TW201122121A - Titanium-copper for electronic component - Google Patents

Abstract

Provided is titanium-copper which has excellent strength and bendability. The titanium-copper is a copper alloy for electronic components which contains 2.0-4.0 mass% Ti, the remainder comprising copper and incidental impurities. The intensity peak of X-ray diffraction from the {220} crystal plane in a rolled surface of the copper alloy has a half-value width ss{220} which satisfies the relationship 3.0=ss{220}/ss0{220}=6.0, wherein ss0{220} is the half-value width of the intensity peak of X-ray diffraction from the {220} 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-grain diameter of 30 [μ]m or smaller in terms of equivalent-circle diameter.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a titanium copper suitable for use as an electronic component such as a connector and a method of manufacturing the same. [Prior Art] In recent years, the miniaturization of electronic devices such as mobile terminals has been progressing steadily. Therefore, the narrow pitch and low profile of the connectors used therein are remarkable. The smaller the connector, the more the width of the pin is. In order to become a smaller folded shape, the member to be used is required to have higher strength to obtain the necessary elasticity and to withstand the harshness of the koji processing. - Curved workability. In this respect, since the strength of the copper alloy containing titanium (hereinafter referred to as "titanium copper") is relatively high, and the stress relaxation property is most advocated in the copper alloy, the horse is different and has been used as a special The signal for the strength is required for the terminal member. Chin copper is an ageing hardening type copper alloy. If a supersaturated solid solution of Ti as a dissolved f atom is formed by solution treatment and heat treatment is performed for a long time from this state at a low temperature, the mother phase is caused by the phase decomposing (sp de-decomposition). Modulation structure (m〇duiated

StrUCtUre) (ie, the periodic variation of Tl 丨 农 农) expands and the strength increases. At this time, the problem lies in the fact that the strength is opposite to the workability of the flex. In other words, if the strength is increased, the bending workability is impaired. Conversely, if the workability is emphasized, the desired strength cannot be obtained. In general, the more the cold rolling reduction ratio (WHng redueti()n) is increased, the more the amount of dissi〇cati〇n is introduced and the higher the density is, so it helps. The position of the nucleation 201122121 will increase, which will increase the strength after aging treatment. However, if the rolling reduction rate is too high, the bending will increase. Therefore, it has become a problem to achieve both strength and bending workability. Therefore, there has been proposed a technique of combining the strength and bending workability of titanium copper from the viewpoint of adding a third element such as Fe, c〇, Ni, or Si (Patent Document 1); and limiting it to solid solution in the matrix phase. The concentration of the impurity element group is such that the second phase particles (Cu-Ti-X-based particles) are precipitated in a specific distribution form to improve the regularity of the modulation structure (Patent Document 2); The density of the trace addition element and the second phase particle (Patent Document 3) and the refinement of the crystal grain (Patent Document 4). In the case of titanium copper, titanium copper is also proposed which has a poor integration of the phase (TiCh) and a better integrated stone 'phase (TiCiu)' with respect to the α phase as the parent phase and Since the point phase has an adverse effect on the bending workability, the other side of the m-thickness and fine dispersion contributes to both strength and bending workability, so the titanium-copper system suppresses " The founder (Patent Document 5). The following techniques have also been proposed: focusing on the crystal orientation and controlling the crystal alignment to satisfy 1{420}/1. {420}:> 1〇 and 1{22〇}/1. {22〇}$3 〇, thereby improving strength, bending workability, and financial stress mitigation (Patent Document 6). [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2008- 308. Various methods have been studied for strength and spine processing, but there is still room for improvement. Therefore, one of the problems of the present invention is to provide an improvement in the properties of titanium and copper from the viewpoint of the difference from the prior art, and to provide a titanium copper having excellent strength and bending workability. Another object of the present invention is to provide a method of producing such a titanium copper. The previous method for producing titanium copper was basically composed of ingot casting, homogenization annealing, hot rolling, (repetitive annealing and cold rolling), final solution treatment, cold rolling, and aging treatment. The titanium copper described in the prior art is also manufactured in the same order. In the course of research by the present inventors to solve the above problems, it has been found that if the final solution treatment is performed after the final solution treatment, the order of the cold treatment is reversed, that is, after replacing the aging treatment with the cold rolling sequence, the last 2 Performing strain relief annealing under appropriate conditions, the bending processability is remarkably improved: that is, the titanium copper produced in the previous order is compared with the titanium copper of the present invention: when the strength is the same, the copper of the present invention The processability of f-curve is better:::::: In order to investigate the cause, the characteristics of the titanium of the present invention and the form of the crystal grain were investigated. Compared with the order of aging treatment, when it is set to ... and ° is cold-rolled again - the difference in the density of the obtained copper is higher than the order of the difference in the order of the difference between the two: : Reducing the same can suppress the cold milk, the right grain shrinkage rate of the crystal grain in the rolling direction is small, then the universal extension, thus improving the bending plus 201122121 workability. The difference in density is difficult to measure directly. The reason for this is that the distribution of the difference rows becomes uneven due to the modulation structure or the distribution of the precipitated particles. In the case of the inter-ground test, it is related to the half-height of the peak value of the 乂-ray diffraction intensity of the {220} crystal plane in the calendering surface. The full width at half maximum (i.e., the width of the diffraction intensity curve in the intensity of the peak intensity of the diffraction intensity curve i / 2 is expressed as 20 0. The half-height width increases with the difference in the density of the cold rolling. Therefore, in the present invention, the state of the difference density is indirectly defined by the half width and the width. One aspect of the present invention completed based on the above findings is a copper alloy for electronic parts containing 2.0 to 4% by mass of Ti, and the remainder consisting of copper and unavoidable impurities; {220} crystallizing from the calendering surface The half-height-width stone {220} of the X-ray diffraction intensity peak of the surface and the half-height width of the X-ray diffraction intensity peak of the {22〇丨 crystal plane from the pure copper standard powder are called 0 {220}, and the following formula is satisfied: 3.0 S Calling {220}/ no 0{220} $6.0; and, when observing the structure of the section parallel to the rolling direction, the average crystal grain size is represented by an approximate circle diameter of 30 or less. In one embodiment of the copper alloy of the present invention, when the structure parallel to the cross-section of the rolling direction is observed, the average crystal grain size (L) parallel to the direction of the rolling direction and the average crystal grain size perpendicular to the direction of the rolling direction (D) The ratio (L / T) is 1 to 4. In another embodiment of the copper alloy of the present invention, the spring bending elastic limit is 600 to 1 MPa. 201122121 Its spring bending elasticity The limit of another embodiment of the copper alloy of the present invention is 3 0 0 ^ 6 〇 Μ Μ P a . In another embodiment, the copper alloy of the present invention contains Mn, Fe, Mg, Cq, %, a, v, which are selected from the group consisting of 〇~〇5 by mass% of the third element group.

