TW200946697A - Cu-ni-si-co-cr alloy for electronic material - Google Patents

Abstract

The issue is to provide a Corson alloy which has significantly improved characteristics, specifically high strength and high conductivity, by better demonstrating the effect of Cr addition to a Cu-Ni-Co-Si type alloy. Disclosed is a copper alloy for electronic materials comprising Ni: 1.0-4.5 mass%, Si: 0.50-1.2 mass%, Co: 0.1-2.5 mass%, Cr: 0.0030-0.3 mass%, and Cu and unavoidable impurities as the remainder. The mass concentration ratio of the total mass of Ni and Co with respect to Si (the [Ni+Co]/Si ratio) is 4 = [Ni+Co]/Si = 5. For the Cr-Si compound with a size in the range of 0.1-5 μm dispersed in the material, the atom concentration ratio of Cr to Si in the dispersed particles is 1 to 5, and the distribution density is from 1x104 particles/mm2 to 1x106 particles/mm2.

Description

200946697 VI. Description of the Invention: [Technical Field] The present invention relates to a precipitation hardening type copper alloy, in particular to a Cu_Ni_si eQ core alloy β suitable for various electronic machine parts. [Prior Art] For use in leads Frames, connectors, pins, terminals, relays, ❹_ and other electronic parts of the electronic (four) copper alloy, as its basic characteristics, is required to be the same as the description _ I τ 目古 & Strength and high electrical conductivity (or thermal conductivity). In recent years, the high-integration, miniaturization, and thin-walling of electronic components have been rapidly progressing, and accordingly, the demand level of copper alloys used in electronic machine parts has been increasing. From the viewpoint of high strength and high electrical conductivity, in recent years, as a copper alloy for electronic materials, the amount of precipitation hardening type copper alloy is increasing to replace the solid solution strengthening copper represented by the former steel, brass, and the like. Combined with H-hardened copper alloy, 'by aging treatment of the solution-treated supersaturated solid solution, the fine precipitates are dispersed, thereby increasing the strength of the alloy and reducing the solid solution in the steel. The amount of elements is increased to improve electrical 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 precipitation-hardened copper alloys, Cu-N-Si-based copper alloys, which are generally called Carson-based alloys, are typical copper alloys having relatively high electrical conductivity, strength, stress relaxation properties, and bending workability. The industry is currently actively developing the alloy -. In the copper alloy, strength and electrical conductivity can be improved by depositing fine Si. 3 200946697 intermetallic compound particles into a copper matrix. It is known that Cu-Ni-Si-based copper alloys can be improved by adding (^ and ^. As with Ni, ~ and the heart can form a compound with & to increase the strength. 〇〇6-283120 (Patent Document u, 'Characteristics (especially strength and electrical conductivity) of a Cu_Ni_Si-based alloy containing Co-ShaCr is considered to be under certain composition conditions and manufacturing conditions, when controlling inclusions When the size, composition, and distribution of the object are significantly improved, the patent document discloses a Cu-Ni-Si-Co-Cr copper alloy for electronic materials, which is characterized by Ni : 〇 5 to 2.5% by mass ' Co : 0.5 to 2.5% by mass, and Si: 0.30 to 1.2% by mass,

