TW200949860A - Cu-ni-si alloy for electronic materials - Google Patents

Abstract

Corson alloy characteristics are improved by controlling the distribution profile of Ni-Si compound particles. Disclosed is a copper alloy for electronic materials comprising Ni: 0.4 to 6.0 mass% and Si: 0.1 to 2.0 mass%, and the remainder of which is composed of Cu and inevitable impurities, in which alloy for electronic materials, small Ni-Si compound particles with a particle size of 0.01 [mu]m or greater and less than 0.05 [mu]m, and large Ni-Si compound particles with a particle size of 0.05 [mu]m or greater and less than 5.0 [mu]m are present. The quantitative density of the small particles is 106 to 1010 particles per 1 mm2, and the quantitative density of the large particles is 1/10,000 to 1/10 the aforementioned quantitative density of the small particles.

Description

200949860 VI. Description of the Invention: Field of the Invention The present invention relates to a Cu-Ni Si-based alloy which is suitable for use in various electronic machine parts. [Prior Art] σ For the electronic materials _ alloys of (4) in various electronic equipment parts such as lead frames, connectors, pins, terminals, relays, switches, etc., it is required to have both high strength and high electrical conductivity (or thermal conductivity). Basic properties. In recent years, the high integration and small (10) and thinning of electronic components have been rapidly developed. The corresponding requirements for copper alloys used in electronic equipment parts are gradually increasing. In recent years, in recent years, in place of a solid solution-strengthened copper alloy represented by copper, yellow steel or the like which is a copper alloy for an electronic material, the use amount of the precipitation hardening type copper alloy is increasing in view of high strength and high electrical conductivity. For the precipitation hardening type copper alloy, # is subjected to aging treatment of the solution-treated supersaturated solid solution, so that the fine precipitates are uniformly dispersed, and the strength of the gold becomes high while the solid in the copper is solid. The amount of dissolved elements reduces the conductivity. Therefore, a material excellent in mechanical properties such as strength and elasticity and excellent in electrical conductivity and thermal conductivity can be obtained.

Among the precipitated hardened copper alloys, a Cu-Ni-Si纟 copper alloy which is generally called a Carson-based alloy has a relatively high copper alloy which is excellent in electrical conductivity, strength, stress relaxation property and bending workability, and It is one of the alloys currently being developed in the industry. This copper alloy improves strength and electrical conductivity by depositing fine & intermetallic compound particles into a copper matrix. 3 200949860 Impact. The precipitation state of the Ni-Si compound particles is caused by the alloy characteristics. Patent No. 3,797,736 (Patent Document u, the particles of the in-service compound particles are pinched. The side is „上和二存3 "m (small particles) and Ni_Si compound particles The particle size is 〇〇3 in m~_ (large particles)' and the ratio of the number of small particles/A particles is set to 1.5 or more. • It also reveals that the small particle size of the particle size is less than G G3 # m It mainly improves the strength and heat resistance of the alloy, but it has little benefit for the shear processability. On the other hand, it also reveals that the large particles with the above particle size have little benefit for improving the strength and heat resistance of the alloy. However, when the shearing process is performed, the stress is concentrated and the source of the microcracks is generated, and the shearing workability is remarkably improved. Further, the copper alloy disclosed in Patent Document 1 has copper as an electric and electronic component. A copper alloy having excellent properties such as strength and heat resistance required for the alloy and having excellent shear workability. As a method for producing a copper alloy disclosed in Patent Document 1, the following has been disclosed. When the content is 4 wt% or more and the content of Si is 1 wt% or more, the crystal particles are particularly likely to be coarsened. Therefore, in order to make the size of the crystal particles within the target range, the solution is applied to the 1300 C after the addition of Si. The above temperature is maintained for 5 minutes or more, so that the two are completely dissolved, and the temperature in the mold is cooled from the casting temperature to the solidification temperature at a cooling rate of 0.3 ° C /sec or more. 2) The hot rolled material after the heat is delayed The mixture was quenched in water, and the cold-rolled material was heated for 5 minutes to 2 hours with 5〇〇200949860. The particles were precipitated. Thereafter, the cold was further carried out, and this time was carried out for 3 minutes (3) to _C for 30 minutes. The above is heated to precipitate small particles. 3) When cooling is performed after the completion of the hot rolling, the cooling is not performed, and the large particles are precipitated after being held for 5 minutes to 2 hours, and then quenched. After the delay, the small particles are precipitated by heating for 3 minutes or more, and the small particles are precipitated. Patent Document 3977376 (Patent Document 2) discloses that it is difficult to form a precipitate in a copper alloy structure, and the like. Precipitate The particle size of the object further focuses on the relationship between the distribution density and the coarsening of the crystal grains, and contains precipitates X composed of Ni and Si, and precipitates containing no or both of them. The substance γ, the particle size of the precipitate χ is set to 0.001 to 0.1 " m, and the particle size of the precipitate Υ is set to ....

