JP5117602B1 - Copper alloy sheet with low deflection coefficient and excellent bending workability - Google Patents

Abstract

An object of the present invention is to provide a lead frame, a connector, a terminal material, etc. for an electric / electronic device, such as an automotive vehicle connector, having a low deflection coefficient in a direction perpendicular to the rolling direction, excellent bending workability and excellent strength. Providing copper alloy sheet materials that are suitable for terminal materials, relays, and switches.
A copper alloy containing one or two of Ni and Co in a total amount of 0.5 to 5.0 mass% and Si of 0.1 to 1.5 mass%, the balance being Cu and unavoidable impurities. In the crystal orientation analysis in the measurement by the EBSD method,
A copper alloy sheet having an area ratio of Cube orientation {100} <001> of 5% or more and an area ratio of NDRDW orientation {012} <221> of 10% or less.
[Selection figure] None

Description

  The present invention relates to a copper alloy sheet and a method for manufacturing the same, and more particularly to a copper alloy sheet that is applied to lead frames, connectors, terminal materials, relays, switches, sockets, and the like for in-vehicle components and electrical / electronic devices, and a method for manufacturing the same. .

Characteristic items required for copper alloy sheet materials used in applications such as lead frames, connectors, terminal materials, relays, switches and sockets for automotive parts and electrical / electronic equipment include, for example, conductivity, yield strength (yield) Stress), tensile strength, bending workability, and stress relaxation resistance. In recent years, the level of these required characteristics has increased as electric and electronic devices have become smaller, lighter, more functional, denser, and used in higher temperatures.
The following changes are mentioned in the situation where the copper alloy sheet material in recent years is used.
First, as the functionality of automobiles, electrical equipment, and electronic devices has increased, the number of connectors has been increasing, and so miniaturization of terminals and contact parts has been progressing. For example, a movement to downsize a terminal having a tab width of about 1.0 mm to 0.64 mm is progressing.
Secondly, the base material is becoming thinner due to the reduction of mineral resources and weight reduction of parts, and in order to maintain the spring contact pressure, a base material with higher strength than before is used. ing.

With the above changes, the following problems have arisen in the copper alloy sheet.
First, with the miniaturization of the terminals, the bending radius of the bending process applied to the contact part and the spring part becomes smaller, and the material is subjected to a stricter bending process than before. Therefore, there is a problem that the material is cracked.
Second, with the increase in strength of materials, there is a problem that cracks occur in the materials. This is because the bending workability of the material is generally in a trade-off relationship with the strength.
Third, when a crack occurs in the bent part applied to the contact part or spring part, the contact pressure of the contact part decreases, the contact resistance of the contact part increases, the electrical connection is insulated, and the connector As the function is lost, it becomes a serious problem.

Several proposals have been made to solve this demand for improvement in bending workability by controlling the crystal orientation. In Patent Document 1, in a Cu—Ni—Si based copper alloy, the crystal grain size and the X-ray diffraction intensity from the {311}, {220}, {200} planes satisfy a certain condition. It has been found that bending workability is excellent. Further, in Patent Document 2, in a Cu—Ni—Si based copper alloy, bending workability is excellent when the crystal orientation satisfies the condition that the X-ray diffraction intensity from the {200} plane and the {220} plane is satisfied. Has been found. Further, in Patent Document 3, it has been found that in a Cu—Ni—Si based copper alloy, bending workability is excellent by controlling the ratio of the Cube orientation {100} <001>. In addition, Patent Documents 4 to 8 propose materials having excellent bending workability defined by X-ray diffraction intensities for various atomic planes. In Patent Document 4, in the Cu—Ni—Co—Si based copper alloy, the X-ray diffraction intensity from the {200} plane is from the {111} plane, {200} plane, {220} plane, and {311} plane. It has been found that bending workability is excellent when the crystal orientation satisfies a certain condition with respect to the X-ray diffraction intensity. Patent Document 5 shows that in a Cu—Ni—Si-based copper alloy, bending workability is excellent when the crystal orientation satisfies the condition that the X-ray diffraction intensity from the {420} plane and the {220} plane is satisfied. Has been issued. In Patent Document 6, it has been found that, in a Cu—Ni—Si based copper alloy, bending workability is excellent when the crystal orientation satisfies a certain condition with respect to the {123} <412> orientation. In Patent Document 7, in a Cu—Ni—Si based copper alloy, in the case of crystal orientation satisfying the condition that the X-ray diffraction intensity from the {111} plane, {311} plane, and {220} plane is satisfied, It has been found that the bending workability (described later) is excellent. Further, in Patent Document 8, in a Cu—Ni—Si based copper alloy, bending is performed when the crystal orientation satisfies the condition that the X-ray diffraction intensity from the {200} plane, {311} plane, and {220} plane is satisfied. It has been found that processability is excellent.
The specifications based on the X-ray diffraction intensity in Patent Documents 1, 2, 4, 5, 7, and 8 specify the accumulation of specific crystal planes in the plate surface direction (rolling normal direction, ND).
Further, due to the miniaturization of the connector, a slight dimensional variation in the connector manufacturing process such as press working and assembly greatly affects the variation in contact pressure, which causes a problem of greatly reducing the manufacturing yield. Therefore, it is required to reduce the deflection coefficient of the copper alloy plate material which is a contact material. The deflection coefficient represents the relationship between the amount of displacement of the contact material and the stress generated thereby, and the lower it is, the more the amount of contact pressure variation caused by dimensional variation can be absorbed. Since the contact material is mainly taken in the direction perpendicular to the rolling direction, the copper alloy sheet material is required to reduce the deflection coefficient in the direction perpendicular to the rolling direction.
Moreover, since the cross-sectional area of a conductor is decreasing with the miniaturization of a connector, high electrical conductivity is calculated | required by the copper alloy used for a connector.

