TW201142048A - Cu-Ag alloy wire and poducing method of Cu-Ag alloy wire - Google Patents
Cu-Ag alloy wire and poducing method of Cu-Ag alloy wire Download PDFInfo
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Abstract
Description
201142048 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種Cu—A人 人厶妗％德』 g D金線、具有由該Cu — Ag σ金線所構成之中心導體 Φ ^ , π U釉電纜、捆束複數根該同軸 電纔而成之同軸電纜束、以— 特別是關於-種具有m g合金線之製造方法。 線。 #具有同導電率且強度更高之Cu — Ag合金 【先前技術】 伴隨著電子設備或醫療設備等各種電氣電子設備之小 义化、輕買化，對該等電氣電子設備所使用之電線期望 更進一步細徑化。 為了即使為細徑亦滿足上述電線所要求之強度及疲勞 特性（對於彎曲、扭轉等之财性），並且使加工性（於拉 線（Wlre drawing)、，絞線、橫向纏繞等加工之加工性）提高， 對於上述電線之導體材料要求破斷強度"咖帥） 、先則上述電線之導體，係使用銅線，但銅線之破 斷強度低，例如，當將其製作成01mm (100"m)以下等 極、.·田線時’於被施加由反覆之f曲或扭轉所產生之應力的 情形時容易發生斷線。 提昇導體材料之破斷強度的一個方法，可舉出添加元 素而加以合金化。例如，於專利文獻丨，記載有一種含有 Ag之Cu — Ag合金線。 [專利文獻1]日本特開2001 - 040439號公報 【發明内容】 201142048 通常，銅合金係藉由增加添加元 之強度，但其及而合站把册 、棱昇破斷強度等 設備等所：田 率下降。對於電子設備或醫療 :=所使用之電線’期望電阻較小，因此若將導電率： 之線材用於導體，則必需增大 · ^ ^ . oJ面積而使電阻下降。 於此情形時’難以達成小徑化。因 使為細徑，亦1有高導雷…B 期望開發出-種即 刀八有问導電率且強度更高之 因此，本發明之一個目的在於提供一種具有古 度更高之Cu—Ag合金線。又， 另=的/、且強 -豨〇 个货月之另-目的在於提供 ㈣ g合金線之製造方法。本發明又另-目的在 的供一種具有由上述Cu_Ag合金線所構成之中 的同軸電鐵、捆束複數根該同軸電纜而成之同軸電鐵束。 [Cu — Ag合金線] 本發明人等選擇Ag作為具有使導電率不易下降、提昇 強度之^果之添加元素’並以Cu_Ag合金線為對象，對具 有與先前之Cu-Ag合金線相等或大於其之較高導電率、且 強度更高之Cu-Ag合金線進行各種研究。其結果獲得如下 見解：藉由Ag以非常細微之粒狀存在，可形成為導電率高 且強度進-步提昇之Cu - Ag合金線。本發明係基於上 解者。 ' < 兄 本發明之Cu-Ag合金線係關於由含有Ag之鋼合金所 構成之線材。該Cu — Ag合金線含有〇.丨質量％以上1 5質旦 %以下之Ag，其餘部分係由Cu以及雜質所構成。於該^ —Ag合金線之剖面中取1 〇〇〇ntnx】〇〇〇nrn以内之任音觀察 視野時，該觀察視野中所存在之Ag之結晶析出物中切斷 201142048 結晶析出物之直線之最大長度為100nm以下之結晶析出物 的面積率為40°/。以上。 本發明Cu — Ag合金線係藉由非常細微之粒狀之Ag均 勻地分散存在，可實現分散強化，可進一步提昇強度，而 且可具有高導電率。 本發明Cu — Ag合金線之一形態，進而可舉出於上述 Ag之結晶析出物含有纖維狀之析出物。201142048 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a Cu-A 厶妗%德』 g D gold wire having a center conductor Φ ^ composed of the Cu-Ag σ gold wire, A π U glazed cable, a bundle of a plurality of coaxial cable bundles formed by the coaxial electric power, and the like, in particular, a manufacturing method having a mg alloy wire. line. #Cu-Ag alloy with the same conductivity and higher strength [Prior Art] With the miniaturization and light-selling of various electrical and electronic equipment such as electronic equipment and medical equipment, the wire expectations for these electrical and electronic equipment Further finer. In order to satisfy the strength and fatigue characteristics (for bending, torsion, etc.) required for the above-mentioned electric wires even for the small diameter, and to process the workability (processing such as wire drawing, stranding, lateral winding, etc.) Improvement) For the conductor material of the above wire, the breaking strength is required, and the conductor of the above wire is copper wire, but the breaking strength of the copper wire is low, for example, when it is made into 01 mm ( 100"m) The following equipotential, . . . field line 'when the stress generated by the repeated f-bend or torsion is applied, the wire breakage is likely to occur. One method of increasing the breaking strength of the conductor material is alloying by adding an element. For example, in the patent document, a Cu-Ag alloy wire containing Ag is described. [Patent Document 1] JP-A-2001-040439A SUMMARY OF THE INVENTION 201142048 Generally, a copper alloy is made by adding strength of an additive element, but it is also a combination of equipment such as a book, a rupture strength, and the like: The field rate has dropped. For electronic equipment or medical treatment: = the wire used is less expected, so if the wire of conductivity: is used for the conductor, it is necessary to increase the area of ^ ^ . oJ to reduce the resistance. In this case, it is difficult to achieve a reduction in diameter. Because of the small diameter, there is also a high-conducting thunder...B. It is expected to develop a kind of tool, that is, the tool has a higher conductivity and higher strength. Therefore, it is an object of the present invention to provide a Cu-Ag having a higher degree of ancientity. Alloy wire. Also, another = /, and strong - 豨〇 another month of the month - the purpose is to provide (four) g alloy wire manufacturing method. Still another object of the present invention is to provide a coaxial electric iron bundle having a coaxial electric iron composed of the above Cu_Ag alloy wire and a plurality of bundled coaxial cables. [Cu-Ag alloy wire] The present inventors selected Ag as an additive element having a property of making it difficult to lower the conductivity and improving the strength, and for the Cu_Ag alloy wire, having the same or the same Cu-Ag alloy wire as the previous Various studies have been conducted on Cu-Ag alloy wires which are larger than the higher conductivity and higher in strength. As a result, the following findings were obtained: by the presence of Ag in a very fine granular form, a Cu-Ag alloy wire having a high electrical conductivity and a stepwise increase in strength can be formed. The present invention is based on the above. ' < Brother The Cu-Ag alloy wire of the present invention relates to a wire composed of a steel alloy containing Ag. The Cu-Ag alloy wire contains Ag in an amount of not less than 5% by mass, and the remainder is composed of Cu and impurities. When the field of view is taken from the cross section of the ^-Ag alloy line in the range of 1 〇〇〇ntnx]〇〇〇nrn, the line of the crystal precipitate of 201142048 is cut off in the crystal precipitate of Ag existing in the observation field. The area ratio of the crystal precipitate having a maximum length of 100 nm or less is 40°/. the above. The Cu-Ag alloy wire of the present invention is uniformly dispersed by the very fine granular Ag, and the dispersion strengthening can be realized, the strength can be further improved, and the electrical conductivity can be high. In one embodiment of the Cu-Ag alloy wire of the present invention, the crystal precipitate of Ag may contain fibrous precipitates.