It is set to 108 to 1012 pieces/mm2, and the number of precipitates γ is set to W. It is also revealed that the number of precipitates X is set to 20 to 2000 times of the precipitate Y in order to achieve both strength and bending workability. The method of producing a copper alloy disclosed in Patent Document 2 as the method of producing a copper alloy of 10!/mm2 has revealed the following. The casting key is subjected to a hot pressing delay, and the ingot is heated at a heating rate of 20 to 2 〇〇 ° c /, 丨, | w small - at 850 to 105 (TCx 0.5 to 5 昧 昧 μ "" And rolling the crucible between the crucibles, and setting the end temperature of the hot rolling to 300 to 700 t: and quenching, thereby generating precipitates X and Υ» after hot rolling, for example, solid solution heat = annealing, annealing, Cold rolling is combined to form a desired thickness. 5 200949860 The above-mentioned solution heat treatment is designed to heat-dissolve Ni and Si precipitated during casting or hot working, and to heat-treat the Si and recrystallize the above. The temperature of the solution heat treatment is adjusted according to the amount of the added amount, for example, the above temperature is 65 〇〇c when the amount of Νι is less than 2.0 to 2.5% by mass, and the temperature is 8 when the amount is less than 2.5 to 3.0% by mass. In the case of the Sui Dynasty, the above temperature is 85 〇 when the amount is less than 3 〇 to 3.5% by mass. The above temperature is 900 when the amount is less than 3 $ 〇 mass %. The amount of Ni is less than 4.0 to 4.5 ❶ / When the temperature is 95 (the amount of TC 'Ni is 4.5 to 5 〇 mass%, the above temperature is 9 峨. [Patent Document 1] Japanese Patent 3 In the case of the copper alloy disclosed in Patent Document 1, only the ratio of the number of small particles to large particles is studied. The number density of the particles is not involved. Further, in Patent Document 1, the large particles and the small particles are separately precipitated by performing the aging treatment twice, but the second particles which are precipitated for the second time are compared with the first time because Since the concentration of Ni and Si in solid solution is low, precipitation is difficult, and since the number density and the particle diameter are small, the beneficial effect on the strength is not sufficient (refer to Comparative Example 5 below). The method of aging treatment also has the following problem: the amount of Ni and Si dissolved in solid solution changes due to the first aging treatment. Therefore, it is difficult to control the particle diameter and density. In the copper alloy disclosed in Patent Document 2, only The particle size of the N "si compound particles is controlled within the range of 〇·〇〇1~0·1/ζηι, and the influence of the Ni-Si compound particles having a larger particle size on the alloy properties has not been studied. 200949860 Patent The large particles disclosed in 2 do not contain precipitates of one or both of Ni and Si. Such large particles are coarsened by the amount of added elements or temperature conditions, and are easily adversely affected by bending workability ( Reference is made to the following Comparative Examples 1 5, 16 and 17). Therefore, an object of the present invention is to improve the characteristics of the Carson-based alloy by more strictly controlling the distribution state of the Ni-Si compound particles. In order to solve the above problems, the inventors have intensively studied and found out that the Ni-Si compound particles precipitated into the copper matrix are classified into particles which are mainly liable to be precipitated into the crystal grains. Ni-Si compound particles (small particles) which are not more than #m, and Ni-Si compound particles (large particles) which are mainly precipitated to the grain boundary and have a particle diameter of 〇·〇5 or more and less than 5.0 //m In addition, the size and the number density of each are controlled, whereby a card bond alloy excellent in balance between strength and conductivity and excellent in bending workability can be obtained. Specifically, the inventors have found that an effective method is to control the small particles to a size of 0.01 or more and less than the range of 〇〇5, and control the number density thereof to 106 to 1 〇ι〇/mm2, and The large particle is controlled to be 0.05 μm or more and less than the range of 5.〇, and the number density thereof is set to 1/1 〇〇〇〇 to 1/1 〇 of the number density of the small particles. One aspect of the present invention which is completed based on the above findings is a copper alloy for an electronic material containing Ni: 0.4 to 6_0% by mass and Si: i to 2.0 mass. /〇, and the remainder consists of cu and unavoidable impurities, which have a particle size of 〇.〇1 or more and do not reach &5 " claws with small particles of compound and particle size of 〇〇5 or more And less than 5 〇 to the claw 7 200949860

Large particles of Ni-Si compound, small particles/mm2, the number density of large particles is 1/10000~1/1〇0, and the number density is 1〇6~1, the number density of the above small particles In the embodiment of the present invention, the average particle diameter of the large particles of the copper alloy for electronic materials of the present invention is 100 with respect to the average grain size of the small particles. % 1〜 In another specific embodiment, the thickness of the square crystal grain parallel to the rolling direction is represented by the corresponding circle diameter. When the copper alloy for electronic material of the present invention is observed in the cross section, the average knot is 5 to 30 m. . In another embodiment, the copper alloy for an electronic material of the present invention further contains a total of U mass% selected from the group consisting of Cr, C〇, Mg, and Mn.

One or more of Fe, Sn, Zn' A1 and P. In another aspect, the present invention relates to a copper-clad product comprising the copper alloy for an electronic material of the present invention. In another aspect, the invention relates to an electronic component comprising the steel alloy for an electronic material of the invention. EFFECTS According to the present invention, it is possible to more effectively enjoy the benefits of Ni-Si-formed particles which are precipitated into a copper matrix, which can improve the characteristics of the alloy. [Embodiment]

Si addition axe

Nl and Si can form a Ni-Si compound particle (Ni2Si or the like) as an intermetallic compound by performing appropriate heat treatment, thereby achieving high strength without deteriorating the conductivity of 200949860. If the amount of addition of Si or Νι is too small, the amount of addition is too large, although it can be practical, and the required strength is obtained. If it is added, the hot workability is lowered. Further, the strength is increased, but the electrical conductivity is remarkably lowered, and the pores are formed from the time of creation. The reason is that it is dissolved in the sin and becomes dissolved. When the intermediate processing is performed, if the amount of addition is increased, the amount of addition may be a reaction. Therefore, if s. * reacts with C or with hair ❹ φ, so that when f is curved, the amount of the bow is increased, and a large amount of inclusions are formed. Therefore, the appropriate Sii^, the amount is 〇. 1~2_〇quality ❶/〇, preferably Jb 〇9 〜1.5% by weight. Appropriate M. This is only 5%. The amount of 敉佳 is 0.2 添加.4~6.0% by mass, preferably 1.0~5.0% by mass. 执ί王两N i - S The precipitates of the compound particles + tt sub-groups are generally composed of stoichiometry, so that the Ni and Si 皙 皙 屮 匕 置 置 置 置 置 置 置 而 而 而 而 而 而 而 而 而 而 而 而 而 而 而 而 而 而 而 而 而 而 而 ( County, the atomic weight of Nl2Sl x2: the atomic weight of Si), also

