JP2011132594A - Titanium-copper for electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide titanium-copper which has excellent strength and bendability. <P>SOLUTION: The titanium-copper is a copper alloy for electronic components which contains 2.0 to 4.0 mass% Ti, the remainder comprising copper and incidental impurities. The intensity peak of X-ray diffraction from the ä220} crystal plane in a rolled surface of the copper alloy has a half-value width βä220} which satisfies the relationship 3.0≤βä220}/β<SB>0</SB>ä220}≤6.0, wherein β<SB>0</SB>ä220} is the half-value width of the intensity peak of X-ray diffraction from the ä220} crystal plane of a standard powder of pure copper. The copper alloy, in a structure examination of a section parallel to the rolling direction, has an average crystal-grin diameter of 30 μm or smaller in terms of equivalent-circle diameter. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to titanium copper suitable as a member for electronic parts such as a connector and a method for producing the same.

  In recent years, electronic devices typified by portable terminals and the like have been increasingly miniaturized, and accordingly, connectors used for such devices tend to have a narrow pitch and a low profile. The smaller the connector, the narrower the pin width, and the smaller the folded shape, so that the members used have high strength to obtain the necessary spring properties and excellent bending workability that can withstand severe bending work. Is required. In this regard, a titanium-containing copper alloy (hereinafter referred to as “titanium copper”) has a relatively high strength and is most excellent in the copper alloy in terms of stress relaxation characteristics. As a signal system terminal member, it has been used for a long time.

  Titanium copper is an age-hardening type copper alloy. When a supersaturated solid solution of Ti, which is a solute atom, is formed by solution treatment, and heat treatment is performed at a low temperature for a relatively long time from that state, a modulated structure that is a periodic variation of Ti concentration in the parent phase is caused by spinodal decomposition. Develop and improve strength. At this time, the problem is that the strength and the bending workability are contradictory. That is, if the strength is improved, the bending workability is impaired, and conversely, if the bending workability is emphasized, a desired strength cannot be obtained. In general, the higher the rolling reduction in cold rolling, the more dislocations are introduced and the dislocation density is higher, so that the number of nucleation sites contributing to precipitation increases and the strength after aging treatment can be increased. However, if the rolling reduction is too high, the bending workability deteriorates. For this reason, it has been an object to achieve both strength and bending workability.

  Therefore, a third element such as Fe, Co, Ni, Si or the like is added (Patent Document 1), the concentration of the impurity element group that dissolves in the matrix phase is regulated, and these elements are added to the second phase particles (Cu-Ti- X-type particles) are precipitated in a predetermined distribution form to increase the regularity of the modulation structure (Patent Document 2), and the density of the trace additive elements and second-phase particles effective to refine the crystal grains is specified. From the viewpoints of (Patent Document 3) and refining crystal grains (Patent Document 4), a technique has been proposed which attempts to achieve both the strength and bending workability of titanium copper.

In the case of titanium copper, there are a β phase (TiCu ₃ ) having poor consistency with the α phase as a parent phase and a β ′ phase (TiCu ₄ ) having good consistency, and the β phase has an adverse effect on bending workability. On the other hand, evenly and finely dispersing the β ′ phase contributes to both strength and bending workability, and titanium copper in which the β ′ phase is finely dispersed while suppressing the β phase has also been proposed ( Patent Document 5).

By paying attention to the crystal orientation and controlling the crystal orientation to satisfy I {420} / I ₀ {420}> 1.0 and I {220} / I ₀ {220} ≦ 3.0, the strength and bending A technique for improving workability and stress relaxation resistance has also been proposed (Patent Document 6).

Japanese Patent Laid-Open No. 2004-231985 JP 2004-176163 A JP-A-2005-97638 JP 2006-265611 A JP 2006-283142 A JP 2008-308734 A

  Thus, various methods have been studied so far for improving the strength and bending workability of titanium copper, but there is still room for improvement. Accordingly, one of the objects of the present invention is to provide titanium copper having excellent strength and bending workability by trying to improve the characteristics of titanium copper from a different viewpoint. Another object of the present invention is to provide a method for producing such titanium copper.

  The conventional titanium copper manufacturing method consists of ingot melting casting → homogenization annealing → hot rolling → (repetition of annealing and cold rolling) → final solution treatment → cold rolling → aging treatment. Was based. The titanium copper described in the background art is also manufactured in the same order.

