TW200900515A - Cu-Ni-Si-Co-based copper alloy for electronic material, and method for production thereof - Google Patents

Abstract

Disclosed is a Cu-Ni-Si-Co-based alloy reduced in the production of a coarse second phase particle. In the process for producing a Cu-Ni-Si-Co-based alloy; (1) the hot rolling is carried out after heating at 950 to 1050 DEG C for 1 hour or longer, and the hot rolling termination temperature is fixed at 850 DEG C or higher, and the cooling is carried out at a rate of 15 DEG C/s or more; and (2) the solution treatment is carried out at 850 to 1050 DEG C, and the cooling is carried out at a rate of 15 DEG C/s or more. Specifically disclosed is a copper alloy for an electronic material, which comprises 1.0 to 2.5 mass% of Ni, 0.5 to 2.5 mass% of Co and 0.30 to 1.20 mass% of Si, with the remainder being Cu and unavoidable impurities.; The copper alloy contains no second phase particle having a particle diameter greater than 10 [mu]m, and contains a second phase particle having a particle diameter of 5 to 10 [mu]m at a density of 50 particles/mm<2> or less in a cross-section parallel to the rolling direction.

Description

200900515 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a precipitation hardening type, a bismuth type copper alloy, and more particularly to a Cu 锸 锸 锸 各种 各种 各种 各种 各种 Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Co-based copper alloy.

[Prior Art J for connectors, openings, relays::: Electronic materials used for sub-machine parts: copper::,: = strength and high conductivity '...thermal conductivity) as basic it is not: Years, the history of electronic parts Sore Ladu ten pay / live. The accumulation and miniaturization between the near and the 、, and the thinness of this, the rapid development of the electronic m crying, the use of parts of the electronic machine gradually increased. The degree of demand for D 4 is also gradually increased from the viewpoint of high strength and high electrical conductivity, and the precipitation of the hardened copper alloy is gradually increased instead of . The gold-enhanced copper alloy, which is a solid solution alloy represented by brass, is a steel alloy for solid two-dimensional materials. Precipitation-hardening copper theory' causes fine precipitates: uniformity of two saturated solid solutions for aging. The amount of solid solution elements in copper is less: [the strength of alpha gold is increased by two while reducing ', and the conductivity is re-expressed. Therefore, it can be used for mechanical properties such as elastic properties, precipitation hardening copper = and =,

Cu'i-Si copper alloy::% is the m-type of the Cassson alloy, and has a more southerous conductivity, strength and bending plus steel alloy, in the industry, the alloy of the bean - Boeing has developed an intermetallic ionized material to precipitate a copper alloy by raising the fine Ni-Si system. Jin out of the copper base 'to seek strength and conductivity 200900515 In order to advance the step-by-step increase of the Carson alloy into the gold into the eight u know the addition of Ni and Si to ... ^ 1 in addition to the characteristics of the poor shadow organization optimization For example, P 4 P is used to develop various technologies for developing sheep. It is known that hunting is done by adding Co to improve the characteristics. In Japanese Unexamined U.S. Patent No. 2 (Patent Document 1), S has a Co-loaded Co, which is the same as Ni, and produces C, /, and forms a chemical &amp; When subjected to aging treatment, the mechanical strength and electrical conductivity are only slightly higher than that of the Cu-Ni-Si man-made 厶 from π tL 守 ... ... 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金 金In the case of the above-mentioned Japanese Patent Publication No. 2005-532477 (Patent Document 2), there is a type of forged copper alloy which is made of nickel by weight. :ι%~ # 0.5~2.0〇/〇, 石夕: (^./❶ 5%, the remaining part of the copper and avoidable impurities constitute 'the total content of nickel and cobalt &amp; η%~ 4.3%' The (Ni+CG)/Si ratio is 2:1 to 7:1, and the forged copper alloy has conductivity of more than 4% IACS. The recording will be combined with Shi Xi to limit the growth of the puller and the rise resistance to softening. J·sheng, it is believed that it will help the ageing hardening compound. If the diamond content is less than 〇. 5 %, the precipitation of the second phase containing the diamond ceramsite will be insufficient. And, the combination 〇.5 % minimum cobalt content and When the content of the bismuth is 5 〇 / 〇, the particle size of the alloy after solid solution is kept below 2 〇 micrometers. When the cobalt content exceeds 2.5 Å, the excess second phase particles are precipitated, resulting in precipitation. The reduction in the workability and the inferior ferromagnetic properties of the copper alloy. The strength of the Cu-Ni-Si alloy containing Co is described in the pamphlet of International Publication No. 2006/101 172 (Patent Document 3). In a certain condition, the composition of 200900515 is greatly improved. Specifically, a copper alloy for electronic materials is described as containing Ni: from about 0.5 to about 25% by mass, c〇: from about 0.5 to about 2.5% by mass and si : 'About 3〇~ about 12% by mass, the remainder consists of CU and unavoidable impurities. The mass ratio of the total mass of 妒 and c〇 to the mass ratio of Si in the composition of the alloy ([Ni+CQ]/ The Si ratio ^ H [Ni + C 〇 ] / Si $ is about 5, and the Berri wave ratio (Ni / Co ratio) of Ni and c 该 in the alloy composition is about ο"$ Ni / Co $ about 2. It is described that if the cold rolling speed after heating is intentionally increased during the solution treatment, the strength of the Cu_Ni_Si copper alloy can be effectively improved, so: cold It is also effective to control the speed by averaging the above-mentioned speed. It is also known that it is preferable to control the coarse inclusions in the copper base. In Japanese Laid-Open Patent Publication No. Hei 2-49369 (Patent Document 4) After the adjustment of the composition of the alloy, the composition contains Mg, Zn, Sn, Fe, Tl, Zr, Cr, A1, p, M^^

