TW201118181A - Titanium-copper for electric component - Google Patents

Abstract

The invention provides a titanium-copper actively precipitating TiCu.sub.3 as the stable phase, and excellent in strength and bending processing property. The copper alloy for the electronic component of this invention contains 2.0 to 4.0 % by mass of Ti, and the remaining portion is composed of copper and inevitable impurities. While utilizing an electron microscope to observe the tissue of the cross-section parallel to a rolling direction, there exists a crystal boundary reaction phase comprising Ti-Cu based particles precipitated along the crystal boundary. The average value Avg (D.sub.2/D.sub.1) of the ratio (D.sub.2/D.sub.1) of a diameter D.sub.2 of the minimum circle of the encircled grain boundary reaction phase of each grain boundary reaction phase with respect to a diameter D.sub.1 of the maximum circle encircled by the grain boundary reaction phase, is 1.0 to 6.0. The average value Avg D.sub. 1 is 0.4 to 2.0micrometer. Moreover, the grain boundary reaction phase occupies 1.5 to 15 percent area of the per 1000 micro square meter of observation field.

Description

[Technical Field] The present invention relates to a titanium copper suitable for use as a member for an electronic component such as a connector, and a method of manufacturing the same. [Prior Art] In recent years, the miniaturization of electronic devices represented by mobile terminals and the like has progressed steadily. Therefore, the narrow pitch and low profile of the connectors used therein have become remarkable. The smaller the connector, the narrower the width (4) of the pin, and in order to be a folded shape, the member to be used is required to have high strength to obtain the necessary elasticity and excellent bending to withstand severe bending. Processability. In this respect, since the copper alloy containing titanium (hereinafter referred to as "titanium copper") has a relatively high strength and the stress relaxation property is the most excellent in the copper alloy, it has been used as a signal terminal member having a particularly required strength since the prior art. . Titanium copper type age hardening type copper alloy. If a solute atom, that is, a supersaturated solid solution of Ti, is formed by solution treatment, and heat treatment is performed for a long time from this state at a low temperature, Ti in the parent phase is caused by spin dai decomposition. The periodic variation of the concentration, that is, the modulation structure is expanded, and the strength is increased. In order to obtain titanium copper excellent in strength and bending workability, how to suppress the stable phase, ie, ΤΊ (: ιΐ3 is an important issue so far. The reason is that since the integration of the stable phase is inferior to that of the parent phase, if the ratio is increased, the ratio is increased. Large, it will have an adverse effect on the workability or strength of f. The stable phase is more likely to occur when the aging treatment is performed at a higher temperature for a long time (aging, coffee, etc.), 201118181, or when the solid solution is sufficient. In order to improve the characteristics of the money, the industry is striving to suppress the formation of a stable phase in a heat treatment such as a solution treatment or an aging treatment (Patent Documents 1 to 4). [Patent Document 1] Japanese Patent Laid-Open No. Hei 20-23-231985 [Patent Document 3] Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. The previous method for realizing the high performance of the copper is to suppress the stable phase (7) of the intermetallic compound particles of TiCu3f and Cu, and the stable phase of the Cu system. It has indeed achieved certain results. However, in order to develop titanium-molybdenum I that meets the increasingly demanding characteristics that are expected to become more stringent in the future, it is considered to be more helpful to use the same method as it has so far to seek new possibilities for Chin. Therefore, one of the problems of the present invention is to provide a titanium copper which is formed by actively depositing a stable phase such as TiCU3 and having excellent strength and bending workability. Further, another object of the present invention is to provide a method for producing such a titanium copper. In order to solve the above problems, the inventors of the present invention have found that the stable phase of the Ti-Cu system is dispersed in the cu matrix phase in the form of undissolved particles in the grain boundary, and does adversely affect the strength or the workability. However, if the stable phase of the bismuth-Cu system locally grows and the surrounding particles aggregate with each other in the form of a population of precipitated particles having a constant size and shape, adverse effects are reduced or harmless. In the present invention, a phase different from the parent phase composed of such a precipitated particle group appearing along the crystal grain boundary is referred to as a "201118181 grain boundary reaction phase". The e i system captures an electron micrograph of the grain boundary reaction phase. Figure +' The phase of the speckle pattern that grows along the grain boundary and is different from the parent phase is the grain boundary reaction phase. One aspect of the present invention based on the above findings is a copper alloy for electronic parts, which contains U to 4.0% by mass of Ti, and the remainder: the damage is composed of copper and unavoidable impurities; and observation by an electron microscope In the case of a structure parallel to the cross section in the rolling direction, there is a grain boundary reaction phase containing Ti Cu-based particles precipitated along the grain boundary, and the diameter 〇2 of the smallest circle surrounding the grain boundary reaction phase of each grain boundary reaction phase is relative to The ratio of the diameter of the largest circle D] of the grain boundary reaction phase (DVDi) is 8.1 (〇2/£) 丨) is 1.0 to 6.0, and the average value of 〇1 is AvgD^ 〇4~2 〇(10) Further, the grain boundary reaction phase accounts for 1.5 to 15% of the area per 1000 from the observation field of m2. In an embodiment of the copper alloy of the present invention, when the microstructure parallel to the cross section in the rolling direction is observed by an electron microscope, the average value Av3 of D2 is 1 · 〇 to 5.0 m. In another embodiment of the copper alloy of the present invention, when the microstructure parallel to the cross section in the rolling direction is observed by an electron microscope, the average crystal grain size is represented by a straight felt of approximately 5 "claws above, 3〇" Hereinafter, the average value AvgD3 of the diameter 〇3 of the largest circle surrounded by the grain boundaries of the crystal grains surrounding the grain boundary reaction phase is AvgD2 < AvgD3. In still another embodiment of the copper alloy of the present invention, Mn, Fe, Mg, Co, Ni, Cr, V, Nb, Mo, 7r, which are selected from the group consisting of 〇, 〇, and 5 Å, are selected from the group consisting of Mn, Fe, Mg, Co, Ni, Cr, V, Nb, Mo, and 7r. q . n

