KR101914322B1 - Copper alloy material and manufacturing method thereof - Google Patents

Abstract

(Zn, Fe, Sn, Ag, Si) of 0.1 to 0.8% by mass of Cr and an additional element group 1 (0.01 to 0.5% by mass in total of at least one element selected from the group consisting of Mg, Ti and Zr) And P) in an amount of 0.01 to 0.5 mass% in total, the balance being composed of copper and unavoidable impurities, and at least one kind selected from the group consisting of an electron rear In the analysis of the crystal orientation of the rolled surface in the scattering diffraction measurement, the area ratio of the crystal grains having the orientation within 15 占 of the difference from the Cube orientation {001} < 100 占 is 3% or more, It is excellent in bending workability, strength, conductivity, and stress relaxation characteristics with a grain boundary Σ3 ratio of 20% or more. This makes it possible to provide lead frames, connectors, and terminals for vehicle mounted parts and peripheral infrastructures such as EVs and HEVs, Material Thereby providing a copper alloy material.

Description

TECHNICAL FIELD [0001] The present invention relates to a copper alloy material and a method of manufacturing the copper alloy material.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper alloy material and a method of manufacturing the same, and more particularly to a copper alloy material and a manufacturing method thereof, , A relay, a switch, a socket, and the like, and a method of manufacturing the copper alloy material.

Examples of characteristics required for copper alloy materials used in applications such as EVs, HEVs, and vehicle-mounted parts, leadframes, connectors, terminations, relays, switches, and sockets in peripheral infrastructures and solar power systems For example, there are conductivity, tensile strength, bending workability, stress relaxation resistance, and the like. In recent years, the system has become higher in voltage and the operating environment has become higher in temperature, and the level of these required characteristics is increasing.

With the above change, the copper alloy material has the following problems.

First, the environment in which the terminals are used is becoming higher in temperature and higher in voltage, so that the demand for heat resistance is getting stronger. Particularly, when a contact pressure is applied to the terminal spring portion under a high temperature, the stress deteriorates over time, which poses a problem of spring reliability. In addition, in the applications listed above, the ambient temperature is rising year by year. In addition, not only the ambient environment but also self-generated heat is a problem because the temperature is high and the current loss is caused.

Secondly, a strong spring property and a constant strength are required for the terminal. On the other hand, if the workability (bending workability) against bending applied to the contact portion or the spring portion is low, the degree of freedom in design becomes low, Throw away. It is generally well known that the bending workability deteriorates due to the increase in thickness. However, thickening the thickness is inevitable in a large current application, and cracks are generated even in the same warpage as conventional connector products .

Copper (Cu) does not reach the level where the spring strength satisfies the required characteristics in pure metal state. Thus, for example, Mg or Sn may be added to strengthen the solid solution, or Cr or Zr may be added to precipitate and reinforce it. On the other hand, for high current applications, it is necessary to have high conductivity and excellent heat resistance.

In this background, Cu-Cr alloys are known to have moderate strength and high conductivity. In Patent Document 1, the workability of stamping (press punching) is improved by adding Mg to a Cu-Cr-based alloy. In Patent Document 2, the bending workability is improved by adding Zr to a Cu-Cr- It has been found that the stress relaxation resistance is improved by adding Ti to the Cu-Cr alloy. As shown in Patent Documents 1 to 3, an example of an additive component and composition of a conventional high-conductivity copper alloy is known.

Further, in Patent Document 4, the Cu-Cr-Zr alloy has excellent bending workability because the ratio of the corresponding grain boundary? 3 at grain boundaries is 10% or more. Patent Document 5 discloses that in the case of a Cu-Cr-Zr alloy, the orientation distribution density of the Brass orientation is 20 or less, and the sum of the Brass orientation and the orientation distribution density between the S orientation and the Copper orientation is controlled to 10 or more and 50 or less Thereby improving the bending workability.

Further, as shown in Patent Documents 6 to 8, a Cu-Mg-based alloy is known. Patent Document 6 discloses a method of reducing mold wear at the time of stamping by adjusting the surface crystal grain size of a Cu-Mg-P alloy, and Patent Document 7 discloses that Mg-P-based compounds precipitated and dispersed in a Cu- In Patent Document 8, the precipitation of a coarse intermetallic compound having a particle diameter of 0.1 mu m or more in a Cu-Mg-P alloy is suppressed, And the bending workability is improved.

: JP-A-11-323463 : Japanese Patent No. 3803981 : Japanese Laid-Open Patent Publication No. 2002-180159 : Japanese Patent No. 4087307 : JP-A-2009-132965 : Japanese Patent No. 3353324 : Japanese Patent No. 4756197 : Japanese Laid-Open Patent Publication No. 2011-241412

However, the invention described in Patent Documents 1, 2, and 3 specifies the Cu-Cr-based alloy component and the crystal grain size, (Mother phase) did not come to improve their own characteristics.

In the inventions described in Patent Documents 6, 7, and 8, the specification of the Cu-Mg alloy component, the crystal grain size, and the particle diameter of the precipitate are specified. However, Control) did not reach the improvement of the characteristics of the figure itself.

In Patent Document 4, in the Cu-Cr-Zr alloy, by performing dynamic cold recrystallization by performing final cold rolling at a specific high work rate, the ratio of the corresponding grain boundary? 3 is set to 10% or more, 5, in the Cu-Cr-Zr based copper alloy, by performing cold rolling at a specific processing degree and heat treatment at a low temperature, the orientation distribution density of the Brass orientation is 20 or less, and the Brass orientation, the S orientation and the Copper orientation Are 10 or more and 50 or less, respectively. The bending workability is improved, but the improvement of the stress relaxation resistance is not achieved.

As described above, it is difficult to attain the characteristics that the conductivity, the tensile strength, the bending workability, and the stress relaxation property are each at a high level and the balance is good and satisfactory in the conventional alloying composition and the conventional production method .

In view of the above problems, an object of the present invention is to provide a copper alloy material excellent in strength and conductivity, particularly excellent in stress relaxation resistance and bending workability, and excellent in balance between these materials, and a method for producing the same It is on. This copper alloy material can be used for automotive parts such as EVs, HEVs, and automotive parts such as lead frames, connectors, and end materials such as peripheral infrastructure and photovoltaic power generation systems, relays, switches and sockets And the like.

The inventors of the present invention have conducted intensive studies to investigate a copper alloy suitable for use in electric and electronic parts. As a result, it has been found that in a structure of a copper alloy material having a predetermined Cu-Cr or Cu-Mg alloy composition, 3% or more of the Cube orientation {100} < 001 > is accumulated in the surface direction ND of the plate, and the ratio of the corresponding grain boundary? 3 in the grain boundary is 20% or more. Workability, and stress relaxation property can be improved at the same time. The present invention is based on these findings.

That is, according to the present invention, the following means are provided.

(1) 0.1 to 0.8% by mass of Cr, 0.01 to 0.5% by mass of at least one selected from the group consisting of the following elements 1 and 2, and the balance copper and inevitable impurities , The area ratio of the crystal grains having a direction in which the difference from the Cube orientation {001} < 100 > is within 15 DEG is 3% or more in the crystal orientation analysis of the rolled surface in the electron backscattering diffraction measurement, The ratio of the corresponding grain boundary? 3 in the copper alloy layer is 20% or more.

Additive element group 1: at least one species selected from the group consisting of Mg, Ti and Zr in a total amount of 0.01 to 0.5 mass%

Additive element group 2: 0.005 to 0.5 mass% of a total of at least one element selected from the group consisting of Zn, Fe, Sn, Ag, Si and P;

(2) The copper alloy material according to (1), which contains 0.01 to 0.5% by mass in total of at least one selected from the above-mentioned additive element group 1 and at least one selected from the additive element group 2.

(3) The copper alloy material according to (1) or (2), wherein the tensile strength is 400 MPa or more and the electrical conductivity is 75% IACS or more.

(4) The copper alloy material described in item (1) or (2) is subjected to a homogenizing heat treatment [Step 1-2] at 600 to 1025 ° C for 10 minutes to 10 hours, Hot rolling at a processing temperature of 500 to 1020 占 폚 at a processing rate of 30 to 98% at a temperature of 300 to 1000 占 폚 for 5 to 180 minutes Cold rolling at a machining ratio of 50 to 95% [Step 1-6], aging treatment at 400 to 650 占 폚 for 30 to 180 minutes [Step 1-9], and annealing at 550 to 700 占 폚 And a stress removal annealing step (Step 1-11) for 5 seconds to 10 minutes are performed in this order.

(5) A method for producing a quartz crystal substrate, which comprises 0.01 to 0.5 mass% of Mg and the balance of copper and unavoidable impurities, wherein in the crystal orientation analysis of the rolled surface in the electron backscattering diffraction measurement, Wherein the area ratio of the crystal grains having the orientation whose difference is within 15 占 is 3% or more and the ratio of the corresponding grain boundary? 3 in the grain boundary is 20% or more.