Cr: 0.09 to 0.5% by mass, and the remaining part is a mass concentration ratio of Si to the total mass of Ni and c〇 in the composition of the copper alloy composed of Cu and unavoidable impurities ([Ni+ The Co]/Si ratio is 4 $ [Ni+c〇]/si $ 5, and the mass concentration ratio of Ni to c〇 in the alloy composition (Ni/c〇 ratio) is 0.5$Ni/C〇S2, and The number of inclusions (P) having a size of the above-mentioned inclusions dispersed in the material, and the number of inclusions (Pc) containing a carbon concentration of 1% by mass or more, Pc is 丨5 n 〇〇〇V m2 or less And the ratio (pc/p) is 0.3 or less. Further, although the Japanese Patent Publication No. 2005_11318 (Patent Document 2) is not a Cu-Ni-Si alloy, it focuses on Cr and Si precipitated in a copper alloy. Compound. By the fact that the CrSi compound having a predetermined size and the number density is finely precipitated in the Cu matrix, and the size of the Cr compound other than CrSi is limited to 200946697 and the press workability can be improved, the etching processability can be ensured. "Patent Document 2 describes a copper alloy for electronic equipment containing Cr: 0.1 to 0.25% by weight, Si: 0.005 to 0.1% by weight, and Zn: 0.1 to 5% by weight, and Sn: 〇 〇5~〇$% by weight, the weight ratio of Cr to Si is 3~25, and the remaining part is composed of Cu and unavoidable impurities. Among the copper alloys, there are 〇〇5^m in the copper matrix. The CrSi compound of the size of the OOm is present in a number density of 1χ1〇3 to 5χ1〇5/mm2, and the copper compound (except the CrSi compound) has a size of 10 μm or less and is excellent in etching workability and press workability. alloy. In the production of the copper alloy, the heat treatment temperature before hot working is set to 850 to 980 t, and after hot working, it is necessary to carry out a process combining cold working and heat treatment at 40 (TC to 600 ° C temperature, or [Patent Document 1] Japanese Patent Laid-Open No. Hei. No. 2006-283120 (Patent Document 2) Japanese Patent Laid-Open Publication No. Hei. No. Hei. In the alloy of the Cu_Ni_Si_C0_Cr alloy of the present invention, the demand for the rapid increase in the electronic components, the miniaturization, the miniaturization, and the thinning of the material properties have been met. However, in Patent Document 1, There is no description about the Cr_SiK compound. In Patent Document 2, there is a description of improving the etching processability and press formability by controlling the number density and size of the CrSi compound. However, 5 200946697 is not considered because no Ni is added. In the formation of a Ni-Si compound or a c〇_si compound, it is only necessary to consider the conditions under which the Cr_Si compound is formed, and in the Cu-Ni-Si-Co-Cr alloy, there is no It is a review of how to control a Cr-Si compound. Therefore, the object of the present invention is to improve the properties of a Cr-Si compound in a Cu-Ni-Si-Co-Cr alloy to improve the characteristics. The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found the following invention. In the Cu-Ni-Si-Co-Cr alloy, Si is set to be excessive in addition to C犯. The c-deuterium corresponding to the amount of Ni added according to the amount of Ni added is surely precipitated to achieve high strength. On the other hand, excess Si is reacted with the added Cr to form a compound to achieve high conductivity. The key point of the invention is to avoid

The combination of Cr and Si is excessively grown, and instead, the growth of Cr_Si compounds is controlled in a manner that is inconsistent with the sufficiency of Si. Specifically, the present inventors focused on the composition, size, and number density of the Cr-Si compound, and found that the effect can be better exerted by controlling the temperature and cooling rate of the heat treatment step. That is, the present invention is a copper alloy for an electronic material containing Ni: 1.0 to 4.5.

Sl 〇'50~1 · 2 mass %, Co : 0.1 ～2.5 mass %, Cr : 0.003 .3 mass /. , <11 and (: 合 total mass is relative to the mass concentration ratio ([Nl + C〇] / Sl 匕) is 4 [Ni + C 〇] / Si $ 5), and the remainder is Cu ° The impurities to be avoided constitute 'for a Cr-Si compound having a size of 0.1200946697 ym~5 vm dispersed in the material, the atomic concentration ratio of the dandan dan particles relative to the Cr is 1 to 5, which is dispersed. Sore 2 Λ Dispersion is greater than lxio 4 / mm2, and below 1 χ 1 〇 6 / mm2. (1) A copper alloy for an electronic material according to (1), wherein the dispersion is 50 or less by weight in a dispersion of more than 5...Cr_Si. ❹ ❹ (3) A copper alloy for electronic materials such as (1) or (7), wherein 0.05 to 2.0% by mass of the copper alloy is selected from the group consisting of "and" or two or more types. (4) As in (1) to (3) A copper alloy for an electronic material further comprising 0._~2.0% by mass selected from the group consisting of Mg, Mn, Ag, p, phantom,

There are two or more kinds of Sb, Be, B, Ti, Zr, ai, and Fe. S (5) - a type of copper alloy, which is a copper alloy according to any one of (1) to (4). (6) An electronic machine part using the copper alloy according to any one of (1) to (5). According to the present invention, the effect of adding the alloying element Cr can be more effectively exhibited, so that a Cu-Ni-Si-Co-Cr alloy for an electronic material having remarkably improved strength and electrical conductivity can be obtained. [Embodiment]