Nb or Mo is one type or two or more types.

Another group of the invention consisting of Zr 'Si, B and P is a copper product (ei〇ngated (3) product^ product) composed of the above copper alloy. Still another aspect of the invention is an electronic component comprising the above copper alloy. Still another aspect of the invention is a connector comprising the above copper alloy. According to still another aspect of the present invention, there is provided a method for producing a copper alloy for an electronic component, which comprises the steps of: containing a second element containing 2.0 to 4% by mass of iT1 and containing 〇~〇5 mass% in total Group f Mn, Fe, Mg, c〇, guilt, v, ^^. , ~, ^^ (4) Any group of ^ or ^ above, and the remaining part of the copper alloy material consisting of copper and inevitable impurities, heating into the 730 ~ 880 ° C Ti solid solution limit becomes The solution treatment is performed at a temperature equal to or higher than the addition amount; after the solution treatment, the aging treatment is performed at a material temperature of 4 〇〇 5 5 ° &lt;&gt;c, and the aging treatment is performed for 1 to 20 hours; and after the aging treatment The final cold rolling is performed at a collapse rate of 〇~4〇%. In one embodiment, the method for producing a copper alloy according to the present invention comprises performing strain relief annealing after final cold rolling, and the strain relief annealing is performed at a material temperature of WOt or more and less than 35 (TC heating is more than hours, 4 hours) The following two 201122121 are heated at a material temperature of 350 ° C or higher, less than 550 t for 0.0001 hours or more, and 20 hours or less 'or a material temperature of 55 〇 ° C or more and 700. (: The following heating is 0.0001 hours or more and 0.003 hours or less. In another embodiment, the method for producing a copper alloy includes performing strain relief annealing after final cold rolling, and the strain relief annealing is performed at a material temperature of 200 ° C or higher and less than 400 ° C for 0.001 to 20 hours. Titanium copper having excellent strength and bending workability can be obtained. [Embodiment] &lt;Ti content&gt; When Ti is less than 2.0% by mass, the formation of the original δ-variation structure of titanium copper cannot be sufficiently obtained. When the mechanism is strengthened, sufficient strength cannot be obtained. When the amount is more than 4.0% by mass, the coarse TiCu3 tends to precipitate, and the strength and bending workability tend to deteriorate. The content of Ti in the copper alloy of the present invention is 2.0 to 4.0 mass%, preferably 2 7 to 3 5 mass%. By appropriately arranging the content of Ti, it is possible to simultaneously achieve suitable use for electronic parts. Strength and bending workability. <Third element> When a certain third element is added to titanium copper, the effect is as follows: that is, it is easy to finely dissolve the crystal grains at a high temperature in which Ti is sufficiently solid-solved. In addition, the third element promotes the formation of a modulation structure, and also has the effect of suppressing the sharpening and coarsening of the Ti-Cu-based stable phase. Therefore, the original aging of titanium copper can be obtained. Age-hardening P〇wer. In Yuqin Copper, the best effect is Fee as for Mn, Mg, CQ, 201122121