JP 2006-009137 A JP 2008-013836 A JP 2006-283059 A JP 2009-007666 A JP 2008-223136 A JP 2007-092135 A JP 2006-016629 A JP-A-11-335756

By the way, the invention described in Patent Document 1 or Patent Document 2 is based on the measurement of crystal orientation by X-ray diffraction from a specific crystal plane, and is very small in the distribution of crystal orientation having a certain spread. It only concerns some specific aspects. Moreover, only the crystal plane in the plate direction (ND) is measured, and it cannot be controlled which crystal plane is oriented in the rolling direction (RD) or the plate width direction (TD). Therefore, the method is still insufficient to completely control the bending workability. In the invention described in Patent Document 3, the effectiveness of the Cube orientation is pointed out, but other crystal orientation components are not controlled, and there are cases where the improvement of bending workability is insufficient. It was. Further, in Patent Documents 4 to 8, only the measurement and control of the specific crystal plane or orientation have been studied, and the bending workability may not be improved as in Patent Documents 1 to 3. It was.
Further, none of the prior art documents discusses reducing the deflection coefficient in the direction perpendicular to the rolling direction.

  In view of the above problems, the object of the present invention is to provide a lead for electrical and electronic equipment that has a low deflection coefficient in the direction perpendicular to the rolling direction, excellent bending workability, excellent strength and conductivity. An object of the present invention is to provide a copper alloy plate material suitable for connectors, terminal materials, relays, switches, and the like for automobiles and the like such as frames, connectors, and terminal materials, and a method for manufacturing the same.

The present inventors have made various studies, studied copper alloys suitable for electrical and electronic component applications, increased the Cube orientation, which is characterized by the EBSD (Electron Back Scatter Diffraction) method, In addition, by reducing the NDRDW orientation, it was found that cracks during bending can be suppressed, and that the deflection coefficient in the vertical direction of rolling can be reduced, and further, the area ratio of the texture orientation component of each orientation is set to a predetermined value. It has been found that the bending workability can be remarkably improved by setting the ratio. In addition, it has been found that by using a specific additive element in this alloy system, the strength can be improved and the deflection coefficient can be reduced without impairing the electrical conductivity and bending workability. The present invention has been made based on these findings.
That is, the present invention provides the following solutions.

