JP5690170B2 - Copper alloy - Google Patents

Description

  The present invention relates to a copper alloy having not only good conductivity but also high strength, excellent bending workability, and excellent stress relaxation resistance, in particular, a connector constituting an electric / electronic component, The present invention relates to a copper alloy for electrical and electronic parts that can be suitably used for energized parts such as lead frames, relays, and switches.

  Copper alloy materials used for current-carrying parts such as connectors, lead frames, relays, and switches that make up electrical and electronic parts are required to have good conductivity in order to suppress the generation of Joule heat due to current flow. High strength is required to withstand the stress applied during assembly and operation of electrical / electronic components. Further, electric / electronic parts are generally formed by bending, and excellent bending workability is required for the material for electric / electronic parts to be bent. Furthermore, in order to ensure the contact reliability of electric / electronic parts, it is also required that the contact pressure is reduced with time, that is, it is excellent in stress relaxation resistance which is durability against stress relaxation.

  Methods for increasing the strength of materials used in these current-carrying parts include adding a large amount of solute elements such as Ni and Si, repeating annealing and rolling during manufacturing, and finishing rolling after aging treatment (tempering) A method for increasing the processing rate is generally known. However, the addition of a large amount of solute elements such as Ni and Si causes an increase in the amount of Ni-Si inclusions, resulting in a problem that bending workability is lowered. Further, in the method of increasing the finish rolling (tempering treatment) rate, the Cube azimuth area rate is lowered, and the problem that the bending workability is similarly lowered occurs.

  Moreover, as a method of improving the bending workability of the material used for the current-carrying parts, a method of decreasing the finish rolling (tempering treatment) rate, a method of refining the crystal grain size, or increasing the Cube orientation area ratio Methods are generally known. However, when the crystal grain size is made finer, the problem that the stress relaxation resistance is lowered occurs.

  Furthermore, as a method of improving the stress relaxation resistance of the material used for the current-carrying parts, a method of reducing the finish rolling (tempering treatment) rate and a method of increasing the crystal grain size are generally known. ing.

  Therefore, even with various conventional technologies, it is possible to simultaneously increase the strength of materials used for current-carrying parts that make up electrical and electronic parts, improve bending workability, and improve stress relaxation characteristics. It can be said that it is very difficult. Therefore, in the past, in view of the characteristics required for each current-carrying part to be manufactured, it has been necessary to take a method of responding by appropriately balancing these characteristics. In particular, among the copper alloys, the Corson alloy (Cu—Ni—Si based copper alloy) is excellent in various characteristics and is inexpensive, and therefore is a copper alloy material suitable for energizing parts constituting electric / electronic parts. In recent years, it has been widely adopted.

  In recent years, electronic devices have been reduced in size and weight, and there is a tendency for copper alloy materials used for terminals and connectors to have a particularly high demand for high strength and thinness. Accordingly, among the strengths, a high 0.2% proof stress (YP) in the direction perpendicular to the rolling direction (TD direction) tends to be particularly required from the viewpoint of the contact pressure strength.

  However, in particular, the Corson alloy has a feature that the difference in strength between the rolling parallel direction (LD direction) and the rolling perpendicular direction (TD direction) is large, that is, the strength in the direction perpendicular to the rolling is higher than the strength in the rolling parallel direction. The characteristic is that it is relatively low. Moreover, there is also a feature that the difference between the tensile strength (TS) and the 0.2% proof stress (YP) is large. For this reason, when this Corson alloy is used for a terminal / connector, the proof stress in the direction perpendicular to the rolling becomes low and the contact pressure strength is insufficient.

  In recent years, various methods for improving the bending workability of this Corson alloy have been proposed. For example, Patent Document 1 proposes a technique for controlling the texture of crystal grains as an effective method for improving the bending workability of a Corson alloy. In Patent Document 1, an average crystal grain size of a Corson alloy containing Ni in a range of 2.0 to 6.0% by mass and Si in a range of 4 to 5 by mass ratio of Ni / Si is set to 10 μm or less. The measurement result by the SEM-EBSP method has a texture where the ratio of the Cube orientation {001} <100> is 50% or more, and has a layered boundary that can be observed by a structure observation with a 300 times optical microscope. A copper alloy plate is disclosed.

