JP5506806B2 - Cu-Ni-Si-Co-based copper alloy for electronic materials and method for producing the same - Google Patents

Cu-Ni-Si-Co-based copper alloy for electronic materials and method for producing the same Download PDF

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JP5506806B2
JP5506806B2 JP2011532878A JP2011532878A JP5506806B2 JP 5506806 B2 JP5506806 B2 JP 5506806B2 JP 2011532878 A JP2011532878 A JP 2011532878A JP 2011532878 A JP2011532878 A JP 2011532878A JP 5506806 B2 JP5506806 B2 JP 5506806B2
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寛 桑垣
尚彦 江良
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JX Nippon Mining and Metals Corp
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper
    • C22C9/06Alloys based on copper with nickel or cobalt as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon

Description

本発明は析出硬化型銅合金に関し、とりわけ各種電子機器部品に用いるのに好適なCu−Ni−Si−Co系銅合金に関する。   The present invention relates to a precipitation hardening type copper alloy, and more particularly to a Cu—Ni—Si—Co based copper alloy suitable for use in various electronic device parts.

コネクタ、スイッチ、リレー、ピン、端子、リードフレーム等の各種電子機器部品に使用される電子材料用銅合金には、基本特性として高強度及び高導電性(又は熱伝導性)を両立させることが要求される。近年、電子部品の高集積化及び小型化・薄肉化が急速に進み、これに対応して電子機器部品に使用される銅合金に対する要求レベルはますます高度化している。   Copper alloys for electronic materials used in various electronic equipment parts such as connectors, switches, relays, pins, terminals, lead frames, etc., can achieve both high strength and high conductivity (or thermal conductivity) as basic characteristics. Required. In recent years, high integration and miniaturization / thinning of electronic components have been rapidly progressing, and the level of demand for copper alloys used in electronic device components has been increased accordingly.

高強度及び高導電性の観点から、電子材料用銅合金として従来のりん青銅、黄銅等に代表される固溶強化型銅合金に替わり、析出硬化型の銅合金の使用量が増加している。析出硬化型銅合金では、溶体化処理された過飽和固溶体を時効処理することにより、微細な析出物が均一に分散して、合金の強度が高くなると同時に、銅中の固溶元素量が減少し電気伝導性が向上する。このため、強度、ばね性などの機械的性質に優れ、しかも電気伝導性、熱伝導性が良好な材料が得られる。   From the viewpoint of high strength and high conductivity, the amount of precipitation hardening type copper alloys is increasing instead of conventional solid solution strengthened copper alloys such as phosphor bronze and brass as copper alloys for electronic materials. . In precipitation-hardened copper alloys, by aging the supersaturated solid solution that has undergone solution treatment, fine precipitates are uniformly dispersed, increasing the strength of the alloy and reducing the amount of solid solution elements in the copper. Electrical conductivity is improved. For this reason, a material excellent in mechanical properties such as strength and spring property and having good electrical conductivity and thermal conductivity can be obtained.

析出硬化型銅合金のうち、コルソン系合金と一般に呼ばれるCu−Ni−Si系銅合金は比較的高い導電性、強度、及び曲げ加工性を兼備する代表的な銅合金であり、業界において現在活発に開発が行われている合金の一つである。この銅合金では、銅マトリックス中に微細なNi−Si系金属間化合物粒子を析出させることによって強度と導電率の向上が図れる。   Among precipitation hardening copper alloys, Cu-Ni-Si copper alloys, commonly called Corson alloys, are representative copper alloys that have relatively high electrical conductivity, strength, and bending workability, and are currently active in the industry. It is one of the alloys being developed. In this copper alloy, strength and conductivity can be improved by precipitating fine Ni—Si intermetallic compound particles in a copper matrix.

コルソン合金にCoを添加することによって特性の更なる向上を図ろうとする試みがなされている。   Attempts have been made to further improve the characteristics by adding Co to the Corson alloy.

特開平11−222641号公報(特許文献1)には、CoはNiと同様にSiと化合物を形成し、機械的強度を向上させ、Cu−Co−Si系は時効処理させた場合に、Cu−Ni−Si系合金より機械的強度、導電性共に僅かに良くなる。そしてコスト的に許されるのであれば、Cu−Co−Si系やCu−Ni−Co−Si系を選択してもよいことが記載されている。当該合金の製造方法として、冷間加工後に再結晶処理を700〜920℃で行い、次に25%以下の冷間加工、420〜550℃での時効処理を行った後、さらに25%以下の冷間加工、及び低温焼鈍を行う方法が記載されている(請求項10)。   In Japanese Patent Application Laid-Open No. 11-222641 (Patent Document 1), Co forms a compound with Si in the same manner as Ni, improves the mechanical strength, and Cu—Co—Si system is Cu-treated. -Slightly better mechanical strength and conductivity than Ni-Si alloys. In addition, it is described that a Cu—Co—Si system or a Cu—Ni—Co—Si system may be selected if allowed by cost. As a manufacturing method of the alloy, after cold working, a recrystallization treatment is performed at 700 to 920 ° C., followed by a cold working of 25% or less, an aging treatment at 420 to 550 ° C., and then an additional 25% or less. A method of performing cold working and low temperature annealing is described (claim 10).

特表2005−532477号公報(特許文献2)には、重量で、ニッケル:1%〜2.5%、コバルト0.5〜2.0%、珪素:0.5%〜1.5%、および、残部としての銅および不可避の不純物から成り、ニッケルとコバルトの合計含有量が1.7%〜4.3%、比(Ni+Co)/Siが2:1〜7:1である鍛錬銅合金が記載されており、該鍛錬銅合金は、40%IACSを超える導電性を有するとされている。コバルトは珪素と組み合わされて、粒子成長を制限し且つ耐軟化性を向上させるために、時効硬化に有効な珪化物を形成するとされている。当該合金の製造方法として、850℃〜1000℃の熱間加工→800℃〜1000℃の溶体化処理→温度350℃〜600℃、30分〜30時間の第一時効焼鈍→10%〜50%の断面積減少させる冷間加工→第一時効焼鈍温度よりも低い温度で行う第二時効焼鈍を実施する方法が記載されている(請求項25、26)。   In Japanese translations of PCT publication No. 2005-532477 (patent document 2), by weight, nickel: 1% to 2.5%, cobalt: 0.5% to 2.0%, silicon: 0.5% to 1.5%, And a wrought copper alloy consisting of the balance copper and inevitable impurities, wherein the total content of nickel and cobalt is 1.7% to 4.3%, and the ratio (Ni + Co) / Si is 2: 1 to 7: 1 The wrought copper alloy is said to have a conductivity greater than 40% IACS. Cobalt is said to combine with silicon to form silicides that are effective for age hardening in order to limit grain growth and improve softening resistance. As a manufacturing method of the alloy, hot working at 850 ° C. to 1000 ° C. → solution treatment at 800 ° C. to 1000 ° C. → temperature annealing at 350 ° C. to 600 ° C., 30 minutes to 30 hours → 10% to 50% A method of performing a second aging annealing performed at a temperature lower than the first temporary annealing temperature is described (Claims 25 and 26).

国際公開第2006/101172号パンフレット(特許文献3)には、溶体化処理において加熱後の冷却速度を意識的に高くすると、Cu−Ni−Si系合金の強度向上効果は更に発揮されることから、冷却速度を毎秒約10℃以上として冷却するのが効果的であることが記載されている(段落0028)。   In WO 2006/101172 pamphlet (Patent Document 3), if the cooling rate after heating is consciously increased in the solution treatment, the strength improvement effect of the Cu—Ni—Si based alloy is further exhibited. It is described that it is effective to cool at a cooling rate of about 10 ° C. or more per second (paragraph 0028).

特開平9−20943号公報には、熱間圧延後、85%以上の冷間圧延を施し、450〜480℃で5〜30分間焼鈍後、30%以下の冷間圧延を施し、更に450〜500℃で30〜120分間時効処理を行うCu−Ni−Si−Co系合金の製造方法が記載されている(請求項5)。   In JP-A-9-20943, after hot rolling, cold rolling of 85% or more is performed, after annealing at 450 to 480 ° C. for 5 to 30 minutes, cold rolling of 30% or less is performed, and further 450 to A method for producing a Cu—Ni—Si—Co based alloy that is subjected to an aging treatment at 500 ° C. for 30 to 120 minutes is described (Claim 5).