One or more of the group consisting of Zr Spb and p. Another aspect of the present invention is a copper-clad product (el〇ngated 201118181 product) 'which is composed of the above-mentioned copper alloy. According to still another aspect of the present invention, an electronic component is provided with the above copper. A type connector is provided with the above steel alloy. Further, the present invention relates to a method for producing a copper alloy for an electronic component, comprising the steps of: containing from 2.0 to 4.0% by mass of the butadiene and containing G to 〇5 mass% selected from the third element a group of Mn, Fe, Mg, c〇, Ni, Cr, : a group of or consisting of copper and an inevitable impurity in the group consisting of: Heating to 730~峨 Ti solid solubility limit becomes the solution treatment with the addition amount of temperature above; after the solution treatment, heating at the material temperature of 4〇〇~5〇〇t~~0 hours The aging treatment; after the aging treatment, the rolling reduction (r〇丨Hng reducti〇n) is 〇40% cold rolling. According to the present invention, it is possible to obtain titanium copper which is a large amount of a stable phase, i.e., TiCu3, and which is excellent in strength and bending workability. [Embodiment] <Ti content> When Τι is less than 2.0 mass 〇/〇, the strengthening mechanism due to the formation of the original tuned structure of titanium copper cannot be sufficiently obtained, so that sufficient strength cannot be obtained, and conversely When the amount exceeds 4.% by mass, the coarse TiCu3 tends to be precipitated, and the strength and bending workability tend to deteriorate. Therefore, the content of Ti in the 6 201118181 copper alloy of the present invention is 2.0 to 4.0 mass 〇 / 〇, and the dry 乂 1 main horse 2 · 7 to 3.5 mass %. By optimizing the content of Ti in this way, it is possible to achieve the strength and bending workability of electronic parts. <Third Element> When a certain third element is added to titanium copper, the effect of solid solution treatment at a relatively high temperature at which Ti is sufficiently solid-solved is also facilitated to be finer and finer. Increased strength. Further, _ θθ , the heart < the third element promotes the formation of the modulation structure. Furthermore, it also has the effect of suppressing the Ti-cu system ^ ^ and the I stable phase. Therefore, it is possible to eat the original age-hardening power of titanium and copper. When the total amount of these elements is 0.05% by mass or more, the effect is exhibited. However, when the total amount exceeds 0.5 mass, the strength and the bending workability tend to deteriorate. Therefore, the selection of g to g. 5 mass% in total is Mn, Fe, Mg, c〇, Ni, Cr, v, Nb of the third element group.

The seed or the mixture of two or more of Mo, Zr, Si, B and P is preferably contained in a total amount of 〜.〇5 to 0.5% by mass. <grain boundary reaction phase> The grain boundary reaction phase is based on the aging principle, and the grain boundary reaction particle morphology /0,, and the grain boundary of the grain are precipitated in the grain boundary. The 丄 and L 疋 are clustered with each other and are not related to the mother. If the reaction phase is observed by electron microscopy, it looks like a speckle pattern. By making the grain boundary reaction phase into a size and shape, the stable phase of the T!-Cu system is taken to reduce or degrade the adverse effects. Since the grain boundary reaction phase grows along the grain boundary along the sister-in-law, surname 曰Μ, and 0-day grain boundaries, if the 曰 曰 曰 杈 杈 杈 , , , , 粒 粒 粒 粒 粒 粒 粒 粒 粒 粒 粒 粒 粒 粒 粒7 201118181 To. Further, there is a tendency that the drying shrinkage ratio of the final cold milk increases. The crucible grains extend in the rolling direction, and along with this, the grain boundary reaction phase also becomes longer in the rolling direction. When the length is extended in a specific direction, the adverse effect on the bending process is not alleviated, so it is preferable that the grain boundary reaction phase grows uniformly in all directions. Therefore, in 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 of the diameter 〇2 of the smallest circle surrounding the grain boundary reaction phase of each grain boundary reaction phase to the straight D1 of the largest circle surrounded by the grain boundary reaction phase (D2/) Di) (hereinafter, the average value of the "grain boundary reaction phase aspect ratio") is 1 . 