JP4934759B2 - Copper alloy sheet, connector using the same, and method for producing copper alloy sheet - Google Patents

Description

  The present invention relates to an excellent copper alloy sheet, and more particularly to a copper alloy sheet that is suitable for connection parts such as automobile terminals and connectors and has excellent strength and bending workability.

  In recent years, there has been an increasing demand for miniaturization and weight reduction of electronic devices, and miniaturization and weight reduction of electric / electronic components have been promoted. The connector terminals have been reduced in height and pitch, and as a result, copper alloy plate materials used for these connector terminals are required to have higher strength and superior bending workability. Conventionally, beryllium copper has been widely used for copper alloy sheets that require high strength and excellent bending workability. However, beryllium copper is very expensive and has strong toxicity to metal beryllium. Therefore, the amount of Corson alloy (Cu—Ni—Si) used as an alloy that can be substituted for these materials is increasing.

Corson alloy is an alloy in which the solubility limit of nickel silicide compound (Ni ₂ Si) in copper changes with temperature. It is a precipitation hardening type alloy that hardens by aging precipitation treatment, and has good heat resistance, electrical conductivity, and strength. .
However, also in this Corson alloy, when the strength of the copper alloy sheet is improved, the conductivity and the bending workability are lowered. That is, in a high-strength Corson alloy, it is a very difficult problem to achieve good conductivity and bending workability.

  For such a problem, as a high-strength copper alloy having excellent bending workability, there is a technique for improving bending workability by controlling the size of precipitates in the Corson alloy (see, for example, Patent Document 1). . Further, a technique for improving strength and bending workability by controlling the crystal grain size of the Corson alloy has been proposed (see, for example, Patent Document 2). However, with connector materials, BW bending is performed with a bend line parallel to the rolling direction, particularly with test pieces cut out parallel to the plate width direction, but these materials satisfy the strength and bending workability required by the market. However, further improvement is required.

  On the other hand, in recent years, attempts have been made to improve bending workability by controlling the texture. For example, there is a method for improving the bending workability by controlling the Cube orientation (see Patent Document 3). In addition, there is one that improves bending workability by increasing the (200) diffraction intensity of X-rays (see, for example, Patent Document 4). However, according to the knowledge of the present inventors, increasing the Cube orientation and (200) diffraction intensity of X-rays is certainly effective in improving the bending workability, but if these are increased, the work hardening when the material is deformed There was a problem that the coefficient was reduced and the tensile strength was lowered.

JP-A-6-184680 JP 2006-161148 A JP 2006-152392 A JP 2009-007666 A

As a result of examining the mechanism in bending of the Corson copper alloy, the present inventors have confirmed that the shear band generated on the surface of the plate during bending is the cause of cracking. In addition, it was confirmed that this shear band can be reduced by accumulating the Cube orientation, but at the same time, a problem was found that the tensile strength was lowered. The reason for this decrease in strength is considered to be that the Cube orientation has a small work hardening coefficient at the time of deformation, so that deformation occurs at a relatively low strength, and the strength does not sufficiently improve and breaks.
In view of the problems as described above, the object of the present invention is to provide excellent bending workability and excellent strength, such as lead frames, connectors, and terminal materials for electric and electronic devices, particularly for automobiles. An object of the present invention is to provide a copper alloy sheet material for electrical and electronic equipment suitable for connectors, terminal materials, relays, switches and the like.

The inventors of the present invention have found that it is possible to achieve both excellent bending workability and high strength by defining the area ratio of crystal orientation grains having a deviation angle within 15 to 30 ° from the Cube orientation within a specific range. . The present invention has been completed based on this finding.
That is, the present invention is the following means.
(1) From a copper alloy composition containing 0.8 to 5% of Ni or Co and 0.2 to 1.5% of Si and the balance Cu and inevitable impurities in mass%. The area ratio of crystal grains having a deviation angle of less than 15 ° from the Cube orientation is less than 10%, and the area ratio of crystal grains having a deviation angle of 15 to 30 ° from the Cube orientation is 15% or more. A copper alloy sheet material for electric and electronic parts which has excellent strength and bending workability controlled.
(2) The copper alloy sheet for electrical and electronic parts according to (1), further containing 0.05 to 0.5% of Cr.
(3) The electrical and electronic component according to (1) or (2), further comprising 0.01 to 1.0% of one or more of Zn, Sn, Mg, Ag, Mn, and Zr in total. Copper alloy plate material .
(4 ) A connector comprising the copper alloy sheet for electrical and electronic parts according to any one of (1) to ( 3 ).
( 5 ) A method for producing a copper alloy sheet for electric and electronic parts according to any one of (1) to (3) , comprising the following steps.
[Casting a molten copper alloy with components adjusted to the composition range described in any one of (1) to (3) ]
[Step of chamfering the ingot, heating at 800-1000 ° C. or homogenizing heat treatment, hot rolling, and water-cooling the hot-rolled plate]
[After hot rolling, and scalped surface, step rolling rate to perform cold rolling the first 70%
[During cold rolling 1 and solution heat treatment, subsequent to intermediate annealing for 5 seconds to 2 hours at 300 to 800 ° C., the step of rolling rate is added 3-80% cold rolling 2]
[600 to 1000 ° C. for 5 seconds to 300 seconds from the step of solution heat treatment]
[After solution heat treatment, the different friction cold rolling difference center line average roughness Ra of a roll to be 0.05~3.0μm the upper roll and the lower roll, working ratio 5-40% cold Process performed as cold rolling 3]
[Step of aging heat treatment at 400 to 600 ° C. for 0.5 to 8 hours]
[Step of performing cold rolling at a processing rate of 0 to 20% and performing low temperature annealing]