Ag之結晶析出物係藉由纖維狀之析出物而存在，可實 現纖維強化。上述形態之Cu—Ag合金線係利用纖維強化與 上述分散強化之混合構造之Ag的析出強化，藉此可實現更 進一步提昇強度。 上述本發明之Cu-Ag合金線可用於同轴電境之中心 導體。本發明之同軸電纜係關於具備具有"艮以上素線之 中心導體、覆蓋該中心導體周圍之絕緣體、以及配置於該 絕緣體周圍之外部導體；上述素線係上述本發明之U 合金線。 同軸電纜，可獲得本發 而且’捆束複數根上述本發明 明之同軸電纜束。 本發明同軸電纜或本發明 Cu Ag合金線用於中心導體， 提昇（疲勞特性）。 同軸電纜束藉由將本發明之 可貫現析出強化所致之強度 [Cu — Ag合金線之製造方法] 度之選擇Ag作為具有導電率不易下降'提昇強 文果之添加元素，並以Cu—Ag合金線為對象，對具有 201142048 與先前之Cu — Ag合金線相同或大於其之較高導電率，又使 強度進一步提昇之方法進行各種研究。其結果獲得如下見 解：藉由將Ag之含量設為特定之範圍，並且精心設計製造 方法’可獲得導電率高且強度進一步提昇之Cu_Ag合金 線。更具體而f，獲得如下見解：於實施拉線加工前，具 備形成使Ag充分固溶於Cu中之狀態的步驟，對已實施拉 線加工之線材實施特定之熱處理而析出Ag，藉此與無上述 使Ag固溶之步驟的情形相比，可獲得具有相同導電率且強 度更高之線材。上述本發明之Cu_Ag合金線可利用下述本 發明之Cu — Ag合金線之製造方法而製造。 此處，於含有某個量之Ag2Cu—Ag合金，岣越多[ 溶於Cu +，則導電率越下降，Ag越多析出，則導電率； 升高。因此，上述所謂「形成使Ag充分固溶於&中之月 ，」’係於含有某個量Ug^ChAg合金中，形成與^ Ag而使導電率變高之狀態相比導電率更低之狀態。 #出有^ Ag之狀態係容易形成於拉線加工前 厂比的㈣造時（特別是冷卻速度較慢之情形時）。 根據以上所述’提出於拉線加工前使Ag充分固溶之， -同時提出利用導電率作為表示Ag固溶 之指標的方案》 T之狀‘切 發明之Cu_Ag合金線之製造方法係關於對由 g之銅合金所構成之鑄造材料實施拉線加卫 該製造方法，形成下述时原材料:當將Ag: ’、’、x(質里％)時（其中，〇」質量％以15質量％) 6 201142048 為貫施上述拉線加工論+ = 之原材料’該原材料之導電率r (%IACS)滿足 ^ V 0.1786 ) xx+ 97者。又，該製造方 法’對已實施上述拉綠Λ 、、策加工之線材，貫施至少1次加埶 度為300°C以上、保持拉„ * …狐 什符時間為0.5小時以上之熱處理。盥上 述導電率C相關之佟杜々 ' 保件式：CS ( — 0.1786) χχ+97之計算 方法將於後文敍述。 上述製造方法’形成使Ag充分固溶之狀態的原材料， 將該原材料供拉線加卫’進而對已實施拉線加工之線材實 施上述特定之熱處理’藉此可使非常細微之粒狀之八呂析 而形成為均勻地分散有該等八层粒之組織。藉由該微粒 之Ag之分散強化，藉此可實現a _八呂合金線之強度提 再力上於拉線加工前析出之Ag利用拉線加工而被拉 ，成纖維狀，T實現藉由纖維強化而提昇強度。可認為， 藉由句勻地刀政存在有上述超微粒之Ag，或存在有纖維狀 之Ag，或兩者共存，可製造導電率及強度均高之cu_ 〇金線。藉由上述本發明之製造方法而獲得之Cu—Ag合金 線，可舉出例如含有〇丨質量％以上15質量％以下之Ag， 其餘。卩分係由Cu以及雜質所構成，且線徑為丨〇〇〇 # m以下 者0 本發明Cu — Ag合金線具有高導電率，並且強度亦高。 本發明Cu— Ag合金線之製造方法可製造高導電率、高強度 之Cu — Ag合金線。 【實施方式】 以下，更詳細地說明本發明。 201142048 [Cu — Ag合金線] 構成本發明之Cu〜金線之 含量為ο.1質量％以上15質量％以下之二元合金（其手^之 為Cu以及雜質)。於八 （其餘部分 被為0.1質量〇/以 容易獲得藉由Ag之析出強化 《情形時， 質量％以下之情形時，容 強度之效果，於為15 夺易抑制伴隨著Ag之過詈鉍山 致之導電率下降。特別是 析出而導 ⑺質量％以下時，可平衡Ag之含量為1質量。以上 率1特定之組成之方_^備;?與高導電 〆 式準偫原料。若原料Cu及眉杻Λ 係使用純度較高者，例如f〇urmnes級（純度9二^ 上者’則雜質較少，特別是於製造細徑之線材時· 以 少可能與斷線相關之異物。 ，·寺，犯夠減 若Ag之含量較少， 容易析出4處，微粒之Ag之大;7 “ 古始^ , g之大小係切斷結晶析出物之 •，之最大長度為1 〇〇nm以下The crystal precipitate of Ag is present by fibrous precipitates, and fiber reinforcement can be achieved. The Cu-Ag alloy wire of the above-described form is further enhanced in strength by precipitation strengthening of Ag in a mixed structure of fiber reinforcement and dispersion strengthening. The above Cu-Ag alloy wire of the present invention can be used for a center conductor of a coaxial electric field. The coaxial cable according to the present invention is characterized in that it has a center conductor having a line of "above", an insulator covering the periphery of the center conductor, and an outer conductor disposed around the insulator; the above-mentioned plain wire is the U alloy wire of the present invention. The coaxial cable is obtained from the present invention and is bundled with a plurality of coaxial cable bundles of the present invention. The coaxial cable of the present invention or the Cu Ag alloy wire of the present invention is used for a center conductor, lifting (fatigue property). The coaxial cable bundle is selected from Ag by the strength of the present invention (the method of manufacturing the Cu-Ag alloy wire), and the Ag is added as an additive element having a conductivity which is not easily lowered, and is enhanced by Cu. The Ag alloy wire is used as a target for various studies on the method in which 201142048 is the same as or greater than the previous Cu-Ag alloy wire, and the strength is further improved. As a result, it was found that a Cu_Ag alloy wire having high conductivity and further strength can be obtained by setting the content of Ag to a specific range and designing the manufacturing method'. More specifically, f is obtained as follows: a step of forming a state in which Ag is sufficiently dissolved in Cu before the wire drawing process is performed, and a specific heat treatment is applied to the wire subjected to the wire drawing to precipitate Ag, thereby A wire having the same conductivity and higher strength can be obtained without the above-described case of the step of solidifying Ag. The Cu_Ag alloy wire of the present invention described above can be produced by the following method for producing a Cu-Ag alloy wire of the present invention. Here, in the case of containing a certain amount of Ag2Cu-Ag alloy, the more ruthenium [in the case of Cu + , the lower the conductivity, and the more Ag is precipitated, the conductivity is increased; Therefore, the above-mentioned "formation of forming Ag to be sufficiently solid-dissolved in &" is based on a certain amount of Ug^ChAg alloy, and the conductivity is lower than that in the state in which the conductivity is increased. State. #出有^ The state of Ag is easily formed in the (4) manufacturing time of the factory before the wire drawing process (especially when the cooling rate is slow). According to the above description, it is proposed to fully dissolve Ag before the wire drawing process, and at the same time, a proposal is made to use the conductivity as an index indicating the solid solution of Ag. The manufacturing method of the Cu_Ag alloy wire of the invention is related to The casting material composed of the copper alloy of g is subjected to the drawing method to form the manufacturing method, and the following raw materials are formed: when Ag: ', ', x (% by mass) (wherein 〇) mass% is 15 mass %) 6 201142048 In order to apply the above-mentioned wire drawing theory + = raw material 'the conductivity r (% IACS) of the raw material satisfies ^ V 0.1786 ) xx+ 97. In addition, this manufacturing method 'sends the wire which has been subjected to the above-mentioned pulling green shovel and has been subjected to a heat treatment at least once with a twisting degree of 300 ° C or more and a holding time of 0.5 hr or more. The calculation method of the above-mentioned conductivity C related to the Du Fu's warranty type: CS (— 0.1786) χχ +97 will be described later. The above-mentioned manufacturing method 'forms a raw material in a state in which Ag is sufficiently solid-solved, and the raw material is supplied The wire is reinforced, and then the above-mentioned specific heat treatment is performed on the wire which has been subjected to the drawing process, whereby the very fine granular shape can be formed to uniformly disperse the structure of the eight-layered particles. The dispersion of Ag of the fine particles is strengthened, whereby the strength of the a_8-alloy alloy wire can be increased. The Ag precipitated before the wire drawing process is pulled by the wire drawing to form a fiber, and the T is realized by fiber strengthening. The strength is increased. It can be considered that the cu_ 〇 gold wire having high conductivity and strength can be produced by the presence of the above-mentioned ultrafine Ag or the presence of fibrous Ag or a coexistence of both. By the above manufacturing method of the present invention The Cu-Ag alloy wire obtained is, for example, Ag containing 15% by mass or more and 5% by mass or less, and the remainder is composed of Cu and impurities, and the wire diameter is 丨〇〇〇# m or less. The Cu-Ag alloy wire of the present invention has high electrical conductivity and high strength. The method for producing a Cu-Ag alloy wire of the present invention can produce a Cu-Ag alloy wire having high conductivity and high strength. [Embodiment] The present invention is described. 201142048 [Cu-Ag alloy wire] The binary alloy of the present invention having a Cu to gold wire content of ο. 1% by mass or more and 15% by mass or less (the hand is Cu and impurities). Eight (the rest is 0.1 mass 〇 / in order to easily obtain the strengthening by Ag precipitation), when the mass is less than the mass, the effect of the capacity intensity, and the suppression of 15 is accompanied by Ag. The conductivity is lowered. In particular, when the precipitation is (7) mass% or less, the content of the Ag can be balanced to 1 mass. The composition of the above specific ratio 1 is _^; and the highly conductive ruthenium bismuth raw material. And the eyebrows are used with higher purity, For example, f〇urmnes grade (purity 9 2 ^ above) is less impurity, especially when manufacturing wire with small diameter. · It is less likely to be related to the broken wire. ·· Temple, it is enough to reduce the content of Ag. Less, it is easy to precipitate 4 places, and the Ag of the particles is large; 7 "The ancient beginning ^, the size of g is the cut of the crystal precipitates, and the maximum length is 1 〇〇 nm or less.