Adding Co and Si

Ni, Co, and Si are formed into an intermetallic compound by performing appropriate heat treatment, and the strength can be increased without deteriorating the electrical conductivity. Hereinafter, the respective addition amounts of Ni, Co, and Si will be described. 7 200946697 ^In order to meet the appropriate strength and conductivity of copper alloy for electronic materials, the addition amount of Nl and Co must be set to Ni: 1.0 to 4.5 mass A, C〇.0.1 〜2. 3 volume / 〇 ' is preferably Ni: 1.0 ~ 2, 0 mass. /. Co: Cao is better than Ni: ι·2~1.8% by mass, Co: 1.2~1.8% by mass. However, when the amount of each addition is less than Ni: 0.5% by mass, Co: 0.5% by mass, it is not available. The required strength; conversely, when surpassing Ni: 2.5 temporary county. / i-i ^ Shell weight / 〇, Co. 2.5% by mass, although the strength can be improved, the electrical conductivity is remarkably lowered, and the hot inter-processability is also lowered, which is not preferable. > Regarding the amount of addition of Si, in order to satisfy the target strength and conductivity, it is required to be 0.30 to 1% by mass, preferably 〇 5 to 〇 8 mass%. However, when the amount of addition of the field Sl is less than 3% by mass, the required strength cannot be obtained. When the amount is more than 1.2% by mass, the strength can be remarkably lowered. Further thermal processing will also be reduced, so it is not good. In the present invention, the weight concentration ratio ([Ni + Co] / Si) of the total amount of Ni and Co in the alloy composition to Sl is further specified. In the present invention, by setting the Ni/Si ratio to be less than the previously stated predetermined range 3, Ni/Si < 7, Bodhisattf > ^, M = 7, that is, by slightly increasing the si The amount added is such that it does not remain, and the synthetic telluride is used to alleviate the excess that does not contribute to precipitation # Ni & c. The decrease of conductivity caused by #Solution is -4 when the weight concentration ratio is [Ni+Co]/Si < 4, because it is the ratio of S i; Mugu Ping asked, not only because of the solution of Si The relationship is low in the electrical conductivity drop of 200946697, and the weldability is deteriorated in the annealing step because the oxide film of si〇2 is formed on the surface layer of the material. In addition, it is easy to coarsen the Ni c〇 si-based precipitated particles which do not contribute to strengthening, and it does not contribute to strength, and conversely, it is easy to become a starting point or a defective portion of cracks during flexing. On the other hand, the ratio of Ni to Co with respect to Si is increased, and when it becomes [Ni+c〇]/si > 5, the conductivity is remarkably lowered, which is not preferable as an electronic material. Therefore, in the present invention, the [Ni + c〇] / Si ratio in the alloy composition is controlled to be in the range of [Ni + Co] / Si$ 5 . [Ni+Co]/Si is better than 4.2$ [Ni+C0]/Si$4.7.

Ni and Co not only help together with the formation of the compound, but the state and Co are related to each other to improve the alloy properties by controlling the combination. . The weight concentration ratio (10). Than), can further promote the rise and fall = sex. By setting the Ni/C 〇 ratio within the range of preferably 0,5gNi/c〇^2, the improvement in strength can be clearly seen. Ni/c is better than the best ^

Ni/Co$ 1.3. ,·= ❹

When the addition of Cr is promoted to the Cu-Ni-Si-Co alloy, if the concentrations of Ni, & and c are increased, the total number of precipitated particles increases, and the strength by precipitation strengthening can be increased. On the other hand, as the concentration of the addition increases, the amount of solid solution which does not contribute to precipitation increases, so that the electrical conductivity decreases, and as a result, the peak intensity of the aging precipitation increases, but the peak intensity of the electrical conductivity decreases. However, if the above-mentioned Cu-Ni-Si alloy is added with 〇〇〇3 to 〇3, and the weight % of Cr is preferably 0.01 to Μ% by mass (^, the final characteristic is such that the drum is the same as Ni , Si and C. Concentration of Cu_Ni|C. Alloy phase:;,, = 9 200946697 Increases electrical conductivity by strength 'Step-by-step improves hot workability and improves material utilization. Cu-Ni-Si- In the C bismuth alloy, the composition of the particles precipitated when Cr is added is easy to precipitate a precipitated particle of a bcc structure containing Cr as a main component, but a compound with Si is also likely to be precipitated. Cr is subjected to an appropriate heat treatment. It is possible to easily precipitate a compound of Si, such as chrome telluride (Cr3Si, etc.) in the copper mother phase, so that it can be used as a Nidi or in the step of forming a combination of alloy properties, solid solution treatment, cold rolling, and aging treatment. The solid solution Si of C〇Si2 or the like is analyzed as a Cr-Si compound. Therefore, it is possible to suppress solidification and containment.