  Further, according to Patent Document 2, the material surface of a copper alloy containing 0.5 to 4.0% by mass of Ni, 0.5 to 2.0% by mass of Co, and 0.3 to 1.5% by mass of Si. The diffraction intensity from the {111} plane is I {111}, the diffraction intensity from the {200} plane is I {200}, and the diffraction intensity from the {220} plane is I {220}, {311} plane Is the diffraction intensity from {200} plane, and the ratio of the diffraction intensity from {200} plane in these diffraction intensities is R {200} = I {200} / (I {111} + I {200} + I {311}), a proposal has been made regarding a copper alloy for electrical and electronic equipment in which R {200} is 0.3 or more.

Furthermore, according to Patent Document 3, X-ray diffraction of {200} crystal planes on a plate surface of a copper alloy containing 0.7 to 4.0% by mass of Ni and 0.2 to 1.5% by mass of Si. Crystal orientation satisfying I {200} / I ₀ {200} ≧ 1.0, where I {200} and X-ray diffraction intensity of the {200} crystal plane of pure copper standard powder are I ₀ {200} Thus, a proposal has been made regarding a copper alloy sheet material that maintains high strength, has little anisotropy, has excellent bending workability, and has excellent stress relaxation resistance.

Moreover, according to Patent Document 4, in a copper alloy sheet containing Ni: 0.7 to 2.5% and Si: 0.2 to 0.7% by mass, 3.0 ≦ I {220} / I Satisfying ₀ {220} ≦ 6.0, 1.5 ≦ I {200} / I ₀ {200} ≦ 2.5, while maintaining the high strength and excellent bending workability of the Corson alloy Proposals have been made on copper alloy sheet materials with improved anisotropy regarding the characteristics of the above.

Furthermore, according to Patent Document 5, in a copper alloy sheet material containing Ni: 0.7 to 4.2% and Si: 0.2 to 1.0% by mass%, I {420} / I ₀ {420 }> 1.0 has been proposed with respect to a copper alloy sheet that exhibits excellent bending workability and stress relaxation resistance while maintaining high strength and high conductivity.

JP 2006-152392 A JP 2009-7666 A JP 2010-275622 A JP 2008-13836 A JP 2008-223136 A

  The present invention has been made in view of the above-described conventional situation, and it is a copper alloy having not only good conductivity but also high strength, excellent bending workability, and excellent stress relaxation resistance. The issue is to provide.

The invention according to claim 1 is a copper alloy containing Ni: 1.5 to 3.6% and Si: 0.3 to 1.0% by mass, with the balance being made of copper and inevitable impurities. In addition, the average crystal grain size of this copper alloy is 15 to 40 μm, and the average area ratio of the Cube orientation {001} <100> is 45% or more and less than 70% as measured by the SEM-EBSP method. The KAM value is 1.0 to 3.0.

  Invention of Claim 2 is a copper alloy of Claim 1 which contains Sn: 0.05-3.0% and / or Zn: 0.05-3.0% by the mass% further.

  The invention according to claim 3 contains, in mass%, one or more of Fe, Mn, Mg, Co, Ti, Cr, and Zr in a total of 0.01 to 3.0%. 2. The copper alloy according to 2.

  According to the present invention, the copper alloy has not only good conductivity, but also high strength, excellent bending workability, and excellent stress relaxation resistance, that is, bending workability and resistance. A high-strength copper alloy having excellent stress relaxation characteristics can be obtained.

It is a front view which shows the test method which calculates | requires the stress relaxation characteristic of copper alloy in an Example, and shows the state which gave the deflection amount to the strip-shaped test piece. It is a front view which shows the test method which calculates | requires the stress relaxation resistance characteristic of a copper alloy in an Example, and shows a permanent deflection when the deflection amount is removed.