〇 ~ 6.0, preferably 2.0 to 5 〇. For example, with respect to the grain boundary reaction phase A shown in Figure 1, the circle U is the smallest circle surrounded by the grain boundary reaction phase, the circle 12, which surrounds the smallest circle of the grain boundary reaction phase. Furthermore, although there are a plurality of grain boundary reactions in contact with each other, the phase factors are different, so that the concentration of the mother phase of the reflected electron image, the element distribution map of the ΕΡΜΑ (ele_tal (4)), or the use of E(10) can be utilized. The orientation maps and the like are distinguished and treated as different grain boundary reaction phases. Further, even if the aspect ratio of the grain boundary reaction phase is controlled, if the grain boundary reaction phase is excessively increased, the adverse effect on the bending workability cannot be alleviated. Further, it should contribute to the fact that the solid solution of the expanded structure of the butyl component is introduced into the grain boundary reaction phase, and sufficient strength cannot be ensured. On the other hand, even if the expansion of the grain boundary reaction phase is insufficient, the adverse effects caused by the stable phase are not alleviated, and the amount of solid solution Ti is too large to ensure the necessary conductivity. Therefore, in the titanium copper of the present invention, when the microstructure parallel to the cross section in the direction of the extension is observed by an electron microscope, the average value of 0| is AvgD 々〇 4 〜 2 〇, preferably 8 201118181 0.4 〜 1 _ 5 " m, Better for 〇, 4~io //m. Further, when the microstructure of the cross section parallel to the rolling direction is observed by an electron microscope, the average value AvgD2 of D2 is, in one embodiment, 〜5〇μΓη, preferably 2〇~5〇 in m, more preferably 2.0~ 3.0 ym. Even if the respective grain boundary reaction phases are of a certain size, if the proportion in the metal structure is not appropriate, the effect will not be exhibited. On the other hand, if the grain boundary reaction phase becomes excessive, it will result in the conversion of the modified structure 2 solid solution component into the grain boundary reaction phase. Therefore, when the microstructure parallel to the cross section of the rolling direction is observed by an electron microscope, the grain boundary reaction phase accounts for 15 to 15% of the area per 1000 Mm 2 of the observation field, preferably 1.6 to 10% of the area, more preferably For an area of 17 to 3 2%. <crystal grain size> 〜, p r seat grain boundary The area ratio of the reaction phase tends to rise above the required defect. Therefore, the average crystal grain size is preferably 30 "m or less, more preferably 2 〇 from (7) or less. The lower limit is set to 1 乂 preferably ' so that the area ratio of the grain boundary reaction phase does not rise above the required, more preferably In the present invention, the average crystal grain size is expressed by the diameter of an approximate circle when the microstructure of the face parallel to the rolling direction is observed by electron microscopy & Ding Qian. ~ Usually, the crystal grain will correspond to the round shape of the rolling direction in the final rolling and cold rolling, but if it is extremely flat due to the difficulty of raising the crucible, the strain will be In the next day, the grain-changing mouth is likely to become a bending brake, and therefore, it is preferable to be as close to a perfect circle as possible. In the embodiment, the crystal grains surrounding the grain boundary and the titanium-copper phase should be The average value AvgD3 of the diameter A of the largest circle surrounded by the grain boundary of the 201118181 crystal grain is defined as 'AvgD2 < AvgD3 when the value is larger than the average value AvgD2 of the diameter d2 of the smallest circle surrounding the grain boundary reaction phase. In this case, it will not damage the bending plus For example, regarding the grain boundary reaction phase A shown in Fig. 2, the circle 13 is the largest circle surrounded by the grain boundaries of the crystal grains surrounding the grain boundary reaction phase. <Use> Copper of the present invention The alloy can be used as a variety of copper-stretching products, for example, a plate, a bar and a wire. The titanium copper of the present invention is not limited, and can be preferably used as an electronic component such as a switch, a connector, a jack terminal, a relay, and the like. <Production Method> The copper of the present invention can be produced by performing appropriate heat treatment and cold rolling in particular in the final solution treatment and subsequent steps. Hereinafter, suitable production will be described in order of each step. Example: 1) The manufacture of ingots is carried out by melting and casting the ingots, basically in a vacuum or in an inert gas environment. If there is a 70-thick melting residue in the dazzling solution, it does not contribute to the strength. Therefore, in order to remove the melting residue, the sample must be sufficiently searched after the third element of the contour is added, and A is kept for a certain period of time. On the other hand, Tian Yuyu is more soluble in cu. Therefore, I added I after refining the third element. , It is preferable that the total content 0~〇.50 is the mass% of the formula selected from the group consisting of Mn, Fe, Mg,

Two or more kinds of Ni, Cr, V, Nb, Mo, Zr, t D « η μ , Sl, B & P are added to Cu, followed by 2. The main Lu T ' and then 2 〇 ~4 〇% by mass of 10 201118181 Ti is added to Cu to make ingots. 2) Homogenization annealing and hot rolling are reduced by solidification segregation or coarser crystals produced during the production of bonds, so they are reduced in the mother phase by homogenization annealing. Remove it. The reason is that it is effective for preventing bending cracking. Specifically, it is preferable to perform homogenization annealing after heating to 900 to 970 c after the production step of the ingot, and then perform hot rolling. In order to prevent the liquid metal brittleness, it is preferably set to 960 ° C or lower before hot rolling and hot rolling, and the pass rate from the initial thickness to the overall rolling reduction ratio of 90% is set to 900 ° C or higher. Further, in order to effectively reduce the segregation of D1 in order to generate moderate recrystallization in each pass, it is sufficient to carry out the rolling reduction per pass at 10 to 20 mm. 3) First solution treatment Thereafter, it is preferred to carry out the solution treatment after cold rolling and annealing as appropriate. The reason for preliminarily solidifying here is to reduce the burden in the final solution treatment. That is, the final solution treatment is not a heat treatment for solid-solubilizing the second phase particles, but is solid-solved, so that only one side of the surface can be recrystallized while maintaining this state, so that a slight heat treatment can be performed. Specifically, the t ′ first-solution treatment treatment may be carried out by setting the heating temperature to 850 to 900 ° C ' 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 rolling 11 201118181 The higher the rolling reduction rate in the intermediate rolling before the final solution treatment, the more uniform and finely formed recrystallized grains in the final solution treatment, so the rolling reduction of the intermediate rolling is set. Got higher. It is preferably 7 〇 to 99%. The rolling reduction ratio is defined by {((thickness before rolling, thickness after rolling V, thickness before rolling) XI 〇〇% }. 