八1」 力一万面，亦右·#A A 析出物含有粗粗之Ag之情形，其大小係「切斷 :物之直線之最大長度超過100nm」。若Ag之含量二“ 所g之結晶析出物，析出纖維狀ug。該纖維狀之々係 八：：之Ag中較大之Ag被拉長而成者。特別是若Ag之 =1:質量%以上’則該纖維狀之Ag使用顯微鏡而變得 :別0 : ^忍為’上述結晶析出物中，大部分為析出物， 與纖維狀之Ag實質上為析出物。而且可 6心為，具有一部分粗粒之Ag為結晶析出物。 ί本發月之Cu Ag合金線而言，於該Cu—Ag合金線 8 201142048 之剖面中取10〇〇nmxl〇00nm以内之任意觀察視 察視野中所存在之Ag之結晶析出物中，微粒之：的該觀 率為術。以上。觀察4野中所存在之Ag之結晶析=面： 除微粒之Ag以外存在有粗粒之Ag的情形。與’ 大小相比，因纖維狀之Ag十分 ’、3野之 ^ ^ 大故未被包含在「顴 所存在之Ag之結晶析出物」。關於該觀察視野之遘取 法，將於後文敍述。藉由形成為均句地分散有微粒之 之組織，可實現分散強化所致之強度提昇。可認為粒 之八§不會對CU-Ag合金線之特性造成不良影響，作亦1 助於特性提高。 亦無 之含量變多’則因為微粒之“以外還存 在有纖維狀之Ag，而可實現纖維強化所致之強度提昇。切 為藉由均句地分散存在有上述微粒之々，或存在有纖維狀 ^ Ag，或兩者共存’該Cu—Ag合金線之導電率及強度均 而0 使粗粒之Ag有助於提高Cu—Ag合金線之特性之方 法，可考慮以下方法。粗粒之^中特別大的^藉由在拉 線加工時被拉長成纖維狀’可實現纖維強化所致之強度提 昇。粗粒之Ag中未成為纖維狀之Ag利用熱處理而固溶於 Cu’使該固溶者儘可能析出成大量微粒之Ag，藉此可實現 分散強化所致之強度提昇。認為關於這類粗粒之岣，藉由 使粗粒之Ag成為微粒、或者成為纖維狀，可實現強度之提 昇。 上述Cu — Ag合金線，代表性的係剖面圓形狀之圓線 201142048 可舉出具有各種線徑者。若線徑為03mnl以下，特別是mm (1 〇〇〇 β m )以下，則較佳為可形成為細徑之電線。又本 發月之Cu — Ag合金線為高導電率且高強度，故可期待不僅 為將極細線絞合而成之絞線，即使為單線亦可充分用作為 電線之導體。藉由適當變更拉線加工時之加工度，亦可形 成線徑為0.01mm(10"m) 〜〇〇8mm(8〇"m)等極細之 Cu - Ag合金線。 本發明之Cu — Ag合金線為高導電率且高強度，其亦取 决於線徑或Ag之含量，可舉出例如線徑為多〇 〇5mm ( 5〇以 m)以下等極細之Cu — Ag合金線，滿足導電率為7〇%iacs 以上、拉伸強度為UOOMPa以上之形態，或者例如線徑為 iMmni〜必3mm之Cu — Ag合金線，滿足導電率為95%iacs 以上、拉伸強度為3〇〇MPa以上之形態。 除此之外，本發明之Cu— Ag合金線可形成為於其表面 :備由Ag、Ag合金、Sn、Sn合金等所構成之鍍敷層的形 態。藉由具備鍍敷層，可提高與焊料之潤濕性或耐蝕性。 於製造具有鍍敷層之Cu — Ag合金線之情形時，鍍敷層之形 成可於拉線加工過程中進行，亦可於最終之拉線後進行/ [同軸電纜以及同軸電纜束] 如圖6所示，本發明之同軸電纜丨具備有：中心導體 11、覆蓋該中心導體丨丨周圍之絕緣體12、以及配置於該絕 ^體12周圍之外部導體丨3。進而，同軸電纜丨具備覆蓋外 部導體13外周之外裝材14。上述中心導體n之特徵在於： 具有丨根以上之素線，該素線係本發明之CU — Ag合金線。 10 201142048 而且，捆束複數根上述本發明之同軸電纜，可獲得本發明 之同轴電規束。將本發明之Cu—Ag合金線用於同軸電境i 之中〜導體1丨，藉此可實現析出強化所致之強度提昇（疲 勞特性）。 [Cu — Ag合金線之製造方法] 本發明之Cu— Ag合金線之製造方法，代表性的係具備 有以下之鑄造步驟、拉線步驟、以及熱處理步驟。 轉造步驟：使用將原料之“及Cu熔解而成之混合炼 融液製作鑄造材料之步驟。 拉線步驟.對經上述鑄造步驟之原材料實施拉線加 工，製作最終線徑之線材之步驟。 —熱處理步驟：對已實施上述拉線加工之拉線材料（亦 :二終線徑之拉線材料）實施至少卜次下述特定之 理之步驟。 中之狀態之固溶原材 特別是準備使Ag充分固溶於cu 料以供作拉線加工之上述原材料。 [鑄造步驟] =鑄造材料之製造，可適當使用連續鑄造。連續錄 .:出例如藉由夹輕⑽一Γ)(ρ， ::二伸’藉此連續地製造長條狀之缚造材料之形 體所：亦可為大氣環境，但若為藉由Ar等惰性氣 體所成為之環境，射防止㈣ &性孔 成上诚lil々K L 心礼化而且，用以形 冷原材料之—形態，可舉出使於誃 炫融液之冷卻速度為8_rc/sec以上吏^、^驟中， .1史鱗造時之冷卻速 11 201142048 度為8.5°C / sec以上，即驟冷’藉此可抑制Ag之析出’從 而可形成使Ag充分固溶之狀態。冷卻速度越快，則越讦抑 制Ag之析出，更佳為1(rc / sec以上。 再者’如上所述於拉伸凝固外殼之形態，若為了加快 冷卻速度而加快拉伸凝固外殼之速度，則恐有凝固外殼無 法充分追隨之虞。因此，上述冷卻速度較佳為於可連續地 製造鑄造材料之範圍内儘可能增大。 於將上述混合熔融液剛要注入至鑄模之前的溫度（例 如’漏斗（tundish)内之熔融液溫度）設為Tm (它），將凝 固開始部位之溫度設為Tc (。〇 )，並將上述混合熔融液自 溫度Tm之測定點移動至溫度Tc之測定點為止之時間設為 tmc ( sec )時，上述鑄造時之冷卻速度（/ sec )為將溫度 差：（Tm—Tc)除以時間tmc所得之值：（Tm—Tc) 為使鑄造時之冷卻速度為8.5°C/sec以上，可舉出例 如將使用水冷銅鑄模為鑄模，或者為了可充分冷卻自鑄模 取出之凝固外殼’ α包圍所取出之凝固外殼周圍之方式而 配置強制冷卻手段。_冷卻手段可舉出❹水冷銅塊、 風扇等之鼓風手段。藉由該等手段可冷卻上述凝固外殼之 周圍環i兄’並利用该已冷卻之環境而冷卻上述凝固外殼。 藉由適當調整強制冷卻手段之、、a 丁 又皿度或凝固外威之取出速户八1" Force 10,000 faces, also right · #A A The precipitate contains coarse Ag, and its size is "cut: the maximum length of the straight line exceeds 100 nm." If the content of Ag is two" of the crystal precipitates, the fibrous ug is precipitated. The larger of the Ag in the fibrous system is: the larger Ag is elongated. Especially if Ag = 1: mass When % or more is used, the fibrous Ag is formed by using a microscope: No. 0: ^Forbearingly, the above crystal precipitates are mostly precipitates, and the fibrous Ag is substantially precipitated. Ag having a part of coarse particles is a crystal precipitate. The Cu Ag alloy wire of the present month is taken in any observation field of 10 〇〇 nm x l 00 nm in the profile of the Cu-Ag alloy wire 8 201142048 In the precipitated crystal of Ag, the apparent ratio of the microparticles is above. The crystal precipitation of Ag existing in the four fields is observed. = Surface: There is a case where coarse Ag is present in addition to Ag of the microparticles. In comparison with the size, the fibrous Ag is very ', and the 3 wild is not included in the "crystal precipitate of Ag existing in the crucible". The method of capturing the observation field will be described later. The strength increase due to dispersion strengthening can be achieved by forming a structure in which particles are uniformly dispersed. It can be considered that the VIII of the granule does not adversely affect the characteristics of the CU-Ag alloy wire, and it also contributes to the improvement of the characteristics. There is also no increase in the content of the particles, because there are fibrous Ags in addition to the "particles", which can achieve the strength enhancement caused by fiber strengthening. It is cut by the uniform dispersion of the particles, or there are Fibrous ^ Ag, or both coexisting 'The conductivity and strength of the Cu-Ag alloy wire are all 0. The coarse-grained Ag helps to improve the characteristics of the Cu-Ag alloy wire. The following method can be considered. The extremely large ^ in the ^ is elongated into a fibrous shape during the processing of the wire to achieve the strength enhancement due to fiber strengthening. Ag in the coarse grain Ag is not fibrous and is solid-dissolved in Cu by heat treatment. The solid solution is precipitated as a large amount of Ag as much as possible, whereby the strength increase due to dispersion strengthening can be achieved. It is considered that the coarse particles are made into fine particles or become fibrous, The above-mentioned Cu-Ag alloy wire, representative round line of the cross-section round shape 201142048, can be cited as having various wire diameters. If the wire diameter is 03mnl or less, especially mm (1 〇〇〇β m ), preferably, it can be formed into a small diameter Wire. The Cu-Ag alloy wire of this month is high in electrical conductivity and high in strength. Therefore, it is expected that a stranded wire which is not only twisted by a very thin wire, but also a single wire can be fully used as a conductor of a wire. It is also possible to form a very fine Cu-Ag alloy wire having a wire diameter of 0.01 mm (10 " m) ~ 〇〇 8 mm (8 〇 " m) by appropriately changing the degree of processing during wire drawing. Cu - Ag alloy of the present invention The wire has high conductivity and high strength, and it also depends on the wire diameter or the content of Ag. For example, a very fine Cu—Ag alloy wire having a wire diameter of more than 5 mm (5 〇m) or less satisfies the conductivity. It is a form of 7〇% iacs or more and a tensile strength of UOOMPa or more, or a Cu-Ag alloy wire having a wire diameter of iMmni to 3 mm, which satisfies a conductivity of 95% iacs or more and a tensile strength of 3 MPa or more. In addition, the Cu-Ag alloy wire of the present invention may be formed on the surface thereof in the form of a plating layer made of Ag, Ag alloy, Sn, Sn alloy, or the like. It can improve the wettability or corrosion resistance with solder. It is used to manufacture Cu-Ag alloy wire with plating layer. In the shape, the formation of the plating layer can be performed during the wire drawing process, or after the final wire drawing / [coaxial cable and coaxial cable bundle] As shown in FIG. 6, the coaxial cable clamp of the present invention has: The center conductor 11, the insulator 12 covering the periphery of the center conductor, and the outer conductor 3 disposed around the insulator 12. Further, the coaxial cable has a material 14 covering the outer periphery of the outer conductor 13. n is characterized by: having a plain wire above the root of the root, the prime wire is a CU-Ag alloy wire of the present invention. 10 201142048 Moreover, the coaxial electrical cable of the present invention can be obtained by bundling a plurality of the coaxial cable of the present invention. bundle. The Cu-Ag alloy wire of the present invention is used in the coaxial electric field i to the conductor 1丨, whereby the strength improvement (work characteristic) due to precipitation strengthening can be achieved. [Method for Producing Cu-Ag Alloy Wire] The method for producing a Cu-Ag alloy wire of the present invention is typically provided with the following casting step, wire drawing step, and heat treatment step. Conversion step: a step of preparing a cast material using a mixed smelting liquid obtained by melting a raw material and Cu. Pulling step: a step of performing a wire drawing process on a raw material subjected to the above casting step to produce a wire of a final wire diameter. - heat treatment step: the wire material (also: the wire material of the two final wire diameters) which has been subjected to the above-mentioned wire drawing processing is subjected to at least the following specific steps. The solid solution material in the state of the state is especially prepared. Ag is sufficiently solid-dissolved in cu for the above-mentioned raw materials for wire drawing. [Casting step] = Manufacture of cast material, continuous casting can be suitably used. Continuous recording: out, for example, by pinching (10) one Γ) (ρ , ::Dishen' to continuously manufacture the shape of the strip-shaped constrained material: it can also be an atmospheric environment, but if it is an environment made of an inert gas such as Ar, the shot prevention (4) & Shangcheng lil々KL is also a kind of ritual, and it can be used to shape the cooling material. The cooling rate of the 誃 誃 融 融 8 8 8 8 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Cooling speed 11 201142048 degrees is 8.5 ° C / sec or more, that is, 'This can suppress the precipitation of Ag' and form a state in which Ag is sufficiently solid-solved. The faster the cooling rate, the more the precipitation of Ag is suppressed, and it is more preferably 1 (rc / sec or more. When the shape of the solidified outer shell is stretched, if the speed of stretching and solidifying the outer shell is accelerated in order to accelerate the cooling rate, the solidified outer shell may not sufficiently catch up. Therefore, the cooling rate is preferably within a range in which the cast material can be continuously produced. The temperature at which the mixed melt is just injected into the mold (for example, the temperature of the melt in the 'tundish) is set to Tm (it), and the temperature at the start of solidification is set to Tc (. 