The decrease in the electrical conductivity caused by Si makes it possible to increase the electrical conductivity without impairing the strength. At this time, if the Si concentration in the Cr particles is low, si will remain in the matrix phase, and thus the conductivity will decrease. On the other hand, if the Si concentration in the Cr particles is higher than the south, the Ni-Si particles are precipitated. Or the Si concentration of the Co-Si particles is reduced, and thus the strength is lowered. Further, when the Si concentration in Cr is high, the coarse Cr-Si compound increases, and the bending, fatigue strength, and the like deteriorate. Further, even if the cooling rate after solid solution is slowed down, or the heat treatment time is excessively prolonged, the Cr-Si compound is coarsened to decrease the Si concentration of the compound, resulting in insufficient Ni_si compound for strengthening. The reason is that the diffusion of Si in Cu is faster than that of Co or Co, so the Cr-Si compound is easily coarsened, so that the precipitation rate of the Cr-Si compound becomes faster than the precipitation of the Ni-Si compound and Co-Si particles. speed. Therefore, if the cooling rate after solution treatment is controlled to avoid the conditions of higher temperature aging conditions being higher temperature and longer, the composition of cr_Si 10 200946697 compound can be controlled, and the mass %~0.3 Zhexi will be the Cr concentration. It is set to 003·003%, and the atomic concentration ratio S of Cr to Si in the Cr-Si compound is again 1 to gas.曰 ^Cr will be preferentially precipitated during the cooling process during dissolution and fabrication.

Therefore, the grain boundary can be strengthened to make it difficult to generate cracks during hot working, and the material rate can be lowered. @ 'Cr which precipitated to the grain boundary during the transfer casting can be re-dissolved in the solution treatment or the like, and the amount of Si added in the usual Cu-grazing Si-based alloy is formed in the subsequent aging precipitation. The Si precipitated in the aging process still maintains the state of solid solution in the matrix phase and inhibits the increase in conductivity. 'But by adding the telluride forming element t Cr , the telluride is further precipitated' and thus the prior CuNiSi core alloy phase. In comparison, the amount of the solid Si can be lowered, so that the electrical conductivity can be increased without impairing the strength. Milling

The size of the Cr-Si compound affects the bending workability and the fatigue strength. When the dispersion density of the Cr_Si compound having a size larger than 5 cm exceeds 5 Å/min, or the dispersion of the Cr-Si compound of 〇1 to 5 μm. When the density exceeds lxlO6/mm2, the processability or fatigue strength of the film is significantly deteriorated. Further, the number density affects the excessive or insufficient concentration of Si in the mother phase, so that the desired strength characteristics cannot be obtained in a state where a large number of particles are largely dispersed. Therefore, the dispersion density of the Cr-Si compound having a size of more than 5 #m is preferably set to 50/mm2 or less, more preferably 3 Å/mm2 or less, and most preferably 10 or less. The density of the Cr-Si compound of 〇1 to 5em may be 1 x 1 〇 6 / min 2 or less, preferably 5 x 1 〇 5 / mm 2 or less, more preferably 1 x l 〇 5 / mm 2 or less. Further, when the dispersion density of Cr-Si compound 200946697 is less than or equal to 4/mm2, the improvement effect by G addition is small, so the dispersion density of the ideal Cr_Si compound needs to exceed lxl 〇4/mm2. In a typical embodiment, the dispersion density of the CrSi compound needs to be 1χ1〇5 pieces/mm2 or more.

