CN1950525A - Copper alloy - Google Patents

Abstract

The invention relates to a copper alloy for electronic machinery and tools, containing Ni 2.0 to 4.5 mass%, and Si 0.3 to 1.0 mass%, with the balance being Cu and unavoidable impurities, which satisfies the following expression: I{311} x A / (I{311} + I{220} + I{200}) < 1.5 wherein I{311} represents an X-ray diffraction intensity from a {311} plane at a sheet surface; I{220} represents an X-ray diffraction intensity from a {220} plane at the sheet surface; I{200} represents an X-ray diffraction intensity from a {200} plane at the sheet surface; and A ( m) represents a crystalline grain size, and which has good bending property.

Description

copper alloy

technical field

The present invention relates to a copper alloy with improved properties.

Background technique

With the new trend of miniaturization and manufacture of high-performance electrical and electronic devices and components, materials used in components such as connectors have been required to undergo severe improvements in various properties. For example, specifically, the plate thickness used at the contact point of the connector spring has become so thin that it has become difficult to ensure sufficient contact pressure. That is, at the contact point of the connector spring, the contact pressure required for electrical connection is obtained from the reaction force obtained from the previously deflected plate (spring plate). Therefore, when the plate is thinned, a greater degree of deflection is required to obtain the same degree of contact pressure. However, when the degree of deflection exceeds the elastic limit of the panel, the panel may undergo plastic deformation. Therefore, it has been required to further increase the elastic limit of the plate.

For the material of the spring contacts of the connector, various other properties such as stress relaxation resistance, thermal conductivity, bending properties, heat resistance, plating adhesion properties, and electromigration resistance are also required. Among various properties, mechanical strength, stress relaxation resistance, thermal and electrical conductivity, and bending properties are important. Although phosphor bronze has often been used for spring contacts of connectors, it does not fully meet the above requirements. Therefore, low beryllium copper alloy (an alloy specified by JISC 1753), which has high mechanical strength and good stress relaxation resistance, and good electrical conductivity, is being replaced in recent years for phosphor bronze.

Copper-nickel-silicon-based alloys are known as examples of contact element materials, which have properties comparable to low-beryllium copper alloys and have relatively high strength as inexpensive and highly safe materials. Another example of a contact element material includes a copper alloy with improved stress relaxation resistance obtained by adding magnesium to a copper-nickel-silicon based alloy. Yet another example of contact element material includes copper alloys having mechanical strength comparable to low beryllium copper alloys obtained by increasing the nickel and silicon content of copper-nickel-silicon-based alloys.

However, low beryllium copper has a problem that it is very expensive and metal beryllium is toxic. Various attempts have been made to increase the strength of copper-nickel-silicon-based alloys. However, excessively increasing the content of nickel and silicon in the copper alloy reduces the bending performance, which is one of the required properties of the connector, thus limiting possible applications of the connector. Specifically, intergranular embrittlement cracking (intergranular embrittlement cracking) of the copper alloy occurs during the bending process, resulting in a decrease in the bending performance of the copper alloy. Accordingly, no copper-nickel-silicon-based alloys having strength, electrical conductivity and bending properties comparable to low beryllium copper alloys have yet been found. Also, even if magnesium is added to copper-nickel-silicon-based alloys, stress relaxation resistance with properties comparable to low beryllium copper alloys cannot be obtained.

Other and further features and advantages of the invention will appear more fully from the following description.

Contents of the invention

According to the present invention, the following solutions are provided:

(1) Copper alloys for electronic devices and components, containing 2.0 to 4.5% by mass of nickel and 0.3 to 1.0% by mass of silicon, with the balance being copper and unavoidable impurities,

It satisfies the following expression (1):

I{311}×A/(I{311}+I{220}+I{200})＜1.5...(1)

Among them, in the expression (1), I{311} represents the X-ray diffraction intensity from the {311} plane (plane) of the sheet surface; I{220} represents the X-ray diffraction intensity from the {220} plane of the sheet surface. X-ray diffraction intensity; I{200} represents the X-ray diffraction intensity from the {200} plane of the plate surface; and A (μm) represents the crystal grain size (crystal grain size), and

It has good bending properties.

(2) Copper alloys for electronic devices and components, containing 2.0 to 4.5% by mass of nickel, 0.3 to 1.0% by mass of silicon, and greater than 0 and less than 0.005% by mass of sulfur, with the balance being copper and unavoidable impurities,

It satisfies the following expression (1):

I{311}×A/(I{311}+I{220}I{200})＜1.5...(1)

Among them, in expression (1), I{311} represents the X-ray diffraction intensity from the {311} plane of the plate surface; I{220} represents the X-ray diffraction intensity from the {220} plane of the plate surface; I{200 } represents the X-ray diffraction intensity from the {200} plane of the plate surface; and A (μm) represents the grain size, and

It has good bending properties.

(3) The copper alloy according to the above item (1) or (2), further containing 0.2 to 1.5% by mass of zinc.

(4) The copper alloy according to any one of (1) to (3) above, further containing 0.01 to 0.2% by mass of magnesium.

(5) The copper alloy according to any one of (1) to (4) above, further containing 0.05 to 1.5% by mass of tin.

(6) Copper alloys used in electronic devices and components, containing 2.0 to 4.5% by mass of nickel, 0.3 to 1.0% by mass of silicon, 0.01 to 0.2% by mass of magnesium, 0.05 to 1.5% by mass of tin, and 0.2 to 1.5% by mass of tin % zinc and less than 0.005% by mass of sulfur, the balance being copper and unavoidable impurities,

It satisfies the following expression (1):

I{311}×A/(I{311}+I{220}+I{200})＜1.5...(1)

Among them, in expression (1), I{311} represents the X-ray diffraction intensity from the {311} plane of the plate surface; I{220} represents the X-ray diffraction intensity from the {220} plane of the plate surface; I{200 } represents the X-ray diffraction intensity from the {200} plane of the plate surface; and A (μm) represents the grain size, and

It has good bending properties.

(7) The copper alloy according to any one of (1) to (6) above, further comprising at least one element selected from the group consisting of 0.005 to 0.3% by mass of zirconium, 0.05 to 2.0% by mass of cobalt, and 0.001 to 0.02% by mass The total content of boron in mass % is 0.001 to 2.0 mass %.

(8) A copper alloy comprising 2.0 to 4.5% by mass of nickel, 0.3 to 1.0% by mass of silicon, 0.1 to 0.5% by mass of chromium, and less than 0.005% by mass of sulfur, with the balance being copper and unavoidable impurities,

It satisfies the following expression (2):

I{311}/(I{311}+I{220}+I{200})＜0.15...(2)

Among them, in the expression (2), I{311} represents the X-ray diffraction intensity from the {311} plane of the plate surface; I{220} represents the X-ray diffraction intensity from the {220} plane of the plate surface; I{ 200} represents the X-ray diffraction intensity from the {200} plane of the plate surface.