〇), when the time from the measurement point of the temperature Tm to the measurement point of the temperature Tc is tmc (sec), the cooling rate (/sec) at the time of the casting is a temperature difference: (Tm) —Tc) The value obtained by dividing the time tmc: (Tm—Tc) In order to make the cooling rate at the time of casting 8.5° C./sec or more, for example, a water-cooled copper mold is used as a mold, or in order to sufficiently cool the mold. Take out The forced cooling means is disposed so as to surround the solidified outer casing that is taken out. The cooling means may be a blasting means such as a water-cooled copper block or a fan. By means of these means, the surrounding ring of the solidified outer casing can be cooled. i brother' and use the cooled environment to cool the solidified outer casing. By appropriately adjusting the forced cooling means, a d and the degree of solidification or solidification
(鑄造速度）等，可調整上述冷卻速度。 XThe casting speed can be adjusted (casting speed) or the like. X
[固溶處理] 之一形態，可舉出對 (可為經上述驟冷所 或者，用以形成上述固溶原材料 藉由上述鑄造步驟所獲得之鑄造材料 12 201142048 得者’亦可為不經上述驟冷所得者）實施固溶處理。士 溶處理較佳為使加熱溫度為60(rc以上，保持 D亥固 時以上’冷卻速度為1.5°C / sec以上。 】、 藉由使加熱溫度為60(TC以上且保持時間為〇 5 、 上，即使鑄造材料中析出冑Ag亦可使Ag充分固溶於t 中。雖然有加熱溫度越高則越可使Ag充分固溶於中11 傾向，但若溫度過高則Cu—Ag合金會開始熔解，故上述^ 熱溫度較佳為850。(：以下。又，雖然處於保持時間越長，^ 有越可使Ag充分固溶於Cu中之傾向，且未特別設置上限則 但較佳為適當地選擇於不會導致生產力下降之範圍 使上述固溶時之冷卻速度為丨5t/sec以上，即驟冷， 藉此可抑制已固溶之Ag析出，從而可形成Ag已充分固溶 之狀態。上述固溶處理時之冷卻速度越快，則越可抑制 之析出，更佳為3。(：/sec以上，並未特別設置上限。 關於上述固溶處理時之冷卻速度（t//sec)，測定於開 始冷卻起經1分鐘後之試樣的溫度，於將此時之溫度設為 几（°c )，將固溶處理溫度設為Tr.(t )時，上述固溶處理 時之冷卻速度為將溫度差：（Tr_Tl)除以時間·· 6〇秒所得 之值。 為使固溶處理時之冷卻速度為15t：//sec以上，可適 當使用強制冷卻手段。例如，可使用水或油、砂等具有流 動性之冷媒直接冷卻；使用風扇等之鼓風；除此之外，可 使用水冷銅塊。利用水冷銅塊之冷卻可藉由如下方式進 行：例如以包圍自熱處理爐取出之線材周圍之方式配置水 13 201142048 冷銅塊，對上述線材之周圍環境進行冷卻。藉由適當調整 冷媒溫度或強制冷卻手段之配置狀態、冷媒量或風量等， 可調整上述冷卻速度。 [拉線步驟] 上述拉線加工（代表性的為冷間）係遍及複數條道次 (pass)進行，直至達到最終線徑為止。各道次之加工度係可 考慮組成（Ag之含量）、最終線徑等而適當調整。 [熱處理] 對已實施拉線加工之線材，具體而言，對於拉線加工 過程中之拉線材料、或者對拉線加工至最終線徑為止之拉 線材料實施特定條件之熱處理，使自充分固溶有岣之狀態 析出Ag。可認為’藉由該熱處自，可析出奈米級 (nan〇-〇rder)等非常微粒之“。可認為，該超微粒之Ag均 勻地刀散存在’藉此Ag之析出量相同，且與主要以存在有 纖，·隹狀之Ag之組織之線材相比，即使導電率為相同程度， 可製造強度更高之Cu — Ag合金線。 上述熱處理（以下，.稱為析出熱處理）可對已實施拉 線加工之線材實施至少1次，亦可實施複數次。於析出熱 處理為1次之情形時，製造步驟少，生產力優異；於析出、 熱處理為複數次之情形時，可增多Ag之析出，特別是微粒 g之析出，提向強度及導電率，或可去除因拉線加工導 入之加工應變而提高導電率，或可容易地進行以後之拉線 上述析出熱處理條件設為：加熱溫度為3〇〇t以上保 14 201142048 古為 〗、時以上。於加熱溫度未達30(TC以及保持時 工廡η “寺時，無法充分析出Ag，或無法充分去除加 支雖 <、、：加熱溫度越高，且保持時間 :物’但例如於超過戰0“g會再次固溶於cu中易 藉此導。電率下降。因此’加熱溫度較佳為以下，特佳 為350 C以上55(rc以下’更佳為彻。c以上4抓以下， 保持時間較佳為〇.5小時以上1〇小時以下。析出熱處理時 之冷卻可舉出例如放置於熱處理爐内㈣自 之爐内冷卻》 (試驗例1 ) 於各種條件下製造CU_A0金材料，調查Ag之含量 與導電率之關係。將其結果示於圖i及表i。 '[Solution treatment] One form may be a pair (may be obtained by the above-mentioned quenching or casting material 12 201142048 obtained by forming the solid solution raw material by the above casting step) The above-mentioned quenching person is subjected to a solution treatment. The melting treatment is preferably such that the heating temperature is 60 (rc or more, and the cooling rate is 1.5 ° C /sec or more when the temperature is maintained at D.), and the heating temperature is 60 (TC or more and the holding time is 〇5). Further, even if yttrium is precipitated in the cast material, Ag can be sufficiently dissolved in t. Although the higher the heating temperature, the more the Ag is sufficiently dissolved in the medium 11 tendon, but if the temperature is too high, the Cu-Ag alloy The melting temperature is preferably 850. (The following is the same. Further, although the longer the holding time is, the more the Ag is sufficiently dissolved in the Cu, and the upper limit is not particularly set. It is preferable to appropriately select a range in which the productivity is not lowered, so that the cooling rate in the above solid solution is 丨5 t/sec or more, that is, quenching, whereby the precipitation of the solid solution Ag can be suppressed, so that the Ag can be sufficiently solidified. In the state of the solution, the faster the cooling rate in the solution treatment, the more the precipitation can be suppressed, and it is more preferably 3. (: / sec or more, the upper limit is not particularly set. The cooling rate at the time of the solution treatment (t //sec), measuring the sample after 1 minute from the start of cooling When the temperature of the solution is set to a few (°c) and the solution treatment temperature is Tr.(t), the cooling rate during the solution treatment is the temperature difference: (Tr_Tl) divided by the time. · The value obtained by 6 sec. The forced cooling means can be used suitably in order to make the cooling rate at the time of a solution process into 15 t or more sec. For example, it can be directly cooled by the fluid-cooling agent, such as water, oil, and sand. A blast is used for a fan or the like; in addition to this, a water-cooled copper block can be used. The cooling by the water-cooled copper block can be carried out by, for example, arranging water around the wire taken out from the heat treatment furnace 13 201142048 cold copper block Cooling the surrounding environment of the wire. The cooling rate can be adjusted by appropriately adjusting the temperature of the refrigerant or the arrangement of the forced cooling means, the amount of refrigerant, or the amount of air. [Wire drawing step] The above-mentioned wire drawing processing (representatively The cold room is carried out over a plurality of passes until the final wire diameter is reached. The degree of processing of each pass can be appropriately adjusted in consideration of the composition (content of Ag), the final wire diameter, etc. [Heat treatment] The wire rod for the wire drawing process has been implemented, specifically, the wire drawing material during the wire drawing process or the wire drawing material until the wire diameter is processed to the final wire diameter is subjected to specific conditions for heat treatment, so that the solid solution is fully dissolved. In the state of Ag, it is considered that "by the heat, a very fine particle such as a nano-scale (nan〇-〇rder) can be precipitated. It is considered that the Ag of the ultrafine particle is uniformly scattered. The amount of precipitation is the same, and the Cu-Ag alloy wire having higher strength can be produced even if the conductivity is the same as that of the wire mainly having the structure of the fiber having the fiber-like shape. The above heat treatment (hereinafter, The wire which has been subjected to the wire drawing processing can be carried out at least once or in a plurality of times. When the precipitation heat treatment is performed once, the number of production steps is small, and the productivity is excellent. When the precipitation and the heat treatment are plural times, the precipitation of Ag, particularly the precipitation of the particles g, the lifting strength and the electrical conductivity, or the like, may be increased. The electrical conductivity is increased by the processing strain introduced by the wire drawing process, or the wire drawing can be easily performed. The above-mentioned precipitation heat treatment conditions are as follows: the heating temperature is 3 〇〇t or more and the heat is 14 201142048. When the heating temperature is less than 30 (TC and the holding time “ "Temple, the Ag cannot be analyzed, or the addition cannot be sufficiently removed.",: The heating temperature is higher, and the holding time is: War 0 "g will be dissolved in cu again, and the conductivity will decrease. Therefore, the heating temperature is preferably below, especially preferably 350 C or more 55 (the following is better than rc). The holding time is preferably 〇5 hours or more and less than 1 hour. The cooling during the precipitation heat treatment may be, for example, placed in a heat treatment furnace (4) cooling from the furnace (Test Example 1) CU_A0 gold material is produced under various conditions. The relationship between the content of Ag and the conductivity is investigated. The results are shown in Figure i and Table i.
