TW200915349A - Cu-Ni-Si-Co based copper alloy for electronic material and its production method - Google Patents

Abstract

This invention provides Cu-Ni-Si-Co copper alloys for electronic materials of excellent strength, conductivity and bending workability. The copper alloy for electronic materials in accordance with this invention contains about 1.0-about 2.5% by weight of Ni, about 0.5-about 2.5% by weight of Co, about 0.30-about 1.2% by weight of Si, and the balance being Cu and unavoidable impurities. Particle diameters: greater than 0.1micron and smaller than 1micron, containing 1 wt% of second particles Ni, Co and Si in parallel to a rolling direction of a profile having the size greater than 10 Λ 4 mm2 and smaller than 10 Λ 7 mm2.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a precipitation hardening type copper alloy, and more particularly to a Cu_Ni-Si-&-type copper alloy suitable for use in various electronic machine parts. [Prior Art] For steel alloys for electronic materials used in various electronic machine parts such as connectors, switches, relays, pins, terminals, lead frames, etc., the basic characteristics are required to have both high strength and high electrical conductivity. Highly integrated and miniaturized, thin-walled (four) material exhibition = : The degree of demand for copper alloys used in electronic machine parts is gradually increasing. From the viewpoint of high strength and high electrical conductivity, as a copper alloy for electronic materials, the use amount of the precipitation hardening type copper alloy is gradually increased, and it is a solid solution strengthening type copper alloy represented by the like. The _ hardening type copper benefit is obtained by aging treatment of the solution-treated supersaturated solid solution, and the fine precipitates are dispersed, so that the alloy is strong (four), and the solid solution element* is at the same time, and the conductivity is improved. Therefore, it is excellent in mechanical properties such as performance, and excellent in elasticity and excellent in electrical conductivity and thermal conductivity. Among the W-hardened copper alloys, it is generally called card (four), alloy (caffe (10) and Cu-Nl~Si-based copper alloys' are representative copper alloys with high electrical conductivity, strength and 5 processability. One of the alloys being developed by the company is a finer H. This copper alloy is enhanced by the precipitation of micro-organismal compound particles in the copper matrix to achieve strength and conductivity of 5 200915349. 2 Further improving the characteristics of the Carson alloy, the addition of Ni and Si to the "gold" component, the adverse effect on the characteristics of the composition of the 曰, and the optimization of the weaving, optimization of the particles Various technologies have been developed. W > ϋα has been enhanced by adding c. $ Japanese Patent Laid-Open No. 222641 (Patent Document υ, D has C. It forms a compound with Si in the same manner as Ni. And to improve the mechanical strength, when the aging treatment of Cu-Γη-c. / 攸叮 顿 C〇~Sl糸, compared to Cu -

