JP2010150669A - Copper alloy material for electrical and electronic device, and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a copper alloy material for electrical and electronic devices which has excellent stress relaxation resistance, electric conductivity, strength, bendability and solder adhesion, and to provide a method for producing the same. <P>SOLUTION: The copper alloy material includes, by mass, 1 to 3% Ni, 0.2 to 1.2% Ti, 0.02 to 0.2% Sn and/or Si and 0.1 to 1% Zn, and the balance Cu with inevitable impurities, and contains at least one selected from among an intermetallic compound containing Ni, Ti and Sn, an intermetallic compound containing Ni, Ti and Si and an intermetallic compound containing Ni, Ti, Sn and Si, wherein the mean particle diameter of the intermetallic compound containing Ni, Ti and Sn, an intermetallic compound containing Ni, Ti and Si or an intermetallic compound containing Ni, Ti, Sn and Si is 5 to 100 nm; distribution density is 1×10<SP>10</SP>to 10<SP>13</SP>pieces/mm<SP>2</SP>; the crystal grain size of a basal phase is 4 to 10 μm; electric conductivity is ≥47.6%IACS; and a stress relaxation rate when it is held at 150°C for 1,000 hr is ≤20%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a copper alloy material for electrical and electronic equipment, and more particularly to a copper alloy material for electrical and electronic equipment suitable for connectors and terminal materials such as connectors and terminal materials for electronic and electrical equipment.

Conventionally, as materials for electrical and electronic equipment, in addition to stainless steel, copper (Cu) materials such as phosphor bronze, red brass, brass, etc., which are excellent in electrical conductivity and thermal conductivity, have been widely used.
In recent years, there has been an increasing demand for miniaturization and weight reduction of electric and electronic equipment and further high density mounting. As miniaturization progresses, the contact area of the contact portion decreases, the thickness of the plate used decreases, and a higher-strength material is required to maintain the same level of reliability as before. In general, a connector “bends” a material, that is, deforms to generate a predetermined contact pressure, and perform electrical conduction and exchange of information signals by a mechanism that fits (joins) each other. Accordingly, it is a fatal defect that the force for fitting (joining) is reduced due to the reduction of the contact pressure during use, and the power supply and the exchange of information signals cannot be performed. This decrease in fitting (joining) force is called stress relaxation (creep resistance) characteristics, and the stress relaxation characteristics do not deteriorate, that is, copper alloys with excellent stress relaxation characteristics are required for materials used in these electronic components. Yes.

Also, depending on the type of connector, it may be connected to a device that generates heat, such as a CPU (integrated processing unit) such as a personal computer. In this case, since the connector material is heated, stress relaxation is promoted and the fitting (joining) force is quickly reduced. Therefore, it is necessary to have a function of quickly dissipating heat. The heat dissipation characteristic is caused by the conductivity of the material, and a material having higher conductivity is required. In addition, the request | requirement of the material with high electroconductivity is also requested | required from the exchange of information using a future high frequency.
Furthermore, miniaturization of electronic and electrical equipment requires materials to have good bending workability. One direction of downsizing is the thinning of equipment. Thinner connectors will lead to lower connector height (low height). Therefore, a material with better workability is required for the connector.

For these reasons, a material having high strength, maintaining excellent conductivity, and excellent stress relaxation resistance and bending workability is desired. Specifically, the strength is 600 MPa or more, the electrical conductivity is preferably 50% IACS or more, the stress relaxation rate is 150 ° C x 1000h after 20% or less, and the R / t of the bending workability guideline is desirable. A material having a performance of 1 or less is required.
As methods for increasing the strength of metal materials, there are generally used the process strengthening method that introduces processing strain into the material, the solid solution strengthening method that dissolves other elements in solid solution, and the precipitation strengthening method that precipitates and strengthens the second phase. Yes.