(6) A copper alloy containing 0.01 to 0.5 mass% of Mg and 0.01 to 0.3 mass% of at least one selected from the group consisting of Zn, Sn, Ag, Si and P in total, the balance being copper and inevitable impurities , The area ratio of the crystal grains having a direction in which the difference from the Cube orientation {001} < 100 > is within 15 DEG is 3% or more in the crystal orientation analysis of the rolled surface in the electron backscattering diffraction measurement, The ratio of the corresponding grain boundary? 3 in the copper alloy layer is 20% or more.

(7) The copper alloy material according to (5) or (6), wherein the tensile strength is 250 MPa or more and the electrical conductivity is 75% IACS or more.

(8) The copper alloy material according to item (5) or (6) is subjected to a homogenization heat treatment [Step 2-2] for 10 minutes to 10 hours at 600 to 1025 ° C, Hot rolling at a processing temperature of 500 to 1020 占 폚 at a processing rate of 30 to 98% [Step 2-3], cold rolling at a finishing rate of 50 to 99% [Step 2-4], heating at 300 to 800 占 폚 for 5 seconds to 180 minutes , Cold rolling at a machining ratio of 50 to 95% [step 2-6], heat treatment at 300 to 800 占 폚 for 5 seconds to 180 minutes [step 2-7], processing rate of 10 to 80 % Of cold working [Step 2-8] and stress-relieving annealing at 300 to 600 ° C for 5 to 60 seconds [Step 2-9] are performed in this order.

Here, the Cu-Cr alloy material described in the above (1) to (3) and the manufacturing method thereof described in the above (4) are also the first embodiment of the present invention.

The Cu-Mg alloy material described in the above (5) to (7) and the production method thereof described in the above (8) are also the second embodiment of the present invention.

The present invention is meant to include both the first and second embodiments, unless otherwise noted.

The copper alloy material centering on the Cu-Cr system of the present invention is excellent in stress relaxation resistance and bending workability, has excellent strength and conductivity, is excellent in EV and HEV, It is suitable for lead frames, connectors, end materials, relays, switches, sockets, etc. for power generation systems.

These and other features and advantages of the present invention will become more apparent from the following description, with reference to the appended drawings, as appropriate.

Fig. 1 is an explanatory view of a test method of stress relaxation resistance in the embodiment, wherein (a) shows a state before heat treatment and (b) shows a state after heat treatment, respectively.

Preferred embodiments of the copper alloy material of the present invention will be described in detail. Here, the "copper alloy material" means that a copper alloy material (having a predetermined alloy composition before processing) is processed into a predetermined shape (for example, a plate, a rods, and the like). As an embodiment, a plate material and a provisional material will be described below.

On the other hand, the copper alloy material of the present invention is characterized by its specific gravity at the crystal grain boundaries and the integration ratio of the texture in the predetermined direction of the rolled plate. However, the copper alloy material has such a characteristic as a copper alloy material And the shape of the copper alloy material is not limited to a sheet material but may be a joining material.

Next, each alloy composition and its added element components will be described.

In the first embodiment of the present invention, as the copper alloy material, for example, it is possible to use a conductive material such as EV, HEV and the like, which is required for a connector such as a vehicle-mounted component and a peripheral infrastructure or a solar power generation system, A Cu-Cr-based alloy is used because it has bending workability and stress relaxation resistance. In the first embodiment of the present invention, the ratio of the length to the total grain boundary length of the corresponding grain boundary? 3, which improves the area ratio of the Cube bearing improving the bending workability and the stress relaxation resistance improving property, , 0.1 to 0.8% by mass of Cr as an additive amount to Cu, and 0.01 to 0.5% by mass of at least one selected from the group consisting of the following additive element group 1 and the following additive element group 2 in total.

Additive element group 1: at least one species selected from the group consisting of Mg, Ti and Zr in a total amount of 0.01 to 0.5 mass%

Additive element group 2: 0.005 to 0.5 mass% of a total of at least one element selected from the group consisting of Zn, Fe, Sn, Ag, Si and P;

Preferably, at least one kind selected from the above-mentioned additive element group 1 and at least one kind selected from the above-mentioned additive element group 2 are contained in a total amount of 0.01 to 0.5 mass%. More preferably, the alloy contains 0.15 to 0.5 mass% of Cr, and contains at least one kind selected from the above-mentioned additive element group 1 and at least one kind selected from the above-mentioned additive element group 2 in a total amount of 0.1 to 0.5 mass%. This is because, by defining the addition amount within this range, both the shape of the parent phase is close to the pure copper structure, so that the development of the Cube orientation can be promoted and the lamination defect energy due to partial employment can be reduced. In addition to the above, the precipitation-type Cu-Cr-based alloy suppresses partial coarsening of crystal grains and promotes stable development of the Cube orientation by the precipitate before entering the heat treatment for finally determining the texture.

In the second embodiment of the present invention, the copper alloy material is required to have conductivity, mechanical strength, bending property and the like required for a vehicle-mounted component, for example, EV, HEV, A Cu-Mg alloy is used as a material having workability and stress relaxation resistance. In the second embodiment of the present invention, the ratio of the length to the total grain boundary length of the corresponding grain boundary? 3, which improves the area ratio of the Cube bearing improving the bending workability and the stress relaxation resistance improving property, , It contains 0.01 to 0.5 mass% of Mg as an additive amount to Cu. In the second embodiment of the present invention, in addition to Mg, at least one kind selected from the group consisting of Zn, Fe, Sn, Ag, Si, and P is added in a total amount of 0.01 to 0.3 mass% And preferably 0.05 to 0.3% by mass of the above-mentioned auxiliary addition elements. This is because, by defining the addition amount within this range, both the parent phase and the pure copper structure are close to each other, so that the development of the Cube orientation can be promoted and the lamination defect energy caused by the employment can be reduced.

Hereinafter, the addition elements of Cu-Cr based copper alloy in the precipitation form in the first embodiment of the present invention will be described.

(Cr)

The first embodiment of the present invention is directed to a Cu-Cr alloy for securing strength and conductivity. The amount of Cr added is 0.1 to 0.8 mass%, preferably 0.15 to 0.5 mass%. By setting the addition amount of Cr within this range, it is possible to precipitate a Cr single component and / or a precipitate composed of a compound of Cr and another element in the form of a copper phase, to bring the parent phase close to pure copper, And promotes nucleation and growth of the Cube orientation {001} < 100 > in the plate thickness direction ND. On the other hand, if the amount of Cr added is too large, these precipitates are precipitated too much, and the solidification does not sufficiently proceed by the subsequent heat treatment, and the strength after the aging treatment tends to decrease. In addition, the stacking fault energy (hereinafter also referred to as SFE) increases and the increase of the corresponding grain boundary? 3 during the heat treatment is suppressed, so that sufficient stress relaxation resistance can not be obtained. On the other hand, if the amount of Cr added is too small, these effects can not be obtained.

The term " compound " as used herein refers to a substance composed of two or more elements, and is, for example, a substance comprising at least Cr and other elements (including Cu). In the present specification, precipitates are meant to include precipitates or crystallizations in which these compounds are present in the grain or grain boundaries of the Cu matrix. Here, Cr-based precipitate of the other examples, Cr groups, for example, when Si is added, may be mentioned Cr-based compounds such as Cr ₃ Si, CrSi. These compounds are different depending on the added element.

(Alloying elements Mg, Ti, Zr, Zn, Fe, Sn, Ag, Si, P)

In the first embodiment of the present invention, in addition to the Cr as the main additive element, at least one kind selected from the group consisting of the following additive element group 1 and the following additive element group 2 as additive elements in a total amount of 0.01 to 0.5 mass% do. Subadding elements are divided into two groups in terms of their action.

Additive element group 1: at least one species selected from the group consisting of Mg, Ti and Zr in a total amount of 0.01 to 0.5 mass%

Additive element group 2: 0.005 to 0.5 mass% of a total of at least one element selected from the group consisting of Zn, Fe, Sn, Ag, Si and P;

At least one kind selected from the above-mentioned additive element group 1 and at least one kind selected from the above-mentioned additive element group 2 in a total amount of 0.01 to 0.5% by mass.

