200426231 玖、發明說明： 【發明所屬之技術領域】 本發明係關於一種無氧銅合金，其中有提高耐 金化材料。此合金尤其適合使用於合金需要良好 良好導電性兩者的目的。本發明亦關於銅合金之 合金之用途。 【先前.技術】 最常使用之銅品質的氧含量，所謂的ETP銅（1 典型上係200-400 ppm。氧在一般的製程中會自 銅中。由於氧會與有害物質結合成較無害之氧化 亦可故意使氧含量維持於一期望值下。銅之導電 當銅愈純時愈高，此外，結合於銅中之氧會使傳導 銅之導熱性係與其之導電性成比例。尤其為改良 亦製造具不高於lOppm之氧含量之所謂的無氧銅 銅之製造中，經由於熔體上方使用保護性還原層 墨），經由使用保護性氣體（例如氮）或經由使用真 止氧與熔融銅接觸。 無氧銅之财溫性已經由將銀合金化於銅中（例女 重量之0 . 0 2 - 0 . 3 % )而獲改良。稍早亦將鎂使用作 化成分，其一般係以非常小的含量使用。一般同 他合金成分。舉例來說，公告118-5118470、1?_八-及J P - A- 0 3 2 9 1 3 4 0中說明此等類型之合金，其係 使用於半導體技術中之連接線。經由熔融，線經 有完美球形之液滴。該材料亦具有良好的拉伸強 312/發明說明書(補件)/93-06/93108493 溫性之合 耐溫性及 製造及銅 :解靭煉） 然結合於 物，因而 性始終係 •性降低。 導電性， 。在無氧 (例如石 空，而防 ]，合金 為微合金 時使用其 62080241 用於製造 形成為具 度。除開 5 200426231 其他材料，鎂亦於例如公告J P - A - 6 3 1 4 0 0 5 2中被建議作為 合金成分。在此，含量3-10ppm之鎂可使銅之軟化溫度降 低。 【發明内容】 本發明之目的係要消除先前技藝之一些缺點，及獲致改 良的無氧銅合金。本發明之基本特徵列於申請專利範圍中。 根據本發明，當計算合金重量時，使超過3 0 ppm之鎂 合金化於無氧銅中。因此，耐溫性獲得改良，同時導電性 及因此導熱性亦維持於高的值下。根據本發明之無氧銅合 金的鱗含量係超過30 ppm，以超過50 ppm較佳。錢含量 不高於180 ppm，以不高於150 ppm較佳。合金之氧含量 不高於10 ppm，以不高於5 ppm較佳，諸如1-3 ppm。此 合金尤其適合使用於需要良好耐溫性，及同時需要良好導 電性或導熱性之產品中。利用根據本發明之鎂合金化，銅 之耐溫性顯著地獲得改良。 【實施方式】 銅之耐溫性一般係以所謂的半軟化溫度（T Μ )表示。然 而，半軟化溫度係顯著地視變形程度而定。為得到可比較 的結果，半軟化溫度一般係以4 0 %及9 4 %之變形程度定義。 銅之導電性一般係以所謂的I ACS值（國際退火銅標準） 表示。其將導電性以標準未合金化銅之導電性的百分比表 示。無氧銅品質之導電性係至少1 0 0 % I A C S。 根據本發明之銅合金的半軟化溫度係至少與含 0 . 3 - 0 . 2 5 %銀之合金為相同數量級。對於4 0 %之變形程度， 6 312/發明說明書(補件)/93-06/93108493 200426231 半軟化溫度係至少3 4 0 °C，以至少3 8 0 °C較佳。對於9 4 %之 變形程度，半軟化溫度係至少3 0 0 °C，以至少3 3 5 °C較佳。 導電性將仍與合金化無關地維持於高的值（超過1 0 〇 % I ACS ) 下。導電性係至少約1 0 1 % I A C S較佳。 對於超過1 8 0 p p m之含量，相對於鎂量之耐溫性的改良 基本上將減弱。導電性及可鑄造性亦將減弱。對於低於3 0 ppm之鎮含量，實質上未獲致财溫性的基本改良。 在此，鎂使純銅之再結晶溫度提高。鎂原子較銅原子 大，因此晶格結構經扭曲，及產生張力。因此，差排之移 動變得更為困難。 由於鎂顯著地較銀便宜，且其之需要量顯著低於銀，因 而藉由本發明，可相較於使用銀獲致費用的節省。由於小 量的合金成分，亦可更自由地選擇合金化技術。 鎮合金化銅可利用與其他品質之無氧銅類似的製造技 術製造，例如以板塊或桿鑄造，作為水平或垂直鑄造。在 一適當的方法步驟中，例如於鑄造爐中，加入所需量的鎂。 由於鎂對於與氧反應敏感，因而必需特別注意對空氣的防 護。此外，在與熔體接觸之裝置中，最好使用不含氧化物 之材料，以使鎂無法與氧結合。於鑄造之後一般接著進行 熱處理及加工。一典型的製造路徑可為板塊向下鑄造，及 利用熱鑄及冷鑄加工。對於此等含量，鎂會產生二次晶粒 結構，當選擇加工溫度時，必需將其列入考慮。 磷、矽及硫會與鎂反應，因而減低耐溫性的改良。因此， 該不純物之總含量不高於1 0 p p m較佳。 7 312/發明說明書(補件)/93-06/93108493 200426231 可將根據本發明之銅使用於需要良好耐溫性之目的 中。其係例如包括數個部分，且使用於將各部分配合在一 起之樹脂之溫度將會上升至高於2 0 0 °C之電馬達的整流 器。此外，可將本發明之銅合金使用於在高溫下塗布之基 板材料中。比方說，太陽能電池板（s ο 1 a r p a n e 1 s )係利用 高溫塗布方法製造。一目的亦係使用於熔接之電極尖端， 以於Μ I G熔接中較佳，及使用於發電機中之扁鋼（f 1 a t b a r s ) 及外形，其中本發明之銅合金取代更為昂貴的銅銀合金。 在根據本發明之合金中，亦可使用其他合金成分。其尤 其係銀及磷。熟知銀會使半軟化溫度提高。銀含量最好不 高於5 0 0 p p in。其他可能的合金成分係例如硫、錫、鋅、 錄、石夕及蹄。其之含量最好不高於5 0 p p m。錫亦會使半軟 化溫度提高，但其之效率不如鎂，且更甚者，其會使傳導 性下降較大程度。 (實施例） 製造鎂合金化之無氧銅合金，其中將合金重量之50、100 及1 5 0 p p m之鎂合金化。將合金之耐溫性及導電性與已知 之銀-銅合金的耐溫性及導電性比較。 由各材料製造8毫米之經退火線。測量線之導電性。其 後將線章伸至6 . 2毫米（變形程度4 0 % )或2毫米（變形程度 9 4 % )厚度。使線於鹽浴中（1小時）在2 5 0 - 5 0 0 °C之範圍内退 火。將結果示於下表，在表中，例如M g 5 0 p p m之標示係指 本發明之合金含有5 0 p p hi錤，及C u A g 0 . 0 3之標示係指先 前技藝之銅合金含有0 . 0 2 7 - 0 . 0 5重量％之銀。 8 312/發明說明書(補件)/93-06/93108493 200426231 合金 Ag[重量％] 導電性 [%IACS] Ί 4 0 % [ °C ] T ^ 9 4%[〇C ] C uA g 0 . 0 3 0.027-0. 05 100.88 340 295 C u A g 0 . 1 0.085-0.12 100.77 360 325 C u A g 0 . 2 0.20-0.25 1 01 . 10 380 340 M g 5 0 p pm — 1 01 . 95 363 310 Mg 10 0 ppm 一 101.40 379 335 MrI5〇Dpm 一 100.84 386 340 明顯可見對於5 0 - 1 5 0 ppm之鎂含量，獲致至少與 0 . 0 2 7 - 0 . 2 5 %之銀含量同樣良好的性質。 