5) Final solution treatment in the final solution treatment, it is preferred to The precipitate is completely solid solution', but if it is heated to the high S of complete removal, the crusted particles are easily coarsened, so the heating temperature is set to the vicinity of the solid solution limit of the second phase particle composition (addition of Τι The amount is 2 〇~4 〇 mass. Within the range, the solid solution limit of Ding 复 is the same as the addition amount of 73〇~84〇, for example, when the addition amount of h is 3.2% by mass & .c or so). Further, if the temperature is rapidly heated to this temperature and the cooling rate is also accelerated, the coarse second phase particles are obtained. The production of the child will be suppressed. Therefore, it is more typical to heat up to 73〇~_ CTi gU tolerance will become the same as the temperature of the same amount of Sha added, more typically two to 730~880 C Ti solid solubility limit will become the same amount of temperature 2 〇C, preferably heated to 0~10. (: the temperature. The shorter the heating time in the final solution treatment, the finer the crystal grain is. The heating time can be set, for example, to 3 () to 9 () seconds, which is more typical; Preferably, at this time point, the second phase granule is not generated as much as possible: the cooling rate is faster, and the cooling stability is more favorable in terms of operational stability. 6) aging treatment final solid solution The treatment is followed by aging treatment. Although it has been conventionally performed after the solution treatment at the end of 201112181, in order to obtain the copper of the present invention, it is preferred to perform the aging treatment without cold rolling after the final solution treatment. . Previously, in order to maintain elongation and obtain high strength: cold rolling with high workability was performed, but bending workability was deteriorated. If the degree of machining is lowered in order to maintain the bending workability, not only the distribution of the strain becomes uneven, but also the strength rise is small. The reason is that if the cold rolling is performed at a low degree of work before the aging treatment, the processing strain is easily distributed unevenly and the formation of the modulation structure becomes uneven, and the resistance to the bending strain is weakened, not only the grain boundary reaction phase but also Hard to expand. The aging treatment can be carried out at a temperature slightly higher than the conventional aging conditions so that the stable phase of the Ti-system precipitated in the grain boundary reaction is aggregated and the grain boundary reaction phase is grown to an appropriate size. When the low-temperature aging treatment is carried out, the grain boundary reaction phase grows along the grain boundary (A becomes large) and grows thinner toward the inside of the grain (di is smaller), so Avg (D2/Di) tends to become large. Specifically, it is preferably heated at a material temperature of 400 to 500 〇c for 2 to 2 hours, more preferably at a material temperature of 400 to 480X: heating for 1 to 16 hours. 7) Final cold rolling After the above aging treatment, the final cold rolling is performed. The strength of the titanium copper can be raised by the final cold working. The cold rolling may not be carried out, but the rolling reduction ratio is preferably 5% or more, more preferably 10% or more, and still more preferably 15% or more for the purpose of obtaining titanium copper of higher strength. However, if the shrinkage ratio is too high, the aspect ratio of the grain boundary reaction phase becomes too large, so the rolling reduction ratio is 40% or less', preferably 30% or less, more preferably 25% or less. 8) Strain annealing According to the construction of electronic parts, different shapes are required. Usually applied 13 201118181 Plastic deformation parts such as bending or notch processing will work harden, and the strength of the material will be further improved. In this way, the structure of the engine is ensured that the structure of the connection is not easily plastically deformed, so that a high spring elastic elastic Hmit is not required. Therefore, in such an application, it is also possible to: perform strain relief annealing. The other side, to the rush; 1 shape after processing will not be plastic, the part of the deformation to ensure the structure of the joint (for example: from the joint of the terminal to the bending process; the distance of the straight part (arm) A long structure, or a configuration in which a notch process or a f-bend process is not applied as a re-type terminal, that is, a structure in which a bending stress is applied to a support arm)" because a resistance to bending deformation is required, so a high spring bend is required. The elastic limit becomes important. = Therefore, especially in applications where the spring bending elastic limit is important, the strain relief annealing is performed after the final cold rolling. It is preferable to bend the spring especially when the final cold rolling reduction ratio is 3% or more. De-strain annealing is performed in applications where the elastic limit becomes important. In addition, the best rate for the final cold is 1 〇 /. In the above case, strain relief annealing is performed in applications where the spring bending elastic limit becomes important. The difference distribution introduced in the cold slab = uniform', but by performing strain relief annealing, the difference rows are rearranged, thereby progressing to increase the strength. However, if the strain relief annealing is excessively performed, the difference is lost and the strength is lowered, which is not preferable. The condition of the strain relief annealing may be a conventional