(9) A copper alloy comprising 2.0 to 4.5% by mass of nickel, 0.3 to 1.0% by mass of silicon, 0.1 to 0.5% by mass of chromium, and less than 0.005% by mass of sulfur, with the balance being copper and unavoidable impurities,

It satisfies the following expression (3):

I{311}×A/(I{311}+I{220}+I{200})＜1.5...(3)

Among them, in the expression (3), I{311} represents the X-ray diffraction intensity from the {311} plane of the plate surface; I{220} represents the X-ray diffraction intensity from the {220} plane of the plate surface; I{200 } represents the X-ray diffraction intensity from the {200} plane of the plate surface; and A (μm) represents the grain size.

(10) The copper alloy according to the above item (8) or (9), further containing 0.2 to 1.5% by mass of zinc.

(11) The copper alloy according to any one of (8) to (10) above, further containing 0.01 to 0.2% by mass of magnesium.

(12) The copper alloy according to any one of (8) to (11) above, further containing 0.05 to 1.5% by mass of tin.

(13) The copper alloy according to any one of the above (8) to (12), further comprising at least one element selected from the following: 0.005 to 0.3% by mass of zirconium, 0.05 to 2.0% by mass of cobalt, 0.005 to 0.3% by mass % titanium, 0.005-0.3 mass % silver and 0.001-0.02 mass % boron.

Hereinafter, the first embodiment of the present invention is meant to include all copper alloys described in the above items (1) to (7).

The second embodiment of the present invention refers to all copper alloys described in the above items (8) to (13).

Here, unless otherwise specified, the present invention is meant to include both the first and second embodiments described above.

Detailed ways

The present invention is explained in detail below.

[First Embodiment]

According to the first embodiment, the bending performance of the copper alloy containing the nickel-silicon compound precipitated in the copper matrix and having moderate mechanical strength can be improved by strictly controlling the integration degree of the crystal orientation and the grain size and conductivity.

Hereinafter, the relationship between the crystal orientations of the copper alloy of the first embodiment (hereinafter, simply referred to as the first copper alloy) will be described. For copper alloys containing nickel and silicon, the inventors of the present invention found that the degree of integration of crystal orientation can be determined by controlling the intensity of X-ray diffraction, and the bending properties and Mechanical strength. That is, when the copper alloy satisfies the following expression (1), the bending properties and mechanical strength of the copper alloy can be improved.

I{311}×A/(I{311}+I{220}+I{200})＜1.5...(1)

Among them, I{311} represents the X-ray diffraction intensity from the {311} plane of the plate surface; I{220} represents the X-ray diffraction intensity from the {220} plane of the plate surface; I{200} represents the {220} plane from the plate surface X-ray diffraction intensity of the 200} plane; and A (μm) represents the grain size.

In the above expression (1), the relationship between the degree of integration of the crystal orientation and the grain size is specified to have a value of less than 1.5, preferably less than 1.2. The lower limit of this value is not particularly limited, but is usually greater than 0.3. Too large a value inhibits both the improvement of the copper alloy bending property and the mechanical strength. The copper alloy containing nickel and silicon recrystallizes and increases its grain size, thereby increasing the integration ratio of the {200} plane and the integration ratio of the {311} plane with respect to the plate surface. The copper alloy is cold rolled at a higher reduction rate to further increase the integration ratio of the {220} plane relative to the plate surface. The relationship between the degree of integration of crystal orientations and the X-ray diffraction intensity is that a high X-ray diffraction intensity provides a high degree of integration of crystal orientations. Here, the integration ratio (integration degree of crystal orientation) of the X-ray diffraction plane refers to the ratio of the crystal growth rate in the direction of each diffraction plane, which can be expressed by the ratio of the X-ray diffraction intensity (I) of each diffraction plane to measure. In the present invention, the integration ratio of the X-ray diffraction surface is represented by the left side of the expression (I) (in this case, A=1). For example, through the processes "hot rolling", "cold rolling", "solution treatment" and "aging treatment" and, if necessary, additional processes "finish cold rolling" and "distortion Elimination of annealing (distortionelimination annealing) "can produce the first copper alloy. The degree of integration and grain size of crystal orientation varies with the processing ratio before solution treatment, and the degree of integration and grain size of solution crystal orientation varies with the combination of the conditions of solution treatment and the processing ratio of cold working. In the present invention, especially when the contents of nickel and silicon are increased, the bending properties of the copper alloy are improved by suppressing the intergranular embrittlement of the copper alloy during bending, and the inventors provide an appropriate range represented by the expression (1) to specify The relationship between crystal orientation integration and grain size.

Alloying elements in the first copper alloy will be described below.

When nickel and silicon are added to copper, nickel-silicon series compounds (Ni ₂ Si phase) are precipitated in the copper matrix, improving mechanical strength and electrical conductivity. The content of nickel is specified in the range of 2.0 to 4.5% by mass. This is because when the nickel content is less than 2.0% by mass, mechanical strength equal to or superior to conventional low beryllium copper alloys cannot be obtained. On the other hand, when the nickel content exceeds 4.5% by mass, precipitation that does not help to improve the mechanical strength occurs during casting or hot working, not only cannot obtain the mechanical strength corresponding to the added nickel content, but also causes damage to the hot workability. and bending properties are adversely affected. The nickel content is preferably 2.2 to 4.2% by mass, more preferably 3.0 to 4.0% by mass.

Since silicon forms a Ni ₂ Si phase together with nickel, the amount of added silicon is determined by the amount of nickel. When the silicon content is less than 0.3% by mass, the same mechanical strength as or superior to the low beryllium copper alloy cannot be obtained, similar to the case where the nickel content is too small. On the other hand, when the content of silicon exceeds 1.0% by mass, the same problems occur as in the case of too large a nickel content. The silicon content is preferably 0.5 to 0.95% by mass, more preferably 0.7 to 0.9% by mass.

Mechanical strength varies with nickel and silicon content, and stress relaxation resistance varies accordingly. Therefore, the content of nickel and silicon should be strictly controlled within the range specified in this embodiment, in order to obtain the same stress relaxation resistance as the low beryllium copper alloy or a better stress relaxation resistance than the low beryllium copper alloy. In addition, the contents of magnesium, tin, and zinc, the grain diameter, and the shape of grains to be described later should also be appropriately controlled.

Magnesium, tin and zinc are important alloying elements constituting the copper alloy of the present invention. These elements in the alloy are related to each other in order to obtain a balanced variety of good properties.

Magnesium mainly improves stress relaxation resistance, but it adversely affects bending properties. The more the magnesium content is, the more the stress relaxation resistance improves, provided that the magnesium content is, for example, 0.01% by mass or more. However, if the magnesium content is too large, the resulting bending properties cannot satisfy the required level. In the case of adding magnesium, it is preferred in the present invention to strictly control the content of magnesium, because compared with conventional copper-nickel-silicon series alloys, the precipitation of Ni ₂ Si phase greatly contributes to the degree of reinforcement, so the bending Performance tends to be poor. The magnesium content is usually 0.01 to 0.2% by mass, more preferably 0.05 to 0.15% by mass.

The correlation between tin and magnesium improves the stress relaxation resistance even more. However, this enhancing effect of tin is not as great as that of magnesium. When the tin content is too low, a sufficient effect of adding tin cannot be sufficiently exhibited, and when the tin content is too large, the electrical conductivity is remarkably lowered. The content of tin is usually 0.05 to 1.5% by mass, more preferably 0.1 to 0.7% by mass.