The effects of Nl, Sl, Cr, v, Nb, Mo, Zr, B*p, and h__F may be effective when added alone, or may be added in combination of two or more, and Fe contains (10) mass. When these elements are cut, it is found that when the total amount of the right side exceeds 0.5% by mass, there is a tendency that the strength of the strength and the bending workability deteriorate. Therefore, the total amount of 〇, Λ, 主, 主, 主, 主, 主, Ni, Ni, Ni, Ni, Ni, Ni, Ni, Ni, Ni, Ni, Ni, Ni, Ni, 。丨 〇 〇 〇 〇 〇 、 、 、 、 、 、 、 、 、 、 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 <Crystal Grain Size> In order to increase the strength and bending workability of titanium copper, the smaller the crystal grains, the better. Therefore, the preferred average crystal grain size is 3 Å, more preferably Π: and more preferably 1 〇 ^ or less. The lower limit is not particularly limited. - Since it is difficult to discriminate the crystal grain size, this case is set to be less than - (&lt;1 core), and such a smaller particle size is also included in the scope of the present invention. Lack: If the end is reduced, the stress relaxation property will be reduced, and it is necessary to have a better condition. In the present invention, the average crystallization &quot; X is expressed by the diameter of an approximate circle observed when observing the structure parallel to the section of the rolling direction by a microscope or an electron microscope. In general, the crystal grains exhibit an elliptical shape extending in the rolling direction corresponding to the final shrinkage ratio in the cold drying. However, in order to improve the bending workability, it is desirable to be as close as possible to a perfect circle and the shape of the crystal grains. There is no anisotropy. In the present invention, since the rolling reduction in cold rolling can be reduced, it is possible to obtain crystal grains having a small extension in the direction of the moon line. However, if the shape of the crystal grain is close to a perfect circle and the final cold rolling is too low, # will result in a strong 201122121. Therefore, in one embodiment of the titanium copper of the present invention, an electron microscope is used. When observing the structure of the cross section parallel to the rolling direction, the ratio (L/τ) of the average crystal grain size (6) parallel to the calendering direction and the direction perpendicular to the rolling direction (L/τ) (hereinafter referred to as The "crystal grain aspect ratio") is 1 to 4, preferably 丨.5 to 3.5, more preferably 2 to 3. &lt;Half-height width&gt; In the present invention, the half-height width of the peak of the diffraction intensity of the 结晶-ray of the crystal face is used as an index of the difference in the density of the discharge. This is based on the above reasons. The half-height-width cold {220} of the X-ray diffraction intensity peak of the {220丨 crystal plane from the calendered surface of titanium and copper, and the half-height of the peak diffraction intensity of the {220} crystal plane from the pure copper standard powder The wide point 〇{22〇) satisfies the following formula: 3. 〇石石{220}/ /5 〇{220}$ 6.0. /3 {220} and cold heading {220} were measured under the same measurement conditions. Pure copper The standard powder is defined by a copper powder of 325 mesh (JIS Ζ8801) with a purity of 99.5%. The cold {220} / /5 0{220} decreases as the difference in density is lowered, and conversely, as the difference in density increases. If the cold {220}/cold 0 {220} becomes smaller, the bending workability will increase, but the strength will decrease. Conversely, if 10,000 {2 2 0 J / /5 〇 {220} is increased, the strength is increased, but the bending workability is lowered. If you want to combine strength and bending workability, you must be 3.0$厶{220}/ 冷〇{220} $6.0, preferably 3.5S /3 {220}/"{220}蕊5.〇. In the conventional method of treating in the order of cold rolling-aging treatment after the final solution treatment, in order to make Θ {220}//5 〇{220} become about 3.0, the 201122121 must be subjected to a rolling reduction rate of nearly 50%. Cold rolling 'However, in the production method of the present invention, it can be achieved at a rolling reduction ratio of about 10 ◦ / 。. Therefore, the crystal grain size can be made smaller and smaller, that is, the bending process can be performed without increasing the difference in density (strength) &lt;Spring Bending Elastic Limit&gt; For the copper alloy of the present invention, the spring bending elastic limit can be adjusted by performing strain relief annealing in the final step as will be described later. Therefore, the above-described full width at half maximum or crystallization can be maintained. The condition of the grain is determined by the desired spring bending elastic limit. For example, the copper alloy of the present invention may have a spring bending elastic limit of 300 to 1000 MPa in one embodiment, and has a high spring bending elastic limit. In the form, it can be set to 6〇〇 1 〇〇〇 MPa ' is preferably set to 8 〇〇 to 1 〇〇〇 MPa, and in the embodiment having a lower elastic limit of elastic bending, it may be 300 to 6 MPa, preferably It can be set to 400 to 600 MPa. &lt;Use&gt; The copper alloy of the present invention can be used as various copper-exposed products such as plates, strips, tubes, rods, and wires. The titanium copper of the present invention is not limited and can be suitably used. Used as a material for electronic parts such as switches, relays, etc. &lt;Manufacturing &gt;

The steps sequentially describe suitable manufacturing examples. Solidification of connectors, jacks, terminals, and subsequent manufacturing. Following, each 1) ingot manufacturing

If it is in a vacuum or a non-melting residue of inert gas, 201122121 does not contribute to the improvement of strength. Therefore, in order to remove the infusible residue, it is necessary to sufficiently stir the third element having a high melting point such as Fe or Cr, and then hold it for a predetermined period of time. On the other hand, since Ti is relatively easily melted, it may be added after melting the third element. Therefore, it is preferable that the total amount of 0 to 〇.5 〇 mass% is selected from the group consisting of Mn, Fe, Mg, and

