TW201035338A - Cu-co-si copper alloy for use in electronics, and manufacturing method therefor - Google Patents

Abstract

Provided is a Cu-Co-Si alloy that has mechanical and electrical properties suitable for a copper alloy for use in electronics, and has uniform mechanical properties. Said copper alloy contains 0.5-4.0% cobalt and 0.1-1.2% silicon by mass, with the remainder comprising copper and unavoidable impurities. The mean grain size is 15-30 [μ]m, and the difference in diameter between the smallest and largest grains in each 0.5 mm2 area is, on average, no more than 10 [μ]m.

Description

201035338 VI. Description of the Invention: [Technical Field] The present invention relates to a precipitation hardening type copper alloy, particularly a Cu-c suitable for use in various electronic machine parts. —si is a copper alloy. [Prior Art] Copper alloys for electronic materials used in various electronic equipment parts such as connectors, switches, relays, pins, terminals, and guides are required to have high strength and high electrical conductivity. (or thermal conductivity) as a base: In recent years, the electronic components have been highly integrated and miniaturized, and the thin-walled fish has developed rapidly. Correspondingly, the requirements for alloys used in electronic machine parts are: The level has gradually increased. From the viewpoint of high strength and high electrical conductivity, 'the use of copper human gold as an electronic material: the use amount of precipitation hardening type copper alloy is gradually increased, instead of: solid solution strengthening copper alloy represented by phosphorus: copper 'brass or the like . The hardening type is based on the aging treatment of the solution-treated supersaturated solid solution, so that the fine precipitates are dispersed and the alloy strength is increased, and the amount of solid solution element is increased. Therefore, the strength can be obtained: the material month "the mechanical f is excellent 'and the conductivity' thermal conductivity is also good.: In the hardened steel alloy, 'generally known as the Cassson alloy' (4) (10) and the t CU~ Nl—^ is a copper alloy that combines high electrical conductivity and strength.

The representative copper alloy for processing is the 'A mouth gold of the industry that is currently in full swing.' This copper alloy achieves an increase in strength and electrical conductivity by depositing micro 3 201035338 = Nl-Sl intermetallic compound particles in a copper matrix. In addition, in Patent Document 1, it is described in the patent document 1 that it is added to the Carson alloy, and it is described that co will be the same as the compound of 81, and the mechanical strength is increased, and when Cu~c〇 is used, the effect is treated. In the case of Cu-Ni-Si, the electrical properties of the alloy are higher than the L-degree of the material, and the yield is better. If it is allowed in cost, prepare for Cu-Co-Si. In the case of adding Co, the optimum addition amount is 〇〇5 to 2, and it is described in Patent Document 2, and it is described that cobalt is contained in the case where the content of the drill is less than the content of the diamond. If the precipitation of the second phase of the Jianghe τ\ a substance exceeds 2.5%, an excessive amount of the second phase particles will be precipitated, = work = lower two and the copper alloy will have an undesired strong magnetic force. "The amount is about 5%5% to about 1.5%. In the optimum form, the cobalt content is about 〇·7% to about 12%. 1 The copper alloy described in the main patent document 3, In order to use the terminal for the vehicle plant and the communication machine, it is developed by connecting the product A n and the material of the product, so that the concentration of Co is 0.5 to 2.5 Wt%, and the conductivity is high. Cu - Co ~ Si 糸3 gold. According to Patent Document 3, because the m / morning metric is in the above range, if the amount added is less than 0.5% by mass, _ 里 / 0 is not obtained. If the strength of the right Co exceeds 2.5% by mass, the thickness of the Co$g ', ', and the strength may be reduced, but the conductivity is remarkably lowered, and the hot workability is also ~2, 〇f4%. Preferably, the copper alloy described in Patent Document 4 is high in strength, and has high electrical conductivity of 201035338 and high bending workability of ~3.〇Wt%. (4) It is a C〇 concentration gauge. If it is 0.1, if the agricultural degree is limited to this range, because the right does not reach this composition range, then ^ ^ ^ ^ r ® Bi f does not have the above effect, and if the super-illusion is added, However, it is not good because of cracking, and m is a crystalline phase, which becomes a binding. [Patent Document 1] Japanese Patent Laid-Open No. 1 2 No. 2 Publication No. 2] Japanese Special Table Purchase No. 7 Bulletin [Patent Document 3] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In the case of the bad II 1 series alloy, the characteristics of the high concentration of Co are added. However, the system believes that: (0 is more powerful than the state can not be fully researched ^ n can improve the mechanical strength and guide the second secret " In the alloy, by increasing the C., Nonglu!' can get the improvement of the characteristics. The door Lo agricultural degree, on the other hand, if the c〇 thicker is further improved, this situation is Then 纴 '4 must be higher temperature to be a good V V V V V V V V V V V V V V V Precipitated crystals and precipitation: 'Solution becomes an obstacle and hinders the growth of crystal grains. Therefore, the human first-phase particles will become uneven in particle size, and the recrystallization in the α-gold will occur. The problem of the mechanical properties is changed. 5 201035338 μ 'This Mum' provides Cu-C〇 with high conductivity, high strength, high strength and high-curvature workability, and mechanical properties. -Si-based alloy. Further, another object of the present invention is to provide a method for producing such a Cu-Co-Si alloy. The inventors of the present invention conducted intensive studies on a method for reducing the deviation of the recrystallization pole, and obtained the following findings: in the production of a high-intensity CqCu-c〇-based alloy, in advance of the solution treatment step, The fine second phase particles are precipitated in the copper matrix phase at equal intervals as much as possible, whereby even if the solution treatment is performed at a relatively high temperature, the crystal grains are pinned by the second phase particles. It doesn't matter if it is +), it will only be too big, and the pinning effect will act on the entire copper matrix, so that the size of the growing recrystallized plate can be equalized. Further, as a result, it is known that a Cu-Co-Si alloy having a small difference in mechanical properties can be obtained. The present invention, which is based on the above-mentioned findings, is a copper alloy for electronic materials, which contains c〇: 〇5 to 4 〇% by mass, and the following part: "% by mass" is made of Cu and is inevitable The composition of the impurities, U mouth daily grain fe is 15~30" m, the average of the difference between the crystal grain size and the minimum crystal grain size per observation field 在5 bribe 2 is large, and. The copper alloy is in the embodiment, the copper is the same, and the entry is made into the door! The electric 卞 枓 ' ' 3 has C〇. 〇.5 ～4·0 mass%, Si: 〇.1~U θ and satisfies The following (1) to (4) _ or more of the composition conditions: ® 0 ' (1) step-by-step contains a maximum of 0.5% by mass of Cr; (7) further contains a total of up to G.5f4% selected from Ag and P One or two or more elements; Mn 201035338 (3) further containing one or two elements in a total amount of up to 2% by mass; domain from Sq