Zinc improves bend properties slightly. The content of zinc is usually in the range of 0.2 to 1.5% by mass. When zinc is added within the prescribed range of 0.2 to 1.5% by mass, even if a maximum amount of 0.20% by mass of magnesium is added, bending performance at a practically non-problematic level can be obtained. In addition, zinc can improve the adhesion performance of tin plating or solder plate, and the electromigration resistance performance. When the zinc content is too low, the effect of zinc addition cannot be sufficiently obtained, and when the zinc content is too large, the electrical conductivity is lowered. The zinc content is preferably 0.3 to 1.0% by mass.

Subconstituent elements effective for improving the mechanical strength, such as cobalt and zirconium, will be described hereinafter.

Like nickel, cobalt forms compounds with silicon to increase mechanical strength. The content of cobalt is usually 0.05 to 2.0% by mass. When the cobalt content is too small, the effect of cobalt addition cannot be sufficiently obtained, and when the cobalt content is too large, bending properties tend to be lowered. The content of cobalt is usually 0.05 to 2.0% by mass, preferably 0.1 to 1.0% by mass.

Zirconium is finely precipitated in copper, thus contributing to the improvement of the mechanical strength of the resulting copper alloy, and providing an effect of reducing the degree of crystal orientation integration represented by the expression (1). When the zirconium content is too small, the effect of zirconium addition cannot be sufficiently obtained, and when the zirconium content is too large, bending properties tend to be lowered. From the above viewpoint, the content of zirconium is usually 0.005 to 0.3% by mass, preferably 0.05 to 0.2% by mass.

When at least two of cobalt, zirconium and boron are contained in the alloy at the same time, it is determined that the total content thereof is generally within the range of 0.001-2.0 mass%, preferably 0.005-2.0 mass%, depending on the required properties. Boron forms a compound with nickel, thus lowering the degree of integration of the crystal orientation represented by the expression (1). When the boron content is too small, the effect of boron addition cannot be sufficiently obtained, and when the boron content is too large, hot workability tends to be lowered. From the above viewpoint, the content of boron is usually 0.001 to 0.02% by mass, preferably 0.005 to 0.01% by mass.

The copper alloy usually contains traces of sulfur. When the sulfur content is too high, it leads to lower hot workability. Therefore, the sulfur content is preferably specified to be less than 0.005% by mass, particularly preferably less than 0.002% by mass.

In the present invention, other elements such as iron, phosphorus, manganese, titanium, vanadium, lead, bismuth and aluminum may be added in appropriate amounts within the range of not degrading basic properties such as mechanical strength and electrical conductivity. For example, manganese has an effect of improving hot workability, and it is effective to add manganese in the range of 0.01 to 0.5% by mass without lowering the electrical conductivity.

The copper alloy containing nickel and silicon recrystallizes and increases its grain size, thereby increasing the integration ratio of {200} and {311} planes with respect to the plate surface. The copper alloy was rolled so as to increase the integration ratio of the {220} plane with respect to the plate surface.

For example, the first copper alloy can be produced through hot rolling, cold rolling, solution treatment and aging treatment processes, and if necessary, additional finishing cold rolling and distortion-eliminating annealing processes. For example, in the production process, the conditions of hot rolling (temperature and time period), the conditions of subsequent cold rolling and solution treatment (temperature and time period), and the conditions of subsequent cold rolling (processing rate) are strictly controlled. Control within a smaller range than normal conditions. Therefore, the integration ratio and grain size of the copper alloy can be controlled so as to satisfy Expression (1).

In the production of the first copper alloy, specifically, by adjusting the hot rolling temperature in the range of 900 to 1000 ° C, the processing rate of cold rolling after hot rolling is adjusted to 90% or more, and the solution treatment temperature is adjusted to Expression (1) can be satisfied by 820˜930° C. for 20 seconds or less, and then adjusting the working ratio of cold rolling to 30% or less.

As used herein, the direction of final plastic working refers to the direction of rolling when rolling is the last plastic working performed, or the direction of final plastic working when drawing (linear stretching) is the last plastic working performed. Stretch direction. Plastic working refers to rolling and drawing, but, for example, working for the purpose of leveling (vertical leveling), such as using a tension leveler, is not included in this plastic working.

[Second embodiment]

According to a second embodiment, copper-nickel-silicon-based alloys are improved to meet recent needs by the following method, the bending properties and mechanical strength of copper alloys containing precipitated nickel-silicon compounds in a copper matrix can be controlled by controlling the chromium content and The degree of integration of crystal orientation is improved.

Hereinafter, each constituent element of the copper alloy of the second embodiment (hereinafter, simply referred to as the second copper alloy) will be described.

It is well known that by adding nickel and silicon to copper, a nickel-silicon series compound (Ni ₂ Si phase) is precipitated in a copper matrix to improve mechanical strength and electrical conductivity. In the present invention, the content of nickel is usually in the range of 2.0 to 4.5% by mass, preferably in the range of 2.2 to 4.2% by mass, and more preferably in the range of 3.0 to 4.0% by mass.

The nickel content is as defined above. This is because when the nickel content is too low, mechanical strength equal to or superior to conventional beryllium-copper alloys cannot be obtained. On the other hand, when the nickel content is too high, precipitates that do not help to improve the mechanical strength are precipitated during casting or hot working, not only cannot obtain the mechanical strength corresponding to the added nickel content, but also cause damage to hot workability and Problems that adversely affect bending properties.

Since silicon forms the _Ni2Si phase together with nickel, the optimum amount of added silicon is determined by determining the amount of nickel. The silicon content is usually 0.3 to 1.0% by mass, preferably 0.5 to 0.95% by mass, more preferably 0.7 to 0.9% by mass. When the silicon content is too small, mechanical strength equal to or better than that of the beryllium-copper alloy cannot be obtained, similar to the case where the nickel content is too small. On the other hand, when the content of silicon is too large, the same problems occur as in the case of too large a nickel content.

The chromium content and X-ray diffraction intensity of the formed copper alloy are controlled, thereby improving the bending performance and mechanical strength of the alloy sheet.

That is, by adjusting the chromium content to 0.1 to 0.5% by mass and satisfying expression (2) or (3) as described below, the bending properties and mechanical strength of the alloy sheet material are improved.

Moreover, chromium exists in the alloy as a chromium compound such as chromium-silicon series or chromium-nickel-silicon series, and it has the effect of suppressing the increase in grain size and reducing the integration of crystal orientation represented by the expression during solution treatment degree of effect. However, too low a chromium content does not provide sufficient effect, while too high a chromium content reduces the bending properties of the alloy. From these viewpoints, the content of chromium is usually 0.1 to 0.5% by mass, preferably 0.15 to 0.4% by mass.

Magnesium, tin and zinc are important alloying elements constituting the copper alloy of the present invention. These elements in the alloy are related to each other to obtain various balanced good properties.