312/發明說明書(補件)/93-06/93108493200426231 (1) Description of the invention: [Technical field to which the invention belongs] The present invention relates to an oxygen-free copper alloy, among which there is a material for improving the metallization resistance. This alloy is especially suitable for the purpose that the alloy needs both good electrical conductivity. The invention also relates to the use of alloys of copper alloys. [Previous. Technology] The most commonly used copper-quality oxygen content is the so-called ETP copper (1 typically 200-400 ppm. Oxygen will be in copper in the general process. Because oxygen will be harmless when combined with harmful substances Oxidation can also deliberately maintain the oxygen content at a desired value. The electrical conductivity of copper is higher when the copper is more pure. In addition, the oxygen incorporated in copper will make the thermal conductivity of the conductive copper proportional to its electrical conductivity. Especially Improve the production of so-called oxygen-free copper copper with an oxygen content not higher than 10 ppm by using a protective reducing layer ink above the melt), by using a protective gas (such as nitrogen) or by using true oxygen stop Contact with molten copper. The financial properties of oxygen-free copper have been improved by alloying silver in copper (eg 0.02-0.3% by weight). Earlier, magnesium was also used as a chemical ingredient, which is generally used in a very small amount. Generally the same alloy composition. For example, Bulletin 118-5118470, 1? _Ya- and J P-A- 0 3 2 9 1 3 4 0 describe these types of alloys, which are connection wires used in semiconductor technology. After melting, the thread passes through perfectly spherical droplets. This material also has good tensile strength 312 / Invention Manual (Supplement) / 93-06 / 93108493 Temperature resistance combined with temperature resistance and manufacturing and copper: Toughening refining) It is bound to the material, so the nature is always reduce. Conductivity,. In the absence of oxygen (such as stone air, and defense), when the alloy is a microalloy, it is used in the production of 62,080,241. In addition to 5 200426231, magnesium is also disclosed in, for example, JP-A-6 3 1 4 0 0 5 It is suggested as an alloy component in 2. Here, the magnesium content of 3-10 ppm can reduce the softening temperature of copper. [Abstract] The purpose of the present invention is to eliminate some of the disadvantages of the prior art and to obtain an improved oxygen-free copper alloy. The basic characteristics of the present invention are listed in the scope of patent application. According to the present invention, when calculating the alloy weight, magnesium alloy exceeding 30 ppm is alloyed in oxygen-free copper. Therefore, the temperature resistance is improved, and the electrical conductivity and Therefore, the thermal conductivity is also maintained at a high value. The scale content of the oxygen-free copper alloy according to the present invention is more than 30 ppm, preferably more than 50 ppm. The money content is not higher than 180 ppm, and preferably not higher than 150 ppm. The oxygen content of the alloy is not higher