Be' controls and selects the manufacturing conditions to control the distribution of inclusions such as precipitates, crystals, and oxides in the base, and materials for the copper alloy. Specifically, it is described that: = copper alloy for electronic materials and conductive electronic materials, the special person has excellent strength: 2 to Si, the remainder is composed of Cu and unavoidable impurities, and the size of inclusions 5~1〇#m is large, and /mm2 is in the section parallel to the direction of the pressure B in the avoidance of the A-μ + M m. The number of lost impurities is less than 50 and 'in this document, it is described that in the semi-continuous process, the solidification of the tungsten produced by ##, resulting in the formation of Ni-Si-based large crystals and precipitates, 200900515 Therefore, the method of controlling this is, that is, "by 8 〇 (temperature above TC, after heating for more than 1 hour, the heat is rolled, the final temperature is 650. 〇 to ^ ', the coarse inclusions 4 Solid solution in the base ' However, if the heat temperature is above 900 C', there will be a large amount of rust [and the occurrence of cracks and other problems during the thermal pressure delay, so it is better to make the heating temperature 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 〇6/1〇1 172 [Patent Document 4] JP-A-2001-49369 [Summary of the Invention]

隹λ,; it is known that c 〇 can be added to the alloy by the above method to improve the strength and conductivity, and the inventors have found that if the CU'Nl-Sl' alloy is added to the mouth of the force The organization observes it, and the coarse second phase particles of the four knives are scattered everywhere. This second phase particle is mainly composed of a c〇(tetra) compound. The coarse second phase particles do not contribute to the strength, but also cause adverse effects on the bending workability. The formation of the phase particles is a Cu-Ni-Si alloy which does not contain Co, even in a suppressable condition. Manufacturing underneath cannot be suppressed. In other words, the Cu-Ni-Si-Co alloy is not touched by the patent document 4. After heating at a temperature of C for more than a few hours, the inter-heat rolling is performed to make the final temperature 纟65 吖 or more to suppress the formation of coarse inclusions, and the coarse second phase particles 8 which are mainly composed of C&quot; 200900515 Fully dissolved in the base. Further, even if the method of increasing the cooling rate after heating in the solution treatment as taught by the patent money 3 does not sufficiently suppress the coarse second phase particles. Therefore, the present invention has been made in order to obtain a Cu Ni Si-Co alloy made of P from the formation of coarse second phase particles. Further, the present invention is also another object of providing a method for producing the Cn-Ni-Si-Co alloy. After the study of the heart, the present invention can be used to suppress the inventors' efforts to solve the above problems, and to perform the inter-thermal rolling and solution treatment under the specific conditions to produce the coarse phase one-phase particles. In the case of the body, it is known that in the manufacturing step of the Cu_Ni_Si_c lanthanide alloy, the hunt can be suppressed to such an extent that it hardly causes any adverse effect on the strength and the bending workability by satisfying the following two conditions. a(1) is 95〇. After heating for 1 hour or more in °~105 generation, the inter-heat rolling is performed, and the temperature at the end of the inter-heat rolling is 85 (rc or more, and then cooled at a cooling rate of 15 ° C /s or more; (2) 85固£&gt;c~105〇°c is solution treated and then cooled at a cooling rate of 15t:/s or more. According to this manufacturing method, the second phase particles having a particle diameter of more than 10/m can be eliminated, and It is