(4) The step-by-step contains a total of 2.0% by mass maximum selected from I

Be B, ΊΊ, Zr, AI and Fe! Species or more than two elements; Sb, and the remainder consisting of Cu and the unavoidable particle size W, per field of view. , 5_2 of the most: knot = crystal The difference between the minimum crystal grain size is below 10 # m. , 铋 and x 'The invention is in another form - the manufacture of a series of copper alloys comprising the following steps: 'Step 1, melt casting of an ingot having a desired composition; Step 2, to 95 CTC~ L〇5 (When TC is heated for more than 1 hour, it is calendered, and the temperature at the end of hot rolling is set at 85 (rc or more, it will be self-cooked)

The average cooling rate to 4 °C is set at 15 °c / S or more for cooling; C Step 3 'Processing is more than 85% cold rolling; Step 4' is performed at 350~500 °C 1 ~24 hours aging treatment; ◎ Step 5, with 950~1〇5 (rc solution treatment, the average cooling rate when the material temperature is lowered from 85 °C to 400 °C is set at 15 5: / s or more The cooling is carried out; the step 6 is carried out by random cold rolling; the step 7 is subjected to aging treatment; and the step 8 is carried out by random cold rolling. In another aspect, the present invention is a steel-stretched product comprising the above copper alloy. According to still another aspect of the invention, there is provided an electronic machine component comprising the copper alloy 201035338. The preferred mechanical niobium alloy according to the invention is characterized in that it has an electrical property and a copper alloy for use as an electronic material. Cu_Co-Si L method with uniform mechanical properties] (addition of Co and Si)

Co and Si can be formed into a high-strength by forming an intermetallic compound by the treatment of the material without causing the conductivity to be inferior. The right Co and Si add 'Dan, not up to 0 1 quality denier 9 / Li y knife is Co: less than 0.5% by mass, Si: °1·1 Berry%, can not get more than 4. Tannin (four), Sl: Exceeding "Quality 4 and the opposite, if c°:, but the conductivity is remarkably lowered, the addition of high-strength Co and Si can be achieved, and the hot workability is deteriorated. Therefore, the quality is %. In Cu- 〇广5~4·0 mass mo.Nu h-c. It is more desirable: two 'because... 2, above, better on top': better C. For high concentration, the amount of Cg: 2.5~4 g ° is better than C〇: 3.2~(Ο质量% s. 5~丨.0 is better quality ^ Becha Z, Sl: 0.65~1.0 quality %. (Cr addition amount)

Cr dissolves in the casting and pulls + people, and the boundary, so the grain boundary force can be divided into two parts: the crystal particles will be preferentially precipitated, so that the cracks are not easily generated during the processing, and the Cr precipitates at the grain boundary are formed. : 'Using solution treatment or the like to re-solidify the molten cast iron, and in the subsequent aging precipitation, 201035338 produces precipitated particles of the (6) structure with Cr as a main component or an object for the usual Cu-Ni-Si alloy. In other words, the addition of ^ > does not contribute to the precipitation of Si, which inhibits the increase in conductivity in the state of being dissolved in the matrix phase, but by adding as an element of the formation of the lithium compound - The precipitation of 'reducing the amount of solid solution Si' can increase the conductivity without damaging the strength. However, if the concentration exceeds 5% by mass, the coarse second phase particles are easily formed, which may impair the product characteristics. Therefore, in the CU-Co-Si alloy of Sakamoto, the maximum amount can be added. % by mass

