TW201217550A - containing 2.0-4.0 mass% of Ti, 0.01-0.15 wt% of one or more of Fe, Co, Ni, Cr, V, Nb, Mo, Mn, Zr, Si, Mg, B and P in total and the remainder containing Cu and unavoidable impurities, and having excellent strength and bendability - Google Patents

Abstract

Provided is a titanium copper with excellent strength and bendability. A copper alloy is a copper alloy used for electronic parts, which contains: 2.0-4.0 mass% of Ti, 0.01-0.15 wt% of one or more of Fe, Co, Ni, Cr, V, Nb, Mo, Mn, Zr, Si, Mg, B and P in total and the remainder containing copper and unavoidable impurities. The integral intensity of x-ray diffraction from a rolled surface of the copper alloy satisfies the relationship of (1) and (2): (1) 30 ≤ (I/I0{220})/(I/I0{200})9 ≤ 5; (2) 0.36 ≤ 2x(I/I0{111})+(I/I0{311}) ≤ 0.48.

Description

[Technical Field] The present invention relates to a titanium copper suitable as a member for an electronic component such as a connector, and a method for producing the same. [Prior Art] In recent years, electronic devices represented by portable terminals and the like have been increasingly miniaturized, and thus the connectors used thereof have become increasingly narrower in pitch and lower in height. The smaller the connector, the narrower the width of the pin, and the more the shape of the process is smaller. Therefore, for the member to be used, it is required to obtain the necessary elastic strength and excellent bending which can withstand severe bending. Processability. In this case, the copper alloy containing titanium (hereinafter referred to as "titanium copper") is superior to all copper alloys because of its relatively high strength, and thus has been used as a signal system terminal for particularly required strength. member. Titanium copper age hardening type copper alloy. When a supersaturated solid solution of ruthenium (as a solute atom) is formed by solution treatment, and heat treatment is performed for a relatively long period of time at a low temperature from this state, the phase separation is caused by the phase separation. The modulation structure develops in the parent phase to increase strength. In this case, it is a problem that if the strength and the bending workability are opposite to each other, the k-strength is deteriorated, and the bending workability is impaired. On the other hand, if the bending workability is emphasized, the desired strength cannot be obtained. In general, the higher the pressing ratio of the calendering is, the larger the difference in the introduced displacement is, and the higher the density of the difference is. Therefore, the nucleation site which contributes to precipitation can be increased, and the strength after the treatment is increased. However, if the rolling reduction rate is excessively increased, the bending process will be performed. Therefore, the object of the present invention is to achieve strength and bending workability.

Coexistence of S 3 201217550. Therefore, it is proposed to improve the characteristics of titanium copper by adding a third element such as Cr, zr, Ni, or Fe to promote the refinement of crystal grains (for example, Japanese Patent Laid-Open No. Hei 6-248375, No. 2, No. 2) 4_231985 and 曰本特开2009-084592). [Patent Document 1] Japanese Laid-Open Patent Publication No. 2004-231985 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2009-084592 The amount of the third element causes the solid solution limit temperature of Ti to rise, and the coarse second phase particles are easily precipitated. Therefore, the solution is previously compensated by performing two solution treatments. Namely, the first solution treatment is carried out at the elevated temperature, whereby Ti is sufficiently solid-solved, and a second re-dissolution treatment is used to obtain a fine recrystallized structure. However, since the method of performing the two solution treatments increases the production time, the production cost, and the energy consumption correspondingly, it is considered that in the case of industrial production, if it is possible to complete the solution treatment, it is more (4). Accordingly, an object of the present invention is to provide a titanium copper which can be produced by performing only one solution treatment and which is excellent in balance between strength and bending workability. Further, another object of the present invention is to provide a method of producing such a titanium steel. In order to solve the above problems, the present inventors have conducted intensive studies and found that when the amount of the third element is strictly suppressed, solid solution and recrystallization can be simultaneously performed by one solution treatment, if compared with the same third element. The characteristics of the titanium copper obtained by the addition amount are inferior to those of 201217550. Further, it has been found that if the crystal orientation of the rolled surface of the titanium copper obtained in this manner is examined by x-ray diffraction measurement (XRD), a characteristic peak is displayed. The present invention completed based on the above findings is a copper alloy containing Ti: 2.0 to 4.0% by mass and containing Fe, c〇, Ν, Cr, V, Nb, Mo, Μ, In the case of Zr, Si, Mg, B, and P, the total amount of 〇·〇1~〇. 1 5 wt%, the remaining part of copper alloy for electronic parts composed of copper and unavoidable impurities, if self-rolling surface The ratio of the integrated intensity of the X-ray diffraction of the {200} crystal plane to the integrated intensity of the X-ray diffraction of the {200} crystal plane of the pure copper standard powder is set to 1/1 〇 {200}, and {220 in the self-rolling surface } The ratio of the X-ray diffraction integral intensity of the crystal plane to the X-ray diffraction integral intensity of the {220} crystal plane of the pure copper standard powder is set to 1/1 〇{220}, and the {311} crystal plane in the self-rolling surface The ratio of the integrated intensity of the X-ray diffraction integral to the X-ray diffraction integral intensity of the {3 u } crystal plane of the pure copper standard powder is set to I〇{3丨丨}, and the X of the {111} crystal plane in the self-rolling surface The ratio of the integrated intensity of the ray diffraction to the integral intensity of the X-ray diffraction of the {111} crystal plane of the pure copper standard powder is set to I / Μ 111}, then full Sufficient to the relationship between (1) and (2). ' (1 ) 30$ ( I/I〇{220} ) / ( I/I0{200} ) S 95 (2) 0.36$2χ (Ι/Ι0{111}) + (ι/ι〇{311}) $0.48 In one embodiment of the copper alloy of the present invention, the relationship of the following (3) is more satisfied. (3) 1.02S (I/I〇{lll}) / (I/l〇{200}) S2.00 In another aspect, the invention is a copper-extended product which is composed of the above-mentioned copper