  In the examination process for solving the above-mentioned problems, the present inventor performs the order of the cold rolling and the aging treatment after the final solution treatment in the reverse order, that is, the order of the aging treatment → cold rolling. In addition, it was found that bending workability is significantly improved when strain relief annealing is finally performed under appropriate conditions. That is, when the titanium copper manufactured according to the conventional procedure and the titanium copper of the present invention are compared, the titanium copper of the present invention is superior in bending workability in the case of the same strength. In order to investigate the cause, the present inventor investigated the structure of titanium copper according to the present invention, and found characteristic points in the dislocation density and the form of crystal grains. Specifically, when cold rolling is performed at the same rolling reduction, the titanium obtained when the order of aging treatment → cold rolling is performed rather than the order of cold rolling → aging treatment It was found that the dislocation density of copper increases. In other words, the reduction ratio during cold rolling necessary to obtain the same dislocation density can be reduced. If the rolling reduction is small, it is possible to suppress the crystal grains from being stretched in the rolling direction during cold rolling, so that bending workability is improved.

  Dislocation density is difficult to measure directly. This is because the dislocation distribution becomes non-uniform depending on the modulation structure and the distribution of the precipitated particles. When the evaluation is attempted indirectly, there is a correlation with the half width of the X-ray line intensity peak of the {220} crystal plane on the rolled surface. The half width is the width (β) of the diffraction intensity curve at an intensity that is ½ of the peak intensity of the diffraction intensity curve, and is represented by 2θ. The half width increases with the dislocation density as the rolling reduction in cold rolling increases. Therefore, in the present invention, the state of dislocation density is indirectly defined using the half width as an index.

This invention completed based on the said knowledge WHEREIN: In 1 side, 2.0-4.0 mass% of Ti is contained, The copper alloy for electronic components which consists of remainder copper and an unavoidable impurity,
Β {220}, which is the half width of the X-ray diffraction intensity peak from the {220} crystal plane of the rolled surface, is β, which is the half width of the X-ray diffraction intensity peak from the {220} crystal plane of the pure copper standard powder. ₀ {220} and the following formula:
3.0 ≦ β {220} / β ₀ {220} ≦ 6.0
And
In the observation of the structure of the cross section parallel to the rolling direction, the average crystal grain size is 30 μm or less in terms of equivalent circle diameter.

  In one embodiment of the copper alloy according to the present invention, in the observation of the structure of the cross section parallel to the rolling direction, the average crystal grain size in the direction parallel to the rolling direction (T) with respect to the average crystal grain size (T) in the direction perpendicular to the rolling direction. L) (L / T) is 1 to 4.

  In another embodiment of the copper alloy according to the present invention, the spring limit value is 600 to 1000 MPa.

  In still another embodiment of the copper alloy according to the present invention, the spring limit value is 300 to 600 MPa.

  In still another embodiment of the copper alloy according to the present invention, the third element group is selected from the group consisting of Mn, Fe, Mg, Co, Ni, Cr, V, Nb, Mo, Zr, Si, B, and P. 1 type or 2 types or more to be contained in a total of 0 to 0.5% by mass.

  In another aspect, the present invention is a copper drawn product made of the above copper alloy.

  In another aspect of the present invention, an electronic component comprising the above copper alloy.

  In another aspect of the present invention, there is provided a connector including the copper alloy.

In yet another aspect of the present invention, Ti is contained in an amount of 2.0 to 4.0% by mass, and optional third element group includes Mn, Fe, Mg, Co, Ni, Cr, V, Nb, Mo, One to two or more selected from the group consisting of Zr, Si, B and P is contained in a total of 0 to 0.5% by mass, with respect to a copper alloy material consisting of the remaining copper and inevitable impurities, 730 to At 880 ° C., a solution treatment is performed in which the solid solubility limit of Ti is heated to a temperature equal to or greater than the addition amount,
Following the solution treatment, an aging treatment is performed by heating at a material temperature of 400 to 500 ° C. for 0.1 to 20 hours,
It is a manufacturing method of the copper alloy for electronic components which performs the final cold rolling of 0-40% of reduction rate following an aging treatment.

  In one embodiment, the method for producing a copper alloy according to the present invention includes a material temperature of 100 ° C. or higher and lower than 350 ° C., and a material temperature of 350 ° C. or higher and lower than 550 ° C., following the final cold rolling. It includes performing strain relief annealing by heating at 0.0001 hours to 20 hours or at a material temperature of 550 ° C. to 700 ° C. for 0.0001 hours to 0.003 hours.