Magnesium improves stress relaxation resistance, but it has an adverse effect on bending properties. The more the magnesium content is, the more the stress relaxation resistance improves, provided that the magnesium content is, for example, 0.01% by mass or more. However, if the magnesium content is too large, the resulting bending properties cannot satisfy the required level. In the case of adding magnesium, it is preferred in the present invention to strictly control the content of magnesium, because compared with conventional copper-nickel-silicon series alloys, the precipitation of Ni ₂ Si phase contributes far to the degree of reinforcement, For this reason, bending performance tends to deteriorate. The magnesium content is usually 0.01 to 0.2% by mass, more preferably 0.05 to 0.15% by mass.

The correlation between tin and magnesium improves the stress relaxation resistance even more. When the tin content is too small, a sufficient effect of adding tin cannot be sufficiently exhibited, and when the tin content is too large, the electrical conductivity is remarkably lowered. The content of tin is usually 0.05 to 1.5% by mass, more preferably 0.1 to 0.7% by mass.

Zinc improves bending properties. The zinc content is usually 0.2 to 1.5% by mass. Even if magnesium is added in a maximum amount of 0.20% by mass, the addition of zinc can provide practically no problem in bending performance. In addition, zinc improves adhesion properties of tin plating or solder plating, and electromigration resistance. When the zinc content is too small, the effect of zinc addition cannot be sufficiently obtained, and when the zinc content is too large, the electric conductivity is lowered. The zinc content is preferably 0.3 to 1.0% by mass.

Zirconium, cobalt, titanium, silver, and boron each have an effect of lowering the degree of integration of crystal orientation expressed by any one of the expressions described below.

Zirconium has the effect of lowering the degree of integration of crystal orientation expressed by this expression, and at the same time contributes to the improvement of the strength of the alloy. However, too low a zirconium content does not provide sufficient effect, while too high a zirconium content reduces the bending properties of the alloy. From these viewpoints, the content of zirconium is usually 0.005 to 0.3% by mass, preferably 0.05 to 0.2% by mass.

Similar to nickel, cobalt forms a compound with silicon to increase the strength of the alloy, and has the effect of reducing the degree of integration of crystal orientation represented by this expression. The content of cobalt is usually 0.05 to 2.0% by mass. When the cobalt content is too small, the effect of cobalt addition cannot be sufficiently obtained, and when the cobalt content is too large, bending properties are lowered. The content of cobalt is preferably 0.1 to 1.0% by mass.

Similar to chromium, zirconium, titanium, silver, and other elements, cobalt has the effect of suppressing an increase in crystal grain size and lowering the degree of integration of crystal orientation represented by this expression.

Boron has the effect of lowering the degree of integration of crystal orientation represented by this expression. Too low a boron content does not provide sufficient effect, while too high a boron content reduces hot workability. From these viewpoints, the content of boron is usually 0.001 to 0.02% by mass, preferably 0.005 to 0.1% by mass.

Titanium improves the heat resistance and mechanical strength of the alloy, and has the effect of suppressing the increase in grain size and reducing the degree of integration of crystal orientation expressed by this expression. A titanium content that is too low does not provide sufficient effects; and a titanium content that is too high leaves undissolved titanium that cannot provide effects and has an adverse effect on plating performance and the like. From these viewpoints, the content of titanium is usually 0.005 to 0.3% by mass, preferably 0.05 to 0.2% by mass.

Silver improves the heat resistance and mechanical strength of the alloy, and has the effect of suppressing the increase in crystal grain size and reducing the degree of integration of crystal orientation represented by this expression. If the silver content is too small, it will not be sufficient to produce the effect of silver addition; while if the silver content is too large, it will lead to high alloy cost even if no adverse effect on the properties obtained by adding large amounts of silver is observed. From the above viewpoint, the content of silver is usually 0.005 to 0.3% by mass, preferably 0.05 to 0.2% by mass.

More preferably, when at least two elements of cobalt, zirconium, titanium, silver and boron are simultaneously contained in the alloy, the total content thereof is specified within the range of 0.005 to 2.0% by mass depending on required properties.

The copper alloy usually contains traces of sulfur. When the sulfur content is too high, it leads to lower hot workability. Therefore, the sulfur content is preferably specified to be less than 0.005% by mass, particularly preferably less than 0.002% by mass.

In the present invention, other elements such as iron, phosphorus, manganese, vanadium, lead, bismuth and aluminum may be added in appropriate amounts within the range of not degrading basic properties such as mechanical strength and electrical conductivity. For example, manganese has the effect of improving hot workability, and addition of manganese in the range of 0.01 to 0.5% by mass is effective without lowering the electrical conductivity.

Next, the crystal orientation of the second copper alloy will be described.

In copper alloys containing nickel and silicon, the resulting crystal recrystallizes and increases its grain size, thereby increasing the integration ratio of {200} and {311} planes to the plate surface. The copper alloy is rolled to increase the integration ratio of the {220} planes to the plate surface.

For example, the second copper alloy can be produced through hot rolling, cold rolling and aging treatment processes, and if necessary, additional finishing cold rolling and distortion eliminating annealing processes. For example, in the production process, the conditions of hot rolling (temperature and time period), the conditions of subsequent cold rolling and solution treatment (temperature and time period), and the conditions of subsequent cold rolling (processing ratio) are strictly controlled. Control within a smaller range than normal conditions, thereby controlling the integration ratio and grain size.

The inventors of the present invention found that a copper alloy having an integration degree of crystal orientation within a specified range, which is determined by X-ray diffraction intensity representing the integration ratio, is improved in bending properties and mechanical strength. Here, the integration ratio of the X-ray diffraction plane (integration degree of crystal orientation) refers to the crystal growth length ratio in the direction of each diffraction plane, and can be expressed as the X-ray diffraction intensity (I) ratio of each diffraction plane Determination. Specifically, a copper alloy satisfying the following expression (2) and having a chromium content within the above specified range can be improved in bending properties and mechanical strength:

I{311}/(I{311}+I{220}+I{200})＜0.15...(2)

where I{311} represents the X-ray diffraction intensity from the {311} plane of the plate surface; I{220} represents the X-ray diffraction intensity from the {220} plane of the plate surface; and I{200} represents the X-ray diffraction intensity from the plate surface X-ray diffraction intensity of the {200} plane.

In the above expression (2), the integration degree value of the crystal orientation is less than 0.15, preferably less than 0.12. The lower limit of this value is not particularly limited, but is usually greater than 0.03. If this value is large, it leads to an improvement in both bending properties and mechanical strength of the copper alloy.

Also, copper alloys satisfying the following expression (3) can be improved in bending properties and tensile strength:

I{311}×A/(I{311}+I{220}+I{200})＜1.5...(3)

Among them, similar to the above, I{311} represents the X-ray diffraction intensity from the {311} plane of the plate surface; I{220} represents the X-ray diffraction intensity from the {220} plane of the plate surface; I{200} represents the X-ray diffraction intensity from X-ray diffraction intensity of the {200} plane of the plate surface; and A (μm) represents the grain size.

In the above expression (3), the relationship between the degree of integration of the crystal orientation and the grain size is specified so as to obtain a value smaller than 1.5, and preferably the value is smaller than 1.2. The lower limit of this value is not particularly limited, but is usually greater than 0.3. Similar to the above, too large a value inhibits improvement of both bending properties and mechanical strength of the copper alloy. Therefore, the grain size is preferably as small as possible, specifically, the grain size is preferably less than 10 μm, more preferably 5-8 μm.