特開平11−222641号公報Japanese Patent Application Laid-Open No. 11-222641 特表2005−532477号公報JP 2005-532477 A 国際公開第2006/101172号パンフレットInternational Publication No. 2006/101172 Pamphlet 特開平9−20943号公報JP-A-9-20943

このように、Cu−Ni−Si系合金にCoを添加することによって、強度や導電性が向上することが知られているが、従来のCu−Ni−Si−Co系合金では同一材料であっても測定箇所によって、強度、応力緩和特性、曲げ粗さといった機械的特性にばらつきが生じやすいという問題があった。   As described above, it is known that the addition of Co to the Cu—Ni—Si based alloy improves the strength and conductivity, but the conventional Cu—Ni—Si—Co based alloy is the same material. However, there is a problem that mechanical characteristics such as strength, stress relaxation characteristics, and bending roughness tend to vary depending on the measurement location.

そこで、本発明は電子材料用の銅合金として好適な機械的及び電気的特性を備え、機械的特性の均一なCu−Ni−Si−Co系合金を提供することを課題の一つとする。また、本発明はそのようなCu−Ni−Si−Co系合金を製造するための方法を提供することを別の課題の一つとする。   Accordingly, an object of the present invention is to provide a Cu—Ni—Si—Co alloy having mechanical and electrical characteristics suitable as a copper alloy for electronic materials and uniform mechanical characteristics. Another object of the present invention is to provide a method for producing such a Cu—Ni—Si—Co alloy.

まず、本発明者はこれまでのCu−Ni−Si−Co系合金は結晶粒の大きさにばらつきが多く、大粒子と小粒子が混在していることを見いだし、この結晶粒径の不均一性が機械的特性のばらつきに繋がっていることを突き止めた。Cu−Ni−Si−Co系合金においては、Coを添加したことで溶体化処理を通常のCu−Ni−Si系合金よりも高温で実施する必要があり、再結晶粒が粗大化しやすい。その一方で、溶体化処理工程の前段で析出していた晶出物や析出物といった第二相粒子が障害物となって結晶粒の成長を阻害する。そのため、Cu−Ni−Si−Co系合金においては再結晶粒のばらつきが通常のCu−Ni−Si系合金よりも大きくなりやすい傾向にある。   First, the present inventor found that conventional Cu-Ni-Si-Co alloys have a large variation in crystal grain size, and large particles and small particles are mixed, and this crystal grain size is uneven. It has been found that the property leads to variations in mechanical properties. In a Cu-Ni-Si-Co-based alloy, it is necessary to perform solution treatment at a higher temperature than ordinary Cu-Ni-Si-based alloys by adding Co, and recrystallized grains are likely to be coarsened. On the other hand, the second phase particles such as crystallized matter and precipitates precipitated in the previous stage of the solution treatment step become obstacles and inhibit the growth of crystal grains. Therefore, in the Cu—Ni—Si—Co based alloy, the variation in recrystallized grains tends to be larger than that in a normal Cu—Ni—Si based alloy.

そこで、本発明者は再結晶粒のばらつきを軽減する手段を鋭意検討したところ、溶体化処理工程の前段で微細な第二相粒子を銅母相中にできるだけ等間隔で一様に析出させておくことで、溶体化処理を比較的高温で行っても第二相粒子のピン止め効果によりそれほど結晶粒が大きくならず、しかも、ピン止め効果が銅母相全体において均等に働くことから成長する再結晶粒の大きさも均一化できるという知見を得た。そして、その結果、機械的特性のばらつきが少ないCu−Ni−Si−Co系合金が得られることが分かった。   Therefore, the present inventor has intensively studied means for reducing the variation in recrystallized grains, and as a result of precipitating fine second-phase particles uniformly in the copper matrix phase at equal intervals in the previous stage of the solution treatment step. Therefore, even if the solution treatment is performed at a relatively high temperature, the crystal grains are not so large due to the pinning effect of the second phase particles, and further, the pinning effect grows evenly in the entire copper matrix phase. The knowledge that the size of recrystallized grains can be made uniform was also obtained. As a result, it was found that a Cu—Ni—Si—Co alloy with little variation in mechanical properties was obtained.

以上の知見を背景にして完成した本発明は一側面において、Ni:1.0〜2.5質量%、Co:0.5〜2.5質量%、Si:0.3〜1.2質量%を含有し、残部がCu及び不可避不純物からなる電子材料用銅合金であって、平均結晶粒径が15〜30μmであり、観察視野0.5mm2毎の最大結晶粒径と最小結晶粒径の差の平均がμm以下である電子材料用銅合金である。
The present invention completed on the basis of the above knowledge, in one aspect, Ni: 1.0-2.5 mass%, Co: 0.5-2.5 mass%, Si: 0.3-1.2 mass %, The balance being Cu and an inevitable impurity copper alloy for electronic materials having an average crystal grain size of 15 to 30 μm and a maximum crystal grain size and a minimum crystal grain size for each observation field of 0.5 mm 2 This is a copper alloy for electronic materials having an average difference of 7 μm or less.

本発明に係る銅合金は一実施形態において、更にCrを最大0.5質量%含有する。   In one embodiment, the copper alloy according to the present invention further contains up to 0.5% by mass of Cr.

本発明に係る銅合金は別の一実施形態において、更にMg、Mn、Ag、及びPから選択される1種又は2種以上を総計で最大0.5質量%含有する。   In another embodiment, the copper alloy according to the present invention further contains one or more selected from Mg, Mn, Ag, and P in a total amount of 0.5 mass% in total.

本発明に係る銅合金は更に別の一実施形態において、更にSn及びZnから選択される1種又は2種を総計で最大2.0質量%含有する。   In yet another embodiment, the copper alloy according to the present invention further contains one or two selected from Sn and Zn in a total of up to 2.0% by mass.

本発明に係る銅合金は更に別の一実施形態において、更にAs、Sb、Be、B、Ti、Zr、Al及びFeから選択される1種又は2種以上を総計で最大2.0質量%含有する。   In yet another embodiment, the copper alloy according to the present invention further includes one or more selected from As, Sb, Be, B, Ti, Zr, Al and Fe in a total of up to 2.0% by mass. contains.

また、本発明は別の一側面において、
−所望の組成をもつインゴットを溶解鋳造する工程1と、
−950℃〜1050℃で1時間以上加熱後に熱間圧延を行い、熱間圧延終了時の温度を850℃以上とし、850℃〜400℃までの平均冷却速度を15℃/s以上として冷却する工程2と、
−加工度85%以上の冷間圧延工程3と、
−350〜500℃で1〜24時間加熱する時効処理工程4と、
−950℃〜1050℃で溶体化処理を行い、材料温度が850℃〜400℃まで低下するときの平均冷却速度を15℃/s以上として冷却する工程5と、
−随意的な冷間圧延工程6と、
−時効処理工程7と、
−随意的な冷間圧延工程8と、
−歪取焼鈍工程9と
を順に行なうことを含む銅合金の製造方法である。
In another aspect of the present invention,
-Step 1 of melt casting an ingot having a desired composition;
Hot rolling is performed after heating at −950 ° C. to 1050 ° C. for 1 hour or longer, the temperature at the end of hot rolling is 850 ° C. or higher, and the average cooling rate from 850 ° C. to 400 ° C. is 15 ° C./s or higher. Step 2 and
-Cold rolling step 3 with a working degree of 85% or more;
An aging treatment step 4 of heating at -350 to 500 ° C for 1 to 24 hours;
Step 5 of performing solution treatment at −950 ° C. to 1050 ° C., and cooling the material at a cooling rate of 15 ° C./s or more when the material temperature is reduced to 850 ° C. to 400 ° C .;
-Optional cold rolling step 6;
An aging treatment step 7;
-Optional cold rolling process 8;
-It is a manufacturing method of the copper alloy including performing the strain relief annealing process 9 in order.

本発明は更に別の一側面において、上記銅合金を備えた伸銅品である。   In still another aspect of the present invention, a copper product having the copper alloy is provided.

本発明は更に別の一側面において、上記銅合金を備えた電子機器部品である。   In another aspect of the present invention, there is provided an electronic device component including the copper alloy.

本発明によれば、結晶粒径が適切な範囲で均一化されているので、機械的特性の均一なCu−Ni−Si−Co系合金が得られる。   According to the present invention, since the crystal grain size is made uniform within an appropriate range, a Cu—Ni—Si—Co alloy having uniform mechanical properties can be obtained.

応力緩和試験法の説明図である。It is explanatory drawing of a stress relaxation test method. 応力緩和試験法の永久変形量に関する説明図である。It is explanatory drawing regarding the amount of permanent deformation of a stress relaxation test method.