The mass ratio of Ni to Si is XT./0. J Piif is Ni/Si = 3 to 7, preferably 3.5 to 5, so that good electrical conductivity can be obtained. When the ratio of Ni is higher than the above mass ratio, the conductivity is liable to decrease, and if the ratio is higher than the mass composition ratio, the hot workability is likely to be deteriorated by the coarse Ni Si crystal. Other vowel streams · h (1 ) Cr' Co

Cr and Co are solid-dissolved in Cu, and coarsening of crystal grains during the solution treatment is suppressed. Further, the Cr and c are used to increase the strength of the alloy. The formation and precipitation of telluride during aging treatment can also help to improve strength and electrical conductivity. These additions of τ agglomerates hardly reduce the conductivity, so they can be actively added. However, when the addition amount of 2009 9498 is too large, there is a risk of damage. Therefore, it is possible to add a total of 1.0% by mass of Cr and Co. One of them or both 'is preferably added 0·005~1.〇% by mass. (2) Mg> Μη

Mg or Μn will react with hydrazine' and thus the deoxidation effect of the glare liquid can be obtained. Further, in general, Mg or Μη is an element added as an element for increasing the strength of the alloy. The most famous effect is to improve the stress relaxation properties, which are called anti-potential properties. In recent years, with the high integration of electronic devices, there is a high current flow, and in semiconductor packages such as BGA (Ball Grid Array), which have low heat dissipation, there is a deterioration of materials due to heat. Oh, it becomes the cause of the malfunction. Especially in the case of the vehicle, there is concern that the heat around the engine causes deterioration, so heat resistance is important: For these reasons, the Mg4Mn system can be actively added with too much added amount, "can ignore the (four) eutectic effect caused by the refusal, so the total can be added up to 〇 _ 5% by mass and _ in: or both Preferably, it is added in an amount of 0.005 to 0.4% by mass. (3) Sn andan 畀 M Mg is dissolved in Cu in the same amount as the guest, W W differently, Sn

Sn. However, if Sn is added in the case of 曰1, a maximum of 0.5% by mass of 811 can be added, which is noticeably degraded. So %. However, when the adverse effects of the texture of 'σ 0·1 to 0.4 are both at the same time, the two are intended to suppress the conductivity: the maximum is 0.8% by mass. The maximum is set to U quality. /... 200949860

η Ζ

Zn has an effect of suppressing solder embrittlement, and the conductivity is lowered. Therefore, it is preferable to add Zn of at most 〇 5 mass%, preferably 〇. 1 to 0.4 mass%.

(5) Fe ' Al ' P These elements are also elements that increase the strength of the alloy. Add as needed. However, if the amount of addition is too large, the properties are deteriorated in accordance with the addition of the elements. Therefore, it is possible to add Fe to the mass of 0.5% by mass or more, preferably 0.005 to 4% by mass. What are the above Cr, Co, Mg, Mn, Sn, Fe, gossip and? When the total amount is more than 1% by mass, the manufacturing property is easily impaired. Therefore, the total amount of these is preferably 1.0% by mass or less, and more preferably 0.5% by mass or less. Compound_Dry in the present invention, the Ni-Si compound particles precipitated into the copper matrix are classified into small particles and large particles, and the respective number density and particle diameter of each of the particles are controlled to control the correlation therebetween. In the present invention, the so-called small particles are Ni-Si compounds with a particle size of 0.01 and no violation of 0·〇5, which means that the large particles 'have a particle size of 〇.05 or more and less than 5 ”: The dimeric particles, the small particles are mainly precipitated into the crystal grains, and the particles are precipitated to the crystal grain boundaries. Further, the so-called Ni_Si means that the particles are detected by elemental analysis. Φ shi π 〜 shame contributes to the strength and heat resistance of weilong, the main particles, the electrical conductivity and the refinement of the crystal grains. The Ni_Si compound particles precipitated into the crystal grains can generally become tens of 11 200949860 A fine precipitate of about nm, in which the Ni-Si compound particles which are not in the crucible 5 have a pinning effect of dislocation, and thus the dislocation density becomes the same as that of the whole alloy. Since the particle size of the Ni_Si compound particles has a small interparticle distance and a large number, the contribution rate to the strength is high, and the heat resistance is improved because it has a function of hindering the movement of the misalignment during heating.

However, if a large strain is applied, the particles of this extent, especially the Ni_Si compound particles which are less than 0.01", are sheared to reduce the surface area of the particles, so the force required for shearing is reduced. Therefore, the misaligned ring does not remain and the misalignment density cannot be increased. Therefore, it is difficult to provide strength to the Ni-Si compound particles which are less than 1 gram, and the sheared particles are again solid-dissolved in the copper matrix to cause conduction. Further, since the sheared particles do not function as nucleation sites for recrystallization, there is a possibility that the recrystallized grains become coarse and coarse, and coarse crystal grains may adversely affect strength or flexibility.