condition. Specifically, it is preferably 2 X at a material temperature of 2 〇 (rc or more and is not reached. c plus # 〇 deleting ~ small, the condition is carried out, if it is low temperature, then More preferably, it is carried out under the conditions of a long time (for example, a material temperature of 2 0 〇~3 〇〇. i C heat of 12 to 20 hours), and if it is high temperature, 14 201118181 is more preferably a short time (for example, at a material temperature) The conditions of 3〇〇~4〇〇r heating 〇_~12 hours). Further, if it is a person skilled in the art, it should be understood that the scale of the surface can be appropriately removed between the above steps. The steps of grinding, grinding, bead blasting, etc. [Examples] The following examples and comparative examples of the present invention are shown, but are provided for a better understanding of the present invention and its advantages, and are not intended to In the case of producing the copper alloy of the present invention, the active metal is added as the second component. Therefore, a vacuum melting furnace is used for the dissolution. Further, in order to prevent the occurrence of the elements specified in the present invention. Produced by impurity elements For the side effects, the original (4) is strictly selected to be used with higher purity. For the addition of Ti in the concentration shown in Table 1, the remaining part is composed of copper and unavoidable impurities. After homogenization annealing for an hour, hot rolling is performed at 900 to i * 95 〇c to obtain a hot-rolled sheet having a thickness of 10 faces. After the skin is cut by plane cutting, lyophilization is performed to form a slat sheet. Thickness (2_〇mm)' and the i-th solution treatment in the slat state. The conditions of the first solution treatment were set to be heated for ig minutes in the 85th generation. The money sheet was not subjected to the i-th solution treatment. Then, in the middle of the cold, the final plate thickness of the cold rolling is adjusted so that the final thickness reaches 〇.1〇_, and then inserted into a rapidly heated annealing furnace for final solution treatment. After that, it is cooled with water. The heating condition at this time is that the material temperature becomes the same temperature as the addition amount in the solid solution limit of the butyl hydrazine (about 峨 at a Ti concentration of 32% by mass, and about 7 at a τπ agronomic degree). η Moment is 15 201118181 4.0 when the mass is set to about MOt) as a benchmark as noted in Table 1. The heating condition was kept for 1 minute (see Table 1). Then, the test piece was subjected to cold-rolling after solution treatment under the conditions recorded in Table 1, and then described in Table 1 in the Ar gas environment. The conditions were subjected to aging treatment. After the scale was removed by pickling, the final cold rolling was carried out under the conditions described in Table 1, and finally annealed under the heating conditions recorded in Table 1 to prepare the inventive examples and comparative examples. [Table 1 - 1] Composition of manufacturing conditions Ti concentration (wt%) Solution treatment (first time) Solution treatment (final) Rolling reduction after solutionization aging treatment Final rolling reduction ratio Annealing Previous Example 3.2 850 〇 C 600 s 820 〇 C 60 s 24% 400. . 3 h 0% - Previous Example 3.2 850〇C 600 s 820〇C 60s 29% 400°C 3h 0% - Previous Example 3.2 850〇C 600 s 820〇C 60s 47% 400°C 3h 0% - Previous Example 3.2 850〇C 600 s 820〇C 60s 24% 380〇C 3h 0% - 16 201118181 [Table 1 - 2] Composition of manufacturing conditions Ti concentration Subcomponent solid solution treatment Solution treatment Final pressure aging treatment Extension rolling annealing (wt% (wt%) (1st) (final) Shrinkage Example A 3.2 - No 820 °C 60s 450 °C 5h 0% None Example B 3.2 - No 820〇C 60s 450〇C 5h 5% No implementation Example c 3.2 - No 820〇C 60s 450〇C 5h 20% No Example D 3.2 - No 820〇C 60s 450°C 5h 40% No Example E 3.2 - No 840〇C 60s 450〇C 5h 0% None Example F 3.2 - No 840 ° C 60 s 450 〇 C 5h 5% No Example G 3.2 - , No 840 ° C 60 s 450 〇 C 5h 20% No Example Η 3.2 - No 840 〇 C 60 s 450 〇 C 5h 40 % None Example 1 3.2 - 850〇C 600 s 820〇C 60s 450〇C 5h 0% None Example J 3.2 - 850〇C 600 s 820〇C 60s 450〇C 5h 5% No ExampleΚ 3.2 - 850 °C 600 s 820°C 60s 450〇C 5h 20% No Example L 3.2 - 850〇C 600 s 820〇C 60s 450〇C 5h 40% None Example 1 3.2 - 850〇C 600 s 820〇C 60s 450°C 5h 0% 300. . 0.008 h Example 2 3.2 - 850〇C 600 s 820〇C 60s 450°C 5h 5% 300°C 0.008 h Example 3 3.2 - 850〇C 600 s 820°C 60s 450°C 5h 10% 300°C 0.008 h Example 4 3.2 - 850 ° C 600 s 820 ° C 60 s 450 ° C 5 h 20% 300 ° C 0.008 h Example 5 3.2 - 850 ° C 600 s 820 ° C 60 s 450 〇 C 5 h 30% 300. . 0.008 h Example Μ 3.2 - 850 〇C 600 s 820°C 60s 450〇C 5h 40% 300. . 0.008 h Example Ν 3.2 - 850 ° C 600 s 820 〇 C 60 s 450 〇 C 5 h 0% 300 ° C 12 h Example 0 3.2 - 850 ° C 600 s 820 ° C 60 s 450 ° C 5 h 5% 300 ° C 12 h Example Ρ 3.2 - 850 ° C 600 s 820 〇 C 60 s 450 〇 C 5h 20% 300 ° C 12 h Example Q 3.2 - 850 〇 C 600 s 820 〇 C 60 s 450 〇 C 5h 40% 300 ° C 12 h Example R 3.2 - 850 〇 C 600 s 820 ° C 60 s 400 ° C 1 h 20% 300 ° C 0.008 h Example S 3.2 - 850 ° C 600 s 820 〇 C 60 s 400 ° C 1 h 40% 300 °C 0.008 h Example 6 3.2 - 850 〇 C 600 s 820 〇 C 60 s 400 ° C 16 h 20% 300 ° C 0.008 h Example 7 3.2 - 850 〇 C 600 s 820 〇 C 60 s 400 ° C 16 h 30 % 300 °C 0.008 h Example 8 3.2 - 850 〇 C 600 s 800. . 60s 480°C 1 h 10% 300°C 0.008 h 17 201118181

Composition Manufacturing Conditions Final Ti Concentration Subcomponent Solid Solution Treatment Solution Treatment Pressure Delay Treatment Annealing (wt%) (wt%) (1st) Rational (final) rolling reduction Example 9 3.2 - 850〇C 600 s 800 °C 60s 480〇C 1 h 20% 300°C 0.008 h Example τ 3.2 - 850 ° C 600 s 800 ° C 60 s 480 〇 C 16 h 20% 300 ° C 0.008 h Example 10 3.2 - 850 ° C 600 s 800 ° C 60 s 480 〇 C 1 h 30% 300 ° C 0.008 h Example U 3.2 - 850 ° C 600 s 800 ° C 60 s 480 ° C 1 h 40% 300 ° C 0.008 h Example V 3.2 - 850 〇 C 600 s 800°C 60s 480〇C 16 h 40% 300°C 0.008 h Example W 3.2 - 850〇C 600 s 840〇C 60s 450〇C 5h 5% 300°C 0.008 h Example X 3.2 - 850 〇C 600 s 840〇C 60s 450〇C 5h 20% 300°C 0.008 h Example Υ 3.2 - 850〇C 600 s 840〇C 60s 450〇C 5h 40% 300°C 0.008 h Example 11 3.2 - 850 〇C 600 s 840 ° C 60 s 450 ° C 5 h 30% 300 ° C 0.008 h Example 12 3.2 - 850 ° C 600 s 860 〇 C 60 s 450 ° C 5 h 20% 300 ° C 0.008 h Example 13 2.2 - 850 〇C 600 s 780°C 60s 480°C 1 h 20% 300°C 0.008 h Example 14 4.0 - 850 〇 C 600 s 840 〇 C 60 s 400 ° C 16 h 10% 300 ° C 0.008 h Example Ζ 4.0 - 850 〇 C 600 s 840 〇 C 60 s 400 ° C 16 h 30% 300 ° C 0.008 h Example 4.0 ' 4.0 - 850 〇 C 600 s 880 〇 C 60 s 400 ° C 16 h 30% 300. . 0.008 h Example 15 3.2 0.2Fe 850〇C 600 s 820〇C 60s 450°C 5h 20% 300°C 0.008 h Example 16 3.2 0.05Zr, O.lCr 850〇C 600 s 820°C 60s 450〇C 5h 20% 300°C 0.008 h Example 17 3.2 O.lCo, 0.05Si 850°C 600 s 820〇C 60s 450°C 5h 20% 300°C 0.008 h 18 201118181 [Table 1-4]