The mechanical strength and electrical conductivity of the Nl Sl alloy will be slightly improved. Therefore, if the cost is allowed, ^ J select Cu-Co~ Sl system or Cu_Ni - C ο - S i system.曰 曰 本 本 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 唬Α 〇5 = two and the remaining part of the copper and the inevitable impurities of the structure and composition: ten content w4.3%, (Ni + c 〇) / si_2: 1 ~ 7 : 1 forged steel alloy 'the forge gold Has more than 40% IACS of electricity. After the combination of Mingfa and Fa, the growth of the particles by π f哏 is formed, so that a sulphate which contributes to the aging effect and the softness of the bismuth is formed. If the cobalt content is less than 0.5%, then it contains a few of them. # a @ t The precipitation of the phase will not be enough and "" combines the most money of (10) Xiaoshi Xi contains the material, the alloy of m money and the best VX Ύ 〇 ^ ^ ® k of G'5% are kept below 20 microns. The content of cobalt in the field exceeds 25%. -, will precipitate excess second phase particles, k becomes less processability, B gives poor strength to steel alloys 200915349 Magnetic properties. In the pamphlet of International Publication No. 2006/101 172 (Patent Document 3), the strength of the Cu-Ni-Si alloy containing 5 Co can be greatly improved under certain composition conditions. Specifically, it is described that copper metal for electronic materials contains Ni: from about 0 5 to about 25 mass%, C. : about 2.5% by mass, and si: about 〇·3〇 to about 丨2% by mass, and the balance is composed of Cu and unavoidable impurities, and the total mass of bismuth and Co in the alloy composition is relative to the mass of Si. The concentration ratio ([Ni+c〇]/匕) is about 5 g [Ni + Co] / Si of about 5, and the "Bere concentration ratio of Co (Ni / c 〇 ratio) in the alloy composition is about 〇 $ $ 约约2 〇<There is a tendency to increase the speed of the cold part after heating when the solution treatment is carried out, so that the strength of the Cu_Ni-Si-based copper alloy can be further enhanced, so that the cooling rate is about every second. Cooling above 1 G ° C is helpful. It is also known to control the coarse inclusions in the copper matrix. Japanese Patent Laid-Open No. 2001-49369 (the patent is incorporated herein by reference). After adjusting the composition of the Nl-Si alloy, it is necessary to p, and can be refined to contain Mg, Zn, Sn, Fe, Ti, Zn, Ag, Be, and control and select the manufacturing conditions to control the precipitates in the matrix, The gentleman 曰 产 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Copper alloy and mine guide, Μ: vibration S ” leaf * body. 'System is a kind of copper alloy for electronic materials, which is characterized by containing 丨〇~4_8wt% of smoke λ 〇3 .ϋ and 〇.2~1.4Wt% of Si, the remainder is composed of impurities that can be avoided by 200915349, and the size of the inclusions is below 1〇μηη, and the number of inclusions of 5~ΙΟμηη is in the calender In the literature, it is described that in the solidification process during casting of semi-continuous casting, coarse crystals and precipitates of Ni-Si type are sometimes formed. Therefore, the method of controlling the same means that "the heating is not carried out after heating at a temperature of 8 〇〇 or more for 1 hour or more, so that the end temperature is 650 ° C or higher, thereby causing the coarse inclusions to be solid-solved. In the matrix, if the heating temperature is above 90 CTC, there will be a large amount of scale and cracking during hot pressing, so the heating temperature is preferably 8 〇〇t > c or less, less than 900 °. C. [Patent Document 1] 曰本特开平n — 222641号 [Special [Patent Document 2] Japanese Patent Publication No. 2005- 532477 [Patent Document 3] International Publication No. 2-6/1〇1172 [Patent Document 4] Japanese Laid-Open Patent Publication No. 2001-49369. It is known that the strength and conductivity can be improved by adding a Cu_Ni_Si-based alloy, but the microstructure of the Cu-Nu-based alloy to which c〇 is added is observed by the Japanese and Japanese people, and it is found that it is distributed compared to when it is not added. More coarse second phase particles. This second phase particle is mainly composed of Co. The coarse second phase particles not only do not contribute to the increase in strength' but also adversely affect the bending workability. In the case of the Cu_Ni-Si-based alloy which does not contain ～, even if it is produced under the condition that the formation of coarse second-phase particles of 200915349 can be produced, the formation of coarse second-phase particles cannot be suppressed. In other words, the Cu—Ni—Si—c〇 alloy is heated at a temperature of 8〇〇〇c to 9〇〇t as described in Patent Document 4, and then hot rolled and the temperature is terminated. The method of suppressing the formation of coarse inclusions at 65 〇t or more does not allow the coarse second phase particles mainly composed of c ruthenium to be sufficiently solid-solved in the matrix. Further, even in the method of increasing the cooling rate after heating in the solution treatment as taught in Patent Document 3, the coarse second phase particles cannot be sufficiently suppressed. In view of the above, the present inventors have disclosed a Cu-Ni-Si-Co alloy which inhibits the formation of coarse second phase particles in the previously unpublished Japanese Patent Application No. 2007-92269. Specifically, an electron comprising Ni:1.〇~2.5 mass%, c〇:〇5 to 25f%, si:〇3 to 1.2% by mass, and the remainder consisting of Cu and unavoidable impurities is disclosed. The copper alloy for materials has no second phase particles having a particle diameter exceeding that of the melon, and the second phase particles having a particle diameter of 5 μm to 10 μm are 50 or less in a cross section parallel to the rolling direction. In order to obtain the copper alloy, it is necessary to pay attention to the following two conditions in the manufacturing process of Cu-Ni_si-c〇 system s gold: (1) The hot rolling is at 95 (rc~105 (rc heating for more than i hours) After that, the temperature at the end of hot rolling is 85 〇t or more, and the cooling is performed at a cooling rate of 15 艽/s or more, and (2) the solution treatment is performed at 85 ° C ~ j 〇 5 〇 The crucible is carried out and cooled at a cooling rate of b / s or higher. The copper alloy of the invention can achieve favorable alloy properties which can improve strength without sacrificing conductivity and bending workability 9 200915349, but still Therefore, the object of the present invention is to provide a Cu-Ni-8 b-based alloy which can have a higher degree of strength, electrical conductivity and bending workability. Further, another aspect of the present invention - A problem is to provide a method for producing the above-mentioned Cu-Ni-Si-Co alloy. The inventors of the present invention have solved the above problems and found that the Cu~Nl_Si_Co alloy is more desirable than Japan. The size of the second phase particle of the size specified in Case No. 69 is small. The presence of particles has an adverse effect on the properties of the alloy. Specifically, it is found that the particle size is above Ο.ΙμΓη, below 1μπι, and the density of each of the particles containing more than 丨% and the second phase of w is an important factor. By making the density of the second phase particles ΐχΐ〇4/my or more and lxl〇7/mm2 or less in the cross section parallel to the rolling direction, the alloy characteristics, particularly the bending workability, can be improved. It is important to control the second phase particles to the above-mentioned density, the hot pressing delay or the subsequent cooling rate of the material. Specifically, it is found in the manufacturing steps of the Cu-Ni-Si-Co alloy, 95 〇χ: ~ι〇5(Γί^σ& After 1 hour or more, hot rolling is performed, and the temperature at the end of hot rolling is 650 ° C or higher, and during the hot rolling or cooling, 2 stages are performed. Cooling, that is, the material temperature is reduced from 85 (rc to 65 〇. (: the average cooling rate is above l ° C / s, less than 15 〇 C / / s for cooling, and from 650 ° C The average cooling rate at 400 ° C is above 15 t > c / s for cooling ' It is very important to control the density of the second phase particles. The invention completed in the context of the above findings is an electronic material 200915349 Lai alloy containing state: 1.0 to 2.5% by mass, Co: 〇·5~2·5篁%, Si: 0.3 ～12 傅番〇 / • Quantity ^, the remainder consists of Cu and unavoidable impurities, particle size: 〇_丨μ 1 M, 1 μηη or less, and each contains i Berry / The second phase particles of Ni, Co and Sl of 6 or more are upper, 1 > 1 〇 7 / 匪 2 or less in a cross section parallel to the rolling direction. f In the embodiment, the copper alloy for electronic materials has no second phase particles having a pulling control of more than one nickname, and the second phase particles having a particle diameter of 5 to 50 have a cross section parallel to the rolling direction. /mm2 or less. In the other embodiment, the copper alloy for electronic materials of the present invention further contains a maximum of 0.5% by mass of cr. In another embodiment, the steel alloy for an electronic material of the present invention further contains one or two or more elements selected from the group consisting of Mg, s, Ag, and p in a total amount of up to 0.5% by mass. The steel alloy for an electronic material of the present invention, and in another embodiment, the step further comprises a total of up to 2.% by mass of an element selected from the group consisting of: or two. In the other embodiment, the bismuth material is a copper alloy, and in another embodiment, one or two or more elements selected from the group consisting of AsUB, 1 Zr, ..., and Fe are contained in a total amount of 2% by mass. In the present invention, the average crystal grain size of the cross section of the present invention is 20 or less. Artificial method for producing the above copper alloy, comprising the steps of: sequentially casting an ingot having a desired composition; 11 200915349 - heating at 950 ° C to l 〇 50 ° C 】 After more than one hour, hot calendering is carried out, and then the temperature at the end of hot calendering is above 65 〇t, and the temperature of the material is lowered from 85 (rc to °c) during hot rolling or subsequent cooling. The average cooling rate is above rC/s, less than 15t/s, and the average cooling rate is reduced from 650 ° C to 400 ° C above 15 t / s step; a cold rolling step; f i. - at 850 t ~ lG5〇t is subjected to solution treatment, and the material is reduced to a temperature of more than 15 t/s at the time of c. Another arbitrary cold rolling step; an aging treatment step; and - cold rolling of Rensi The present invention is also a copper alloy using the above copper alloy. m'r An electronic machine part using the above copper alloy. The present invention can be further connected due to the second phase state of a specific size. X 4 two system its distribution improves the characteristics of k liter alloy, especially Bending workability. [Embodiment] [Addition of Ni, Co, and Si]