Therefore, it is advantageous to control the number density of small particles having a particle diameter of 〇.〇1 of (7) or more and not reaching. Small particles contribute more to the improvement of strength. However, in the case of small particles, the conductivity tends to decrease. Therefore, in order to achieve a balance between strength and conductivity, the number density of small particles must be set to . /mm2. The number density of small particles can be measured by tissue observation using a transmission electron microscope. On the other hand, the Ni-Si compound particles precipitated to the crystal grain boundaries are precipitates having a size of about several hundred nm to several. Among them, 〇〇5 m or more and less than 5.0 "n^Ni.Si compound particles can be used as hard particles not to be sold 12 200949860. e Ni_si compound particles can be used as small particles to enhance the strength and heat resistance of the alloy. Sex, but because of the larger particle size, the number of particles is smaller than that, and because of the large distance between particles, the contribution to strength and heat is smaller than that of small particles. However, even if a large strain is applied, it will not be Shearing, so that the conductivity is hardly lowered. Further, shearing the unsheared particles can function as a nucleation site at the time of recrystallization. Therefore, it is easy to form fine crystal grains by large particles. Fine crystal grains are particularly useful for strength and flexibility. If the particle size exceeds 5 逐步, the Ni&Si applied to form small particles will be insufficient and the strength will be easily lowered. When the material is subjected to Ag plating or the like, the plating thickness is locally thickened and there is a defect that causes a protrusion. Therefore, it is advantageous to control the number density of large particles of 0.05 or more and less than 5 Å. Large particles contribute to the refinement of crystal grains and the improvement of conductivity. On the other hand, if the number of large particles increases, the number density of small particles tends to decrease, so the ratio of the number of large particles to small particles is When it is not in the proper range, the strength and electrical conductivity cannot be balanced. In the case of a crucible, if the number of large particles increases, the strength decreases, and if the number of small particles increases, the conductivity decreases. Therefore, in order to achieve the balance between strength and conductivity, it is necessary to set the number density of large particles in the particle size range of 0.05 or more and less than 5. 设为 as 1/1 of the number density of small particles. 1/1〇. The number density of large particles can be measured by scanning electron microscopy for tissue observation. By controlling the difference between the average particle diameters of the small particles and the large particles within an appropriate range, the advantages of both the small particles and the large particles can be exerted, and at the same time, the effect of supplementing the disadvantages of both is increased. Preferably, the ratio of the average particle diameter of the large particles to the average particle diameter of the small particles is 2 to 1 Torr. = The grain size is fine in terms of strength and flexibility. However, if the crystal grain is too small, the balance between the large particle deposited to the grain boundary and the small particle in the precipitate is destroyed. Therefore, the copper to grain of the present invention

When observing the cross section in the thickness direction parallel to the rolling direction, it is preferable that the average crystal grain size in the case of the corresponding circle diameter is set to 5 to X.

Hi 0 Manufacturing method Hereinafter, a method for producing a copper alloy according to the invention will be described. The copper alloy can be produced by a part of the characteristic steps of the conventional Cu-N1_Si alloy. First, a solution obtained by electrolyzing copper 'Ni, si: using an atmospheric melting furnace. Then, the bright liquid pound is caused into an ingot. After that, the heat is extended, and then the cold rolling and heat treatment are repeated, and the solid and aging treatment is performed from the strip of thickness and characteristics or the heat treatment of P. In the solution treatment, the N-Sl-based compound is solid-dissolved in the 〇11 mother phase and recrystallized from the c-phase at a high temperature of _~1GGn:. Hot rolling is also used as a solution treatment. In order to suppress the coarsening of the crystal particles, it is important to add Ni and Si and keep the solution at a temperature above the helium for 5 minutes or more. The second door is preferably controlled by the 'heating temperature' holding time before the hot rolling, and is known to be controlled at the end of the hot rolling. However, in general, when the concentration of SNi*Si becomes high, cracking occurs in hot rolling when the heating temperature is higher. Therefore, the heating temperature of (4) before the extension of 200949860 is set to 800~i00 (the high temperature of about rc, and the lower temperature is selected when the shape of the fracture is generated. When the selection is less than 8 (), the lower is lower, in order to reduce Crystallized particles must be extended for holding time, although they are also affected by temperature', but by holding them for about 3 hours, most of the particles are less than 5, and then the plate thickness at the end of the hot rolling is less than 2〇_, so the cooling becomes faster. 'The precipitation of precipitates which do not contribute to the characteristics can be suppressed. With regard to the temperature at this time, the hot rolling can be completed at a temperature of 60 (TC or higher, but in the subsequent step, when it is difficult to solidify) It is effective to end the hot rolling at a lower temperature. ^ Further, when the hot rolling is used as the solution treatment, the precipitated particles may be precipitated by air cooling after leaving (placement cooling). Therefore, it is effective to perform cooling such as water cooling as needed. Further, in the present invention, the conditions of the solution treatment are strictly controlled. Specifically, in order to sufficiently dissolve the additive element, particularly Ni, it is selected according to the concentration of ruthenium. Certain course The above solid solution temperature. However, if the solid solution temperature is too high, the crystal grain size becomes too large, so that the solid solution solubility is not high. Specifically, if the Ni concentration is high, the temperature is set to a higher temperature. The approximate standard is as follows: when the Ni concentration is 1.5%, the solution temperature is 650 to 700 ° C, and when the Ni concentration is 2.5%, the solution temperature is set to 8 〇〇 to 850 ° C, if Ni When the concentration is 3.5 〇 / 〇, the solution temperature is set to about 9 〇〇 to 950 ° C. More generally, it is set to y = i25 x + 500 ± 25 (where x is the added concentration of Ni (% by mass) y is the degree of solution temperature ()). In addition, in order to concentrate the precipitation state of large particles and small particles within the range specified by the present invention, it is important to be at right angles to the rolling direction 15 200949860