(1) An alloy composition in which any one or two of Ni and Co are contained in a total amount of 0.5 to 5.0 mass%, Si is contained in an amount of 0.2 to 1.5 mass%, and the balance is made of copper and inevitable impurities. In crystal orientation analysis in EBSD (Electron Back Scatter Diffraction) measurement,
A copper alloy sheet having an area ratio of Cube orientation {100} <001> of 5% or more and an area ratio of NDRDW orientation {012} <221> of 10% or less.
(2) One or two kinds of Ni and Co are contained in a total amount of 0.5 to 5.0 mass%, Si is contained in an amount of 0.2 to 1.5 mass%, and Sn, Zn, Ag, Mn, B, P , Mg, Cr, Fe, Ti, Zr and Hf at least one selected from the group consisting of 0.005 to 2.0 mass% in total, the balance having an alloy composition consisting of copper and inevitable impurities, EBSD In crystal orientation analysis in (Electron Back Scatter Diffraction) measurement,
A copper alloy sheet having an area ratio of Cube orientation {100} <001> of 5% or more and an area ratio of NDRDW orientation {012} <221> of 10% or less.
(3) A copper alloy containing 0.5 to 5.0 mass% of any one or two of Ni and Co, 0.2 to 1.5 mass% of Si, and the balance being Cu and inevitable impurities The manufacturing method of the copper alloy board | plate material characterized by performing the following process 2-process 12 with respect to an ingot in this order .
[Step 2: the pressurizing Engineering ratio 10% to 70% cold rolling 1]
[Step 3: Homogenization heat treatment at a temperature of 900 to 1050 ° C. for 2 minutes to 10 hours]
[Step 4: Hot working]
[Step 5: Water cooling]
[Step 6: Face milling]
[Step 7: Cold rolling 2 with a processing rate of 50 to 99%]
[Step 8: Intermediate annealing at 300 to 800 ° C. for 5 seconds to 2 hours]
[Step 9: Cold rolling 3 with a processing rate of 3 to 80%]
[Step 10: Solution heat treatment in a temperature range of 700 to 1020 ° C.]
[Step 11: Aging precipitation heat treatment at 350 to 600 ° C. for 5 minutes to 20 hours]
[Step 12: Finish rolling at a processing rate of 5 to 50%]
(4) Containing any one or two of Ni and Co in a total amount of 0.5 to 5.0 mass%, Si in a range of 0.2 to 1.5 mass%, Sn, Zn, Ag, Mn, B, P A total of at least one selected from the group consisting of Mg, Cr, Fe, Ti, Zr and Hf with respect to a copper alloy ingot containing 0.005 to 2.0 mass% in total, the balance being Cu and inevitable impurities The manufacturing method of the copper alloy board | plate material characterized by performing the following process 2-process 12 in this order .
[Step 2: the pressurizing Engineering ratio 10% to 70% cold rolling 1]
[Step 3: Homogenization heat treatment at a temperature of 900 to 1050 ° C. for 2 minutes to 10 hours]
[Step 4: Hot working]
[Step 5: Water cooling]
[Step 6: Face milling]
[Step 7: Cold rolling 2 with a processing rate of 50 to 99%]
[Step 8: Intermediate annealing at 300 to 800 ° C. for 5 seconds to 2 hours]
[Step 9: Cold rolling 3 with a processing rate of 3 to 80%]
[Step 10: Solution heat treatment in a temperature range of 700 to 1020 ° C.]
[Step 11: Aging precipitation heat treatment at 350 to 600 ° C. for 5 minutes to 20 hours]
[Step 12: Finish rolling at a processing rate of 5 to 50%]
(5) connectors, characterized in that a copper alloy sheet according to (1) or (2).

The copper alloy sheet of the present invention has a low deflection coefficient in the direction perpendicular to the rolling direction, excellent bending workability and excellent strength, such as lead frames, connectors and terminal materials for electric and electronic equipment, automobiles, etc. Suitable for in-vehicle connectors, terminal materials, relays, switches, etc. Since the deflection coefficient is low, the contact pressure variation in the manufacturing process can be suppressed, and the yield can be improved.
In addition, the method for producing a copper alloy sheet according to the present invention has a low bending coefficient, excellent bending workability, and excellent strength, such as lead frames, connectors, and terminal materials for electric and electronic devices, which are mounted on automobiles. It is suitable as a method for producing a copper alloy sheet material suitable for connectors, terminal materials, relays, switches, etc.

It is explanatory drawing which shows typically crystal orientation of Cube direction and NDRDW direction. It is explanatory drawing which shows typically the relationship between a gauge length (L), a load (W), and the deflection amount (f).

  A preferred embodiment of the copper alloy sheet material of the present invention will be described in detail. Here, the “copper alloy material” means a material obtained by processing a copper alloy material into a predetermined shape (for example, a plate, a strip, a foil, a bar, a wire, or the like). Among them, the plate material refers to a material having a specific thickness, stable in shape, and having a spread in the surface direction, and in a broad sense, includes a strip material and a tubular material in which the plate is tubular. Here, in the plate material, “material surface layer” means “plate surface layer”, and “material depth position” means “position in the plate thickness direction”. The thickness of the plate material is not particularly limited, but it is preferably 8 to 800 μm, and more preferably 50 to 70 μm, considering that the effects of the present invention are better manifested and suitable for practical applications.

In order to clarify the cause of the occurrence of cracks during bending of a copper alloy sheet, the present inventors investigated in detail the metal structure of the material after bending deformation. As a result, it was observed that the base material was not uniformly deformed, but the deformation was concentrated only in the region of a specific crystal orientation, and the non-uniform deformation progressed. Then, it was found that due to the non-uniform deformation, wrinkles with a depth of several μm and fine cracks were generated on the surface of the base material after bending. And when there were many Cube directions, it turned out that a nonuniform deformation | transformation is suppressed, the wrinkles which generate | occur | produce on the surface of a base material are reduced, and a crack is suppressed.
In addition, the present inventors have found that there is an effect of reducing the deflection coefficient in the vertical direction of rolling by increasing the Cube orientation and simultaneously reducing the NDRDW orientation. It is considered that the NDRDW orientation has a (524) plane oriented in the vertical direction of rolling and is a relatively dense crystal plane that contributes significantly to the deflection coefficient.
The relationship between the Cube orientation and the NDRDW orientation is shown in FIG. Circles indicate metal atoms, and squares indicate crystal lattices. The horizontal direction in FIG. 1 is the width direction of the plate material, and the vertical direction indicates the rolling direction.
The deflection coefficient is expressed by the following formula (1).
E = 4 W / b · (L / t) ³ · 1 / f (1)
(E: Deflection coefficient, b: Sample width, t: Sample plate thickness, W: Load, L: Gage length, f: Deflection amount)
FIG. 2 schematically shows the relationship with the deflection amount f when a load of W is applied to the sample 1 having the gauge length L.

