WO2010113553A1

WO2010113553A1 - Cu-co-si copper alloy for use in electronics, and manufacturing method therefor

Info

Publication number: WO2010113553A1
Application number: PCT/JP2010/052375
Authority: WO
Inventors: 拓磨恩田; 寛桑垣
Original assignee: 日鉱金属株式会社
Priority date: 2009-03-31
Filing date: 2010-02-17
Publication date: 2010-10-07
Also published as: US20120031533A1; EP2415887A1; TWI422692B; KR101317096B1; EP2415887B1; CN102099499A; TW201035338A; KR20110071020A; JP4708485B2; EP2415887A4; CN102099499B; JP2010236071A

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 μm, and the difference in diameter between the smallest and largest grains in each 0.5 mm² area is, on average, no more than 10 μm.

Description

Cu—Co—Si based copper alloy for electronic materials and method for producing the same

The present invention relates to a precipitation hardening type copper alloy, and more particularly to a Cu—Co—Si based copper alloy suitable for use in various electronic device parts.

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.

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.

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, the strength and conductivity can be improved by precipitating fine Ni—Si intermetallic compound particles in the copper matrix.

Attempts have been made to further improve the characteristics by adding Co to the Corson alloy.

In Patent Document 1, Co forms a compound with Si in the same way as Ni, improves mechanical strength, and Cu—Co—Si based alloys are more mechanical than Cu—Ni—Si based alloys when subjected to aging treatment. It is described that a Cu—Co—Si based alloy may be selected if both strength and conductivity are improved and cost is allowed. The optimum addition amount in the case of adding Co is 0.8. It is said to be 05 to 2.0 wt%.

Patent Document 2 describes that cobalt should be 0.5 to 2.5% by mass. This is because when the cobalt content is less than 0.5%, the precipitation of the cobalt-containing silicide second phase becomes insufficient, and when it exceeds 2.5%, excessive second-phase particles are precipitated, and the workability And the copper alloy is imparted with undesirable ferromagnetic properties. Preferably, the cobalt content is from about 0.5% to about 1.5%, and in the most preferred form, the cobalt content is from about 0.7% to about 1.2%.

The copper alloy described in Patent Document 3 has been developed mainly for use as terminals and connector materials for in-vehicle and communication devices, and has a high Co concentration of 0.5 to 2.5 wt%. It is a Cu-Co-Si alloy that achieves conductivity and medium strength. According to Patent Document 3, the reason why the Co concentration is defined in the above range is that when the addition amount is less than 0.5% by mass, a desired strength cannot be obtained, and when the Co content exceeds 2.5% by mass, the increase in strength is not achieved. This is because the electrical conductivity is remarkably lowered and the hot workability is deteriorated, and Co is preferably 0.5 to 2.0% by mass.

The copper alloy described in Patent Document 4 was developed for the purpose of realizing high strength, high conductivity, and high bending workability, and the Co concentration is specified to be 0.1 to 3.0 wt%. Yes. The reason for limiting the Co concentration in this way is that the above effect is not exhibited below the composition range, and addition exceeding the composition range is not preferable because it causes a crystallization phase during casting and causes casting cracks. It is described that there is.

JP 11-222641 A JP 2005-532477 A JP 2008-248333 A JP-A-9-20943

As described above, it is known that Co addition contributes to the improvement of the properties of the copper alloy. However, as described in the above-mentioned prior art documents, if the Co content is increased, the manufacturability and the alloy properties are adversely affected. In a Cu—Co—Si based alloy, improvement in characteristics when Co is added at a high concentration has not been sufficiently studied. However, Co is said to improve mechanical strength and conductivity compared to Ni, and there remains a possibility that characteristics can be improved by further increasing the Co concentration in Cu-Co-Si alloys. Conceivable.
On the other hand, when the Co concentration is further increased, it is necessary to perform the solution treatment at a higher temperature. In such a case, the recrystallized grains are likely to be coarsened. Further, the second phase particles such as crystallized substances and precipitates precipitated in the previous stage of the solution treatment process become obstacles and inhibit the growth of crystal grains. Therefore, there arises a problem that non-uniformity of recrystallized grains in the alloy is increased and variation in mechanical properties of the alloy is increased.