However, if the amount of QG3f is less than %, the effect is small, so it is preferable to add 〇.03 to 〇.5 mass%, more preferably 0.09 to 〇.3 mass%. (Mg, Mn, Ag, and p addition amount) When a small amount of Mg, Mn, Ag, and p is added, the product characteristics such as strength and stress relaxation characteristics are improved without impairing the electrical conductivity. The effect of addition is mainly achieved by dissolving the above Mg, Μη, Ag, and p in the matrix phase, but it is also possible to further advance by including the Mg, Mn, and A^p in the second phase particles. The effect. However, if the total concentration of Mg, Mn, VIII is more than 0.5%, the characteristic improvement effect will be saturated, and the room manufacturability will be impaired. Therefore, it is the largest in the Cu~c〇-81 alloy of the present invention. The total amount of addition of 0.5% by mass is selected from ^, 隐^ and ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ However, if it is less than 〇, 〇1 mass% ’ is less effective, so it is preferable to add 〇.01 to 〇.5 mass% in total ‘more preferably 〇〇4 to 〇·2 mass%. (addition of Sn and Ζη) 201035338

When Sn and Zn are added in a small amount, product characteristics such as strength, stress relaxation property, and plating property can be improved without impairing electrical conductivity. The effect of addition is mainly exerted by solidifying the above-mentioned Zn and Zn in the mother phase. However, if the sum of Sn and the total amount exceeds 2.0% by mass, the characteristic improvement effect will be saturated and the manufacturability will be impaired. Therefore, in the Cu-c〇-Si-based alloy of the present invention, a total of 2.0% by mass of one or two selected from the group consisting of Sn&Zn can be added. On the other hand, if it is less than 0.05% by mass, since the effect is small, it is preferable to add 〇. 5~2. 〇 mass% in total, and more preferably 0.5 H.0 mass% in total. (As, Sb, Be, B, Ti, Zr, Magic and Call for As, Sb, Be, B, Ti, .. .. Zr, A1 and Fe, adjust the amount of addition according to the "characteristics" In order to improve the conductivity characteristics such as stress relaxation characteristics and mineralization properties, the above-mentioned As, Sb, Be ' b, Ti, Zr, -D, 1 and F e are solid-solubilized in the parent phase. Add the effect, but also by making the second phase:

Be, B'Ti, Zr, A1 and Fe, or 3 have the effect of As, Sb' and exert a further effect of less than ^, the second phase particle composed of jin. However, if the _ _ _ mass % ', the characteristic improvement effect will be the same as: "The prime" exceeds 2.0, which is in the Cu-C of the present invention. -Si-based alloy: phase-cutting manufacturability. 〇% by mass is selected from..., and the two's maximum addable amount is 吱2 recorded ο I·1, Zr, A1, and Fe of more than one type. However, if it is less than 〇•(10), it is smaller. Good AΆ 'Liu, because of its effect, the total is added 〇.00 1~2 n and 曰n/ is added 0. 〇5~!.〇f quantity%.. Bellow%, better for total When the total amount of Mg' Μη, Α ρ, g Sn Zn, As, Sb, Be, B, and 10 201035338 Ή, Zr, Α1, and Fe is more than 3% by weight, the manufacturing property is easily impaired. The total amount is equal to or less than 1.5% by mass. The best crystal size is Ο Ο The crystal grains have an effect on the strength, and the strength is proportional to the crystal grain size - 1/2 power. The HaU_Petch equation is generally true. In addition, coarse crystal grains deteriorate the bending workability and become the main cause of surface roughness during bending. The alloy, in general, the refinement of crystal grains can improve the strength, and is therefore preferable. Specifically, it is preferably 30#m or less, more preferably 23#m or less. The Cu-c〇-Si alloy is a precipitation-strengthened alloy. Therefore, it is necessary to pay attention to the precipitation of the second phase particles. The second phase particles in W have (4) Tilu, ·:::Γ: The second phase particles hardly improve the strength of the strong production. The second phase particles are better precipitated in the crystal grains. The right, and σ daily particle size becomes smaller, then the grain boundary day In the meantime, the m boundary area will become larger. Therefore, in the aging treatment, the first phase particles are preferentially precipitated out of the crystal grains, and the crystal grain first phase particles are ordered, which is more than #太μ,八韦系耘Specifically, it is preferably 15_ or more, more preferably (4). In the present invention, the average crystal grain size is average. The average crystal grain size is preferably 18 to 2λ (4) 15 to 30 (4). , can be two: by the effect of increasing the average crystal grain size, and by the precipitation = the strong fruit produced by the grain. The crystal grain size of the range: the effect of the fruit is 6 HM, and the bending is excellent. 11 201035338 The workability and the stress relaxation property. In the present invention, the crystal grain size, the thickness direction of the rolling direction is -糸' using a microscope pair Parallel to the minimum circle of the smallest circle * 仃 observation, surrounded by the respective crystal grains, the so-called average crystal diameter of the towel 1 refers to the average value thereof. In the present invention, the average observation difference of the mother observation field 〇 5 mm 2 crystal grain size The average particle size and the minimum average are preferably ^, / 2, preferably 7... The actual lowest value of the difference: 2: It is difficult to achieve on the occasion, so it will be Here, the so-called maximum, 'type is best 3 to 7,. The largest social day observed in the ^ 〇 5 5 面 观察 观察 观察 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = In the present invention, the difference in particle diameter, after iron, is the average of the difference between the large crystal grain size and the minimum crystal grain size.乍 is to take the large crystal grain size and the minimum crystal maximum crystal grain size and the minimum 纴 θ particle size are both 曰 “the difference between the vertical diameter is small, this refers to the crystal heart and mind, which can reduce the deviation of the same - characteristic As a result, the mechanical copper product or the electronic machine zero of the mother's measurement site will be qualitatively improved: the extension (manufacturing method) obtained by the invention of the copper alloy is qualitatively improved. The Carson-based copper alloy is also in the furnace and will be electrolyzed. Among copper, s/, ^, Baixian uses the melt melted by the atmosphere. Then: the raw material is melted to obtain the desired composition heart, and "^ 彳 ^ 融 (4) causes the ingot. Then, a strip or crucible of thickness and characteristics is subjected to hot rolling, cold rolling and heat treatment. :, with the 肀〃 有 有 〉 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷In the solution treatment, it is heated at a high temperature of about 700 to about 1 Torr (the temperature of the rc is such that the second phase particles are solid-solubilized in the Cu matrix and the Cu matrix is recrystallized. Sometimes the hot rolling is also used. For solution treatment, in the aging treatment, it is heated in a temperature range of about 35 〇 to about 55 ° C for more than 1 hour, so that the second phase particles which have been solid-solved in the solution treatment are in the form of nanometer-sized fine particles. Precipitation. In this aging treatment, 'strength and conductivity will increase. In order to obtain higher strength, cold rolling may be performed before and/or after aging treatment. Further, cold rolling is performed after aging treatment. In the case of cold rolling, strain relief annealing (low temperature annealing) may be performed. Between the above steps, grinding, grinding, shot blasting, etc., for removing rust scale on the surface are appropriately performed. The copper alloy of the present invention is basically also subjected to the above-described process, but in order to control the deviation of the average crystal grain size and the crystal grain size within the range specified by the present invention, as described above, it is important that the solution treatment step is before the step of solution treatment. Pre-made fine The second phase particles are precipitated in the copper matrix phase at equal intervals and in the same manner as possible. In order to obtain the copper alloy of the present invention, it is particularly necessary to carry out the production while paying attention to the following points. First, during solidification during casting It will inevitably produce coarse crystals, which will inevitably produce coarse precipitates during the cooling process during casting. Therefore, in the subsequent steps, the crystals must be dissolved in the matrix phase. 950. (:~1〇50. (: After hot rolling for 1 hour or more, and the temperature at the end of hot rolling is set to 85〇〇c or more, even if c〇 has been added, it has been added. In the case of Cr, the above crystals may be solid-cooled in the parent phase. The temperature conditions above 9501 are higher than those of other Carson-based alloys 13 201035338. If the temperature is set, if it is ^ ^^ ^ 〇 C0〇r Right heat rolling 刖 保持 保持 保持 保持 保持 保持 保持 保持 保持 保持 保持 保持 保持 保持 保持 保持 保持 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固懕...B, the temperature at the end of the bundle is less than 850 °c J, because the solid solution of the element is re- owing m 兀 曰冉 曰冉 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人At this time, if the cooling rate is slow, the compound containing C 〇 or Cr will be precipitated again. When this composition is used to increase the strength: When processing (aging treatment), it is precipitated due to cooling. The precipitate is the core: it is a large precipitate 16 that does not contribute to the improvement of strength, so high strength cannot be obtained. Therefore, it is necessary to increase the cooling rate as much as possible, specifically, 15 c/s or more. At a temperature of about 40 rc, the precipitation of the second phase granule is significant, so it does not reach 400. The cooling rate of 〇 is not a problem. Therefore, in the present invention, the material temperature is from 85 (rc to 4 〇 (the average cooling rate of rc is set to 15 ° C / s or more), preferably 2 (TC / s or more for the cold part. The so-called '' The average cooling rate from 850 ° C to 400 ° C", the core temperature of the material temperature from 85 ° C to 65 ° C cooling time I' and by "(850 - 4 〇 〇) (t:) / cooling time (4)" and the calculated value (C / s). As a method of speeding up the cooling, water cooling is most effective. However, since the coldness is changed by the temperature of the water used for water cooling' Therefore, it is possible to further accelerate the cooling by ordering the water temperature management. If the water temperature is 25 ((: above), the daily cooling will not be able to obtain the required cooling rate, so it is better to keep it below 2 5 C. When the material is placed in a tank containing water for water cooling, the temperature of the water 14 201035338 will rise and it will easily become at 25 < t ί · Μ ^ ^ ^ four, which is preferably in the form of a mist (cold or phase) Spraying to cool the material by fixing it, or to raise the constant low temperature: below yc. Also, add a water-cooled nozzle or increase The cooling rate can be increased by the addition of 1%. The water of 4 is subjected to cold rolling after hot rolling. Out, the beginning of 4 XP, in order to uniformly precipitate the precipitate, the cold rolling is performed to increase to 70% Vi I - ^ ^ ^ + 1 set strain, preferably cold rolling is performed at a rate of 〇%, and it is better to carry out cold rolling at a rate of 85/ 卜 刮. If not, the rolling on the good... : Calendering, and after the heat treatment is not treated, the precipitate will not repeat the hot rolling and the subsequent cold rolling combination. The first aging is performed after the cold rolling. n&amp;yt ^ . Right before the implementation of this step, there are ^ phase particles, then in the implementation of this step, the second phase particles will grow in step, and thus there will be a difference in the initial grain in this step, but This private ❹ * first phase pull in the middle (four) 士 ^ ^ in this t Ming, because in the previous step U is uniformly precipitated in a uniform size. Η "The second phase particle effect aging treatment timeliness If the temperature is too low, the amount of precipitation of the second phase particles that are pinned will be reduced, and the solution will be produced by solution treatment. On the other hand, if the age of the grain = the size of the grain becomes inconsistent, the second phase particles will become the second largest, and the second phase particles will not Even if the aging time is longer, the second phase is longer and must be set to an appropriate aging time. 15 201035338 1 to 24 at 350~500 °C The flute of the hour - aging treatment, compared with #350 °C and less than 400 °C 1), D2~24 hours of the first - treatment '400 ° C and above and less than 450t into a 4 Ding 6 ~ 1 2 hours of the first effect treatment, to 45 (TC or more and less than 500. (: Perform 3 aging treatment, which can be used to make the second phase of the fine second uniform 6::=: phase. If it is such a structure, it can be similarly produced in the solution treatment of the mother r step. The growth of the recrystallized grains is pinned to obtain a uniform composition having a small variation in crystal grain size. μ is subjected to a solution treatment after the first aging treatment. Here, the second phase particles (four) are The fine and uniform recrystallized grains are grown. Therefore, the solid solution temperature must be 95 (rc~1〇5 (rc. Here, the recrystallized grains grow first), and then the first precipitation is precipitated. The two-phase particles are solid-solved, so the growth of recrystallized grains can be controlled by the effect of nailing. However, because the first phase of the particles is solid solution, the nailing effect will disappear, so if it continues for a long time, it will be cold. The % recrystallized grain will become larger. For the time of proper solution treatment, it is 6 〇 seconds when it is 95 generations or more and does not leak t. 3 〇〇 seconds, preferably 12 〇 18 Leap seconds; 30 seconds to 18 seconds, preferably 6 seconds to 12 seconds, less than 1 〇 (8). c and less than 1 〇 5 〇 ° C. Even if it is solid In the cooling process after the treatment, in order to avoid precipitation of the second phase particles, the material temperature is lowered from 85 (rc to 4 〇〇 (&gt;c, the average cooling rate should be 15 t/s or more, preferably 赃/s or more). ^ After the solution treatment, the second aging treatment is carried out. The second aging treatment may be a condition that is useful for the miniaturization of the precipitate, but the setting and the time are set so that the precipitate does not Example 16 201035338 时 处理 之 々 々 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 The size of the effect of the effect of the treatment of the situation is increasing the position of the precipitation, using the position to promote age hardening, thereby achieving strength improvement. In the case of the second aging treatment, 'use the precipitate to promote work hardening, from: The strength is increased. Cold rolling can also be performed before and/or after the second aging treatment.