(Regulation by EBSD measurement)
When the area ratio of Cube orientation {1 0 0} <0 0 1> specified by the EBSD method is 5% or more and the area ratio of NDRDW orientation {0 1 2} <2 2 1> is 10% or less In addition, the above effects can be obtained. The Cube orientation is more preferably 10% or more, and most preferably 15% or more. There is no particular upper limit, but if it is 50% or more, the strength may decrease or the press punchability may decrease, and it is necessary to make it less than 47% depending on the required strength and application. It is.
The NDRDW orientation is more preferably 8% or less, and most preferably 6% or less. Conventionally, there is no known device that simultaneously controls the area ratio of atomic planes having these orientations.

  The crystal orientation display method in the present specification takes a rectangular coordinate system in which the rolling direction (RD) of the material is the X axis, the sheet width direction (TD) is the Y axis, and the rolling normal direction (ND) is the Z axis. Using the index (h k l) of the crystal plane each region in which is perpendicular to the Z axis (parallel to the rolling surface) and the index [u v w] of the crystal direction parallel to the X axis, (h k l) Shown in the form [u v w]. For the equivalent orientations under the cubic symmetry of the copper alloy, such as (1 3 2) [6 -4 3] and (2 3 1) [3 -4 6], It uses {h k l} <u v w> using the parenthesis symbol. The six types of orientations in the present invention are indicated by the indices as described above.

The EBSD method was used for the analysis of the crystal orientation in the present invention. EBSD is an abbreviation for Electron Back Scatter Diffraction (Electron Back Scattering Diffraction). Reflected Electron Kikuchi Line Diffraction (Kikuchi Pattern) generated when a sample is irradiated with an electron beam in a Scanning Electron Microscope (SEM). This is the crystal orientation analysis technology used. In the present invention, a 500 μm square sample area containing 200 or more crystal grains was scanned in 0.5 μm steps, and the orientation was analyzed.
In the present invention, the crystal grains having the texture orientation components of the Cube orientation and the NDRDW orientation and the area of the atomic plane thereof are defined by whether or not they are within a predetermined shift angle range described below.
Regarding the deviation angle from the ideal orientation indicated by the index, (i) the crystal orientation of each measurement point, and (ii) the orientation of either Cube or NDRDW as the target ideal orientation, The rotation angle was calculated around the rotation axis common to (ii), and the deviation angle was calculated. For example, with respect to the S orientation (2 3 1) [6 -4 3], (1 2 1) [1 -1 1] is rotated by 19.4 ° with the (20 10 17) direction as the rotation axis. This angle was taken as the deviation angle. The common rotation axis is three integers of 40 or less, and the one that can be expressed by the smallest angle among them is adopted. The deviation angle is calculated for all measurement points, and the first decimal place is an effective number. The area of crystal grains having an orientation of 10 ° or less from the deviation angle of the Cube orientation and NDRDW orientation is the total measurement area. To obtain the area ratio of the atomic plane in each direction.
The information obtained in the azimuth analysis by EBSD includes azimuth information up to a depth of several tens of nanometers at which the electron beam penetrates into the sample. It was described as an area ratio.
By using EBSD measurement for analysis of crystal orientation, it differs greatly from the measurement of the accumulation of specific atomic planes in the plate direction (ND) by the conventional X-ray diffraction method. Since it can be obtained with higher resolution, it is possible to acquire completely new knowledge about the crystal orientation that governs the bending workability.

  In the EBSD measurement, in order to obtain a clear Kikuchi diffraction image, it is preferable to perform the measurement after mirror polishing the surface of the substrate using colloidal silica abrasive grains after mechanical polishing. The measurement was performed from the plate surface.

(Alloy composition, etc.)
・ Ni, Co, Si
A copper alloy is used as the connector material of the present invention. In order to obtain the area ratio satisfying the specific crystal orientation accumulation relationship of the present invention having the electrical conductivity, mechanical strength and heat resistance required for the connector, a precipitation type alloy including a Corson alloy is used.
This is because, in a solid solution type alloy such as phosphor bronze or brass, a minute region having a Cube orientation in the cold-rolled material, which becomes a nucleus of Cube orientation grain growth in crystal grain growth during heat treatment, is reduced. This is because in a system with low stacking fault energy such as phosphor bronze and brass, a shear band is likely to develop during cold rolling.

  In the present invention, nickel (Ni), cobalt (Co), and silicon (Si), which are the first additive element group to be added to copper (Cu), are controlled by controlling the addition amount of Ni—Si, Co. It is possible to improve the strength of the copper alloy by precipitating a compound of -Si and Ni-Co-Si. The total amount of Ni and Co added is 0.5 to 5.0 mass%, preferably 0.6 to 4.5 mass%, more preferably 0.8 to 4.0 mass%. When it is desired to increase the conductivity according to the application, it is preferable to make Co essential. Further, the Si content is 0.2 to 1.5 mass%, preferably 0.3 to 1.2 mass%. If the total addition amount of these elements is too large, the electrical conductivity is lowered, and if it is too small, the strength is insufficient.