Ni, Co, and Si' can be formed by performing appropriate compounds, and can be formed without treatment.

Ni ^ Co^ ς· Fully high strength. The amount of W Co and 81 added, if Ni reaches 0.5% by mass, ς. soil 4 builds 1,0 ft. %, Co does not, S 丨 does not reach 0.3% by mass, then & ^ is not, conversely, if χτ · 4 can not pass to the strong right 所需 more than 2. 5 I South strong C 〇 more than 2.5 quality J2 200915349

When Si is more than 1.2% by mass, the strength can be increased, but the electrical conductivity is remarkably lowered and the hot workability is also deteriorated. Therefore, the amounts of addition of Ni and Si are such that Ni is 〜2·5 mass%, c〇 is 〇5 to 2·5 mass%, and Si is 0.3 to U mass%. The addition amount of Ni, c〇 and Si is preferably Ni: 1.5 to 2.0% by mass, C〇: 〇.5 to 2 〇% by mass, and si: 〇% by mass.

[Cr addition amount] Since Cr is preferentially precipitated in the grain boundary during the cooling process during the dazzle casting, the grain boundary can be strengthened, and cracking is less likely to occur during hot working, and the yield can be suppressed. In other words, when it is melted and cast, it is precipitated at the grain boundary. Although it is re-dissolved by solid solution treatment, it may form precipitated particles of bcc structure mainly composed of Cr or the like when it is precipitated in the subsequent aging. ^ The compound. The amount of W added in the usual Cu-Ni-Si alloy

Among them, Si which is not helpful in aging precipitation is directly dissolved in the mother phase to suppress an increase in conductivity, but it is possible to further reduce the amount of solid solution by adding Cr which is a constituent element of the telluride to precipitate out of the stone. The conductivity can be improved without impairing the strength. However, if the Cr concentration exceeds 〇 5 mass%, it is easy to form Cr of Cu-Ni~ Si- which is a coarse second phase particle of the invention. However, if it is not 〇.〇3 is added 〇·〇3~〇.5 mass%, ‘so it will damage the product characteristics. Therefore, in the present Co-based alloy, "up to 0.5% by mass of mass%" can be added, and since it is small in effect, it is preferably more preferably 0.09 to 0.3% by mass. [Addition amount of Mg, Mn, Ag, and antimony] Mg Mn, Ag, and p are added in a small amount, and the electrical conductivity is not impaired, and product properties such as strength and stress relaxation properties can be improved. The effect of addition, 13 200915349 is mainly due to the fact that it is dissolved in the matrix phase, and can be further exerted by being contained in the second phase particles. However, if the total concentration of iVig, Μη, Ag, and p exceeds 0.5%, then in addition to the characteristics of M & 4 A. The improvement of the social property will reach saturation, which will also impair the manufacturability. Therefore, in the Cu-Ni-Si-Co 糸a gold of the present invention, one or two or more elements selected from the group consisting of Mg, Mn, Ag, and P may be added in a total amount of up to 0.5 mass%/0. However, if the right side is less than 0.01% by mass, since the effect is small, it is preferable to add a total of 〇1 to 质量%, more preferably 〇.〇4 to 〇.2% by mass. , 〇 [Addition of Sn and Zn]

Sn and Zn' are also added in a small amount, and the electrical conductivity is not impaired, and the properties of the product such as strength, stress relaxation property, mineralization, and the like can be improved. The effect of the addition is mainly due to the fact that it is dissolved in the parent phase. However, if the sum of the gentlemen and the total amount exceeds 2.0% by mass, in addition to the fact that the sexual improvement effect will be saturated, the manufacturing property will be impaired. Therefore, in the Cu-Nl~Si-Co system of the present invention, a total of up to 2 〇 τ ^ s can be added to the element selected from the group consisting of Sn and Zn or two kinds of elements. However, if it does not reach 〇 „ , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , [As, Sb, Be, Β, Ti, Zr, A1, and Fe]