  The copper alloy sheet of the present invention has high strength, good bending workability, and high conductivity. Moreover, said physical property of a copper alloy board | plate material can also be improved further by adding another additive element. Furthermore, it is possible to improve the heat release resistance and migration resistance during soldering, and improve the workability and stress relaxation characteristics during hot rolling.

The preferred metal structure of the copper alloy sheet material for electrical and electronic parts of the present invention having high strength, good bending workability and high conductivity 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 and stable in shape and having a spread in the surface direction, and in a broad sense, includes a strip material. 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 addition, although the copper alloy plate material of this invention prescribes | regulates the characteristic with the integration rate of the atomic surface in the predetermined direction of a rolled sheet, this should just have such a characteristic as a copper alloy plate material. Therefore, the shape of the copper alloy sheet is not limited to a sheet or a strip, and in the present invention, the pipe can be interpreted and handled as a sheet.

(Average particle size)
The average crystal grain size of the copper alloy sheet of the present invention is preferably 50 μm or less. When the average crystal grain size is less than or equal to the above upper limit, it is preferable that a shear band that causes cracking is not easily generated in both the good way (GW) bending process and the bad way (BW) bending process. Here, Good Way means the rolling parallel direction, and Bad Way means the rolling vertical direction. The crystal grain size was determined by JIS H 0501 (cutting method).

(Regulation by EBSD measurement)
The texture of the copper alloy sheet material of the present invention is a measurement result by the SEM-EBSD method (described later) in order to achieve both strength and bending workability, and the deviation angle (azimuth difference) from the Cube orientation is 15 °. Having a texture in which the area ratio of crystal grains less than 10% is less than 10% and the area ratio of crystal grains having a deviation angle from the Cube orientation of 15 to 30 ° is 15% or more, preferably 20% or more and less than 50% Is.

In the case of a copper alloy sheet, a texture called a Cube orientation, a Goss orientation, a Brass orientation, a Copper orientation, an S orientation, etc. as shown below is formed, and there are crystal planes corresponding to them.
The formation of these textures differs depending on the processing and heat treatment methods even in the same crystal system. In the case of a texture of a material such as a plate material by rolling, the texture is represented by a face and a direction, the face is represented by {ABC}, and the direction is represented by <DEF>. 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. Each region is expressed in the form of (hkl) [uvw] using the index (hkl) of the crystal plane perpendicular to the Z axis and the index [uvw] of the crystal direction parallel to the X axis. Along with the above notation, each direction is expressed as follows.
Cube orientation {001} <100>
Goss orientation {011} <100>
Rotated-Goss orientation {011} <011>
Brass orientation {011} <211>
Copper orientation {112} <111>
S orientation {123} <634>
P direction {011} <111>

As described above, the texture of ordinary copper alloy sheets consists of a considerable number of orientation factors. However, if the composition ratio of these crystal planes changes, the plastic behavior of the materials such as sheets changes, and the workability such as bending is improved. Changes.
When the texture of a conventional Corson-based high-strength copper alloy sheet is manufactured by a normal method, the S orientation {123} <634>, other than the Cube orientation {001} <100>, as in Examples described later, The Brass orientation {011} <211> is the main component, and the ratio of the Cube orientation decreases. For this reason, in particular, in BW bending, a shear band is easily generated and bending workability is deteriorated. On the other hand, when the bendability is improved by increasing the accumulation of crystal grains having a deviation angle of less than 15 ° from the Cube orientation, there arises a problem that the strength is lowered.