  In another embodiment, the method for producing a copper alloy according to the present invention includes performing strain relief annealing by heating at a material temperature of 200 ° C. or more and less than 400 ° C. for 0.001 to 20 hours following the final cold rolling. .

  According to the present invention, titanium copper excellent in strength and bending workability can be obtained.

<Ti content>
If Ti is less than 2.0% by mass, a sufficient strengthening mechanism cannot be obtained due to the formation of the original modulation structure of titanium copper, so that sufficient strength cannot be obtained. Conversely, if Ti exceeds 4.0% by mass, coarse TiCu ₃ tends to precipitate, and the strength and bending workability tend to deteriorate. Therefore, the content of Ti in the copper alloy according to the present invention is 2.0 to 4.0 mass%, preferably 2.7 to 3.5 mass%. Thus, by optimizing the Ti content, both strength and bending workability suitable for electronic components can be realized.

<Third element>
When the predetermined third element is added to titanium copper, there is an effect of easily refining crystal grains and improving the strength even when solution treatment is performed at a high temperature at which Ti is sufficiently dissolved. In addition, the predetermined third element promotes the formation of the modulation structure. Furthermore, there is an effect of suppressing rapid coarsening of the Ti—Cu-based stable phase. Therefore, the original age hardening ability of titanium copper can be obtained.

  In titanium copper, Fe has the highest effect. And in Mn, Mg, Co, Ni, Si, Cr, V, Nb, Mo, Zr, B, and P, the effect according to Fe can be expected, and even if added alone, the effect is seen, but two or more Multiple additions may be made.

  When these elements are contained in an amount of 0.05% by mass or more in total, the effect appears, but when the total exceeds 0.5% by mass, the balance between strength and bending workability tends to deteriorate. Accordingly, the total of one or more selected from the group consisting of Mn, Fe, Mg, Co, Ni, Cr, V, Nb, Mo, Zr, Si, B, and P as the third element group is 0 to 0 in total. It can contain 0.5 mass%, and it is preferable to contain 0.05-0.5 mass% in total.

<Crystal grain size>
In order to improve the strength and bending workability of titanium copper, the smaller the crystal grains, the better. Therefore, the preferable average crystal grain size is 30 μm or less, more preferably 20 μm or less, and still more preferably 10 μm or less. The lower limit is not particularly limited, but it is difficult to discriminate the crystal grain size. Therefore, such a situation is set to less than 1 μm (<1 μm), and such a small grain size is also included in the scope of the present invention. However, if the stress relaxation characteristic is required, it is preferably 1 μm or more since the stress relaxation characteristic is deteriorated if it becomes extremely small. In the present invention, the average crystal grain size is represented by the equivalent circle diameter in the structure observation of the cross section parallel to the rolling direction by observation with an optical microscope or electron microscope.

  In general, the crystal grains have an elliptical shape that extends in the rolling direction according to the rolling reduction in the final cold rolling, but in order to improve the bending workability, it is as close to a perfect circle as possible and anisotropic to the crystal grain shape. It is desirable not to have sex. In the present invention, since the reduction ratio in cold rolling can be reduced, crystal grains with less stretching in the rolling direction can be obtained. However, if the rolling reduction of the final cold rolling is made too low in an attempt to bring the crystal grain shape closer to a perfect circle, the strength becomes insufficient. Therefore, in one embodiment of the titanium copper according to the present invention, in the observation of the structure of the cross section parallel to the rolling direction by an electron microscope, the direction of the direction parallel to the rolling direction with respect to the average grain size (T) in the direction perpendicular to the rolling direction. The ratio (L / T) of average crystal grain size (L) (hereinafter referred to as “crystal grain aspect ratio”) is 1 to 4, preferably 1.5 to 3.5, more preferably 2 to 2. 3.

<Half width>
In the present invention, the half width of the X-ray line intensity peak of the {220} crystal plane on the rolled surface is used as an index of dislocation density. This is for the above reason. In the titanium copper according to the present invention, β {220}, which is the half width of the X-ray diffraction intensity peak from the {220} crystal plane of the rolled surface, is X-ray from the {220} crystal plane of the pure copper standard powder. Β ₀ {220} which is the half width of the diffraction intensity peak and the following formula:
3.0 ≦ β {220} / β ₀ {220} ≦ 6.0
Meet. β {220} and β ₀ {220} are measured under the same measurement conditions. The pure copper standard powder is defined as a copper powder having a purity of 99.5% with a 325 mesh (JIS Z8801).