As, Sb, Be, B, Ti, Zr, A1 » ^ f A1 and Fe, can also improve the conductivity, strength, stress relaxation characteristics, mineralization, etc. by adjusting the amount of addition. · ·,, 袅 驭迮 袅 袅 characteristics. The effect of the addition is mainly due to the fact that S is dissolved in the mother phase and is also played by the 4 people. It can also be formed by the second phase, 3, and the second phase of the new composition. Particles, to play the effect of the step. 14 200915349 However, if the total of these elements exceeds 352 〇 mass%, in addition to the characteristic change D effect will be saturated, it will also damage the manufacturability. In the Cu-Ni-Si-Co-prepared human antimony alloy of the present invention, a total of up to 2 〇 mass% of one of AS Sb, Be, B, Ti, Zr, A1 and Fe may be added or More than 2 kinds of τ. However, if the amount of G(10)i f is less than 5%, the total amount of GKG f is preferably added, and more preferably 〇〇5 to 1_0% by mass. When the total amount of the above-mentioned Mg, Mn, Ag, P, Sn, Zn, As, Sb, Be, B, Ti, Δ, AI, and Fe is more than 3% by weight, the manufacturing property is easily impaired. Preferably, the total amount of these elements is S 2.0 f or less, more preferably 1.5% by mass or less. [Distribution condition of the second phase particles] The card & gold can be deposited by the appropriate aging treatment to precipitate the nano-sized fine second phase particles mainly composed of the intermetallic substance α, without causing the 'privacy rate deterioration. And it is possible to increase the strength. However, the Cu-state: Co-Sl alloy of the present invention is different from the conventional Cu-Ni-si-based Carson alloy, and it is easy to produce coarseness due to the active addition of Co as a necessary tool for ageing precipitation hardening. Second phase particles. The coarse second phase particles are preferable because they cause a decrease in alloy characteristics. In the present invention, the second phase particles mainly refer to the telluride, but are not limited thereto, and the crystals produced by the solidification process of the casting are melted and the precipitates generated after the crucible is heated. Precipitates produced by the cooling process after the solution treatment in the cooling process after rolling, and precipitates generated during the aging treatment. 15 200915349 Coarse second phase particles, first, the particle size is above Ο.ίμιη, below 1μιη, and each contains more than (10) Ni, c〇, and the second phase particles, which does not help to strengthen, and cannot be obtained. It is expected that the aging effect will strengthen and positively add the effect of C〇. In addition, the second phase particles containing only Ni, c〇, one or two elements of ^(9) or more do not contribute to strengthening, but if In the case of the second phase particles containing Ni, c〇, and Si of _ or more at the same time, the degree of enhancement of the damage is small. Therefore, the second phase particle system of such a size and containing each of 沁Co and Si is not originally required, and also contributes to the precipitation of the fine second phase particles in order to improve the precipitation of the fine second phase particles.

The utilization of Si is preferably such that the coarse second phase particles are first dissolved in the matrix phase prior to aging treatment. Therefore, the second phase particles which are formed by the process of homogenization annealing, hot rolling, and the like of the ingot may be sufficiently solid-solved at a high temperature during the solution treatment. However, if the solution treatment is carried out for a long period of time at a high temperature, coarsening of the recrystallized grains will be caused. This is not preferable because the bending workability of the product is greatly deteriorated. Further, the second phase particles having a certain degree of largeness also have a pinning effect of preventing grain boundary movement due to coarsening of crystal grains. From this point of view, after repeated investigations, the inventors have found that the copper alloy finally obtained has a particle diameter of 〇·_ or more and (10) or less, and each of which contains iwt% or more of Ni, c〇, and Si. When the phase particles are made in a range of 1×10 pieces/mm 2 or more and 1×10〇7 lower jaws ε parallel to the rolling 々L, both the strength and the bending workability can be balancedly improved. (4) The number of second phase particles of the grain # last unfinished lxl〇4 / 16 200915349 f