Accordingly, the present invention provides a Cu—Co—Si alloy having high conductivity, high strength, and high bending workability, and having a uniform mechanical property and containing a high concentration of Co. Let's take one issue. Another object of the present invention is to provide a method for producing such a Cu—Co—Si based alloy.

The present inventor has intensively studied a means for reducing the variation in recrystallized grains. As a result, in the production of a Cu—Co—Si based alloy containing Co at a high concentration, fine second phase particles are formed before the solution treatment step. In the copper matrix phase, the crystal grains are not so large due to the pinning effect of the second phase particles even if the solution treatment is performed at a relatively high temperature, The knowledge that the size of the recrystallized grains growing can be made uniform because the pinning effect works uniformly in the entire copper matrix. As a result, it has been found that a Cu—Co—Si based alloy with little variation in mechanical properties can be obtained.

The present invention completed on the basis of the above knowledge, in one aspect, contains Co: 0.5 to 4.0% by mass, Si: 0.1 to 1.2% by mass, with 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 per observation field of 0.5 mm ² is 10 μm or less It is a copper alloy.

In one embodiment, the copper alloy according to the present invention further contains up to 0.5% by mass of Cr.

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 up to 0.5% by mass.

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.

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.

In another aspect of the present invention,
-Step 1 of melt casting an ingot having the desired composition;
Perform hot rolling after heating at −950 ° C. to 1050 ° C. for 1 hour or longer, set the temperature at the end of hot rolling to 850 ° C. or higher, and cool at an average cooling rate from 850 ° C. to 400 ° C. to 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;
Performing a solution treatment at −950 to 1050 ° C., and cooling at an average cooling rate of 15 ° C./s or higher when the material temperature decreases from 850 ° C. to 400 ° C .; and
-Optional cold rolling process 6;
-Aging treatment step 7;
-Optional cold rolling process 8;
It is a manufacturing method of the copper alloy including performing sequentially.

In yet another aspect, the present invention is a copper-drawn product provided with the above copper alloy.

In still another aspect, the present invention is an electronic device component including the copper alloy.

According to the present invention, a Cu—Co—Si alloy having mechanical and electrical characteristics suitable as a copper alloy for electronic materials and uniform mechanical characteristics can be obtained.

It is explanatory drawing of a stress relaxation test method. It is explanatory drawing regarding the amount of permanent deformation of a stress relaxation test method.

(Co and Si addition amount)
Co and Si form an intermetallic compound by performing an appropriate heat treatment, and can increase the strength without deteriorating the electrical conductivity.
If the addition amounts of Co and Si are less than Co: 0.5 mass% and Si: less than 0.1 mass%, the desired strength cannot be obtained. Conversely, Co: more than 4.0 mass%, Si: 1. If it exceeds 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 Co and Si were set to Co: 0.5 to 4.0% by mass and Si: 0.1 to 1.2% by mass.
In the Cu—Co—Si system, higher strength is desired than in the Cu—Ni—Si system and Cu—Ni—Si—Co system, so a high concentration of Co is desired, 2.5% or more, more preferably 3. 2% or more is desirable. That is, the addition amount of Co and Si is preferably Co: 2.5 to 4.0% by mass, Si: 0.5 to 1.0% by mass, more preferably Co: 3.2 to 4.0% by mass. %, Si: 0.65 to 1.0 mass%.

(Addition amount of Cr)
Since Cr preferentially precipitates at the crystal grain boundaries during the cooling process during melt casting, 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 alloy, Si that did not contribute to aging precipitation suppresses the increase in conductivity while remaining in solid solution in the matrix phase, but the silicide-forming element Cr is reduced. By adding and further depositing silicide, the amount of dissolved Si can be reduced, and the electrical 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—Co—Si 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% by mass, it is preferably added in an amount of 0.03 to 0.5% by mass, more preferably 0.09 to 0.3% by mass.