  The most effective method for increasing the strength of a copper alloy is to increase the finish rolling (tempering treatment) rate. However, if the finish rolling (tempering treatment) rate is increased, the bending workability and stress relaxation resistance of the copper alloy will be reduced. Moreover, the most effective means for improving the stress relaxation resistance is to increase the crystal grain size of the copper alloy. However, when the crystal grain size is increased, the bending workability of the copper alloy is reduced. Therefore, when trying to obtain a copper alloy that combines strength, bending workability, and stress relaxation resistance with conventional techniques, the finish rolling (tempering treatment) rate and crystal grain size are controlled to achieve strength. , To obtain a copper alloy that has the contradictory properties of high strength, excellent bending workability, and excellent stress relaxation properties, by adopting a method that appropriately balances bending workability and stress relaxation resistance. Was impossible.

  In view of such conventional problems, the present inventors have intensively conducted experiments and research in order to obtain a copper alloy having high strength, excellent bending workability, and excellent stress relaxation resistance.

  First, the present inventors pay attention to a KAM (Kerner Average Misoration) value correlated with the dislocation density, and by examining the KAM value in detail with SEM-EBSP, it is necessary to increase the strength of the copper alloy. It was found that the reduction ratio of the final cold rolling can be estimated.

  In addition, the present inventors investigated in detail the texture before and after the final cold rolling in the manufacturing process of the copper alloy by SEM-EBSP, and the crystal orientation before rolling was determined even when the copper alloy was rolled. It was found that many crystal grains remained retained. That is, it was confirmed that if the area ratio of the Cube orientation {001} <100> before the final cold rolling is high, the area ratio of the Cube orientation after the final cold rolling can be kept high. In the techniques described in Patent Document 1 and Patent Document 2 described above, the final rolling rate is controlled to be low in order to control the texture. It has been found that the area ratio of the Cube orientation can be increased even if the final rolling rate is increased by repeating the treatment twice and by devising the solution treatment method.

  It was also found that the larger the crystal grain size, the higher the area ratio of the Cube orientation. In particular, when the crystal grain size is 40 μm or less, it is confirmed that the contribution to the improvement in bending workability due to the increase in the area ratio of the Cube orientation exceeds the contribution to the reduction in bending workability due to the coarsening of the crystal grains. We were able to. Therefore, it has been found that the bending workability can be sufficiently maintained by increasing the crystal grain size up to a certain size (40 μm) in order to improve the stress relaxation resistance. It is possible to increase the crystal grain size by devising a solution treatment method.

    As a result of the above experiment and research, the average crystal grain size of the copper alloy is 15 to 40 μm, and the average area ratio of the Cube orientation {001} <100> is 45% or more in the measurement result by the SEM-EBSP method. In addition, by setting the KAM value to 1.0 to 3.0, it is possible to obtain a copper alloy having high strength, excellent bending workability, and excellent stress relaxation resistance, which are the problems of the present invention. The inventors have found that this is possible.

  Hereinafter, embodiments of the present invention will be specifically described for each requirement. First, requirements regarding the structure of the copper alloy of the present invention will be described in order. In the following description, when the average crystal grain size and the average area ratio in the texture are described, “average” may be omitted and the crystal grain diameter and the area ratio may be simply described.

(Average crystal grain size)
The average crystal grain size of the copper alloy is 15 to 40 μm. When the crystal grain size is 40 μm or less, the degree of contribution to the improvement of bending workability due to the increase in the area ratio of the Cube orientation exceeds the degree of contribution to the reduction of bending workability due to the coarsening of the crystal grains. The bending workability of the alloy is improved. However, if the crystal grain size exceeds 40 μm, the contribution due to the coarsening of the crystal grains becomes dominant and the bending workability is lowered. Therefore, the upper limit of the crystal grain size is 40 μm. A more preferable crystal grain size is 30 μm or less. On the other hand, when the crystal grain size is less than 15 μm, the stress relaxation resistance is deteriorated.