There are a Cu-Be alloy (C17200), a Cu-Ni-Si alloy (C70250), a Cu-Fe alloy (C19400), a Cu-Cr alloy (C18040), etc. using a precipitation strengthening method. However, C17200 uses a strengthening mechanism that precipitates Be in the Cu matrix, so that the strength is 1000 MPa or more, the stress relaxation rate is 20% or less, and the bending workability is good, but the conductivity is about 25% IACS. is there. It is also true that beryllium (Be) is concerned about its use due to its environmental problems.
C70250 has a strength of 600 MPa or more, a stress relaxation rate of 20% or less, and good bending workability by precipitating an intermetallic compound consisting of Ni-Si in the Cu matrix, but it has a conductivity of 50% IACS or more. do not become.

C19400 uses a strengthening mechanism that precipitates iron (Fe) in the Cu matrix, and its strength is 600MPa and conductivity is about 65% IACS, but the stress relaxation rate and bending workability have the required characteristics. I'm not satisfied.
The electrical conductivity of C18040 is about 80% IACS and the strength is about 600MPa. Like C19400, the stress relaxation rate and bending workability cannot satisfy the required characteristics.
Thus, there is no material that can satisfy the characteristics required by any precipitation strengthening technique, and there is a strong demand for the development of new materials.

On the other hand, in the copper alloy material for electronic devices, there is an example in which Ni-Ti intermetallic compounds are uniformly and finely precipitated in a Cu matrix to improve strength and conductivity (for example, Patent Document 1).
Moreover, there is an example in which the adhesion between the lead frame and the resin is improved by adding aluminum (Al), silicon (Si), manganese (Mn), and magnesium (Mg) to the Cu-Ni-Ti alloy ( For example, Patent Document 2).
However, even these copper alloy materials cannot satisfy the strength, electrical conductivity, bending workability, and stress relaxation resistance at the same time. I can't meet.

JP-A-63-219540 JP-A 61-157651

  Accordingly, an object of the present invention is to provide a new copper alloy material for electrical and electronic equipment and a method for producing the same, which are excellent in strength, electrical conductivity, bending workability, stress relaxation resistance, and solder adhesion.

The present inventors are a precipitation strengthening method that precipitates and strengthens the second phase, and in the course of conducting research on strengthening with an intermetallic compound composed of nickel (Ni) and titanium (Ti), tin (Sn), silicon By changing the intermetallic compound by adding (Si), it is possible to produce a material that can almost satisfy the required properties of strength, electrical conductivity, bending workability, stress relaxation resistance, and solder adhesion. I found.
That is, the present invention
(1) Ni is 1 to 3 mass%, Ti is 0.2 to 1.2 mass%, one or both of Sn and Si is 0.02 to 0.2 mass%, Zn is 0.1 to 1 mass%, and The remainder consists of impurities that are unavoidable with Cu, intermetallic compounds composed of Ni, Ti, and Sn, intermetallic compounds composed of Ni, Ti, and Si, or intermetallic compounds composed of Ni, Ti, Sn, and Si. The average particle size of an intermetallic compound containing at least one, consisting of Ni, Ti, and Sn, an intermetallic compound consisting of Ni, Ti, and Si, or an intermetallic compound consisting of Ni, Ti, Sn, and Si is 5 ~ 100nm, distribution density is 1 × 10 ¹⁰ ~ 10 ¹³ / mm ² , crystal grain size of parent phase is 4μm or more and 10μm or less, conductivity is 47.6% IACS or more, and kept at 150 ° C for 1000 hours A copper alloy material for electrical and electronic equipment, characterized by having a stress relaxation rate of 20% or less when
(2) A method for producing a copper alloy material for electrical and electronic equipment according to (1), wherein a solution treatment is performed at 850 ° C. or more for 35 seconds or less, and the solution treatment temperature is 50 ° C./sec or more. Electrical and electronic equipment characterized in that it is cooled to 300 ° C at a cooling rate of 50 ° C, then cold-rolled at a rolling rate exceeding 0% and 50% or less, and subjected to aging treatment at 450 to 600 ° C for 5 hours or less Method for producing copper alloy material,
(3) A method for producing a copper alloy material for electrical and electronic equipment according to (1), wherein a solution treatment is performed at 850 ° C. or more for 35 seconds or less, and the solution treatment temperature is 50 ° C./sec or more. And cooling to 300 ° C. at a cooling rate of 450 ° C., followed by aging treatment within 450 hours at 450 to 600 ° C. to provide a method for producing a copper alloy material for electrical and electronic equipment.
In the present invention, the electric and electronic equipment includes in-vehicle equipment.