Ni, Cr, V, Nb, M〇, Zr, Si', or a mixture of two or more types added to the Cu towel, and then Ti is added to the Cu in a manner of containing 2 〇 to 4% by mass. To make a spin. 2) Homogenization annealing and hot rolling Because the solidification segregation or crystals generated during the production of the ingot are coarse, it is desirable to reduce the solidification in the matrix by homogenization annealing as much as possible. It is removed. The reason is: to prevent f breaks. Specifically, it is preferable to heat-anneal to 9 〇〇 to 97 〇 3 24 hours after the production step of the ingot, and then perform hot rolling. In order to prevent liquid metal brittleness, it is preferable to set X in the hot rolling and hot rolling, and the rolling reduction ratio from the initial thickness to the whole is 90 (TC or more), and η is regressive and effective. Τ·^ It is sufficient to produce moderate recrystallization in each pass. - The amount of rolling per pass is 10~20 3). After the first solution treatment, it is melted. In the melting treatment, it is preferred to carry out the cold rolling and the annealing in an appropriate manner, and then to perform the fixing in advance. That is, the final solution treatment is not used to make

S 12 201122121 The heat treatment of the solid solution of the two-phase particles is carried out, and since it has been solid-solved, it is only necessary to recrystallize while maintaining this state on one side, and thus a slight heat treatment may be performed. Specifically, in the first solution treatment, the heating temperature may be 850 to 90 CTC and may be carried out for 2 to 1 minute. It is preferable to accelerate the temperature increase rate and the cooling rate at this time as much as possible, and the second phase particles are not precipitated here. Further, the first solution treatment may not be performed. 4) Intermediate calendering The higher the rolling reduction ratio of the intermediate calendering t before the final solution treatment, the more the recrystallized grains in the final solution treatment can be controlled to be fine and fine. Therefore, the rolling reduction ratio of the intermediate calendering is preferably from 7 〇 to 99%. The rolling reduction ratio is defined by {((thickness before rolling - thickness after rolling) 厚度 thickness before rolling ^ 100%}. &quot; 5) Final solid solution treatment, the most 'final solid solution treatment, ideal If the precipitate is completely solidified, if the temperature is high until the total temperature is removed, the crystal grains are easily coarsened. Therefore, the heating temperature is set to a temperature near the solid solution limit of the second phase particle composition (the addition amount of Ti is 2). In the range of 〇~4 〇% by mass, the solid solution limit of Ti becomes the same as the addition amount of 73 〇~ please. C or so, for example, the addition of Τι is 3.0% by mass. Moreover, if the temperature is rapidly heated to the temperature and the cooling rate is also accelerated, the generation of the coarse second phase particles is inhibited by J. Therefore, the solid solution limit of Ti heated to 730 to 8801 is usually added and added. The same, the field; S: w μ s Λ . ~ 嗔 Τ 更 · More typically is heated to a solid solution limit of 730 π 1 to bend the same temperature as the addition of high ~ 2 〇 t and preferably Heat to a temperature of 0~1〇〇c. 13 201122121 The shorter the heating time in the final solution treatment, the more the coarsening of the particles can be suppressed. The heating time can be set, for example, to π sec., and the typical y = 30 to 60 sec. That is, it is easy to generate the second phase particles at this time point, and if it is to be finely and uniformly dispersed, the strength and the bending workability j are hardly impaired. However, since there is a tendency for the coarse person to grow further in the final aging treatment, even if the second phase particle is generated at this point: it is necessary to make it smaller and smaller as much as possible. 6) Aging treatment The aging treatment is carried out after the final solution treatment. Although the conventional example has been subjected to cold rolling after the final solution treatment, the point of obtaining the titanium copper of the present invention is that after the final solution treatment, the aging treatment is directly performed without performing cold rolling. The reason for this is that the difference in density can be improved even in the case of aging treatment: cold rolling. Although it is not intended to limit the invention according to the theory, it is considered to be related to the crystallinity in the crystal grains and the generation of shear bands. Generally, if calendering is carried out, the crystals will be strained due to the introduction of the difference row, and the full width at half maximum. If the half-height width is smaller, the crystallinity is higher. If the full width at half maximum is larger, the crystallinity is lower. If the crystallinity is high, the aging treatment is performed, and the bending process is performed. The cut tape is easy to expand and is likely to cause bending cracking. If the aging treatment is performed after solid solution, the precipitation reaction is uniformly performed in the crystal grains, and the modified structure or the fine second phase particles are easily spread uniformly. By controlling the microstructure to be cold-rolled by aging treatment, the crystallization is more susceptible to strain than in the case where the aging treatment is not performed, and the shear band is more difficult to expand. However, if the degree of processing is increased, the difference in density It will increase the 201122121 too much and damage the bending workability. Therefore, even for the lower processing degree, the expansion of the shear band can be made and the high strength can be obtained. Since the aging treatment is after the melting treatment Therefore, the strain that becomes the driving force for precipitation is less, so it can be carried out at a slightly higher temperature than the conventional aging condition. Specifically, it is preferably heated at a material temperature of 400 to 50 (0.1 to 2 hours under TC, more Preferably, the material temperature is 400 to 480. (: heating is performed for 1 to 16 hours. 7) The final cold rolling is performed after the above aging treatment, and the final cold rolling is performed. The final cold working can increase the strength of the titanium copper. The cold rolling is performed, but the higher strength is obtained, and the rolling reduction ratio is set to 5% or more, preferably more than 10,000% or more, more preferably 15% or more. However, if the rolling reduction ratio is too high, the crystallization is performed. The grain aspect ratio becomes too large and the effect of improving the f-curvature property is reduced. Therefore, the rolling reduction ratio is set to 4 G% or less, preferably 3 G% or less, more preferably 25% or less. 8) Strain annealing Corresponding to the structure of the electronic component, it is required to process different shapes. Usually, the portion where plastic deformation such as bending or notch processing is performed is hardened, and the strength of the material is further increased. Since the bending portion is used to secure the pressure The structure is not easy to plastic (four), so there is no need to compare The spring bends the elastic limit. Therefore, it is not necessary to perform strain relief annealing for such a use. On the other hand, the structure that is not plastically deformed when the shape after punching is processed is ensured (for example, the contact from the terminal) The structure from the part to the bending process = the straight part (arm) is long, or is not like a fork type terminal: a structure having a notch processing or a bending process, that is, a structure in which a bending stress is applied to the arm) There is a need for resistance to bending deformation, so the higher 15 201122121 spring bending elastic limit becomes important. Therefore, especially in applications where the spring b-flexile limit is important, strain relief annealing will be performed after the final cold rolling. In the case of the final cold rolling reduction ratio of 3% or more, it is preferable to perform strain relief annealing in an application in which the spring bending elastic limit is important. λ, in the case where the final cold-drying emulsion shrinkage rate is 10% or more, it is particularly preferable to perform strain relief annealing in an application in which the elastic bending limit of the magazine is important. The condition of the strain relief annealing may be a conventional condition, but the difference in the ranks of the people in the cold rolling may be unevenly distributed. # By performing strain relief annealing and rearranging the difference rows, it is possible to further increase the strength. However, if the strain relief annealing is excessively performed, the difference is eliminated and the strength is lowered && is not good. For example, it is heated at a material temperature of (10) t or more and not more than 3 50 C for 0.001 hour or more and I π*. J is less than 40 hours on the sputum, and the material temperature is less than 550 at 350 C or more. (: Heat O.OOOi hour J. Keep the sputum for less than 20 hours, and the material temperature is 550 〇C or more and 700 ° ((:: ～ below the η u L heating for 0.0001 hours or more 0_0 0 3 hours or less, compared佳佳在. The grazing is carried out under the condition of a material temperature of 200t or more and less than 400°C for 0.001~2〇 hours, more preferably for the material ^degree 350°C or more and less than 55CTC heating 0 0ηι Λ &quot; Ο Ο 〇〇 〇 〇 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 批 5 批 批 批 批 批The temperature is still short (for example, the material temperature is 550~70 (TC below force 0 Λ (pieces are carried out. Under heating 0.001~0.003 hours) and then 'if the field practitioners, ....^ ^ It should be understood that steps such as grinding, grinding, bead blasting, etc. of the scale of J, upper surface, and the surface of the surface may be appropriately performed between the above steps.