Ni、Co及びSiの添加量
Ni、Co及びSiは、適当な熱処理を施すことにより金属間化合物を形成し、導電率を劣化させずに高強度化が図れる。
Ni、Co及びSiの添加量がそれぞれNi:1.0質量%未満、Co:0.5質量%未満、Si:0.3質量%未満では所望の強度が得られず、逆に、Ni:2.5質量%超、Co:2.5質量%超、Si:1.2質量%超では高強度化は図れるが導電率が著しく低下し、更には熱間加工性が劣化する。よってNi、Co及びSiの添加量はNi:1.0〜2.5質量%、Co:0.5〜2.5質量%、Si:0.3〜1.2質量%とした。Ni、Co及びSiの添加量は好ましくは、Ni:1.5〜2.0質量%、Co:0.5〜2.0質量%、Si:0.5〜1.0質量%である。
Addition amounts of Ni, Co, and Si Ni, Co, and Si form an intermetallic compound by performing an appropriate heat treatment, and can increase the strength without deteriorating conductivity.
When the addition amounts of Ni, Co and Si are less than Ni: 1.0% by mass, Co: less than 0.5% by mass, and Si: less than 0.3% by mass, the desired strength cannot be obtained. If it exceeds 2.5% by mass, Co: more than 2.5% by mass, and Si: more than 1.2% by mass, the strength can be increased, but the electrical conductivity is remarkably lowered, and the hot workability is further deteriorated. Therefore, the addition amounts of Ni, Co, and Si were set to Ni: 1.0 to 2.5 mass%, Co: 0.5 to 2.5 mass%, and Si: 0.3 to 1.2 mass%. The addition amount of Ni, Co, and Si is preferably Ni: 1.5 to 2.0 mass%, Co: 0.5 to 2.0 mass%, and Si: 0.5 to 1.0 mass%.

Crの添加量
Crは溶解鋳造時の冷却過程において結晶粒界に優先析出するため粒界を強化でき、熱間加工時の割れが発生しにくくなり、歩留低下を抑制できる。すなわち、溶解鋳造時に粒界析出したCrは溶体化処理などで再固溶するが、続く時効析出時にCrを主成分としたbcc構造の析出粒子またはSiとの化合物を生成する。通常のCu−Ni−Si系合金では添加したSi量のうち、時効析出に寄与しなかったSiは母相に固溶したまま導電率の上昇を抑制するが、珪化物形成元素であるCrを添加して、珪化物をさらに析出させることにより、固溶Si量を低減でき、強度を損なわずに導電率を上昇できる。しかしながら、Cr濃度が0.5質量%を超えると粗大な第二相粒子を形成しやすくなるため、製品特性を損なう。従って、本発明に係るCu−Ni−Si−Co系合金には、Crを最大で0.5質量%添加することができる。但し、0.03質量%未満ではその効果が小さいので、好ましくは0.03〜0.5質量%、より好ましくは0.09〜0.3質量%添加するのがよい。
The added amount Cr of Cr preferentially precipitates at the grain boundaries in the cooling process during melt casting, so that the grain boundaries can be strengthened, cracks during hot working are less likely to occur, and yield reduction can be suppressed. That is, Cr that has precipitated at the grain boundaries during melt casting is re-dissolved by solution treatment or the like, but during subsequent aging precipitation, precipitated particles having a bcc structure mainly composed of Cr or a compound with Si are generated. In a normal Cu—Ni—Si based alloy, Si that does not contribute to aging precipitation suppresses the increase in conductivity while being dissolved in the matrix, but the silicide forming element Cr is not added. By adding and further depositing silicide, the amount of dissolved Si can be reduced, and the conductivity can be increased without impairing the strength. However, when the Cr concentration exceeds 0.5% by mass, coarse second-phase particles are easily formed, so that product characteristics are impaired. Therefore, Cr can be added to the Cu—Ni—Si—Co alloy according to the present invention at a maximum of 0.5 mass%. However, since the effect is small if it is less than 0.03 mass%, it is preferable to add 0.03-0.5 mass%, more preferably 0.09-0.3 mass%.

Mg、Mn、Ag及びPの添加量
Mg、Mn、Ag及びPは、微量の添加で、導電率を損なわずに強度、応力緩和特性等の製品特性を改善する。添加の効果は主に母相への固溶により発揮されるが、第二相粒子に含有されることで一層の効果を発揮させることもできる。しかしながら、Mg、Mn、Ag及びPの濃度の総計が0.5%を超えると特性改善効果が飽和するうえ、製造性を損なう。従って、本発明に係るCu−Ni−Si−Co系合金には、Mg、Mn、Ag及びPから選択される1種又は2種以上を総計で最大0.5質量%添加することができる。但し、0.01質量%未満ではその効果が小さいので、好ましくは総計で0.01〜0.5質量%、より好ましくは総計で0.04〜0.2質量%添加するのがよい。
Addition amounts of Mg, Mn, Ag and P Mg, Mn, Ag and P improve the product properties such as strength and stress relaxation characteristics without adding a small amount of addition by adding a small amount. The effect of addition is exhibited mainly by solid solution in the matrix phase, but further effects can be exhibited by inclusion in the second phase particles. However, if the total concentration of Mg, Mn, Ag, and P exceeds 0.5%, the effect of improving the characteristics is saturated and manufacturability is impaired. Accordingly, one or more selected from Mg, Mn, Ag and P can be added to the Cu—Ni—Si—Co alloy according to the present invention in a total amount of up to 0.5 mass%. However, since the effect is small if it is less than 0.01% by mass, it is preferable to add 0.01 to 0.5% by mass in total, more preferably 0.04 to 0.2% by mass in total.

Sn及びZnの添加量
Sn及びZnにおいても、微量の添加で、導電率を損なわずに強度、応力緩和特性、めっき性等の製品特性を改善する。添加の効果は主に母相への固溶により発揮される。しかしながら、Sn及びZnの総計が2.0質量%を超えると特性改善効果が飽和するうえ、製造性を損なう。従って、本発明に係るCu−Ni−Si−Co系合金には、Sn及びZnから選択される1種又は2種を総計で最大2.0質量%添加することができる。但し、0.05質量%未満ではその効果が小さいので、好ましくは総計で0.05〜2.0質量%、より好ましくは総計で0.5〜1.0質量%添加するのがよい。
Even in the addition amounts Sn and Zn of Sn and Zn, the addition of a small amount improves product properties such as strength, stress relaxation properties, and plating properties without impairing electrical conductivity. The effect of addition is exhibited mainly by solid solution in the matrix. However, if the total amount of Sn and Zn exceeds 2.0% by mass, the effect of improving characteristics is saturated and manufacturability is impaired. Therefore, one or two selected from Sn and Zn can be added to the Cu—Ni—Si—Co-based alloy according to the present invention in a maximum of 2.0 mass% in total. However, since the effect is small if it is less than 0.05% by mass, it is preferable to add 0.05 to 2.0% by mass in total, and more preferably 0.5 to 1.0% by mass in total.

As、Sb、Be、B、Ti、Zr、Al及びFe
As、Sb、Be、B、Ti、Zr、Al及びFeにおいても、要求される製品特性に応じて、添加量を調整することで、導電率、強度、応力緩和特性、めっき性等の製品特性を改善する。添加の効果は主に母相への固溶により発揮されるが、第二相粒子に含有され、若しくは新たな組成の第二相粒子を形成することで一層の効果を発揮させることもできる。しかしながら、これらの元素の総計が2.0質量%を超えると特性改善効果が飽和するうえ、製造性を損なう。従って、本発明に係るCu−Ni−Si−Co系合金には、As、Sb、Be、B、Ti、Zr、Al及びFeから選択される1種又は2種以上を総計で最大2.0質量%添加することができる。但し、0.001質量%未満ではその効果が小さいので、好ましくは総計で0.001〜2.0質量%、より好ましくは総計で0.05〜1.0質量%添加するのがよい。
As, Sb, Be, B, Ti, Zr, Al and Fe
For As, Sb, Be, B, Ti, Zr, Al, and Fe, the product properties such as conductivity, strength, stress relaxation properties, plating properties, etc. can be adjusted by adjusting the amount added according to the required product properties. To improve. The effect of addition is exhibited mainly by solid solution in the parent phase, but it can also be exhibited by forming the second phase particles having a new composition or contained in the second phase particles. However, if the total amount of these elements exceeds 2.0% by mass, the effect of improving characteristics is saturated and manufacturability is impaired. Therefore, in the Cu—Ni—Si—Co alloy according to the present invention, a total of one or more selected from As, Sb, Be, B, Ti, Zr, Al and Fe is 2.0 at the maximum. Mass% can be added. However, since the effect is small if it is less than 0.001% by mass, it is preferable to add 0.001-2.0% by mass in total, more preferably 0.05-1.0% by mass in total.