Although K mm2 can be made to have high strength, this means that the solid solution amount of the second phase particles in the solid phase is high in the solution treatment, and the distribution of the second phase particles is scattered. Therefore, a sufficient pinning effect cannot be obtained, and crystal grains will be coarsened, resulting in deterioration of bending workability. On the other hand, in the case where the second phase particles having a particle diameter of more than ΐχΐ〇2/mm2 remain, the solid solution amount of the second phase particles in the solution treatment is small, and the crystal grains can be suppressed. It is coarsened, but it is impossible to obtain product characteristics, particularly strength, depending on the amount of addition of the alloying elements. The residual density of the second phase particles having the particle diameter is more preferably 个5 pieces/mm2 or more and lx10 pieces/my or less. The second phase particles having a particle diameter of Ο.ίμηι or more and 1 μΓη or less can be observed by combining the elemental mapping of the FE-EPMA and the image analysis software, and the particles dispersed in the observation field can be measured. Concentration, number and particle size. Whether or not each of the second phase particles contains Ni, Co, Si' on iwt% & can be judged by quantitative analysis by EPMA. In the present invention, the particle diameter of the second phase particles means the diameter of the smallest circle surrounding the particles when the second phase particles are observed under the above conditions. Is the particle size larger than the coarse second phase? Regardless of its composition, it does not help to increase the strength, but also reduces the bending workability. In particular, since the second phase particles having a particle diameter of more than 1 〇μηι are significantly deteriorated in bending workability, the upper limit must be 1 〇μη ΐ β. Therefore, in a preferred embodiment of the present invention, 'there is no particle diameter exceeding 1 〇. Ϊ́ηΐ2 second phase particles. When the second phase particles having a particle diameter of 5 μΓη to ΙΟμηη are within 5〇/^^2, the strength and the f-cut property are not seriously impaired. Therefore, in another preferred embodiment of the present invention, the cross section of the second 17 200915349 phase particles having a particle diameter of 5 μm to 1 μm is parallel to the rolling direction of 5 Å/my or less, more preferably 25 More / mm2, more preferably 2 / / claw 2, the best is η / my or less. When the ratio of the second phase particles having a particle diameter of more than 1 μίη and less than 5 μm is suppressed, the coarsening of the crystal grain size in the solution treatment stage may be coarsened in the aging treatment after the aging treatment. Compared with the second phase particles above _, it is considered that the influence of the characteristic deterioration is smaller. Further, the particle diameter and the number of the second phase particles having a particle diameter of more than 1 μm may be phased by the second phase particles having a particle diameter of 01 to 1 μη1 in the range of the present invention; The section of the rolling section is subjected to an electron microscope after observation, and an electron microscope such as 4 ΕΡΜΑ is used to observe the [crystal grain size]. The copper alloy of the present invention is obtained by the distribution condition of the second phase particles. Appropriate to prevent coarsening of recrystallized grains during solution treatment, and thus the crystal grains are also fine. In one embodiment, in the copper alloy of the present invention, the average crystal grain size of the cross section orthogonal to the rolling direction (measured by the m-cutting method) is 20 or less, and in a typical embodiment, at 18 Below handsome, in a more typical embodiment, it is 5~15μιη. [Manufacturing method] The general process of the Caston copper alloy is firstly melted by using an atmospheric melting furnace to dissolve the electrolytic μ, Ni, Si, Co, etc., ρ & original materials to obtain the desired composition. The melt solution. Next, the smelt is cast into an ingot ', and then hot calendered' and then subjected to cold rolling and heat treatment, and finished into a strip and foil having a thickness and characteristics of 18 200915349.固 Solution treatment, 俜 about 7 Λ ... #Solution treatment and aging treatment. The dance is performed at a high temperature of about 700 to about 1, and (4) one-phase particles are solid-dissolved in the base, and I is heated so that it is also heat-calendered to double/recrystallize. Sometimes 550 〇C r ^ t double treatment, is about 35 〇 ~ dissolved second phase particles with nanometer fine granules = solution treatment solid effect treatment can improve strength and conductivity... Cold rolling is performed before and/or after aging. Also, ^ degree' is sometimes calendered, and the main newspaper is ancient* after the aging period. ^ After the cold rolling, the strain relief annealing (low temperature peeling = Γ, can be suitably used to remove the surface oxidation record) grinding, bead blasting, pickling, etc. Even the present invention The copper alloy has undergone the above-mentioned process, in order to make the particle size of the finally obtained copper alloy G, it will be more than 1μηΐ, the following second phase grain: (or even the particle size exceeds 1μηι The shape of the second phase particles is controlled in the desired state. Therefore, it is very important to strictly control the thermal elongation and solid solution treatment. Because of the Cu-initiating alloy of the present invention, it is in < Cu-N! Unlike the St-Cassin alloy, the α Ni Co Si-based alloy of the present invention is positively added with C which tends to coarsen the second phase particles. (Additionally (7) is added as an aging precipitation hardening. This is due to the fact that the formation and growth rate of the second phase particles formed by the addition of c〇 and Ni and W are sensitive to the temperature and cooling rate during the heat treatment. During the solidification process, due to the thick knot Crystal Society 19 200915349

Therefore, if the holding temperature before the delay is less than 95 (rc, the solid solution will be insufficient. If it exceeds 105 (TC', the material may melt. Also, when the hot rolling is finished, the temperature is less than 6501: In this case, since the element to be solid-solved is precipitated again, it is difficult to obtain high strength. Therefore, in order to obtain high strength, it is preferred to terminate the hot rolling at 650 ° C and then rapidly cool it. It is dissolved in the mother phase. If it is hot-grinded after 950 hours or more and hot rolled or more, even if Co (even 〇) is added, the temperature condition above 950 °C is lower than that of ' It is a higher temperature. When hot pressing, but during hot rolling before solution treatment or during solution treatment, if the first phase particles are too solid solution, they are used to inhibit recrystallized grains during solution treatment. The coarsened second phase particles having a pinning effect will be insufficient, resulting in coarsening of the crystal grains. Therefore, the second phase particles must remain to some extent during the hot pressing delay before the solution treatment. 'When hot rolling or subsequent cooling, The rate of temperature reduction of the material is very important. The focus is on the cooling rate from 85 ° C to 650 ° C and from 650 ° C to 400 ° C. Specifically - when the material temperature is reduced from 850 ° C to At 650 ° C, the average cooling rate is above i ° C / s, less than 15 ° C / s, preferably above 3 ° C / s, i2 ° during hot rolling or subsequent cooling. C / / s below 'better than 5 ° C / S or more, below HTC / s. Also, when the material temperature is reduced from 650 ° C to 400 ° C 'has the average cooling rate above 15 〇 c 20 200915349, Preferably, it is 17 ° C / s α. In this way, the second phase particles which are effective as pinning particles can be precipitated. If the cooling rate from 85 (TC to 65 (TC is less than rc/s), The second phase particles will be excessively precipitated and coarsened, resulting in difficulty in performing a better solidification/bonding treatment, and impairing strength and bending workability. On the way of hot rolling, the temperature of the material is slowly lowered, but due to its The speed is generally as slow as 〇1 to l°C/s, so in 650~85 (the area of rc is subjected to hot pressing delay, it is necessary to deliberately perform cooling.