S 5 201217550 Gold. In still another aspect, the invention is a copper alloy. The part 'which is provided with the above invention is a copper alloy in still another aspect. ^逑接益, which has the above described invention in another aspect. The method of steel according to the invention of the present invention comprises the following steps: The first part of the phantom gold-manufactured pair contains Ti·· 2.0~4_〇% by mass, r χτ χ and contains a selected from the group consisting of Fe, Co, N!, Cr, V , Nb, M〇, Mn, z, t 妯 n n n n n,, B, and P, one of the above ~ count 0.01 ~ 0.15 weight 0 / 〇, left private de Α α α gun 7 1 knife field And the inevitable miscellaneous shells used in the electronic parts of the steel scn〇r ^ prepared raw materials 'heated to 730 ~ 880 C within 1 solid solution limit and the addition temperature of the solution treatment, the phase of the ship south 〇 〇 Τ Τ Τ Τ Τ 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 The aging treatment is carried out for a period of 15 hours; and the 'solution treatment is performed only once. The second manufacturing method of the steel alloy of the present invention is the following another method, which includes the following Step: 3 has a D1 · 2.0 to 4 · 〇 mass %, and contains a selected from Fe,

One or more of Ni, Cr, V, Nb, M〇, Mn, ☆, (1), 蚴, B, and p U 0·01 〇 〇 · i 5 wt% 'The remainder is composed of copper and unavoidable impurities The electronic parts are heated with a copper alloy raw material to a temperature higher than the solid solution limit of 73 〇 880 C, which is the same as the addition amount of 〇1 to the second generation of the 201217550 temperature, and after the solution treatment, the material temperature is performed. It is set to an aging treatment of 3 〇〇〇c or more and less than 700 ° C for 0.001 to 12 hours, and after the aging treatment, the final cold rolling is performed at a rolling reduction ratio of 5 to 4%; and the solution treatment is performed only once. The titanium copper of the present invention is excellent in strength and bending workability, and can be produced by performing one-time solution treatment, so that the industrial production value is high. [Embodiment] <Ti content> When Ti is less than 2.0% by mass, since the reinforcing mechanism due to the formation of the original copper-transformed structure cannot be sufficiently obtained, sufficient strength cannot be obtained, and if it exceeds 4·〇% by mass, it becomes easy to precipitate coarse

TiCh has a tendency to deteriorate in strength and bending workability. Therefore, the content of the ruthenium in the copper alloy of the present invention is 2 〇 4 to 4 % by mass, preferably 2 7 to 3 % by mass. Thus, by optimizing the content of Ti, it is possible to simultaneously achieve strength and bending workability for electronic parts. <Third element:> When the third element of the standard is added to titanium copper, it has an effect of improving the strength by crystallizing the crystal grains even when the solution is sufficiently solid-dissolved at a high temperature. The third element of the regulation promotes the formation of a modulation structure. Further, it has an effect of suppressing the sharpening of the stable phase of the Ti-Cu system. Therefore, the original age hardening ability of titanium steel can be obtained. In the case of titanium 锢Φ,, the highest effect is Fe. Furthermore, it is expected that Mn, Mg, Co, Νι, Si, v, Nb, M〇, Zr>, B and p

S 7 201217550

Fe is a standard effect, and it can also be effective by adding a single addition to the field, but it is also possible to add two or more types in combination. When the total amount of these elements is 0.1% by mass or more, the effect is exhibited. However, when the total amount exceeds 〇·15% by mass, it is difficult to achieve sufficient solid solution and appropriate recrystallization by one-time solution treatment. In the presence of particles, the balance between strength and bending workability tends to deteriorate. Therefore, it is possible to contain a total of 0.01 to 0.15 mass 1 selected from the group consisting of Mn, Fe, c〇, and the third element group.