  The copper alloy material of the present invention is excellent in strength, electrical conductivity, bending workability, stress relaxation resistance, and solder adhesion. Furthermore, the strength should be 600 MPa or more, the stress relaxation rate should be 20% or less after 150 ° C x 1000h, the conductivity should be 47.6% IACS or more, and the bending workability guideline R / t should be 1 or less. These metal materials are alloy materials suitable for electrical and electronic equipment, on-vehicle terminals / connectors, relay switches, and the like.

It is typical explanatory drawing of the test method of a stress relaxation characteristic. It is a typical explanatory view of a solder adhesion test method.

The preferred embodiments of the present invention will be described below.
In the present invention, an intermetallic compound composed of Ni, Ti, and Sn (hereinafter referred to as “Ni—Ti—Sn”) precipitated in the Cu matrix, and an intermetallic compound composed of Ni, Ti, and Si (hereinafter, “ Ni-Ti-Si ") or an intermetallic compound consisting of Ni, Ti, Sn and Si (hereinafter referred to as" Ni-Ti-Sn-Si ") significantly improves the properties of the alloy. Let This is completely different from the case where Ni-Ti precipitates are formed in the conventional alloys, and these intermetallic compounds exhibit extremely high stress relaxation resistance.

  As described above, when Ni—Ti is finely dispersed in the Cu matrix, the strength is improved by the precipitation strengthening mechanism, and at the same time, the conductivity is increased. At this time, Ni-Ti-Sn, Ni-Ti-Si or Ni-Ti-Sn-Si was individually or combined and finely dispersed in the Cu matrix, and compared with the case where Ni-Ti was precipitated. And shows a very large amount of reinforcement. By this effect, a material having good strength and conductivity can be obtained. In addition, even if the Ni-Ti compound is dispersed at the same time, the effect appears, and the higher the dispersion density of Ni-Ti-Sn, Ni-Ti-Si or Ni-Ti-Sn-Si, the greater the amount of reinforcement. . In that case, the dispersion density of Ni—Ti—Sn, Ni—Ti—Si, or Ni—Ti—Sn—Si is preferably equal to or greater than that of Ni—Ti.

Next, stress relaxation characteristics will be described. Compared to the case where Ni-Ti is finely dispersed in the Cu matrix, Ni-Ti-Sn, Ni-Ti-Si, or Ni-Ti-Sn-Si are individually or combined in the Cu matrix. When it is finely dispersed, the stress relaxation resistance is remarkably improved. On the other hand, the stress relaxation rate cannot be achieved below 20% with Ni-Ti precipitates alone.
This is because the crystal structure of Ni-Ti-Sn, Ni-Ti-Si or Ni-Ti-Sn-Si is different from that of Ni-Ti compounds. It is thought that the stress relaxation resistance can be remarkably improved by finely dispersing the intermetallic compounds having different crystal structures in the Cu matrix.

Stress relaxation is a phenomenon in which dislocations in a metal move and strain is released, and the force to fix the dislocations is Ni-Ti-Sn, Ni-Ti-Si, or Ni-Ti-Sn-Si. A phenomenon that is larger than Ni-Ti compounds and difficult to relax was found.
This desired property can be obtained by the content of the components specified below.

  The reason why the Ni content is limited to 1 to 3 mass% is that if it is less than 1 mass%, the amount of strengthening by precipitation is small and sufficient strength cannot be obtained, and the stress relaxation characteristics cannot be improved. In addition, if Ni exceeds 3 mass%, excessive Ni is dissolved in the matrix even after the aging treatment, leading to a decrease in conductivity. Further, the solution treatment temperature becomes a temperature near the melting point, and it cannot be produced by an industrially stable process. Furthermore, a solution treatment for a long time at a high temperature is required, and the problem arises that the crystal grains become coarse and bending workability is poor. The content of Ni is preferably 1.4 to 2.6 mass%, more preferably 1.8 to 2.3 mass%.