β {220} / β ₀ {220} decreases as the dislocation density decreases, and conversely increases as the dislocation density increases. When β {220} / β ₀ {220} is decreased, the bending workability is improved but the strength is decreased. Conversely, when β {220} / β ₀ {220} is increased, the strength is improved but the bending workability is lowered. In order to achieve both strength and bending workability, it is necessary that 3.0 ≦ β {220} / β ₀ {220} ≦ 6.0, and 3.5 ≦ β {220} / β ₀ { It is preferable that 220} ≦ 5.0. As in the prior art, in the manufacturing method performed in the order of cold rolling → aging treatment after the final solution treatment, in order to make β {220} / β ₀ {220} about 3.0, Although it was necessary to perform rolling, in the manufacturing method of the present invention, it can be achieved at a reduction rate of about 10%. Therefore, the crystal grain aspect ratio can be reduced while increasing the dislocation density (strength), that is, the bending workability can be maintained.

<Spring limit value>
In the copper alloy according to the present invention, the spring limit value can be adjusted depending on whether or not the strain relief annealing is performed in the final process, as will be described later. Therefore, the spring limit value required while maintaining the above-described half width and crystal grain conditions can be created. For example, the copper alloy according to the present invention may have a spring limit value of 300 to 1000 MPa in one embodiment, and 600 to 1000 MPa, preferably 800 to 1000 MPa in an embodiment having a high spring limit value. In an embodiment having a low spring limit value, the pressure can be 300 to 600 MPa, and preferably 400 to 600 MPa.

<Application>
The copper alloy according to the present invention can be provided as various copper products, such as plates, strips, tubes, bars and wires. The titanium copper according to the present invention is not limited, but can be suitably used as a material for electronic components such as switches, connectors, jacks, terminals, and relays.

<Production method>
Titanium copper according to the present invention can be produced by carrying out appropriate heat treatment and cold rolling, particularly in the final solution treatment and the subsequent steps. Below, a suitable manufacture example is demonstrated one by one for every process.

1) Ingot production Ingot production by melting and casting is basically performed in a vacuum or in an inert gas atmosphere. If the additive element remains undissolved during melting, it does not effectively act on strength improvement. Therefore, in order to eliminate undissolved residue, it is necessary to add a high melting point third element such as Fe or Cr, and after sufficiently stirring, hold for a certain period of time. On the other hand, since Ti is relatively easily dissolved in Cu, it may be added after the third element is dissolved. Therefore, Cu includes one or more selected from the group consisting of Mn, Fe, Mg, Co, Ni, Cr, V, Nb, Mo, Zr, Si, B, and P in total from 0 to 0.0. It is desirable to add so as to contain 50% by mass, and then add Ti so as to contain 2.0 to 4.0% by mass to produce an ingot.

2) Homogenization annealing and hot rolling Solidification segregation and crystallized material generated during ingot production are coarse, so it is desirable to make it as small as possible by dissolving it in the parent phase as much as possible by homogenization annealing. This is because it is effective in preventing bending cracks.
Specifically, after the ingot manufacturing process, it is preferable to perform hot rolling after heating to 900 to 970 ° C. and performing homogenization annealing for 3 to 24 hours. In order to prevent liquid metal embrittlement, it is preferable that the temperature is 960 ° C. or lower before and during hot rolling, and that the pass from the original thickness to 90% of the total rolling reduction is 900 ° C. or higher. And in order to raise | generate moderate recrystallization for every pass and to reduce the segregation of Ti effectively, it is good to implement the amount of rolling reduction for every pass at 10-20 mm.

3) First solution treatment It is then preferable to perform the solution treatment after appropriately repeating cold rolling and annealing. The reason why the solution treatment is performed in advance is to reduce the burden in the final solution treatment. That is, in the final solution treatment, it is not a heat treatment for dissolving the second phase particles, but is already in solution, so it is only necessary to cause recrystallization while maintaining that state. Just heat treatment. Specifically, the first solution treatment may be performed at a heating temperature of 850 to 900 ° C. for 2 to 10 minutes. In this case, it is preferable to increase the heating rate and the cooling rate as much as possible so that the second phase particles do not precipitate. Note that the first solution treatment may not be performed.