Conduct a characteristic evaluation. The results of the respective test pieces obtained under the following conditions are not in Table 2. &lt;Strength&gt; A test piece was prepared in such a manner that the stretching direction was parallel to the rolling direction. The tensile test of the test piece was carried out in accordance with JIS - 2241, and the G. 2% versus force (YS) in the parallel direction of the rolling was measured. &lt;Bending workability&gt; The W bend test in which the Badway (the bending axis and the rolling direction are the same direction) is measured according to 1S Ή 3 130 ', and the ratio of the minimum radius (mbr) to the plate thickness (t) is not generated. MBR/t value. 19 201118181 <Average crystal grain size> The measurement of the average crystal grain size is obtained by cutting the cross section to expose the number of crystal grains per unit area after the cross section. Specifically, the number of crystal grains present in the frame was made 100. The cross section was observed by SIM in parallel with the rolling direction by FIB, and a frame of an approximate circle of /mxlOO of the average of the crystal grains was calculated and calculated. Further, the crystal grains which traverse the frame are counted as 1/2. The area of the frame 1 〇〇〇〇 v divided by the total number of crystal grains is the average of the area of each crystal grain. Since the direct control of the perfect circle having the area is an approximate circle diameter, it is set as the average crystal grain size. &lt;Grain boundary reaction phase&gt; After the cross section parallel to the rolling direction was cut by FIB, the cross section was exposed, and the cross section was observed by SIM, and the observation field 丨〇〇 &quot; mx丨〇〇 々 m was taken. By affiliated EDS (Energy Dispersive x_ray

Spectrometer) confirms that the black portion of the speckle pattern constituting the grain boundary reaction phase is T i C u 3 . Regarding the respective grain boundary reaction phases, the diameter Di of the largest circle surrounded by the grain boundary reaction phase and the straight line Da' of the smallest circle surrounding the grain boundary reaction phase were respectively determined on the photograph, and 〇2 was obtained for each grain boundary reaction phase. /〇1. D2/D is obtained for all the grain boundary reaction phases of the measurable D! and D2 included in the observation field, and the average value is set to Avg (D2/D〇. Further, the measured enthalpy and D2 are determined. The average value is set to AvgDt and AvgD2, respectively. Further, the diameter D3 of the largest circle surrounded by the grain boundary of the crystal grain is measured on each crystal grain surrounding the grain boundary reaction phase, and will be examined at 20 201118181. : In the middle, the average value of all D3 is set to A*. The V-like knife is used to determine the area occupied by the grain boundary reaction phase in the above-mentioned photograph of 1000" m2 observation field, and calculate 5 P position. The average value is set as the area in the observation field per 1 000 &quot; m2 of the grain boundary reaction phase. &lt;Spring bending elastic limit (Kb) &gt; Spring bending elastic limit (Kb) is based on JIS H3 130 ( Alloy No. C1990), repeated bending test was carried out, and the maximum surface stress was measured according to the bending moment of residual permanent strain. 21 201118181 [Table 2 - 1] Structural characteristics Avg. (D2/D,) Avg.D 丨(/zm) Grain boundary reaction phase area / 1000 μ m2 (%) Avg.D2 (μπι) Average crystal grain size (//m) Avg.D3 (/ / m) Strength (MPa) Curve Kb (MPa) Previous Example 1 4.3 0.3 2.2 1.3 15 11 845 1 634 Previous Example 2 9.0 0.2 2.4 1.8 15 8.3 856 2 642 Previous Example 3 58.8 0.2 4.1 11.8 15 6.0 878 3 659 Previous Example 4 6.0 0.1 0.8 0.6 15 11 805 1 604 22 201118181 [Table 2 - 2] Structural characteristics Avg. (D2/D,) Avg.D, (//m) Grain boundary reaction phase area / 1000 gm2 (%) Avg.D2 (ym) average crystal grain size ((iv) Avg_D3 (gm) strength (MPa) distortion Kb (MPa) Example A 1.4 1.3 2.6 1.9 13 12 816 0 561 Example B 2.1 0.9 2.8 1.9 13 10 855 0.2 492 Example c 2.7 0.8 2.6 2.1 13 7 1023 1.4 256 Example D 2.8 0.8 2.6 2.1 13 5 1028 1.8 154 Example E 1.4 1.3 1.7 1.9 21 19 821 0 564 Example F 2.1 0.9 1.7 1.9 21 16 857 0.2 493 Example G 2.7 0.8 1.7 2.1 21 11 1028 1.6 257 EXAMPLES 2.8 0.8 1.7 2.1 21 9 1038 1.9 156 Example I 1.4 1.3 2.1 1.9 16 14 825 0 567 Example J 2.1 0.9 2.3 1.9 16 12 854 0.0 491 Example κ 2.7 0.8 2.1 2.1 16 9 1032 1.2 258 Example L 2.8 0.8 2.1 2.1 16 7 1042 1.7 156 Example 1 1.4 1·3 2.1 1.9 16 14 835 0 574 Example 2 2.1 0.9 2.3 1.9 16 12 863 0.0 594 Example 3 2.5 0,8 2.1 2.0 16 10 947 0.5 651 Example 4 2.7 0.8 2.1 2.1 16 9 1040 1.2 715 Example 5 2.8 0.8 2.1 2.1 16 7 1049 1.7 721 Example Μ 2.8 0.8 2.1 2.1 16 7 1056 2.1 726 Example Ν 1.4 1.3 2.1 1.9 16 14 840 0 630 Example 0 2.1 0.9 2.3 1.9 16 12 867 0.0 651 Example 2.7 2.7 0.8 2.1 2.1 16 9 1046 1.2 785 Example Q 2.8 0.8 2.1 2.1 16 7 1055 1.7 792 Example R 2.9 0.5 1.5 1.4 16 9 1005 1.0 691 Example S 2.9 0.5 1.5 1.4 16 8 1016 1.0 699 Example 6 5.1 0.5 1.6 2.5 16 8 1018 1.0 700 Example 7 5.4 0.5 1.6 2.5 16 6 1029 1.6 708 Example 8 3.4 1.4 9.1 4.6 10 7 936 0.4 644 23 201118181 [Table 2 - 3] Structural characteristics Avg. (D2/D,) Avg.D, (ym) Grain boundary reaction phase area / 1000 μ m2 (%) Avg.D2 Um) Average crystal grain size ((iv) Avg.D3 (//m) Strength (MPa) Distortion Kb (MPa) Example 9 4.0 1.3 9.1 5.2 10 6 995 1.0 684 Example T 4.0 1.3 14.8 5.2 10 6 987 1.3 679 Example 10 4.2 1.3 9.1 5.4 10 4 1007 1.1 692 Example U 4.2 1.3 9.1 5.4 10 7 1015 1.1 698 Example V 4.2 1.3 14.8 5.4 10 6 1023 1.8 703 Example W 2.1 0.9 1.7 1.9 25 24 856 0 589 Example X 2.7 0.8 1.7 2.1 25 21 1033 1.4 710 Example Y 2.8 0.8 1.7 2.1 25 8 1042 1.9 716 Example 11 5.4 0.4 1.7 2.3 25 10 1047 1.8 720 Example 12 4,5 0.4 1.6 1.8 29 17 1083 2.2 745 Example 13 2.2 0.6 1.6 1.3 18 11 917 0.4 630 Example 14 2.7 1.8 13.3 4.8 6 5 1065 2, 2 732 Example Z 2.7 1.8 13.3 4.8 6 5 1080 2.4 743 Example A' 2.7 1.8 5.3 4.8 15 13 1060 2.1 729 Example 15 2.7 0.8 2.1 2.0 14 8 1071 1.8 736 Example 16 2.7 0.8 2.2 2.1 15 9 1081 2.2 743 Example 17 2.8 0.8 2.2 2.2 14 7 1049 1.4 721 24 201118181 [Table 2 — 4]