(Addition amount of Mg, Mn, Ag and P)
Mg, Mn, Ag, and P improve the product characteristics such as strength and stress relaxation characteristics without loss of electrical conductivity 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. Therefore, one or more selected from Mg, Mn, Ag and P can be added to the Cu—Co—Si 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.

(Addition amount of Sn and Zn)
Even in the case of Sn and Zn, addition of a small amount improves product characteristics such as strength, stress relaxation characteristics, 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, a maximum of 2.0% by mass in total of one or two selected from Sn and Zn can be added to the Cu—Co—Si based alloy according to the present invention. However, if the amount is less than 0.05% by mass, the effect is small. Therefore, 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 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—Co—Si based alloy according to the present invention, one or more selected from As, Sb, Be, B, Ti, Zr, Al, and Fe are added up to 2.0 mass% in total. 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 to 2.0% by mass in total, more preferably 0.05 to 1.0% by mass in total.

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.

(Crystal grain size)
The crystal grain influences the strength, and the Hall Petch rule is generally established that 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.

On the other hand, since the Cu—Co—Si 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.

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.

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.

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 differences is ideally 0 μm, but is practically difficult, 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.

The small difference between the maximum crystal grain size and the minimum crystal grain size means that the crystal grain size is uniform, which reduces the variation in the mechanical properties of each measurement location within 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.

(Production method)
In a general manufacturing process of a Corson-based copper alloy, first, an atmospheric melting furnace is used to melt raw materials such as electrolytic copper, 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. to cause the second phase particles to be dissolved in the Cu matrix and simultaneously to recrystallize the Cu matrix. The solution treatment may be combined with hot rolling. In the aging treatment, the second phase particles that are heated in the 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 aging and / or after aging. In addition, when cold rolling is performed 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.

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.

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. Hot rolling is performed after holding at 950 ° C. to 1050 ° C. for 1 hour or more, and if the temperature at the end of hot rolling is 850 ° C. or more, even if Co and further Cr are added, they are dissolved in the matrix. 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.

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 the present invention, cooling is performed at an average cooling rate of the material temperature from 850 ° C. to 400 ° C. at 15 ° C./s or more, preferably 20 ° C./more. “Average cooling rate when decreasing from 850 ° C. to 400 ° C.” means measuring the cooling time when the material temperature decreases from 850 ° C. to 650 ° C., and “(850-400) (° C.) / Cooling time (s)” The value (° C./s) calculated by.

水 Water cooling is the most effective way to speed up 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. 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.

¡Cold rolling is performed after hot rolling. This cold rolling is carried out for the purpose of increasing the strain that becomes a precipitation site in order to deposit precipitates uniformly, and cold rolling is preferably carried out at a rolling reduction of 70% or more, and at a rolling reduction of 85% 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.

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 3 at 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.

After the first temporary 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 must be 950 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, an appropriate solution treatment time is 60 to 300 seconds, preferably 120 to 180 seconds at 950 ° C. or more and less than 1000 ° C., preferably 30 to 180 seconds, preferably 60 to 120 seconds at 1000 ° C. or more and less than 1050 ° C. is there

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 decreased from 850 ° C. to 400 ° C. is 15 ° C./s or more, preferably 20 ° C. / Should be greater than or equal to s.

Execute the second aging treatment 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. An example of the aging treatment condition is 1 to 24 hours in a temperature range of 350 to 550 ° C., more preferably 1 to 24 hours in a temperature range of 400 to 500 ° C. The cooling rate after the aging treatment hardly affects the size of the precipitate. 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.

The Cu—Co—Si based alloy of the present invention can be processed into various copper products, such as plates, strips, tubes, rods and wires, and the Cu—Co—Si based copper alloy according to the present invention is a lead. It can be used for electronic parts such as frames, connectors, pins, terminals, relays, switches, and foil materials for secondary batteries.