(Average area ratio of Cube orientation)
The Cube orientation {001} <100> is an orientation in which more slip systems can be active. By accumulating 45% or more of the Cube orientation by area ratio, it becomes possible to suppress the development of local deformation and improve the bending workability of the copper alloy. If the accumulation rate (area ratio) of the Cube-oriented grains is too low, the development of the local deformation described above cannot be suppressed, and the bending workability of the copper alloy is lowered. Therefore, in the present invention, the average area ratio of the Cube orientation {001} <100> is set to 45% or more, more preferably 50% or more. On the other hand, the larger the crystal grain size of the copper alloy, the higher the area ratio of the Cube orientation. For this reason, it is considered that it is difficult to set the area ratio of the Cube orientation to 70% or more when the crystal grain size capable of obtaining excellent bending workability is 40 μm or less. Therefore, the range of the area ratio of the substantial Cube orientation is 45 to 70%.

(KAM value)
The KAM value is 1.0 to 3.0. If the KAM value is less than 1.0, the dislocation density is insufficient, so that the yield strength is considerably smaller than the tensile strength, and as a result, the yield strength in the direction perpendicular to the rolling direction is reduced. On the other hand, if the KAM value is larger than 3.0, the transition density becomes too high and the bending workability deteriorates.

(Measuring method of average grain size, texture, KAM value)
The present invention uses a crystal orientation analysis method in which a field emission scanning electron microscope (FESEM) is mounted on a field emission scanning electron microscope (FESEM). The texture of the surface portion of the alloy in the plate thickness direction is measured, and the average crystal grain size is measured.

  In the EBSP method, an EBSP is projected onto a screen by irradiating an electron beam onto a sample set in a FESEM column. This is taken with a high-sensitivity camera and captured as an image on a computer. In the computer, the orientation of the crystal is determined by analyzing this image and comparing it with a pattern obtained by simulation using a known crystal system. The calculated crystal orientation is recorded as a three-dimensional Euler angle together with position coordinates (x, y) and the like. Since this process is automatically performed for all measurement points, tens of thousands to hundreds of thousands of crystal orientation data can be obtained at the end of measurement.

  Here, in the case of a normal copper alloy sheet, mainly formed a texture composed of many orientation factors called Cube orientation, Goss orientation, Brass orientation, Copper orientation, S orientation, etc. as shown below. There is a corresponding crystal plane. These facts are described in, for example, “Cross Texture” (published by Maruzen Co., Ltd.) edited by Shinichi Nagashima and “Light Metal” commentary Vol. 43, 1993, P285-293, and the like. The formation of these textures differs depending on the processing and heat treatment methods even in the case of the same crystal system. In the case of a texture of a plate material by rolling, it is expressed by a rolling surface and a rolling direction, the rolling surface is expressed by {ABC}, and the rolling direction is expressed by <DEF> (ABCDEF indicates an integer). Based on the expression, each direction is expressed as follows.

Cube orientation {001} <100>
Goss orientation {011} <100>
Rotated-Goss orientation {011} <011>
Brass orientation {011} <211>
Copper orientation {112} <111>
(Or D direction {4411} <11118>)
S orientation {123} <634>
B / G direction {011} <511>
B / S orientation {168} <211>
P direction {011} <111>

  In the present invention, basically, those whose orientations deviate within ± 15 ° from these crystal planes belong to the same crystal plane (orientation factor). Further, a boundary between crystal grains in which the orientation difference between adjacent crystal grains is 5 ° or more is defined as a crystal grain boundary.

  In addition, in the present invention, the measurement area 300 × 300 μm is irradiated with an electron beam at a pitch of 0.5 μm, the number of crystal grains measured by the crystal orientation analysis method is n, and each measured crystal grain size is x The average crystal grain size is calculated as (Σx) / n.