than 10 ppm, preferably not higher than 5 ppm, such as 1-3 ppm. This alloy is particularly suitable for products that require good temperature resistance and also need good electrical or thermal conductivity. .Usage based The magnesium alloy of the invention significantly improves the temperature resistance of copper. [Embodiment] The temperature resistance of copper is generally expressed by the so-called semi-softening temperature (T M). However, the semi-softening temperature is significantly dependent on the degree of deformation In order to obtain comparable results, the semi-softening temperature is generally defined by the degree of deformation of 40% and 94%. The conductivity of copper is generally expressed by the so-called I ACS value (International Annealed Copper Standard). It will be The conductivity is expressed as a percentage of the conductivity of standard unalloyed copper. The conductivity of oxygen-free copper quality is at least 100% IACS. The semi-softening temperature of the copper alloy according to the present invention is at least 0.3-0. The 25% silver alloy is of the same order of magnitude. For a degree of deformation of 40%, 6 312 / Invention Specification (Supplement) / 93-06 / 93108493 200426231 The semi-softening temperature is at least 3 4 0 ° C, and at least 3 8 0 ° C is preferred. For a degree of deformation of 94%, the semi-softening temperature is at least 300 ° C, preferably at least 3 3 5 ° C. The electrical conductivity will still be maintained at a high value regardless of alloying (over 100% I ACS). The conductivity is at least about 101% IACS. For contents exceeding 180 ppm, the improvement of temperature resistance relative to the amount of magnesium will basically be weakened. Electrical conductivity and castability will also be weakened. For town contents below 30 ppm, substantially no money is obtained Basic improvement in temperature. Here, magnesium increases the recrystallization temperature of pure copper. Magnesium atoms are larger than copper atoms, so the lattice structure is distorted and tension is generated. Therefore, the movement of the differential rows becomes more difficult. Since magnesium is significantly cheaper than silver, and its required amount is significantly lower than silver, with the present invention, cost savings can be achieved compared to the use of silver. Due to the small amount of alloy composition, the alloying technology can also be selected more freely. Ballast-alloyed copper can be manufactured using similar manufacturing techniques to other qualities of oxygen-free copper, such as plate or rod casting, as horizontal or vertical casting. In a suitable method step, for example in a casting furnace, the required amount of magnesium is added. Since magnesium is sensitive to the reaction with oxygen, special care must be taken to protect it from air. In addition, in devices in contact with the melt, it is preferred to use materials that do not contain oxides so that magnesium cannot combine with oxygen. After casting, heat treatment and processing are generally followed. A typical manufacturing path can be slab casting