The work type or two or more kinds of the group consisting of Ni, Cr, V, Nb, Mo, Zr, Si, B, and p preferably contain a total of 〇1〇〇8% by mass. Integral intensity of ray diffraction> The titanium copper of the present invention is obtained by diffraction of the integrated intensity of the χ ray diffraction of the {2〇〇} crystal plane from the calendered surface with respect to the {200 } crystal plane of the pure copper standard powder. The ratio of the integrated intensity of the shot is set to J/LPOO}, the integral intensity of the X-ray diffraction of the {22〇} crystal plane from the calendered surface is relative to the integral intensity of the X-ray diffraction of the {22〇} crystal plane of the pure copper standard powder. The X-ray diffraction integral intensity of the {3 11} crystal plane in the self-calendering surface is set to 1/1 〇{22〇}, and the X-ray diffraction integral intensity of the {3 11 } crystal plane of the pure copper standard powder is The ratio of the integrated intensity of the χ ray diffraction of the {in} crystal plane in the self-rolling surface to the 积分 ray diffraction integral intensity of the {111} crystal plane of the pure copper standard powder is set as 1 / 1 〇 {311} 1/ I〇{ 111}, the relationship between (1) and (2) below is satisfied. (1) 30'(I/I0{220}) / (1/10{200}) $95 (2) 0.36^2x (I/I〇{lll}) + (I/I〇{311}) ^0.48 The crystal orientation of the {200} crystallized surface which is mainly developed by solution treatment, which becomes less than 201217550 after the solution treatment (1/1〇{220}) / (1/1〇{200}) Minimum value. In this case, if the cold-pressed Ebene {220} crystallized surface is solidified after the solution treatment, it will gradually develop according to the cold rolling ratio (工/I〇{220} ) / ( ι/Ι〇{ 2〇〇}) becomes bigger. Therefore, (j/^220}) / (1/1〇{200}) can be said to be an indication of the degree of cold rolling in one aspect. Right (I/I〇{220}) / d/^poo}) is too small to obtain sufficient strength. On the other hand, if (I/I〇{22〇}) / (1/1〇{2〇 〇}) If it is too high, then the bending workability will deteriorate. If the balance between strength and bending workability is considered, it is preferably set to 3〇$ (J/K220)) / (丨/hpoq) $ 95 ' More preferably set to 40$ ( 1/1.{220} ) / ( 1/ 10{200} ) $ 70. Further, for the titanium copper to which the third element is added, the solution treatment is performed twice in order to obtain the desired strength and bending workability, so that the { 2 〇〇} crystal surface is excessively developed after the second solution treatment. Then, if cold rolling is performed, the crystal orientation of the {111} crystal plane-{3丨丨} crystal plane will occur, so the {111} crystal plane and the {3 11} crystal plane will be rolled by cold rolling. The shrinkage rate develops sequentially, and finally the orientation to the {220} crystal plane becomes larger. However, since the orientation of the {200} crystal plane after the solution treatment is large, it remains relatively much after cold rolling. On the other hand, the orientation of the {111} crystal plane and the {3 ii} crystal plane in the transition phase becomes 2x ( Ι / Ι〇 {111} ) + ( I / I 〇 {311} ) > 0.48 » Since the copper of the present invention is subjected to only one solution treatment, the degree of development of the {200} crystal plane after the solution treatment is small. Therefore, the orientation to the {220} crystal plane after cold rolling is dominant, and the distribution to the {111} crystal plane and the {311} crystal plane is less. Typically, the titanium copper of the present invention satisfies 2χ (1/1〇{111}) + (1/1.{311}) S 0.48, preferably full

S 9 201217550 足 2χ ( I/I0{111} ) + ( I/I0{311} ) $ 0·45. However, if the solution treatment is insufficient, 2χ(Ι/Ι〇{111}) + (Ι/Ι〇{311}) becomes too small to obtain good bending workability. Therefore, it is preferable to satisfy 〇·36$2χ (1/1〇{111}) + (1/10{311}), and it is better to satisfy 〇.38 S2x (I/I0{lll}) + d/iopil }). The reason why the weight of Ι/Ι0{ΐιΐ} is multiplied by 2 is that the larger the development of the {200} crystal plane after the solution treatment is, the more the remaining {111} crystal plane is more likely to remain, and the larger the causal relationship . Further, in the preferred embodiment, the copper alloy of the present invention further satisfies the relationship of (3). (3) 1.02$ (I/I0{111}) / (1/10{20〇}) $2.00 (ϊ/Ι〇{111}) / (1/1〇{200}) can be expressed after solution treatment The degree of easiness of rotation from the {2 〇〇} crystal to the {111} crystal plane caused by cold rolling. Although the reason is not clear 'But by setting (1〇{丨丨丨丨)/( j /1〇{200}) to this range, the balance between strength and bending workability can be further improved. More preferably 1.10S / (1/1(){200}:) $