  In the present invention, the measurement area 300 × 300 μm is irradiated with an electron beam at a pitch of 0.5 μm, the crystal orientation area measured by the crystal orientation analysis method is measured, and the average of each orientation relative to the measurement area is measured. The area ratio was determined.

  Here, the crystal orientation distribution may be distributed in the thickness direction. Therefore, it is preferable to obtain some points arbitrarily in the thickness direction by obtaining an average.

  Moreover, KAM value was calculated | required by measuring the orientation difference in a crystal grain using EBSP. This KAM value was defined as (Σy) / n, where n is the number of crystal grains and y is the orientation difference of each measured crystal grain. This KAM value has been reported to correlate with the dislocation density, which is described in, for example, “Materials” (Journal of the Society of Materials Science, Japan) Vol. 58, no. 7, P568-574, July 2009, and the like.

(Chemical composition of copper alloy)
Next, the reasons for limiting the components of the copper alloy of the present invention will be described. Hereinafter, the content of each element is simply described as%, but all indicate mass%.

Ni: 1.5-3.6%
Ni has the effect of securing the strength and conductivity of the copper alloy by crystallizing or precipitating a compound with Si. If the Ni content is less than 1.5%, the amount of precipitates generated becomes insufficient, the desired strength cannot be obtained, and the crystal grains of the copper alloy structure become coarse. On the other hand, if the Ni content exceeds 3.6%, the electrical conductivity is lowered, and the number of coarse precipitates is excessively increased, so that the bending workability is lowered. Therefore, the Ni content is in the range of 1.5 to 3.6%.

  Note that the strength level of the copper alloy varies depending on the Ni content. When the Ni content is 1.5% or more and less than 2.0%, the 0.2% proof stress (YP) in the direction perpendicular to the rolling direction (TD direction) is 650 MPa or more. At this time, bending workability becomes evaluation criteria A-B indicated in Japan Copper and Brass Association technical standard JBMA-T307. Further, when the Ni content is 2.0 to 3.6%, the 0.2% yield strength (YP) in the direction perpendicular to the rolling direction (TD direction) is 700 MPa or more. At this time, bending workability becomes evaluation criteria AC described in Japan Copper and Brass Association technical standard JBMA-T307.

Si: 0.3 to 1.0%
Si improves the strength and electrical conductivity of the copper alloy by crystallizing or precipitating a compound with Ni. If the Si content is less than 0.3%, the formation of precipitates becomes insufficient, the desired strength cannot be obtained, and the crystal grains of the copper alloy structure become coarse. On the other hand, when the content of Si exceeds 1.0%, the number of coarse precipitates is excessively increased and bending workability is deteriorated. Therefore, the Si content is in the range of 0.3 to 1.0%.

  The strength level of the copper alloy varies depending on the Si content. When the Si content is 0.3% or more and less than 0.5%, the 0.2% yield strength (YP) in the direction perpendicular to the rolling direction (TD direction) is 650 MPa or more. At this time, bending workability becomes evaluation criteria A-B indicated in Japan Copper and Brass Association technical standard JBMA-T307. When the Si content is 0.5 to 1.0%, the 0.2% proof stress (YP) in the direction perpendicular to the rolling direction (TD direction) is 700 MPa or more. At this time, bending workability becomes evaluation criteria AC described in Japan Copper and Brass Association technical standard JBMA-T307.

  The copper alloy of the present invention is composed of copper and unavoidable impurities in addition to the above elements, but may contain the following elements alone or in combination.

Zn: 0.05-3.0%
Zn is an element effective for improving the heat-resistant peelability of Sn plating and solder used for joining electronic components and suppressing thermal peeling. In order to exhibit such an effect effectively, it is necessary to contain 0.05% or more. However, if the Zn content exceeds 3.0%, the wet-spreading property of molten Sn and solder is deteriorated, and the electrical conductivity is greatly reduced. Therefore, Zn takes the range of 0.05 to 3.0% in consideration of the heat resistant peelability improving effect and the conductivity lowering effect.