Cu — Ag合金材料係按以下方法製作。準備純度為 99‘99/Qa _L之電氣銅為原料Cu ’準備純度為99別％以上之 銀粒（Ag )為原料Ag，投人至高純度碳製㈣，於連續鱗 造裝置内使其真空料，製作轉有&及Ag之混合溶融 液。銀粒，添加量如圖卜表i所示，以相對於混合溶融液 之Ag含量（濃度）成為〇」質量％〜丨5質量％之方式進〜 調整。 .仃 使用所獲得之混合熔融液與高純度碳製鑄模藉由連續 鑄造，製造線徑為#8.0mm之剖面圓形狀之鑄造材料。於圖 1中，以▲所示之試樣（鑄造（徐冷））係利用自然放冷而 使鑄造時之冷卻速度為(未達8 5t/sec)之試 樣，以□所示之試樣（鑄造（驟冷））係以包圍自上述鑄模 15 201142048 取出之凝固外殼周圍之方式配置水冷銅等之強制冷卻手 段，使冷卻速度為l〇°C / sec ( 8.5°C / sec以上）之試樣’ 以♦所示之試樣（固溶處理材料）係對以▲所示之鑄造材 料（鑄造時之冷卻速度為2.5°C/sec)已實施760°C><2小 時、冷卻速度為9°C / sec ( 1.5°C / sec以上）之固溶處理之 試樣。The Cu-Ag alloy material was produced in the following manner. Prepare an electric copper having a purity of 99'99/Qa_L as a raw material Cu'. Prepare a silver particle (Ag) having a purity of 99% or more as a raw material Ag, and inject it into a high-purity carbon (4), and vacuum it in a continuous scale forming apparatus. Ingredients, make a mixed solution of & and Ag. The amount of silver particles added is adjusted as shown in Table i, and is adjusted so that the Ag content (concentration) of the mixed molten solution is 〇"% by mass" to 5% by mass.仃 A cast material having a cross-sectional shape of a wire diameter of 8.0 mm was produced by continuous casting using the obtained mixed melt and a high-purity carbon mold. In Fig. 1, a sample (casting (Xu Leng)) shown by ▲ is a sample which is cooled by casting using natural cooling to be (less than 85 t/sec), and is tested by □ The sample (casting (quenching)) is provided with a forced cooling means such as water-cooled copper so as to surround the solidified outer casing taken out from the above-mentioned mold 15 201142048, and the cooling rate is l 〇 ° C / sec (8.5 ° C / sec or more). The sample "sample shown by ♦ (solution treatment material) was applied to the casting material indicated by ▲ (the cooling rate at the time of casting was 2.5 ° C / sec), and 760 ° C was carried out for > 2 hours. A solution treated at a cooling rate of 9 ° C / sec (1.5 ° C / sec or more).
[表U 試樣 No. Ag濃度 (wt%) 導電率（IACS%) 近似式值 固溶♦ 鑄造（驟冷）□ 鑄造（徐冷）▲ 1-1 1 93 96 98 97 1-2 3 87 91 97 96 1-3 5 83 88 97 96 1-4 10 79 83 97 95 1-5 15 75 79 96 94 如表1及圖1所示可知，即使Ag之含量相同，導電率 亦會因製造條件而不同。具體而言，可知，於Ag之含量相 同之情形時’（1 )鑄造時之冷卻速度較快之情形時相較於 較慢之情形時導電率更低，（2 )即使放慢鑄造時之冷卻速 度’若於鑄造後實施固溶處理，則導電率亦會變低。而且， 可認為如此導電率下降之原因在於，藉由加快鑄造時之冷 部速度’或於鑄造後實施固溶處理，而處於使Ag固溶於 Cu中之狀態。由此可以說，為上述表示「Ag固溶於中 之狀態」之指標’可將上述鑄造時之冷卻速度較慢時之導 電率作為閥值。 因此’欲想出近似Ag之含量與上述冷卻速度較慢時之 16 201142048 導電率之關係之數學式。根據圖丨所示之資料，上述鑄造 時之冷卻速度較慢時之導電率可視為將含量作為變數 之-次函數。因此，若使用市t之試算表軟體（啊心⑽ software) Microsoft Corporati〇nf「Εχ(^」求出上述鑄造 時之冷卻速度較慢時之導電率之近似線，則於將Ag之含量 設為X (質量％)，導電率設為”’求出^卜❾⑺㈧ xx+97。若使用該近似式，則上述所謂「Ag固溶於cu中 足 CS ( — 0.1786 ) χχ+ 97 之狀態 之狀態」，係具有與上述鑄造時之冷卻速度較慢時之導電率 相等或其以下之導電率的狀態’ # ’導電率c(%IAcs)滿 (-試驗例2 於各種條件下製造由Cu — Ag合金所構成之原材料，對 該原材料進行拉線加工以及適當熱處理而製造Cu _ Ag合 金線，檢查導電率（％IACS)、拉伸強度（MPa)。 各試樣係按以下方法製作。準備與試驗例1相同之原 料’並以使Ag之含量（濃度）成為表2所示之量之方式準 備Cu與Ag之混合熔融液’以與試驗例1相同之方式藉由 連續鑄造而製造線徑多8 .〇mm之剖面圓形狀之鑄造材料。對 於各鎮造材料，以成為表2所示之冷卻速度之方式變更鑄 造時之冷卻條件。冷卻速度未達8.5°C/sec之試樣係藉由 自然放冷之試樣。冷卻速度為8.5。(： / sec以上之試樣係以 包圍自鑄模取出之凝固外殼周圍之方式配置水冷銅塊而使 上述周圍之環境冷卻之狀態、或配置風扇而藉由鼓風進行 冷卻、或將該等強制冷卻手段組合起來而加以驟冷之試 17 201142048 使鑄造時之 樣，藉由適當調整水冷銅塊之溫度或風量等 冷卻速度不同。 料π崎逯材料之試樣（ ―1、2—3、2—3—2'2—5、2-7、2- 1G、2— 12'2— 14 係對已獲得之鎮造材料實施拉線加工，於表2所示之㈣ 時’於表2所示之條件下實施巾 r I她中間熱處理（析出熱處理） 後’進而實施拉線加工所獲得之最終線徑為外〇4咖之鱗 材（Cu — Ag合金線 鑄造材料及熱處理條件之 2-6、2-8' 2-9、2- 表2之製造條件之欄記載有 試樣（Νο·2—2、2—4、2—4~~2 η、2-13'2-15)係對已獲得之料材料於表2所示之熱 處理條件下實施熱處理（固溶處理）㈣施拉線加工，於 表2所7F之線;U a夺’於表2所示之條件下實施中間熱處理 (析出熱處理）後，進而實施拉線加工所獲得之最終線徑 為⑽4_之線材（Cu—Ag合金線）。於表2之熱處理（固 溶處理）條件下，所謂「驟冷」，係指於自加熱溫度起之冷 卻步驟中藉由水冷而冷卻。 試樣Νο·2— 100係對已獲得之鑄造材料（線徑郝〇mm) 於表2所示之條件下實施熱處理（固溶處理）後實施拉 線加工，於表2所示之線徑時，於表2所示之條件下實施 中間熱處理後，進而實施拉線加工所獲得之最終線徑為 彡0.04mm之線材（Cu__ Ag合金線）。試樣N〇 2 — 11〇係對 已獲得之鑄造材料（線徑^8 〇mm )實施拉線加工，於表2 所不之線控時，於表2所示之條件下實施中間熱處理後， 18 201142048 進而實施拉線加工所獲得之最終線徑為0〇 〇4mm之線材 (Cu - Ag合金線）。試樣n〇.2 - 1 20係對已獲得之鑄造材 料（線徑08.0mm)不實施上述固溶處理，實施拉線加工直 至線徑為06.6mm為止，並對所獲得之拉線材料（線徑為 多6.6 mm)於表2所示之條件下實施熱處理（固溶處理）後， 進而實施拉線加工，於表2所示之線徑時，於表2所示之 條件下實施中間熱處理後，進而實施拉線加工所獲得之最 終線徑為00.04mm之線材（Cu - Ag合金線）。 對已獲得之鑄造材料（線徑08.〇mm )、鑄造材料（線徑 M.Omm)實施固溶處理所得之固溶處理材料（線徑08 〇mm) 分別測定導電率（％IACS )。將其結果示於表2。又，對已 實‘施中間熱處理（析出熱處理）之Cu—Ag合金線，分別測 定已實施該熱處理之線徑為0.6mm或外9mm時之拉伸強 度（MPa)以及導電率（％IACS)。將其結果示於表2。又， 對於最終線徑為00.04mm之線材亦測定拉伸強度（Mpa )以 及導電率（％IACS )。將其結果示於表2。拉伸強度係根據 JISZ 2241 ( 1998 )之規定而測定（標點距離GL為1〇 。 導電率係藉由電橋法而測定。 [表2] 19 201142048[Table U Sample No. Ag concentration (wt%) Conductivity (IACS%) Approximate formula solid solution ♦ Casting (quenching) □ Casting (Xu cold) ▲ 1-1 1 93 96 98 97 1-2 3 87 91 97 96 1-3 5 83 88 97 96 1-4 10 79 83 97 95 1-5 15 75 79 96 94 As shown in Table 1 and Figure 1, even if the content of Ag is the same, the electrical conductivity will be due to the manufacturing conditions. And different. Specifically, it can be seen that when the content of Ag is the same, '(1) the cooling rate at the time of casting is faster, the conductivity is lower than in the case of slower, and (2) even when casting is slowed down. The cooling rate 'if the solution treatment is carried out after casting, the electrical conductivity is also lowered. Further, it is considered that the reason why the conductivity is lowered is that the Ag is solid-dissolved in Cu by accelerating the cold portion speed at the time of casting or by performing a solution treatment after casting. From this, it can be said that the index "the state in which Ag is dissolved in the medium" can be used as the threshold value when the cooling rate at the time of casting is slow. Therefore, the mathematical expression of the relationship between the content of Ag and the above-mentioned cooling rate is relatively high. According to the data shown in Fig. 导电, the conductivity at the time of slow cooling at the time of casting can be regarded as a sub-function of the content as a variable. Therefore, if you use the trial software of the city t (a heart (10) software) Microsoft Corporati〇nf "Εχ (^) to find the approximate line of conductivity when the cooling rate is slow at the time of casting, set the content of Ag For X (% by mass), the conductivity is set to "' to find ^ ❾ (7) (eight) xx + 97. If the approximation is used, the above-mentioned "Ag is dissolved in cu in the state of CS ( - 0.1786 ) χχ + 97 State" is a state in which the conductivity is equal to or lower than the conductivity at the time of the cooling at the time of casting, and the conductivity is c (%IAcs) is full (-Test Example 2 is manufactured under various conditions by Cu) — A raw material composed of an Ag alloy, which was subjected to wire drawing and appropriate heat treatment to produce a Cu _Ag alloy wire, and the electrical conductivity (% IACS) and tensile strength (MPa) were examined. Each sample was produced by the following method. Prepared the same raw material as in Test Example 1 and prepared a mixed melt of Cu and Ag in such a manner that the content (concentration) of Ag became the amount shown in Table 2, and manufactured by continuous casting in the same manner as in Test Example 1. The wire diameter is more than 8. 〇mm section round shape casting For each of the granitic materials, the cooling conditions at the time of casting were changed so as to have the cooling rate shown in Table 2. The sample having a cooling rate of less than 8.5 ° C/sec was a sample which was naturally cooled. 