possible to suppress the number of second phase particles having a particle diameter of 5 centimeters to ... m to 5 Å/mm or less. If the distribution conditions of such second phase particles are present, the strength and bending workability may be adversely affected. Although it is also known that the strength and conductivity can be improved by adding Cr, it is added to the Si-based alloy, and the coarse second-phase particles are more easily formed. It is easy to form a telluride because of Cr t. 200900515 In the case of 粗/u, for example, in Patent Document 2, it is described that the chromium content is less than 0.08%, and that there is a penny. However, if the method according to the present invention is used, even if the number of times is increased,叮4 can also suppress the formation of coarse Cr telluride. The effect of the surface is more prominent, and combined with the effect of adding Co, it can be more twisted and twisted and added with the characteristics of the ascending alloy. Based on the above findings, the invention is based on the invention. Copper alloy jade for electronic materials, containing Ni. ι·〇~2 5 temporary denier 0/ 5 shell $%, Co: 〇·5 ～2.5 mass%, Si. 0.30~1.20 mass%, surplus. ^力士— The P-knife of the phantom is composed of Cu and inevitable impurities, and there are two phase particles of the sputum that are more than 1 〇&gt;# m, and in the cross section parallel to the rolling direction, the granules are 1. The second phase particles of #m~10am are at 50/mm2 or less. The electronic material of the present invention uses 5 cups of copper for everyone. In one embodiment, the grain 彳&lt;τ&lt; The second phase particles having a position of 5 &quot;m~1〇#m are 25/mm2 or less. The copper alloy for electronic materials of the present invention further contains Cr up to 〇.5 mass in the embodiment. In another embodiment, the steel for electronic material of the present invention further comprises a material selected from the group consisting of Mg, P, as, Sh, s W, Be, B, Mn, Sn Groups of s, Ti, Zr, A, Fe, Zn, and Ag + s , n are at least one of the alloying elements in the group, and the total amount of the alloying elements is as large as 2·〇% by mass. The present invention is also used to manufacture +. ^ The above copper alloy manufacturing method comprises the following steps: - a step of casting the ingot having the desired composition by dazzle casting; 乂950 C~l〇5〇C heating for more than one hour Inter-calendering, 10 200900515 The temperature at the end of the calender calendering is at 8 5 〇 ° c in μL from above, and is cooled to 4 〇〇t at an average cooling rate of 15 ΐ:/s or more; - Cold rolling Step; solid solution treatment at a temperature of 15 ° C / S or more - at 85 ° ° C ~ l 〇 5 ° ° c cooling the cooling rate to 400. (3 steps; - any cold rolling step; - aging treatment step; and - any cold rolling step. The present invention is a copper alloy using the above copper alloy. Electronic parts of alloys. According to the present invention, since generation of coarse second phase particles can be suppressed, it is possible to provide a less

Wsi-c. The system is complete. The influence of the second brother-phase puller ^, that is, because of the negative effects caused by the addition of Co and Cr, the bad effect...^ U is a positive effect on the alloy's characteristics. Without sacrificing conductivity and curvature processing, [Embodiment] [Distribution condition of second phase particles] Right is Carson 糸 alloy', which can be buried by ##, ^ Μ „ , ^ ^ , Τ The proper heat treatment of the yoke by the shell yoke causes the electric potential of the fish-based compound to deteriorate, and the younger-phase particles are precipitated, and the lead is not required to be high-strength. Adding C., even -C..., the second phase particles are easily coarsened.

The particle size is 1 &quot; m L helps, the coarse 2nd phase particles are not only for strength