上記したMg、Mn、Ag、P、Sn、Zn、As、Sb、Be、B、Ti、Zr、Al及びFeの添加量が合計で3.0%を超えると製造性を損ないやすいので、好ましくはこれらの合計は2.0質量%以下とし、より好ましくは1.5質量%以下とする。   Preferably, if the total amount of Mg, Mn, Ag, P, Sn, Zn, As, Sb, Be, B, Ti, Zr, Al, and Fe exceeds 3.0% in total, manufacturability is easily lost. The total of these is 2.0% by mass or less, more preferably 1.5% by mass or less.

結晶粒径
結晶粒は強度に影響を与え、強度が結晶粒径の−1/2乗に比例するというホールペッチ則が一般に成立する。また、粗大な結晶粒は曲げ加工性を悪化させ、曲げ加工時の肌荒れの要因となる。従って、銅合金においては一般に、結晶粒は微細化することが強度向上のためには望ましい。具体的には30μm以下とするのが好ましく、23μm以下とするのがより好ましい。
The grain size affects the strength, and the Hall Petch rule is generally established in which the strength is proportional to the -1/2 power of the crystal grain size. In addition, coarse crystal grains deteriorate bending workability and cause rough skin during bending. Therefore, in general, in a copper alloy, it is desirable to refine crystal grains in order to improve strength. Specifically, it is preferably 30 μm or less, and more preferably 23 μm or less.

一方、本発明のようなCu−Ni−Si−Co系合金は、析出強化型の合金であるため、第二相粒子の析出状態にも留意する必要がある。時効処理において結晶粒内に析出した第二相粒子は強度向上に寄与するが、結晶粒界に析出した第二相粒子はほとんど強度向上にほとんど寄与しない。従って、強度向上を図る上では第二相粒子を結晶粒内に析出させるのが望ましい。結晶粒径が小さくなると、粒界面積が大きくなるので、時効処理時に第二相粒子は粒界に優先的に析出しやすくなる。第二相粒子を結晶粒内に析出させるためには結晶粒はある程度の大きさが必要となる。具体的には15μm以上とするのが好ましく、18μm以上とするのが更により好ましい。   On the other hand, since the Cu—Ni—Si—Co alloy as in the present invention is a precipitation strengthening type alloy, it is necessary to pay attention to the precipitation state of the second phase particles. The second phase particles precipitated in the crystal grains in the aging treatment contribute to the strength improvement, but the second phase particles precipitated in the crystal grain boundaries hardly contribute to the strength improvement. Accordingly, in order to improve the strength, it is desirable to precipitate the second phase particles in the crystal grains. As the crystal grain size becomes smaller, the grain boundary area becomes larger, so that the second phase particles tend to preferentially precipitate at the grain boundaries during the aging treatment. In order to precipitate the second phase particles in the crystal grains, the crystal grains need to have a certain size. Specifically, it is preferably 15 μm or more, and more preferably 18 μm or more.

本発明では平均結晶粒径を15〜30μmの範囲に制御することとしている。平均結晶粒径は好ましくは18〜23μmである。平均結晶粒径をこのような範囲に制御することによって結晶粒微細化による強度向上効果と析出硬化による強度向上効果の両方をバランス良く享受することができるようになる。また、当該範囲の結晶粒径であれば優れた曲げ加工性及び応力緩和特性を得ることが可能である。   In the present invention, the average crystal grain size is controlled in the range of 15 to 30 μm. The average crystal grain size is preferably 18 to 23 μm. By controlling the average crystal grain size in such a range, it is possible to enjoy both the strength improvement effect by crystal grain refinement and the strength improvement effect by precipitation hardening in a balanced manner. In addition, if the crystal grain size is in this range, it is possible to obtain excellent bending workability and stress relaxation characteristics.

本発明においては、結晶粒径とは、圧延方向に平行な厚み方向の断面を顕微鏡で観察したときの、個々の結晶粒を取り囲む最小円の直径のことを指し、平均結晶粒径とはその平均値である。   In the present invention, the crystal grain size refers to the diameter of the smallest circle surrounding each crystal grain when a cross section in the thickness direction parallel to the rolling direction is observed with a microscope. Average value.

本発明では観察視野0.5mm2毎の最大結晶粒径と最小結晶粒径の差の平均が10μm以下であり、好ましくは7μm以下である。差の平均は0μmが理想的であるが、現実的には難しいので下限は現実の最低値から3μmとし、典型的には3〜7μmが最適である。ここで、最大結晶粒径というのは一つの観察視野0.5mm2中に観察される最大の結晶粒径であり、最小結晶粒径というのは同一視野中に観察される最小の結晶粒径である。本発明では複数の観察視野で最大結晶粒径と最小結晶粒径の差をそれぞれ求め、その平均値を最大結晶粒径と最小結晶粒径の差の平均としている。In the present invention, the average of the difference between the maximum crystal grain size and the minimum crystal grain size per observation field 0.5 mm 2 is 10 μm or less, preferably 7 μm or less. The average of the difference is ideally 0 μm, but it is difficult in practice, so the lower limit is set to 3 μm from the actual minimum value, and typically 3 to 7 μm is optimal. Here, the maximum crystal grain size is the maximum crystal grain size observed in one observation field 0.5 mm 2 , and the minimum crystal grain size is the minimum crystal grain size observed in the same field of view. It is. In the present invention, the difference between the maximum crystal grain size and the minimum crystal grain size is obtained in a plurality of observation fields, and the average value is set as the average of the difference between the maximum crystal grain size and the minimum crystal grain size.

最大結晶粒径と最小結晶粒径の差が小さいということは結晶粒径の大きさが均一であることを指し、同一材料内における測定箇所毎の機械的特性のばらつきを軽減する。その結果、本発明に係る銅合金を加工して得た伸銅品や電子機器部品の品質安定性が向上することになる。   A small difference between the maximum crystal grain size and the minimum crystal grain size means that the crystal grain size is uniform, and reduces variations in mechanical characteristics of each measurement location in the same material. As a result, the quality stability of the copper products and electronic device parts obtained by processing the copper alloy according to the present invention is improved.

製造方法
コルソン系銅合金の一般的な製造プロセスでは、まず大気溶解炉を用い、電気銅、Ni、Si、Co等の原料を溶解し、所望の組成の溶湯を得る。そして、この溶湯をインゴットに鋳造する。その後、熱間圧延を行い、冷間圧延と熱処理を繰り返して、所望の厚み及び特性を有する条や箔に仕上げる。熱処理には溶体化処理と時効処理がある。溶体化処理では、約700〜約1000℃の高温で加熱して、第二相粒子をCu母地中に固溶させ、同時にCu母地を再結晶させる。溶体化処理を、熱間圧延で兼ねることもある。時効処理では、約350〜約550℃の温度範囲で1時間以上加熱し、溶体化処理で固溶させた第二相粒子をナノメートルオーダーの微細粒子として析出させる。この時効処理で強度と導電率が上昇する。より高い強度を得るために、時効前及び/又は時効後に冷間圧延を行なうことがある。また、時効後に冷間圧延を行なう場合には、冷間圧延後に歪取焼鈍(低温焼鈍)を行なうことがある。
上記各工程の合間には適宜、表面の酸化スケール除去のための研削、研磨、ショットブラスト酸洗等が適宜行なわれる。
Manufacturing Method In a general manufacturing process of a Corson copper alloy, first, an atmospheric melting furnace is used to melt raw materials such as electrolytic copper, Ni, Si, and Co to obtain a molten metal having a desired composition. Then, this molten metal is cast into an ingot. Thereafter, hot rolling is performed, and cold rolling and heat treatment are repeated to finish a strip or foil having a desired thickness and characteristics. Heat treatment includes solution treatment and aging treatment. In the solution treatment, heating is performed at a high temperature of about 700 to about 1000 ° C., so that the second phase particles are dissolved in the Cu matrix and at the same time the Cu matrix is recrystallized. The solution treatment may be combined with hot rolling. In the aging treatment, the second phase particles heated in a temperature range of about 350 to about 550 ° C. for 1 hour or more and solid-dissolved by the solution treatment are precipitated as fine particles of nanometer order. This aging treatment increases strength and conductivity. In order to obtain higher strength, cold rolling may be performed before and / or after aging. Moreover, when performing cold rolling after aging, strain relief annealing (low temperature annealing) may be performed after cold rolling.
Between the above steps, grinding, polishing, shot blast pickling and the like for removing oxide scale on the surface are appropriately performed.