A preferred range of the addition amount of each of these added elements is as follows. The amount of Mg to be added is preferably 0.01% by mass to 0.5% by mass, and more preferably 0.05% by mass to 0.3% by mass. The addition amount of Ti is preferably 0.01% by mass to 0.2% by mass, and more preferably 0.02% by mass to 0.1% by mass. The amount of Zr added is preferably 0.01 to 0.2 mass%, more preferably 0.01 to 0.1 mass%. The amount of Zn to be added is preferably 0.05% by mass to 0.3% by mass, and more preferably 0.1% by mass to 0.2% by mass. The amount of Fe to be added is preferably 0.05% by mass to 0.2% by mass, and more preferably 0.1% by mass to 0.15% by mass. The amount of Sn to be added is preferably 0.05% by mass to 0.3% by mass, and more preferably 0.1% by mass to 0.2% by mass. The addition amount of Ag is preferably 0.05% by mass to 0.2% by mass, and more preferably 0.05% by mass to 0.1% by mass. The amount of Si to be added is preferably 0.01% by mass to 0.1% by mass, and more preferably 0.02% by mass to 0.05% by mass. The amount of P added is preferably 0.005 mass% to 0.1 mass%, more preferably 0.005 mass% to 0.05 mass%. If the addition amount of each element is too small, the addition effect can not be obtained.

Each of these additive elements fulfills the following roles.

Mg is solved to improve the stress relaxation resistance. If the addition amount of Mg is too large, a Mg compound is formed and adversely affected by dissolution, casting and hot rolling, and the composition is markedly deteriorated. Further, in addition to causing deterioration of conductivity, nucleation and growth of Cube orientation {001} < 100 > in ND is suppressed by an increase in the amount of a large amount, and the bending workability becomes insufficient.

Ti and Zr improve the stress relaxation resistance and strength by solidification, precipitation and crystallization. If the addition amount of Ti and Zr is too large, a Ti-based or Zr-based compound is formed to adversely affect melting, casting, and hot rolling, thereby remarkably deteriorating the productivity. When the addition amount of Ti and Zr is too large to be present in a solid solution state, besides causing deterioration in conductivity, nucleation and growth of the Cube orientation {001} < 100 > And the bending workability becomes insufficient.

In the range of the predetermined amount of Zn, the resistance to peeling of the plating and the solder is improved and contributes to the improvement of the strength, though slightly. If the added amount of Zn is too large, the conductivity is lowered by the employment, and besides the nucleation and growth of the Cube orientation {001} < 100 > in the ND is suppressed by the increase of the high capacity, and the bending workability becomes insufficient.

Fe is finely precipitated in the form of a compound in the form of a compound or a group within the above-specified range. As a group, it precipitates and contributes to precipitation hardening. It also precipitates as an Fe-based compound. In either case, there is an effect of suppressing the growth of crystal grains, thereby finer crystal grains, and satisfactory bending workability is improved by improving the dispersion state of crystal grains of the Cube orientation {001} < 100 >.

Sn promotes hardening of the solid solution and also the work hardening at the time of rolling. Further, by adding them simultaneously with Mg, it is possible to further improve the stress relaxation resistance characteristics by adding them individually. If the added amount of Sn is too large, the conductivity is lowered by the employment, and the generation and growth of the Cube orientation {001} < 100} in the ND are suppressed by an increase in the amount of a large amount, and the bending workability becomes insufficient.

Ag has an effect of improving the stress relaxation resistance even by itself, and when added simultaneously with Mg, Zr, and Ti, it is possible to further improve the stress relaxation resistance of the Ag. If the addition amount of Ag is too large, the effect is saturated, and the effect on the cost is large, which is not preferable.

Si has an effect of improving the stress relaxation resistance even by itself, and when added simultaneously with Mg, Zr, and Ti, the stress relaxation property can be further improved as compared with the case where each of them is added singly. Further, the pressing property is improved. If the added amount of Si is too large, the conductivity is lowered by the employment, besides the nucleation and growth of the Cube orientation {001} < 100 > in the ND is suppressed by the increase of the high capacity, and the bending workability becomes insufficient.

P can improve the flow of molten metal during melting and casting, and can improve the stress relaxation resistance property alone or in a compound state. If the amount of P added is too large, the conductivity is lowered by the employment, and the generation and growth of the Cube orientation {001} < 100 > nuclei in the ND are inhibited by an increase in the amount of a large amount, and the bending workability becomes insufficient.

Hereinafter, the additive elements of the solid solution type Cu-Mg-based synchronous alloy in the second embodiment of the present invention will be described.

The second embodiment of the present invention contains 0.01 to 0.5 mass% of Mg as an essential additional element. In addition to the Mg, it may further contain at least 0.01 mass% of at least one species selected from the group consisting of Zn, Sn, Ag, Si and P as optional additional elements.

The preferable ranges of the addition amounts of the main addition and the auxiliary addition elements are as follows. The amount of Mg to be added is preferably 0.01 to 0.3 mass%, more preferably 0.05 to 0.25 mass%. The amount of Zn to be added is preferably 0.05 to 0.3 mass%, more preferably 0.1 to 0.2 mass%. The amount of Sn to be added is preferably 0.05 to 0.2 mass%, more preferably 0.1 to 0.15 mass%. The amount of Ag to be added is preferably 0.01 to 0.15 mass%, more preferably 0.05 to 0.1 mass%. The amount of Si to be added is preferably 0.01 to 0.05 mass%, more preferably 0.02 mass% to 0.03 mass%. The amount of P added is preferably 0.001 to 0.1 mass%, more preferably 0.005 mass% to 0.05 mass%.

(Alloying elements Mg, Zn, Sn, Ag, Si, P)

Each of the additional elements brings about the above-mentioned action.

On the other hand, in the present invention, the unavoidable impurities included in the remainder are conventional ones, and examples thereof include O, F, S, and C. The content of unavoidable impurities is preferably 0.001 mass% or less.

(Organized organization)

The EBSD method was used to analyze the crystal orientation of the rolled surface in the present invention. EBSD is abbreviation of Electron Back Scatter Diffraction (EBSD). It is a reflection electron kikuchi ray diffraction (kikuchi pattern) which occurs when a sample is irradiated with an electron beam in a Scanning Electron Microscope (SEM) Is a crystal orientation analysis technique using In the present invention, the sample was scanned at a step of 0.5 mu m with respect to a sample area of 500 mu m square including 200 or more crystal grains, and the orientation was analyzed.

On the other hand, in the EBSD measurement, it is preferable to carry out the measurement after mirror polishing of the substrate surface by using abrasive particles of colloidal silica after mechanical polishing in order to obtain a clear Kikuchi ray diffraction image. Measurements were made from the plate surface.

In the present invention, the area ratio of the Cube orientation {001} < 100 > means the area ratio of the Cube orientation {001} < 100 & Refers to the ratio of the area of the grain to the entire measuring area. The information obtained in the orientation analysis by the EBSD method includes orientation information up to a depth of several tens of nanometers at which the electron beam enters the sample but is sufficiently small with respect to the area to be measured. did. Since the azimuth distribution changes in the thickness direction, it is preferable to arbitrarily take a number of points in the thickness direction of the azimuthal analysis by the EBSD method and take an average. Unless otherwise stated, the area ratio of a crystal plane having a certain crystal orientation will be referred to as a measurement obtained in this manner.

In the present invention, the area ratio of the Cube orientation {001} < 100 > on the rolled surface is 3% or more, preferably 6% or more. The upper limit is not particularly limited, but is usually 90% or less. By controlling the area ratio of the Cube orientation in this manner, the bending workability can be improved.

On the other hand, in the present invention, the area ratio of the Cube orientation {001} < 100 > when the surface of the rolled surface (rolled surface in contact with the rolling roll) is observed is defined.

(Corresponding grain boundary Σ3)

Corresponding grain is a special grain boundary with high geometrical consistency, and the smaller the value of Σ defined as the inverse of the corresponding lattice point density, the higher the consistency. Among them, it is known that the compatible grain boundary? 3 has small disorder of regularity at grain boundaries and low grain boundary energy. In particular, since there are few defects promoting stress relaxation in the structure, heat resistance is more excellent.

In the present invention, the ratio of the corresponding grain boundary? 3 in the crystal grain boundaries is 20% or more, preferably 30% or more, and more preferably 40% or more. The upper limit is not particularly limited, but is usually 90% or less. The stress relaxation characteristics can be improved by controlling the ratio of the corresponding boundary layer? 3 in this manner. On the other hand, the ratio of the corresponding intergranular sphere? 3 is defined as the sum of the lengths of the corresponding intergranular spheres? 3 to the total sum of the lengths of the intergranular phases on the observation plane measured by the ESBD method or the like, ) / (Sum of lengths of all grain boundaries) x 100 (%). Details of the corresponding boundary layer? 3 and its measuring method will be described below.