Lifting, and will also reduce the workability of A σ. In particular, since the two-phase particles having a particle diameter exceeding 10 0 / m 11 200900515 have a marked deterioration in bending workability, it is necessary to make the upper limit Wm. In the case where the second phase particles of the particle size of 5/m to 1 〇#m are within 50 W, the strength and bending workability are not impaired. According to the present invention, it is possible to sufficiently suppress the coarsening of the c-telluride and the second phase particles of the c-table, and it is not necessary to be the above-mentioned requirement for the distribution of the phase-phase particles. The particle diameter and the number of the second phase particles can be measured by SEM observation after the cross section of the opposite material is parallelized. In the present invention, the particle diameter of the 帛2-phase particles means the diameter of the smallest circle surrounding the particles when the SEM observation is performed under the conditions. Therefore, in one embodiment of the present invention, the second phase particles having a particle diameter of more than 1 Å are not present, and the second phase particles having a particle diameter of 〜1 〇/im are as follows in the cross section parallel to the rolling direction. In a preferred embodiment of the present invention, there is no second phase particle having a particle size exceeding the claw, and a second phase particle having a particle diameter of 5 to i0/zm in a cross section parallel to the rolling direction is 25 &amp;;…the following. In a preferred embodiment of the present invention, there is no second phase particle having a particle size exceeding 〇#m, and the particle size is 5βηι~l〇#mi in the cross section parallel to the rolling direction. 2 (M@/mm2 or less. In the further preferred embodiment of the present invention, the second phase particles having a particle diameter of more than 1 Å are not present, and the particle diameter is in the cross section parallel to the rolling direction. : ^ "The second phase particles of the claw are below ^ &amp; (4). In the present invention, the second phase particles mainly refer to the stone slick compound 'but not limited to this' or may be in the solidification process of the refining and casting The resulting crystals were cooled with 12 200900515 after tb rtrl 4 .

/, the raw precipitate, the crushed mountain produced during the heat-pressed A 郃 process, the precipitate, the precipitate produced during the cooling process after the solution treatment, ;g y_ n± 1 &gt; A ΓΧΓ ΓΧΓ Γ . The precipitate produced during the treatment process. [Addition of Ni, Co and Si]

Ni Co and Sl ' can be formed by a suitable heat treatment to form a compound, and the conductivity # is not interdependent. %% is maintained and can be increased in strength.

Ni, Co, and Si add force to each of them, Geχτ., 咏 咏 咏 Gary right Ni has not reached 1_〇 quality. Hey, c〇 is not up to 0.5 quality! %, Si did not reach 03 temporary promotion. /η 士士里/0, you can't get the intensity you want. 'Inversely' If Ni exceeds 2.5% by mass, co exceeds 25 quality."

When Si exceeds U mass%, the strength can be increased, but the lead is remarkably lowered, and the hot workability is also reduced. Therefore, the addition amount of Ni, c〇 and Si is made to be: U~2.5 mass. /. , C〇: 0.5~2·5 quality denier %' ^0.30 42% by mass. Preferably, m: i 5 to 2 〇 mass% 0.5 to 2.0 mass%, Si · 〇·5 ̄ίο mass%. [Cr addition amount]

Cr ' can be formed by pre-existing Cr or by the form of Cr-based compound (which is a compound with Si) by appropriate heat treatment, and it is not affected by the strength of the copper matrix, and can be made conductive. The rate is improved. Since r total 丄 μ this can be added with Cr maximum 〇 5 mass% in the Cn-Ni-Si-Co system of the present invention. However, if the right side does not reach 〇.〇3 mass% 'the effect is small', if it exceeds 0.5 mass%, it will form an undissolved particle which does not contribute to strengthening, and the workability is impaired. Therefore, it is preferable to add 0.03 to 0.5 mass. %, more preferably 0_1~0.3 temporary θ. [Other addition elements] Further, various effects can be obtained by adding a predetermined amount of Mg, ρ, As, sb, Be, β, 13 200900515 Μη, Sn, Ti, Zr, Al, Fe, Ζη, and Ag'. In addition to the insufficiency of each other, not only the strength and electrical conductivity, but also the effect of improving the manufacturability (such as the improvement of the bending workability, the plating property, and the hot workability affected by the micronization of the ingot structure), In view of the characteristics, one or more of the above elements are appropriately added to the Cu-Ni-Si-Co alloy of the present invention. In this case, the total amount is at most 2.0% by mass, preferably 0.001 to 2_0. %, more preferably 〇.〇1~1 · 0 mass%. On the other hand, if the total amount of these elements is less than 0.001% by mass, 'the desired effect cannot be obtained'. If it exceeds 2.0% by mass, the electrical conductivity will be remarkably lowered, and the manufacturability will be remarkably deteriorated, so good. [Manufacturing Method] The general process of the Caston copper alloy is firstly using an atmospheric melting furnace to melt the raw materials such as electrolytic copper, Ni, Si, and Co to obtain a desired molten liquid. In addition, the molten liquid scale is prayed. Then, the inter-heat rolling is performed, and the inter-cold rolling and heat treatment are repeated, and the finished product is formed into a strip and a box of thickness and characteristics. Heat treatment, with solid solution treatment and aging treatment: solution treatment, heating at a high temperature of about 700 ~ about t, the compound of the cessil compound 'c〇_Si compound is dissolved in the base of the base: Recrystallize. Sometimes the solution treatment can also be carried out by calendering at a temperature of about 350 to about 550. When s is added in the temperature range of 〇, at the time of 8: upper, the solid solution is precipitated in the form of fine particles. Increase strength and electrical conductivity. In order to obtain f 夕 出 / / / / / / / / / / / / / / / / / / / , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Moreover, after the aging, the cold room is strengthened. In the case of 200900515, strain relief annealing (low temperature annealing) is sometimes performed after cold rolling. The polishing, the grinding, the bead blasting, and the like for removing the surface oxidized skin may be carried out as appropriate between the above steps. Although the copper alloy of the present invention has undergone the above-described process, in order to prevent coarsening of the second phase particles, it is necessary to strictly control the heat-intercalation and solution treatment. In the solidification process during casting, coarse crystals are inevitably formed, and coarse precipitates are inevitably formed during the cooling process. Therefore, in the subsequent step, the second phase particles must be dissolved in the matrix phase, and if it is maintained at 95 〇t~1〇5 (rc for more than i hours, heat-calendering is performed, and The temperature at the end of the calender calendering is 〇85 〇. If the above is added, even if co is added, even in the case of Cr, the solid solution may be dissolved in the matrix phase. The temperature condition above 95 ,, other Kason The temperature is set below the monthly opening v-phase '. If the temperature before the hot rolling is less than 95CTC, the solid solution will be insufficient. If it exceeds 〇5〇