本発明に係る銅合金においても基本的には上記の製造プロセスを経るが、平均結晶粒径及び結晶粒径のばらつきを本発明で規定する範囲に制御するためには、前述したように、溶体化処理工程の前段で微細な第二相粒子を銅母相中にできるだけ等間隔で一様に析出させておくことが重要である。本発明に係る銅合金を得るためには、特に以下の点に留意しながら製造する必要がある。   The copper alloy according to the present invention basically undergoes the above manufacturing process, but in order to control the average crystal grain size and the variation in crystal grain size within the range defined by the present invention, as described above, the solution It is important to deposit fine second-phase particles uniformly in the copper matrix phase at equal intervals before the chemical treatment step. In order to obtain the copper alloy according to the present invention, it is necessary to manufacture while paying particular attention to the following points.

まず、鋳造時の凝固過程では粗大な晶出物が、その冷却過程では粗大な析出物が不可避的に生成するため、その後の工程においてこれらの晶出物を母相中に固溶する必要がある。950℃〜1050℃で1時間以上保持後に熱間圧延を行い、熱間圧延終了時の温度を850℃以上とすればCo、更にはCrを添加した場合であっても母相中に固溶することができる。950℃以上という温度条件は他のコルソン系合金の場合に比較して高い温度設定である。熱間圧延前の保持温度が950℃未満では固溶が不十分であり、1050℃を超えると材料が溶解する可能性がある。また、熱間圧延終了時の温度が850℃未満では固溶した元素が再び析出するため、高い強度を得ることが困難となる。よって高強度を得るためには850℃で熱間圧延を終了し、速やかに冷却することが望ましい。   First, coarse crystals are inevitably generated in the solidification process during casting, and coarse precipitates are inevitably generated in the cooling process. Therefore, it is necessary to dissolve these crystals in the matrix in the subsequent steps. is there. If hot rolling is performed after holding at 950 ° C. to 1050 ° C. for 1 hour or longer, and the temperature at the end of hot rolling is 850 ° C. or higher, even if Co and further Cr are added, it is dissolved in the matrix phase. can do. The temperature condition of 950 ° C. or higher is a higher temperature setting than other Corson alloys. If the holding temperature before hot rolling is less than 950 ° C., solid solution is insufficient, and if it exceeds 1050 ° C., the material may be dissolved. Further, when the temperature at the end of hot rolling is less than 850 ° C., the dissolved element is precipitated again, and it is difficult to obtain high strength. Therefore, in order to obtain high strength, it is desirable to finish the hot rolling at 850 ° C. and cool it quickly.

このとき、冷却速度が遅いとCoやCrを含有するSi系化合物が再び析出してしまう。このような組織で強度上昇を目的とした熱処理(時効処理)を行う際、冷却過程で析出した析出物を核として強度に寄与しない粗大な析出物に成長するため高い強度を得ることができない。従って、冷却速度はできるだけ高くし、具体的には15℃/s以上にする必要がある。ただし、第二相粒子の析出が著しいのは400℃程度までなので、400℃未満における冷却速度は問題とならない。よって、本発明では材料温度が850℃〜400℃までの平均冷却速度を15℃/s以上、好ましくは20℃/以上として冷却することとしている。“850℃〜400℃まで低下するときの平均冷却速度”とは材料温度が850℃〜650℃まで低下する冷却時間を計測し、“(850−400)(℃)/冷却時間(s)”によって算出した値(℃/s)をいう。   At this time, if the cooling rate is slow, the Si-based compound containing Co or Cr is precipitated again. When performing a heat treatment (aging treatment) for the purpose of increasing the strength in such a structure, a high strength cannot be obtained because the precipitate deposited in the cooling process grows into a coarse precipitate that does not contribute to the strength. Therefore, the cooling rate should be as high as possible, specifically 15 ° C./s or more. However, since the precipitation of the second phase particles is remarkable up to about 400 ° C., the cooling rate below 400 ° C. is not a problem. Therefore, in this invention, it is supposed that it cools by setting the average cooling rate to material temperature 850 degreeC-400 degreeC as 15 degreeC / s or more, Preferably it is 20 degreeC / more. “Average cooling rate when the temperature decreases from 850 ° C. to 400 ° C.” means that the cooling time when the material temperature decreases from 850 ° C. to 650 ° C. is measured, and “(850-400) (° C.) / Cooling time (s)” The value (° C./s) calculated by.

冷却を速くする方法としては水冷が最も効果的である。ただし、水冷に使用する水の温度により冷却速度が変わるため、水温の管理をすることでより冷却を速くすることができる。水温が25℃以上だと所望の冷却速度を得ることができない場合があるため、25℃以下に保持するのが好ましい。水を溜めた槽内に材料を入れて水冷すると、水の温度は上昇し25℃以上になり易いため、材料が一定の水の温度(25℃以下)で冷却されるように霧状(シャワー状又はミスト状)にして噴霧したり、水槽に常時冷たい水を流すようにしたりして水温上昇を防ぐのが好ましい。また、水冷ノズルの増設や単位時間当たりにおける水量を増加することによっても冷却速度の上昇させることができる。   Water cooling is the most effective method for speeding up the cooling. However, since the cooling rate varies depending on the temperature of the water used for water cooling, the cooling can be further accelerated by managing the water temperature. Since the desired cooling rate may not be obtained when the water temperature is 25 ° C. or higher, it is preferably maintained at 25 ° C. or lower. When a material is placed in a tank in which water is stored and cooled with water, the temperature of the water rises and tends to be 25 ° C. or higher, so that the material is cooled in a mist (shower) at a constant water temperature (25 ° C. or lower). It is preferable to prevent the water temperature from rising by spraying it in the form of a mist or mist) or by allowing cold water to always flow through the water tank. The cooling rate can also be increased by adding water cooling nozzles or increasing the amount of water per unit time.

熱間圧延後は冷間圧延を実施する。この冷間圧延は、均一に析出物を析出させるために、析出サイトとなる歪を増やす目的で実施し、冷間圧延は圧下率85%以上で実施するのが好ましく、圧下率95%以上で実施するのがより好ましい。冷間圧延をせず、熱間圧延の直後に溶体化処理を実施すると析出物が均一に析出しない。熱間圧延及びその後の冷間圧延の組み合わせは適宜繰り返しても良い。   Cold rolling is performed after hot rolling. This cold rolling is performed for the purpose of increasing the strain that becomes a precipitation site in order to precipitate precipitates uniformly, and cold rolling is preferably performed at a reduction rate of 85% or more, and at a reduction rate of 95% or more. More preferably. If the solution treatment is performed immediately after the hot rolling without cold rolling, the precipitates are not uniformly deposited. The combination of hot rolling and subsequent cold rolling may be repeated as appropriate.

冷間圧延後に第一時効処理を実施する。本工程を実施する前に第二相粒子が残存していると、本工程を実施したときにそのような第二相粒子は更に成長するので、本工程で初めて析出する第二相粒子と粒径に差が生じてしまうが、本発明においては前段の工程で第二相粒子はほぼ消滅させているため、微細な第二相粒子を均一な大きさで一様に析出させることが可能である。
ただし、第一時効処理の時効温度が低すぎるとピン止め効果をもたらす第二相粒子の析出量が少なくなり、溶体化処理で生じるピン止め効果が部分的にしか得られないので、結晶粒の大きさがばらつく。一方、時効温度が高すぎると第二相粒子が粗大になり、また不均一に第二相粒子が析出するために、第二相粒子の粒径の大きさがばらついてしまう。また、時効時間が長いほど第二相粒子が成長していくので、適度な時効時間に設定する必要がある。
第一時効処理は350〜500℃で1〜24時間、好ましくは350℃以上400℃未満では12〜24時間、400℃以上450℃未満では6〜12時間、450℃以上500℃未満では3〜6時間行うことにより、母相中に微細な第二相粒子を均等に析出させることができる。このような組織だと、次工程の溶体化処理で生じる再結晶粒の成長を一様にピン止めすることができ、結晶粒径にばらつきの少ない整粒組織を得ることができる。
The first temporary effect treatment is performed after cold rolling. If the second phase particles remain before this step is carried out, such second phase particles will grow further when this step is carried out. In the present invention, since the second phase particles are almost disappeared in the preceding step, it is possible to precipitate fine second phase particles uniformly in a uniform size. is there.
However, if the aging temperature of the first temporary effect treatment is too low, the amount of precipitation of the second phase particles that bring about the pinning effect is reduced, and only a partial pinning effect caused by the solution treatment can be obtained. The size varies. On the other hand, if the aging temperature is too high, the second phase particles become coarse, and the second phase particles precipitate non-uniformly, so that the size of the second phase particles varies. Further, since the second phase particles grow as the aging time is longer, it is necessary to set an appropriate aging time.
The first temporary treatment is 350 to 500 ° C. for 1 to 24 hours, preferably 12 to 24 hours at 350 to 400 ° C., 6 to 12 hours at 400 to 450 ° C., 3 to 450 to 500 ° C. By carrying out for 6 hours, fine second phase particles can be uniformly deposited in the mother phase. With such a structure, the growth of recrystallized grains generated in the solution treatment in the next step can be uniformly pinned, and a sized structure with little variation in crystal grain size can be obtained.