Uo. In order to make (I/I0{ni}) / (1/1〇{2〇〇}) into the above range, it is effective to perform the predetermined heat treatment before the cold rolling after the solution treatment as described later. <Use> The copper alloy of the present invention can be provided in the form of various copper-extension products such as plates, strips, tubes, rods and wires. The titanium copper of the present invention is not limited, and it can be preferably used as a material for electronic parts such as switches, connectors, jacks, terminals, relays, and the like. 201217550 <Preparation method> The titanium copper of the present invention can be treated by a paste-only one-time solution.

In the step, appropriate heat treatment and A 夂 calendering are carried out for the production. Hereinafter, preferred manufacturing examples will be described in order of each step. οIngot manufacturing Manufacture and use of dazzling and praying to make Degan Ganzi _ water Ik ingots, basically in a vacuum or inert gas environment. If there is a melting residue added in the molten bath solution, the strength can not be increased. Therefore, in order to eliminate the melting residue, it is necessary to maintain a fixed time after the addition of Fe戎rr Menggu β fly C and the third element of the melting point after the third element is sufficiently stirred. Another ancient product, 另J, because Ti is easier to melt

In the case of Cu, it is added after the melting of the third element. Therefore, it is preferable to be selected from Fe, Co, Ni, 〇, '/ xTu

In the group consisting of Lr, V, Nb, Mo, Μη, Zr, Si, Mg, B, and P, one or two or more of them are added in a total amount of 〇〇1 to 0.15% by mass. Cu, technicians and v. The λ J force a Lu ' is added by adding Ti in an amount of 2 〇 to 4 〇 by mass to produce an ingot. 2) Homogenization annealing and hot calendering are relatively coarse as the solidification segregation or crystals produced during the manufacture of the prayer bond, so it is desirable to use the homogenization annealing to make it as solid as possible in the matrix phase to reduce 'and as much as possible Eliminate it. The reason is that this can effectively prevent bending cracking. Specifically, it is preferred to carry out heat rolling after heating to 9 〇〇 to 97 ° C for 3 to 24 hours after the ingot production step. In order to prevent the brittleness of the liquid metal, it is preferable to set the pass before the hot rolling and the hot rolling to 9 6 t or less, and the pass from the original thickness to the overall rolling reduction rate of 9〇% is set to 900° 201217550 (pass). Above C. Further, in order to effectively reduce the segregation of Ti by causing moderate recrystallization per pass, it is sufficient to carry out the reduction of each pass to 10 to 20 mm. 3) Intermediate calendering The intermediate calendering is carried out in solution treatment. The more the rolling reduction ratio of the intermediate rolling is increased, the more the recrystallized grains in the solution treatment can be controlled to be uniform and fine. However, if the final solution treatment is carried out by excessively increasing the degree of processing, the recrystallization texture may develop to cause plastic anisotropy and impair press formability. Therefore, the rolling reduction of the intermediate calendering is preferably from 70 to 99%. The rolling reduction ratio is defined by {((thickness before calendering, thickness after calendering) / thickness before calendering). 4) Solution treatment After the intermediate rolling, a solution treatment is carried out once. It is preferable that the precipitate is completely dissolved in the solution treatment. However, if the temperature is too high until the precipitate completely disappears, the crystal grains are easily coarsened. Therefore, the heating temperature is set to be a solid solution of the second phase particles. Temperature in the vicinity of the limit (in the range where the amount of addition of Ti is in the range of 2.0 to 4.0% by mass, the temperature at which the solid solution limit of Ti is equal to the amount of addition is 730 to 84 (about TC, for example, if the amount of addition of Ti is 32% by mass) , if it is heated to this temperature quickly, and also accelerates the cooling rate, the generation of coarse second phase particles can be suppressed. Therefore, Ti is usually solidified by heating to 730 to 880 ° C. The temperature is equal to or higher than the added amount, and is more typically heated to a temperature of 730 to 88 〇t. The solid solution limit is the same as the temperature at which the addition amount is 0 to 2 (the temperature of TC is preferably high to 〇~1). 〇 ° C temperature. In the present invention, although only one solution treatment is carried out, but by 12 201217550