-Other elements Cr has the effect of making crystal grains fine and improving bendability. The Cr content is preferably 0.03 to 1.0 mass%, more preferably 0.16 to 0.24 mass%. If the amount is too small, the effect is insufficient. If the amount is too large, a large number of coarse crystallized substances are generated, and the bendability is rather deteriorated.
Sn, Zn, Ag, Mn, B, P, Mg, Fe, Ti, Zr, and Hf improve the bending workability by improving the strength or suppressing the coarsening of crystal grains.
When other elements are contained, a total of at least one selected from the group consisting of Sn, Zn, Ag, Mn, B, P, Mg, Cr, Fe, Ti, Zr and Hf is 0.005 to 2. It is contained in an amount of 0 mass%, preferably 0.08 to 0.95 mass%.
When there are too many of these additive elements, the harmful effect which reduces electrical conductivity will be produced. If these additive elements are too small in total, the effect of adding these elements is hardly exhibited.
Inevitable impurities in the alloy composition include ordinary ones such as O, H, S, Pb, As, Cd, and Sb.

(Manufacturing method etc.)
Next, a method for controlling the area ratio of the Cube orientation and the NDRDW orientation will be described. Here, a plate material (strip material) of a precipitation-type copper alloy will be described as an example, but the present invention can be applied to a solid solution alloy material, a dilute alloy material, and a pure copper material.
In general, a method for producing a precipitation-type copper alloy involves casting a copper alloy material [Step 1] to obtain an ingot, homogenizing heat treatment [Step 3], and hot working such as hot rolling [Step 4]. ], Water cooling [step 5], chamfering [step 6], cold rolling 2 [step 7] are performed in this order to form a thin plate, and a solution heat treatment [step 10] is performed in a temperature range of 700 to 1020 ° C. to form solute atoms. After the solid solution is re-dissolved, the required strength is satisfied by aging precipitation heat treatment [Step 11] and finish cold rolling [Step 12]. In this series of steps, the texture of the material is roughly determined by recrystallization that occurs during the intermediate solution heat treatment [Step 10], and finally by the orientation rotation that occurs during finish rolling [Step 12]. It is determined.
The Cube orientation area ratio formed in this general process is usually 3% or less, and the bending workability and the deflection coefficient are inferior.

The copper alloy material of the present invention comprises an intermediate annealing [Step 8] at 300 to 800 ° C. for 5 seconds to 2 hours between the cold rolling 2 [Step 7] and the solution heat treatment [Step 10]. Cold rolling 3 [Step 9] with a rolling rate of 3 to 80% is added. The purpose of the intermediate annealing is to obtain a sub-annealed structure that is not completely recrystallized but partially recrystallized at a lower temperature than the solution heat treatment. In the cold rolling 3, microscopically non-uniform strain can be introduced by rolling at a relatively low processing rate. By the effect of these two steps, the Cube orientation can be increased in the recrystallization texture in the solution heat treatment. A more preferable range of the intermediate annealing [Step 8] is 400 to 700 ° C. for 10 seconds to 1 minute, and a more preferable range is 500 to 650 ° C. for 15 seconds to 45 seconds. A more preferable range of the processing rate of the cold rolling 3 [Step 9] is 5 to 65%, and a more preferable range is 7 to 50%.
Conventionally, the heat treatment such as the intermediate annealing [step 8] is performed in order to reduce the strength by recrystallizing the material in order to reduce the load in the rolling of the next step. The purpose of rolling is to reduce the plate thickness. If the capacity of a normal rolling mill is used, it is common to employ a processing rate exceeding 80%. The purpose of these two steps in the present invention is to give priority to the crystal orientation after recrystallization, unlike these general contents.

In this step, an NDRDW orientation may occur as a sub-azimuth, and in order to reduce this, it is effective to cold-roll 1 [Step 2] the ingot. The NDRDW orientation is likely to develop when the crystal grain size is coarse in the hot rolling [Step 4], and it is important to reduce the crystal grain in the hot rolling. In the present invention, it has been found that by introducing the cold rolling 1 [step 2] to the ingot, the cast structure is recrystallized in the homogenization heat treatment [step 3], and the crystal grains can be actively reduced. It was. As a result, the NDRDW direction of the sub direction can be reduced.
A preferred range of cold rolling 1 [Step 2] is 10 to 70%. If it is lower than this range, the effect is insufficient, and if it is higher, rolling cracks are likely to occur. A more preferable range is 20 to 50%.