K ',, and ' from 650 to 850. . In the area, increasing the cooling rate to a certain level is not a good method. Therefore, if the cooling rate is higher than the above, the second phase particles will not be precipitated or will be precipitated only slightly, so that the number required for the solid solution treatment step (4) to hinder the movement of the recrystallized grain boundary cannot be obtained. The crystal grains are coarsened, and the f-curvature property is deteriorated. In the area of 4〇〇C~650°C, try to improve the cooling "Good. The average cooling rate must be above 15 °C / s, preferably A is above /8. In order to prevent the precipitation of the second phase particles from 65〇~ = to the extent necessary: the second degree = the first, the precipitation of the phase particles is more significant around the battle, so the cooling rate is not reached It does not pose a problem. The cooling rate can be adjusted by heating the belt and the cooling belt after the rolling is completed... Tian Bai - again (4). When necessary, the mouth should be 4: to apply a water-cooled spray, and slow cooling to sigh the wind circulation device. The second phase particles precipitated in the above manner will reduce the particle size and the number of the solid solution 21 200915349 in the intermediate step, although the number of pellets will increase during the aging treatment, but The conditions of the solution treatment and the aging treatment are the appropriate conditions described later, so that in the final product, the second phase particles having a particle diameter of one or more and one or less (even the second phase particles of the granules exceeding _) have The distribution pattern of desire. In the case of solution treatment, the same as the suspect, - Γ, the door can also be made by the solution treatment temperature of 850 ° C ~ 1050 ° C, so that the first phase of the first Futian & The phase particles are solid-solved. In the cold part process after the solution treatment, since there is no necessity to precipitate the second phase particles, the average coldness of the C should be = 15 ° /su, preferably at the scratch Above, even if the cooling rate after hot rolling is not controlled, and only the coldness after the solid treatment is controlled, the coarse second phase particles cannot be sufficiently suppressed by the subsequent aging treatment. The cooling rate after hot rolling, The cooling rate after solution treatment needs to be controlled together. The method of making the cooling fast is the most effective in water cooling. However, since the cooling rate changes due to the temperature of the ruler and the water used, the temperature of the tube can be controlled. To make the cooling faster. If the water temperature is above, then the cooling speed required (4) is sometimes impossible, so it is better to keep it under 25 c ;; 6. Place the material in a tank with water. Water cooling inside, because the temperature of the water is easy to rise, Man 2 $ IV I· η rises 5 C or more, so It is sprayed in a mist (spray t mist) or keeps cold water flowing into the water tank to cool the material at a solid U water temperature (below the hunger) to prevent the water temperature from rising. Also, it can be cooled by a water-cooled nozzle. Add or increase the amount of water per unit time to increase the cooling catch. In the present invention, the thermal delay of "from 850t to 650t: when 22200915349 average cooling rate" means that the measured material temperature is reduced from 8501 to 65.冷却 ° C cooling time, and then "(85 〇 - 65 〇) (β (: cooling time (s), the value obtained (< t / s). "From 65 (rc reduced to 4 〇 The average cooling rate at the time of ”, in the same way, refers to the value ((C/s) obtained by "(650 - 400) (t cooling time (s) '. Also, during solid solution treatment" "Average cooling rate up to 4 °C" means the time during which the measured material is cooled from the solution treatment temperature to 400t, and then "(Solid temperature - 4 〇〇) (death) / cooling time (S)" The value obtained (.c / s ). The conditions of the aging treatment are conventionally used as long as it is effective for miniaturization of precipitates. The condition may be, but it is necessary to pay attention to setting the temperature and time so that the precipitate is not coarsened. If one of the aging treatment conditions is in the range of 35 〇, its temperature is 1 to 24 hours, more preferably 400 to 5 〇. (The temperature range of rC is 1 to 24 hours. In addition, the cooling rate after aging treatment hardly affects the size of the material. The Cu-Ni-Si-c lanthanide alloy of the present invention can be processed into various kinds of copper. Products such as plates, strips, tubes, rods and wires, and the Cu-沁-Si-Co-based copper alloy of the present invention can be applied to lead frames, connectors, pins, terminals, relays, switches, secondary batteries Use electronic parts such as foils. [Examples] The present invention and the comparative examples are shown below, but the examples are merely provided to provide a better understanding of the present invention and its advantages, and not to limit the present invention. [Discussion on the influence of the manufacturing conditions on the properties of the alloy] The copper alloy of the composition of δ contained in Table 1 (composition number 1) was melted at 2330015C in a high-frequency melting furnace of 23 200915349, and cast into a thickness of 3 〇mm casting. Then, the ingot is heated to 1 Torr (TC, and then hot rolled to a thickness of 丨 at various end temperatures (hot rolling end temperature), and the cooling rate is controlled, and after the hot rolling is finished, various types are used. The cooling rate was rapidly cooled to 400, and then placed in the air for cooling. Then, in order to remove the scale of the surface, the end face was cut to a thickness of 9 mm, and then cold-rolled to a plate having a thickness of 0.15 mm, followed by 950°. C solution treatment was carried out for 12 seconds, and then immediately cooled to 4 ° C after various cooling rates, and then placed in the air for cooling. Then cold rolling to 〇 1 〇 mm, then at 450 ° C The test piece was prepared by applying an aging treatment for 3 hours in an inert atmosphere, and finally cold rolling to 0.08 mm to prepare a test piece. [Table 1] Composition Ni Co Si ~----- Cr 1·0~2.5 0.5~2.5 0·3 ～1.2 〇·〇9~〇s 1 1.8 1.1 0.65 The crystal grain size, particle size distribution and quantitative analysis, strength, and conductivity of the second phase particles were measured for each test piece obtained in the above manner. And evaluation of the characteristics of bending workability.