16 S 201122121 [Embodiment] The examples and comparative examples of the present invention are for the purpose of promoting an understanding of the present invention, and the advantages of the present invention are not intended to limit the invention. When the copper alloy of the present invention is used, since the active metal is added as the second component, a vacuum melting furnace is used in the dissolution to prevent the occurrence of unexpected side effects due to the addition of the impurity element other than the element specified in the present invention. The raw materials are strictly selected for use with higher purity. First, 'Mn, Fe, Mg, Co, Ni, Cr, V, Nb, Mo,

Zr Si, B and P were respectively added to cu in the compositions shown in Table 1, and Ti of the composition shown in the table was added. In order to avoid the insoluble residue of the added element, the retention time after the addition was also taken into consideration, and then the same was injected into the mold in the Ar environment, and an ingot of about 2 kg was separately produced. 17 201122121 [Table i] Table 1 · Adding elements (% by mass)

No. Ti Μ Fe Fe Mg Co Ni Cr V Nb Mo Zr Si BP 1 3.0 2 3.0 3 3.0 4 3.0 5 3.0 6 3.0 7 2.0 8 4.0 9 3.0 0.05 0.1 0.05 0.1 0.1 0.1 10 3.0 0.05 0.1 0.05 0.1 0.1 0.1 11 3.0 0.1 0.1 0.1 0.05 0.05 0.05 0.05 12 3.0 0.1 0.1 0.1 0.05 0.05 0.05 0.05 Inventive Example 13 3.0 14 3.0 15 3.0 16 3.0 17 3.0 18 3.0 19 3.0 20 3.0 21 3.0 22 3.0 23 3.0 24 3.0 25 3.0 26 3.0 1 3.0 2 3.0 3 3.0 4 3.0 to 5 3.0 to 6 3.0 Example 7 3.0 8 3.0 9 3.0 10 3.0 11 3.0 After the homogenization annealing of the above ingot at 950 ° C for 3 hours ,