  The reason for limiting the Ti content to 0.2 to 1.2 mass% is that if it is less than 0.2% mass, the amount of strengthening due to precipitation is small and sufficient strength cannot be obtained, and the stress relaxation characteristics cannot be improved. It is. Moreover, when Ti exceeds 1.2 mass%, excessive Ti is dissolved in the matrix even after the aging treatment, so that the conductivity is lowered. In addition, a solution treatment for a long time at a high temperature is required, resulting in a problem that the crystal grains become coarse and bending workability is poor. The Ti content is preferably 0.5 to 1.1 mass%, more preferably 0.7 to 1.0 mass%.

  Sn forms precipitates with Ni, Ti, and Si, and improves strength, conductivity, bending workability, stress relaxation characteristics, and the like. The reason why the Sn content is limited to 0.02 to 0.2 mass% is that when it is less than 0.02 mass%, the stress relaxation rate is inferior because there are few precipitates composed of Ni, Ti, and Sn. On the other hand, if it exceeds 0.2 mass%, excessive Sn remains in a solid solution, resulting in poor conductivity and bending workability. Moreover, the stress relaxation rate is inferior. This seems to be due to the fact that the constituent ratios of the elements in the precipitates are different. The Sn content is preferably 0.05 to 0.15 mass%, more preferably 0.08 to 0.12 mass%.

  The reason why the Si content is limited to 0.02 to 0.2 mass% is that when it is less than 0.02 mass%, the stress relaxation rate is inferior because there are few precipitates composed of Ni, Ti, and Si. In addition, the conductivity is inferior because excess Si is dissolved in the matrix. Furthermore, the stress relaxation rate is inferior. This seems to be due to the fact that the constituent ratios of the elements in the precipitates are different. On the other hand, when the content exceeds 0.2 mass%, when a desired precipitate is formed, excess Si is dissolved in the copper matrix and the conductivity is lowered. The Si content is preferably 0.05 to 0.15 mass%, more preferably 0.08 to 0.12 mass%.

The intermetallic compound has a size and an average particle diameter of 1 to 100 nm as an equivalent volume sphere equivalent diameter, and a distribution density of 1 × 10 ¹⁰ to 10 ¹³ particles / mm ² provides strength and bending workability. Excellent and preferable.
If the average particle size of the intermetallic compound is less than 5 nm, the effect of improving the strength by precipitation is insufficient, and if it exceeds 100 nm, the problem of not contributing to the improvement of the strength by precipitation occurs. The average particle size is more preferably 10 to 60 nm, and more preferably 20 to 50 nm.
Moreover, if the distribution density of intermetallic compounds is less than 1 × 10 ¹⁰ pieces / mm ² , the effect of improving the strength by precipitation is insufficient, and if it exceeds 1 × 10 ¹³ pieces / mm ² , coarse precipitates are formed at the grain boundaries. It becomes easy to form and the problem of deteriorating bending workability occurs. The distribution density is more preferably 3 × 10 ^{10 to} 5 × 10 ¹² pieces / mm ² , more preferably 1 × 10 ^{11 to} 3 × 10 ¹² pieces / mm ² .
On the other hand, the crystal grain size of the parent phase is preferably 10 μm or less. If it exceeds 10 μm, the bending workability will deteriorate. Preferably it is 5 micrometers or less. Here, the crystal grain size refers to the major axis.

  Zn improves solder adhesion and has the effect of preventing plating peeling. A preferred application of the present invention is electronic equipment, many of which are joined with solder. Therefore, the improvement in solder adhesion leads to an improvement in the reliability of parts, which is an essential characteristic required for electronic equipment applications. There is a recent debate on the effect of Zn (for example, Journal of Copper Technology Research vol. 026 (1987) p51-p56). Among these, when Zn is added, the heat-resistant peelability is considered good. The addition of Zn suppresses the formation of voids and suppresses the concentration of Ni and Si at the interface between the base material and the diffusion layer, thereby improving the heat-resistant peelability. This example is a Cu-Ni-Si alloy of the same precipitation type alloy, but the same effect was confirmed in the present invention.