In the production of the second copper alloy, for example, by adjusting the hot rolling temperature in the range of 900 to 1000°C, the processing ratio of cold rolling after hot rolling is adjusted to 90% or more, and the solution treatment temperature is adjusted to 820 to 800°C. 930° C. for 20 seconds or less, and the processing ratio of the subsequent cold rolling adjusted to 30% or less, expression (2) or (3) can be satisfied.

According to the present invention, it is possible to provide a copper alloy as a material for a terminal, a connector, a switch, etc., which has, for example, excellent mechanical strength, electrical conductivity, and bending properties, and sometimes also has excellent durability in addition to these properties. Stress relaxation and plating adhesion.

The copper alloy of the present invention has, for example, excellent mechanical strength, electrical conductivity and bending properties (the first embodiment described above), and also has excellent stress relaxation resistance (the second embodiment described above) in addition to the above properties. Copper alloy materials obtained by processing copper alloys can be used to produce small high-performance components for electrical and electronic devices and components. For example, the copper alloy of the present invention can be preferably applied to terminals, connectors, or switches, as well as general-purpose conductive materials for lead frames, relays, and the like.

Example

The present invention will be described in more detail based on the following examples, but the present invention is not limited to these examples. In the following Examples, Examples 1 and 2 correspond to examples of the first embodiment, and Examples 3 and 4 correspond to examples of the second embodiment.

(Example 1)

The copper alloys each have the composition shown in Table 1 (ingot numbers A to V, WA to WH, X and Z), each alloy was melted in a high-frequency melting furnace by a direct current method, and cast into An ingot with a thickness of 30 mm, a width of 100 mm and a length of 150 mm. Then, these ingots were heated to 1000°C. After maintaining the ingots at this temperature for 1 hour, the obtained ingots were each hot-rolled into a plate having a thickness of 12 mm, followed by rapid cooling.

Then, both end surfaces of each hot-rolled sheet were cut (chamfered) by 1.5 mm to remove the oxide film on each surface. The obtained sheet is processed into a sheet having a thickness of 0.15 to 0.25 mm by cold rolling (a). Then, the cold-rolled sheet was heat-treated for 15 seconds while changing the solution treatment temperature in the range of 825-925°C, and immediately thereafter cooled at a cooling rate of 15°C/sec or more. Then, an aging treatment is carried out at 475°C for 2 hours in an inert gas atmosphere, and then, depending on the sample, if necessary, cold rolling (c) is carried out as a final plastic working to adjust the final plate thickness to 0.15 mm. After aging treatment or final plastic working, the samples were subjected to low-temperature annealing at 375° C. for 2 hours to manufacture copper alloy sheets (samples 1 and 5 to 41 ), respectively.

(Example 2)

Copper alloy sheets having a thickness of 0.15 mm were produced by separately processing copper alloys (ingot No. J) having compositions shown in Table 1 under the following conditions. That is, the production conditions were the same as the production steps of Example 1 from the start of melting to the removal of the oxide film after hot rolling. Then, the obtained sheet is processed to a thickness of 0.15 to 0.5 mm by cold rolling (a), followed by heat treatment at a solution treatment temperature in the range of 825 to 925° C. for 15 seconds. Immediately thereafter, the plate was cooled at a cooling rate of 15°C/sec or more.

Then, depending on the sample, if necessary, the resulting plate was subjected to cold rolling (b) at a processing ratio of 50% or less, and then, under the same conditions as in Example 1, aged in an inert gas atmosphere, respectively treatment, final plastic working (cold rolling (c) to a final plate thickness of 0.15 mm), followed by low temperature annealing to produce copper alloy plates (samples 2 to 4).

Table 1 Ingot No. Ni mass% Si mass% Mg mass% Sn mass% Zn mass% S mass % Other elements mass% A 3.8 0.89 - - - 0.002 - B 3.4 0.83 - - - 0.002 - C 3.2 0.77 - - - 0.002 - D. 3.8 0.9 0.1 - - 0.002 - E. 3.8 0.9 - 0.15 - 0.002 - f 3.8 0.9 - - 0.5 0.002 - G 3.8 0.9 0.1 0.15 - 0.002 - h 3.8 0.9 0.1 - 0.5 0.002 - I 3.8 0.9 - 0.15 0.5 0.002 - J 3.8 0.9 0.1 0.15 0.5 0.002 - K 3.5 0.84 0.1 0.16 0.47 0.002 - L 3.3 0.78 0.1 0.16 0.48 0.002 - N 3.8 0.89 0.1 0.15 0.5 0.002 Zr:0.1 o 3.8 0.89 0.1 0.15 0.5 0.002 Co:0.25 P 3.8 0.89 0.1 0.15 0.49 0.002 B:0.01 Q 5 1.17 0.1 0.21 0.49 0.002 - R 3.8 0.9 0.1 0.15 1.7 0.002 - S 3.8 0.9 0.38 0.2 0.5 0.002 - T 3.8 0.89 0.08 2.01 0.5 0.002 - V 4.1 0.9 0.1 0.15 0.48 0.002 B:0.03 WA 2.3 0.56 - - - 0.002 - WB 2.3 0.56 0.1 - - 0.002 - WC 2.2 0.54 - 0.15 - 0.002 - WD 2.3 0.56 - - 0.5 0.002 - we 2.4 0.55 0.1 0.15 - 0.002 - WF 2.3 0.56 0.1 - 0.5 0.002 - WG 2.4 0.55 - 0.15 0.5 0.002 - WH 2.3 0.56 0.1 0.15 0.5 0.002 - x 3.8 0.9 0.1 0.15 0.5 0.011 - Z 1.7 0.27 0.1 0.15 0.5 0.002 -

Note: The balance of each alloy is copper and unavoidable impurities;

"-" was not added.

The (1) crystal grain diameter, (2) crystal orientation, (3) tensile strength, (4) electrical conductivity and (5) bending properties of each of the thus-produced copper alloy sheets were tested and determined.

Grain diameter (1) was measured according to JIS H 0501 (cutting method).

The crystal orientation (2) was determined by irradiating the surface of the copper alloy plate (0.15 mm in thickness) in the final product state with X-rays; and measuring the intensity from the diffraction surface. Among them, the respective diffraction intensities of the {200}, {220} and {311} planes, which show a strong correlation with the bending properties, are compared to obtain the crystal orientation intensity ratio (I{311}×A/(I{311}+I {220}+I{200})). Conditions for X-ray irradiation were: X-ray source CuKα1; tube voltage 40 kV; and tube current 20 mA.

Using a #5 test piece described in JIS Z 2201 formed from each sample plate, the tensile strength (3) was determined in accordance with JIS Z2241.

Conductivity was determined according to JIS H 0505 (4).

Bending properties were measured based on the method described in JIS H 3110 (5). A test piece with a width of 10 mm was bent under a load of 1000 kgf. Cut the test piece in the GW direction (bending axis perpendicular to the rolling direction) or in the BW direction (bending axis parallel to the rolling direction). The bending properties were determined by the ratio R/t, where R represents the minimum bending radius at a limit of crack formation and t represents the thickness of the test piece.