The L si alloy of the present invention can be cured into various copper products, for example, can be processed into sheets, strips, tubes, rods and wires, and the Cu-c〇:Sl-based copper alloy of the present invention can be used for a lead frame, Electronic components such as connectors, pins, terminals, relays, switches, and foils for secondary batteries. [Examples] The present invention and comparative examples are shown and described, but the present invention is not intended to limit the present invention in order to provide a further understanding of the present invention and its advantages. In the high frequency melting furnace, 13 〇〇. (: A copper alloy having the composition of the components contained in Table 1 (Example) and Table 2 (Comparative Example) was melted and cast into an ingot having a thickness of 30 mm. Then, the ingot was heated to 1 Torr ( After rc, hot rolling is carried out until the plate thickness is l〇mm, and the rising temperature (temperature at the end of hot rolling) is set to 900 ° C. After the end of hot rolling, the material temperature is lowered from 85 ° C to 400 ° The average cooling rate at C is set to 丨8°c / s and is water-cooled, and then placed in the air for cooling. Then, in order to remove the scale of the surface, the surface is cut until the thickness is 9 mm, and then formed by cold rolling. The thickness is 17 201035338 0.15 mm. Then, the aging treatment is carried out for 3 to 12 hours at various aging temperatures (several comparative examples are not subjected to the effect treatment), and then solid solution is performed at various solid solution temperatures for 120 seconds. After treatment, the average cooling rate of the material temperature from 85 ° C to 400 ° C is immediately set to 18. 8 / 8 and water cooling, and then placed in the air for cooling. Then, cold rolling to 0.10 mm, Then implement 45 small in an inert atmosphere at 45 (rc) The second aging treatment was carried out, and cold waste was extended to 〇.〇8 mm to prepare test pieces. Various characteristics of each test piece obtained in the above manner were evaluated by the following method. Dry average crystal grain size Regarding crystal grain size, The sample is buried in the resin in such a manner that the observation surface is parallel to the thick direction of the rolling direction. (4) Mechanical polishing ^ After the mirror surface is polished, the volume is mixed with 10 volumes of water per 1 volume. A solution of a concentration of 36% hydrochloric acid was dissolved in 5% of the weight of the solution. The sample was immersed in the solution prepared in the above manner for 10 seconds to cause metal structure to appear. , Lee: The mirror magnifies the above metal structure by 100 times, and observes the observation of 〇w: taking a sheet, a W piece, and finding the smallest circular diameter surrounding all the crystal grains'. The average value is calculated for each observation field, and 15 points are obtained. The average value of the observed field of view is taken as the average crystal grain size. (2) The average of the difference between the maximum crystal grain size and the minimum crystal grain size is the crystal grain size measured per crystal grain size, and the average value of the needle is / Minimum value 'The value of the observation angle of 15 observation fields is taken as the average of the difference between the maximum crystal grain size and the minimum crystal grain size. 18 201035338 (3) The strength is about the strength, and the tensile test is performed in the parallel direction of rolling, and the measurement is measured. Safety limit stress (YS: MPa). The deviation of the strength of the measured part is the difference between the maximum intensity and the minimum intensity at 3 ,, and the average intensity is the average value of 30. (4) Conductivity with respect to conductivity (EC · % IACS) is determined by measuring the volume resistivity of the double bridge. The deviation of the conductivity of the measurement site is the difference between the maximum intensity and the minimum intensity at 3 ' 'the average conductivity is 30. average value. (5) Stress relaxation characteristics The stress relaxation characteristics are shown in Fig. 1. They are processed on a test piece of thickness t = 0 · 〇 8 mm of width 丨〇 mm X length and 100 mm, with punctuation distance! The height is determined by the load stress of 25 mm' and the height y 〇 is 〇 2% of the safety limit stress, and the bending stress is applied, and the heating is performed at 15 〇t.