4) Intermediate rolling As the rolling reduction in the intermediate rolling before the final solution treatment is increased, the recrystallized grains in the final solution treatment can be controlled more uniformly and finely. Therefore, the rolling reduction of the intermediate rolling is preferably 70 to 99%. The rolling reduction is defined by {((thickness before rolling−thickness after rolling) / thickness before rolling) × 100%}.

5) Final solution treatment In the final solution treatment, it is desirable to completely dissolve the precipitates, but if heated to a high temperature until it completely disappears, the crystal grains tend to coarsen, so the heating temperature is the second phase. The temperature is around the solid solubility limit of the particle composition (the temperature at which the solid solubility limit of Ti becomes equal to the addition amount in the range where the addition amount of Ti is 2.0 to 4.0% by mass is about 730 to 840 ° C, For example, when the addition amount of Ti is 3.0 mass%, it is about 800 ° C.). And if it heats rapidly to this temperature and a cooling rate is also made fast, generation | occurrence | production of coarse 2nd phase particle | grains will be suppressed. Therefore, typically, heating is performed at a temperature at which the solid solubility limit of Ti at 730 to 880 ° C. is the same as the addition amount, and more typically, the solid solubility limit of Ti at 730 to 880 ° C. is the same as the addition amount. It is heated to a temperature that is 0 to 20 ° C. higher, preferably 0 to 10 ° C. higher than the temperature at which it becomes.

  Moreover, the coarsening of a crystal grain can be suppressed when the heating time in the final solution treatment is shorter. The heating time can be, for example, 30 to 90 seconds, and typically 30 to 60 seconds. Even if the second phase particles are generated at this point, if they are finely and uniformly dispersed, they are almost harmless to strength and bending workability. However, since coarse particles tend to grow further in the final aging treatment, the number of second-phase particles at this point must be reduced as much as possible.

6) Aging treatment An aging treatment is performed following the final solution treatment. Conventionally, cold rolling is usually performed after the final solution treatment, but in order to obtain titanium copper according to the present invention, aging is immediately performed without performing cold rolling after the final solution treatment. It is important to do the processing. This is because the dislocation density can be increased even with the same rolling reduction as compared with the case where cold rolling is performed before the aging treatment. Although it is not intended that the present invention be limited by theory, it is believed that there is a correlation between the crystallinity within the crystal grains and the occurrence of shear bands. In general, when rolling is performed, dislocations are introduced, so that crystals are distorted and a half width is increased. When the half width is small, the crystallinity is high, and when the half width is large, the crystallinity is low. When an aging treatment is performed in a state of high crystallinity and bending is performed, a shear band is likely to develop, which tends to cause bending cracking. When aging is performed after solution treatment, the precipitation reaction proceeds uniformly in the crystal grains, and the modulated structure and fine second-phase particles tend to develop uniformly. When cold rolling is performed after controlling to such a structure by aging, the crystals are more likely to be distorted and the shear band is less likely to develop than when not aging. However, when the degree of work increases, the dislocation density increases excessively and the bending workability is impaired. Therefore, even if the degree of processing is low, high strength can be obtained while suppressing the development of the shear band. Since the aging treatment is carried out after the solution treatment, there is little distortion as a driving force for precipitation, so it is better to carry out the aging treatment at a slightly higher temperature than the conventional aging conditions. Specifically, it is preferable to heat at a material temperature of 400 to 500 ° C. for 0.1 to 20 hours, and it is more preferable to heat at a material temperature of 400 to 480 ° C. for 1 to 16 hours.

7) Final cold rolling After the aging treatment, final cold rolling is performed. The strength of titanium copper can be increased by the final cold working. This cold rolling need not be carried out, but in order to obtain high strength, the rolling reduction is set to 5% or more, preferably 10% or more, more preferably 15% or more. However, if the rolling reduction is too high, the crystal grain aspect ratio becomes too large and the effect of improving the bending workability is reduced. Therefore, the rolling reduction is set to 40% or less, preferably 30% or less, more preferably 25% or less. .

