φ φ I ^ L. £ 2. Such as t ^ 2. Phase Π Book whistle η b £ lb £ lt ^ L b ^ L Cut n Cut nb £ l Whistle ^ Ω. 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Description of the invention (11) Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Cooperative printed magnetic effect § ε inch 1 oo 1 CO Cp ON CN CNl «ο t " '< 1 other α + β j Ni allergy 〇〇〇〇〇〇〇 〇 〇 〇 〇〇〇X conductivity IACS% \ Η On 〇ON On On CO cn CO r- color tone 4Ή in ¢ 1 4Ή 4Ή cut ¢ 1 yellow yellow i ¢ 1 ΐΠ but 4Ή alloy composition (mass%) 1 1 1 1 1 1 1 1 1 1 1 1 1 s 1 CN1 1 1 1 1 1 CnI 1 1 1 ο 1 1 1 1 1 1 1 1 1 1 r- i 1 1 1 1 1 1 1 1 rH 1 1 1 1 1 ι / Ί 1 1 fi 1 cn \ '< CO 1 1 1 1 1 ， (CO uo CN | CO esi CN CN CO υη ο CN 1 ο r—Η ο cn t—H 〇5 VD esi ι / Ί CO ί〇τ—Η remainder remainder remainder remainder remainder remainder remainder remainder 1 remainder Part of the remainder of the remainder of the remainder of the remainder of the remainder of the remaining part \ < OCI CO Γ un 卜 〇On On τ—Η C ^ l cn contreshing 悔 W _ (郜 κ 蓐: 孽 — (Please read the precautions on the back before (Fill in this page)
、1T 本紙張尺度適用中國國家標準（CNS ) A4規格（2IOX297公釐） 573026 A7 B7 五、發明説明（12) 測試樣品之評佔： 關於色調，使用Sic砂紙及鑽石糊將所得的測試樣品 鏡面拋光，使用光度計（CR-3 00，Minolta Co·，Ltd製造）測 量，並將測量結果藉由JIS Z 8729規定之L*、a*及b*表示 ，如果a*及b*是在先前說明之範圍內，則將色調記錄成’白 色’，否則記錄主要的顏色，本發明全部測試樣品之色調都 是白色，具體地說是白色接近無色。 關於導電性，將各測試樣品之樣品表面鏡面拋光，將 數位導電計（AutoSigma 3000，Hocking Kabushiki Kaisha 製 造）之測量探针放置與樣品表面接觸，並測量導電値，發現 本發明測試樣品之値非常良好在1 2 % IA C S或更低，因此 可見渦電流在用偵探測器測量期間將非常困難發生，對於 與偵探測器對應，此點及下述磁化強度係非常重要的性質 〇 關於鎳過敏，根據測試樣品是否含鎳進行評估，符號 ’ 〇 ’表示不含鎳且符號’ X ’表示含鎳，本發明全部測試樣品都 不含鎳且因此是沒有因爲鎳造成的過敏問題之材料。 關於結構，將所得的測試樣品進行結構觀察，本發明 之測試樣品只由α -相組成。 使用交變梯度力磁強計（型號 AFGM 2900-04C， Princeton Measurements Corp.製造）測量所得的各測試樣品 之磁化強度，將約〇 · 1克測試樣品放在電磁鐵之磁場內，使 用電磁鐵產生1 8 KOe之磁場，並經由改變磁場測量測試樣 品之磁化強度，測量速率是5 0毫秒/點，發現本發明測試樣 本紙張尺度適用中國國家標隼（CNS ) A4規格（210 X297公釐） I---------^^水-- (請先閱讀背面之注意事項再填寫本頁)、 1T This paper size applies the Chinese National Standard (CNS) A4 specification (2IOX297mm) 573026 A7 B7 V. Description of the invention (12) Evaluation of test samples: Regarding the color tone, use Sic sandpaper and diamond paste to mirror the test sample Polishing was measured using a photometer (CR-3 00, manufactured by Minolta Co., Ltd.), and the measurement results were expressed by L *, a *, and b * specified in JIS Z 8729. If a * and b * were previously Within the scope of the description, the hue is recorded as 'white', otherwise the main color is recorded. The hue of all the test samples of the present invention is white, specifically white is nearly colorless. Regarding the electrical conductivity, the surface of each test sample was mirror-polished, the measurement probe of a digital conductivity meter (AutoSigma 3000, manufactured by Hocking Kabushiki Kaisha) was placed in contact with the surface of the sample, and the electrical conductivity was measured. Good at 12% IA CS or lower, so it can be seen that eddy current will be very difficult to occur during the measurement with the detection detector. For correspondence with the detection detector, this point and the following magnetization are very important properties. About nickel allergy The evaluation is based on whether the test sample contains nickel. The symbol '0' means nickel-free and the symbol 'X' means nickel. All the test samples of the present invention are nickel-free and therefore are materials without allergy problems caused by nickel. Regarding the structure, the obtained test sample was subjected to structural observation, and the test sample of the present invention consisted of only an α-phase. The magnetization of each