  On the other hand, the texture of the copper alloy sheet of the present invention has a strength and bendability in which the area ratio of crystal grains having a deviation angle from the Cube orientation {001} <100> of 15 to 30% is 15% or more. It shall have an excellent texture. However, in the present invention, if the area ratio of the crystal grains having a deviation angle of 15 to 30 ° from the Cube orientation is 15% or more, it is possible to allow other orientations to exist as sub-azimuths.

  The measurement of the degree of accumulation of orientation grains having a deviation angle of 15 to 30 ° from the Cube orientation {001} <100> of the texture of the copper alloy sheet material is based on the data obtained by measuring the electron microscope texture by SEM using EBSD. It is obtained by performing an azimuth analysis using an azimuth distribution function (ODF). Here, a 1200 μm square sample area containing 400 or more crystal grains was scanned in 0.5 μm steps, and the orientation was analyzed. Since these orientation distributions change in the thickness direction of the material, it is preferable to obtain the orientation distribution by arbitrarily analyzing the orientation distribution at several points in the thickness direction and taking the average.

  This SEM-EBSD method is an abbreviation for Scanning Electron Microscopy-Electron Back Scattered Diffraction Pattern Method. In other words, each crystal grain appearing on a scanning electron microscope (SEM) screen is irradiated with an electron beam, and the individual crystal orientation is identified from the diffracted electrons.

Regarding the deviation angle from the ideal orientation indicated by the above index, the rotation angle was calculated around a common rotation axis, and was taken as the deviation angle. 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 is defined as a deviation angle. A common rotation axis that can be expressed at the smallest angle is adopted. The deviation angle is calculated for all measurement points, and the first decimal place is an effective number. The area of each crystal grain having an orientation of less than 15 ° and within 15-30 ° from the Cube orientation is the total measurement area. To obtain the area ratio.
In the EBSD measurement, in order to obtain a clear Kikuchi line diffraction image, the surface of the substrate was mirror-polished using a colloidal silica abrasive after mechanical polishing, and then the measurement was performed.

  Here, the characteristics of the EBSD measurement will be described as contrast with the X-ray diffraction measurement. The first point is that ND // (111), (200), (220) that can be measured by the X-ray diffraction method satisfies the Bragg diffraction conditions and provides sufficient diffraction intensity. ), (311), and (420) planes, and the deviation angle from the Cube orientation corresponds to 15 to 30 °, such as ND // (511) plane and ND // (951) plane. The crystal orientation expressed by a high index cannot be measured. That is, by adopting the EBSD measurement, information about their orientation is obtained for the first time, and the relationship between the specified alloy structure and the action becomes clear. Second, X-ray diffraction measures the amount of crystal orientation contained within about ± 0.5 ° of ND // {hkl}, whereas the EBSD measurement uses the Kikuchi pattern. Information on an alloy structure that is not limited to a specific crystal plane and an extremely wide range of alloy structures is comprehensively obtained, and it becomes clear that the entire alloy material is difficult to specify by X-ray diffraction. As described above, contents and properties of information obtained by EBSD measurement and X-ray diffraction measurement are different. In addition, unless otherwise indicated in this specification, the result of EBSD was performed with respect to the ND direction of a copper alloy board | plate material.

(Alloy composition, etc.)
Next, the reason for limitation of the chemical component composition in the copper alloy sheet material of the present invention will be described (all the content% described is mass%).

・ Ni, Co, Si
The Ni content is 0.5 to 5.0%. Ni is an element that is contained together with Si to be described later, forms a Ni2Si phase precipitated by aging treatment, and contributes to improving the strength of the copper alloy sheet. When there is too little content of Ni, the said Ni2Si phase will run short and the tensile strength of a copper alloy board cannot be raised. On the other hand, when there is too much content of Ni, electrical conductivity will fall and hot rolling workability will deteriorate. Therefore, the Ni content is in the range of 0.5 to 5.0%, preferably 1.5 to 4.0%.

  The Co content is 0.5 to 5.0%. Co is an element that is contained together with Si and contributes to improving the strength of the copper alloy sheet by forming a Co2Si phase precipitated in the same manner as Ni by aging treatment. When the content of Co is too small, the Co2Si phase is insufficient, and the tensile strength of the copper alloy sheet cannot be increased. On the other hand, when there is too much content of Co, electrical conductivity will fall. Moreover, hot rolling workability deteriorates. Therefore, the Co content is in the range of 0.5 to 5.0%, preferably 0.8 to 3.0%.