By satisfy | filling the said content, the characteristic requested | required of the copper alloy board | plate material for connectors, for example can be satisfied. In one preferred embodiment of the copper alloy sheet according to the present invention, the bending coefficient in the vertical direction of rolling is 120 GPa or less, the 0.2% proof stress is 600 MPa or more, the conductivity is 30% IACS or more, and the bending workability is tested. Bending can be performed without cracks in a 180 ° contact bending test with a half width of 1 mm. More preferred embodiments of the respective characteristics satisfy at least one of 110 GPa or less for the deflection coefficient in the vertical direction of rolling, 650 MPa or more for 0.2% proof stress, and 50% IACS or more for conductivity, and more preferably One of the advantages of the present invention is that the 0.2% proof stress is a copper alloy sheet having good characteristics of 700 MPa or more, and that such characteristics can be realized.
In the present invention, the 0.2% proof stress is a value based on JIS Z2241. Moreover, said% IACS represents the electrical conductivity when the resistivity 1.7241 × 10 ⁻⁸ Ωm of universal standard annealed copper (International Annealed Copper Standard) is 100% IACS.

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

Example 1
An alloy containing the elements in the column of alloy components in Table 1 and the balance consisting of Cu and inevitable impurities was melted in a high-frequency melting furnace and cast to obtain an ingot. Using this state as a providing material, test materials for copper alloy sheet materials of Invention Examples 1 to 16 and Comparative Examples 1 to 12 were manufactured by any one of the following methods A to J. Table 1 shows which of A to J was used. The final thickness of the alloy plate was 150 μm unless otherwise specified.

(Manufacturing method A)
Perform cold rolling 1 of 20 to 50%, perform homogenization heat treatment at a temperature of 900 to 1050 ° C. for 3 minutes to 10 hours, perform hot working, then cool with water, and chamfer to remove oxide scale went. Thereafter, cold rolling 2 with a processing rate of 50 to 99% was performed, intermediate annealing was performed at a temperature of 400 to 700 ° C. for 10 seconds to 1 minute, and cold rolling 3 with a processing rate of 5 to 65% was performed. . Thereafter, a solution heat treatment is performed at a temperature of 800 to 950 ° C. for 5 seconds to 50 seconds, an aging precipitation heat treatment is performed at a temperature of 350 to 600 ° C. for 5 minutes to 20 hours, and a finish rolling of 5 to 50% is performed. And temper annealing was performed at a temperature of 300 to 700 ° C. for 10 seconds to 2 hours.

(Manufacturing method B)
Perform cold rolling 1 to 10 to 70%, perform homogenization heat treatment at a temperature of 900 to 1050 ° C. for 3 minutes to 10 hours, perform hot working, then cool with water, and chamfer to remove oxide scale. went. Thereafter, cold rolling 2 with a processing rate of 50 to 99% was performed, intermediate annealing was performed at a temperature of 300 to 800 ° C. for 5 seconds to 2 hours, and cold rolling 3 with a processing rate of 3 to 80% was performed. . Thereafter, a solution heat treatment is performed at a temperature of 800 to 950 ° C. for 5 seconds to 50 seconds, an aging precipitation heat treatment is performed at a temperature of 350 to 600 ° C. for 5 minutes to 20 hours, and a finish rolling of 5 to 50% is performed. And temper annealing was performed at a temperature of 300 to 700 ° C. for 10 seconds to 2 hours.

(Manufacturing method C)
Perform cold rolling 1 to 10 to 70%, perform homogenization heat treatment at a temperature of 900 to 1050 ° C. for 3 minutes to 10 hours, perform hot working, then cool with water, and chamfer to remove oxide scale. went. Thereafter, cold rolling 2 with a processing rate of 50 to 99% was performed, intermediate annealing was performed at a temperature of 300 to 800 ° C. for 5 seconds to 2 hours, and cold rolling 3 with a processing rate of 3 to 80% was performed. . Thereafter, a solution heat treatment was performed at a temperature of 800 to 950 ° C. for 5 seconds to 50 seconds, and an aging precipitation heat treatment was performed at a temperature of 350 to 600 ° C. for 5 minutes to 20 hours.

(Manufacturing method D)
Cold rolling 1, intermediate annealing, and cold rolling 3 were not performed, and the others were produced in the same manner as in step B.

(Manufacturing method E)
Cold rolling 3 was not performed, and the others were produced in the same manner as in step B.

(Production method F)
Intermediate annealing was not performed, and the others were manufactured in the same manner as in Step B.

(Manufacturing method G)
Cold rolling 1 was not performed, and the others were produced in the same manner as in Step B.

(Manufacturing method H)
The intermediate annealing and the cold rolling 3 were not performed, and the others were produced in the same manner as in the process B.