Sn and Zn are added to the Cu_Ni_Si-based alloy of the present invention in a total amount of 〇〇5 to 2% by mass, and are selected from the group consisting of Sn and Zn, and one or two or more types may be selected, which may be less inferior in strength and electrical conductivity. In the case of improvement, stress relaxation characteristics and the like are improved. When the amount added is less than 0.05% by mass, the effect is insufficient. When the amount is more than 2% by mass, the manufacturability such as castability and hot workability and the electrical conductivity of the product are impaired. Therefore, it is preferable to add 〇.〇5 ~ 2. 〇 quality%. Other added elements 可 By adding specific amounts of Mg, Mn, Ag, P, As, Sb, B x Ti, Zr, Al, and Fe, various effects can be exhibited, and the strength and conductivity can be improved by complementing the complementary feet. Further, it is also possible to improve manufacturability such as bending workability, plating property, or improvement in hot workability by miniaturization of ingot structure, and thus, in the Cu_Ni_si-C〇Cr alloy of the present invention, visible One or two or more of these halogens are added in an amount of 2% by mass or less in total. With respect to the added amount, when the total amount of the elements is less than 0.001% by mass, the desired effect cannot be obtained, and when the total amount of the elements exceeds 2.0% by mass, the electrical conductivity is lowered or the manufacturability is The deterioration becomes remarkable, so the total amount is preferably set to 〇〇〇1 to 2〇% by mass, and more preferably set to 〇〇丨~丨〇% by mass. Further, the element contained in the range of the present invention, which does not specifically affect the adverse effects of the present invention, may be added to the above-mentioned "Cu_Ni_si_c〇_Cr alloy". Next, the manufacturing method of the present invention will be described. The U-Nl-Sl-C〇-Cr alloy of the present invention can be controlled by a Cu-Ni-Si system in addition to the conditions of m treatment and aging treatment of the Ni-si compound, the C0-Si and the Cr-S4 compound. The alloy is manufactured by a conventional manufacturing method.

Ο First use an atmospheric melting furnace to dissolve the electrical copper, Ni, Si, Co, and Cr raw materials to obtain a desired liquid. Then, the solution is cast into a cast ingot; the moxibustion is subjected to hot pressing & and is subjected to cold calendering and heat treatment in turn, and is processed into a strip or foil having a desired thickness and characteristics. The heat treatment has a solution treatment and an aging treatment. In the solution treatment, the Ni-Si compound, the c〇-Si compound, and the Cr_si compound are dissolved in the Cu mother phase by heating at a high temperature of 7 〇〇 to (7) (eight) 艽, and the Cu mother phase is recrystallized. . The solution treatment is sometimes doubled by hot calendering. The cooling rate in the solution treatment is also as important as the heating temperature. Since the cooling rate after heating is not previously controlled, a water tank is provided on the exit side of the heating furnace for water cooling, or air cooling under an atmospheric atmosphere. At this time, the cooling rate is likely to fluctuate due to the setting of the heating temperature, and the previous cooling rate is in the range of rC/sec or less to 1 (rc/sec or more. Therefore, it is difficult to control the characteristics of the alloy system as in the example of the present invention. The cooling rate is preferably in the range of it:/sec to lot:/second. In the aging treatment, the heating is performed at a temperature of 350 to 550 C, and heating is preferably performed for 3 to 24 hours to dissolve the solution. The solid solution of Ni and si 13 200946697 and the compound of cr and Si are precipitated as fine particles. The strength and conductivity increase with this aging treatment. In order to obtain higher strength, sometimes in time and/or aging After the cold rolling is performed, the cold pressing delay is performed after the aging, and the stress annealing is performed after the cold rolling (1〇w temperature annealing). The Cu-Ni-Si-Co-Cr system of the present invention is used. In one embodiment, the steel alloy can be set to a 0.2% safety limit stress of 75 〇Mpa or more and a conductivity of 5 〇% IACS or more, and further can be set to 〇2% safety limit stress of 8 〇〇Mpa or more and electrical conductivity. 50 〇 / 〇 IACS or more It is also possible to set the 〇2% safety limit stress to 850 MPa or more and the conductivity to be 5 〇% IACS or more. The Cu-Ni-Si-Co-Cr alloy of the present invention can be processed into various kinds of copper, such as a plate, Strips, tubes, rods and wires, further, the Cu-Ni-Si-based copper alloy of the present invention can be used for lead frames, connectors, pins, terminals, which simultaneously require high strength and high electrical conductivity (or thermal conductivity). Electronic device parts such as relay switches and foils for secondary batteries. [Embodiment] Specific examples of the present invention are shown below, but these embodiments are provided for a better understanding of the present invention and its advantages, and are not intended to limit the invention. The copper alloy used in the examples of the present invention has the same as shown in Table 1.