The analysis of the corresponding boundary grain boundary? 3 is performed by CSL (Coincidence Site Lattice Boundary) analysis using the software "Orientation Imaging Microscopy v5" (trade name) manufactured by EDAX TSL. Corresponding grain boundary? 3 is, for example, a grain boundary in which neighboring grains have a rotation angle relationship of 60 degrees based on the rotation axis of < 1 1 1 >. Therefore, the grain boundary corresponding to the corresponding grain boundary? 3 is analyzed from the orientation relationship of adjacent grain boundaries by using the software. Then, the total grain boundary length of the rolled surface in the measurement range and the corresponding grain boundary? 3 are measured and defined as the ratio of the corresponding grain boundary? 3 (length of corresponding grain boundary? 3) / (total grain boundary length) do. On the other hand, in the measurement using the soft, a case where neighboring pixels have a slope (deviation) of 15 degrees or more is determined as a grain boundary.

Specifically, the measurement is performed under the condition that the scan step is 0.5 mu m in the measurement region of about 500 mu m square including 200 or more crystal grains by the EBSD method, and the length of the corresponding grain boundary & Measure the length. When the azimuth difference (deviation) of neighboring pixels in the measurement object is 15 degrees or more, it is determined that the boundary is boundary, and on the other hand, the boundary boundary? 3 corresponding to neighboring pixels is determined. The ratio of the sum of the lengths of the corresponding grain boundaries? 3 to the sum of the lengths of all grain boundaries from the length of all the grain boundaries on the rolled surface and the length of the corresponding grain boundary? The sum of the lengths of the corresponding intergranular elements? 3) / (the sum of the lengths of all the intergranular elements) x 100, and this is regarded as the ratio of the corresponding intergranular elements? 3 in the grain boundary. In the present specification, this is simply referred to as " ratio (%) of the corresponding boundary layer? 3 ".

(Manufacturing method)

Next, a method for producing the copper alloy material of the present invention (a method for controlling its crystal orientation and grain boundary state) will be described.

In the first embodiment of the present invention, the Cu-Cr-based copper alloy is obtained by subjecting the ingot of the casting [Step 1-1] to homogenization heat treatment [Step 1-2], and hot working [Step 1-3] (Intermediate annealing) [step 1-5], cold working [step 1-6] (step 1 - 6), or the like Specifically, cold rolling), aging treatment (aging precipitation heat treatment) [Step 1-9], and stress relief annealing [Step 1-11] are performed in this order. After the cold working [Step 1-6], before the aging treatment [Step 1-9], if necessary, heat treatment [Step 1-7] and cold working [Step 1-8] ) May be performed in this order. After the above aging treatment [Step 1-9], before the stress relief annealing [Step 1-11], if necessary, finishing cold working [Step 1-10] (specifically, cold rolling) is performed again It is also good.

The conditions of the respective steps of the aging treatment [Step 1-9], the cold working [Step 1-10] and the stress relief annealing [Step 1-11] are appropriately adjusted in accordance with desired strength and properties such as conductivity.

In the copper alloy material of the first embodiment of the present invention, the driving force of the Cube bearing development is imparted to the texture of the copper alloy material by hot working [step 1-3] in the series of steps, and aging treatment -9], the corresponding boundary layer? 3 develops by the heat treatment [Step 1-7]. Processes 1-6, 1-8, or 1-8 (for example, cold rolling), which are roughly determined by the intermediate heat treatment [Steps 1-5] -10]. ≪ / RTI >

The heat treatment [Step 1-7] and the cold working [Step 1-8] may be omitted. Even if these are not carried out, a desired aggregate structure can be obtained by performing the aging treatment [Step 1-9] under a predetermined condition. By performing the heat treatment [Step 1-7], the aging treatment [Step 1-9] can be performed in a shorter time.

The above cold working [Step 1-6] has an action to accelerate the development of the corresponding grain boundary? 3 in the heat treatment in the subsequent process by applying stress to the material, in addition to adjusting the plate thickness.

In the first embodiment of the present invention, after the heat treatment [Step 1-7] is finished, the ratio of the area ratio of the Cube orientation to the total grain boundary of the corresponding grain boundary? 3 is almost finally determined. For this reason, in the subsequent steps after the heat treatment [step 1-7], if the structure is in the desired control range, for example, thinning by the cold working [step 1-8], aging treatment [step 1-9] (Improvement in mechanical strength and recovery of electric conductivity at the same time), aging treatment [Step 1-9], high-strength annealing by the cold working [Step 1-10], stress relieving annealing [Step 1- 11], free cold working and heat treatment may be combined with each other.

Typical examples of the heat treatment / processing conditions in the first embodiment of the present invention and preferable conditions of each step will be specifically described below.

It is preferable that the homogenization heat treatment [step 1-2] is performed at 600 to 1025 ° C for 10 minutes to 10 hours. The homogenization heat treatment time may be 2 to 10 hours. The hot working step 1-3 is preferably carried out at a working temperature of 500 to 1020 ° C and a working rate of 30 to 98%. The cold working [step 1-4] is preferably performed at a machining rate of 50 to 99%. This processing ratio may be 50 to 95%. The intermediate heat treatment (intermediate annealing) [Step 1-5] is preferably performed at 300 to 1000 ° C for 5 seconds to 180 minutes. The cold working [step 1-6] is preferably performed at a machining rate of 50 to 95%.

The heat treatment [Step 1-7] is preferably performed at 650 to 1000 ° C for 5 to 60 seconds. The cold working step 1-8 is preferably carried out at a machining rate of 10 to 60%.

The aging treatment (aging precipitation heat treatment) [Step 1-9] is preferably performed at 400 to 650 ° C for 30 to 180 minutes. The finish cold working [step 1-10] is preferably performed at a machining rate of 0 to 70%. Here, the machining rate of 0% means that the machining is not performed, and in this case, the cold machining [Step 1-10] is omitted. The above stress relief annealing [Step 1-11] is preferably performed at 550 to 700 ° C for 5 seconds to 10 minutes. The stress relieving annealing time may be 5 seconds to 60 seconds.

After each heat treatment or after the rolling process, acid cleaning or surface polishing may be performed depending on the oxidation or roughness of the surface of the material by a tension leveler depending on the shape. After hot rolling [Step 1-3], it is usually water-cooled (quenched).

Preferable examples of combinations of the respective steps in the first embodiment of the present invention include Manufacturing Method 1 to Manufacturing Method 4 in Examples to be described later.

Here, the machining rate is a value defined by the following equation.

Processing rate (%) = (t ₁ -t ₂ ) / t ₁ × 100

In the formula, t ₁ represents the thickness before rolling and t ₂ represents the thickness after rolling.

In the second embodiment of the present invention, the Cu-Mg-based copper alloy is obtained by subjecting the ingot subjected to the casting [step 2-1] to homogenization heat treatment [step 2-2], hot working [step 2-3] (Intermediate annealing) [Step 2-5], and cold working [Step 2-6] (intermediate annealing) are carried out in the same manner as in Example 1, (Specifically, cold rolling), heat treatment [step 2-7], finish cold working [step 2-8] (specifically, cold rolling) and stress relieving annealing [step 2-9] Can be manufactured.

The conditions of the stress relieving annealing (step 2-9) are suitably adjusted according to characteristics such as desired strength, conductivity, elongation, and springiness (stress relaxation resistance).

In the copper alloy material of the second embodiment of the present invention, the driving force of the Cube bearing development is imparted to the texture of the copper alloy material in the series of steps by hot working [step 2-3], and the heat treatment [step 2- 7], the corresponding boundary layer Σ3 develops. Then, the rough texture of the texture is determined by the intermediate heat treatment [Step 2-5], and finally determined by the rotation of the bearing that occurs during the cold working (i.e., finish cold rolling) performed at the last [Step 2-8].

The cold working [Step 2-6] has an action of accelerating the development of the corresponding grain boundary? 3 in the heat treatment in the subsequent step [Step 2-8], besides adjusting the plate thickness.

In the second embodiment of the present invention, after the heat treatment [step 2-7] is finished, the ratio of the area ratio of the Cube orientation to the total grain boundary of the corresponding grain boundary? 3 is almost finally determined. Therefore, in the subsequent step of the heat treatment [step 2-7], if the structure is within the desired control range, for example, the thinning by cold working including high strength [step 2-8], the stress relief annealing A free cold working and a heat treatment may be combined with respect to the spring property and recovery of elongation by [Step 2-9]. On the other hand, the heat treatment at a temperature exceeding 600 캜 and the cold rolling or the like with a reduction ratio of more than 80% may change the area ratio of each crystal orientation and the grain boundary state. For this reason, in the second embodiment of the present invention, after the heat treatment [Step 2-7], the heat treatment at the high temperature and the processing at the high processing rate are not performed.

Typical examples of the heat treatment / processing conditions in the second embodiment of the present invention and preferred conditions of each step are specifically described below.