Sn: 0.05-3.0%
Sn dissolves in the copper alloy and contributes to strength improvement. In order to exhibit this effect effectively, it is necessary to contain 0.05% or more. However, if the Sn content exceeds 3.0%, the effect is saturated and the conductivity is greatly reduced. Therefore, Sn is taken in the range of 0.05 to 3.0% in consideration of the strength improvement effect and the conductivity lowering effect.

0.01 to 3.0% of one or more of Fe, Mn, Mg, Co, Ti, Cr and Zr in total
These elements are effective in reducing the crystal grains. Further, by forming a compound with Si, the strength and conductivity are improved. In order to effectively exhibit these effects, it is necessary to selectively contain one or more of Fe, Mn, Mg, Co, Ti, Cr, and Zr in a total of 0.01% or more. . However, if the total content of these elements exceeds 3.0%, the compound becomes coarse and the bending workability is impaired. Therefore, the content of these elements when selectively contained is in the range of 0.01 to 3.0% in total. In the examples to be described later, these elements are only examples of one kind, but these elements express the above-mentioned common effect, and these elements are classified into two kinds with the predetermined total content. Even if it contains above, the same effect is expressed.

(Production conditions)
In order to produce the copper alloy (copper alloy plate) of the present invention, it is necessary to repeat the solution treatment twice in a series of production processes of the copper alloy and to devise a solution treatment method. is there. The series of manufacturing steps will be described in the order of processes: hot rolling, cold rolling, solution treatment (first time), cold rolling, solution treatment (second time), aging treatment, and cold rolling. At this time, the solution treatment may be repeated twice or more. In order to produce the copper alloy of the present invention, the solution treatment (first and second times) out of these series of steps needs to be devised and controlled in detail.

  In both the solution treatment (first time) and the solution treatment (second time), the temperature increase rate is set to 0.1 ° C./s or less, and the temperature decrease rate is set to 100 ° C./s or more. When the rate of temperature increase is higher than 0.1 ° C./s, it becomes difficult to set the area ratio of the Cube orientation of the copper alloy to 45% or more, and the bending workability is described in the Japan Copper and Brass Association Technical Standard JBMA-T307. It will fall below evaluation standard D. On the other hand, when it becomes slower than 100 ° C./s, precipitation occurs during cooling, and sufficient precipitation cannot be obtained by the subsequent aging treatment, and the strength of the copper alloy is lowered.

  The treatment temperature for the solution treatment (first time) is 750 to 850 ° C., and the treatment temperature for the solution treatment (second time) is not less than 900 ° C. and not less than the treatment temperature of the solution treatment (first time). When at least one of the solution treatment temperatures (first and second times) is lower than the above-mentioned minimum temperature, it becomes difficult to make the area ratio of the Cube orientation of the copper alloy 45% or more, and the bending workability deteriorates. Resulting in. On the other hand, when at least one of the solution treatment temperatures (first and second times) is higher than the above-described maximum temperature, the average crystal grain size of the copper alloy is likely to be 40 μm or more, and the bending workability is increased. It will deteriorate.

  After the solution treatment, the copper alloy of the present invention is produced by performing aging treatment-final cold rolling-low temperature annealing as in the case of producing a general copper alloy. The aging treatment temperature is preferably 400 to 500 ° C. Moreover, the rolling reduction of final cold rolling shall be 25 to 60%. When the rolling reduction is less than 25%, the KAM value becomes small and the strength is lowered. On the other hand, when the rolling reduction exceeds 60%, the KAM value often exceeds 3.0, and sufficient bending workability cannot be obtained.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, and the present invention is implemented with appropriate modifications within a range that can meet the gist of the present invention. These are all included in the technical scope of the present invention.

  Examples of the present invention will be described below. Copper alloy thin plates of Cu—Ni—Si—Zn—Sn based copper alloys having various chemical composition shown in Table 1 were produced under various conditions shown in Table 1, and average crystal grain size, texture, KAM value, etc. The plate properties, such as the plate structure, strength and conductivity, bending workability, and stress relaxation resistance were investigated and evaluated. The results are shown in Table 2 and Table 3.