When the surface was observed, the temperature and time of the solution treatment were adjusted so that the crystal grain size after the 111-melting treatment was in the range of 5 to 3 Å. Further, if the thickness of the material at the time of the solution treatment is large, even if water-cooling is performed after the solution treatment, a sufficient cooling rate cannot be obtained, and the solid-added additive element precipitates during the cooling process. Therefore, it is preferable to set the thickness of the plate when the solidification treatment is performed to 〇 3 or less. Further, in order to suppress the precipitation of the added halogen, it is preferable to set the average cooling rate from the solid solution temperature to 40 (TC to 1 (rc/sec or more, more preferably 15 or more seconds). If the thickness is 0.3 mm The following degree can be achieved by air cooling, but it is more preferably water-cooled. However, even if the cooling rate is increased, the opening y of the product is deteriorated, so it is preferable to set the cooling rate to 3 〇 <) c / sec or less, more preferably 20 ° C / sec or less. After the solution treatment, it is important to perform cold working at an appropriate degree of processing (depression ratio) depending on the desired characteristics. When the degree of processing is too high, the anisotropy is exhibited in the bending workability, and if the degree of processing is too low, the strength does not become excessive. If the effect of improving the bending workability is improved by the large particles, it is preferable. After the solution treatment, cold rolling is performed at a processing degree of 20 to 50%. The degree of processing (%) can be obtained by (the thickness before processing, the thickness of the sheet after processing) / the thickness before processing χ 1〇〇 In addition, in the present invention, the conditions of aging treatment are also important. Manufacturing

In the case of the copper alloy of the invention, it is preferred to control the distribution state of the large particles and the small particles by the primary aging treatment. In the patent document, a method of precipitating large particles and small particles by performing two aging treatments is generally employed, but in general, Ni and Si which are solid-dissolved in copper are known in a state where the analyte is precipitated. 16 200949860 The concentration will become lower '(4) Bu si is not easy to spread, making it difficult to precipitate. Therefore, the present invention cannot obtain small particles of a desired number density. Further, since the second aging treatment is affected by the size of the precipitated particles generated in the first aging treatment, it is difficult to control the particle diameter and density. In order to utilize the primary aging treatment, the large particles and the small particles are in the required range. The premise is that in the previous step, the solution treatment and the cold rolling are appropriately performed, but it is important to keep the temperature and time at the same time. The appropriate range. The strength and electrical conductivity are increased by this aging treatment. The aging treatment is carried out at a temperature of 3 Torr to 600 ° C for 0.5 to 50 h, but the higher the heating temperature, the shorter the time required, and the lower the heating temperature, the longer the time required. The reason for this is that the Ni_Si compound particles are easily coarsened when heated for a long period of time at a high temperature. If the heating is performed for a short period of time at a low temperature, the Ni_Si compound particles are not sufficiently precipitated. Specifically, at 300~50 (TC can be set to y=_〇115χ+61 (χ is the heating temperature (°C), y is the aging time (h)); at 5〇〇~ Q 60〇C In the case of y = -0.0275x + 17.25 (X is the heating temperature (〇c), y is the aging time (h)). For example, at 60 (rc is set to 〇5 h~lh, at 500). (: It is set to 2h~5h, and it can be set to ι〇h~20h at 4〇〇t. In order to obtain higher strength, cold rolling can be performed after aging treatment. Cold after aging treatment In the case of calendering, stress relief annealing (low temperature annealing) may also be performed after cold rolling. The copper alloy of the present invention can be processed into various copper extending articles, for example, into sheets, strips, tubes, rods, and wires, and further, the present invention Copper alloy can be used for lead frames that require high strength and high electrical conductivity (or thermal conductivity), and electronic equipment such as 17200949860, pin 'terminals, a electric appliance, switch, and secondary battery. EXAMPLES Specific examples of the present invention are disclosed below, but the examples are for easier understanding of the present invention and its advantages. The present invention is not limited to the present invention. In the high-frequency melting furnace, a copper alloy having various components described in Tables 1 to 4 is melted at 1400 (TC), and cast into a thickness of 3 Å ingots. m: After adding (10) to < i hours, hot rolling is performed until the sheet thickness is 10 mm (the material temperature at the end of hot rolling is °C), and it is rapidly cooled in water. The rust is subjected to surface grinding until the thickness is mm Μ, and (4) is made by cold rolling to a plate having a thickness of 0.2 mm. Secondly, after solid solution treatment is carried out under the conditions described in Tables ~ to 4, it is cooled in water until it is cooled. At this time, the crystal grain size changes depending on the concentration of the added element or the solid solution condition. Thereafter, the film is subjected to cold rolling until the thickness is 〇1, and finally, the conditions described in Tables i to 4, Each test piece was produced by aging treatment in an inert atmosphere. Tables (Examples) and Table 3 (Comparative Examples) show examples of production of Cu-Ni-Si-based copper alloys, and Tables 2 and 4 show further appropriate Added with Mg, Cr, S Example of production of Cu.Ni_Si-based copper alloy of n, Zn, Mn, and Fe. Each characteristic of each alloy obtained as described above was evaluated, and the results are shown in Tables 1 to 4.