(Manufacturing method I)
According to the manufacturing method of Unexamined-Japanese-Patent No. 2006-283059 of patent document 3, it manufactured as follows.
It was melted under charcoal coating in the atmosphere by an electric furnace, and castability was judged. The molten ingot was hot-rolled and finished to a thickness of 15 mm, and it was visually determined whether cracks occurred during hot-rolling. Subsequently, the hot-rolled material is subjected to cold rolling and heat treatment (cold rolling 1 → solution annealing, cold rolling 2 → aging treatment → cold rolling 3 → short annealing), and a thickness of 0. A 25 mm copper alloy sheet was produced. Here, the processing rate of the cold rolling 1 was 95% or more, the processing rate of the cold rolling 2 was 20% or less, and the processing rate of the cold rolling 3 was 1 to 20%. The solution annealing was held at an actual temperature of 800 to 950 ° C. for 30 seconds or less, and after the holding, cooling was performed at a cooling rate of 10 ° C./second or more. The aging treatment was carried out using a batch furnace at a body temperature of 400 to 600 ° C. for 1 to 8 hours, and after the holding, the furnace was cooled at a cooling rate of less than 10 ° C./second. In the short-time annealing, the solid temperature was maintained at 400 to 550 ° C. for 30 seconds or less by a continuous annealing furnace, and after the holding, the cooling was performed at a cooling rate of 10 ° C./second or more.

(Manufacturing method J)
According to the manufacturing method of Japanese Patent Application Laid-Open No. 2008-223136 of Patent Document 5, “melting / casting → hot rolling → cold rolling → solution treatment → intermediate cold rolling → aging treatment → finishing cold rolling → low temperature annealing” It manufactured by the process and each condition was performed as follows.
Using the ingot that has been melted and cast, hot rolling is performed at a temperature range of 950 ° C. to 700 ° C., and a rolling rate of 40% or more in a temperature range of less than 700 ° C. to 400 ° C. Went. Cold rolling was performed at a cold rolling rate of 90% or more. The solution treatment is performed at a temperature of 700 to 850 ° C. for 10 seconds to 10 minutes so that the temperature rise time from 100 ° C. to 700 ° C. is 20 seconds or less and the average grain size of the recrystallized grains is 10 to 60 μm. did. Intermediate cold rolling was performed in a range where the cold rolling rate was 50% or less. The aging treatment was performed at a temperature of 400 to 500 ° C. and for a treatment time of 1 to 10 hours. The finish cold rolling was performed in a range where the cold rolling rate did not exceed 50%. The low-temperature annealing was performed so that the material temperature was 150 to 550 ° C., and the holding time was 5 seconds or longer and within 1 hour.

  In the processes A, B, and C, when the processing rate of the cold rolling 1 exceeded 70%, the production was stopped because the rolling crack occurred.

  After each heat treatment and rolling, acid cleaning and surface polishing were performed according to the state of oxidation and roughness of the material surface, and correction with a tension leveler was performed according to the shape.

Each characteristic was measured and evaluated for this specimen as follows. Here, the thickness of the test material was 0.15 mm. The results are shown in Table 1.
a. Area ratio of Cube orientation and NDRDW orientation:
By the EBSD method, measurement was performed in a measurement region of about 500 μm square under the condition that the scan step was 0.5 μm. The measurement area was adjusted based on the inclusion of 200 or more crystal grains. As described above, with respect to the deviation angle from the ideal orientation, the rotation angle is calculated around the common rotation axis, and is set as the deviation angle. The rotation angle with each direction was calculated for every rotation axis. The rotation axis that can be expressed at the smallest angle is adopted. The deviation angle is calculated for all measurement points, the first decimal place is a significant figure, the area of crystal grains with an orientation within 10 ° from each orientation is divided by the total measurement area, and the area ratio is calculated. did.

b. Deflection factor:
The deflection coefficient in the direction perpendicular to the rolling direction was measured based on the technical standard (JCBA T312 (2002)) of the Japan Copper and Brass Association. If it was 120 GPa or less, it was determined that the deflection coefficient was sufficiently low.

c. 180 ° adhesion bending workability [bending workability]:
GW (Good Way) obtained by punching with a press perpendicularly to the rolling direction to a width of 1 mm and a length of 25 mm, and W bent so that the axis of bending is perpendicular to the rolling direction is W to be parallel to the rolling direction. The bent one was designated as BW (Bad Way). Bending was performed according to JIS Z 2248. Preliminary bending was performed using a 0.4 mm R 90 ° bending mold, and then contact bending was performed using a compression tester. The presence or absence of cracks on the outside of the bent part was observed by visual observation with a 50 × optical microscope, and the presence or absence of cracks was investigated. The case where there was no crack in the bent portion was judged as ◯, and the case where there was a crack was judged as ×.

e. 0.2% yield strength [YS]:
Three test pieces of JIS Z2201-13B cut out from the rolling parallel direction were measured according to JIS Z2241, and the average value was shown. Here, the YS value of 600 MPa or more was assumed to be excellent in strength.
f. Conductivity [EC]:
The specific resistance was measured by a four-terminal method in a constant temperature bath maintained at 20 ° C. (± 0.5 ° C.) to calculate the conductivity. In addition, the distance between terminals was 100 mm. Here, the one having an EC value of 30% IACS or more is considered to have excellent conductivity.
g. Average crystal grain size was measured based on JISH0501 (cutting method).