From the results shown in Table 2, it is apparent that Samples 1, 5 to 19 (Example 1) and Samples 2 to 4 (Example 2) each have excellent performance, satisfying that the bending performance (R/t) is less than 2, The tensile strength is 800 MPa or more and the electrical conductivity is 35% IACS or more. Also, Samples 34 to 41 had somewhat low tensile strength, but each had excellent properties satisfying bending property (R/t) of less than 2 and electrical conductivity of 35%IACS or more.

In contrast, Samples 20 to 25 (Comparative Examples) each had a value of Expression (1) out of the range specified by the present invention, and had remarkably poor bending properties, presumably because the solution treatment temperature was too high.

Since the contents of nickel and silicon were too large, cracks occurred during the thermal working, so sample 26 (comparative example) could not be normally produced.

Sample 27 (comparative example of the present invention regarding the above claim (3)) satisfies the value of Expression (1) and has excellent bending properties. However, the electrical conductivity of this sample was poor due to the high zinc content.

Sample 28 (comparative example of the present invention with respect to the above claim (4)) had poor bending properties due to too high a magnesium content.

Because the tin content was too high, edge cracks occurred during cold rolling, so Sample 29 (comparative example of the present invention with respect to the above claim (5)) could not be produced.

Since the boron content was too high, cracks occurred during the thermal processing, so Sample 31 (comparative example of the present invention regarding the above claim (7)) could not be normally produced.

Since the sulfur content was too high, cracks occurred during hot working, so the production of sample 32 (comparative example of the present invention with respect to the above claim (2)) was stopped.

Sample No. 33 provided a value outside the range specified by the expression (1) of the present invention. The content of nickel and silicon in this sample is too small, the mechanical strength is poor, and it is far from the performance of beryllium copper alloy.

Table 2 Ingot No. sample number The value of expression (1) Bending properties (R/t) tensile strength Conductivity GW BW MPa %IACS this invention A 5 0.67 1.0 1.0 815 39 B 6 0.71 1.0 1.0 820 39 C 7 0.61 1.0 1.0 820 40 D. 8 0.63 1.5 1.5 810 38 E. 9 0.66 1.0 1.0 815 37 f 10 0.61 1.0 1.0 820 38 G 11 0.6 1.5 1.5 810 37 h 12 0.57 1.0 1.0 825 38 I 13 0.58 1.0 1.0 820 37 J 1 0.99 1.0 1.0 810 36 J 2 0.57 1.0 1.0 820 36 J 3 0.54 1.5 1.5 860 36 J 4 0.4 1.0 1.0 820 37 K 14 1.18 1.0 1.0 820 37 L 15 1.23 1.0 1.0 825 38 N 17 0.6 1.0 1.0 810 35 o 18 0.46 1.0 1.0 815 36 P 19 O.56 1.0 1.0 805 36 WA 34 0.43 0.5 0.5 734 42 WB 35 0.44 0.5 0.5 743 40 WC 36 0.63 0.75 0.5 732 39 WD 37 0.54 0.5 0.5 724 40 we 38 0.5 0.5 0.5 722 37 WF 39 0.41 0.75 0.5 741 38 WG 40 0.61 0.5 0.5 735 37 WH 41 0.96 0.5 0.5 720 36 comparative example J 20 6.06 2.0 2.0 820 35 J twenty one 4.12 2.5 2.5 825 35 J twenty two 3.06 3.5 3.5 855 35 J twenty three 1.7 3.0 3.0 850 36 K twenty four 2.96 2.5 2.5 825 37 L 25 3.12 2.5 2.5 830 34 Q 26 Cracking during hot working R 27 0.65 1.0 1.0 820 30 S 28 0.71 2.0 2.0 815 33 T 29 cracking during cold working V 31 Cracking during hot working x 32 Cracking during hot working Z 33 3.96 1.0 1.0 644 41

(Example 3)

Each copper alloy has the composition shown in Table 3 (Ingot Nos. 2-A to 2-O, 2-PA to 2-PH, 2-Q to 2-S, 2-Z and 2-A-1) , each alloy was melted in a high-frequency melting furnace by a direct current method, and cast into an ingot with a thickness of 30 mm, a width of 100 mm, and a length of 150 mm. Then, these ingots were heated to 1000°C. After keeping the ingots at this temperature for 1 hour, each of the obtained ingots was hot rolled into a plate with a thickness of 12 mm, followed by rapid cooling.

Then, both end surfaces of each hot-rolled sheet were cut (chamfered) by 1.5 mm to remove the oxide film. The obtained sheet is processed into a sheet having a thickness of 0.15 to 0.25 mm by cold rolling (2-a). Then, the solution treatment temperature was changed within the temperature range of 825-925°C, the cold-rolled sheet was heat-treated for 15 seconds, and then immediately cooled at a cooling rate of 15°C/sec or more. Then, aging treatment was performed at 475°C for 2 hours in an inert gas atmosphere, and then, if necessary, depending on the sample, cold rolling (2-c) was performed as final plastic working to adjust the final plate thickness to 0.15 mm. After aging treatment or final plastic working, the samples were subjected to low-temperature annealing at 375°C for 2 hours to produce copper alloy plates (sample numbers 2-0 to 2-2, 2-1-1 and 2-5 to 2 -30).

(Example 4)

Copper alloy plates having a thickness of 0.15 mm were produced by separately processing copper alloys (ingot No. 2-B) having compositions shown in Table 3 under the following conditions. That is, the production conditions were the same as the production process of Example 3 from the start of melting to the removal of the oxide film after hot rolling. Then, the obtained sheet was processed to a thickness of 0.15 to 0.5 mm by cold rolling (2-a), followed by heat treatment at a solution treatment temperature in the range of 825 to 925° C. for 15 seconds. Immediately thereafter, the plate was cooled at a cooling rate of 15°C/sec or more. Then, depending on the sample, if necessary, the resulting plate was subjected to cold rolling (2-b) at a working ratio of 50% or less, and then, under the same conditions as in Example 3, in an inert gas atmosphere Aging treatment, final plastic working (cold rolling (2-c) into sheets with a final thickness of 0.35 mm), followed by low-temperature annealing produced copper alloy sheets (samples 2-3 and 2-4), respectively.