  These Ni and Co may contain 0.5 to 5.0% in total. When both Ni and Co are contained, both Ni2Si and Co2Si precipitate during the aging treatment, and the aging strength can be increased. If the total content of Ni and Co is too small, the tensile strength cannot be increased. If it is too large, the electrical conductivity and hot rolling processability are lowered. Accordingly, the total content of Ni and Co is in the range of 0.5 to 5.0%, preferably 0.8 to 4.0%. In particular, when high conductivity is required, it is preferable that the amount of Co added is larger than the amount of Ni added.

Si is contained together with Ni and Co, and forms a Ni2Si or Co2Si phase precipitated by aging treatment, thereby contributing to an improvement in the strength of the copper alloy sheet. The balance between conductivity and strength is best when the Si content is stoichiometrically Ni / Si = 4.2 and Co / Si = 4.2. Therefore, the content of Si should be such that Ni / Si, Co / Si, and (Ni + Co) / Si are in the range of 3.2 to 5.2, preferably 3.5 to 4.5.
If the Si is excessively contained outside this range, the tensile strength of the copper alloy sheet can be increased, but the excessive amount of Si is dissolved in the copper matrix, and the conductivity of the copper alloy sheet is increased. The rate drops. Moreover, when Si is contained excessively, the castability in casting, the hot and cold rolling processes are also reduced, and casting cracks and rolling cracks are likely to occur. On the other hand, if it is out of this range and the Si content is too small, the precipitation phase of Ni2Si or Co2Si is insufficient and the tensile strength of the plate cannot be increased.

-Other elements In addition to the said composition, a copper alloy may contain 0.01 to 0.5% of Cr. Cr has an effect of refining crystal grains in the alloy, and contributes to improvement of the strength and bending workability of the copper alloy sheet. If the amount is too small, the effect is not obtained. If the amount is too large, a crystallized product is formed during casting, and the aging strength is lowered. A preferable content is 0.05 to 0.3%.

  The high-strength copper alloy sheet material of the present invention includes, in addition to the above basic composition, as additive elements in mass%, Sn: 0.05 to 1.0%, Zn: 0.01 to 1.0%, Ag: 0.00. It may contain one or more of 01 to 1.0%, Mn: 0.01 to 1.0%, Zr: 0.1 to 1.0%, Mg: 0.01 to 1.0%. Good. Here, when it contains 2 or more types, a total shall be 0.01-1.0%. These elements are elements having a common action and effect for further improving any one of strength, conductivity, and bending workability, which are the main purposes of the copper alloy of the present invention. Below, the characteristic effect of each element and the significance of the content range are described.

  Sn is an element mainly improving the strength of the copper alloy sheet, and is selectively contained when used for applications in which these characteristics are important. When there is too little content of Sn, the strength improvement effect will be inadequate. On the other hand, when Sn is contained, the conductivity of the copper alloy plate tends to decrease. In particular, when there is too much Sn, it becomes difficult to make the electrical conductivity of the copper alloy plate material 20% IACS or more. Therefore, when it contains, it is preferable to make content of Sn into 0.01 to 1.0% of range.

  By adding Zn, it is possible to improve the heat-resistant peelability and migration resistance during soldering. If there is too little content of Zn, the effect will become inadequate. On the other hand, if Zn is contained, the conductivity of the copper alloy plate tends to decrease. If too much Zn is contained, it is difficult to make the conductivity of the copper alloy plate 20% IACS or more. Therefore, the Zn content is preferably in the range of 0.01 to 1.0%.

  Ag contributes to an increase in the strength of the copper alloy sheet. If the content of Ag is too small, the effect is insufficient. On the other hand, even if Ag is excessively contained, the effect is saturated, which is not preferable. Therefore, when it is made to contain, it is preferable to make content of Ag into the range of 0.01 to 1.0%.

  Mn mainly improves the workability of the alloy in hot rolling. If the Mn content is too small, the effect is insufficient. On the other hand, when there is too much Mn, the hot-water flow property at the time of casting of a copper alloy will deteriorate, and a casting yield will fall. Therefore, when it contains, the content of Mn is made 0.01 to 1.0% of range.

  Zr mainly refines the crystal grains and improves the strength and bending workability of the copper alloy plate. If the Zr content is too small, the effect is insufficient. On the other hand, when there is too much Zr, a compound will be formed and workability, such as rolling of a copper alloy plate, will fall. Therefore, when it contains, content of Zr shall be 0.01 to 1.0% of range.

  Mg improves stress relaxation characteristics. Therefore, when the stress relaxation property is required, it is selectively contained in the range of 0.01 to 1.0%. If the amount of Mg is too small, the intended effect is insufficient, and if it is too large, the electrical conductivity is lowered, which is undesirable.