8.5. (: / sec or more of the sample is placed around the solidified outer casing taken out from the mold to arrange the water-cooled copper block to cool the surrounding environment, or to arrange a fan to be cooled by air blowing, or These forced cooling means are combined and quenched. 17 201142048 For the case of casting, the cooling rate is different by appropriately adjusting the temperature or air volume of the water-cooled copper block. Samples of π rugged materials ( ― 1, 2 —3, 2—3—2′2—5, 2-7, 2- 1G, 2—12′2—14 The wire drawing process is performed on the obtained materials of the town, as shown in Table 4 (IV) After the intermediate heat treatment (precipitation heat treatment) of the towel r I was carried out under the conditions shown in Table 2, the final wire diameter obtained by the wire drawing process was a scale material of the outer crucible (Cu-Ag alloy wire casting material and heat treatment). Conditions 2-6, 2-8' 2-9, 2 Table 2 Manufacturing conditions Samples (Νο·2-2, 2-4, 2-4~~2 η, 2-13'2-15) were subjected to heat treatment under the heat treatment conditions shown in Table 2 for the obtained materials. (Solution treatment) (4) Stroke line processing, in the line of 7F in Table 2; U a wins the intermediate heat treatment (precipitation heat treatment) under the conditions shown in Table 2, and then the final wire diameter obtained by the wire drawing process It is a wire of (10)4_ (Cu-Ag alloy wire). Under the condition of heat treatment (solution treatment) of Table 2, "quenching" means cooling by water cooling in the cooling step from the heating temperature. The sample Νο·2—100 is subjected to heat treatment (solution treatment) under the conditions shown in Table 2 for the obtained casting material (wire diameter Hao Hao mm), and then subjected to wire drawing processing, and the wire diameter shown in Table 2 is shown. At the time of performing the intermediate heat treatment under the conditions shown in Table 2, the wire rod (Cu__Ag alloy wire) having a final wire diameter of 彡0.04 mm obtained by wire drawing was further processed. The sample N〇2—11〇 is subjected to wire drawing processing on the obtained casting material (wire diameter ^8 〇mm). When the wire is not controlled in Table 2, after the intermediate heat treatment is performed under the conditions shown in Table 2 , 18 201142048 Further, the wire rod (Cu - Ag alloy wire) whose final wire diameter is 0〇〇4 mm obtained by the wire drawing process is implemented. Sample n〇.2 - 1 20 The obtained casting material (wire diameter 08.0 mm) was not subjected to the above solution treatment, and was subjected to wire drawing until the wire diameter was 06.6 mm, and the obtained wire material was After the heat treatment (solution treatment) was carried out under the conditions shown in Table 2, the wire diameter was 6.6 mm. Further, the wire drawing process was carried out, and in the wire diameter shown in Table 2, the middle was carried out under the conditions shown in Table 2. After the heat treatment, a wire (Cu - Ag alloy wire) having a final wire diameter of 00.04 mm obtained by wire drawing was further processed. The conductivity (% IACS ) of the solution-treated material (wire diameter 08 〇 mm) obtained by subjecting the obtained cast material (wire diameter 08.〇mm) and casting material (wire diameter M.Omm) to solution treatment was measured. The results are shown in Table 2. Further, for the Cu-Ag alloy wire which has been subjected to the intermediate heat treatment (precipitation heat treatment), the tensile strength (MPa) and the electrical conductivity (% IACS) when the wire diameter of the heat treatment was 0.6 mm or the outer 9 mm were measured. . The results are shown in Table 2. Further, the tensile strength (Mpa) and the electrical conductivity (% IACS) were also measured for the wire having a final wire diameter of 00.04 mm. The results are shown in Table 2. The tensile strength was measured in accordance with JIS Z 2241 (1998) (the puncture distance GL was 1 。. The conductivity was measured by the bridge method. [Table 2] 19 201142048
201142048 如表2所示可知，有Ag之含量越多則強度越高之傾 向。特別可知，使鑄造時之冷卻速度為8.5。(： / sec以上， 對鑄造材料實施特定條件之固溶處理，形成導電率c (%IACS)滿足CS (—0.1786) χχ十97之固溶原材料，對 該固溶原材料實施拉線加工，進而實施有特定之熱處理（析 出熱處理）之s式樣Ν 〇. 2 — 1〜2 — 1 5係於該熱處理剛結朿 後’具有與铸造材料（冷卻速度較慢者。參照表1之鎮造 (徐冷））相等或其以上之導電率，並具有高強度。而且可 知’上述試樣Ν 〇 · 2 — 1〜2 — 1 5即使於最終線徑時亦具有高 強度。 又’將Ag之含量相同之試樣加以比較。與藉由上述特 定之條件所製造之試樣No.2—3、2—4、2—3-2、2—4—2 相比可知，鑄造時之冷卻速度較慢、固溶處理時201142048 As shown in Table 2, the higher the content of Ag, the higher the strength. In particular, it was found that the cooling rate at the time of casting was 8.5. (: / sec or more, the solution material is subjected to a solution treatment under specific conditions to form a solid solution material having a conductivity c (% IACS) satisfying CS (-0.1786) χχ10 97, and the solid solution material is subjected to wire drawing processing, and further The s design of the specific heat treatment (precipitation heat treatment) is carried out. 2 — 1~2 — 1 5 is after the heat treatment just after the crusting 'has the material with the casting (the cooling rate is slower. Refer to Table 1 for the town ( Xu Leng)) Conductivity of equal or higher, and high strength. It is also known that 'the above sample Ν 〇 · 2 - 1~2 - 15 has high strength even at the final wire diameter. The samples of the same content are compared. Compared with the samples No. 2-3, 2-4, 2-3, 2, and 2-4, which are manufactured by the above specific conditions, the cooling rate at the time of casting is known. Slower, solution treatment
"/JQL 度較低且冷卻速度亦較慢之試樣Νο·2 — 1 〇〇，鑄造時之A卻 速度較慢且未實施固溶處理之試樣Νο·2 — 11 〇，即使固，容户 理後之導電率較高，拉線過程中之熱處理剛結束後、以及 最終線徑時之強度均較低。又，與試樣Νο.2 — 4、：> — ^ — 3 ~ 2、 2— 4— 2相比可知，將拉線前之原材料不為特定之固溶原材 料之试樣Ν 〇. 2 — 1 2 0的強度較低。 對所獲得之試樣No.2-3-2、2—4-2’用顯微鏡觀筹 其剖面（500倍），並將利用影像處理對該觀察像進行力】 而成者示於圖2。於圖2中，細長之帶狀物係所析出之 被拉長而成者。可知該纖維狀之Ag之大小為微量級，長 為數十/zm程度。 又 21 201142048 接者’進行Ag之έ士 Η把山 ,^ ^ ^ ^ 8 、'.σ曰曰析出物之觀察。若於顯微鏡照片 中可確涊纖維狀之A則 S⑺4纖維狀之Ag不存在之部位， 選取A g之結晶析出物之觀家用4接 覜察用s式樣。為排除纖維狀之Ag， 觀察用試樣較佳為於縱剖（ 之切斷面）上進行Hr 之拉線方向 n”二察之。二該…試… 微鏡進行觀察，藉此可確認Ag之結晶析出物。電子』 圖3’表示關於試樣N0 2— 3 2 — 4 '2_㈣之剖面之 穿透式電子顯微鏡照片（15麵倍）。觀察視野為 440nmx326nni-^ γ» ^ ^ ^ 之q域。於該觀察視野中所存在之Α 士曰 析出:勿中’數出切斷結晶析出物之直線之最大長度為二 :下（微幻之析出物的個數，並計算該微粒之合計面積。 g之結晶析出物係將觀察視野中含整體之微粒作為 u县 < 於觀察視野之輪廟部位之局部缺欠之微粒則不作 一貝，對象。圖4表示說明圖3之顯微鏡照片中所存在 g之。S曰析出物中’作為微粒而數出之Ag之示意圖 圖4 ^中之虛線騎之圓所包圍之Ag為微粒。表3表示 述各式樣中，結晶析出物之合計面積、微粒之 觀察視野中之处a t , t 丨卸積、 中之”曰析出物之面積率、以及結晶析出物 ❹之面積率。