table 3 Ingot No. Ni mass% Si mass% Mg mass % Sn mass% Zn mass% Cr mass% S mass% Other elements mass% 2-Z 3.74 0.89 - - - 0.23 0.002 - 2-A 3.76 0.89 - - 0.49 0.25 0.002 - 2-A-1 3.75 0.89 0.10 0.15 - 0.24 0.002 - 2-B 3.78 0.9 0.09 0.15 0.49 0.21 0.002 - 2-C 3.52 0.83 0.11 0.16 0.51 0.22 0.002 - 2-D 4.1 0.95 0.10 0.15 0.52 0.2 0.002 - 2-E 3.21 0.72 0.09 0.14 0.5 0.19 0.002 - 2-F 3.79 0.9 0.12 0.15 0.48 0.24 0.002 Ag: 0.1 2-G 3.8 0.91 0.10 0.15 0.47 0.21 0.002 Co: 0.31 2-H 3.81 0.92 0.08 0.17 0.51 0.2 0.002 Zr: 0.17 2-I 3.76 0.89 0.10 0.15 0.5 0.25 0.002 Ti: 0.16 2-J 3.76 0.91 0.09 0.14 0.5 0.6 0.002 - 2-K 5 1.17 0.11 0.21 0.49 0.23 0.002 - 2-L 3.78 0.88 0.08 0.16 1.7 0.21 0.002 - 2-M 3.81 0.92 0.38 0.20 0.5 0.2 0.002 - 2-N 3.74 0.87 0.08 2.01 0.48 0.19 0.002 - 2-O 3.76 0.9 0.12 0.17 0.52 0.1 0.002 - 2-PA 2.3 0.56 - - - 0.27 0.002 - 2-PB 2.3 0.56 0.10 - - 0.27 0.002 - 2-PC 2.3 0.56 - 0.14 - 0.27 0.002 - 2-PD 2.3 0.56 - - 0.51 0.27 0.002 - 2-PE 2.3 0.56 0.10 0.14 - 0.27 0.002 - 2-PF 2.3 0.56 0.10 - 0.51 0.27 0.002 - 2-PG 2.3 0.56 - 0.14 0.51 0.27 0.002 - 2-PH 2.3 0.56 0.10 0.14 0.51 0.27 0.002 - 2-Q 3.8 0.89 0.11 0.15 0.46 0.22 0.011 - 2-R 3.78 0.91 0.10 0.16 0.5 - 0.002 - 2-S 1.7 0.27 0.10 0.14 0.51 0.27 0.002 -

Note: The balance of each alloy is copper and unavoidable impurities;

"-" was not added.

(1) crystal grain diameter, (2) crystal orientation, (3) bending properties, (4) tensile strength, (5) electrical conductivity and (6) of copper alloy sheets produced in each of Examples 3 and 4 were tested and measured. ) resistance to stress relaxation.

(1) The grain diameter (size) was measured according to JIS H 0501 (section method).

(2) The crystal orientation was determined by: irradiating the surface of the copper alloy plate (thickness: 0.15 mm) in the final product state with X-rays; and measuring the intensity from the diffraction surface. Among them, comparing the diffraction intensities of I{220}, I{200}, and I{311} planes, the integration degree of crystal orientation (I{311}/(I{311}+I{220}+I{200 })) and (I{311}×A/(I{311}+I{220}+I{200})). Conditions for X-ray irradiation were: X-ray source CuKα1; tube voltage 40 kV; and tube current 20 mA.

(3) Bending properties were measured based on the method described in JIS H 3110. A test piece with a width of 10 mm was bent under a load of 1000 kgf. Cut the test piece in the GW direction (the bending axis perpendicular to the rolling direction) or the BW direction (the bending axis parallel to the rolling direction). The bending properties were determined by the ratio R/t, where R represents the minimum bending radius at the limit of crack formation and t represents the thickness of the test piece.

(4) Using the #5 test piece described in JIS Z 2201, determine the tensile strength in accordance with JIS Z 2241.

(5) Determine the electrical conductivity in accordance with JIS H 0505.

(6) As an indicator of stress relaxation resistance, the stress relaxation ratio (S.R.R) was determined by applying the one-side holding block method of the Japan Standard Electronics Materials Manufacturers Association (EMAS-3003), where the adjusted Stress was loaded so that the maximum surface stress was 80% YS (80% of yield strength, or 0.2% of proof stress), and the resulting test piece was kept in a constant temperature room at 150° C. for 1000 hours.

The results are shown in Table 4.

Table 4 Ingot No. sample number grain size The value of expression (2) The value of expression (3) Bending properties (R/t) tensile strength Conductivity SRR μm GW BW MPa %IACS % this invention 2-Z 2-0 5 0.10 0.50 1.0 1.0 850 38 9.3 2-A 2-1 5 0.11 0.55 1.0 1.0 850 38 9.7 2-A-1 2-1-1 5 0.12 0.60 1.0 1.0 850 38 9.5 2-B 2-2 5 0.12 0.60 1.0 1.0 850 36 9.2 2-B 2-3 5 0.09 0.45 1.5 1.5 890 36 8.9 2-B 2-4 5 0.08 0.40 1.0 1.0 860 37 9.5 2-C 2-5 5 0.10 0.50 1.0 1.0 830 38 9.2 2-D 2-6 5 0.12 0.60 1.5 1.5 870 35 8.5 2-E 2-7 5 0.11 0.55 1.0 1.0 810 39 9.2 2-F 2-8 5 0.10 0.50 1.0 1.0 855 36 9.0 2-G 2-9 5 0.11 0.55 1.0 1.0 860 35 9.5 2-H 2-10 5 0.09 0.45 1.0 1.0 855 35 9.3 2-I 2-11 5 0.10 0.50 1.0 1.0 850 36 9.6 2-PA 2-23 5 0.11 0.51 0.5 0.75 732 40 10.2 2-PB 2-24 5 0.1 0.55 0.5 0.75 731 39 10.4 2-PC 2-25 5 0.09 0.52 0.5 0.5 730 38 9.9 2-PD 2-26 5 0.11 0.51 0.75 0.5 729 39 10.4 2-PE 2-27 5 0.1 0.52 0.75 0.75 721 38 10.1 2-PF 2-28 5 0.12 0.5 0.5 0.5 712 39 9.9 2-PG 2-29 5 0.13 0.52 0.75 0.5 734 38 9.5 2-PH 2-30 10 0.13 1.3 1 1 720 37 9.7 comparative example 2-A 2-12 20 0.25 5.00 2.5 2.5 850 38 8.8 2-B 2-13 20 0.23 4.60 2.5 2.5 855 37 8.2 2-J 2-14 10 0.13 1.30 2.0 2.0 840 35 9.7 2-K 2-15 Cracking during hot working 2-L 2-16 5 0.13 0.65 1.5 1.5 845 30 9.4 2-M 2-17 10 0.14 1.40 2.0 2.0 815 36 9.5 2-N 2-18 cracking during cold working 2-O 2-19 10 0.21 2.10 2.5 2.5 820 37 9.7 2-Q 2-20 Cracking during hot working 2-R 2-21 15 0.20 3.00 2.5 2.5 840 37 9.8 2-S 2-22 10 0.13 1.30 1.0 1.0 640 42 12.5

As is apparent from the results shown in Table 4, samples 2-0 to 2-2, 2-1-1 and 2-5 to 2-11 (Example 3) and samples 2-3 and 2-4 (Example 4) Each has excellent performance, satisfying that the bending performance (R/t) is less than 2, the tensile strength is 810 MPa or more, the electrical conductivity is 35% IACS or more and the stress relaxation rate is 10% or less all performance. Also, Samples 2-23 to 2-30 have slightly low tensile strength, and some have slightly low stress relaxation ratios, but each has excellent properties satisfying bending property (R/t) of less than 2 and electrical conductivity 35% IACS or both.

Contrary to the above, Samples 2-12 and 2-13 (Comparative Examples) have respective values of expression (2) or (3) out of the range specified by the present invention, and have remarkably poor bending properties, presumably because of solid Caused by too high solution temperature.

Samples 2-14 (comparative examples) had poor bending properties due to too large a chromium content.