&lt;Inspection&gt; In the prior examples 1 to 4, the stable phase of the Ti_cu system was dispersed in the Cu matrix phase in the form of undissolved particles at the grain boundary, and cold rolling was performed between the final solution treatment and the aging treatment. For example, in this case, the growth of the grain boundary reaction phase is small, and the area ratio is also small. The balance between strength and bending workability is also poor. Examples 1 to 17 are examples in which aging treatment is carried out without cold rolling after the final solution treatment. In the examples 丨~7, the final solution treatment was fixed to 820 C x 60 s to change the conditions of aging treatment and final calendering. It can be seen that the balance between the strength and the tortuous workability is remarkably improved as compared with the previous examples. Further, from Examples 1 to 5 or Examples 6 to 7, it is understood that AvgCDVD, as the final rolling shrinkage rate increases, also increases. In the examples 8 to 10, the final solution treatment was carried out as an example. Compared with the examples i to 7, the average particle diameter was decreased in the examples η to ΐ2, and the temperature of the final HI dissolution treatment was increased. Therefore, the average particle diameter is increased as compared with the embodiment of the work-7. As is apparent from Examples 13 and 14, when the Ti concentration is increased, the strength tends to increase. Examples 15 to 17 are examples in which a third element is added. It is understood that the effect of the present invention is maintained even if the second element is added. In the examples A to Η, the i-th solid solution treatment and the strain relief annealing were not performed, but the titanium copper of the present invention excellent in balance between strength and bending workability was obtained. However, since the strain relief annealing is not performed, the Kb value is small as compared with the case where the strain relief annealing is performed. In Examples I to L, although the strain relief annealing was not performed, the titanium copper of the present invention excellent in balance between strength and bending workability was obtained. Similarly, the Kb value was smaller than that of the Example Μ, and the final rolling reduction ratio was increased to 40% with respect to Example 5, and the strength was slightly increased. In the examples Ν to Q, in comparison with Examples 1 to 5 and Μ, the elongation annealing time was extended, and it was found that the spring bending elastic limit was slightly improved when compared at the same rolling reduction ratio. 26 201118181 Examples R and S are aging treatments on the low temperature side. Although the area of the grain boundary reaction phase is reduced compared with Example 4 and Μ, the balance between strength and bending workability is still superior to the comparative example. . The examples are an example in which aging treatment is carried out for a long period of time as compared with Example 9. Although the area of the grain boundary reaction phase is increased, the balance between strength and bending workability is still superior to the comparative example. Example U is an example of improving the final cold-shrinking ratio compared with Example 9. Although the diameter A of the smallest circle surrounding the grain boundary reaction phase is slightly large, the balance between strength and bending workability is still superior to comparison. example. In Example V, compared with Example 9, the aging treatment time was longer and the cold rolling reduction ratio was higher, but the balance between strength and bending workability was still superior to the comparative example. In the implementation of your I W ~ wipes, the average crystal grain size is slightly larger due to the temperature at which the final solution treatment is set on the side of the product, but the balance between strength and bending workability is still superior to the comparative example. In the examples, the titanium concentration of the present invention is such that the Ti concentration is 4% by mass. However, the titanium copper of the present invention having excellent balance between strength and bending workability can be obtained. Comparative Examples 1 to 8 are examples in which aging treatment is carried out without cold rolling after the final solution treatment in the same manner as in the examples, but the heat treatment conditions and/or rolling conditions of either of them are not suitable. The bending processability is not sufficiently improved. Compared with the first example, the temperature of the solid solution treatment is too high, so the grain boundary reaction phase is coarsened, and the area ratio of the grain boundary reaction phase is large, and the grain size is also large. 27 201118181 Fruit; 5廄Γ例2系' Because the rolling reduction rate in the final calendering is too high, the grain boundary reaction phase and crystal grains are flattened. In the car 3 series, the grain boundary reaction phase is flattened because the rolling reduction rate in the final rolling is too high. Since the solution treatment temperature is high, the crystal grains are large. Since the crystal grain size is larger, the grain boundary area is decreased, and the grain boundary reaction phase change i is the same, and the area ratio of the grain boundary reaction phase is decreased. In the case of the 4 series, since the solid solution treatment temperature is low, the crystal grains become small, and since the rolling reduction ratio in the final rolling is too high, the grain boundary reaction phase and the crystal grains are flattened. Comparative Example 5 is due to the excessively high rate of shrinkage in the final calendering.