(Manufacturing method etc.)
Next, the preferable manufacturing method (preferable embodiment) of the copper alloy sheet | seat material of this invention is demonstrated below.
The Corson alloy sheet according to the present invention includes steps of casting, hot rolling, cold rolling 1, intermediate annealing, cold rolling 2, solution heat treatment, cold rolling 3, aging heat treatment, finish cold rolling, and low temperature annealing. It is manufactured after. The manufacturing method itself of the copper alloy sheet of the present invention can be manufactured by the same method as that of the conventional Corson alloy. Although it is necessary to limit the manufacturing conditions of each process to a texture, it is preferable to strictly manage the conditions of intermediate annealing and cold rolling 3 in order to manufacture the copper alloy sheet of the present invention.

In the present embodiment, the casting is performed by casting a molten copper alloy whose components are adjusted to the above composition range. And after chamfering an ingot, it heats at 800-1000 degreeC, or it heat-rolls, Then, it hot-rolls and the board after hot rolling is water-cooled.
After hot rolling, the surface is chamfered and cold rolling 1 is performed. If the rolling rate of this cold rolling 1 is sufficiently high, the Brass direction and S direction will not develop too much even if the final product is manufactured thereafter, and the area ratio with a deviation angle from the Cube direction of 15 to 30 ° is sufficient. Can be increased. Therefore, it is preferable that the rolling rate of the cold rolling 1 is 70% or more.

The copper alloy material of the present invention is obtained by subjecting cold rolling 2 having a rolling rate of 3 to 80% between cold rolling 1 and solution heat treatment to intermediate annealing at 300 to 800 ° C. for 5 seconds to 2 hours. It is characterized by adding. In the intermediate annealing, by performing the heat treatment at a temperature lower than the solution heat treatment temperature, it is possible to obtain a sub-annealed structure in which the material is not completely recrystallized but partially recrystallized. In cold rolling 2, microscopically non-uniform strain can be introduced into the material by rolling at a relatively low processing rate. By the effect of these two steps, a desired crystal orientation can be obtained in the recrystallization texture in the solution heat treatment. A more preferable range of the intermediate annealing 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 2 is 5 to 55%, and a further preferable range is 7 to 45%.
Conventionally, heat treatment such as the intermediate annealing has been performed in order to reduce the strength by recrystallizing the material in order to reduce the load in the next rolling process. 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 the intermediate annealing and cold working in the present invention is to give priority to the crystal orientation after recrystallization, unlike these general contents.

  In this embodiment, the solution treatment is performed at 600 to 1000 ° C. for 5 to 300 seconds. Since necessary temperature conditions vary depending on the Ni and Co concentrations, it is necessary to select appropriate temperature conditions according to the Ni and Co concentrations. When the solution temperature is equal to or higher than the above lower limit, the strength is sufficiently maintained in the aging treatment step, and when the solution temperature is equal to or lower than the upper limit, the material is not softened more than necessary, and shape control is suitably realized. . At this time, it is preferable that the area ratio of crystal grains having a deviation angle of 15 to 30 ° from the Cube orientation is 15 to 50%.

  After the solution treatment, cold rolling 3 of 5 to 40% is performed. When cold rolling is performed at this processing rate, the texture is preferably within the scope of the present invention. According to the knowledge of the present inventors, when different friction rolling is performed with rolls having different roughness of the roll of cold rolling, the crystal grains with a deviation angle of less than 15 ° from the Cube orientation are slightly rotated, and from the Cube orientation. Can be accumulated in a direction with a deviation angle of 15 to 30 °. This is presumably because, in different friction rolling, plastic restraint differs between the upper and lower surfaces of the rolled material, and shear deformation is slightly introduced due to the difference in plastic restraint. Here, the difference in the center line average roughness Ra between the upper roll and the lower roll is preferably 0.05 to 3.0 [mu] m, and more preferably 2.4 to 2.8 [mu] m. The roughness of the roll may be adjusted by roughening the roll with abrasive paper. The cold rolling 3 has the effect of increasing the amount of aging precipitation and contributes to the improvement of strength.