The amount of permanent deformation (height) y shown in Fig. 2 after 1 hour is measured, and the stress relaxation rate U1 - (y - / (y〇 - y1) (mm)) x 100 (%)} is calculated. The yi is the initial curvature height before the load stress. The deviation of the stress relaxation rate at the measurement site is the difference between the maximum strength and the minimum intensity at 30 points. The average stress relaxation rate is the average value of the 30 points. (6) The bending workability and the bending workability are performed by the surface roughness of the curved portion, and the Bad Wend (the bending axis and the rolling direction are the same, &quot;) according to JIS H 3130. The surface of the curved portion is analyzed by a microscope to obtain the standard defined by JIS B 〇6〇1 (4). The deviation of the bending roughness of the measurement portion 19 201035338 is the difference between the maximum Ra and the minimum Ra at 30, and the average bending roughness is The average of Ra at this 30.

20 201035338

Bending roughness deviation (//m) IT) 〇ο Ο 00 Ό Ο 1—^ ο ο ο ο ο ON dod (N 00 o IQ dd 〇〇〇o σ\ d 1—H 00 d stress relaxation deviation (%) &lt;N ι〇(Ν 00 寸 CN 1—^ ΓΛ ΟΟ &lt;Ν m ΓΛ Bu CO r- ΓΛ 00 fN or〇or〇(N inch o fN Ό cn 0C intensity deviation (MPa) in &lt; N 00 CN 沄ΓΛ ΟΟ CN ΓΛ ON m 'O m 00 ro o On ro 00 mo Average bending 〇m) Ο CS 00 t—Η &lt;Ν S CN m (Ν fN (Ν S &lt;Ν &gt; '( CN g (N in &lt;N 艺CN(N tN &lt;N &lt;N (N 00 (N N (N (N (N rN) (N (N (N (N r) S r〇00 00 00 (N 00 On 00 SS Ό CO O OO Average conductivity (%IACS) &lt;N m ν〇ι〇00 ^Τ) 00 m IT) (N ι /Ί 沄fN »r&gt; (N 沄l〇ίΓ赞ί艺jn ί-Η !〇卜卜00 00 (/Ί 00 卜卜00 00 v〇00 CO g Os 〇On 00 ON OO m Os GO &lt; N 00 ON 00 grade α diameter-minimum particle size (ym) 00 00 as ^Τ) 00 00 卜 OS Ό Bu Bu 〇 oo average crystal grain size (&quot;m) 卜m &lt;Ν OS ΟΝ 0\ rs Ir^ (N oo cs CN Os O S OO 5 姨 target &amp; θ ΨΑ w ο Os ο ιη Cs 1020 1020 1020 1020 1020 1020 1020 1020 1050 | 1050 1020 1020 1050 1050 1020 1020 aging temperature Ο T JTl Ο ο »Τϊ ο ι〇 inchο ΙΤ) o inch Oo IT) ooo JO ooo 1〇oo Composition (% by mass) Other Ο ο ο ο Ο oooo 〇O.lMg 0.1 Mg O.lMg O.lMg oo &lt;Ν Ο Ο ο (Ν ο (Ν Ο Ο oooo 〇oooo CN d (N d Ο Ο Ο 00 00 00 00 00 ο 吞 Ο d d d d d d d d d d d d d d d d d d d d d d — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — Γ Ο Γ 〇 〇 CJ 卜 ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο 〇\ 〇r—^ ΓΛ 2 00 00 201035338 Bending roughness deviation (em) ί-Η r- dd 〇VO Ό d Ο Ο CO οο ο ο δ 〇fN d (N d 〇 od 00 dv〇o On U -) 〇dso stress relaxation deviation (%) ό fN o cn Os (N inch CN inch ΙΛ (Ν (N &lt;N 卜r&quot;~H inch ro (N inch (N 00 ΓΛ ΓΛ ro r^&gt; (N寸 inch cn mouth strength bias Difference (MPa) ΓΛ &lt;N m ON 沄〇\ ro C\ (N Os ro r〇r^) P; 00 rN mean bending 〇m) 00 o (N 卜1—H fN \〇r—&lt;&lt;;N ri\ (N ri 〇(Ν CO ο &lt;Ν »-Η ί Η N fN CO ΓΛ iN 00 o ri 00 iH (N (N (N N(N &lt;N &lt;N g CN 艺(N &lt;N (N CN SS 00 iN 00 〇\ 00 00 00 § Os 00 s 00 Pan S ΓΊ 00 IT) 00 ro 00 (N OO (N 00 Average Conductivity (%IACS) mmmm ro 〇&gt; Swallow (N芬 夺 夺 平均 平均 平均 平均 平均 平均 Ch Ch Ch Ch Ch Ch Ch Ch Ch Ch Ch Ch Ch Ch Ch Ch Ch 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 Trail-minimum particle size (/«m) 00 00 r- 00 \〇卜卜 in 00 o \o 00 Λ Λ ON On 卜 average crystal grain size (Um) ^Ti IT) m (N 00 04 Bu Q\ Di ά ά 20 1020 1020 1050 1050 1020 1020 1050 1050 1020 1020 1020 1020 1020 1020 1050 1050 1050 1050 aging temperature Cc) oo inch ο ^Τ) ο ο ur&gt; ο omooooo ο oo ITi oo composition (% by mass) Other oo ο Ο O.lMg O.lMg 丨O.lMg O.lMg 0.5Sn i 0.5Zn O.lAg | 1 0.5Sn 0.5Zn 丨O.lAg 〇〇oo rsj d (N o rsj d Ν Ο Ν (Ν Ο fS) d &lt;Ν d (N iooo (N irN dd 卜 d 1—^ r- o 卜Ο &lt;- Ο Ο Ο dot dot dot dot dot dot dot dot dot dot dot dot dot dot dot dot dot dot dot fO oo 00 00 rn 00 00 rS Ο Ζ Q\ CN (Ν (Ν ΓΛ to (N CN 00 (N (N fN mm ΓΛ ΓΛ 201035338