S 18 201122121 was hot rolled at 900 to 950 ° C to obtain a plate having a plate thickness of a city. After the scale is removed by plane cutting, cold rolling is performed to form a strand *', a roll (2_0 mm), and a second solid solution treatment in a strip state. The first = the conditions of the solution treatment were set to be heated at 850 t for 1 minute. In the case of the flamingo, the i-th solid solution treatment is not carried out in some of the examples. Then, in the cold rolling of the middle door, the cold-rolling adjustment intermediate thickness is performed so that the final thickness becomes 0.10 mm, and then inserted into the rapidly heating annealing furnace to perform the final solid solution domain. After that, it is cooled with water. The heating condition of the material is such that the material temperature is the same as the solid solution limit of Ti and the addition amount (about 8 〇〇t when the Ti concentration is 3.0% by mass, and about % C when the Ti concentration is 2 〇% by mass). When the Ti concentration was 4 〇 mass %, about 84 (rc) was used as a standard, and the heating conditions described in Table 2 were maintained for i minutes, respectively, and then aging treatment was carried out under the conditions of Table 2 in the Ar environment. After the scale was removed by pickling, the cold rolling was carried out under the conditions shown in Table 2, and the test pieces of the inventive examples and the comparative examples were prepared by annealing under the heating conditions of 纟2 jin. The test piece omits the aging treatment immediately after the solution treatment. 19 201122121 [Table 2]

No. Solution treatment (1st time) Solution treatment (2nd time) Aging treatment Cold rolling aging treatment / strain relief annealing temperature time temperature time temperature time rolling reduction temperature time (°C) (8) (°C) (s CC) (h) (%) CC) (h) 1 850 600 800 60 400 6 10 400 0.005 2 850 600 800 60 450 6 15 400 0.005 3 850 600 800 60 480 6 20 400 0.005 4 850 600 800 60 450 6 25 400 0.005 5 850 600 800 60 450 6 30 400 0.005 6 850 600 820 60 450 6 15 400 0.005 7 850 600 730 60 450 15 400 0.005 8 850 600 840 60 450 6 15 400 0.005 9 850 600 820 60 450 6 15 400 0.001 10 850 600 820 60 450 6 15 200 20 11 850 600 820 60 450 6 15 400 0.001 12 850 600 820 60 450 6 15 200 20 hair 13 850 600 830 30 450 6 15 400 0.005 Ming 14 850 600 800 60 450 6 3 400 0.005 Example 15 850 600 800 60 400 10 25 400 0.005 16 850 600 800 60 500 3 25 400 0.005 17 850 600 800 60 450 6 15 No 18 850 600 800 60 450 6 25 No 19 850 600 800 60 450 6 25 150 40 20 850 600 800 60 450 6 25 200 20 21 850 600 800 60 450 6 25 600 0.0005 22 No 800 60 450 6 15 400 0.005 23 No 800 60 450 6 25 400 0.005 24 No 800 60 450 6 15 No 25 No No 800 60 450 6 25 No 26 850 600 800 60 450 6 25 200 0.0028 1 850 600 800 60 No 24 400 5 2 850 600 800 60 No 29 400 5 3 850 600 800 60 No 47 400 5 4 850 600 800 60 450 6 50 No incomparable 5 850 600 900 60 450 6 30 No No 6 No 900 60 450 6 30 No Case 7 No 900 60 No No 30 450 6 8 No 800 60 No No 30 400 5 9 No 900 60 450 6 30 400 0.005 10 850 600 900 60 450 6 30 400 0.005 11 850 600 800 60 450 6 25 750 0.001

S 20 201122121 Evaluation of characteristics of each of the obtained test pieces The results are shown in Table 3 using the following conditions. &lt;Strength&gt; A was used as the test piece of JIS13B so that the stretching direction 妫 and the direction of the stretching were parallel. Further, the pressurizing mechanism is used to test the test piece according to JIS-Z2241, and the calendering tester is measured.埯10仃 direction. 2% stamina (YS). &lt;Bending workability&gt; A : W bending According to JISH3130, the bending radius is twice as large as the plate thickness and

Apply BadWay (f crankshaft and rolling direction are in the same direction k (four) I. The case where no crack occurs is set to 〇, and the case where crack occurs is set to X. B: 180° bending the test piece against a specific fillet radius (The angle of the block of c〇rner (8) is 90. Bending, the plate having a thickness of 2 times (2R) of the fillet radius (corner radius R) is clamped to 90. The inner side of the bent portion is along the plate. The end face is folded 180. The value (R/t) obtained by dividing the minimum radius of curvature (R) of the outer curved surface of the bent surface after the bending process by the thickness (1) is set as an index of bending workability. The fillet radius is changed by 0.01 mm each time. &lt;Conductivity&gt; The conductivity (Ec: %IACS) is measured by a four-terminal method according to JIS Η 0505'. &lt;Average crystal grain size&gt; Measurement of average crystal grain size The section cut parallel to the rolling direction 21 201122121 by FIB, thereby exposing the cross section, observing the cross section by SIM, and calculating the number of crystal grains per unit area, and obtaining the average diameter of the approximate circle of the crystal grains. Specifically, it is a box of 100 y mx 100, and l'i is calculated. It is the number of crystal grains in the frame. · Again, for the crystal grains that traverse the frame, it is counted as 1/2. The area of the frame is 1 0000 M m2 divided by the total amount of crystal grains, which is The average value of the area of one crystal grain. Since the diameter of the perfect circle having this area is a diameter of an approximate circle, it is set as the average crystal grain size. &lt;crystal grain size aspect ratio&gt; Parallel by electrolytic grinding After the microstructure of the cross section in the rolling direction appeared, the observation field 100 zzmxioo was taken by an electron microscope (焱 焱 XL3 〇 SFEG manufactured by Philips). According to JISH 〇 5〇1, the average perpendicular to the direction of the rolling direction was obtained by the cutting method. The crystal grain size and the average crystal grain size parallel to the direction of the rolling direction were calculated, and the aspect ratio was calculated. <Half-height width> For each test piece, an X-ray winding such as a rib surface 2_ was used for each test piece. In the following apparatus, the diffraction intensity curve of the I-face is obtained under the following conditions and the half-height of the χ-ray diffraction intensity of the {22〇} crystal plane is measured. Under the same measurement conditions, the copper is also pure. Powder standard test FWHM determined heart} {22G. In standard steel powder sample, {220} plane of the peak lines are shown in the vicinity of 74. 20.