  A specific method for producing a copper alloy plate is as follows: a kryptor furnace is melted in the atmosphere under charcoal coating, cast into a cast iron book mold, and a 50 mm thick ingot having the chemical composition shown in Table 1 is obtained. It was. And after chamfering the surface of the ingot, it was hot-rolled at a temperature of 950 ° C. until the thickness became 20 to 30 mm, and rapidly cooled in water from a temperature of 750 ° C. or higher. Next, after removing the oxide scale on the surface, cold rolling was performed until the thickness became 0.25 to 0.45 mm.

  Then, using a batch furnace with a temperature rising rate of 0.03 to 0.05 ° C./s, a salt bath furnace with a temperature rising rate of 10 to 50 ° C./s, or an electric heater, various types described in Table 1 Under the conditions, solution treatment (first time) was performed, followed by water cooling.

  Subsequently, the copper alloy plate was cold-rolled to make the thickness of the copper alloy plate 0.2 to 0.35 mm. Then, using a batch furnace with a temperature rising rate of 0.03 to 0.05 ° C./s, a salt bath furnace with a temperature rising rate of 10 to 50 ° C./s, or an electric heater, various types described in Table 1 Under the conditions, solution treatment (second time) was performed, and then water cooling was performed.

  The samples after solution treatment (annealing) were subjected to aging treatment-final cold rolling to obtain a copper alloy plate having a thickness of 0.15 mm. The copper alloy sheet cold-rolled sheet was subjected to a low-temperature annealing treatment of 480 ° C. × 30 s in a salt bath furnace to obtain a final copper alloy sheet.

(Metal structure)
Average crystal grain size, average area ratio in each orientation, and KAM value:
A structure observation piece was collected from each obtained copper alloy thin plate, and in the manner described above, the average crystal grain size and the average area ratio of each orientation were measured, and a crystal mounted with a backscattered electron diffraction image system on a field emission scanning electron microscope. Measured by orientation analysis. Specifically, the surface of the rolled surface of the copper alloy thin plate was mechanically polished, and further subjected to electrolytic polishing after buffing to prepare a sample whose surface was adjusted. Thereafter, crystal orientation measurement and crystal grain size measurement by EBSP were performed using FESEM (JEOL JSM 5410) manufactured by JEOL Ltd. The measurement area was an area of 300 μm × 300 μm, and the measurement step interval was 0.5 μm.

  The KAM value was obtained by measuring the orientation difference in the crystal grains using EBSP. This KAM value was defined as (Σy) / n, where n is the number of crystal grains and y is the orientation difference of each measured crystal grain.

Tensile test:
The tensile test was performed using a JIS No. 13 B test piece in which the longitudinal direction of the test piece was the rolling direction, at a room temperature, a test speed of 10.0 mm / min, and GL = 50 mm using a 5882 type Instron universal testing machine And 0.2% proof stress (MPa) was measured. In this tensile test, three test pieces under the same conditions were tested, and the average value thereof was adopted.

  In this tensile test, the Ni content is 1.5 to 3.6%, the Si content is 0.3 to 1.0%, and the Ni content is 1.5% or more and 2.0%. Or 0.2% proof stress (YP) in the direction perpendicular to the rolling direction (TD direction) when the condition that the Si content is 0.3% or more and less than 0.5% is also satisfied. A thing of 650 MPa or more is evaluated as having high strength. Other than that, a 0.2% yield strength (YP) in the direction perpendicular to the rolling direction (TD direction) of 700 MPa or more is evaluated as having high strength.

conductivity:
Conductivity is measured by measuring the electrical resistance with a double-bridge resistance measuring device by processing a strip-shaped test piece having a width of 10 mm and a length of 300 mm by milling with the longitudinal direction of the test piece as the rolling direction. Calculated by the method. In this measurement as well, three test pieces under the same conditions were measured and the average value thereof was adopted. In this measurement, one having an electrical conductivity of 30% IACS or higher is evaluated as having high conductivity.