8) Strain relief annealing Different shape processing is required depending on the structure of the electronic component. In general, a portion subjected to plastic deformation such as bending or notching is work-hardened, and the strength of the material is further increased. In such a structure in which the contact pressure is ensured at the bent portion, plastic deformation is difficult, and thus a high spring limit value is unnecessary. Therefore, it is not necessary to perform strain relief annealing in such applications.
On the other hand, a structure that guarantees contact pressure at a site that is not subjected to plastic deformation during shape processing after press punching (eg, a structure in which the distance between the contact part of the terminal and the bent part (arm) is long, or a fork-type terminal In such a structure in which notching or bending is not performed and the bending stress is applied to the arm), a high spring limit value is important because resistance to bending deflection is required.
Therefore, in applications where the spring limit value is particularly important, strain relief annealing is performed after the final cold rolling. In particular, when the rolling reduction of the final cold rolling is 3% or more, it is preferable to perform strain relief annealing in applications where the spring limit value is important. Further, when the rolling reduction of the final cold rolling is 10% or more, it is particularly preferable to perform strain relief annealing in applications where the spring limit value is important. The conditions for strain relief annealing may be conventional conditions, but dislocations introduced by cold rolling are unevenly distributed. By performing strain relief annealing, the dislocations are rearranged, whereby the strength can be further increased. However, excessive strain relief annealing is not preferable because dislocations disappear and strength decreases. Therefore, for example, the material temperature is 100 ° C. or more and less than 350 ° C., 0.001 hour or more and 40 hours or less, the material temperature is 350 ° C. or more and less than 550 ° C., 0.0001 hour or more and 20 hours or less, or the material temperature is 550 ° C. or more and 700 ° C. or less. Heating may be performed for 0.0001 hours or more and 0.003 hours or less, preferably at a material temperature of 200 ° C. or more and less than 400 ° C. for 0.001 to 20 hours, and 0 at a material temperature of 350 ° C. or more and less than 550 ° C. It is more preferable to perform the heating under the condition of 0.001 to 0.5 hours. If the temperature is low, the heating is performed for a long time (for example, heating at a material temperature of 200 to 300 ° C. for 10 to 20 hours). It is more preferable to carry out under the condition of heating at ˜700 ° C. or less for 0.001 to 0.003 hours.

  A person skilled in the art will understand that steps such as grinding, polishing, and shot blast pickling for removing oxide scale on the surface can be appropriately performed between the above steps.

  Examples of the present invention will be described below together with comparative examples, but these examples are provided for better understanding of the present invention and its advantages, and are not intended to limit the invention.

  When manufacturing the copper alloy of the present invention example, Ti, which is an active metal, is added as the second component, so a vacuum melting furnace was used for melting. In addition, in order to prevent unexpected side effects due to mixing of impurity elements other than the elements defined in the present invention, raw materials having a relatively high purity were carefully selected and used.

  First, after adding Mn, Fe, Mg, Co, Ni, Cr, V, Nb, Mo, Zr, Si, B and P to Cu in the compositions shown in Table 1, Ti having the composition shown in the same table was added. Each was added. After sufficient consideration was given to the retention time after the addition so that there was no undissolved residue of the added elements, these were injected into the mold in an Ar atmosphere to produce about 2 kg of ingots.

  After the homogenization annealing which heats at 950 degreeC with respect to the said ingot for 3 hours, it hot-rolled at 900-950 degreeC, and obtained the hot-rolled sheet of 10 mm in thickness. After descaling by chamfering, cold rolling was performed to obtain a strip thickness (2.0 mm), and a primary solution treatment was performed on the strip. The conditions for the primary solution treatment were heating at 850 ° C. for 10 minutes. In some examples, the first solution treatment was not performed. Next, in the intermediate cold rolling, the intermediate plate thickness is adjusted so that the final plate thickness is 0.10 mm, cold rolling is performed, and then inserted into an annealing furnace capable of rapid heating to perform the final solution treatment. And then water cooled. The heating conditions at this time are the temperatures at which the solid solubility limit of the material temperature is the same as the added amount (about 800 ° C. at a Ti concentration of 3.0% by mass, about 730 ° C. at a Ti concentration of 2.0% by mass, Ti concentration of 4 Each sample was held for 1 minute under the heating conditions shown in Table 2 on the basis of 0.0 mass% and about 840 ° C.). Next, an aging treatment was performed under the conditions described in Table 2 in an Ar atmosphere. After descaling by pickling, cold rolling was performed under the conditions described in Table 2, and finally, annealing was performed under the respective heating conditions described in Table 2 to obtain test pieces of invention examples and comparative examples. Depending on the test piece, the aging treatment immediately after the solution treatment was omitted.