The boundary reaction phase and the crystal grain are flat, and the L-structure is decimated. Moreover, since the aging temperature is too high, the grain boundary reaction phase is coarsened. In Comparative Example 6, the grain shrinkage rate in the final calendering is too high, so the grain is too high. The boundary reaction phase and '". The sundial is flattened. χ ′ Because the solution treatment temperature is too high, the temperature is too high, and the grain boundary reaction phase is coarsened, and the grain boundary reaction phase has a large area ratio and the crystal grains are also large. In Comparative Example 7, since the solid solution treatment temperature is low, the crystal grains become small. Since the aging treatment temperature is high, the grain boundary reaction phase is coarsened, and since the rolling reduction rate in the final calendering is too high, the grain boundary reaction The phase and the crystal grains are flattened. In Comparative Example 8, since the solid solution temperature was too high, the crystal grain size was coarsened. Although the desired aging treatment was carried out, the grain boundary reaction phase was flattened by the formation of the reaction phase along the grain boundary. Since the particle diameter is large, the distance from the diffusion to the grain boundary in the aging treatment becomes long, and the supply of Ti 28 201118181 atoms to the reaction phase is insufficient, and thus the area ratio of the grain boundary reaction phase is low. In Comparative Example 9, since the aging treatment temperature was low, Avg (D2/D|) was increased and the shape of the grain boundary reaction phase was not appropriate, and the bending was deteriorated. In Comparative Example 10, since the aging treatment temperature was too high, AvgD2 was increased and the grain boundary reaction phase was coarsened. Comparative Examples 11 to 1 3 were used and the aging treatment temperature was changed. The area ratio is also inappropriate. The solution treatment temperature was set to be low, and in addition to the smaller crystal grain size, the grain boundary reaction phase comparison example A reduced the rolling reduction ratio in the final cold rolling with respect to Comparative Example 8, but compared with the comparative example. When 8 is the same, the crystal grain size is coarsened, and Avg (D2/Di) is also increased. Comparative Example B is an example in which the reduction ratio in the final cold is reduced with respect to Comparative Example 10, but Avg (D2/Dl) is still large, and the balance is not obtained. [Simple description of the diagram] Figure 1-1 shows an example of the grain boundary reaction phase A observed by an electron microscope. Figure 1 - 2 is a diagram of reducing the magnification of Figure 1-1. [Explanation of main component symbols] 11 The largest circle surrounded by the grain boundary reaction phase 12 The smallest circle surrounded by the grain boundary reaction phase 13 The largest circle surrounded by the ancestors of the grain 1 α ^ 7 surrounding the grain boundary reaction phase Α grain boundary reaction phase 29

Claims (1)

201118181 VII. Patent application scope: 1. A copper alloy for electronic parts, which contains 2.0 to 4.0% by mass of Ti, and the remainder is composed of copper and unavoidable impurities; or 2.0 to 4% by mass. Further, Ti is further contained in a group consisting of Mn 'Fe, Mg, Co, Ni, Cr, V, Nb, Mo ' Zr, Si, B, and P which are 第 0.5 0.5% by mass of the third element group. i or more than two, and the remainder is composed of copper and unavoidable impurities; when the microstructure parallel to the cross section of the rolling direction is observed by an electron microscope, 'there is a grain containing Ti-Cu-based particles precipitated along the grain boundary The boundary reaction phase, the average value Avg of the ratio (D2/D,) of the diameter D2 of the smallest circle surrounding the grain boundary reaction phase of each grain boundary reaction phase to the diameter a of the largest circle surrounded by the grain boundary reaction phase (D2/D) D2/D丨) is 1〇~6〇' The average value of 〇1 is 〇·4~2.0 Am, and the 'grain boundary reaction phase accounts for i.5~15% of the area of view. 2. The copper alloy of the i-th aspect of the patent application, wherein the average value of D2, AvgD2, is ι·〇~5 〇 μ m when the microstructure of the cross section parallel to the rolling direction is observed by an electron microscope. 3_For example, in the first application of the patent scope, the steel alloy of the two brothers, in which the microstructure parallel to the profile of the pressure, the sputum, and the sag is observed by an electron microscope, the granules are only The diameter table of the approximate circle, M ^ ^ is 5^m or more, and the number of days around the grain boundary reaction phase is 4 Ρή ^ m ^ ^, and 0 day, under the 30/zm, the grain of the crystal grain The diameter of the largest circle surrounded by d3 AvgD3 〇 Thousand mean AvgD3 is AvgD2 4. A steel-stretched product consisting of a copper alloy of any one of claims 1 to 3 of claim 30 201118181. (5) - A type of copper alloy having any one of claims 1 to 3. A connector of the present invention has a copper alloy as claimed in any one of claims. 7. A method for producing a copper alloy for an electronic component, comprising the steps of: having 2.0 to 4.0% by mass of Ti for 3, and the remaining portion of copper alloy material composed of copper and unavoidable impurities, or containing 2. ~4〇% by mass of Ti' is further contained in total. ～5% by mass of one or two selected from the group consisting of Mn, Fe, Mg, Co, Ni, Cr, v, can, m〇, &amp;, ^ b and P of the third element group Above, and the remaining part is made of copper and a copper alloy material which is not made of impurities, and is heated to 73 〇 to 88 〇. The solid solution limit of the ruthenium t becomes a solution treatment 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 to 5 Torr (rc heating 〇.1 to 2 hours); After the aging treatment, the cold rolling is performed at a rolling reduction ratio of 〇~4〇%. 8. Drawings (as in the next page) 31