• Dry material: Cu tube • Tube voltage: 40 kV • Tube current: 40 mA

S 22 201122121 • Scanning speed: 5 ° / min • Sampling width: 0.02 ° • Measuring range (2 0 ) : 60° to 80° &lt;Spring bending elastic limit (Kb) &gt; Spring bending elastic limit (Kb) is based on JIS H 3130 (alloy No. C 1 990), a repeated bending test was carried out, and the maximum surface stress was measured from the bending moment of the residual permanent strain. 23 201122121

β {220} / β 〇{220} Crystalline i YS EC Bending workability Kb No Average crystal grain size ("m) Aspect ratio (L/T) (MPa) %IAC c R/t = 2 180. Bending (MPa o W Bend 1 3.1 7 1.8 880 16 〇0.7 814 2 3.6 15 2.1 935 14 〇1.5 878 3 3.9 15 2.4 965 16 〇2.2 898 4 4.3 15 2.7 1000 13 〇2.9 940 5 4.6 15 3.0 1030 13 〇2.9 958 6 3.5 25 2.1 930 13 〇1.5 860 7 3.2 16 2.1 880 16 〇1.4 825 8 5.5 12 2.1 1050 10 〇3.3 972 9 3.9 10 2.1 975 13 〇1.6 902 10 4.0 10 2.1 980 13 〇1.7 907 11 4.0 10 2.1 985 11 〇1.8 911 12 4.1 10 2.1 990 11 〇2.0 916 Inventive Example 13 3.5 30 2.1 924 13 〇1.8 864 14 3.0 15 1.3 800 14 〇0.0 780 15 4.1 15 2.7 992 13 〇2.9 942 16 4.6 15 2.7 977 16 〇2.9 909 17 3.6 15 2.1 921 14 〇1.5 320 18 4.3 15 2.7 973 .13 〇2.9 487 19 4.3 15 2.7 1002 13 〇2.9 952 20 4.3 15 2.7 1004 13 〇2.9 954 21 4.3 15 2.7 994 13 〇2.9 944 22 3.8 15 2.1 931 15 〇1.8 858 23 4.5 15 2.7 1003 13 〇3.0 943 24 3.8 15 2.1 909 14 〇 1.8 336 25 4.5 15 2.7 972 13 〇 3.0 527 26 4.3 15 2.7 1004 13 〇 2.9 924 1 1.2 12 2.6 845 13 〇 1.5 814 2 2.7 7 2.9 880 12 X 2.5 860 3 2.9 25 5.1 880 12 X 3.7 980 4 6.1 15 5.4 1050 13 X 6.1 370 to 5 4.6 40 5.3 980 .13 X 4.2 490 compared to 6 4.6 40 5.3 974 13 X 4.4 490 Example 7 2.8 40 5.3 804 14 X 4.4 875 8 2.8 7 2.9 848 12 X 2.3 828 9 4.6 40 5.3 991 13 X 4.7 922 10 4.6 40 5.3 997 13 X 4.4 939 11 2.6 15 2.7 734 7 〇 0.0 702 s 24 201122121 &lt;Exploration&gt; It is understood that the strengths of the invention examples Nos. 1 to 25 and the bending workability are improved satisfactorily. . Inventive Examples 13 to 26 are modified examples in which the manufacturing steps are changed. In the inventive example 13, the second solution treatment temperature was set to be high, and the upper limit average crystal grain size was obtained. Inventive Example 4, since the final cold rolling has a low rolling reduction ratio, /3 becomes the lower limit of the patent application range, and the aspect ratio is also lowered, but since it is within the range of the present invention, the balance between strength and bending workability is good. Improve the ground. Inventive Example 5 is a result obtained by setting the aging treatment temperature to the lower limit as compared with the inventive example N〇 4. Inventive Example 6 is a result obtained by setting the aging treatment temperature to the upper limit as compared with the inventive example No. 4. Inventive Example 1 The examples of the strain relief annealing in the steps of the invention examples No. 2 and the invention example No. 4 are omitted, respectively. It is understood that even if the strain relief annealing is omitted, the value of 10,000 is within the scope of the present invention. Internally, the balance between strength and bending workability is improved satisfactorily. With respect to Inventive Examples 1 7 and 18, strain relief annealing was carried out in Inventive Examples 19, 20 and 21, whereby the strength and value were increased. In the examples 22 to 25, the first solid solution treatment was omitted, and the No. 24 and 25 systems were not subjected to the strain relief annealing. It is understood that the first solid solution treatment is omitted and the strain reduction is not performed. Annealing, the value of yS is also within the range defined by the present invention, and the balance between strength and bending workability is favorably improved. Inventive Example 26 is an example in which strain relief annealing is performed at a low temperature for a short period of time. On the other hand, in Comparative Examples No. 1 to 3, since cold rolling was performed without performing aging treatment after the solution treatment, the full width at half maximum was small, and the balance between strength and f-lubricity was inferior to the invention. Further, although the aging treatment was performed after the solution treatment in Comparative Example N〇4 25 201122121 to 5, the dry shrinkage ratio in the cold sample was higher in Comparative Example No. 4, and the full width at half maximum was too large. Therefore, the balance between the strength and the odd-shaped workability is inferior to the invention. In Comparative Example No. 5, since the heating temperature in the solution treatment was too high, the crystal grain size increased. Although the final cold rolling has a higher rolling reduction ratio, a relatively high strength is obtained, but the bending workability is poor. In the comparative examples Νο.ό, 7, 9, and 10, since the solid solution temperature is too high, the crystal grain size exceeds the upper limit, and the bending process [biodegradation ° is again] in the comparative examples 7 and 8, due to the solution treatment in the solution After the cold rolling is performed without aging treatment, the full width at half maximum is small, and the balance between strength and bending workability is poor. In Comparative Example No. 11, since the strain relief annealing was carried out at a high temperature, recrystallization was started to cause a decrease in the density of the poor discharge and a decrease in the point, and since the solid solution was started again, the strength and the electrical conductivity were lowered. [Simple diagram description] None [Main component symbol description] None