Fine recrystallized grains. Soluble, also obtained coarse crystal grains

Further, when the heating time in the solution treatment is short, it can be suppressed. The heating time can be, for example, 30 to 90 seconds, and the step after the solid/valley treatment is usually performed (cold rolling-aging treatment mode). After the solution treatment, the final cold rolling and aging treatment can be sequentially performed. The strength of titanium copper can be increased by the final cold working. The cold rolling reduction ratio affects the integrated strength of the above crystal orientation. In order to satisfy the integral strength of various crystal orientations specified in the present invention, the rolling reduction ratio is preferably 5 to 40 / ❶', preferably 丨〇 〜 3 〇 %, and more preferably 15 to 25%. The aging treatment is carried out after the above cold rolling. The aging treatment may be carried out under customary conditions, for example, preferably at a material temperature of 3 Torr to 5 Torr for 0.1 to 15 hours, more preferably at a material temperature of 350 to 45 (TC heating for 0: 5 to 8 hours). 5)) The step after solution treatment (aging treatment - cold rolling mode) is preferably followed by aging treatment and finally cold rolling after solution treatment. In the past, although it is customary to perform cold rolling after the final solution treatment, it can be easily set to 1.02 S by immediately performing aging treatment without cold rolling after the final solution treatment, and then performing cold rolling. 1/ Mill} ) / ( I/I〇{2〇〇} ) $ 2.00 range, strength and bending

S 13 201217550 Balance of sexuality. If the titanium copper after the solid/combination treatment is heat-treated, the electrical conductivity will increase with the development of the cycle and the structure of the structure. Therefore, the degree of annealing can be regarded as the value of # before and after annealing. According to the study by the present inventors, the heat treatment is preferably carried out under the conditions of a conductivity of 5 to 8% iACs (preferably 4% IACS). The specific conditions in the above-mentioned increase in the electrical conductivity are such that the material temperature is set to 3 〇〇 (>c or less and it is not heated for 0.001 to 12 hours. The heat treatment is preferably carried out under any of the following conditions. Set the material temperature to 300. (: Above and less than 400. (: Heating for 0.5 to 3 hours, set the material temperature to 4 〇〇. (: Above and not up to 500. 〇 Heat 〇〇 1~ 0.5 hours to material The temperature is set to 500 ° C or more and less than 600. It is heated to 〇〇〇 1 to 0.01 hours to set the material temperature to 600 ° C or more and less than 700 T: heating 0.001 to 0.005 hours and 'heat treatment is better than any of the following conditions • The material temperature is set to 350 ° C or more and less than 400. (: Heating for 1 to 3 hours. Set the material temperature to 400. (: Above and less than 500 ° C heating for 0.2 to 0.5 hours • Material temperature Set to 500 ° C or more and less than 550 ° C heating 0.005 ~ 0 · 01 hours 14 201217550 . Set the material temperature to 55 (TC above and less than 6 〇 (rc heating 〇〇〇 1 ~ 0.005 hours. Material temperature Set to 600. (: above and not up to 65 (rc heating 〇〇〇 25 ~ 〇 · 〇〇 5 hours above) After the treatment, the final cold rolling is carried out. The strength of the titanium copper can be increased by the final cold working. The cold rolling shrinkage rate affects the integrated strength of the above crystal orientation. In order to satisfy the various & crystals specified in the present invention The integral intensity of the orientation is set to 5 to Φ. It is preferably set to 1 〇 to 3 〇 ° / ° 'more preferably set to 15 to 25 〇 / 〇. Force, /tr (4) 5,) After the final cold rolling, the force annealing or aging treatment may be carried out as needed. The conditions of the aging treatment may be the conventional conditions: the aging treatment is slightly performed earlier, and the balance of the strength processing is improved by riding. The aging treatment is preferably carried out at a material temperature of 300 to 40 (arc heating for 3 to 12 hours. The aging treatment is preferably carried out under any of the following conditions. When the material temperature is set to be more than one bribe and not reached Continue heating Μ hours. Set the material temperature to 3 voyages or more and less than 3 ah. Heat the Μ small. Set the material temperature to 38 generations or more and not reach _. (: Add #3~6 hourly treatment is better In order to carry out the following conditions - 'to set the temperature of the material Gifts or more and less than 6 is heated shoe