The crystal grain size is obtained by filling the sample with a resin so that the observation surface is perpendicular to the rolling direction, and after mechanically grinding the surface to be mirror-finished, 10 parts by volume of hydrochloric acid having a concentration of 36% with respect to 100 parts by volume of water. In the solution in which the ratio is mixed, the dissolved iron is 5% by weight of the solution. Z 24 200915349 The sample was immersed in the solution obtained in the above manner for 1 〇 second to cause the metal structure to appear. Next, the above-mentioned metal structure was magnified to 3 times by an optical microscope, and photographed, and a line of 2 mm was drawn at intervals of 25 mm on the photograph by a cutting method (Jish 0501) prescribed by Jis. , in the width direction of the plate parallel to the sample, "5 lines, and 5 lines orthogonal to the width direction of the sample plate, a total of 1 line", and then calculate the number of crystal grains n cut by the above line segment, and then .... With (10) / (10) (10). )) The formula is obtained. The number of fields of view observed was an arbitrarily selected field of view for the center portion of the thickness of each sample. The second phase particles are subjected to electrolytic polishing on the surface of the material to cool the base of U, and the first phase particles remain* appear. The electrolytic polishing liquid is adjusted by using phosphoric acid, sulfuric acid or pure water. When observing the second phase particles having a particle size of only 0.1 1 μm, it can be obtained by FE-EPMA (electrolytic radiation type: JXA-8500F manufactured by JEOL Ltd.) at an observation magnification of 3 times (observation field of view 3) 〇μιηχ3〇μιη), observe at any 1G. The measurement of the particle size and distribution of the second phase particles can be calculated by combining the observation of the secondary electron image with the attached image analysis software to calculate the number of second phase particles having a particle diameter of 0.1 to _, and calculating each number. The number of μηι2. Further, in each particle of the particle size distribution, the representative of the particle is subjected to quantitative analysis, and the particle size distribution and the concentration distribution data of the second phase particle dispersed in the observation field are used for analysis, thereby confirming the second phase. Each of the particles contains 1% by mass or more of Ni, c〇, and Si. On the other hand, when the second phase particles having a particle diameter of more than 1 μm are observed, the method is also used to observe the phase of the second phase particles of Μ~1 μηη, 25 200915349 at a magnification of 1000 times (the observation field of view 100 χ 120 μηι) Observe any W, and calculate the number of precipitates with a particle size of 5~10μηι and the number of precipitates with a particle diameter exceeding ι〇μηι, and then calculate the number of each lmm2. The concentration of the second phase particles is also measured. The quantitative analysis is performed in the same manner as the second phase particles of the particle size 〇_1~1μηι. The 〇 strength is measured by the tensile test in the parallel direction of rolling, to measure the 安全. 2 % safety limit stress (YS : MPa ~ Conductivity (EC, % IACS) is obtained by measuring the volume resistivity of the bridge with the use of the bridge. 4 The evaluation of the processability is performed by the usual 9 〇. The bending test is difficult. Mastering the improvement of bending workability, 18G is performed with astm_e_29〇. Bending and edging. The test is carried out under the condition of the ratio of the thickness of the sample to the radius of the f-curve of ^ 2 (4). The stomach (the bending axis and the rolling direction are The same side J sounds ° In the case of mussels, the surface of the bent portion was observed by an optical microscope. When the crack was not observed, it was judged that there was no practical problem, and if it was cracked, it was X. The manufacturing conditions and results are shown in Table 2. 200915349 [(N<] characteristic electric 〇〇〇〇XXXXXX conductivity (% IACS) 芝 m in in <n (four) geisha S g 〇〇ο ON 00 Ο ο 00 ο Ον 00 ο 窆Ο ο ο in o ss s Particle size of the second phase particle (μηι) >10/mm2 〇ο ο Ο ο inch ο o 00 〇 /mm2 _ί 〇rH Ό f ·Η ^-Η IT) 〇\ οο yri 卜卜r- 1 1 1—( 〇xlO4 /mm2 ss m 芝 § Ο <Ν (Ν 〇\ c5 4537 6485 8731 00 d 9822 crystal grain size | _I ε η 00 οο Ο IT) CN inch cn m CN (N solid solution Processing ο Ο f 〇 00 00 00 00 00 00 Bu Bu 00 00 Hot rolling cooling rate (°C/s) 650~400°C 宕宕 Cooling rate (°C/s) 850 ~ 650. ο m ο <η CN CN m 〇rt in iH 1 Hot calendering end temperature __0C)__ ο 00 ο ο ο ο ο ο oo Ο ο ο Ο ο ooo (N oov〇Z (Ν m inch in \〇 00 00 Os 〇 200915349

In the alloy of No _1 to 4, since the distribution conditions of the second phase particles are appropriate, the strength, electrical conductivity, and bending workability are excellent.

Since the alloy of No. 5 is from 850 to 65 (the cooling rate of TC is too large, the number of second phase particles having a particle diameter of 0 · 1 to 1 μη is reduced, and the crystal grain size is coarsened, resulting in deterioration of bending workability. In the alloy of Νο·6, since the cooling rate from 650 to 400 ° C is too small, the number of coarse second phase particles is increased, and both strength and bending workability are deteriorated.

In the alloy of No. 7, since the cooling rate after the solution treatment was too small, the number of coarse second phase particles was increased, and both the strength and the bending workability were deteriorated.

In the alloy of No. 8, since the cooling rate from 650 to 400 ° C is small and the cooling rate after the solution treatment is too small, the number of coarse second phase particles is increased, and the strength and bending workability are deteriorated.

The alloy of No. 9 is equivalent to the alloy of the Japanese Patent No. 2〇〇7_〇92269. Since the cooling rate is from 850 to 65 (the cooling rate of rc is too large, the second phase particles of the particle position 0 · 1 to 1 are caused. The number of the particles is reduced, and the crystal grain size is coarsened to deteriorate the bending workability.