The composition of Sn ' Zn, Mg ' Mn, c 〇 and Ag is appropriately added to the copper alloy in which the contents of Nl, Sl, C 〇 and Cr are changed. Further, the copper bismuth gold knife used in the comparative example is an eu_Ni_Si_C〇-Cr alloy having parameters other than the range of the present invention. Use a high frequency blaze furnace to 1300. (The temperature of each of the copper alloys of the composition of each of the components of the invention is shown in Table 1 and is cast into an ingot having a thickness of 30 mm. Then, the ingot is heated at a temperature of TC, and then hot-rolled to The thickness of the plate is l〇mm, and then the cooling is performed quickly. To remove the scale of the surface (sca), planar cutting is performed until the thickness is 8 mm, and then a plate having a thickness of 0.2 mm is formed by cold rolling. Then, in the Ar gas The solution treatment is carried out in an ambient atmosphere, and the amount of Ni and Cr is increased by 800 to 1 Torr (the temperature of rc is maintained for 12 sec., and then the cooling rate is changed to cool to room temperature. The cooling rate is obtained by 〇 & The gas flow rate of the sample after the direction heating is controlled, and the maximum temperature reached from the sample is cooled to 40 (the time until rc is used as the cooling rate. The furnace cooling speed g5t: /s when the gas is not blown, and Example of retarding the cooling rate 'The cooling rate when cooling the output side of the heating surface is set to rC/s. Thereafter, the cold rolling is extended to 〇lmm and finally according to the amount of addition' to the temperature of 柳~55 (the temperature of rc is inert Every atmosphere Application: ~12 hours of aging treatment to produce samples. The properties of the alloys obtained in this way are characterized by strength and electrical conductivity. For strength, tensile testing in the parallel direction of rolling; ^ Safety limit stress (7) -MPa), and the electrical conductivity (Ec; %iacs) is determined by measuring the volume resistivity of the W-bridge. The evaluation of the bending property is based on the ratio of the radius of the W-shaped mold to the radius A. , '9G Guarding under the condition that the ratio of the test plate thickness to the curved peach is 1:: Mirror observation... The surface of the working part will be unobserved and the crack is practically no problem, and the 〇 will be marked, and the crack X will be observed. The fatigue test is based on JIS Z 2273, the month of application: the number of repetitions marked as broken is the second stress (Mpa). Until 15 200946697

The observation of the Cr-Si compound was carried out by electrolytic polishing on the surface of the material, and was observed by FE-AES (manufactured by Sakamoto Electronics Co., Ltd., JUMP-7800F), and the size was 〇1; The particles are used as objects, and are splashed with Ar+ to remove the elements (C, Ο) actually adsorbed on the surface layer, and then the Eugene spectrum (eight “奵”) of each particle is measured, and the detected elements are determined by the sensitivity coefficient method. When the weight concentration is converted as a semi-quantitative value, the particle of & is detected. The composition (Cr/Si) of the Cr g compound

The J plant dispersion density is defined as the average composition of the Cr-Si particles and the average number of the minimum circle _ field of view of the large-scale analysis of FE-AES. The results are shown in Tables 1 and 2. 16 200946697 Hearing: Chicken*0/0