The homogenization heat treatment [Step 2-2] is preferably performed at 600 to 1025 DEG C for 10 minutes to 10 hours. The homogenization heat treatment time may be 1 to 5 hours. The hot working [step 2-3] is preferably carried out at a working temperature of 500 to 1020 ° C and a working rate of 30 to 98%. The cold working [step 2-4] is preferably performed at a machining rate of 50 to 99%. This processing ratio may be 50 to 95%. The intermediate heat treatment (intermediate annealing) (Step 2-5) is preferably performed at 300 to 800 ° C for 5 seconds to 180 minutes. The cold working [step 2-6] is preferably performed at a machining rate of 50 to 95%. The heat treatment [Step 2-7] is preferably performed at 300 to 800 ° C for 5 seconds to 180 minutes. The heat treatment temperature may be 300 to 600 占 폚, or 400 to 800 占 폚, 600 to 800 占 폚. The heat treatment time may be 30 to 180 minutes, or 5 to 60 seconds. The cold working [step 2-8] is preferably performed at a machining rate of 10 to 80%.

The stress relief annealing (Step 2-9) is preferably performed at 300 to 600 ° C for 5 to 60 seconds.

After each heat treatment or after the rolling process, acid cleaning or surface polishing may be performed depending on the oxidation or roughness state of the material surface by a tension leveler depending on the shape. After hot rolling [Step 2-3], it is usually water-cooled (quenched).

Preferable examples of combinations of the respective steps in the second embodiment of the present invention include Manufacturing Method 10 to Manufacturing Method 14 in Examples to be described later.

The copper alloy material of the first embodiment of the present invention can satisfy the characteristics required for a vehicle-mounted component such as an EV, an HEV, and a lead frame, a connector, and a terminal of a peripheral infrastructure or a solar power generation system. Among these properties, the conductivity satisfies 75% IACS or more, preferably 80% IACS or more. As for the tensile strength, 400 MPa or more is satisfied. The bending workability was evaluated by a value (R / t) obtained by dividing the minimum bending radius (R: unit mm) at 90 ° W bending capable of bending without cracking by the plate thickness t (unit: mm) R / t? 0.5 when the tensile strength is less than 550 MPa and R / t = 0.5 to 1 when the tensile strength is 550 MPa or more and less than 700 MPa, respectively. The stress relaxation resistance is evaluated by the stress relaxation ratio (SR) determined according to Nippon Shindo Kogyo Kabushiki Kaisha JCBA T309: 2004 (stress relaxation test method by bending of copper and copper alloy thin plate) , And the stress relaxation rate of 35% or less can be satisfied. A concrete measurement method of the stress relaxation ratio (SR) will be described in detail in the following embodiments. Regarding the bending workability and the stress relaxation resistance, both of them have a good characteristic that the result of both of the copper alloy material produced by the conventional method and the balance thereof is the same in the same composition.

The copper alloy material of the second embodiment of the present invention can satisfy the characteristics required for a lead frame, a connector, a terminal, and the like of a vehicle-mounted component around an EV, an HEV, and a peripheral infrastructure or a solar power generation system . Among these properties, the conductivity satisfies 75% IACS or more, preferably 80% IACS or more. As for the tensile strength, 250 MPa or more is satisfied. The bending workability is evaluated by a value (R / t) obtained by dividing the minimum bending radius (R: unit mm) capable of bending without cracking by the plate thickness (t: unit mm), and the degree of tensile strength of the copper alloy material However, when the test plate thickness is 0.4 to 2 mm and the bending width is 10 mmw, when the tensile strength is 250 MPa or more and less than 400 MPa, R / t = 0 at 180 ° warpage and tensile strength 400 MPa or more When it is less than 500 MPa, R / t = 0 at 90 ° warpage is satisfied, respectively. With respect to the stress relaxation resistance, the above-mentioned stress relaxation ratio (SR) can satisfy 35% or less. Regarding the bending workability and the stress relaxation resistance, both of them have a good characteristic that the result of both of the copper alloy material produced by the conventional method and the balance thereof is the same in the same composition.

Example

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

Example 1-1, Comparative Example 1-1 (Cu-Cr alloy)

As shown in Table 1-1 and Table 1-2, at least one kind (additive element group 1) selected from the group consisting of Mg, Ti and Zr and Zn , At least one selected from the group consisting of Fe, Sn, Ag, Si, and P (additional element group 2), and the remainder being composed of Cu and unavoidable impurities, into a high-frequency melting furnace , And this was cast [Step 1-1] to obtain ingot. Thereafter, homogenizing heat treatment at a temperature of 600 ° C to 1025 ° C for 10 minutes to 10 hours [Step 1-2], hot rolling at a processing temperature of 500 to 1020 ° C at a processing rate of 30 to 98% . Further, cold rolling (process 1-4) with a machining ratio of 50 to 99% and intermediate heat treatment (process 1-5) at 300 to 1000 占 폚 for 5 seconds to 180 minutes were carried out. Thereafter, cold rolling with a machining rate of 50 to 95% [Step 1-6] was carried out. Up to this point is the upper process. 1 to 1-22 (Examples of the present invention) and Test Nos. 1 to 3 (hereinafter, referred to as " test materials " (Test material) of the copper alloy material of Comparative Examples 1-23 to 1-50 (Comparative Example). On the other hand, when the conditions of the above-mentioned upper process were changed, they were shown in the following Processes 1 to 7.

As the production method 8 and the production method 9, all steps of the production steps corresponding to the examples of Patent Document 4 and Patent Document 5 are shown below.

(Preparation method 1)

After the above steps (casting [step 1-1] to cold rolling [step 1-6], the same applies hereinafter), aging treatment [step 1-9] is performed at 400 to 650 ° C for 30 to 180 minutes , Stress removing annealing [Step 1-11] in which cold rolling [Step 1-10] is performed at a processing rate of 25% and then maintained at 550 to 700 ° C for 5 to 60 seconds in a continuous heating furnace, . On the other hand, instead of the above conditions, the homogenization heat treatment [Step 1-2] was performed at 600 to 1025 ° C for 2 to 10 hours, and the cold rolling [Step 1-4] was performed at a processing rate of 50 to 99%. Heat treatment [Steps 1-7] and cold rolling [Steps 1-8] were not performed.

(Preparation Method 2)

After the above-mentioned steps, the heat treatment [Step 1-7] is performed at 650 to 1000 ° C for 5 to 60 seconds, cold rolling [Step 1-8] is performed at a processing rate of 25% 9] was carried out at 400 to 650 ° C. for 30 to 180 minutes, and the stress relieving annealing [Step 1-11] was carried out at 550 to 700 ° C. for 5 to 60 seconds in the daytime. Cold rolling [Step 1-10] was not performed.

(Preparation Method 3)

After the upper step, the aging treatment [Step 1-9] is performed at 400 to 650 ° C for 30 to 180 minutes, the cold rolling [Step 1-10] is performed at a processing rate of 50% Stress-removing annealing [Step 1-11] was conducted at 700 占 폚 for 5 to 60 seconds. Heat treatment [Steps 1-7] and cold rolling [Steps 1-8] were not performed.

(Preparation Method 4)

After the upper step, the heat treatment [Step 1-7] is performed at 650 to 1000 ° C for 5 to 60 seconds, and the cold rolling [Step 1-8] is performed at a processing rate of 30% 9] is carried out at 400 to 650 ° C for 30 to 180 minutes, subjected to cold rolling [Step 1-10] at a processing rate of 25%, and then subjected to stress relief annealing 1-11].

(Preparation method 5)

After the upper step, the aging treatment [Step 1-9] is performed at 450 to 600 ° C for 30 to 180 minutes, the cold rolling [Step 1-10] is performed at a processing rate of 25% Stress-removing annealing [Step 1-11] was conducted at 700 占 폚 for 5 to 60 seconds. On the other hand, in place of the above conditions, the hot rolling [step 1-3] was conducted at a processing temperature of 300 to 450 ° C and a processing rate of 30 to 98%. Heat treatment [Steps 1-7] and cold rolling [Steps 1-8] were not performed.

(Preparation method 6)

After the upper step, the aging treatment [Step 1-9] is performed at 400 to 650 ° C for 30 to 180 minutes, the cold rolling [Step 1-10] is performed at a processing rate of 25% Stress-removing annealing [Step 1-11] was conducted at 700 占 폚 for 5 to 60 seconds. On the other hand, in place of the above conditions, the cold rolling [Step 1-6] was carried out at a machining rate of 30%. Heat treatment [Steps 1-7] and cold rolling [Steps 1-8] were not performed.

(Method 7)

After the upper step, the aging treatment [Step 1-9] is performed at 300 to 350 ° C for 30 to 180 minutes, the cold rolling [Step 1-10] is performed at a processing rate of 25% Stress-removing annealing [Step 1-11] was conducted at 700 占 폚 for 5 to 60 seconds. Heat treatment [Steps 1-7] and cold rolling [Steps 1-8] were not performed.