Regarding the strength, the tensile strength test and the 0.2% safety limit stress (MPa) were measured in the parallel direction of rolling. 18 200949860 The measured resistivity is measured using a double bridge, by (%IACS). The rate of electric charge is evaluated in the evaluation of Baoqu's according to JISH3m. . The Wf curve test of the crankshaft at a right angle to the direction of the extension and the direction of the same direction of the crankshaft and the direction of the ^, the ratio of the fracture radius (MBR) to the thickness (1), i.e., the MBR/t value, is determined. Immediately after the solution treatment, the crystal grain size β was measured by a scanning electron microscope (SEM, Scanning Electron Microscope) HITACHI-S-4700, and a cross section in the thickness direction parallel to the rolling direction was cut by FIB to prepare a sample. The crystal grain size was in the width direction of the machine direction, and the average value of one crystal grain was determined. In addition, since the solution treatment is followed by a cold delay, so in the final product, the crystal grain thickness f is broken in the direction and extends in the rolling direction but the area is retained, so that the obtained result is the same as that of the final product. . The crystal grain size can be determined from the final product by the following method. First, the cross section in the thickness direction of the flattening direction is subjected to electrolytic polishing, and the scraped surface structure is observed by ..., and the number of leaves is increased in the number of crystal grains per unit area. Then 'to total the area of the entire field of view, calculate the total number of crystal grains counted by the eight mites, calculate the product of each crystal grain, and calculate the circle with the same area according to the area=( Corresponding to the circle diameter)' and as the average crystal grain size. The particle size of large and small particles can be observed from any profile. It is carried out as follows: LVg|j is parallel to the rolling direction of the product. Large particles of 10 19 200949860 fields of view are observed by a scanning electron microscope (HITACHI-S-4700) by a transmission electron microscope ( HITACHI-H-9000) Observed small particles of 10 fields of view and performed them in such a manner that about 100 particles were observed. When the size of the precipitate is 5 to 100 nm, the image is taken at a magnification of 500,000 to 700,000 times. When the size of the precipitate is 1 to 5000 nm, it is 5 to 100,000 times. Shooting at magnification. In addition, the size of the precipitate is less than 5 nm and cannot be observed. The size of the precipitates greater than 5000 nm can be observed using a scanning electron microscope. With respect to the particles observed in the above manner, the area can be calculated from the long diameter and the short diameter of each particle, and the diameter (corresponding to the circle diameter) of the circle having the same area as the area can be calculated from the area. Particle size. Divided into small particles and large particles according to the particle diameter, and the sum of the particle diameter and the number of particles + is calculated. The sum of the particle diameters is taken as the average particle diameter, and the sum of the number of particles is divided by the total area of the observation field. And find a number density. Here, the term "long diameter" refers to the length of the longest line segment in the line segment passing through the center of gravity of the particle at the intersection of the boundary line with the particle at both ends; the so-called short diameter means the center of gravity passing through the particle and has The length of the shortest line segment in the line segment that intersects the boundary line of the particle. It was confirmed that the observed particles were Nisi by using a scanning electron microscope equipped with an EDS (Energy Dispersive Spectrometer), and in particular, an elemental distribution map of a field emission electron microscope with high precision analysis. The compound particles were confirmed to be smaller precipitates by using the elemental distribution map of a transmission electron microscope equipped with an EELS (Electron Energy Loss Spectroscope) 20 200949860 method. Furthermore, in the final product, there are many cases where there are many misalignments and it is difficult to observe precipitates. In this case, for the convenience of observation, it is also possible to precipitate the precipitates 20 (the temperature around TC is subjected to stress relief annealing. , General* Use electrolytic grinding to make a sample of a penetrating electron microscope, but it can also be measured by FIB (Focused I〇n Beam).

21 200949860 [Ιΐ ¢5 St *1 Η « *1 〇〇ο oo ο ο 00 ο 00 o 00 oo IS — •s fS VJ a V) — V) — v〇o 〇°雪〇〇ο fS d Μ Ο — 00 o »/} ifi· ΙΛ in — V) 1/} — Price υ ¥ S 00 *η ΙΑ Μ 9Π Wear MS «Λ »J 9 •J) If) V6 m S fn fn κ M 0.2% safe Limiting stress (MPa) S; ΙΛ 00 ο NO NO <s N6 Tf 3 00 3 Μ V) Ρ P 卜 — P s 卜 卜 卜θθ 卜 ss 〇 \ ss 90 S3 00 go 00 5; <ss IT J|^ p * geisha S η S to so If) se 00 ΙΛ v〇S se 00 se S3 卜 s 9S QO 卜 s M 00 00 s; 5: *Λ in ss Bu Bu Η Η « Γε US 屮 〇尧 〇尧 〇 〇 X X X X X X X X X X Ti Ti Ti Ti Ti Ti Ti Ti Ti 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 X Ch o iM 9\ 〇0Θ o QO 00 o Saint oo pay oov « e - PN X o 4 how if ♦/ Ί 2 Η Η 七 七 七 p p p p p p rp rp rp rp rp rp rp rp rp rp rp rp rp rp rp rp rp rp rp rp rp rp rp rp rp ο — ο 〇_ 2 oo rp o fp oo (4) For oo ri o fp o $5 it ΙΛ 2 VC s〇Os 00 (4) \〇(4) 2 If) 2 ON 00 fo 〇 9\ 00 J2 ri On Os 〇 o o 00 s 卜 e ΙΛ Bu «1 屮? 4 S .· · 00 00 <s M {5 S tfi fo 筘2 S 2 K — 2 JS S s 屮 4 4 4 + (邾00 If) _ W η 9s rj ? IfJ in 15 fn M vs sc ΙΛ 9N 00 en sc ve in »Λ 〇— If) 5i s Os fo OS P nf^i S rj o Fortunately, W a 啻«5 Ε 啻IT) ο — rs f^> o If) o fS , 卜o s m in e jq 3 芑Ρ e ο in o *Λ *f) l〇o δ se "ΊΤ os in s in m K s «Λ VJ vs s in 〇 l〇jq in o tfi ΙΛ s V) 5 OS s »Λ Ϊ! Cap seven (four) Bu s »Λ js Os rj ve 00 V) r- «λ s 00 o r< ?5 f5 rt rt ® w ο V) \〇〇V) ^oooo 〇 ios 〇S 00 o 费 00 o *n cc ooo 〇\ IT) s; jq 〇\ ol〇9\ s 9v S Os Μ Μ Φ long, "-3⁄4 ι 谗·? 1 φ V) fo ο ό Fn ο M f^id P; e M fS e rn so 1/) e 〇〇o ve V) c5 ve lf> e in ΙΛ o «ft 00 o 00 oo rj o ο ο IS WH ~ fO — ~ IO d 〇5 This 5" s ri words fS S ri this fee ss <^isss 5 s fO ss νϊ s ri _ fs w Lmm « 曰田 J2 ini Ik 百 i « Ϊ « 5 百 i Ik i 螬 4« 200949860