G 17 宣萚Η ΙΟ S) Oi tsj s> KJ s 00 —- 5: d: 1—». ct^U; :〇〇OS V» u> to Ιλ h—· k) bo bo bo bo bo bo ►—» bo bo — bo ►—* bo — bo bo N-* bo bo 1—* bo bo bo μ—&bo; bo bo % ok) 〇bs o On Ο bs ο ΟΝ ο 〇\ O b\ ob \ O ON 〇〇\ oa\ o σ\ 〇b\ 〇os 〇Os 〇σ\ O σ\ ob\ o Os 〇Os o bs Ρ Η-» ρ o u> o io pp ρ 1 0.05 0.005 p N- * p · —· p | 0.05 | [0.005 I pp — p 1—* | 0.05 | | 0.005 | ppp | 0.05 | | 0.005 ] p 〇Ν> — Lft In NJ b — bb ο 1—^ oo — o N -* o — b ►—» o 1—» b ►—· HM oot—* ono u> o Iti oso Ul owo u> o 1>j ga o U\ o Ιλ o Lh δ o 0 01 o Lft o Ih N p 1—> p 1—» <1 p Ν-» p H»· <1 Others Ν> o Private Ι 〇-U *••4 •u •U household 4^- • Private one ♦ [Ni+Co]/Si 950 950 V〇<-Λ o 1000 900 ο so ο Ο ο 00 o 00 8 00 ogoo 900 900 s Os〇o 900 oo og 00 ο oo o 1 800 Solution temperature (xl20s) i...— 1—· N—* 1—» ο — > —* — 1—* u Private cooling rate (°C/s) 450 450 450 450 450 450 ' 450 450 ! 450 1 1 450 1 a: o 450 L 450 450 450 450 450 450 — ..450 450 450 450 i: 〇1 450 aging temperature (°C) 〇σ\ 〇\ 〇 \ as σν Os ΟΝ Os Os o\ 〇\ 〇\ σ\ 〇\ On Os ON ON Os 〇\ On Aging time (h) 0.67 0.91 0.87 0.96 0.60 0.60 0.60 0.28 0.18 1 0.70 1 0.70 I 0.70 | 0.32 1 0.20 0.75 0.75 0.75 0.34 0.22 0.87 0.87 0.87 0.40 ! 0.26 0.1 ~ 5μιη Dispersion density of Cr-Si particles (χΙΟ6 / mm2) ts) N) S) 00 00 00 Is) Ν) 00 JO to K> N-· 0\ To K) S) to S3 K) -j N) OS to Os s> On fj 00 〇^ |Sst ts) [Ο U) io Is) bo NJ •U Ν) ▲ Κ) ▲ Μ '〇\ S) Os ιο Ιλ K) Lr, KJ Ui JO a K) NJ bo N) bo S) bo UJ bb N) VO SJ to — U) — Composition of Cr-Si particles ί_ 00 〇\ u> 00 u» Οι 00 s Ό 〇\ oo o 00 ο 00 to 00 Μ L/1 00 00 o 00 o Ln 00 KJ\ oo o | 840 1 | 820 1 V O LA <•/1 v〇o \〇o I 770 1 s; KJi o Μ ΚΑ 念 6 0Q ν〇t-Λ <-h u> Ui N> KJt 1—» Ut N) V» i〇 U> KJ\ tyi U> no η o ο o 〇o Ο Ο Ο ooo 0 〇o 0 0 0 0 oo 0 O o 0 曲曲加工1 310 | u>1—> | 290 1 1 330 1 \ >Λ L/t ·—< 3,05 KJ* ow ow K) 00 o | 280 | N> 00 o I 270 1 1 305 1 | 300 1 N> | 290 1 N) 00 a K) 00 o ! 280 2?5" K) 00 o K> Fatigue 1_

S1J 200946697 Fatigue ν-> ν〇(Ν o <N 〇<N JQ ΪΝ <Ν ο CN ν〇<Ν ir> VO <Ν ο <Ν Vi (Ν <Ν <Ν S (Ν ο is JO (Ν S CN l〇艺CN jn (N s (Ν 别曲i 加工1 Ο 0 oo Ο ο ο Ο ο Ο ο Ο XX Ο 0 XXXX GO 妄苳>Λ 9 »〇 W» 妄»η so 妄<Ν ι〇Ο ρ P «η 卜Ο卜 S 卜〇卜*η ν〇g Ο ο Ρ «ο 00 S 卜*> ο 卜g Bu VJ 00 o *n OS \o iTi VO V) Composition of ρ Cr-Si particles 1 m - mouth 00 CN 00 γ4 卜 (Ν 1 1 Ο Γ〇 00 οι ο rn «S Ο so is o ; V〇o l> mouth f .f^-C ρϊδ wu CO inch w>>η *η (S m inch to inch 1 • •Ο ν-> (Ν ο ο VO Ό 00 S 0.1 〜5μτη Dispersion density of Cr-Si particles (χΙΟ6/mm2) ο ο 2 〇二Ο ο ο Μ ο ο ο Ο 2 ο 2 ο I 1 ::'2: Bu 0.003 0.009 ΛΟ s J2 ^ So φ * ^ ν 〇v〇\ov〇νο VO ν〇ο Ό ο ν〇Ό ν〇ν〇Ό Ό VO v〇Ό aging temperature CC) inch o JO ο •ο Ο «ο inch Inch inch Ο η inch pair Ο JO inch ο ι〇ο inch osi inch cooling rate CC/S) inch inch inch 〇ο ο ο ο >η »〇«ο JO oo ο solution temperature (xl20s) ο 00 o 00 ο 00 ο Μ 00 00 00 00 00 00 00 00 00 00 00 00 00 ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ir> Ο cS ο m Ο ο Γ〇ο ο ο ο poo ο p ϋ 0.005 S of—J 1-^ 0.005 S ο FH ο ι ν : rl, , r * S ο S ο Ό W-) ο VO 〇o VO o o o o o o o o o o o o o o o o o ο οο 00 ΟΟ οο 00 OO 00 00 οο <N »〇Ό 00 <7\ ο (Ν m 2 »〇2 r- 00 Os 200946697 Inventive Examples 1 to 24, by appropriate cooling Degrees, so that the dispersion density of the compound cr_Si lxl〇6 or less, and the Cr / Si is in the range of i~5, while the good properties. On the other hand, in Comparative Examples 1 to 10, since Co was not contained, since Comparative Examples n and 12 did not contain Cr, the strength and electrical conductivity could not reach high order. In Comparative Examples 13 and 14, since the cooling rate was slow, the Cr_Si compound was excessively grown, so that sufficient strength could not be obtained and the bending workability was also poor. In Comparative Examples 15 and 16, since the cooling rate was fast, the Cr_Si compound did not grow, and excess Si was solid-dissolved into the alloy, and the strength and electrical conductivity were deteriorated. In Comparative Examples 17 and 18, since the aging temperature was high, the compound was excessively grown, so that sufficient strength could not be obtained and the bending workability was also poor. Further, in the coarse particles, Cu, Ni, and the like are diffused, and the Si concentration in the particles is lowered, and the Cr/Si ratio is relatively increased. In Comparative Examples 19 and 2, since the concentration of Cr was too high, the Cr-Si compound excessively grew, and sufficient strength could not be obtained, and the bending workability was also poor. [Simple description of the diagram] (None) [Explanation of main component symbols] (None) 19