In the case of c, there is a possibility that the material (4) may be melted. If the temperature of 3 inches is less than 8501 ′, the solid solution may be precipitated again, so that high strength cannot be obtained. ^ After the above-mentioned first-phase particles are solid-solved, if the cold after the end of the hot rolling is cold, the degree is slower. And, or c. The bismuth compound is extracted from the right side in the later step, 'the heat treatment for the purpose of lifting the strong metal (the double treatment when V. V), because it will precipitate during the cooling process. The precipitate is a nucleus, a precipitate, and therefore the I method is obtained as a coarseness of the strength and the help of the method. However, if the average cooling 15 200900515 u is increased, the precipitation of the compound is more significant. . Specifically, when it is 15 ° C /s or more, precipitation of the telluride can be suppressed. . The same is true for the core treatment, and the second phase particles can be solid-solved by setting the solution treatment temperature to 850 C 1 050 c '. The cooling after the solution treatment is also as described above for the reason that it is not required to be fast 'i 4Q (the average cooling rate of rc is the same ', and is above 5 C / s. If the cooling rate after the inter-heat rolling is not controlled, Only the cooling rate after the solution treatment is controlled, and the coarse second phase particles cannot be sufficiently suppressed by the subsequent aging treatment. The q speed after the hot rolling and the cooling rate after the solution treatment must be the same. The above average cooling rate after the end of the hot rolling and after the solution treatment is preferably 20 ° C / s or more. The method of rapid cooling, the most effective method of water cooling, but because of the use of water cooling The temperature of the water will change the cooling rate, so the cooling can be made faster by controlling the water temperature. If the water temperature is above 25t, sometimes the desired cooling rate will not be obtained, so it is better to protect it: 25 C or less. If the material is placed in a tank in which water is stored for water cooling, then 25^@@ is preferred; the mist is foggy (spray or mist) to make the material in a certain amount of water,卩 卩, / / below) Or to prevent the water temperature from rising by the way that cold water always flows to the sink. Moreover, the cooling rate can be increased by adding a water-cooled nozzle and increasing the amount of water per unit hour.