第一時効処理の後は溶体化処理を行う。ここでは、第二相粒子固溶させながら、微細でを均一な再結晶粒を成長させる。そのため、溶体化温度は950℃〜1050℃とする必要がある。ここでは、再結晶粒が先に成長し、その後に第一時効処理で析出した第二相粒子が固溶することから、再結晶粒の成長をピン留め効果によって制御することが可能となる。ただし、第二相粒子が固溶した後はピン留め効果がなくなるので、長時間溶体化処理を続けると、再結晶粒が大きくなってしまう。そこで、適切な溶体化処理の時間は950℃以上1000℃未満では60秒〜300秒、好ましくは120〜180秒であり、1000℃以上1050℃未満では30秒〜180秒、好ましくは60秒〜120秒である   After the first temporary effect treatment, solution treatment is performed. Here, fine and uniform recrystallized grains are grown while solid solution of the second phase particles. Therefore, the solution temperature needs to be 950 ° C to 1050 ° C. Here, the recrystallized grains grow first, and then the second phase particles precipitated by the first temporary effect treatment are in solid solution. Therefore, the growth of the recrystallized grains can be controlled by the pinning effect. However, since the pinning effect is lost after the second phase particles are dissolved, the recrystallized grains become large if the solution treatment is continued for a long time. Therefore, a suitable solution treatment time is 60 seconds to 300 seconds, preferably 120 to 180 seconds at 950 ° C. or more and less than 1000 ° C., and preferably 30 seconds to 180 seconds, preferably 60 seconds to 1000 ° C. or more and less than 1050 ° C. 120 seconds

溶体化処理後の冷却過程においても、第二相粒子の析出を回避するために、材料温度が850℃〜400℃まで低下するときの平均冷却速度を15℃/s以上、好ましくは20℃/s以上にすべきである。   Even in the cooling process after the solution treatment, in order to avoid the precipitation of the second phase particles, the average cooling rate when the material temperature is reduced to 850 ° C. to 400 ° C. is 15 ° C./s or more, preferably 20 ° C. / Should be greater than or equal to s.

溶体化処理後には第二時効処理を実施する。第二時効処理の条件は析出物の微細化に有用であるとして慣用的に行われている条件で構わないが、析出物が粗大化しないように温度及び時間を設定することに留意する。時効処理の条件の一例を挙げると、350〜550℃の温度範囲で1〜24時間であり、より好ましくは400〜500℃の温度範囲で1〜24時間である。なお、時効処理後の冷却速度は析出物の大小にほとんど影響を与えない。第2時効の前の場合は、析出サイトを増やし、析出サイトを利用して時効硬化を促進させて強度上昇を図る。第2時効の後の場合は、析出物を利用して加工硬化を促進させて強度上昇を図る。第二時効処理の前及び/又は後に冷間圧延を実施することもできる。第二時効処理後の冷間圧延後には応力緩和特性を向上させるために歪取焼鈍を実施する。歪取焼鈍は慣用的な加熱条件でよいが、例えば焼鈍温度250℃〜400℃で1〜24時間、好ましくは250℃〜350℃で1〜24時間行う。   A second aging treatment is performed after the solution treatment. The conditions for the second aging treatment may be those conventionally used as useful for refining the precipitates, but note that the temperature and time are set so that the precipitates do not become coarse. If an example of the conditions of an aging treatment is given, it will be 1 to 24 hours in the temperature range of 350-550 degreeC, More preferably, it is 1 to 24 hours in the temperature range of 400-500 degreeC. The cooling rate after the aging treatment hardly affects the size of the precipitates. In the case before the second aging, precipitation sites are increased, and age hardening is promoted by using the precipitation sites to increase the strength. In the case after the second aging, the precipitate is used to promote work hardening and increase the strength. Cold rolling can also be performed before and / or after the second aging treatment. After cold rolling after the second aging treatment, strain relief annealing is performed in order to improve stress relaxation characteristics. The strain relief annealing may be performed under conventional heating conditions. For example, the annealing temperature is 250 ° C. to 400 ° C. for 1 to 24 hours, preferably 250 ° C. to 350 ° C. for 1 to 24 hours.

本発明のCu−Ni−Si−Co系合金は種々の伸銅品、例えば板、条、管、棒及び線に加工することができ、更に、本発明によるCu−Ni−Si−Co系銅合金は、リードフレーム、コネクタ、ピン、端子、リレー、スイッチ、二次電池用箔材等の電子部品等に使用することができる。   The Cu—Ni—Si—Co based alloy of the present invention can be processed into various copper products, such as plates, strips, tubes, bars and wires, and the Cu—Ni—Si—Co based copper according to the present invention. The alloy can be used for electronic components such as lead frames, connectors, pins, terminals, relays, switches, and secondary battery foils.

以下に本発明の実施例を比較例と共に示すが、これらの実施例は本発明及びその利点をよりよく理解するために提供するものであり、発明が限定されることを意図するものではない。   Examples of the present invention will be described below together with comparative examples, but these examples are provided for better understanding of the present invention and its advantages, and are not intended to limit the invention.

表1(実施例)及び表2(比較例)に記載の成分組成の銅合金を、高周波溶解炉で1300℃で溶製し、厚さ30mmのインゴットに鋳造した。次いで、このインゴットを1000℃に加熱後、板厚10mmまで熱間圧延し、上り温度(熱間圧延終了温度)900℃とした。熱間圧延終了後は材料温度が850℃〜400℃まで低下するときの平均冷却速度を18℃として水冷却し、その後は空気中に放置して冷却した。次いで、表面のスケール除去のため厚さ9mmまで面削を施した後、冷間圧延により厚さ0.15mmの板とした。次いで、第一時効処理を種々の時効温度で3〜12時間実施した後、種々の溶体化温度で溶体化処理を120秒行い、その後、直ちに材料温度が850℃〜400℃まで低下するときの平均冷却速度を18℃として水冷却し、その後は空気中に放置して冷却した。次いで0.10mmまで冷間圧延して、450℃で3時間かけて不活性雰囲気中で第二時効処理を施して、更に0.08mmまで冷間圧延をした後、最後に300℃で3時間かけて不活性雰囲気中で歪取焼鈍をして、試験片を製造した。   Copper alloys having the component compositions described in Table 1 (Examples) and Table 2 (Comparative Examples) were melted at 1300 ° C. in a high frequency melting furnace and cast into 30 mm thick ingots. Next, the ingot was heated to 1000 ° C. and then hot-rolled to a plate thickness of 10 mm to obtain an ascending temperature (hot rolling end temperature) of 900 ° C. After the hot rolling was completed, the material was cooled with water at an average cooling rate of 18 ° C. when the material temperature decreased from 850 ° C. to 400 ° C., and then left in the air for cooling. Next, the surface was chamfered to a thickness of 9 mm for removing the scale, and then a plate having a thickness of 0.15 mm was formed by cold rolling. Next, after performing the first temporary effect treatment at various aging temperatures for 3 to 12 hours, the solution treatment is performed at various solution temperatures for 120 seconds, and then the material temperature immediately decreases to 850 ° C. to 400 ° C. The water was cooled at an average cooling rate of 18 ° C. and then left in the air for cooling. Next, it was cold-rolled to 0.10 mm, subjected to a second aging treatment in an inert atmosphere at 450 ° C. for 3 hours, and further cold-rolled to 0.08 mm, and finally at 300 ° C. for 3 hours. The specimen was manufactured by strain relief annealing in an inert atmosphere.