Evaluation of bending workability BW (MBR/t) fS fS rj — — IS GW (MBR/t) is <s η •s «Μ Conductivity (%UCS) QO >η 9 5 0.2% Safety limit stress (MPa ) 00 os 00 S 00 00 ss 00 suspicion "2 4 % VO s 00 00 So g 00 00 s s s precipitate small particle number density (number / mm2 > 2xlOA8 3 χ 10 Λ 8 4 χ 10 Λ 8 3 χ 10 Λ 8 3 χ 10 Λ 8 3 χ 10 Λ 8 3xlOA8 small particles / large particles The number of Dong ratio 10A4 10Λ4 10Λ4 10A4 10Λ4 10Λ4 10A4 Large particle / small particle size ratio in o 1 ο js V) 00 — Small particle diameter (um) 2 ο 2 — 2 s 2 屮t 4 S < «1 — 5 ν〇V) — 00 1"N IQ — Manufacturing condition aging condition time /hm νϊ ΙΛ Vi «η a degree /ic tn ιη !ϊ V) 1/) Wear in Wear If) The size of the base granule / Fim — S ο 00 rj 2 Solution treatment rate / to S ο ose eose 00 s 00 Alloy grade into second additive element / Wt% oe Mg : 0.1-Cr : 0.1 Sn : 0.3-Zn : 0.3 fS eas Cr : 0.1«C〇: 0_1 Fe : 0.1-P : 0.03 笫 Adding element jt/wt% 〇ΙΛ es CD in o V) ό oe 2 ri 5 r4 ri s ri e V) S rl |Example 22| 1 Example 23| 1 Example 24| |Pour 2S|1 Capital Example 26 1 Capital Example 27| |Example 28 200949860 [ε<] Compensatory bending workability BW (MBR /t) Due to the breakage in the hot court, it is impossible to investigate because of the break in the hot press, so it is impossible to investigate ve ο 0Θ ο 00 00 ο V6 GW (MBR/t) VI vs μ Φ (4) — Guide rate (%IACS) 5! oe 5 3 This guide se 0.2%$ Full WL stress (MPa) 00 \n V) S3 〇s S 00 QO This ο 卜 IT) Μ Μ Tensile strength (MPa) 00 ΙΛ «Λ 00 00 s 00 3 Ο VC If) 00 precipitates small particle number density (pieces / mm2) 2χ10Λ4 3χ10Λ10 5χ10Λ2 4χ10Λ4 1χ10Λ5 1 1 1 2χ10Λ8 Small particles / large rough number ratio 10Λ2 10A7 10Λ3 10Λ2 10Λ3 1 1 10Λ7 Large Particle / small rough size ratio 203.3 〇 \ 5 00 00 1 ο 1 ιη 小耝子 "(rnn) 00 1/) (4) S 1 00 ΡΠ 1 Large particle range (nm) 5754 W) 3578 • Λ 1 00 1 f"N Manufacturing condition aging condition 瑾condition time /h \η VI 550t ' 450tx5 h(2 ^.) ΙΛ Ο ο ο IS ο 1/3 铋m ε 6- 碡ε w Shout S temperature / TC IT) e Ο Ο S S S ο 大小 大小 / / / / j 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 00 Ο Μ s 00 ο Μ -6-6- alloy 绂成1? 1 Μ \〇〇ο o in o ο ζ ο ο Ο ο i 2 ri 〇 〇 ri ri 菝 ri ri Γ Γ 4 s ri Ο ν> ri 2.50 Comparative Example 1 1 Comparative Example 2 | 1 Comparative Example 3 1 1 Comparative Example 4 | Comparative Example 5 | [«; Comparative Example δ| 1 Comparison "17 1 Comparative Example 8 1 1 Comparison "9 1 1 Comparative Example 1〇| Comparative Example 11 200949860 ο ο Evaluation of bending workability BW (MBR/t) IS fs «Λ ΙΛ v> GW (MBR/t) <s IS versus conductivity (%IACS) fj in o oo m se 0.2%$ Limiting stress (MPa) s BU IS 00 00 Bu 0Θ Bu S Bu tensile strength (MPa) QO 00 in s 00 00 s 00 «S 00 00 Precipitate small particle number density 2xlOA8 3χ10Λ8 3χ10Λ8 2χ10Λ8 3χ10Λ8 3xlOA8 3χ10Λ8 Small particles/ The number of large particles is 10Λ4 10Λ4 10Λ4 10A4 10Λ4 10Λ4 10Λ4 Large particle/small particle size ratio rj V) 297.8 00 «Λ 328.4 463.3 343.7 屮百* e , 〇〇1 7 ο 2 ο Particle diameter (nm) 2459 Os 6253 V) 4598 7412 6874 Manufacturing condition aging condition time / h V) 1/) If) m ifi rl IT) ri a degree /ic o 5 o V) io Child o 1/) l〇 V) ΙΟ 53⁄4 size of crystal grain / (im rj e ϋ ^ Wip 姨 W $ face _ Μ o 00 o 00 eso 00 osos ο S alloy composition 添加 two added element / wt% Mg : 0.8-Cr : 0.8 Sn · 0.8~Zn · 0*8 Fe : 0.6-P : 0.5 Ti : 2.0 oso iq e Cr : 1.0-Zr A1 : 0.3-Zr : Ti: 0.1-Zr : _additive factor / wt% so 7i 〇in o O Sn ozoo 2 s ci s r4 words <so in ri S 1 Comparative Example 12| 1 Comparative Example 13| 1 Comparative Example 14| 1 Comparative Example 15| Comparative Example 16 I Comparative Example 17| 1 Comparative Example 18 200949860 Table 1 The copper alloy corresponding to the examples of the present invention recorded in Table 3 shows that the balance of strength, electrical conductivity and bending workability is well maintained. In Comparative Example 1, since Si was deviated from the range of composition, Ni/Si also became an inappropriate ratio, and cracks occurred in hot rolling due to coarse crystals. In Comparative Example 2, since Ni was deviated from the composition range, Ni became an excessive state. Therefore, hot workability is deteriorated, and breakage occurs in hot rolling. In Comparative Example 3, since the solid solution temperature was low, coarse particles remained. As a result, although the electrical conductivity is high, the number density of small particles is reduced, and the strength is lowered. "In addition, when bending, coarse particles are used as a starting point to cause fracture. In Comparative Example 4, since the solid solution temperature was high, the crystal grain size became large, and the large particles decreased, while the number of small particles increased. Therefore, although the strength is high, the electrical conductivity is lowered. Since the crystal grains at the time of solid solution are large, the bending property is deteriorated by the grain boundary breakage at the time of bending. Comparative Example 5 corresponds to the copper alloy disclosed in Patent Document 1. Since the secondary aging treatment was performed, the size of the small particles precipitated in the second aging treatment was small, and the number density was remarkably reduced. Although the ratio of large particles to small particles is appropriate 'but the intensity of the small particles is too low, the strength is low. In Comparative Example 6, since the aging treatment temperature was high, coarse precipitates increased. As a result, the density of small particles decreases and the strength decreases. Further, although the electrical conductivity is considered to be high, since the aging treatment temperature is high, the electrical conductivity is also lowered by the re-solidification phenomenon. The bending system breaks with coarse particles as a starting point. 26 200949860 In Comparative Example 7, due to the aging; ^ ^ The burial time is too long, so the size of the small particles becomes larger, and the number density of the small particles becomes smaller as the pass becomes smaller, and the strength decreases. In Comparative Example 8, the strength at the time of aging was lowered. The reason is too short, so the particles are not precipitated. J In Comparative Example 9, the early fish was too long due to the aging effect, so that it was impossible to distinguish the large particles from being low. Almost 4 losses', so the conductivity is higher, but the strength ❹ intensity is better than the case ' 'Because the aging treatment time is too short, so no particles are precipitated. ^Comparative Example U is equivalent to the cold rolling between the disclosures of Patent Document 2, so it is large. The number of particles decreases and the conductivity decreases. In the second::12, because of the excessive amount of Mg added, the coarse inclusions such as Mg0 increase, and the volume is too high. (4) to use. However, the strength was precipitated by Cr and Si. In Comparative Example 13, the amount of heat-resistant peeling was increased, so that the electrical conductivity was lowered. However, due to the addition of the comparative example 14, the amount of addition of ρ is large, and the amount of curved frog is less, and the inclusion is increased. Furthermore, the strength is increased due to the precipitation of Fe. In I::15, since the amount of addition of Τί is large, the conductivity is remarkably lowered. In 116, since Zr is added in a large amount, the z-inclusion is increased by one curvature. The resulting Comparative Example 1 7 tf» This produced a large amount of coarse precipitates. Defects due to the money (protrusions). Comparative Example 18 In Φ 丄 18, a large number of defects (protrusions) were generated during electroplating due to coarse precipitates of Cu-Zr and Cu-Ti (No. 27 200949860). [Simple description of the diagram] None [Key component symbol description] None 28