About each obtained test piece, characteristic evaluation was performed on the following conditions. The results are shown in Table 3.
<Strength>
A JIS No. 13B specimen was prepared using a press so that the tensile direction was parallel to the rolling direction. The specimen was subjected to a tensile test according to JIS-Z2241, and the 0.2% proof stress (YS) in the rolling parallel direction was measured.
<Bending workability>
A: W bending In accordance with JIS H 3130, when a W-bending test of Badway (bending axis is the same direction as the rolling direction) is performed with a mold having a bending radius that is twice the plate thickness, The case where cracking occurred was marked as x.
B: 180 ° bending The test piece is pressed against a corner of a block having a predetermined corner radius (R) to bend 90 °, and a thickness (2R) that is twice the corner radius inside the 90 ° bent portion. The plate is folded 180 ° along the end face of the plate (corner radius R). The value (R / t) obtained by dividing the minimum bending radius (R) that does not cause cracks on the outer bending surface after 180 ° bending by the plate thickness (t) was used as an index of bending workability.
The corner radius was changed by 0.01 mm.
<Conductivity>
In accordance with JIS H 0505, the conductivity (EC:% IACS) was measured by a four-terminal method.
<Average crystal grain size>
The average crystal grain size is measured by cutting a cross section parallel to the rolling direction with FIB, exposing the cross section, observing the cross section with SIM, and counting the number of crystal grains per unit area. The average equivalent circle diameter was obtained. Specifically, a frame of 100 μm × 100 μm was created, and the number of crystal grains present in this frame was counted. Note that all the crystal grains crossing the frame were counted as ½. The average value of the area per crystal grain is obtained by dividing the frame area of 10,000 μm ² by the total. Since the diameter of the perfect circle having the area is the equivalent circle diameter, this was defined as the average crystal grain size.
<Crystal grain size aspect ratio>
The structure of the cross section parallel to the rolling direction was revealed by electropolishing, and then an observation field of view 100 μm × 100 μm was photographed with an electron microscope (Philips XL30 SFEG). Based on JISH0501, the average crystal grain size in the direction perpendicular to the rolling direction and the average crystal grain size in the direction parallel to the rolling direction were determined by a cutting method, and the aspect ratio was calculated.
<Half width>
For each test piece, a diffraction intensity curve of the rolled surface was obtained under the following measurement conditions using an X-ray diffractometer manufactured by Rigaku Electric Co., Ltd. model Ultima 2000, and the half value of the X-ray line intensity peak of the {220} crystal plane was obtained. The width β {220} was measured. Under the same measurement conditions, the half-value width β ₀ {220} was also obtained for the pure copper powder standard sample. In the copper powder standard sample, the peak of the {220} plane appeared at 2θ around 74 °.
・ Target: Cu tube ・ Tube voltage: 40 kV
・ Tube current: 40 mA
・ Scanning speed: 5 ° / min
・ Sampling width: 0.02 °
Measurement range (2θ): 60 ° -80 °
<Spring limit value (Kb)>
As for the spring limit value (Kb), a repetitive deflection test was carried out in accordance with JIS H3130 (alloy number C1990), and the surface maximum stress was measured from the bending moment in which permanent strain remained.