  The reason why the content of Zn is limited to 0.1 to 1 mass% is that if it is less than 0.1 mass%, the effect of the heat-resistant peeling property does not appear, and if it exceeds 0.5 mass%, there is a problem that the conductivity is lowered. It is. The Zn content is preferably 0.2 to 0.8 mass%, more preferably 0.35 to 0.65 mass%.

The copper alloy material according to the present invention is produced, for example, by processes such as hot rolling, cold rolling, solution treatment, aging treatment, and further finish cold rolling and strain relief annealing as necessary. In this production process, the intermetallic compound can be brought within the scope of the present invention by controlling the conditions of the solution treatment (temperature) and the cooling rate in the subsequent cooling. The hot rolling temperature is, for example, 850 to 1000 ° C., and the cold rolling performed next can be performed at a processing rate of 90% or more, for example.
Further, in one embodiment of the production method of the present invention, a solution treatment is performed at 850 ° C. or more for 35 seconds or less, and the solution treatment temperature is cooled to 300 ° C. at a cooling rate of 50 ° C./sec or more. Cold rolling is performed at a rolling processing rate exceeding 0% and 50% or less, and aging treatment is performed at 450 to 600 ° C. within 5 hours. Further, in another embodiment of the production method of the present invention, a solution treatment is performed at 850 ° C. or more within 35 seconds, and the solution treatment temperature is cooled to 300 ° C. at a cooling rate of 50 ° C./sec or more. Next, an aging treatment is performed at 450 to 600 ° C. within 5 hours.
Subsequent finish cold rolling is preferably 30% or less.

In the present invention, the solution treatment is preferably performed at 850 ° C. or higher and within 35 seconds. When the temperature is lower than 850 ° C., recrystallization is not performed, and the bending workability is greatly reduced (deteriorated). Moreover, even when recrystallization is performed, it becomes an unsolubilized state, and there are crystallized substances and coarse precipitates, and the maximum precipitation strengthening amount cannot be obtained by later aging. Furthermore, there is a concern that bending workability may be reduced due to the remaining of these. The cooling after the solution treatment is preferably performed at 300 ° C. at a cooling rate of 50 ° C./second or more. This is because once it is less than 50 ° C./second, the element once dissolved causes precipitation. The precipitate in that case is coarse and therefore does not contribute to strengthening.
The upper limit of the solution temperature is preferably 1000 ° C. or less from the viewpoint of the cost of fuel and the like. When the solution time exceeds 35 seconds, the bending workability deteriorates due to the coarsening of crystal grains. More preferably, it is within 25 seconds.

The cold rolling subsequent to the solution treatment is not performed or, if it is performed, the cold working rate is preferably 50% or less. If it exceeds 50%, the bending workability deteriorates. More preferably, it is 30% or less.
The aging treatment is preferably performed at 450 to 600 ° C. within 5 hours. If it is less than 450 ° C, precipitation is insufficient and the strength is insufficient. If the temperature exceeds 600 ° C., the precipitate becomes coarse and does not contribute to the strength. Preferably it is 480 degreeC-560 degreeC.

  In the present invention, the final plastic working direction refers to the rolling direction when the last plastic working is rolling, and the drawing direction when drawing (drawing). The plastic processing is rolling processing or drawing processing, and does not include processing for the purpose of correction (straightening) such as a tension leveler.

  The copper alloy material for electrical and electronic equipment of the present invention is not limited thereto, but can be suitably used for connectors, terminals, relays / switches, lead frames, and the like.

  Next, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.