In the present invention, "the average cooling rate to 400 ° C," means that the calculated material is cooled from the inter-heat rolling final temperature or the solution treatment temperature to 4 Torr. I 2009 I 16 200900515 守守' (Solution temperature) ·40〇) (0c) / Threshold rc/s when cooling. The condition of aging treatment calculated by (S), σ is equal to f % / , and should contribute to the precipitation Micronization, the conditions for the use of ten 丨 丨 以 以 估 估 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - An example of the condition of recognizing, β - is in the temperature range of 550 。. ", , θ Select #阁 ^ More preferably in the 400~500 C / 度度干围half half f f The cooling rate after the treatment, f&quot; the hand does not have any influence on the size of the precipitate. The Cu-Ni-Si-Co alloy of the present invention can be processed into various coppers. Product, illusion plate's strips, tubes, rods and wires, such as the Guardian and the Cu-Ni-Si-Co copper alloy of the present invention, can be used for wire mouth 0 疋 疋 亚 、, terminal An electronic component such as a relay, a switch, or a foil for a secondary battery, etc. [Embodiment] Hereinafter, embodiments of the present invention are shown as a comparative example, but the embodiments are merely for understanding the present invention and The advantages provided by the present invention are not limited to those of the present invention. In a high-frequency melting furnace, a copper alloy composed of various components described in Table 1 is dissolved at 130 (rc), and cast into an ingot having a thickness of 3 mm. Then, after the ingot was heated to the looot, the heat was repeatedly extended to a plate thickness of 10 mm at various final temperatures (heat-to-calender temperature γ), and rapidly cooled to 40 (TC, and finally at 100 t: or less at various cooling rates. Then, in order to remove the scale on the surface, planar cutting is performed to a thickness of 9 mm, and then a plate having a thickness of 〇, 3 mm is formed by cold rolling. Then, a solution treatment of 12 sec is performed at 950 t: and then various cooling is performed immediately. The speed is cooled to 4 〇 (rc, finally below 17 200900515 c. After 3 hours in an inert atmosphere, the final gas is 50 °. The cost of the test is made to produce a test piece. Each test piece, in the following manner 1 The distribution, strength, conductivity and f-processability of the material, and the analysis of the particles of the heart, the mechanical grinding using the diameter i # m, the material parallel to the dust square fine: stone abrasive grain - monument # , '(Bomei) in the aqueous solution of ferric chloride, side, 隹仃 see &quot;, dipping for 2 minutes. By etching: the second phase particles appear. Make a M [field hair:::: submicroscope , by the LIPS company, the magnification of the coffee times (observation field of view = Chuan "„〇, any section of this section is observed arbitrarily, the number of precipitates of particle size $~μ ” is calculated, and the particle size exceeds 1〇” The number of precipitates is then calculated for each number of 1 mm 2 . The second phase: b telluride can be confirmed by analyzing the representative form by using FE_SEM coffee (dispersive X-ray analysis). In the case of the strength, a tensile test in the parallel direction of rolling can be performed to measure the 〇2% safety limit stress (YS: MPA). Conductivity (EC; % IACS) can be obtained from the volume resistivity measured by the Wheatstone bridge. The bending workability was evaluated by a W-bend test using a W-shaped metal mold using a W-shaped metal mold at a ratio of a sample thickness to a bending radius of 1 using a W-bend test. Bending processing. In the evaluation, the surface of the bent portion was observed with an optical microscope, and the case where no crack was observed was judged to be practically no problem, and it was expressed as 〇, and in the case of cracked 18 200900515, it was X. The results are shown in Table 1. \ 19 200900515 \ Bending processability 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 conductivity %IACS On 1—H un (Ν ιη 1—Η Ό Strength MPa 〇00 〇 00 〇CO § 00 00 s 00 as 00 o 冢og 00 S 00 ο ο οο 00 m oo 00 o 00 o Ch 00 Os 00 ο Precipitate &gt;10//m/mm2 〇〇〇〇ο ο ooooo 〇 ο ο ο ooooo ο ο Precipitates 5 ～10//m/mm2 rn Bu Τ-Η m oo 1—^ m (N 00 CN 卜r—( m ΓΛ IT) &lt;N oo (D 00 1—Η Solution treatment (method) Water-cooling 1 Water-cooling 1 Water-cooling 2 Water-cooling 2 Water-cooling 2 Water-cooling 