<Discussion>
Invention Example No. 1 to 25 show that the strength and bending workability are improved in a well-balanced manner. Inventive Examples 13 to 26 are modified examples in which the manufacturing process is changed. In Invention Example 13, the second solution treatment temperature was set higher, and an upper limit average crystal grain size was obtained. Inventive Example 14 has a low rolling reduction in the final cold rolling, so β is the lower limit of the claims and the aspect ratio is also low, but it is within the specified range of the present invention, so strength and bending workability are well balanced. It has improved. Invention Example 15 is Invention Example No. This is the result of setting the aging treatment temperature to the lower limit as compared to 4. Invention Example 16 is Invention Example No. This is the result of setting the aging treatment temperature to the upper limit compared to 4. Invention Examples 17 and 18 are Invention Examples No. 2 and Invention Example No. This is an example in which the strain relief annealing in step 4 is omitted, and even when the strain relief annealing is omitted, the value of β is within the range defined by the present invention, and it can be seen that the strength and bending workability are improved in a well-balanced manner. In contrast to Inventive Examples 17 and 18, in Inventive Examples 19, 20, and 21, the strength and Kb value increased by performing strain relief annealing. Invention Examples 22 to 25 are examples in which the first solution treatment was omitted. 24 and 25 are examples in which the strain relief annealing was not performed, but the first solution treatment was omitted, and the value of β was within the specified range of the present invention even without the strain relief annealing. It can be seen that the strength and bending workability are improved in a well-balanced manner. Invention Example 26 is an example in which the strain relief annealing is performed at a low temperature in a short time.
On the other hand, Comparative Example No. In Nos. 1 to 3, since the cold rolling is not performed after the solution treatment, the half width is small, and the balance between strength and bending workability is inferior to that of the inventive examples. Comparative Example No. In Nos. 4 to 5, the aging treatment was performed after the solution treatment. In No. 4, the reduction ratio in cold rolling was high and the half width was too large, so the balance between strength and bending workability was inferior to that of the inventive examples. Comparative Example No. In No. 5, the crystal grain size was increased because the heating temperature in the solution treatment was too high. Since the final cold rolling reduction was high, relatively high strength was obtained, but bending workability was poor. Comparative Example No. In 6, 7, 9 and 10, since the solution temperature was too high, the crystal grain size exceeded the upper limit, and the bending workability deteriorated. Further, in Comparative Examples 7 and 8, since the cold rolling was performed without performing the aging treatment after the solution treatment, the half width was small, and the balance between strength and bending workability was poor. Comparative Example No. In No. 11, since strain relief annealing was performed at high temperature, recrystallization began, the dislocation density decreased, β decreased, and re-solution began, so the strength and conductivity decreased.

Claims (11)

It is a copper alloy for electronic parts containing 2.0 to 4.0% by mass of Ti, consisting of the remaining copper and inevitable impurities,
Β {220}, which is the half width of the X-ray diffraction intensity peak from the {220} crystal plane of the rolled surface, is β, which is the half width of the X-ray diffraction intensity peak from the {220} crystal plane of the pure copper standard powder. ₀ {220} and the following formula:
3.0 ≦ β {220} / β ₀ {220} ≦ 6.0
And
A copper alloy having an average crystal grain size represented by an equivalent circle diameter of 30 μm or less in a structure observation of a cross section parallel to the rolling direction.   In the structure observation of the cross section parallel to the rolling direction, the ratio (L / T) of the average crystal grain size (L) in the direction parallel to the rolling direction to the average crystal grain size (T) in the direction perpendicular to the rolling direction is 1 to 1. The copper alloy according to claim 1, which is 4.   The copper alloy according to claim 1 or 2, wherein the spring limit value is 600 to 1000 MPa.   The copper alloy according to claim 1 or 2, wherein the spring limit value is 300 to 600 MPa.   As the third element group, one or more selected from the group consisting of Mn, Fe, Mg, Co, Ni, Cr, V, Nb, Mo, Zr, Si, B, and P are added in a total amount of 0 to 0.0. The copper alloy as described in any one of Claims 1-4 containing 5 mass%.   A copper product comprising the copper alloy according to any one of claims 1 to 5.   The electronic component provided with the copper alloy as described in any one of Claims 1-5.   The connector provided with the copper alloy as described in any one of Claims 1-5. A group comprising 2.0 to 4.0% by mass of Ti, and an optional third element group consisting of Mn, Fe, Mg, Co, Ni, Cr, V, Nb, Mo, Zr, Si, B and P The total solid content of Ti is added at 730 to 880 ° C. with respect to the copper alloy material containing 0 to 0.5% by mass in total of 1 type or 2 types selected from Perform solution treatment to heat above the temperature that is the same as the amount,
Following the solution treatment, an aging treatment is performed by heating at a material temperature of 400 to 500 ° C. for 0.1 to 20 hours,
The manufacturing method of the copper alloy for electronic components which performs the final cold rolling of 0-40% of reduction rate following an aging treatment.   Subsequent to the final cold rolling, the material temperature is 100 ° C. or higher and lower than 350 ° C. and is 0.001 hour or longer and 40 hours or shorter, the material temperature 350 ° C. or higher and lower than 550 ° C. is 0.0001 hour or longer and 20 hours or shorter, or the material temperature 550 ° C. or higher. The manufacturing method of the copper alloy for electronic components of Claim 9 including performing the strain relief annealing which heats 0.0001 hours or more and 0.003 hours or less at 700 degrees C or less.   The manufacturing method of the copper alloy for electronic components of Claim 9 including performing the stress relief annealing which heats 0.001 to 20 hours at material temperature 200 degreeC or more and less than 400 degreeC following final cold rolling.