EXAMPLES 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.

A copper alloy having the composition described in Table 1 (Example) and Table 2 (Comparative Example) was melted at 1300 ° C. in a high-frequency melting furnace and cast into an ingot having a thickness of 30 mm. 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 allowed to cool in the air. 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. The first temporary effect treatment was then carried out at various aging temperatures for 3 to 12 hours (some comparative examples were not subjected to this aging treatment), followed by solution treatment at various solution temperatures for 120 seconds, and thereafter Immediately, 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, 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 finally cold-rolled to 0.08 mm to produce a test piece.

Various characteristics of each test piece obtained in this way were evaluated as follows.

(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) 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 the average difference between the maximum crystal grain size and the minimum crystal grain size.

(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) 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) 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) 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. Alloys 1 to 6 are examples of the present invention relating to alloys with relatively low Co concentrations (0.7 and 2.0 mass%), and the average strength is reduced by the low Co concentration, There is little variation in various characteristics.
No. Alloys 7 to 36 are examples of the present invention relating to alloys having a high Co concentration (3.0% by mass or more), all having strength and conductivity suitable for electronic materials, and variations in characteristics. Few.
No. The alloys Nos. 37 to 44 were not subjected to the first temporary effect treatment, and the strength and bending workability deteriorated due to the coarsening of the crystal grain size during the solution treatment.
No. Alloys 45 to 48 are not subjected to the first temporary effect 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.
No. In the alloys Nos. 49 to 54, the aging temperature of the first temporary treatment was too low and the number of second phase particles was small, so that the crystal grain size was coarsened during the solution treatment and the strength and bending workability were deteriorated. In addition, the variation in crystal grain size increased. As a result, the variation in characteristics became large.
No. In alloys 55 to 56, the amount of Co added was too large, so that the strength and conductivity deteriorated.
No. In the alloys 57 to 64, the aging temperature of the first temporary effect treatment was too high, and the second-phase particles grew non-uniformly, so that the crystal grain size varied. As a result, the variation in characteristics became large.

Claims

Co: 0.5 to 4.0% by mass, Si: 0.1 to 1.2% by mass, the balance being a copper alloy for electronic materials consisting of Cu and inevitable impurities, having an average crystal grain size of 15 A copper alloy for electronic materials having an average difference of 10 μm or less between the maximum crystal grain size and the minimum crystal grain size for each observation field 0.5 mm 2 ˜30 μm.
Furthermore, the copper alloy for electronic materials of Claim 1 which contains 0.5 mass% of Cr at the maximum.
Furthermore, the copper alloy for electronic materials of Claim 1 or 2 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.
The copper alloy for electronic materials according to any one of claims 1 to 3, further comprising a total of 2.0% by mass of one or two selected from Sn and Zn in total.
The electron according to any one of claims 1 to 4, further comprising a total of 2.0% by mass in total of one or more selected from As, Sb, Be, B, Ti, Zr, Al and Fe. Copper alloy for materials.
-Step 1 of melt casting an ingot having the desired composition;
Perform hot rolling after heating at −950 ° C. to 1050 ° C. for 1 hour or longer, set the temperature at the end of hot rolling to 850 ° C. or higher, and cool at an average cooling rate from 850 ° C. to 400 ° C. to 15 ° C./s or higher. Step 2 and
-Cold rolling step 3 with a working degree of 70% or more;
An aging treatment step 4 of heating at −350 to 500 ° C. for 1 to 24 hours;
Performing a solution treatment at −950 to 1050 ° C., and cooling at an average cooling rate of 15 ° C./s or higher when the material temperature decreases from 850 ° C. to 400 ° C .; and
-Optional cold rolling process 6;
-Aging treatment step 7;
-Optional cold rolling process 8;
The method for producing a copper alloy according to any one of claims 1 to 5, comprising sequentially performing the steps.
A drawn copper product comprising the copper alloy according to any one of claims 1 to 5.
Electronic component comprising the copper alloy according to any one of claims 1 to 5.