2 1 Water-cooling l 1 Water-cooling 1 Water-cooling 1 Water-cooling 1 Water-cooling 1 Water-cooling 1 Water-cooling 2 Water-cooling 2 Water-cooling 2 Water-cooling 2 Water-cooling 1 Water-cooling 1 Water-cooling 1 Water-cooling 1 Water cooling 1 Water cooling 1 Cooling 〇〇 Η Η m VO i oo 1—( 00 f'«Ή 00 oo 00 1—H oo I丨1 Ο ι—Η in IT) 1—^ Ό * 1 ^ 00 00 τ- ^ 00 τ-Η OO rH 00 οο &gt;&quot;&lt; Hot rolling (method) Water cooling 1 Water cooling 1 Water cooling 2 Water cooling 2 Water cooling 2 Water cooling 1 1 Water cooling l Water cooling 1 Water cooling 1 Water cooling 1 Water cooling 1 Water cooling 1 water cooling 2 water cooling 2 1 water cooling 2 water cooling 1 water cooling 1 water cooling 1 water cooling 1 water cooling 1 water cooling 1 water cooling 1 cooling miscellaneous 00 ί—^ Ό 1—Η oo r_____A oo οο Τ—^ οο rH 00 Produce &lt; 00 οο r11 i Last; ON 〇00 00 〇00 o 〇\ oo ο o C\ ο 沄00 00 Ο οο o ο s ο ο s ο ο ο Composition (mass 〇/〇) Ms O.lMg O.lMg O.lMg O.lMg O.lMg O.lMg O.lMg O.lMg (N &lt;Ν (Ν CN (Ν (N CN CN o ( Ν (N 0.05 ^t; 0.65 0.65 0.65 0.65 0.65 0.65 ; 0.54 0.54 ] _1 0.81 0.81 0.65 0.65 0.65 0.65 ! 0.65 1_ 0.65 0.54 0.54 0.81 0.81 0.65 0.65 〇1—^ ρ («' &lt; ρ 1—( ρ ρ Η p \Ω 'O to r__ Η 1—H p ρ ι—Η ρ r*H p 1 Ο ρ in »—* ir> ρ ρ r Η 〇〇00 , &lt; 00 oq &gt;' &lt; 00 r ' Η oo oo r Ή 00 OO f 00 00 r_ — οο 00 ^-Η OO ΟΟ II oo 1—( oo r__ &lt; oo 1 CO r—* oo r-^ οο ι &quot;4 oo ϊ—Η 〇1 1 CN inchoo o\ o r-^ r— * CN rn ΙΟ Γ- OO (Ν 200900515 〇〇X 〇 〇XXXXX -,-- _ XX _ - ο - 芽 芽 芽 CO 芽 芽 芽 芽 3 Rs (N .1—&lt;: ΓΟ cn -r cn r*^ ΠΊ . inch m V〇il〇os no. Ξ -»—Η 〇r—« § T?H ΓΠ 4^ CO CO cn; _ 3 r^, cn ri Today: mfk CN 1 m 1 介 &&lt;rv t Ϊ m rn' .ώ m '4' rn 2 »r, ΓΟ 1—H rn Bu 2: JU m ; m will cn i % (N c \ % cn $ CO im 1 s cn i |p| cn $ ο ο. .〇o 〇«η W, ο o Ό o 〇ο 00 :g: 00; s 00 .O- CT) 00 o oo oc 00 〇3 1 III 耀II ti·&quot;1 iofr—too Ϊ—( 〇s ;: ο·; 04 o (N (N 〇&lt;N (N 〇&lt;N (N CN (N 〇 (N ρ·' ο ο o VO in v〇o ί〇〇oo !2 ;2 〇s ST—H rn cn opp l_ _&lt; pr—^ P , 丨 — pr—&lt; o F.._&lt; p ρ ϊ&gt; CN οο , &lt; oq 1 &lt; 00 1 — 00 &lt;&lt; oo r H 00 i 1 00 CO 1 ( OO i — l oo OO rH 00 ”H oo 00 f— ΓΊ (Ν 04 Ό ( N 〇\ (N 沄m CN m £ i ιί : 20090 0515 In Table 1, 'water a for the cooling condition after calendering is in the relative test piece volume (deleted (9) mm3) 5G times the water ^ 2 impregnation", water-cooled 2 is 10% more water than the water-cooled 3, water; 2 ΐIn the t5t3 booster port 20% water, and use the running water to make the water in the sink temperature below #. The air-cooling system is placed in the air for cooling. The volume of the water-cooled test piece for the cooling condition of the solution treatment--the water volume of the water tank = the water-cooling force of 3, the amount of water, the water cooling &quot; 22 liters of water , you m, Shi, ^ ^ 3 Use W water to the water temperature control tube in the sink at 2 5, N under the v. The air cooling system is placed in the air to cool. Each test piece will be described below. Νο.1~Ν〇.22 is an embodiment of the present invention. Both the bending processability and the bending processability are high. &amp; Conductivity - Lin Biao II is an example of no addition of co and Cr. It can be seen that in this case, even if it is not rotated, the intercalation, or the cooling condition at the time of solution treatment, it is possible to suppress the coarse precipitate. "Inhibition 攸 No. 24 shows that even if only a small amount of # &amp; is added, if there is no control condition and the final temperature, a considerable amount of precipitates are generated, that is, c is likely to be precipitated. 1 Very Ν〇·25 series The test piece of N〇24 was further added with a small amount of precipitates. Thus 19, precipitates. j is easy to produce and No. 27 is suitable for cooling conditions after hot rolling, and the cooling conditions at the time of the field and the solution treatment are not appropriate. (5)—take 22 200900515 Ν〇·28 is an example where the final temperature is appropriate, but the cooling conditions after hot rolling and solution treatment are not appropriate. Ν〇.29 is a case where the cooling conditions at the final temperature and the solution treatment are appropriate, but the cooling conditions after the inter-heat rolling are not appropriate. Ν〇·30 is an example in which the composition conditions are appropriate, but the cooling conditions and the final temperature are not appropriate. Ν〇·3 1 is suitable for the composition conditions, but the cooling conditions and the final temperature are not appropriate. f