(Production process 8) (Production process corresponding to the example of patent document 4)

And the ingot was homogenized (in Patent Document 4, the temperature was 900 DEG C or more and 300 minutes or more, and thus 950 DEG C for 500 minutes). Further, hot working and solution treatment were performed, and final cold rolling was carried out to adjust the thickness to 0.15 mm and to perform aging treatment. The conditions for the cold rolling were 20% for each pass and 98% for the whole pass according to the contents. In the hot working step where no condition is specified in Patent Document 4, hot rolling was carried out smoothly and then water-cooled. The solution treatment process was performed at 800 ° C for 1 hour. The aging treatment was carried out at 400 DEG C for about 30 minutes.

(Production process 9) (Production process corresponding to the example of patent document 5)

Cast, heated to 950 캜, and hot-rolled smoothly to a thickness of 8 mm, and then water-cooled. Thereafter, the steel sheet was cold-rolled to a thickness of 1 mm and then annealed at 800 ° C for 300 minutes (Patent Document 5 describes that the annealing was merely carried out for 300 minutes because annealing was not described in the patent document 5). Subsequently, the steel sheet was cold-worked at 40% in the degree of processing, and the heat treatment at 500 ° C for 1 minute was repeated three times to obtain a thickness of 0.22 mm.

On the other hand, in each of the aforementioned methods 1 to 7, after each heat treatment or rolling, pickling or surface polishing according to the oxidation or roughness condition of the material surface was calibrated by the tension leveler according to the shape.

Among the above, the following properties were examined for the sealant produced by Production Method 1. Here, the thickness of the sealing material is 0.15 mm unless otherwise specified. The results of the present invention examples are shown in Table 2-1, and the results of the comparative examples are shown in Table 2-2. The results are shown in Tables 3-1 and 3-2 for the test materials of Comparative Examples, which were produced in Production Method 5. Table 4-1 shows the result of the disclosure material of the present invention example produced in Production Methods 2 to 4, and Table 4-2 shows the results of the disclosure materials of Comparative Examples manufactured by Production Methods 6 to 9.

a. Area ratio of Cube orientation {001} < 100 >:

The measurement was performed under the condition that the scan step was 0.5 mu m in the measurement region of about 500 mu m in four directions by the EBSD method. As described above, the area of the arc surface of the crystal grains having an angle outside the range of ± 15 ° from the orientation of the Cube was obtained, and the area was divided by the total area to be measured to obtain the area ratio of the crystal grains in the Cube orientation. In the following tables, this is simply expressed as " Cube area ratio (%) ".

b. The ratio of the corresponding grain boundary? 3 in the crystal grain boundary:

The measurement was performed under the condition that the scan step was 0.5 mu m in the measurement region of about 500 mu m in four directions by the EBSD method. The grain boundaries of the object to be measured were such that the azimuth difference between adjacent crystals was 15 degrees or more and the ratio of the sum of the lengths of the corresponding boundaries < RTI ID = 0.0 > In each of the following tables, (the sum of the lengths of the corresponding boundaries " 3 ") / (the sum of the lengths of all the boundaries) 100 is expressed as "

d-1. Bending workability:

The bending test method was performed in accordance with JIS Z 2248.

(Good Way), which was obtained by bending W such that the axis of bending was perpendicular to the rolling direction, and W-bending such that the W-axis was parallel to the rolling direction. Bad Way), and the bending portion was observed with an optical microscope at a magnification of 200 times, and the presence of cracks was investigated. t is the plate thickness (mm), R is the 90 ° W bending minimum bending radius (mm). GW and BW satisfy R / t? 0.5 when the tensile strength is less than 550 MPa and R / t? 0.5 when the tensile strength is less than 550 MPa and less than 700 MPa, , And when there was a crack, it was judged as "not possible (X)". On the other hand, the conventional material having the same composition and satisfying the above-described conditions and having a smaller bending radius R than other properties (tensile strength, conductivity, stress relaxation resistance) Quot; good " ("? &Quot;).

e. Tensile strength [TS]:

Three test pieces of JIS Z2201-13 B cut from the rolling parallel direction were measured in accordance with JIS Z2241, and the average values thereof were shown.

f. Conductivity [EC]:

The specific resistance was measured by a division method in a thermostatic chamber maintained at 20 占 폚 (占 0.5 占 폚) to calculate conductivity. On the other hand, the distance between the terminals was 100 mm. (EC) of 75% IACS or more and "less than 75% IACS" were designated as "(X)".

g. Stress relaxation ratio [SR]:

The test was carried out under the conditions after being maintained at 150 占 폚 for 1000 hours in accordance with JCPA T309: 2004 (stress relaxation test method by bending of copper and copper alloy thin plate bath) of Nippon Shindo Kogyo Co., Ltd. as shown below. Using a cantilever block type jig, the stress relaxation ratio (SR) was obtained by applying an initial stress of 80% of the proof stress and using the amount of displacement after the test at 150 占 폚 for 1000 hours to evaluate the stress relaxation resistance.

Fig. 1 is an explanatory diagram of a test method for stress relaxation resistance. Fig. 1 (a) shows a state before heat treatment, and Fig. 1 (b) shows a state after heat treatment. As shown in Fig. 1 (a), the position of the test piece 1 when the initial stress of 80% of the proof stress is applied to the test piece 1 held by the cantilever on the test bench 4 is a distance of? ₀ from the reference. The position of the test piece 2 after maintaining the temperature at 150 DEG C for 1000 hours (heat treatment in the state of the test piece 1) and removing the load is the distance of H _t from the standard as shown in Fig. 1 (b). 3 is the test piece when no stress is applied, and its position is the distance of H ₁ from the reference. From this relationship, the stress relaxation rate (%) was calculated as (H _t -H ₁ ) / ( _{0 -} H ₁ ) × 100.隆₀ is the distance from the reference to the test piece 1, H ₁ is the distance from the reference to the test piece 3, and H _t is the distance from the reference to the test piece 2.

When the stress relaxation ratio SR was less than 35%, it was evaluated as " () ", and when the stress relaxation ratio SR was 35% or more, it was judged as " not (x) ". On the other hand, the stress relieving rate (SR) satisfies the condition that the stress relaxation ratio (SR) is less than 35% and the other characteristics (tensile strength, conductivity, bending workability) (&Quot; & cir &) " for smaller inventions.

[Table 1-1]

[Table 1-2]

Table 1-1 shows the copper alloys according to the present invention (alloy Nos. 1 to 22) with the alloy composition within the range of the present invention, Table 1-2 shows the copper alloys (alloy No. 23 to 50). The unit is mass%. Blank indicates no addition, and the balance is Cu and unavoidable impurities.

Hereinafter, evaluation of each alloy was made as follows. When all of these characteristics satisfy the requirements of the present invention or the preferable characteristics of not less than the preferable value or less, the alloy characteristics are considered to be sufficient and the properties of each of these properties It is said that the alloy characteristics are poor. When the copper alloy material obtained by the manufacturing method of the present invention has the same alloy composition and both or both of the bending workability and the stress relaxation resistance property become better than the copper alloy material obtained by the conventional manufacturing method , It was judged to be an excellent copper alloy material which is not conventionally known.

In the case where the organization satisfies the requirements of the present invention with respect to the ratio of the area ratio of the Cube bearing of the product and the ratio state of the counterpart grain boundary Σ3 to the organization within the specified range, The organization was out of scope. It is to be noted that the production process conditions are within the scope of the present invention in the case where the production process is within the range defined in the present invention for each of the production processes shown as Production Process 1 to Production Process 9, And the cases where the processes outside the scope of the present invention are combined are outside the scope of the present invention.

[Table 2-1]

[Table 2-2]

Table 2-1 shows the present invention in which the alloy composition is within the range of the present invention and manufactured by the manufacturing method within the scope of the present invention. With respect to the present invention, they satisfied the organization specified in the present invention, and the alloy characteristics were satisfactory.

Table 2-2 shows a comparative example in which the alloy composition is outside the specified range of the present invention, but produced by the manufacturing method within the specified range of the present invention. In these comparative examples, at least one of the alloy characteristics was poor, or hot cracks occurred during the production, and the subsequent process could not be carried out. Even if the structure and the manufacturing conditions are within the range of the present invention, if the alloy composition is outside the range defined by the present invention, the desired alloy characteristics are inferior, resulting in a manufacturing problem and a defective product.

[Table 3-1]

[Table 3-2]

Table 3-1 shows a comparative example in which the alloy composition is within the range of the present invention, but manufactured by the manufacturing method outside the range of the present invention. Table 3-2 shows a comparative example in which the alloy composition is out of the specified range of the present invention and manufactured at the same time by the manufacturing method outside the specified range of the present invention.

In Comparative Examples 2-1 to 2-22 and 2-23 to 2-50 manufactured by Production Method 5 described above, since the thermal history in the hot rolling [Step 1-3] was insufficient, the area of the desired Cube orientation It was not.