Claims (1)

200949860 : VII. Patent application scope: : K A steel alloy for electronic materials, which contains Ni: 〇.4~6.0% by mass, Si·' 0.1~2.0% by mass' and the remainder is composed of Cu and unavoidable impurities. Composition;; there are Ni-Si having a particle size of more than °·01 and not reaching 0·05 /zm, small particles of a compound, and large particles of a compound having a particle diameter of 0.05 and less than 5.0 ^; small particles The number density is ι〇ό~1〇1〇/mm The number density of the large particles is the number density of the small particles l/ioooo 〇~1/1〇〇2·as in the scope of the patent application A copper alloy for an electronic material, wherein a ratio of an average particle diameter of the large particles to an average particle diameter of the small particles is 2 to 1 Å. 3. The copper alloy for electronic materials according to the scope of the application or the second item, wherein the average crystal grain size is represented by a corresponding circle diameter of 5 to 3 Å when viewed from a cross section in the thickness direction parallel to the rolling direction. claw. 4. A copper alloy for electronic materials, which contains Ni: 〇4~6〇% by mass, Sl: 0·1~2.〇% by mass, and the total amount of the step-by-step is the largest! 〇% by mass of one or more selected from the group consisting of Cr, Co, Mg, Mn, Fe, Sn, Zn, A1 and P, and the remainder consisting of Cu and unavoidable impurities; Small particles of 0.01 or more and less than 0.05 Mni2Ni Si compound, and large particles of Nl-Sl compound having a particle diameter of 0.05 // m or more and less than 5 〇 from the melon; the number density of small particles is 1〇6~1〇 Ιο/mm2, the number density of large particles is ~1/10 of the number density of the small particles. 5. The copper alloy for electronic materials according to item 4 of the patent application is large. 29 200949860 The ratio of the average particle diameter of the particles to the average particle diameter of the small particles is 2 to 100. 6. For the copper alloy for electronic materials according to item 4 or 5 of the patent application, wherein the average crystal grain size is 5 to 30 /zm in terms of the diameter of the corresponding circle when viewed from the cross section in the thickness direction parallel to the rolling direction. . 7. A type of copper alloy which is composed of a copper alloy according to any one of claims 1 to 6. 8. An electronic component comprising the copper alloy according to any one of claims 1 to 6. Eight, schema · None 30