ΐ= »Invite at ο ι-Η v〇O) 〇\ O) 〇(N SS (N On 2 fN Γ〇g FH I-**&lt; 〇iH stress relaxation deviation (%) ο ιτ! ΌΌ « Ri 00 ... inch '«/) ιτϊ fN 'O fO ro i〇 — Ό 寸 inch to 00 inch _ _ _茗yn fN ΟΝ m iTi 00 ΓΛ 00 m CN fN i〇 average bending 〇m) 00 ro ro s rn &lt;N rn rn ο Γ〇fN 00 m rn S (Ν s &lt;N Ό O) ON fN g rn XT* ^ d\ f ^ wm 00 Ό 00 00 S r〇00 vo 00 ν〇JO rn m 00 00 Average Conductivity (%IACS) 00 &gt;Τ) CO in (N m IT) σ\ IT) ?; &lt;N tri (N Ό Average Strength (MPa) 〇\ yr\ Bu ON O m 00 § r- s O ΓΛ CO 卜 卜 卜 〇 (N m JO 〇 r〇00 卜 00 Μ ^ Φ-^Ι - minimum particle size (/ / m) &lt; N m 2 mm 00 inch inch 2 00 (N + mg一艺cs CO rs &lt;N Ό m CN (N (N CO et al. Os 00 geisha & θ ΨΑ w ο ι〇ο ososr-H 〇s Ο ο 1—^ 宕Ο 〇s »·Ή ο ο r*H Ο iri Os og ο Os o 〇\ sos T—&lt; aging temperature CC) 1 1 1 i 1 1 1 1 1 1 1 1 omo cn Composition (% by mass) ο oo O ο ο O ο ο o 〇 Oo O ο ooo ο fN d CN d (Ν Ο ο o &lt;N d (N doo ΰ5 卜ί-Η ο d r-d 卜o Γ- ο ο r~* d Ο Ο di di-l 卜d r- o 卜o F-&lt; 卜o 卜o ο υ ο o r4 o ΓΛ or〇ο Γ〇ο o ΓΛ ο ΓΟ ο cn oor〇o rn or〇o rn 〇% Ρ: 00 m 〇\ m 〇τ ~^ ζ] $ On 201035338