The aging treatment is performed at 400 to 600 ° C. for 0.5 to 8 hours. Since necessary temperature conditions vary depending on the Ni and Co concentrations, it is necessary to select appropriate temperature conditions according to the Ni and Co concentrations. When the temperature of the aging treatment is not less than the above lower limit value, the strength is sufficiently maintained without decreasing the amount of aging precipitation. Moreover, when the temperature of an aging treatment is below the said upper limit, a precipitate will not coarsen and intensity | strength is maintained.
The processing rate of finish cold rolling after solution treatment is preferably 0 to 20% or less. If the processing rate is too high, the Cube orientation grains may be rotated to the Brass, S, and Copper orientations, and the texture may fall outside the scope of the present invention.
The characteristics of the copper alloy plate manufactured according to the present invention can be confirmed by verification by EBSD analysis whether the structure of the copper alloy plate is within a specified range.

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

  Examples of the present invention will be described below. Copper alloys having various compositions shown in Table 1 below were cast to produce copper alloy plates, and properties such as strength, conductivity and bendability were evaluated.

  First, it cast by DC (Direct Chill) method and obtained the ingot of thickness 30mm, width 100mm, and length 150mm. Next, these ingots were heated to 900 ° C., held at this temperature for 1 hour, hot-rolled to a thickness of 14 mm, and quickly cooled. Next, both sides were chamfered 1 mm each to remove the oxide film, and then cold rolled 1 with a rolling rate of 90 to 98% was performed. Thereafter, heat treatment was performed at 600 to 700 ° C. for 1 hour, and cold rolling 2 was performed at a cold rolling rate of 5 to 20%. Thereafter, solution treatment was performed under various conditions of 700 to 950 ° C. and immediately cooled at a cooling rate of 15 ° C./second or more. Next, cold rolling 3 with a rolling rate of 5 to 40% was performed. At this time, a roll having a difference in surface roughness Ra between the upper and lower rolls of 0.05 to 3.0 μm was used. Next, an aging treatment was performed at 400 to 600 ° C. for 2 hours in an inert gas atmosphere, and then finish rolling with a rolling rate of 20% or less was performed, so that the final plate thickness was adjusted to 0.15 mm. After finish rolling, various properties were evaluated using materials subjected to low-temperature annealing at 400 ° C. for 30 seconds.

  With respect to the copper alloy plate thus produced, in each example, a sample cut out from the copper alloy plate after aging treatment was used, and the following tests and evaluations were performed.

The structure of the copper alloy plate sample, the area ratio of crystal orientation grains with a deviation angle of less than 15 ° from the Cube orientation, and the area ratio of crystal orientation grains with a deviation angle of 15 to 30 ° or less were measured by the method described above. These results are shown in the table.
As an EBSD measuring apparatus, OSL5.0 HIKARI manufactured by TSL was used.

Moreover, (1) area ratio of each crystal orientation grain, (2) tensile strength, (3) electrical conductivity, and (4) bendability of the copper alloy sheet sample were evaluated.
(1) The area ratio of crystal orientation grains showed an area ratio of a deviation angle of less than 15 ° from the Cube orientation and an area ratio of a deviation angle of 15 to 30 ° from the Cube orientation.
(2) Tensile strength was determined according to JIS Z 2241 using No. 5 test piece described in JIS Z 2201. The tensile strength is shown rounded to an integral multiple of 5 MPa.
(3) The electrical conductivity was determined according to JIS H 0505.
(4) The bending workability is performed with a bending test piece width w of 5 mm, bending 90 ° with a bending R = 0 to 0.6, and having a minimum bending radius (R) and plate thickness (t) with no cracks. The ratio was defined as R / t.

  Examples 1 to 31 in Table 1 show examples of the present invention. Examples 1-31 have a texture within the scope of the present invention, and are excellent in strength and bending workability.

  Table 2 shows a comparative example for the present invention. In Comparative Examples 1, 2, and 5, the tensile strength is remarkably low because the content of Ni or Co is less than the range defined by the present invention. In Comparative Examples 3, 4, 6, and 7, since the content of Ni or Co was too large, the production was stopped because cracks occurred during hot rolling.

Table 3 is an example of investigating the influence of the difference in the average roughness Ra of the upper and lower rolling rolls of the cold rolling 3 on the texture using the same ingot as in the example of Table 1. In Examples 10-2, 10-3, 22-2, 22-3, 29-2, and 29-3 in Table 3, the texture is within the range of the examples of the present invention, and is excellent in strength and bending workability. On the other hand, in Comparative Examples 10-2, 22-2, and 29-2, since the difference in Ra was small, the area ratio with a deviation angle of less than 15 ° from the Cube orientation was high, and the strength decreased. In Comparative Examples 10-3, 22-3, and 29-3, since the difference in Ra was large, the area ratio within a deviation angle of 15 ° to 30 ° from the Cube orientation was low, and bending workability was lowered.
The surface roughness Ra of the roll was measured according to JIS B 0601.