15 S 201217550 Set the material temperature to 360. (: Above and less than 3 80 °C heating for 5~6 hours, the material temperature is set above 380〇c and less than 4〇〇t: heating for 4~6 hours, the industry should understand the above The steps of grinding, grinding, beading, pickling, etc., for removing the rust scale on the surface may be appropriately performed between the steps. [Examples] Underarms and showing examples and comparative examples of the present invention, In order to better understand the present invention and its advantages, it is not intended to limit the present invention. In the production of the copper alloy of the present invention, since the addition of the active metal as the second component is used, it is used in the melting. In addition, in order to prevent the occurrence of unexpected side effects due to the incorporation of the impurity element other than the elements specified in the present invention, the raw materials used are strictly selected to be relatively pure. First, as shown in Table 1. The composition, respectively, Mn, Fe, Mg, respectively, added to the composition shown in the table "Ti. In order not to make the remaining elements of the dazzling residue, but also fully consider the retention time after the addition, along the environment will The injection into the mold In the middle, about 2kg of ingot was separately produced. After the homogenization annealing of the ingot for 3 hours, the hot rolling was performed at 9 〇〇 to 95 (TC was hot-rolled to obtain a sheet thickness of 1 〇). The plate is removed by the end face cutting, and then cold rolled to form a strip thickness of 16 201217550 mm). According to the test piece, the processing conditions are set to be the second largest: solution treatment. The first solid The first solid solution treatment is not carried out: ", 1 minute wide. In addition, in the invention example, the thickness of the back plate becomes 0 25 in the middle of the cold, and the thickness of the middle is adjusted in the form of the most, and the mm. The cold rolling and the annealing furnace which can be heated at a constant speed are subjected to the final solution treatment, and then, the heating condition of the workpiece is the same as the temperature at which the material temperature is the same as the addition amount (at T&quot When the agricultural degree is 32% by mass, about 73 (rc, when the concentration of T is 2.0% by mass) is about 73 (rc, when the Ti concentration is u mass%, about 84 (TC' at about Ti concentration of 2.9 mass%) 79〇. The reference is based on the heating conditions described in "1" for i minutes. Then, in the Ar environment, it is recorded by the watch. The conditions are subjected to the first aging treatment. After the scale is removed by pickling, the final cold rolling is carried out under the conditions described in Table \. Finally, the aging treatment is carried out under the respective heating conditions shown in Table 1, and the invention examples and comparisons are obtained. The test piece of the example. The aging treatment after the solution treatment is sometimes omitted according to the test piece. 17 1 201217550 [ϊ<]

Manufacturing Steps 第二 | Second Aging Treatment | 丨 Time (h) | so \〇s〇n£> Ό so SO so Ο s〇Ό so NO v〇I Temperature (°c) | I 400 I 1_ 400 1 1 400 L 400 I 400 I 400 1 400 1 400 〇o I 400 IL 350 IO »/> s 1 350 I ι 350 1 350 I 沄ΓΛ 350 350 1_____ S 1 350 | I final cold rolling | | %) | (N ΙΛ (N Ι /Ί (N <N <N ΙΛ (N ir, ΙΛ <N »Λ (N iTt (N PM *Λι <N ΙΛ (S ίΝ ιη «η 〇iN <S «λ <N — | First aging treatment | | Difference between EC before and after heat treatment (%1ACS) 1 1 i 1 1 1 1 1 1 1 1 e*\ Ό Inch I time (h) I 1 1 1 1 1 1 1 1 1 1 i_M·_1 1__Ml_I | o.oi | | 0.006 1 | o.oi | Ο I 0.003 1 !_Mi_1 | o.oi | | 0.005 1 0.006 0.006 | o.oi | 0.01 1 I Temperature (°c) | 1 1 1 1 1 1 I 1 1 1 o 沄1_5〇p__1 O 1550__I 〇!_450__1 ο S 1__500__1 〇•λ o »Ti 〇·/*> ο 1 Final solution treatment | |Time ( Min) — — — — 丨 temperature (ΐ) | oggog | 800 1 S 〇〇o 00 in 00 CC o 00 V» § I_« IP__! | 820 I s 00 Ο JQ 1_85〇Ι 00 S 00 1/1 so 〇00 s oo oo First solution treatment | 1 I 1 1 1 | 850°〇7.5 minutes钹I | 850ΪΧ7.5 cents I 850°〇7.5分钹1 | 850°〇7.5 cents I | 850ΐ>7.5 cents 1 1 1 1 | 850e〇7.5 min | 1 1 1 1 1 1 1 1 1 1 Alloy composition | 1 3rd element 1 1 (wt%) io | 0.01 Fe 1 | 0.15Fe | | 0.17Fe 1 | 0.17Fe 1 o | O.OlFe | 1 0.15Fe | | 0.17Fe | 1 0.17Fe | o | O.OlFe 1 | 0.15Fe 0.2Fe | | 0.08Fe | 1 0.08Fe 1 1 0.08Fe 1 | 0.08Fe 1 | 0.08Fe 1 | 0.08Fe | O.OlCo O.OINi O.OlCr 0.01V O.OlNb O.OlMo O.OIMn O .OlZr O.OlSi 0.01 Mg 0.01B 0.01P | 0.08Fe | 1 0.08Fe 1 - (wt%)] cn <N ΓΛ rn «Ν ΓΛ On ri <N r*><N<N rn <N Os (N CM pn <N rn <N rn <N η ο (N <N rn rn <N rn (N rn (N CO Comparative Example | Invention Example | Invention Example | Comparative Example | Comparative Example | Comparative Example | Comparative Example | 1 Comparative Example | Comparative Example | Comparative Example | Comparative Example | I Invention Example | I Invention Example | I Comparative Example | I Invention Example | 1 Invention Example ι 1 Invention Example ι 1 Inventive Example i Inventive Example: |Inventive Example! WORKING EXAMPLES Inventive Example 1 Comparative Example 1 1 Comparative Example I 6^—— ίΝ m TJ· \〇 卜 00 〇 〇 卜 00 00 & & & 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 Evaluation of characteristics The result <strength> The test piece was added in such a manner that the stretching direction was parallel to the rolling direction. According to the claw-Z2241, the tensile test of the test piece was performed to determine the 0.2% proof stress (YS) in the parallel direction of the calendering. <Bending workability> The w-bend test of Badway (the same direction in which the bending axis and the rolling direction are the same) in accordance with JIS H3130, and the ratio of the minimum radius (mbr) to the thickness (t) which does not cause cracking is measured, that is, MBR /t value. <x. ray diffraction measurement> For each test piece, an X-ray diffraction apparatus of a model Hnt Uhima2000 manufactured by Rigaku Corporation was used, and the diffraction intensity of the calendered surface was obtained under the following measurement conditions. The integrated intensity I of the surface, {2〇〇} crystal plane, {22〇} crystal plane, and {3 11} crystal plane. Under the same measurement conditions, the pure copper powder standard sample was also obtained (the integral intensity of the 丨丨丨丨 crystal plane, {2 〇〇丨 crystal plane, {220} crystal plane, {311} crystal plane 1 〇, calculation 1 /1〇{111}, 1