Even when the composition of the alloy is within the range specified in the present invention, when it is produced by a production method outside the specified range of the present invention, the specified structure can not be obtained and the alloy characteristic is insufficient. If the alloy composition is outside the range defined in the present invention, it is found that the alloy characteristics are insufficient regardless of the state of the structure. If the alloy composition is out of the range specified in the present invention, the alloy characteristics are poor even if it is produced by any manufacturing method outside the specification of the present invention.

[Table 4-1]

[Table 4-2]

Table 4-1 and Table 4-2 show the alloying compositions 3, 6, 9, 11, 15, 18, 20, and 22 in the copper alloy material prepared in Production Methods 2 to 5 and 6 to 9 ≪ / RTI > In the case of manufacturing according to the production method within the scope of the present invention of the production methods 2 to 4, when the alloy satisfies the characteristics of the alloy and is manufactured by the production method outside the scope of the present invention of the production methods 6 to 7, And even if the specifications are satisfied, the characteristics are significantly lower than those of the present invention.

Of the above, in Comparative Examples 3-25 to 3-32 produced by Production Method 6, the processing rate in the cold rolling [Step 1-6] before the aging treatment [Step 1-9] was too low, The state of the desired corresponding boundary grain boundary? 3 is not attained, and the stress relaxation resistance characteristic is poor.

Further, in Comparative Examples 3-33 to 3-40 prepared in Production Method 7, since the heating temperature in the aging treatment [Step 1-9] was too low and the thermal history was insufficient, And the stress relaxation characteristics were poor. In addition, the area ratio of the Cube orientation was too small, so that the conductivity was poor and the bending workability was also poor.

In addition, the specimens of Comparative Examples 8 and 9 corresponding to Patent Document 4 were different from the specimens of the present invention, resulting in poor bending workability. In addition, the conductivity was poor and the stress relaxation resistance was also poor.

Example 2-1 and Comparative Example 2-1 (Cu-Mg alloy)

As shown in Table 5-1 and Table 5-2, as shown in the alloy composition, Mg is contained as an indispensable element, and at least one element selected from the group consisting of Zn, Fe, Sn, Ag and Si is added as optional elements , And the remainder is composed of Cu and unavoidable impurities is melted by a high-frequency melting furnace, and the ingot is obtained by casting [Step 2-1]. Thereafter, homogenization heat treatment at 600 to 1025 DEG C for 1 to 5 hours [Step 2-2], hot rolling at a processing temperature of 500 to 900 DEG C at a processing rate of 30 to 98% [Step 2-3] . Cold rolling (step 2-4) with a machining ratio of 50 to 99%, intermediate heat treatment at 300 to 800 占 폚 for 5 seconds to 180 minutes (step 2-5) was carried out. Thereafter, cold rolling with a machining ratio of 50 to 95% (Step 2-6) was carried out. Up to this point is the phase process. This state is set as the supporting material, and as the lower step, the production method of any one of Production Methods 10 to 17 or Production Process 8 or 9 described above is used, and Test Nos. 4-1 to 4-10 (Inventive Example) 11 to 4-18 (comparative example). On the other hand, when the conditions of the above-mentioned upper process were changed, they were shown in the following Processes 10 to 17.

(Production method 10)

After the above-mentioned steps (from casting [step 2-1] to cold rolling [step 2-6], the same applies hereinafter), heat treatment [step 2-7] is carried out at 300 to 600 ° C for 30 to 180 minutes, Cold rolling [Step 2-8] was conducted at a processing rate of 20%, and then subjected to stress relief annealing [Step 2-9] held at 300 to 600 占 폚 for 5 to 60 seconds. On the other hand, in place of the above conditions, the cold rolling step [Step 2-4] was performed at a machining rate of 50 to 95%.

(Preparation method 11)

After the upper step, the heat treatment [Step 2-7] is performed at 300 to 600 ° C for 30 to 180 minutes, the cold rolling [Step 2-8] is performed at a processing rate of 40% And then subjected to stress relief annealing (Step 2-9) held for 60 seconds.

(Preparation method 12)

After the upper step, the heat treatment [Step 2-7] is performed at 600 to 800 ° C for 5 to 60 seconds, and the cold rolling [Step 2-8] is performed at a processing rate of 20% And then subjected to stress relief annealing (Step 2-9), which was held for 60 seconds.

(Production method 13)

After the upper step, the heat treatment [Step 2-7] is performed at 600 to 800 ° C for 5 to 60 seconds, and the cold rolling [Step 2-8] is performed at a processing rate of 45% And then subjected to stress relief annealing (Step 2-9), which was held for 60 seconds.

(Manufacturing method 14)

After the upper step, the heat treatment [Step 2-7] is performed at 400 to 800 ° C for 5 to 60 seconds, and the cold rolling [Step 2-8] is performed at a processing rate of 75% And then subjected to stress relief annealing (Step 2-9), which was held for 60 seconds.

(Production method 15)

After the upper step, the heat treatment [Step 2-7] is performed at 300 to 600 ° C for 30 to 180 minutes, the cold rolling [Step 2-8] is performed at a processing rate of 20% And then subjected to stress relief annealing (Step 2-9), which was held for 60 seconds. On the other hand, instead of the above conditions, the hot rolling [Step 2-3] was conducted at a processing temperature of less than 300 to 500 ° C and a processing rate of 30 to 98%.

(Production method 16)

After the upper step, the heat treatment [Step 2-7] is performed at 300 to 600 ° C for 30 to 180 minutes, the cold rolling [Step 2-8] is performed at a processing rate of 40% And then subjected to stress relief annealing (Step 2-9), which was held for 60 seconds. On the other hand, instead of the above conditions, the hot rolling [Step 2-3] was conducted at a processing temperature of less than 300 to 500 ° C and a processing rate of 30 to 98%.

(Preparation method 17)

After the upper step, the heat treatment [Step 2-7] is performed at 600 to 800 ° C for 5 to 60 seconds, and the cold rolling [Step 2-8] is performed at a processing rate of 90% And then subjected to stress relief annealing (Step 2-9), which was held for 60 seconds.

(Manufacturing Method 8) and (Manufacturing Method 9) were performed in the same manner as in Example 1-1 and Comparative Example 1-1.

On the other hand, in each of Production Methods 10 to 17, after each heat treatment or rolling, acid cleaning or surface polishing was performed by the tension leveler according to the shape depending on the oxidation or roughness state of the material surface.

Of the above, the following properties were examined for the publicly known materials produced by Production Method 10. Here, the thickness of the sealing material is 0.15 mm unless otherwise specified. The results of the present invention examples are shown in Table 6-1, and the results of the comparative examples are shown in Table 6-2. The results are shown in Tables 7-1 and 7-2, respectively, of the comparative example. [Table 8-1] Table 8-1 shows the result of the disclosure material of the present invention example produced in Production Methods 11 to 14, -2 is the result of the disclosure material of the comparative example made in Production Processes 16 to 17 or Production Processes 8 to 9. [

d-2. Bending workability:

The bending test method is performed in accordance with JIS Z 2248. The samples with TS = 250 to 400 MPa were subjected to 180 ° contact bending (pressing and bending method, R = 0) and samples with TS = 400 to 500 MPa were subjected to 90 ° bending (W bending, R = 0). The sample was cut to a width of 10 mm and a length of 25 mm perpendicularly to the rolling direction, and GW (Good Way), which was bent so that the axis of warp was perpendicular to the rolling direction, and BW Way), and the bending portion was observed with an optical microscope of 200 times, and the presence of cracks was examined. GW and BW were judged to be " (X) " when cracks were not generated in each condition and had good bending workability, and " not (X) " On the other hand, with respect to the conventional material satisfying the above-mentioned conditions and having the same composition and the same strength and having improved warpage, "good (?)" Was adopted.

Meanwhile, a. Cube area ratio, b. The ratio of the corresponding boundary grain Σ3, e. Tensile Strength [TS], f. Conductivity [EC], g. The stress relaxation ratio [SR] was tested and evaluated in the same manner as in Example 1-1 and Comparative Example 1-1.

[Table 5-1]

[Table 5-2]

Table 5-1 shows the copper alloys (alloys Nos. 2-1 to 2-10) according to the present invention having the alloy composition within the range of the present invention, Table 5-2 shows the copper compositions of the comparative examples Alloy (alloys No. 2-11 to 2-18). The unit is mass%. Blank indicates no addition, and the balance is Cu and unavoidable impurities.

Hereinafter, evaluation of each alloy was made as follows. When alloy characteristics are taken as the bending workability, the tensile strength, the conductivity and the stress relaxation resistance property and all these characteristics satisfy the requirements of the present invention or the preferable characteristics of not less than the preferable value, When any one of the characteristics is not satisfied, it is said that the alloy characteristics are poor. When the copper alloy material obtained by the manufacturing method of the present invention has the same alloy composition and both or either of the bending workability and the stress relaxation resistance property are made better than the copper alloy material obtained by the conventional manufacturing method Was judged to be an excellent copper alloy material that was not available in the past.