S 26

Claims (1)

201122121 VII. Scope of application for patents: 1.----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- It contains 2.0 to 4.0% by mass of ?1 and is contained in total. Second, % is selected from the group consisting of Mn, Fe, Mg, C〇, Ni., fl Nb ' Mo ' Zr ' Si ' R » dr ' ^ ' and P group The remaining part is made of copper and inevitable, and the electronic parts made of gold are made of copper: from! The peak of the diffraction intensity of the radiant ray of the (10)} crystal plane is south width/5 (22()} and the full width at half maximum of the diffraction intensity peak of the {22_ crystal plane from the pure copper standard powder / 3 〇 {220} The following formula: 、,,, 3.〇$点{220} / 召.{220} $ 6.0 ; and, when observing the structure of the section parallel to the rolling direction, the average crystal grain size is expressed as approximately the diameter of the circle. &quot; m below. 2. The copper alloy of claim i, wherein the average crystal grain size (L) parallel to the direction of the rolling direction and the direction perpendicular to the rolling direction when observing the structure parallel to the section of the rolling direction The ratio (L/T) of the average crystal grain size (7) in the direction is 1 to 4. 3 · The copper alloy of the first or second aspect of the patent application has a spnng bending elastic limit of 600 to 1000. MPa. The copper alloy of the 1st or 2nd patent scope of the female patent application has a spring bending elastic limit of 300~600 MPa. 5.—A kind of copper extension product, which belongs to the fourth to fourth of the patent application scope. Copper alloy composition. 27 201122121 6. A copper alloy for electronic components. . Shu Li range of 4 to 7 .- copper alloys according to any connector comprising Paragraph range of the patent to any one of four 8.1 - electronic components using the method of producing a copper alloy It includes the following steps to the county containing 2_〇~4.〇. π. The amount of Τι, and the total amount of Mn, Fe, Mg, Co, Ni, Cr, V, (10) (10) ^ ^ and ^ 冓 〇 〇 〇 〇 选自 为 为 为 第 第 第 第Any of the group or the above-mentioned type, and the remaining part of the copper alloy material composed of copper and the unavoidable impurity f, is heated to a temperature of 730~88, and the solid solution limit becomes the same temperature as the addition amount. The above solution treatment; after the solution treatment, the aging treatment is carried out at a material temperature of 4 Torr to 5 〇〇〇c for 0.1 to 20 hours; and) after the aging treatment, the reduction ratio is 〇~4〇. The final cold rolling of %. 9. The method for producing a copper alloy for electronic parts according to the patent application 帛8, which comprises performing strain relief annealing after final cold rolling, wherein the strain relief annealing is at a material temperature of 10 Å or more and less than 350 eC. Heating for 0.001 hour or more and 40 hours or less, heating at a material temperature of 35 〇艽 or more, less than 55 〇, heating for 0.0001 hours or more, 20 hours or less, or heating at a material temperature of 55 〇 &lt; t or more and 700 ° C or less for 0.0001 hours or more. , 0.003 hours or less. 10. The method for producing a copper alloy for an electronic component according to claim 8 of the patent application, which comprises performing strain relief annealing after the final cold rolling, wherein the strain relief annealing is performed at a material temperature of 20 (TC or more, less than 400 t, heating 0.001) 20 small S 28 201122121 hours. Eight, schema: no 29