このようにして得られた各試験片につき各種の特性評価を以下のようにして行った。   Various characteristics of each test piece thus obtained were evaluated as follows.

(1)平均結晶粒径
結晶粒径は、試料を観察面が圧延方向に対し平行な厚み方向の断面となるように樹脂埋めし、観察面を機械研磨にて鏡面仕上げ後、水100容量部に対して濃度36%の塩酸10容量部の割合で混合した溶液に、その溶液の重量の5%の重量の塩化第二鉄を溶解した。こうして出来上がった溶液中に試料を10秒間浸漬して金属組織を現出させた。次に、前記金属組織を光学顕微鏡で100倍に拡大して観察視野0.5mm2を一枚の写真に撮り、個々の結晶粒を取り囲む最小円の直径をすべて求め、各観察視野に対して平均値を算出し、観察視野15箇所の平均値を平均結晶粒径とした。
(1) Average crystal grain size The crystal grain size was determined by filling the sample with a resin so that the observation surface had a cross section in the thickness direction parallel to the rolling direction, and mirror-finishing the observation surface by mechanical polishing, and then 100 parts by volume of water. In a mixed solution of 10 parts by volume of hydrochloric acid having a concentration of 36%, ferric chloride having a weight of 5% of the weight of the solution was dissolved. The sample was immersed in the solution thus prepared for 10 seconds to reveal the metal structure. Next, the metallographic structure is magnified 100 times with an optical microscope, an observation field of view of 0.5 mm 2 is taken in a single photograph, and the diameters of the smallest circles surrounding each crystal grain are all determined. The average value was calculated, and the average value at 15 observation fields was taken as the average crystal grain size.

(2)最大結晶粒径−最小結晶粒径の差の平均
平均結晶粒径を求めたときに測定した結晶粒径について、最大値と最小値の差を視野毎に求め、観察視野15箇所の平均値を最大結晶粒径−最小結晶粒径の差の平均とした。
(2) Average of the difference between the maximum crystal grain size and the minimum crystal grain size For the crystal grain size measured when the average crystal grain size was determined, the difference between the maximum value and the minimum value was determined for each field of view, The average value was defined as the average difference between the maximum crystal grain size and the minimum crystal grain size.

(3)強度
強度については圧延平行方向の引張り試験を行って0.2%耐力(YS:MPa)を測定した。測定箇所による強度のばらつきは30箇所の最大強度―最小強度の差とし、平均強度はこの30箇所の平均値である。
(3) Strength Regarding the strength, a 0.2% proof stress (YS: MPa) was measured by performing a tensile test in the rolling parallel direction. The variation in intensity between the measurement points is the difference between the maximum intensity and the minimum intensity at 30 points, and the average intensity is the average value of these 30 points.

(4)導電率
導電率(EC;%IACS)についてはダブルブリッジによる体積抵抗率測定により求めた。測定箇所による導電率のばらつきは30箇所の最大強度−最小強度の差とし、平均導電率はこの30箇所の平均値である。
(4) Conductivity Conductivity (EC;% IACS) was determined by volume resistivity measurement using a double bridge. The variation in conductivity depending on the measurement location is the difference between the maximum strength and the minimum strength at 30 locations, and the average conductivity is the average value of these 30 locations.

(5)応力緩特性
応力緩和特性は、図1の様に幅10mm×長さ100mmに加工した厚みt=0.08mmの各試験片に標点距離lは25mmで高さy0は負荷応力が0.2%耐力の80%になるように高さを決定、曲げ応力を負荷し、150℃にて1000時間加熱後の図2に示す永久変形量(高さ)yを測定し応力緩和率{[1−(y−y1)(mm)/(y0−y1)(mm)]×100(%)}を算出した。なお、y1は応力を負荷する前の初期のソリの高さである。測定箇所による応力緩和率のばらつきは30箇所の最大強度―最小強度の差とし、平均応力緩和率はこの30箇所の平均値である。
(5) Stress relaxation characteristics As shown in FIG. 1, the stress relaxation characteristics are as follows. Each test piece with a thickness t = 0.08 mm processed to a width of 10 mm and a length of 100 mm is 25 mm in length and y 0 is the load stress. The height is determined to be 80% of 0.2% proof stress, bending stress is applied, and the amount of permanent deformation (height) y shown in FIG. The rate {[1- (y-y 1 ) (mm) / (y 0 -y 1 ) (mm)] × 100 (%)} was calculated. Y 1 is the initial warp height before stress is applied. The variation in the stress relaxation rate depending on the measurement location is the difference between the maximum strength and the minimum strength at 30 locations, and the average stress relaxation rate is the average value of these 30 locations.

(6)曲げ加工性
曲げ加工性は、曲げ部の肌荒れにより評価した。JIS H 3130に従って、Badway(曲げ軸が圧延方向と同一方向)のW曲げ試験を行い、曲げ部の表面を共焦点レーザー顕微鏡で解析し、JIS B 0601規定のRa(μm)を求めた。測定箇所による曲げ粗さのばらつきは30箇所の最大Ra−最小Raの差とし、平均曲げ粗さはこの30箇所のRaの平均値である。
(6) Bending workability Bending workability was evaluated by rough skin of the bent part. In accordance with JIS H 3130, a Badway (bending axis is the same direction as the rolling direction) W-bending test was performed, and the surface of the bending portion was analyzed with a confocal laser microscope to obtain Ra (μm) defined in JIS B 0601. The variation in the bending roughness depending on the measurement location is the difference between the maximum Ra and the minimum Ra at 30 locations, and the average bending roughness is the average value of Ra at 30 locations.

No.2〜10、12〜34の合金は、本発明の実施例(No.1及び11は参考例)であり、電子材料用に適した強度及び導電率を有し、特性のばらつきも少ない。
No.35〜37、46〜48の合金は、第一時効処理を行っておらず、溶体化処理時に結晶粒径が粗大化して強度及び曲げ加工性が劣化した。
No.38、39、42、44、49、50の合金は、第一時効処理の時効温度が低すぎ、第二相粒子が少なかったため、溶体化処理時に結晶粒径が粗大化して強度及び曲げ加工性が劣化した。また、結晶粒径のばらつきが多くなった。その結果、特性のばらつきが大きくなった。
No.40、41、43、45、51〜54の合金は、第一時効処理の時効温度が高すぎ、第二相粒子が不均一に成長したため、結晶粒径がばらついた。その結果、特性のばらつきが大きくなった。
No.55及び56はCoの添加量が多すぎたため、強度及び導電率が劣化した。
No.57〜60は第一時効処理を行っておらず、溶体化温度が低い。第二相粒子が十分に固溶せず、また、結晶粒が小さすぎたので、強度及び応力緩和特性が劣化した。
No. The alloys of 2 to 10 and 12 to 34 are examples of the present invention (Nos. 1 and 11 are reference examples) , have strength and conductivity suitable for electronic materials, and have little variation in characteristics.
No. In the alloys of 35 to 37 and 46 to 48, the first temporary effect treatment was not performed, and the crystal grain size was coarsened during the solution treatment to deteriorate the strength and the bending workability.
No. The alloys of 38, 39, 42, 44, 49, and 50 have an aging temperature of the first temporary effect treatment that is too low and there are few second-phase particles, so that the crystal grain size becomes coarse during the solution treatment and the strength and bending workability are increased. Deteriorated. In addition, the variation in crystal grain size increased. As a result, the variation in characteristics became large.
No. In the alloys of 40, 41, 43, 45, and 51 to 54, the aging temperature of the first temporary effect treatment was too high, and the second phase particles grew non-uniformly. As a result, the variation in characteristics became large.
No. In 55 and 56, since the amount of Co added was too large, the strength and conductivity deteriorated.
No. Nos. 57 to 60 are not subjected to the first temporary treatment and have a low solution temperature. Since the second phase particles were not sufficiently dissolved and the crystal grains were too small, the strength and stress relaxation characteristics were deteriorated.