No. 32 is an example in which the cooling conditions at the time of solution treatment are appropriate, but the cooling conditions after the final temperature and the inter-heat rolling are not appropriate. Νο·33 is the same as No. 31. Both are examples in which the cooling conditions and the final temperature are not appropriate, and the cooling rate after the heat-to-heat rolling is made slower.

No. 34 is an example in which the cooling rate after the solution treatment is further lowered with respect to no. Νο·3 5 is an excess of Co, and the cooling conditions and the final temperature are not suitable. /

No. 36 is an example in which a small amount of Cr is further added to the test piece of No. 35. [Simple description of the diagram] [Explanation of main component symbols] *, ,, 23

Claims (1)

200900515 X. Patent application scope: 1. A copper alloy for electronic materials, the person in charge contains Ni: 1.0~2 5 #旦%, Co: 0.5~2.5 mass%, Si: 〇. Quality 8th, 丄π川~12〇% by mass, the remaining Kia Knife is made of Cu and the inevitable impurities, σ Zhe-toxic, there is no first phase particle with particle size exceeding 10 /zm, and parallel to the pressure ^ t Λ ^ direction The cross-section, the particle diameter A ~ the core W, the second phase particle is "below the core". The copper alloy for the electronic material according to the first aspect of the patent application, wherein the cross section in the direction of the rolling direction, the granules &lt; τ &lt;rabbit &lt; particles are below 25 / mm 2 . β - phase 3 · as claimed in the first or second top of the patent > + ^ ^ member of the copper alloy for electronic materials, "in, further containing Cr up to 〇 5 mass%. 4. If the application of the patent scope 丨 or 2 Gansbee copper alloy for electronic materials, ,, further contains a selected from the group consisting of g As, bismuth, Be, B, Mn, Sn, Τι, Zr, A, Fe, Zn and pain At least one of the groups of the secret group consists of &amp; Meng elements up to a maximum of 2.0 mass 〇 /0. 5. For example, in the third paragraph of the patent application scope, the mine has been selected from the copper alloy of the electronic material for the female 丨a, JL, and the further step is selected from the group consisting of Mg, P, As, Sb, Be, B Mn Sr; The alloying element σ at the group of ^^ and ^ is up to 2.0 mass 0/〇. 6·—A kind of electronic material using a copper alloy to mix and bite &lt; a granule method, which is used to manufacture the Leigong from any of the first to fifth patent scopes of May 5 from 丨人&gt; The material is made of copper alloy, and the following steps are carried out in sequence: - the step of melt casting the ingot having the desired composition; - adding 95 (TC ~ 1050 〇 C for 1 hour to ^ from "... small k After the above, the inter-heat rolling is performed, 24 200900515. The temperature at the end of the hot rolling is 850 ° C or higher, and the step is cooled to 400 ° C at an average cooling rate of 15 ° C /s or more; - the cold rolling step - a solution which is solution treated at 850 ° C to 10 ° C, cooled to 400 ° C at an average cooling rate of 15 ° C /s or more; - any cold rolling step; - aging treatment step; And - any cold rolling step. 7. - Copper alloy, which is a copper alloy for electronic materials according to any one of claims 1 to 5. 8. Type of electronic parts, the scope of application for patent use A copper alloy for electronic materials according to any one of items 1 to 5. XI. Schema: No 25