又，將試樣Νο·2一卜2—2亦一併示於表3之 22 201142048 [表3]"/JQL with a lower degree of cooling and a slower cooling rate Νο·2 — 1 〇〇, A when casting is slower and does not undergo solution treatment Νο·2 — 11 〇, even if solid The conductivity of the household is higher, and the strength after the heat treatment in the wire drawing process and the final wire diameter are lower. Further, as compared with the samples Νο.2 — 4, :> — ^ — 3 ~ 2, 2— 4-2, it is known that the raw material before the wire drawing is not a sample of a specific solid solution material. — 1 2 0 is less intense. The obtained sample No. 2-3-2, 2-4-2' was microscopically observed (500 times), and the image was processed by image processing. The result is shown in Fig. 2. . In Fig. 2, the elongated strip is formed by the elongation of the precipitate. It is understood that the size of the fibrous Ag is in the order of several tens/zm. 21 201142048 Receiver's conduct of the Ag gentleman Η 山 山 , ^ ^ ^ ^ 8 , '. σ 曰曰 precipitation observation. If the fibrous A is confirmed in the micrograph, the S(7)4 fibrous Ag is not present, and the crystal precipitate of A g is selected. In order to exclude the fibrous Ag, the observation sample is preferably subjected to the longitudinal direction (cut surface) of the Hr wire drawing direction n". Secondly, the test is performed by micromirror. Crystalline precipitate of Ag. Electron Figure 3' shows a transmission electron micrograph (15 faces) of the section of the sample N0 2 - 2 2 - 4 '2_(4). The field of view is 440 nm x 326 nni-^ γ» ^ ^ ^ The q domain. The Α 曰 于 于 于 : : : : : : 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 : : : : : : : : : : : : : The total area of g. The crystal precipitates of g are the particles of the whole field in the observation field of view as the u county. The particles that are partially impaired in the part of the observation field are not made of one object. Figure 4 shows the microscope of Fig. 3. In the photo, g is present in the S 曰 precipitate. The schematic diagram of Ag as a microparticle is shown in Fig. 4 ^. The Ag surrounded by the dotted circle is a microparticle. Table 3 shows the crystallization precipitate in each of the patterns. Total area, where the observation field of the particles is at, t 丨 unloading, The area ratio of the precipitated material and the area ratio of the crystal precipitates. In addition, the sample Νο·2 卜 2-4 is also shown in Table 3 22 201142048 [Table 3]
試樣N〇 結晶析出物 微粒/結晶 析出物 lOOnrn 以下 (微粒） 結晶析出物/ 觀察視野Sample N〇 Crystal precipitates Particles/crystals Precipitates lOOnrn or less (Particles) Crystal precipitates / Observation field
已實施特定之熱處理之試樣n〇2_ 在9個微粒，結晶析出物 觀察視野中存 啊出物中之被粒之面積率為68 9%。 對鑄造材料已實施固溶處理 ， 邮六— 忒樣No·2—4於觀察視野中 子之結晶析出物中全部為微粒，該微粒之 個，與試樣n3相比析出更多 相同、但鑄造時之冷卻速度較慢且未實施固溶處 Νο·2— 11〇與绒枵n 1 ， 或樣 、。策Ν.2 — 3、2 — 4相比，於觀察視野中所 在之微粒較少而為4個，結晶析出物中之微粒之面積率為 與上述試樣Ν〇2—3、2—4相比Ag之含量更多之 試樣Νο·2 -卜2-2中，亦取得與試樣Ν〇·2—3、2 — 之結果。 ~ 圖5表示說明構成本發明之Cu_Ag合金線之組織之示 意圖。於圖中，矩形框内之橢圓狀體與黑圓表示已析出之 Ag，白圓表示固溶之Ag。成為表2所示之導電率以及拉伸 強度之個原因，可認為與如圖2所示由Ag被拉長而以纖 維狀存在所引起之纖維強化有關，或與如圖3所示由奈米 級之非常細微之Ag粒均勻地分散存在所引起之分散強化有 23 201142048 關’或者與具有兩者之混合組織有關。可認為上述混合組 織係藉由以下方法而并！占.点,^ ^ 凌而形成·例如，如圖5所示，對鑄造材 料實施固溶處理而使已析出之Ag固溶，形成為使Ag之固 溶量增加之狀態’若對該固溶處理材料實施拉線加工則 述固冷處理時未固溶而析出之Ag藉由拉線加工被拉長而 成為纖維狀’進而實施上述析出熱處理，藉此已固溶之“ 成為微細之粒量析出。與此㈣’例如，若禱造時 、卻速度較陵’則會大量析出較大的々，如上所述該八呂 藉由拉 '線加工而被拉長，但即使進而實施上述析出熱處 理’亦不太析出粒狀之Ag ’而主要僅存在纖維狀之Ag。可 認為由於此種Ag之存在狀態之差異，而產生如上所述強度 之差異。 除此之外，根據該試驗結果，可以說存在如下傾向： 相較於使鑷造時之冷卻速度$ 8 5t之試樣，對 鑄造材料以特定之條件下實施有固溶處理之試樣的強度變 得更高。又，可以說於拉線過程中實施之上述特定之熱處 理（析出熱處理）存在如下傾向：於線徑越粗時實施，最 線徑時之強度進而變得越高。進而，可以說即使於上述 特定之熱處理（析出熱處理）後導電率相同之情形時，亦 存在如下傾向：固溶原材料形成時之冷卻速度越快，該熱 處理後以及最終線徑時之強度均會進而變得越高。 根據上述試驗結果，可以說於製造具有特定量之Ag之 CU Ag合金線時’準備已成為充分固溶有Ag之狀態之固 溶原材料作為供拉線加工之原材料，對已實施拉線加工之 24 201142048 線材實施上述析出熱處理，藉此可獲得與具有相同量之Ag 之先前之Cu — Ag合金線相比，具有相等或其以上之導電率 且強度更高之線材。 再者，本發明並不限定於上述實施形態，可不脫離本 發明之要旨而進行適當變更。例如，可適當變更Ag之含量、 鑄造時之冷卻速度、固溶處理之條件（溫度、保持時間、 冷卻速度）、實施固溶處理或析出熱處理之線徑、析出熱處 理之條件（加熱溫度、保持時間）等。 [產業上之可利用性] 本發明Cu — Ag合金線可適當使用於行動電話等行動 電子設備、汽車等所載置之電子零件、醫療設備、工業用 機器人等各種電氣電子設備之電線，代表性的為同軸電纜 之導體（中心導體或屏蔽導體）β本發明Cu_Ag合金線2 製造方法可適當使用於高導電率、高強度之上述本發明Cu Ag合金線之製造。本發明同軸電纜以及本發明同軸電纜 束可適當使用於上述各種電氣電子設備之供電配線。' 【圖式簡單說明】 圖1係表示於使製造條件不同而製作之各種Cu—Ag合 金材料中，Ag之含量與導電率之關係之圖表。 σ 圖：係對拉線材料實施熱處理（析出熱處理）後之線 材（少2.6 mm)之顯微鏡照片（5〇〇倍）， 樣 No.2- ? 圖3 材（4 0.9 rum」之ιSample n〇2_ which has been subjected to a specific heat treatment. In 9 particles, the area ratio of the particles in the crystallization of the precipitates was 68 9%. The casting material has been subjected to a solution treatment, and all of the crystal precipitates in the observation field neutrons are particles, and the particles are more identical than the sample n3, but The cooling rate during casting is slow and the solid solution is not implemented Νο·2-11 〇 and velvet n 1 , or the like. Compared with the results of 2, 3, 2 - 4, there are 4 particles in the observation field, and the area ratio of the particles in the crystal precipitation is the same as the above samples Ν〇 2 - 3, 2-4. The results of the samples Ν〇··2 - 3, 2 - were also obtained in the sample Νο·2 - 卜 2-2 which was more than the content of Ag. ~ Fig. 5 is a view showing the structure of the Cu_Ag alloy wire constituting the present invention. In the figure, the elliptical body and the black circle in the rectangular frame indicate the precipitated Ag, and the white circle indicates the solid solution of Ag. The reason for the electrical conductivity and tensile strength shown in Table 2 is considered to be related to the fiber reinforcement caused by the elongation of Ag as shown in Fig. 2, or by the presence of a fiber as shown in Fig. 3. The dispersion enhancement caused by the very fine dispersion of Ag particles in a fine manner is related to or in combination with a mixed structure of the two. The above mixed structure can be considered to be by the following method! For example, as shown in FIG. 5, the casting material is subjected to a solution treatment to solid-dissolve the precipitated Ag, and is formed in a state in which the solid solution amount of Ag is increased. When the melt-treated material is subjected to the wire drawing process, the Ag which is not solid-solved during the solid-cooling treatment is elongated by the wire drawing process and becomes a fibrous shape, and the precipitation heat treatment is carried out, whereby the solid solution is solidified. Precipitation. And (4) 'For example, if the prayer is made, but the speed is higher than the tomb', a large amount of cockroaches will be precipitated. As mentioned above, the louver is elongated by the drawing, but even if the above precipitation is carried out The heat treatment 'does not precipitate granular Ag' and mainly contains fibrous Ag. It is considered that the difference in strength as described above occurs due to the difference in the existence state of such Ag. In addition, according to the test result It can be said that there is a tendency that the strength of the sample subjected to the solution treatment under the specific conditions of the cast material becomes higher than that of the sample having a cooling rate of $ 8 5t at the time of the casting. Said to be implemented in the process of pulling the wire The heat treatment (precipitation heat treatment) has a tendency to be performed when the wire diameter is coarser, and the strength at the maximum wire diameter is further increased. Further, it can be said that the conductivity is the same even after the specific heat treatment (precipitation heat treatment) described above. At the same time, there is a tendency that the faster the cooling rate at