test sample was measured using an alternating gradient force magnetometer (model AFGM 2900-04C, manufactured by Princeton Measurements Corp.). About 0.1 g of the test sample was placed in a magnetic field of an electromagnet, and an electromagnet was used. Generate a magnetic field of 18 KOe and measure the magnetization of the test sample by changing the magnetic field. The measurement rate is 50 milliseconds / point. It is found that the paper size of the test sample of the present invention is applicable to the Chinese National Standard (CNS) A4 specification (210 X297 mm). I --------- ^^ Water-- (Please read the precautions on the back before filling this page)
、1T 經濟部智慧財產局員工消費合作社印製 573026 A7 _ B7 五、發明説明（13) 口口即使在18 ICOe之強磁場下只有50 menu /克或更低之非常 低的磁化作用，在表內，負値之磁化作用表示反磁性，且 (請先閱讀背面之注意事項再填寫本頁) 暗指磁化作用是接近〇之値，而且，’_，表示沒有進行測量 〇 從上述結果可以看出爲了得到具有極佳磁化作用及導 電性之材料，使用根據本發明之合金組成物及根據發明之 製造方法非常重要。 而且，對於本發明之測試樣品，硬度是1 〇〇〇 Hv或更 高，80 %變形後沒有裂縫等，對於抗褪色及抗季節裂化可 以得到極佳的結果。 經濟部智慧財產局員工消費合作社印製 根據無鎳白銅合金及生產本發明無鎳白銅合金之方法 ，此合金具有極佳強度及硬度、延展性、極佳的加工性、 抗腐蝕性、抗褪色及抗季節裂化，並有極佳的白色，且因 此可提供具有高裝飾價値之合金，而且，因爲此合金不含 鎳，沒有鎳過敏問題，另外，即使在1 8 KOe之強磁場下也 只有非常低的磁化作用，因此當進行調查使用針偵測器在 縫製物件例如衣服尋找扣針時，此合金不會造成針偵測器 故障，由於這些特點，此合金非常合適作爲裝飾品之合金 使用，特別是作爲在物件中經由縫製連接的合金使用，而 且，根據生產本發明無鎳白銅合金之方法，可以輕易地生 產具有上述極佳性質之合金，且因此可提供具有上述極佳 性質之合金用於不同的用途。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） _ 16 _Printed by 1T Consumer Intellectual Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 573026 A7 _ B7 V. Description of the invention (13) The mouth has a very low magnetization of 50 menu / g or less even under the strong magnetic field of 18 ICOe. Here, the magnetization of negative 値 indicates diamagnetism, and (please read the precautions on the back before filling this page), which implies that the magnetization is close to 〇, and '_' means that no measurement has been performed. From the above results, you can see In order to obtain a material having excellent magnetization and electrical conductivity, it is very important to use the alloy composition according to the present invention and the manufacturing method according to the present invention. Moreover, for the test sample of the present invention, the hardness is 1000 Hv or higher, and there is no crack after 80% deformation, etc., and excellent results can be obtained for resistance to fading and seasonal cracking. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs According to the nickel-free white copper alloy and the method for producing the nickel-free white copper alloy of the present invention, this alloy has excellent strength and hardness, ductility, excellent processability, corrosion resistance, and fade resistance And anti-seasonal cracking, and has excellent white, and therefore can provide alloys with high decorative value, and because this alloy does not contain nickel, there is no nickel allergy problem, in addition, even under the strong magnetic field of 18 KOe only Very low magnetization, so when investigating the use of a needle detector to find needles in sewing items such as clothes, this alloy will not cause the needle detector to malfunction. Due to these characteristics, this alloy is very suitable for use as an alloy for decorations Particularly, it is used as an alloy connected by sewing in an object, and according to the method for producing the nickel-free copper alloy of the present invention, an alloy having the above excellent properties can be easily produced, and therefore an alloy having the above excellent properties can be provided For different purposes. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) _ 16 _