<Production Example 1>
An alloy having a composition containing Ni, Ti, Mg, Zr, Zn, Sn, and Si shown in Tables 1 to 3 and the balance being Cu is melted in a high-frequency melting furnace, and this is melted at 10 to 30 ° C./second. An ingot having a thickness of 30 mm, a width of 100 mm, and a length of 150 mm was obtained by casting at a cooling rate. After holding the ingot at 1000 ° C. for 1 hour, a hot rolled sheet having a thickness of about 10 mm was finished with a hot rolling mill. The hot-rolled material was scraped about 1.0 mm on both sides to remove the oxide film, then cold-rolled to a thickness of 0.29 mm, and then subjected to a solution treatment in an inert gas at 950 ° C. for 15 seconds. The cooling rate after conversion to 300 ° C. was about 3 seconds (about 300 ° C./second). Further, it was cold-rolled to 0.23 mm, subjected to aging treatment at 550 ° C. for 2 hours, rolled to a thickness of 0.2 mm, and then subjected to low-temperature annealing at 350 ° C. for 2 hours to obtain Reference Examples 1 to 18 and Invention Example 40. To 57 and Comparative Examples 60 to 67 and Comparative Examples 70 to 73 were obtained as test materials.

For each plate material thus obtained, [1] tensile strength, [2] conductivity, [3] stress relaxation property (SR), [4] bending workability (R / t), [5] crystal The particle size (GS), [6] size and density of the precipitate (PPT), and [7] solder adhesion were examined by the following methods. The measurement method for each evaluation item is as follows.
[1] Tensile strength (TS): Three test pieces of JIS-13B cut out from the rolling parallel direction were measured according to JIS-Z2241, and the average value (MPa) was shown.
[2] Conductivity (EC): A 10 x 150 mm test piece cut out from the rolling parallel direction was prepared and measured in a thermostat controlled at 20 ° C (± 1 ° C) using a four-terminal method. The average value (% IACS) was shown. The distance between terminals is 100 mm.
[3] Stress relaxation property (SR): Measured under conditions of 150 ° C. × 1000 h in accordance with Japan Electronic Materials Association Standard EMAS-3003. FIG. 1 is an explanatory diagram of a test method for stress relaxation characteristics. FIG. 1A is an explanatory diagram schematically showing the measurement of the initial deflection amount δ ₀ . 1 is a test piece, 4 is a sample stage. The cantilever method was adopted and 80% of the 0.2% proof stress was applied as the initial stress. This was followed by exposure at 150 ° C. for up to 1000 hours. The test piece is at the position indicated by 2 in FIG. In FIG.1 (b), 3 shows the position of the test piece which does not produce a bending. Permanent deflection amount [delta] _t is the value of _H t -H _1.
Therefore, the stress relaxation rate (%) is represented by δ _t / δ ₀ × 100. This test examines the change in stress under a constant strain for a long time when used as a terminal material and the like, and an alloy having a smaller relaxation rate is considered better.

[4] Bending workability (R / t): The plate material is cut into a width of 10 mm and a length of 25 mm (the length direction and the rolling direction are parallel GW, the vertical direction is BW), and the bending radius R = 0 to W ( 90 °), and the presence or absence of cracks in the bent portion was visually observed with a 50 × optical microscope. The evaluation criteria was the critical bending radius at which no crack was obtained, and expressed as R / t (R is the bending radius and t is the plate thickness).
[5] Crystal grain size (GS): The crystal structure before final processing was observed with a scanning electron microscope (200 to 1000 times) and measured according to the cutting method of JIS-H0501.
[6] Precipitate (PPT): The size of the precipitate was observed with a transmission electron microscope, and after taking a photograph of × 100K to × 200K, the diameter was measured to obtain an average value of 10 to 50 pieces. The density was calculated by dividing by the measured area.