I〇{200}, l/i〇{220}, 1/1〇{311} ' Find (i/i〇{220} ) / ( I /1〇{20〇} ), 2x( 1/ 1 〇{111} ) + ( i/i〇{31 i }) and (!/][“"” ) / ( 1/1〇{200}). • Dry: Cu ball • Tube voltage: 40kV. Tube current: 40mA 'Scan speed: 5°/min 201217550. Sampling range: 〇.〇2°. Measuring range (2Θ) : 60°~80° L clothing No. 1 Comparative Example 2χ(Ι/Ι〇{111}) + (m〇{3ii}) :0_35j...· (I/I〇{lll}) / (I/I〇{200}) W〆354〇·66, (I/I〇{220}) / (I/I〇{20〇l2^ 54.94 __ YS (MPa) 836 弩曲(MBR/t) 1.5 2 3 Invention Example 发明 Invention Example 0.39 0.45 1.01 0.95 63.02 __ 72.16 880 892 1.5 1.5 4 Comparative Example 'i·*' f. 0.56 ; 56.64 一^jj 890 2.5 5 Comparative Example ν^^6, J 0:47;:,· 57.78 ^, 896 2.5 6 Comparative Example. 57;'57 ^ .- ; 36.98 753 1 7 Comparative Example—,· 0^,5.: 35.09 a _ 793 1 g Comparative Example 0.55^.; i 28.77 , 846 1.5 9 Comparative Example 81.81!^ —3 Wen 4 must be 864 1.5 10 Comparative Example > Item 0. —79,,::, 14.71 ____. 887 2.5 11 Comparative Example 1.22 47.24 929 nAC 3 1? Invention Example 0.39 1.04 41.37 One ^ 945 2 η Inventive Example 0.41 1.31 68.89 980 2.5 14 Comparative Example 0.92. a 0.78, 'V -\ 20.67, 985 2.5 15 Invention Example 0.38 1.06 52.06 A _ 960 2 16 Invention Example 0.40 1.18 50.08 920 1.5 】7 invention example 0.41 1.13 50.56 ______ 1015 2.5 18 invention example 0.48 1.03 35.08 __ 820 0 19 invention example 0.47 1.93 90.13 one __ 1008 2.5 20 invention example 0.41 1.20 53.81 one _ 900 1.5 21 invention example 0.48 1.10 39.62 >_ 956 2 22 Invention Example 0.41 1.33 71.27 971 2 23 Comparative Example 0.55 0.90 ?! ^22.70, ^1^. 755 0 24 Comparative Example 0.40 125.67-two r 8» ill · ' 1015 4 <Inspection>