and hot and cold casting. For these levels, magnesium produces a secondary grain structure that must be taken into account when selecting the processing temperature. Phosphorus, silicon, and sulfur react with magnesium, thereby reducing the improvement in temperature resistance. Therefore, the total content of the impurities is preferably not higher than 10 p p m. 7 312 / Invention Specification (Supplement) / 93-06 / 93108493 200426231 The copper according to the present invention can be used for purposes requiring good temperature resistance. It is, for example, a rectifier for an electric motor that includes several parts, and the temperature of the resin used to fit the parts will rise above 200 ° C. In addition, the copper alloy of the present invention can be used in a substrate material coated at a high temperature. For example, solar panels (s ο 1 a r p a n e 1 s) are manufactured using a high temperature coating method. One purpose is also used for welding electrode tips, which is better in M IG welding, and flat steel (f 1 atbars) and shapes used in generators, where the copper alloy of the present invention replaces the more expensive copper and silver alloy. In the alloy according to the invention, other alloy components can also be used. It is especially silver and phosphorus. It is well known that silver increases the semi-softening temperature. The silver content is preferably not higher than 500 p p in. Other possible alloy compositions are, for example, sulfur, tin, zinc, iron, stone, and hoof. Its content is preferably not higher than 50 p p m. Tin can also increase the semi-softening temperature, but its efficiency is not as good as that of magnesium, and moreover, it can reduce the conductivity to a large extent. (Example) A magnesium alloyed oxygen-free copper alloy was produced, in which magnesium alloys of 50, 100, and 150 p p m were alloyed. The temperature resistance and electrical conductivity of the alloy were compared with the temperature resistance and electrical conductivity of known silver-copper alloys. Annealed wires of 8 mm were made from each material. Measure the conductivity of the wire. Then stretch the wire cap to a thickness of 6.2 mm (deformation 40%) or 2 mm (deformation 94%). Anneal the wire in a salt bath (1 hour) in the range of 250-500 ° C. The results are shown in the following table. In the table, for example, the labeling of M g 50 ppm means that the alloy of the present invention contains 50 pp hi 及, and the labeling of Cu A g 0.03 refers to the copper alloy of the prior art. Contains 0.027 to 0.05% by weight of silver. 8 312 / Description of the Invention (Supplement) / 93-06 / 93108493 200426231 Alloy Ag [wt%] Electrical conductivity [% IACS] Ί 40% [° C] T ^ 9 4% [〇C] C uA g 0. 0 3 0.027-0. 05 100.88 340 295 C u A g 0. 1 0.085-0.12 100.77 360 325 C u A g 0. 2 0.20-0.25 1 01. 10 380 340 M g 5 0 p pm — 1 01. 95 363 310 Mg 10 0 ppm-101.40 379 335 MrI50〇Dpm-100.84 386 340 It is clear that for a magnesium content of 50-150 ppm, a silver content of at least 0.02 7-0.25% is obtained. Nature. 312 / Invention Specification (Supplement) / 93-06 / 93108493