the time of forming the solid solution material, the higher the strength after the heat treatment and the final wire diameter. According to the above test results, it can be said that a specific amount of Ag is produced. In the case of the CU Ag alloy wire, the solid solution material which has been sufficiently solid-dissolved with Ag is prepared as a raw material for the wire drawing processing, and the above-mentioned precipitation heat treatment is performed on the 24 201142048 wire material which has been subjected to the wire drawing process, thereby obtaining and having A wire having a conductivity equal to or higher than that of the previous Cu—Ag alloy wire of the same amount of Ag, and having a higher strength. Further, the present invention is not limited to the above embodiment, and may be omitted without departing from the gist of the present invention. Make appropriate changes. For example, the content of Ag, the cooling rate during casting, and the conditions of solution treatment (temperature, protection) can be appropriately changed. The time, the cooling rate, the wire diameter of the solution treatment or the precipitation heat treatment, the conditions of the precipitation heat treatment (heating temperature, holding time), etc. [Industrial Applicability] The Cu-Ag alloy wire of the present invention can be suitably used in the action Wires for various electrical and electronic equipment such as mobile electronic devices, electronic components, medical equipment, and industrial robots, such as telephones, are representative of coaxial cable conductors (center conductor or shield conductor). β Cu_Ag alloy wire of the present invention. (2) The manufacturing method can be suitably used for the production of the Cu Ag alloy wire of the present invention having high conductivity and high strength. The coaxial cable of the present invention and the coaxial cable bundle of the present invention can be suitably used for the power supply wiring of the above various electric and electronic devices. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the relationship between the content of Ag and the conductivity in various Cu-Ag alloy materials produced by different manufacturing conditions. σ Figure: A photomicrograph (5 〇〇) of a wire (less than 2.6 mm) after heat treatment (precipitation heat treatment) of the wire material, sample No. 2 - Fig. 3 Material (4 0.9 rum)
」之穿透式電子顯微鏡照片 (析出熱處理）後之線 照片（150000倍），圖 25 201142048 3 ( I)表示試樣n〇.2_ 3，圖3 ( II)表示試樣n〇.2~~ 4，圖 3 ( ΙΠ)表示試樣 No.2- 110。 圖4係對圖3之顯微鏡照片中所存在之Ag之結晶析 物進行說明的示意圖。 一 5係對構成本發明Cu — Ag合金線之組織進行 不意圖。 /3之 係本發明之同軸電纜之斜視圖。 【主要元件符號說明】 1 同軸電纜 11中心導體 12絕緣體 13外部導體 14外裝材 26Line photo (150000 times) after transmission electron micrograph (precipitation heat treatment), Fig. 25 201142048 3 (I) shows sample n〇.2_3, and Fig. 3 (II) shows sample n〇.2~ ~ 4, Figure 3 (ΙΠ) shows sample No. 2-110. Fig. 4 is a schematic view for explaining a crystal precipitate of Ag existing in the micrograph of Fig. 3. The fifth series is not intended to constitute the structure of the Cu-Ag alloy wire of the present invention. /3 is a perspective view of the coaxial cable of the present invention. [Main component symbol description] 1 Coaxial cable 11 center conductor 12 insulator 13 External conductor 14 Exterior material 26
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| JP6238274B2 (en) * | 2013-03-11 | 2017-11-29 | 株式会社Uacj | Copper alloy seamless pipe for hot and cold water supply |
| JP6244588B2 (en) * | 2013-03-11 | 2017-12-13 | 株式会社Uacj | Copper alloy seamless pipe for heat transfer tubes |
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| JP6529346B2 (en) * | 2015-06-04 | 2019-06-12 | 古河電気工業株式会社 | High bending fatigue resistance copper based alloy wire |
| CN105261422A (en) * | 2015-10-30 | 2016-01-20 | 西北有色金属研究院 | Preparation method of high-strength high-conductivity copper-silver alloy wire |
| US10472709B2 (en) | 2015-12-11 | 2019-11-12 | Apple Inc. | High strength, high conductivity electroformed copper alloys and methods of making |
| KR102117808B1 (en) * | 2016-05-16 | 2020-06-02 | 후루카와 덴키 고교 가부시키가이샤 | Copper alloy wire |
| CN108431255B (en) * | 2016-12-01 | 2021-04-02 | 古河电气工业株式会社 | Copper alloy wire |
| CN108463568B (en) * | 2016-12-02 | 2020-11-10 | 古河电气工业株式会社 | Copper alloy wire rod and method for manufacturing copper alloy wire rod |
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| CN111032892B (en) * | 2018-03-20 | 2021-12-14 | 古河电气工业株式会社 | Copper alloy wire rod and method for producing copper alloy wire rod |
| JP7171667B2 (en) * | 2020-09-25 | 2022-11-15 | 日立金属株式会社 | Conductive wire and cable |
| WO2023085305A1 (en) | 2021-11-12 | 2023-05-19 | 古河電気工業株式会社 | Cu-ag alloy wire |
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| JP7322247B1 (en) | 2022-06-07 | 2023-08-07 | Ｓｗｃｃ株式会社 | Cu-Ag alloy wire and manufacturing method thereof |
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| WO2024177092A1 (en) * | 2023-02-21 | 2024-08-29 | 古河電気工業株式会社 | Copper–silver alloy wire |
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| JP2714555B2 (en) * | 1992-09-17 | 1998-02-16 | 科学技術庁金属材料技術研究所長 | High strength and high conductivity copper alloy sheet material |
| JP3325641B2 (en) * | 1993-03-31 | 2002-09-17 | 株式会社フジクラ | Method for producing high-strength high-conductivity copper alloy |
| JP2000199042A (en) * | 1998-11-04 | 2000-07-18 | Showa Electric Wire & Cable Co Ltd | PRODUCTION OF Cu-Ag ALLOY WIRE ROD AND Cu-Ag ALLOY WIRE ROD |
| JP3856073B2 (en) | 1999-07-28 | 2006-12-13 | 住友電気工業株式会社 | Method for producing Cu-Ag alloy |
| JP4311277B2 (en) * | 2004-05-24 | 2009-08-12 | 日立電線株式会社 | Manufacturing method of extra fine copper alloy wire |
| JP4973437B2 (en) * | 2007-10-16 | 2012-07-11 | 日立電線株式会社 | Copper alloy wire, copper alloy twisted wire, coaxial cable, multi-core cable, and copper alloy wire manufacturing method |
| JP2009249660A (en) * | 2008-04-02 | 2009-10-29 | Sumitomo Electric Ind Ltd | Drawn wire material, stranded wire, coaxial cable and cast material for drawn wire material |
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2010
- 2010-10-12 JP JP2010230069A patent/JP5713230B2/en active Active
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2011
- 2011-04-27 KR KR1020177030149A patent/KR101843707B1/en active IP Right Grant
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- 2011-04-27 WO PCT/JP2011/060291 patent/WO2011136284A1/en active Application Filing
- 2011-04-27 KR KR1020127027874A patent/KR101790812B1/en active IP Right Grant
- 2011-04-27 KR KR1020187001843A patent/KR101870603B1/en active IP Right Grant
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| KR101870603B1 (en) | 2018-06-22 |
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| JP5713230B2 (en) | 2015-05-07 |
| KR20170121307A (en) | 2017-11-01 |
| CN102869805A (en) | 2013-01-09 |
| CN102869805B (en) | 2014-12-03 |
| KR101843707B1 (en) | 2018-03-29 |
| KR20180011344A (en) | 2018-01-31 |
| KR101790812B1 (en) | 2017-10-26 |
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