  Subsequently, in order to clarify the difference from the copper alloy sheet material according to the present invention, the copper alloy sheet material produced under the conventional production conditions, the copper alloy sheet material is produced under the conditions, and the same characteristic items as described above are evaluated. Went. In addition, the processing rate was adjusted so that the thickness of each board | plate material might become the same thickness as the said Example unless there is particular notice. In any case, in consideration of general manufacturing conditions at the time of filing of the present application, different friction rolling was not adopted in cold rolling after solution heat treatment.

(Comparative Example 101) ... Conditions of JP2009-007666 A metal element similar to that of Invention Example 1-1 is blended, and an alloy composed of Cu and inevitable impurities is melted in a high-frequency melting furnace. This was cast at a cooling rate of 0.1 to 100 ° C./second to obtain an ingot. This was held at 900 to 1020 ° C. for 3 minutes to 10 hours, then hot worked, then water quenched, and chamfered to remove oxide scale. In the subsequent steps, the copper alloy c01 was manufactured by performing the processes of steps A-3 and B-3 described below.
The manufacturing process includes one or more solution heat treatments, and here, the process is classified before and after the last solution heat treatment, and the process up to the intermediate solution is A-3 process, It was set as B-3 process in the process after intermediate solution.

Step A-3: A cold working with a cross-sectional reduction rate of 20% or more is performed, a heat treatment is performed at 350 to 750 ° C. for 5 minutes to 10 hours, a cold working with a cross-sectional reduction rate of 5 to 50% is performed, and 800 A solution heat treatment is performed at ˜1000 ° C. for 5 seconds to 30 minutes.
Step B-3: Cold work (with no cross friction) with a cross-section reduction rate of 50% or less, heat treatment at 400 to 700 ° C. for 5 minutes to 10 hours, and cold work with a cross-section reduction rate of 30% or less And temper annealing at 200 to 550 ° C. for 5 seconds to 10 hours.

  The obtained specimen c01 was different from the above example in terms of the production conditions in terms of the presence or absence of different friction rolling, and the result was that the required properties for the tensile strength were not satisfied.

(Comparative Example 102) ... Conditions of Japanese Patent Application Laid-Open No. 2006-283059 The copper alloy having the composition of Example 1-1 of the present invention was melted in the atmosphere under charcoal coating in an electric furnace to determine whether casting was possible. . The molten ingot was hot-rolled to a thickness of 15 mm. Subsequently, this hot-rolled material is subjected to cold rolling and heat treatment (cold rolling 1 → solution annealing, cold rolling 2 (no different friction) → aging treatment → cold rolling 3 → short annealing). A copper alloy thin plate (c02) having a predetermined thickness was produced.

  The obtained specimen c02 was different from Example 1 in terms of manufacturing conditions in the presence or absence of intermediate annealing and cold rolling 2 and in the presence or absence of differential friction rolling, and did not satisfy bending workability.

(Comparative Example 103) ... Conditions of Japanese Patent Application Laid-Open No. 2006-152392 The alloy having the composition of the present invention example 1-1 was melted under a charcoal coating in the atmosphere in a kryptor furnace and cast into a cast iron book mold. An ingot having a thickness of 50 mm, a width of 75 mm, and a length of 180 mm was obtained. Then, after chamfering the surface of the ingot, it was hot-rolled at a temperature of 950 ° C. until the thickness became 15 mm, and rapidly cooled into water from a temperature of 750 ° C. or higher. Next, after removing the oxide scale, cold rolling was performed to obtain a plate having a predetermined thickness.

  Subsequently, after performing a solution heat treatment using a salt bath furnace and heating at a temperature for 20 seconds, after quenching in water, the cold-rolled sheet of each thickness is subjected to finish cold rolling (no friction) in the latter half. did. At this time, as shown below, the cold-rolled sheet (c03) was obtained by variously changing the cold rolling processing rate (%). As shown below, these cold-rolled plates were subjected to aging treatment at various temperatures (° C.) and times (hr).

Cold working rate: 95%
Solution treatment temperature: 900 ° C
Artificial age hardening temperature x time: 450 ° C x 4 hours Thickness: 0.6mm

  The obtained test body c03 was different from Example 1 in terms of manufacturing conditions in the presence or absence of intermediate annealing and cold rolling 2 and in the presence or absence of differential friction rolling, and did not satisfy bending workability.