Since the contents of nickel and silicon were too large, cracks occurred during the thermal working, so samples 2-15 (comparative examples) could not be normally produced.

The electrical conductivity of samples 2-16 (comparative example of the present invention related to the above claim (10)) was poor due to too high zinc content.

Samples 2-17 (comparative examples of the present invention pertaining to the above claim (11)) were excellent in stress relaxation resistance, but were remarkably poor in bending properties because the magnesium content was too high.

Since the tin content was too high, cracks appeared during the cold working process, so samples 2-18 (comparative examples of the present invention related to the above claim item (12)) could not be normally produced.

Since the value of Expression (2) or (3) of Sample 2-19 (Comparative Example) was out of the range specified by the present invention, its bending property was remarkably poor.

Because the sulfur content was too large, cracks occurred during the thermal working, so Samples 2-20 (comparative examples) could not be normally produced.

Since the value of Expression (2) or (3) of Sample 2-21 (Comparative Example) was out of the range specified by the present invention, its bending properties were remarkably poor.

Since the contents of nickel and silicon were too small, sample 2-22 (comparative example) was remarkably poor in mechanical strength and stress relaxation resistance.

Industrial Applicability

The copper alloy of the present invention is preferred as a material for terminals, connectors and lead frames, and it is also preferred as a general conductive material such as for switches and relays.

While the invention has been described in relation to our present embodiments, it is our intention that the invention not be limited to any detail of the specification unless otherwise stated, but construed broadly within the spirit and scope as set forth in the appended claims.

Claims (14)

1. a copper alloy that is used for electronic equipments and element comprises the nickel of 2.0～4.5 quality % and the silicon of 0.3～1.0 quality %, and surplus is copper and unavoidable impurities,

It satisfies following expression formula (1):

I{311}×A/(I{311}+I{220}+I{200})＜1.5…(1)

Wherein, in expression formula (1), the I{311} representative is from { the X-ray diffraction intensity of 311} face on plate surface; The I{220} representative is from { the X-ray diffraction intensity of 220} face on plate surface; The I{200} representative is from { the X-ray diffraction intensity of 200} face on plate surface; And A (μ m) represents grain size, and

It has good bending property.

2. according to the copper alloy of claim 1, it also comprises at least a element in the tin of the magnesium of the zinc that is selected from 0.2～1.5 quality %, 0.01～0.2 quality % and 0.05～1.5 quality %.

3. require 1 copper alloy according to aforesaid right, it also comprises at least a following element that is selected from: the cobalt of the zirconium of 0.005～0.3 quality %, 0.05～2.0 quality % and the boron of 0.001～0.02 quality %, its total content are 0.001～2.0 quality %.

4. copper alloy that is used for electronic equipments and element, comprise 2.0～4.5 quality % nickel, 0.3～1.0 quality % silicon and greater than 0 and less than the sulphur of 0.005 quality %, surplus is copper and unavoidable impurities,

It satisfies following expression formula (1):

I{311}×A/(I{311}+I{220}+I{200})＜1.5…(1)

Wherein, in the expression formula (1), the I{311} representative is from { the X-ray diffraction intensity of 311} face on plate surface; The I{220} representative is from { the X-ray diffraction intensity of 220} face on plate surface; The I{200} representative is from { the X-ray diffraction intensity of 200} face on plate surface; And A (μ m) represents grain size, and

It has good bending property.

5. according to the copper alloy of claim 4, it also comprises at least a element in the tin of the magnesium of the zinc that is selected from 0.2～1.5 quality %, 0.01～0.2 quality % and 0.05～1.5 quality %.

6. require 4 copper alloy according to aforesaid right, it also comprises at least a following element that is selected from: the cobalt of the zirconium of 0.005～0.3 quality %, 0.05～2.0 quality % and the boron of 0.001～0.02 quality %, its total content are 0.001～2.0 quality %.

7. copper alloy that is used for electronic equipments and element, comprise magnesium, 0.05～1.5 quality % of silicon, 0.01～0.2 quality % of nickel, 0.3～1.0 quality % of 2.0～4.5 quality % tin, 0.2～1.5 quality % zinc and less than the sulphur of 0.005 quality %, surplus is copper and unavoidable impurities

It satisfies following expression formula (1):

I{311}×A/(I{311}+I{220}+I{200})＜1.5…(1)

Wherein, in expression formula (1), the I{311} representative is from { the X-ray diffraction intensity of 311} face on plate surface; The I{220} representative is from { the X-ray diffraction intensity of 220} face on plate surface; The I{200} representative is from { the X-ray diffraction intensity of 200} face on plate surface; And A (μ m) represents grain size, and

It has good bending property.

8. according to the copper alloy of claim 7, it also comprises at least a following element that is selected from: the cobalt of the zirconium of 0.005～0.3 quality %, 0.05～2.0 quality % and the boron of 0.001～0.02 quality %, its total content are 0.001～2.0 quality %.

9. an Albatra metal-, comprise nickel, 0.3～1.0 quality % of 2.0～4.5 quality % silicon, 0.1～0.5 quality % chromium and less than the sulphur of 0.005 quality %, surplus is copper and unavoidable impurities,

It satisfies following expression formula (2):

I{311}/(I{311}+I{220}+I{200})＜0.15…(2)

Wherein, in the expression formula (2), the I{311} representative is from { the X-ray diffraction intensity of 311} face on plate surface; The I{220} representative is from { the X-ray diffraction intensity of 220} face on plate surface; With { the X-ray diffraction intensity of 200} face of I{200} representative from the plate surface.

10. according to the copper alloy of claim 9, it also comprises at least a element in the tin of the magnesium of the zinc that is selected from 0.2～1.5 quality %, 0.01～0.2 quality % and 0.05～1.5 quality %.

11., also comprise at least a following element that is selected from: the silver of the cobalt of the zirconium of 0.005～0.3 quality %, 0.05～2.0 quality %, the titanium of 0.005～0.3 quality %, 0.005～0.3 quality % and the boron of 0.001～0.02 quality % according to the copper alloy of claim 9.

12. an Albatra metal-, comprise nickel, 0.3～1.0 quality % of 2.0～4.5 quality % silicon, 0.1～0.5 quality % chromium and less than the sulphur of 0.005 quality %, surplus is copper and unavoidable impurities,

It satisfies following expression formula (3):

I{311}×A/(I{311}+I{220}+I{200})＜1.5…(3)

Wherein, in the expression formula (3), the I{311} representative is from { the X-ray diffraction intensity of 311} face on plate surface; The I{220} representative is from { the X-ray diffraction intensity of 220} face on plate surface; The I{200} representative is from { the X-ray diffraction intensity of 200} face on plate surface; And A (μ m) represents grain size.

13. according to the copper alloy of claim 12, it also comprises at least a element in the tin of the magnesium of the zinc that is selected from 0.2～1.5 quality %, 0.01～0.2 quality % and 0.05～1.5 quality %.

14. according to the copper alloy of claim 12, it also comprises at least a following element that is selected from: the silver of the cobalt of the zirconium of 0.005～0.3 quality %, 0.05～2.0 quality %, the titanium of 0.005～0.3 quality %, 0.005～0.3 quality % and the boron of 0.001～0.02 quality %.