[7] Solder adhesion: Solder adhesion was tested according to the explanatory diagram schematically shown in FIG. The test material was cut to 20 × 20 mm, and the material surface was subjected to electrolytic degreasing as a pretreatment to obtain a material 13 having a thickness of 6 mm. Sn—Pb eutectic solder is deposited on the surface of the material 13 to form a solder portion 12, and a φ2 mm iron wire 11 (about 100 mm in length) coated with Cu on the Fe wire is formed at a right angle between the material 13 and the wire 11. (Fig. 2 (a)).
The test piece with the wire 11 was heated in the atmosphere, and the solder connection strength between the iron wire 11 and the material 13 before and after heating was measured. The heating condition was 150 ° C. × 500 h in a constant temperature bath, and after taking out from the constant temperature bath, it was sufficiently cooled by air cooling and then subjected to a tensile test in the direction of the arrow as shown in FIG. The tensile test was performed at room temperature with a load cell speed of 10 mm / min. In the tensile test, the tensile strength of the test material 13 peeled from the interface between the wire 11 of the test material and the solder part 12 was determined. In addition, the thing which did not peel from an interface and the iron wire 11 slipped out from the solder part 12 judges that the contact | adherence with the iron wire 11 and solder was bad, and is not made into evaluation object.
Similarly, the tensile strength before heat treatment is also measured, and the strength of the test material 13 before heat treatment and the strength of the test material 13 after heat treatment are measured. If the strength decrease is 50% or less, ○, 50% or more Was evaluated as x. If the joint strength does not decrease with time (the strength remaining rate is high), the solderability is good and the reliability is high.

In addition, the identification of the precipitate is performed by observation with a transmission electron microscope, and 5 to 10 precipitates are analyzed with an EDX analyzer (energy dispersive apparatus) attached to the transmission electron microscope, and Ni, Ti, Mg, Analysis peaks of Zr, Sn, and Si were confirmed. Moreover, the diffraction image was image | photographed with the transmission electron microscope, and it confirmed that it became a diffraction image different from the case where the Ni-Ti precipitate is formed. That is, the fact that the diffraction images are different indicates that precipitates other than Ni-Ti are formed. For taking a diffraction image, crystal grains having about 10 to 100 precipitates were selected and evaluated for identification.
The evaluation results of the above [1] to [7] are also shown in Tables 1 to 3.

  As is clear from Tables 1 and 2, all of Reference Examples 1 to 18 and Invention Examples 40 to 57 had excellent stress relaxation characteristics of 20% or less.

Comparative Example 60 was inferior in tensile strength because a sufficient amount of precipitation strengthening could not be obtained because Ni was small. Moreover, since the density | concentration of Ni-Ti precipitate was not enough and Sn and Si were not added, the stress relaxation rate was inferior.
Since Comparative Example 61 has a large amount of Ni and Ti, a solution treatment for a long time at a high temperature is required, and the crystal grains become coarse and bending workability is inferior. Even when aging treatment was performed, the conductivity was inferior because excess Ni and Ti were dissolved in the matrix. Moreover, since Sn and Si were not added, the stress relaxation rate was inferior.
Since Comparative Example 62 has a large amount of Ni, a solution treatment for a long time at a high temperature is required, and the crystal grains become coarse and bending workability is inferior. Moreover, since Ni was excessive, the density of the Ni-Ti precipitate which contributes to the strength was lowered and the tensile strength was inferior. Even after aging treatment, the conductivity was inferior because excess Ni was dissolved in the matrix. Furthermore, since Sn and Si were not added, the stress relaxation rate was inferior.

Since Comparative Example 63 contained a large amount of Ti, a solution treatment for a long time at a high temperature was required, the crystal grains were coarsened, and the bending workability was inferior. Even after aging treatment, the conductivity was inferior because excess Ti was dissolved in the matrix. Furthermore, since Sn and Si were not added, the stress relaxation rate was inferior.
Since Comparative Example 64 has a small amount of Sn, the stress relaxation rate was inferior because there were few precipitates composed of Ni, Ti, and Sn.
Since Comparative Example 65 contained a large amount of Sn, excess Sn remained in solid solution, and both conductivity and bending workability were poor. Moreover, the stress relaxation rate was inferior.

In Comparative Example 66, since the amount of Si was small, the amount of precipitates composed of Ni, Ti, and Si was small, so the stress relaxation rate was inferior.
Since Comparative Example 67 had a large amount of Si, a solution treatment for a long time at a high temperature was required, the crystal grains were coarsened, and the bending workability was inferior. In addition, the conductivity was inferior because excess Si was dissolved in the matrix. Furthermore, the stress relaxation rate was inferior.
Since Comparative Examples 70 and 71 did not contain Zn, solder adhesion deteriorated.