(Comparative Example 104) ... Conditions of JP-A-2008-223136 The copper alloy shown in Example 1 was melted and cast using a vertical continuous casting machine. A sample with a thickness of 50 mm was cut out from the obtained slab (thickness 180 mm), heated to 950 ° C., extracted, and hot rolling was started. At that time, the pass schedule was set so that the rolling rate in the temperature range of 950 ° C. to 700 ° C. was 60% or more and the rolling was performed even in the temperature range of less than 700 ° C. The final pass temperature of hot rolling is between 600 ° C and 400 ° C. The total hot rolling rate from the slab is about 90%. After hot rolling, the surface oxide layer was removed (faced) by mechanical polishing.
Subsequently, after performing cold rolling, it used for the solution treatment. The temperature change during the solution treatment was monitored by a thermocouple attached to the sample surface, and the temperature raising time from 100 ° C. to 700 ° C. in the temperature raising process was determined. The ultimate temperature is adjusted within the range of 700 to 850 ° C. according to the alloy composition so that the average crystal grain size after solution treatment (the twin boundary is not regarded as a grain boundary) is 10 to 60 μm. The holding time in the temperature range of 850 ° C. was adjusted in the range of 10 sec to 10 min. Subsequently, the plate material after the solution treatment was subjected to intermediate cold rolling (without different friction) at a rolling rate, and then subjected to an aging treatment. The aging treatment temperature was adjusted to a material temperature of 450 ° C., and the aging time was adjusted to a time when the hardness peaked at 450 ° C. according to the alloy composition. The optimum solution treatment conditions and aging treatment time according to such an alloy composition have been grasped by preliminary experiments. Next, finish cold rolling was performed at a rolling rate. About what performed finish cold rolling, the low temperature annealing which puts it in a 400 degreeC furnace for 5 minutes after that was given after that. In this way, a test material c04 was obtained. If necessary, chamfering was performed in the middle, and the thickness of the specimen was adjusted to 0.2 mm. The main production conditions are described below.

[Conditions of JP-A-2008-223136 Example 1]
Hot rolling rate at less than 700 ° C to 400 ° C: 56% (1 pass)
Before solution treatment Cold rolling rate: 92%
Intermediate cold rolling Cold rolling rate: 20%
Finish cold rolling Cold rolling rate: 30%
Temperature rising time from 100 ° C to 700 ° C: 10 seconds

  The obtained specimen c04 differs from the above-described Example 1 in terms of production conditions in the presence or absence of intermediate annealing and cold rolling 2 and in the presence or absence of differential friction rolling, and did not satisfy bending workability.

Claims (5)

  Copper alloy consisting of a copper alloy composition containing 0.8 to 5% of Ni or Co and 0.2 to 1.5% of Si and the balance Cu and unavoidable impurities in mass% The plate material, the area ratio of crystal grains having a deviation angle of less than 15 ° from the Cube orientation was controlled to less than 10%, and the area ratio of crystal grains having a deviation angle of 15 to 30 ° from the Cube orientation was controlled to 15% or more, A copper alloy sheet for electrical and electronic parts having excellent strength and bending workability.   Furthermore, the copper alloy sheet | seat for electrical and electronic components of Claim 1 which contains 0.05-0.5% of Cr. Furthermore, the copper alloy board | plate material for electrical and electronic components of Claim 1 or 2 which contains 0.01-1.0% of 1 type or 2 types or more in total in Zn, Sn, Mg, Ag, Mn, and Zr . The connector which consists of a copper alloy board | plate material for electrical and electronic components of any one of Claims 1-3 . It is a manufacturing method of the copper alloy board | plate material for electric and electronic components of any one of Claims 1-3, Comprising: The manufacturing method of the copper alloy board | plate material for electric and electronic components which has the following processes.
[Step of casting a molten copper alloy whose components are adjusted to the composition range according to any one of claims 1 to 3 ]
[Step of chamfering the ingot, heating at 800-1000 ° C. or homogenizing heat treatment, hot rolling, and water-cooling the hot-rolled plate]
[After hot rolling, and scalped surface, step rolling rate to perform cold rolling the first 70%
[During cold rolling 1 and solution heat treatment, subsequent to intermediate annealing for 5 seconds to 2 hours at 300 to 800 ° C., the step of rolling rate is added 3-80% cold rolling 2]
[600 to 1000 ° C. for 5 seconds to 300 seconds from the step of solution heat treatment]
[After solution heat treatment, the different friction cold rolling difference center line average roughness Ra of a roll to be 0.05~3.0μm the upper roll and the lower roll, working ratio 5-40% cold Process performed as cold rolling 3]
[Step of aging heat treatment at 400 to 600 ° C. for 0.5 to 8 hours]
[Step of performing cold rolling at a processing rate of 0 to 20% and performing low temperature annealing]