Claims (9)

Ni:1.0〜2.5質量%、Co:0.5〜2.5質量%、Si:0.3〜1.2質量%を含有し、残部がCu及び不可避不純物からなる電子材料用銅合金であって、平均結晶粒径が15〜30μmであり、観察視野0.5mm2毎の最大結晶粒径と最小結晶粒径の差の平均がμm以下である電子材料用銅合金。 For electronic materials containing Ni: 1.0 to 2.5 mass%, Co: 0.5 to 2.5 mass%, Si: 0.3 to 1.2 mass%, the balance being Cu and inevitable impurities A copper alloy for electronic materials having an average crystal grain size of 15 to 30 μm and an average difference between the maximum crystal grain size and the minimum crystal grain size for each observation visual field of 0.5 mm 2 being 7 μm or less. 平均結晶粒径が15〜30μm(但し、20μm以下を除く)である請求項1に記載の電子材料用銅合金。2. The copper alloy for electronic materials according to claim 1, wherein the average crystal grain size is 15 to 30 [mu] m (excluding 20 [mu] m or less). 更にCrを最大0.5質量%含有する請求項1又は2に記載の電子材料用銅合金。 Furthermore, the copper alloy for electronic materials of Claim 1 or 2 containing 0.5 mass% of Cr at the maximum. 更にMg、Mn、Ag、及びPから選択される1種又は2種以上を総計で最大0.5質量%含有する請求項1〜3の何れか一項に記載の電子材料用銅合金。 Furthermore, the copper alloy for electronic materials as described in any one of Claims 1-3 which contains a maximum of 0.5 mass% of the 1 type (s) or 2 or more types selected from Mg, Mn, Ag, and P in total. 更にSn及びZnから選択される1種又は2種を総計で最大2.0質量%含有する請求項1〜何れか一項に記載の電子材料用銅合金。 Furthermore, the copper alloy for electronic materials as described in any one of Claims 1-4 which contains a maximum of 2.0 mass% of 1 type or 2 types selected from Sn and Zn in total. 更にAs、Sb、Be、B、Ti、Zr、Al及びFeから選択される1種又は2種以上を総計で最大2.0質量%含有する請求項1〜何れか一項に記載の電子材料用銅合金。 Furthermore, the electron as described in any one of Claims 1-5 which contains a maximum of 2.0 mass% of the 1 type (s) or 2 or more types selected from As, Sb, Be, B, Ti, Zr, Al, and Fe in total. Copper alloy for materials. −所望の組成をもつインゴットを溶解鋳造する工程1と、
−950℃〜1050℃で1時間以上加熱後に熱間圧延を行い、熱間圧延終了時の温度を850℃以上とし、850℃〜400℃までの平均冷却速度を15℃/s以上として冷却する工程2と、
−加工度85%以上の冷間圧延工程3と、
−350〜500℃で1〜24時間加熱する時効処理工程4と、
−950℃〜1050℃で溶体化処理を行い、材料温度が850℃〜400℃まで低下するときの平均冷却速度を15℃/s以上として冷却する工程5と、
−随意的な冷間圧延工程6と、
−時効処理工程7と、
−随意的な冷間圧延工程8と、
−歪取焼鈍工程9と
を順に行なうことを含む請求項1〜何れか一項に記載の銅合金の製造方法。
-Step 1 of melt casting an ingot having a desired composition;
Hot rolling is performed after heating at −950 ° C. to 1050 ° C. for 1 hour or longer, the temperature at the end of hot rolling is 850 ° C. or higher, and the average cooling rate from 850 ° C. to 400 ° C. is 15 ° C./s or higher. Step 2 and
-Cold rolling step 3 with a working degree of 85% or more;
An aging treatment step 4 of heating at -350 to 500 ° C for 1 to 24 hours;
Step 5 of performing solution treatment at −950 ° C. to 1050 ° C., and cooling the material at a cooling rate of 15 ° C./s or more when the material temperature is reduced to 850 ° C. to 400 ° C .;
-Optional cold rolling step 6;
An aging treatment step 7;
-Optional cold rolling process 8;
-The manufacturing method of the copper alloy as described in any one of Claims 1-6 including performing the strain relief annealing process 9 in order.
請求項1〜の何れか一項に記載の銅合金を備えた伸銅品。 The copper-stretched article provided with the copper alloy as described in any one of Claims 1-6 . 請求項1〜の何れか一項に記載の銅合金を備えた電子機器部品。 The electronic device component provided with the copper alloy as described in any one of Claims 1-6 .
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8784337B2 (en) 2010-03-31 2014-07-22 Boston Scientific Scimed, Inc. Catheter with an improved flexural rigidity profile
US8795254B2 (en) 2008-12-10 2014-08-05 Boston Scientific Scimed, Inc. Medical devices with a slotted tubular member having improved stress distribution
US8821477B2 (en) 2007-08-06 2014-09-02 Boston Scientific Scimed, Inc. Alternative micromachined structures
US9901706B2 (en) 2014-04-11 2018-02-27 Boston Scientific Scimed, Inc. Catheters and catheter shafts

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6246454B2 (en) * 2011-11-02 2017-12-13 Jx金属株式会社 Cu-Ni-Si alloy and method for producing the same
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JP6310004B2 (en) * 2016-05-27 2018-04-11 Jx金属株式会社 Cu-Co-Ni-Si alloy for electronic parts
CN106244849A (en) * 2016-10-13 2016-12-21 龙岩学院 A kind of preparation method of intensified by ultrasonic wave high property copper alloy
CN108642419A (en) * 2018-05-31 2018-10-12 太原晋西春雷铜业有限公司 A kind of corson alloy band and preparation method thereof that bending is excellent
CN110195166A (en) * 2019-04-17 2019-09-03 宁波兴业盛泰集团有限公司 A kind of warping resistance CuNiCoSi used for lead frame system's alloy and its manufacturing method
CN112410646A (en) * 2020-10-16 2021-02-26 扬州千裕电气有限公司 Electronic composite material
CN113234958A (en) * 2021-04-25 2021-08-10 江苏青益金属科技股份有限公司 Alloy wire suitable for constant-temperature sheath of petroleum delivery pipeline and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008266783A (en) * 2007-03-26 2008-11-06 Furukawa Electric Co Ltd:The Copper alloy for electrical/electronic device and method for manufacturing the same
JP2009007666A (en) * 2007-05-31 2009-01-15 Furukawa Electric Co Ltd:The Copper alloy for electrical and electronic equipment
WO2009122869A1 (en) * 2008-03-31 2009-10-08 日鉱金属株式会社 Cu-Ni-Si-Co COPPER ALLOY FOR ELECTRONIC MATERIAL AND PROCESS FOR PRODUCING THE SAME

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01122264A (en) 1987-11-05 1989-05-15 Nec Corp Image output device
JP3408021B2 (en) 1995-06-30 2003-05-19 古河電気工業株式会社 Copper alloy for electronic and electric parts and method for producing the same
US7182823B2 (en) 2002-07-05 2007-02-27 Olin Corporation Copper alloy containing cobalt, nickel and silicon
EP1873267B1 (en) 2005-03-24 2014-07-02 JX Nippon Mining & Metals Corporation Copper alloy for electronic material
JP4068626B2 (en) * 2005-03-31 2008-03-26 日鉱金属株式会社 Cu-Ni-Si-Co-Cr-based copper alloy for electronic materials and method for producing the same
JP5156317B2 (en) * 2006-09-27 2013-03-06 Dowaメタルテック株式会社 Copper alloy sheet and manufacturing method thereof
US9034123B2 (en) * 2007-02-13 2015-05-19 Dowa Metaltech Co., Ltd. Cu—Ni—Si-based copper alloy sheet material and method of manufacturing same
US20090183803A1 (en) * 2007-12-21 2009-07-23 Mutschler Ralph A Copper-nickel-silicon alloys

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008266783A (en) * 2007-03-26 2008-11-06 Furukawa Electric Co Ltd:The Copper alloy for electrical/electronic device and method for manufacturing the same
JP2009007666A (en) * 2007-05-31 2009-01-15 Furukawa Electric Co Ltd:The Copper alloy for electrical and electronic equipment
WO2009122869A1 (en) * 2008-03-31 2009-10-08 日鉱金属株式会社 Cu-Ni-Si-Co COPPER ALLOY FOR ELECTRONIC MATERIAL AND PROCESS FOR PRODUCING THE SAME

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8821477B2 (en) 2007-08-06 2014-09-02 Boston Scientific Scimed, Inc. Alternative micromachined structures
US8795254B2 (en) 2008-12-10 2014-08-05 Boston Scientific Scimed, Inc. Medical devices with a slotted tubular member having improved stress distribution
US8784337B2 (en) 2010-03-31 2014-07-22 Boston Scientific Scimed, Inc. Catheter with an improved flexural rigidity profile
US9901706B2 (en) 2014-04-11 2018-02-27 Boston Scientific Scimed, Inc. Catheters and catheter shafts

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