Bending workability:
The bending test of the copper alloy plate sample was performed by the following method. A plate material having a width of 10 mm and a length of 30 mm is cut out from a copper alloy plate sample, and is bent 90 ° to Good Way (the bending axis is perpendicular to the rolling direction) under a condition of a bending radius of 0.10 mm under a load of 1000 kgf (about 9800 N). went. Thereafter, 180 ° contact bending was performed with a load of 1000 kgf (about 9800 N), and the presence or absence of cracks in the bent portion was visually observed with a 50 × optical microscope. In that case, the evaluation of the crack was evaluated by A to E described in the Japan Copper and Brass Association Technical Standard JBMA-T307.

  In this bending test, the Ni content is 1.5 to 3.6%, the Si content is 0.3 to 1.0%, and the Ni content is 1.5% or more and 2.0%. Less than or less than 0.5% or less than 0.5% of the condition, if the evaluation criteria described in JBMA-T307, the Japan Copper and Brass Association Technical Standard is B or more Suppose that bending workability is excellent. In addition, it is assumed that bending workability is excellent when the evaluation standard described in the Japan Copper Bending Association Technical Standard JBMA-T307 is C or higher.

Stress relaxation resistance:
The stress relaxation resistance (stress relaxation rate) was measured using a cantilever method shown in FIGS. 1 and 2 by collecting a test piece from a copper alloy plate sample. Specifically, first, a strip-shaped test piece 1 having a width of 10 mm was cut out from a copper alloy plate sample so that the length direction was a direction perpendicular to the rolling direction of the plate material. Subsequently, after fixing one end of the strip-shaped test piece 1 to the rigid body test stand 2, a size of d (= 10 mm) as shown in FIG. The amount of deflection was given. The span length L is determined such that a surface stress corresponding to 80% of the material yield strength is applied to the material. In this state, the strip-shaped test piece 1 is kept in an oven at 180 ° C. for 24 hours and then taken out, and the permanent strain δ (shown in FIG. 2) when the deflection amount d is removed is measured, and RS = (δ / d ) × 100, the stress relaxation rate (RS:%) was obtained. In this measurement, a stress relaxation rate of 20% or less is considered excellent in stress relaxation resistance.

  In Invention Examples 1 to 15 shown in Table 1, as shown in Table 2, the average crystal grain size, the average area ratio of the Cube orientation, and the KAM value are controlled within specified ranges.

  As a result, in these inventive examples, as shown in Table 3, the above-described acceptance criteria for the copper alloy of the present invention were satisfied.

  On the other hand, in Comparative Examples 16 to 19, the content of any alloy element does not satisfy the range defined in the present invention. In Comparative Examples 20 to 29, any one or more of the average crystal grain size, the average area ratio of the Cube orientation, and the KAM value could not be controlled within the range defined by the present invention.

  As a result, as shown in Table 3, in these comparative examples, at least one item was not satisfied among the acceptance criteria of the copper alloy of the present invention described above.

1 ... Strip-shaped specimen 2 ... Rigid body test stand

Claims (3)

It is a copper alloy containing Ni: 1.5-3.6%, Si: 0.3-1.0%, and the balance consisting of copper and inevitable impurities,
The average crystal grain size of this copper alloy is 15-40 μm,
And as a result of measurement by the SEM-EBSP method, the average area ratio of the Cube orientation {001} <100> is 45% or more and less than 70% ,
A copper alloy having a KAM value of 1.0 to 3.0.   Furthermore, the copper alloy of Claim 1 which contains Sn: 0.05-3.0% and / or Zn: 0.05-3.0% by the mass%.   Furthermore, the copper alloy of Claim 1 or 2 which contains 0.01-3.0% in total of 1 type, or 2 or more types among Fe, Mn, Mg, Co, Ti, Cr, Zr by the mass%.