Nos. 2 and 3 are examples of the invention, and it is understood that the strength and the bending workability are improved in a balanced manner. Further, in Examples 12 and 13 which were subjected to aging treatment after solution treatment, it was found that the balance between strength and bending workability was further improved. In addition, No. 15 is an invention example in which the Fe concentration is 0.08 mass%, the invention example in which the No. 16 system concentration is the lower limit value, and the No. 17 series invention in which the Ti concentration is the upper limit value, and the Νο· 18 series Inventive example of reducing the rolling reduction ratio of the final cold rolling, N〇. i 9 20 201217550 is an invention example in which the rolling reduction ratio of the final cold rolling is increased, and No. 20 is an invention example in which the second aging treatment is not performed. On the other hand, Nos. 1 and 11 are comparative examples in which the Fe concentration is too low. Ν〇·4, 5 and 14 are comparative examples in which the Fe concentration is too high. In particular, Ν〇·14 corresponds to a previous example in which the Fe concentration is 〇.2% by mass and two solution treatments are performed. However, in the invention example, the balance between the strength and the bending workability is obtained. A comparative example in which N〇6 to 1〇 is subjected to two solution treatments can better understand the balance-enhancing effect of the strength and the f-workability of the present invention as compared with the invention. No. 23 is a comparative example in which the final cold shrinkage rolling reduction ratio is excessively lowered, and n〇.24 is a comparative example in which the rolling reduction ratio of the final cold rolling is excessively increased. [Simple diagram description] None [Main component symbol description] None

21 S

Claims (1)

201217550 VII. Patent application scope: 1. A copper alloy containing Ti: 2.0 to 4.0% by mass and containing Fe, Co, Ni, Cr, V, Nb, Mo, Mn, Zr, Si, Mg, One or more of B and P are 0.01 to 〇·15 by weight in total. /〇, the remaining part of the copper alloy for electronic parts consisting of copper and unavoidable impurities, if the X-ray diffraction integral intensity of the {200} crystal plane from the calendered surface is {200} crystallized relative to the pure copper standard powder The ratio of the X-ray diffraction integral intensity of the surface is set to 1 / 1 〇 {200}, and the integral intensity of the X-ray diffraction of the {220} crystal plane in the self-calendering surface is relative to the {220} crystal plane of the pure copper standard powder. The ratio of the integrated intensity of the ray diffraction is set to 1/1 〇{220}, and the integrated intensity of the X-ray diffraction of the {311] crystal plane from the calendered surface is relative to the X-ray of the {3丨丨} crystal plane of the pure copper standard powder. The ratio of the diffraction integral intensity is set to 1 (>{3丨丨}, the X-ray diffraction integrated intensity of the {111} crystal plane from the calendered surface is compared with the X-ray diffraction of the {111} crystal plane of the pure copper standard powder. When the ratio of the integral intensity of the shot is set to I / " {111}, the relationship between the following (1) and (2) is satisfied, (1) 30^ (I/I0{220}) / (1/1〇{200}) ^95 (2) 0.36^ 2x (1/1〇{111}) + (1/1〇{311}) ^ 0.48 〇2. As in the copper alloy of claim 1, the following further satisfies the following (3) Relationship, (3) 1.02$ / (J/W200" $2 3. A copper-extension product consisting of a copper alloy of the first or second patent application scope. 4. An electronic component that has a steel alloy of claim 1 or 2. 22 201217550 5 - a connector having a copper alloy 13 having the patent application scope or item 2. 6. A method for manufacturing a copper alloy according to claim 1 or 2, comprising the steps of: containing Ti: 2.0~ 4.0% by mass, and containing at least one selected from the group consisting of Fe, c〇, Ni, Cr, V, Nb, Mo, Mn, heart, &, 峋, B, and p, 0.01 to 〇. 'The remaining part of the copper alloy raw material for electronic parts consisting of copper and unavoidable impurities is heated to a temperature higher than the temperature of 〇~2〇t at the same temperature as the solid solution limit and the addition amount of 73〇880 C. After the solution treatment, after the solution treatment, the final cold rolling is performed at a rolling reduction ratio of 5 to 4%, and after the final cold rolling, the material temperature is 3 〇〇 5 5 〇〇, and the aging treatment is performed for 〇.丨~U hours. And the solution treatment is only carried out once. 7. The scope of the patent claim is 丨The method for producing a copper alloy according to the second aspect includes the steps of: containing Ti: 2_〇 to 4.0% by mass, and containing a selected from the group consisting of Fe, c〇, Ni, Cr, V, Nb, Mo, Mn, Zr, Si, Mg B&pt^4 or more, a total of 0. (Η~〇.15% by weight, the remaining part of the copper alloy material for electronic parts composed of copper and inevitable quality, heated to 73, 〇880 C Τι solid solution The temperature at which the limit and the amount of addition are the same is higher than the temperature of 〇~ temperature, and < After the solution treatment, the material temperature is set to ·. c above the bribe heating 0.001~12 hours aging treatment, Heda 23 S 201217550 After the aging treatment, the final cold rolling of the rolling reduction rate of 5~40%; and the solution treatment is only carried out once. twenty four