As for the organization, if the organization satisfies the requirements of the present invention with respect to the ratio of the cubic area ratio of the product and the corresponding boundary grain ratio Σ3 within the specified range, It was outside the scope of regulation. The production process conditions are within the range defined in the present invention for each of the production processes shown as Production Process 10 to Production Process 17, Production Process 8 and Production Process 9, while the production process conditions are within the range of the present invention, And the cases where the processes outside the scope of the present invention are combined are excluded from the scope of the present invention.

[Table 6-1]

[Table 6-2]

Table 6-1 shows the present invention in which the alloy composition is within the range of the present invention and manufactured by the manufacturing method within the scope of the present invention. With respect to the present invention, they satisfied the organization specified in the present invention, and the alloy characteristics were satisfactory.

Table 6-2 shows a comparative example prepared by the production method within the range of the present invention except for the alloy composition outside the specified range of the present invention. In these comparative examples, either one or more of the alloy characteristics were poor, or hot cracks occurred during the production, and the subsequent processes could not be carried out. Even if the structure and the manufacturing conditions are within the range of the present invention, the alloy composition is out of the range specified by the present invention, the desired alloy characteristics are inferior, resulting in a manufacturing problem and a defective product.

[Table 7-1]

[Table 7-2]

Table 7-1 shows a comparative example in which the alloy composition is within the range defined by the present invention but manufactured by a manufacturing method outside the specified range of the present invention. Table 7-2 shows a comparative example in which the alloy composition is out of the range specified in the present invention and manufactured by a manufacturing method outside the specified range of the present invention.

In Comparative Examples 5-1 to 5-10 and 5-11 to 5-18 produced by Production Method 15 described above, since the thermal history in the hot rolling [Step 2-3] was insufficient, the area of the desired Cube orientation It was not.

Even when the alloy composition is within the range specified in the present invention, it can be understood that when the alloy is manufactured by a production method outside the specified range of the present invention, the specified structure can not be obtained and the alloy characteristics are insufficient. If the alloy composition is outside the range defined in the present invention, it is found that the alloy characteristics are insufficient regardless of the state of the structure. If the alloy composition is out of the range specified in the present invention, the alloy characteristics are poor even if it is produced by any manufacturing method outside the specification of the present invention.

[Table 8-1]

[Table 8-2]

In Tables 8-1 and 8-2, Formulas 11 to 14, 16 to 17, 8, and 13 are prepared for Forms 2-4, 2-5, 2-7, 2-8, 9 shows the results of the alloy characteristics of the copper alloy material. In the case of producing by the manufacturing method within the scope of the present invention of the production methods 11 to 14 and by the production method satisfying the alloy characteristics and manufactured by the manufacturing method outside the range of the production methods of Production methods 16 to 17, 8, and 9 of the present invention, Even if the characteristics are far below the specifications and satisfy the specifications, the characteristics are significantly lower than those of the present invention. Also, in Comparative Example prepared in Production Method 8 corresponding to Patent Document 4 and in Production Example 9 corresponding to Patent Document 5, the result was also inferior.

Of the above, in Comparative Examples 6-21 to 6-25 produced by Production Method 16, since the thermal history in the hot rolling [Step 2-3] was insufficient, the area ratio of the desired Cube orientation was not obtained and the bending workability This was a lagging result.

Further, in Comparative Examples 6-26 to 6-30 manufactured by Production Process 17, since the processing rate of the final cold rolling [Step 2-8] was too high to be processed strongly, the crystal grains rotated, The bearing relationship as the area ratio of the Cube orientation is destroyed and the stress relaxation property and the bending workability are inferior.

In Comparative Examples 6-31 to 6-35 prepared in Production Method 8, cold rolling (cold rolling) after hot rolling (corresponding to [Process 2-3]) (Corresponding to [Step 2-4] above) was not performed, and the machining ratio was too high in the final cold rolling (corresponding to [Step 2-6] above). The structure obtained in this comparative example had a too small area ratio of the Cube orientation of less than 3% and a too small ratio of corresponding grain boundaries Σ3 of less than 20%, resulting in poor resistance to stress relaxation and bending workability.

In Comparative Examples 6-36 to 6-40 prepared in Production Method 9, the heating time in the intermediate heat treatment (corresponding to [Step 2-5] above) was compared with the example according to the present invention according to the above- Is too long, and the heat treatment (corresponding to the above [Step 2-7]) is repeated three times. The texture obtained in this Comparative Example was too small, i.e., the area ratio of the Cube orientation was less than 3%, resulting in poor bending workability.

As can be seen from the above description of the present invention, the copper alloy material of the present invention is suitable for vehicle-mounted parts such as EVs and HEVs, lead frames, connectors, and end materials such as peripheral infrastructures and solar power generation systems.

While the present invention has been described in conjunction with the embodiments thereof, it is to be understood that the invention is not limited to the details of the description, and is not to be construed as limiting the scope of the invention as defined in the appended claims. I think it is natural to be interpreted.

The present application claims priority based on Japanese Patent Application No. 2011-186253, filed on August 29, 2011, which is hereby incorporated by reference herein in its entirety.

Claims (8)

0.1 to 0.8% by mass of Cr, 0.01 to 0.5% by mass in total of at least one selected from the group consisting of the following elements 1 and 2, and the balance copper and inevitable impurities,
In the analysis of the crystal orientation of the rolled surface in the electron backscattering diffraction measurement, the area ratio of the crystal grains having the orientation within the range of 15 DEG or less from the Cube orientation {001} < 100 & And the ratio of the corresponding grain boundary? 3 in the copper alloy material is 20% or more.
Additive element group 1: at least one species selected from the group consisting of Mg, Ti and Zr in a total amount of 0.01 to 0.5 mass%
Additive element group 2: 0.005 to 0.5 mass% of a total of at least one element selected from the group consisting of Zn, Fe, Sn, Ag, Si and P; The method according to claim 1,
At least one kind selected from the above-mentioned additive element group 1 and at least one kind selected from the additive element group 2 in a total amount of 0.01 to 0.5 mass%. 3. The method according to claim 1 or 2,
A copper alloy material having a tensile strength of 400 MPa or more and a conductivity of 75% IACS or more. A process for producing a copper alloy material according to any one of claims 1 to 3, which comprises homogenizing heat treatment at a temperature of 600 to 1025 占 폚 for 10 minutes to 10 hours [step 1-2] Cold rolling with a machining rate of 50 to 99% [Step 1-4] at 300 to 1000 占 폚 for 5 seconds to 180 minutes, an intermediate heat treatment at a temperature of 10 to 20 占 폚 1-5], cold rolling at a machining rate of 50 to 95% [Step 1-6], aging at 400 to 650 ° C for 30 to 180 minutes [Step 1-9] and annealing at 550 to 700 ° C for 5 seconds to 10 minutes (Step 1-11) of the step (1) is carried out in this order. 0.01 to 0.5 mass% of Mg, the balance of copper and unavoidable impurities,
In the analysis of the crystal orientation of the rolled surface in the electron backscattering diffraction measurement, the area ratio of the crystal grains having the orientation within the range of 15 DEG or less from the Cube orientation {001} < 100 & And the ratio of the corresponding grain boundary? 3 in the copper alloy material is 20% or more. Wherein the alloy contains 0.01 to 0.5 mass% of Mg and contains 0.01 to 0.3 mass% in total of at least one selected from the group consisting of Zn, Sn, Ag, Si and P, the balance being copper and unavoidable impurities,
In the analysis of the crystal orientation of the rolled surface in the electron backscattering diffraction measurement, the area ratio of the crystal grains having the orientation within the range of 15 DEG or less from the Cube orientation {001} < 100 & And the ratio of the corresponding grain boundary? 3 in the copper alloy material is 20% or more. The method according to claim 5 or 6,
A copper alloy material having a tensile strength of 250 MPa or more and a conductivity of 75% IACS or more. The copper alloy material according to claim 5 or 6 is subjected to a homogenizing heat treatment [Step 2-2] at 600 to 1025 占 폚 for 10 minutes to 10 hours, Cold rolling with a machining rate of 50 to 99% [Step 2-4] at 300 to 800 ° C for 5 seconds to 180 minutes, intermediate heat treatment at a temperature of 1020 ° C 2 to 5], cold rolling at a machining rate of 50 to 95% [step 2-6], heat treatment at 300 to 800 ° C for 5 seconds to 180 minutes [step 2-7], cold working at a machining rate of 10 to 80% Step 2-8] and stress relieving annealing at 300 to 600 占 폚 for 5 to 60 seconds [step 2-9] are carried out in this order.

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