<Production Example 2>
An alloy having the same composition as in Reference Example 15 of Production Example 1 was used, and the solution treatment conditions, the cold working conditions to be performed next, and the aging conditions to be performed were variously changed. Other manufacturing conditions are the same as those in Manufacturing Example 1. Furthermore, the evaluation items [1] to [7] were measured in the same manner as in Production Example 1. Table 4 shows the solution conditions and the evaluation results.

As is clear from Table 4, Reference Examples 81 to 88 have excellent characteristics.
On the other hand, in Reference Examples 91 and 92, since the cooling rate was slow, the precipitates became coarse and the stress relaxation rate was inferior.
In Reference Example 93, since the solution temperature was low, the solid solution of the elements contributing to precipitation decreased, the precipitation density during aging treatment decreased, and the stress relaxation rate was inferior.
In Reference Example 94, since the solution temperature was low, the solid solution of the elements contributing to precipitation decreased, the precipitation density during aging treatment decreased, and the stress relaxation rate was inferior.

In Reference Example 95, since the solution treatment time was long, the crystal grains became coarse and the bending workability was poor.
Reference Example 96 was not recrystallized because it was not solution-treated, and the cold work rate after hot rolling was 90% or more, so the structure was fibrous and the crystal grain size could not be measured. . Moreover, since there are few precipitates which contribute to precipitation, bending workability and the stress relaxation rate were inferior.
Since Reference Example 97 had a high cold working rate after solution treatment, bending workability was inferior.
Since Reference Example 98 had a high aging temperature, the precipitates became coarse and the strength was poor.
Since Reference Example 99 has a low aging temperature, the strength of the precipitate was inferior because the size of the precipitate was very small.
In Reference Example 100, since the aging time was long, the precipitates became coarse, so the strength was inferior.

1, 2, 3 Sample 4 Sample stand 11 Iron wire 12 Solder part 13 Material

Claims (3)

Ni is 1 to 3 mass%, Ti is 0.2 to 1.2 mass%, one or both of Sn and Si is 0.02 to 0.2 mass%, Zn is 0.1 to 1 mass%, and the balance is Cu At least one intermetallic compound consisting of Ni, Ti and Sn, an intermetallic compound consisting of Ni, Ti and Si, or an intermetallic compound consisting of Ni, Ti, Sn and Si. Containing, an intermetallic compound composed of Ni, Ti, and Sn, an intermetallic compound composed of Ni, Ti, and Si, or an average particle diameter of an intermetallic compound composed of Ni, Ti, Sn, and Si is 5 to 100 nm, When the distribution density is 1 × 10 ¹⁰ to 10 ¹³ particles / mm ² , the crystal grain size of the parent phase is 4 μm or more and 10 μm or less, the conductivity is 47.6% IACS or more, and it is kept at 150 ° C. for 1000 hours A copper alloy material for electrical and electronic equipment, characterized by a stress relaxation rate of 20% or less.   The method for producing a copper alloy material for electrical and electronic equipment according to claim 1, wherein a solution treatment is performed at a temperature of 850 ° C or more and 35 seconds or less, and a cooling rate of 50 ° C / sec or more from the temperature of the solution treatment. The copper alloy for electric and electronic equipment is characterized by being cooled to 300 ° C. and then cold-rolled at a rolling rate exceeding 0% to 50% and aging treatment at 450 to 600 ° C. within 5 hours. Material manufacturing method.   The method for producing a copper alloy material for electrical and electronic equipment according to claim 1, wherein a solution treatment is performed at a temperature of 850 ° C or more and 35 seconds or less, and a cooling rate of 50 ° C / sec or more from the temperature of the solution treatment. A method for producing a copper alloy material for electrical and electronic equipment, comprising cooling to 300 ° C. and then performing an aging treatment at 450 to 600 ° C. within 5 hours.

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