As shown in Table 1, Examples 1 to 15 of the present invention were all good in properties. However, since Example 15 of the present invention had a high cube azimuth area ratio, the strength was slightly lower than that of the present invention of the same component.

On the other hand, as shown in Table 1, in the sample of the comparative example, one of the characteristics was inferior.
That is, in Comparative Example 1, since the total amount of Ni and Si was small, the density of precipitates contributing to precipitation hardening was lowered and the strength was inferior. In Comparative Examples 2 and 3, the conductivity was inferior because the total amount of Ni and Si was large. In Comparative Example 4, the conductivity was inferior due to the large amount of other elements added.
In Comparative Examples 5, 6, 7, and 10, the Cube orientation area ratio was low, and the bending workability and the deflection coefficient were inferior. In Comparative Examples 8 and 9, although the Cube orientation area ratio was within the range of the present invention, the deflection ratio was inferior because the area ratio of the NDRDW orientation was high. In Comparative Examples 11 and 12, the Cube orientation area ratio was low, the NDRDW orientation area ratio was high, and the bending workability and the deflection coefficient were inferior.
Thus, the combination of the three processes of cold rolling 1, intermediate annealing, and cold rolling 3 had a synergistic effect on the compatibility of bending workability and deflection coefficient.

1 sample

Claims (5)

It has an alloy composition containing either 0.5 or 5.0 mass% in total of any one or two of Ni and Co, 0.2 to 1.5 mass% of Si, and the balance consisting of copper and inevitable impurities, In crystal orientation analysis in EBSD (Electron Back Scatter Diffraction) measurement,
A copper alloy sheet having an area ratio of Cube orientation {100} <001> of 5% or more and an area ratio of NDRDW orientation {012} <221> of 10% or less. One or two of Ni and Co are included in a total amount of 0.5 to 5.0 mass%, Si is contained in an amount of 0.2 to 1.5 mass%, Sn, Zn, Ag, Mn, B, P, Mg, A total of at least one selected from the group consisting of Cr, Fe, Ti, Zr and Hf is contained in an amount of 0.005 to 2.0 mass%, with the balance being an alloy composition consisting of copper and inevitable impurities. EBSD (Electron Back) In crystal orientation analysis in Scatter Diffraction (electron backscatter diffraction) measurement,
A copper alloy sheet having an area ratio of Cube orientation {100} <001> of 5% or more and an area ratio of NDRDW orientation {012} <221> of 10% or less. A copper alloy ingot containing one or two of Ni and Co in a total amount of 0.5 to 5.0 mass%, Si of 0.2 to 1.5 mass%, and the balance of Cu and inevitable impurities On the other hand, the manufacturing method of the copper alloy board | plate material characterized by performing the following process 2-process 12 in this order .
[Step 2: the pressurizing Engineering ratio 10% to 70% cold rolling 1]
[Step 3: Homogenization heat treatment at a temperature of 900 to 1050 ° C. for 2 minutes to 10 hours]
[Step 4: Hot working]
[Step 5: Water cooling]
[Step 6: Face milling]
[Step 7: Cold rolling 2 with a processing rate of 50 to 99%]
[Step 8: Intermediate annealing at 300 to 800 ° C. for 5 seconds to 2 hours]
[Step 9: Cold rolling 3 with a processing rate of 3 to 80%]
[Step 10: Solution heat treatment at 700 to 1020 ° C.]
[Step 11: Aging precipitation heat treatment at 350 to 600 ° C. for 5 minutes to 20 hours]
[Step 12: Finish rolling at a processing rate of 5 to 50%] One or two of Ni and Co are included in a total amount of 0.5 to 5.0 mass%, Si is contained in an amount of 0.2 to 1.5 mass%, Sn, Zn, Ag, Mn, B, P, Mg, A total of at least one selected from the group consisting of Cr, Fe, Ti, Zr, and Hf contains 0.005 to 2.0 mass%, and the remainder of the copper alloy ingot consisting of Cu and inevitable impurities is as follows . The manufacturing method of the copper alloy board | plate material characterized by performing the process 2-the process 12 in this order .
[Step 2: the pressurizing Engineering ratio 10% to 70% cold rolling 1]
[Step 3: Homogenization heat treatment at a temperature of 900 to 1050 ° C. for 2 minutes to 10 hours]
[Step 4: Hot working]
[Step 5: Water cooling]
[Step 6: Face milling]
[Step 7: Cold rolling 2 with a processing rate of 50 to 99%]
[Step 8: Intermediate annealing at 300 to 800 ° C. for 5 seconds to 2 hours]
[Step 9: Cold rolling 3 with a processing rate of 3 to 80%]
[Step 10: Solution heat treatment at 700 to 1020 ° C.]
[Step 11: Aging precipitation heat treatment at 350 to 600 ° C. for 5 minutes to 20 hours]
[Step 12: Finish rolling at a processing rate of 5 to 50%] A connector comprising the copper alloy sheet according to claim 1.

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