Bending roughness deviation (#m) S 1—^ 00 »~·Η inch 00 r〇(Ν 00 ο 〇\ (Ν 00 »—Η 3 ο 1—Η r—Η s (N \q stress relaxation deviation ( %) C\ in 00 ui ο inch inch»vS Ν inch inch»ri C\ intensity deviation (MPa) m ο 〇\ IT) *T) (N IT) s fl fN SC\ (N (N average bending (qing) inch Ro s; r4 C\ (N &lt;NC\ Ν (N f—« ΓΛ rN ο CN ν〇ΓΟ &lt;Ν inchΓΊ (Ν (Ν g (Νo inch (N 卜r-^ (N 5S fN , Ro 00 (N 00 00 (N 00 S in 00 00 (Ν 00 g (Ν 00 ΓΟ 00 ir&gt; CO S m 00 average conductivity (% IACS), etc. 'T) 00 ΓΊ o 沄CN 沄 average strength (MPa) (N 00 00 00 VsO 00 G\ r^i 00 yr) S o 00 ON § 00 00 00 00 Ο 冢Ό (Ν Ό Ό 00 00 卜 C\ 00 g to m 〇\ :§ΐλ· Granule-minimum Particle size 〇m) Jn ^T) ro iT) (N (N 〇\ ΙΛ) (Ν 00 (Ν CN ι/Ί CS 宕 average crystal grain size (Um) C\ Os (N inch U&quot;) 00 (Ν ΓΟ (Ν {/Ί (Ν C\ CA ® reading 1020 1050 1020 1050 1020 1020 1020 1050 1020 : 1050 1020 1050 1020 1050 aging temperature CC) onoo ro oo $ o ^Τ) ο iri tT) ao un tn composition (mass%) 1 other; ! O.lMg O.lMg 〇〇oo ο ο O.lMg O.lMg ο o O.lMg O.lMg oo iN d (N do fN d ο ο ο ο (Ν Ο &lt;N d (N d &lt;N d Λ o 卜dr^d T-H 卜o (N (N rH r- ο Η Γ- ο ο ι Η 卜 d d d d or or —&lt; 卜o r-d 〇U o ro oor*ior〇卜 inch* 卜 inch - ο ΓΛ ο ΓΟ ο Γ^Ί ο ΓΛ ο rn o ro o ΓΟ o ro 〇Z in (N ir&gt; IT) Ό 00 〇\ ιη S 3 CS MD r〇S 201035338 Alloy of alloys 1 to 6 is an alloy having a low Co concentration (〇7 and 2〇% by mass), which is an example of the present invention, and the average strength is low in concentration. It becomes smaller, but the variation of various characteristics is small.

The alloy of No. 7 to 36 is an alloy of Co Hando high (3% by mass or more), which is an embodiment of the present invention, and all of them have strength and electrical conductivity suitable for electronic materials, and the deviation of characteristics is also less.

The alloy of No. 37 to 44 was not subjected to the first aging treatment, and the crystal grain size was coarsened during the solution treatment, so that the strength and the bending workability were deteriorated.

The alloy of No. 45 to 48 was not subjected to the first aging treatment, and the solid solution temperature was low. The second phase particles are not sufficiently solid-solved, and since the crystal grains are too small, the strength and stress relaxation characteristics are deteriorated.

The alloy of No. 49 to 54 was too low in the first day of the treatment, and the second phase particles were small. Therefore, the crystal grain size was coarsened during the solution treatment, and the strength and the bending workability were deteriorated. The deviation of the x' crystal grain size is large. As a result, the variation in characteristics becomes large. The alloy of Νο·55~56 is deteriorated in strength and electrical conductivity due to excessive addition.

Alloy No. 57-64, the aging temperature due to the first aging treatment is too high. The first phase particles grow unevenly, so the crystal grain size is uneven. As a result, the variation in characteristics becomes large. [Simple description of the drawing] Fig. 1 is an explanatory diagram of the stress relaxation test method. Fig. 2 is an explanatory view of the amount of permanent deformation of the stress relaxation test method. 25 201035338 [Explanation of main component symbols] 1 Punctuation distance t Thickness y Permanent deformation amount (height) y〇 Prevail 26

Claims (1)

201035338 VII. Patent application scope: 1. A copper alloy for electronic materials, which contains c〇: 〇.5~4 ()% by mass, Si · 0.1~1.2% by mass, and the remainder is made of cu and unavoidable impurities. The average crystal grain size is 丨5 to 3 〇#m, and the average difference between the maximum crystal grain size and the minimum crystal grain size per 0.5 mm 2 of the observation field is 1 m or less. 〇2· A copper alloy for electronic materials containing Co: 0.5 to 4.0% by mass, S!: 〇.1 to 1.2% by mass 'and full of the following (1) to (4) any of the above-mentioned composition conditions: (1) Further, it contains a maximum of 〇·5 mass% of cr; (2) Progressively contains a total of 0.5% by mass of one or more elements selected from the group consisting of Mg, Mn, Ag, and P; (3) Progress contains the largest total 2.0% by mass of an element selected from the group consisting of Sn and Zn; (4) further comprising a total of up to 2% by mass selected from the group consisting of As, 讥, Be, B, Ti, Zr, ... i species or "heavier elements; and the remainder consists of Cu and unavoidable impurities, the average crystal grain size is 15~3 -, the difference between the maximum crystal grain size and the minimum crystal grain size of the field of view 〇.5_2 The average is 丨〇# m or less. 3. The method for manufacturing a copper alloy is the copper alloy used in the manufacture of the first or second patent scope of the patent application, which comprises the following steps: Step 1: The ingot to be composed is melt-casted; the step is called 2' ah ~ Saki plus ... after hours of heat to heat the end of the hot rolling The temperature is set at 85 (rc or more, and the average cooling rate from 8 thieves 27 201035338 to 400 ° C is set to be above 15 ° C / s for cooling; step 3, cold rolling with a degree of processing of 70% or more; 4. Perform aging treatment with 3 5 〇~5 〇〇 °C for 1~2 4 hours; Step 5, with 95〇~1〇5〇. (: Solution treatment, the material temperature drops from 850 °C Up to 4 〇 (the average cooling rate at rc is set at 15 it/8 or more for cooling; step 6, optional cold rolling; step 7, aging treatment; step 8, optional cold rolling. 4. Copper, alloy. ..., copper alloy with patent application range 1 or 2, copper alloy of zero-type electronic equipment. You have the patent application scope 1 or 2, pattern: (such as the next page) 28