In the alloy of No. 1 ’, the temperature at the end of the hot rolling is too low, so that the number of the first phase particles which are coarse and coarse is increased, and both the strength and the bending workability are deteriorated. [Discussion of the influence of the composition on the properties of the alloy] The copper alloys of the various compositions described in Table 3 were melted in a high-frequency furnace at 1300 C, and cast into an ingot having a thickness of 30 mm. Then, 28 200915349 After heating the ingot to 1 ooo °C, the end temperature (hot calendering end temperature) is 700 C' and the hot rolling is performed to a thickness of 1 〇mm, while controlling the cooling rate, hot rolling At the end, it was quickly cooled to 4 ° C at various cooling rates and then placed in air for cooling. In either case, the average cooling rate from 850 to 65 °C is 10. 〇/8, from 650 to 400. The average cooling rate of the 马 ’ ’ 去除 removal table is 20. (: / ; The end face is cut to a thickness of 9 mm, and then cold-rolled to a plate having a thickness Z of 0_15 mm. Then, after a solution treatment of 12 sec seconds at 95 rc, the cooling rate is immediately 18 C/s. Cool it to, then place it in the air to cool the D-base, then cover it, then cold-calender it to 〇10mm, then apply it to the inert atmosphere at 450 °C for 1 hour. Aging treatment, and finally cold rolling to 0_08mm 'made test piece. 29 200915349

Characteristic electric conductivity (%IACS) σ; target S' 缌s Ο οο οο Ο g ο ο σ\ S 〇\ ο <Ν σ\ m oo 5: ▼ "H 〇\ oo Q\ OO o 5; W >10 /mm2 ο ο ο ο ο ο ο ο oooo Φτ 屮羿Ί 〇 l in /mm2 00 ο inch inch tn inch inch 0.1 ~1 xlO4 / Mm2 : CN g iT) τ—Η CN 00 ΙΛ (Ν CN r*H 00 ΙΛ 00 r~< m νο mv〇1-H ιτ·Η 1—H 00 Crystal grain size B zL ν〇CN ί» Η Ο m (Ν cn cn m CN Other 0.1 Mg O.lMg O.lMg, 0.5Sn, 0·5Ζη O.lMg, 0.5Sn, 0·5Ζη, 0.03B O.lAg ί 0.03P ΰ ι—1 ι— Η ί-H ο ιη ν〇Ο iTi ϊ> ο ^Τ) 00 ο 0.65 \Ti ο 0.65 in v〇〇o in 〇in \〇o 0.70 ο Ο iTi τ—Η οο Ο ο Ο oo 〇 oo Τ Τ ο οο 00 00 00 00 00 00 00 OO oo o <N d Z ι 1 (Ν γ〇 inch iT) ν〇Ο 00 〇\ <N CN 200915349 One-phase particle distribution processability is excellent

The alloy of No. ll to 22 is suitable for the strength, electrical conductivity and bending properties of any of the above conditions. However, when '〇·15 is compared, the difference between the two is whether or not Cr is added, and 0.1% by mass of 夕ρ and ^ of Cr of No. 15 are added, and the strength and electric conductivity are excellent. Also, even if you add other elements added to the ancient ^ 1 , the intensity will be improved. [Simple description of the diagram] None [Key component symbol description] None i 31

Claims (1)

200915349 X. Application for patents: 1. A steel alloy for electronic materials containing Ni: "%, Co: ~25 皙. / c· . 2.1 2 The quality of 2.1 Berry%, Si: 0.30~1.2 The quality of the division is divided by the CU and the unavoidable miscellaneous treasure, the remaining part, and the second ==: 1 =, the particles are parallel to The section of the rolling direction is lxlG4, m2 or more and 1X103 4 5 / mm2 or less. 2·For example, the steel alloy for electronic materials as claimed in Article -6... The second phase particles having a particle diameter exceeding ΙΟμηη, grain, horse 5 The cross-section of the two-phase particles of 〜l〇um is less than 5 平行 in parallel with the direction of the rolling. 3. The steel alloy for electronic materials of the patent range 帛i of the claim month satisfies any of the following 1) to 4) or The second or more conditions are as follows: 1) further containing up to 0.5% by mass of Cr; 2) further containing a total of up to 0.5% by mass, g only 〇/〇 and one or more of Mg and P The element; 'Ag 3) further contains a total of at most 2.0% by mass /0 < an element selected from the group consisting of Sn and 7 or 2; B 1 of 32 B, Ti, Zr, A1 and Fe 1 or 2 The above elements, Be, 2 4. The copper for electronic materials 3 as in the second paragraph of the patent application has the following 丨)~8) one or more The composition of the product has a maximum of 〇·1 mass%<Cr; 5 2) Progress contains a total of up to 0.1% by mass of the white 6 运目]Vlg, 7 and Ρ1 or Two or more elements; n, Ag 8 further contains a total of up to 2.0% by mass of A^s, RVi 200915349 3) The step contains a total of up to 2.0% by mass of one or two selected from the group consisting of Sn and Zn. 4) The step-in-step contains a total of up to 2.% by mass of the elements selected from B, T!, Zr, A1, and Fe, or two or more elements. The copper alloy for electronic materials is below the average crystal grain size of the cross section orthogonal to the rolling direction. 6_-The method for producing a copper alloy for electronic materials includes the following steps: The step of ingot casting to be melt-casting; - hot rolling after heating at 95 (TC~d.c) for more than 1/2 hours, then the temperature at the end of hot rolling is 65 〇t: or more, and hot rolling Average cooling of the material temperature from 85 〇 to 650 ° C during cooling on the way or after hot rolling The speed is above rC/s, less than 15 of it /\, and from 650. (: reduced to 40 (the average cooling rate of TC is above 15t / s; a cold rolling step; one at 85 〇 1 ~ 1〇5〇.(: The step of performing solution treatment and lowering the temperature of the material to 400 ° C, the average cooling rate is above 15 ° C / s. · an arbitrary cold rolling step; an aging treatment step; An optional cold rolling step. 7. - A type of copper alloy is used as a copper alloy of any one of the claims 1-4. 33 200915349 8. The copper alloy is a copper alloy of the fifth application patent. 9. An electronic machine part using the copper alloy of any one of claims 1 to 4. 1 〇. — A kind of electronic machine parts, which is a copper alloy using the fifth item of the patent application. Η一,图: Benefit 34