Claims (1)

200946697 VII. Patent application scope: 1. A copper alloy for electronic materials containing Ni:1 〇~45 mass%, Si: 0.50~1.2 mass%, c〇: 〇"~2 5 mass%, Cr: 〇 kiss ~ 0.3% by mass, which, committed with c. The total mass is relative to the mass concentration ratio ([NHC〇]/Si tb) as 4 release i+c〇]/Sig5, and the remainder consists of ^ and unavoidable impurities; for the size dispersed in the material For a Cr y compound of 〇1//m~5^m, the atomic concentration ratio of Cr to Si in the dispersed particles is greater than lxl0, w, and ixi〇M@w is © 2. If the size of the first item of the patent application is greater than 5, the dispersion density is less than 50/mm2. The copper alloy for an electronic material, wherein the Cr-Si compound of β m is 3. The metal of the first application of the patent range </ RTI> further contains 〇〇5~ species or two or more. The copper material for the electronic material of item 2 or 2 is 0% by mass of one selected from the group consisting of Sn and Zn. 4. For example, the copper material for electronic materials in the second inferior item 2 of the patent application scope, further containing 〇〇〇1~2 〇% of the amount selected from the group consisting of Mg, Μη, AP, As, Sb, Be, B, One or two kinds of Ti, Zr, Al β A1 and Fe are _fc 5. A copper alloy for electronic materials, and fa is produced containing Ni: 1.0 to 4.5. Si : 0·50 ～ 1.2% by mass μ (1) 激县~ 0.1~2.5% by mass, Cr·· 〇.003 0.3 mass/〇, 1选自+ selected from Sn and Zn, or 2 or more types: 0.05~2.0乂, selected from Mg, Mn, Ag ' P, agr As, Sb, Be, B, Ti, Zr 20 200946697; 1 or 2 or more of A1 and Fe: 0.001 to 2.0% by mass, wherein Ni and Co The mass concentration ratio ([Ni+c〇]/Si ratio) of the total mass to Si is 4 S [Ni+Co]/Si $5, and the remainder is composed of cu and unavoidable impurities; The size of the material in the material is O.lym~5; in the Cr-Si compound of czm, the atomic concentration ratio of Cr to Si in the dispersed particles is 1 to 5; ❹ the dispersion density is greater than ΙχΙΟ4/ Mm2, but below lxl〇6/mm2. 6. The copper alloy for electronic materials according to claim 5, wherein the dispersion density is 5 Å/mm2 or less for a Cr-Si compound having a size larger than 5 #m in the material. 7 '' Kind of copper alloy, which uses the steel alloy of any one of the claims 1 to 6. 8' kinds of electronic machine parts, which are used in any of the steel alloys of any one of the above-mentioned patents. Eight, schema: (none) 21