TW200907077A - High-strength and high-electric conductivity copper alloy having excellent hot workability - Google Patents

Abstract

To provide a copper alloy for electronic parts composed of a Cu-Ni-P based alloy having satisfactory hot workability and exhibiting high strength, high electric conductivity and high thermal conductivity without impairing its bending workability.The high-strength and high-electric conductivity copper alloy having excellent hot workability, is a copper alloy having a composition containing, by mass, 0.50 to 1.00% Ni and 0.10 to 0.25% P so as to satisfy the ratio between the Ni content and the P content, Ni/P: 4.0 to 5.5, and 0.005 to 0.070% B, <=0.0050% O, and one or more selected from Fe, Co, Mn, Ti and Zr by <=0.05% in total, and the balance Cu with inevitable impurities, wherein regarding the sizes of the second phase grains, provided that the major axis is denoted as a and the minor axis is denoted as b, the second phase grains having a of 20 to 50 nm and the aspect ratio a/b of 1 to 5 occupy >=80% of the area ratio of all the second phase grains with the major axis a of >=5 nm included in the copper alloy. The copper alloy may optionally contain one or more selected from Sn and In by 0.01 to 1.0% in total.

Description

200907077 IX. Description of the Invention: [Technical Field] The present invention relates to a high-strength, high-conductivity copper alloy for electronic equipment parts, and more particularly to a small-sized, highly integrated semiconductor backup lead and Among copper alloys for terminal connectors, copper alloys for electronic parts, which are excellent in hot workability and which do not deteriorate bending workability and are particularly excellent in strength, electrical conductivity, and thermal conductivity. [Prior Art] Copper and copper alloys are widely used in various applications as electronic components such as connectors and lead terminals, and flexible circuit substrates, in response to the rapid development of IT (Information Technology). The high functionality, miniaturization, and thinning of information equipment require further improvements in strength (strength, bending workability, and electrical conductivity). In addition, a high-power semiconductor device is used, and a lead-frame 〇ead frame material for a semiconductor device is used, and a Cu_Ni_Si system or Cu_Fe_p or Cu_Cr-Sn having excellent heat dissipation (electric conductivity) is used. , precipitation alloys such as Cu-Ni-P. Patent Document 1 discloses an adjustment in a Cu-Ni-P alloy.

An alloy having strength, electrical conductivity, and stress relaxation resistance in terms of Ni, P, and Mg components. SUMMARY OF THE INVENTION In general, in the casting of a copper alloy, such as continuous or semi-continuous casting, it is required to "cure" and cool "with a few millimeters (_) of the surface layer of the block in the casting of the copper alloy. time. Therefore, in the cooling process during solidification of 200907077 and after solidification, the alloying elements exceeding the solid solution limit (soUd s〇lubiHty limh) which is solid solution to the matrix at room temperature will be crystallized. Gradation or precipitation in the grain boundary and crystal grains. In particular, the Ni-P compound which is crystallized or precipitated at the crystal grain boundary of the Cu-Ni_P-based alloy has a melting point lower than the melting point of the parent phase Cu, and therefore, the stress due to the uneven strain in the solidification or the like And external forces can cause damage to one part of the Ni-P compound. Further, if the Νι-Ρ compound is softened or liquid-phased upon heating by hot rolling, cracks may occur during hot rolling. As a result, the Cu-Ni-P alloy has a problem that cracks occur during casting or hot working, but the patent document is not aware of the existence of this problem. An object of the present invention is to provide a copper alloy for an electronic component comprising a Cu-Ni-p-based alloy or a Cu_Ni-P-Mg-based alloy, which prevents the problem of the upper p-alloy, that is, prevents the scale manufacturing process. Cracks are generated during heating or heat-warming in a medium or hot working process, and are excellent in hot workability, and exhibit high strength, high electrical conductivity, and high thermal conductivity without impairing bending workability. In order to achieve the above object, the inventors of the present invention have repeatedly conducted research and found that: W can obtain Cu-Ni having excellent hot workability and excellent strength and conductivity without impairing bending workability by the following constitution. -P alloy and Cu-Ni-P-Mg alloy. The present invention relates to a high-strength and high-conductivity copper alloy having excellent hot workability, and has a Ni. 0.50% to 1.00% (in the present specification, a component ratio is expressed as a percentage of a bismuth system), P: 0.10. %~0.25%, content ratio of Ni to p 6 200907077 Rate 1^/?: 4. 〇~5.5, and, 6:0.0050/. ~0.070%, 〇:0〇〇5〇% The content of one or more of 'Fe, Co, Mn, Ti, and Zr is 〇〇5% or less, preferably 〇_〇3% or less' and remaining Partly composed of cu and unavoidable impurities, characterized by: For the second phase particle size, when the long diameter is a and the short diameter is b, the long diameter a is 20 nm to 50 nm before the final cold rolling. Further, the total area of the second phase particles having an aspect ratio a/b of u with respect to all of the second phase particles contained in the copper alloy accounts for 8 Å. /〇 above (area ratio Cl), and the conductivity is 45% IACS (Internati〇nal Annealed Copper Standard). Further, the present invention is a high-strength, high-conductivity copper alloy excellent in hot workability, which contains Ni: 0.50% to 1.00%, p: 〇_1〇% to 〇25%, called 0.01 to 0.20%, Ni and The content ratio of P is Ni/p : 4.0 to 5.5, and B: 0.005 〇 / 〇 ^ 0.070 〇 / 〇, 〇: 〇. 〇〇 5 〇〇 / 〇 α Τ &gt; Fe ^ Co ^ Μ η &gt; Ti &gt The total juice in one or more of Zr is 〇〇5% or less, preferably less than 〇, and the remaining part of 纟Cu and unavoidable impurities are characterized by:

Has the short-diameter rabbit 1 in the final cold milk, Q (1) sister 仫b horse 10~25 nm and the aspect ratio a/b is 2~5 0 of the second phase particles enough |) the above two phase particles (Β) and The long diameter a is 2 〇 nm to 50 nm and the aspect ratio a/b is not overflowed. The sum of the second phase particles (c) of the 〇 〇 〇 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对The sum of the areas accounts for more than 8 〇 0 / 〇 (area rate C2), and the conductivity is 45% ια. the above. The copper alloy of the present invention, in addition to ς and further among the species of Sn and ηη, contains 0.01% to 1.0% in total. 200907077 In the present day and the month, by adding a specific amount of B to the Cu-patch alloy or the Cu_Ni-p_Mg-based alloy, the crystallization or precipitation of the Ni_p compound to the crystal grain boundary is suppressed. Less · Again. The high temperature brittleness and the improvement of hot workability. [Embodiment] Next, the reason and the effect of limiting the numerical range of the composition of the constituents of the "B" of the copper in the present invention will be described together. [Ni amount]

Ni has a function of solid-solution in the alloy to ensure strength, stress relaxation resistance, and heat resistance (maintenance of ruthenium strength at a high temperature), and precipitates a compound of the following p to contribute to improvement of the strength of the alloy. However, if the content of Ni is less than 0.50%, the required strength cannot be obtained. On the other hand, if the content of niobium exceeds 1.00%, the electrical conductivity is remarkably lowered, so that the tensile strength is not obtained at 650 MPa. The above conductivity is high strength and high conductivity of 45% IACS or more. Therefore, the alloy of the present invention has a Ni content of 0.50% to 1.00%.

[P amount J precipitates a compound of P and Ni to improve the strength and heat resistance of the alloy. When the right P content is less than 0.10%, the precipitation of the compound is insufficient, so that the required strength cannot be obtained. On the other hand, if the P + amount exceeds 35G25%1, the balance of Ni and p in the skin will be balanced, resulting in an excess of p in the alloy, so that the amount of solid solution P increases and the conductivity is remarkably lowered. Therefore, the alloy of the present invention has a p content of 0.10% to 0.25 Å. . [Ni/P ratio j 8 200907077 Even if the content of Ni and p is within the above-defined range, if the Ni/P content ratio Ni/P is not within the range of the stoichiometric composition of the second phase particles, That is, when Ni/P is less than 4.0, the solid solution amount of p will increase, and when Ni/p exceeds 5 · 5, the solid solution amount of Νι will increase 'and the conductivity will be significantly lowered, so it is not good. . Therefore, the alloy of the present invention has a Ni/p ratio of 4 Torr to 5 5 , preferably 4.5 to 5 Å. [Mg amount] A compound of Mg and Ni and p is precipitated to increase the strength and heat resistance of the alloy. Further, in the following method, if Mg is not added to produce a Cu_Ni_P-based alloy, second-phase particles having an aspect ratio a/b of 丨~5 which is close to granular are obtained, and in this case, Mg is added to produce a Cu_Ni_p-based alloy. Then, a fibrous second phase particle having an aspect ratio a/b of 2 to 50 is obtained. In this case, high strength can be achieved compared to the same amount of Cu_Ni_P alloy in which Ni and P are the same. Further, this effect is greater than the effect of the strength increase obtained by the Mg solid solution. ...,: However, if the Mg content is less than 〇1%, the required strength and heat resistance cannot be obtained. On the other hand, if the content exceeds Ο.,. , the processability during rolling is significantly reduced, and the electrical conductivity is significantly reduced. And: the second phase = the size that does not meet the following conditions, that is, the length is a, the short diameter is b, the aspect ratio _ 2 and the short diameter b is 1 〇 ~ "The second phase particle (8) cuts the second phase particle of the second phase particle (6) of the second phase particle (8) and the second phase particle of the second phase particle (6), so that the area ratio C2 of the total of (B) and (6) is lowered, which is not preferable. Therefore, (10) of the Cu-based _p_Mg-based alloy of the present invention contains 0·01% to 0.20%, preferably 〇〇2 to 〇15%. Μ 200907077 [B amount] B-line inhibition in Cu-Ni-P The cooling process of the alloy or the Cu_Ni-P-Mg alloy during solidification or solidification and the crystallization or precipitation of the Ni-P compound at the grain boundary during hot working heating, thereby improving the hot workability of the alloy. However, if the content of B is less than 0.005°/, the effect of improving the hot workability cannot be obtained. On the other hand, if the content of B exceeds 0.07〇%, Ni is generated during melting or solidification. a compound such as PB or BP. The compounds containing B are not dissolved in the Cu mother phase in the solution treatment, and therefore, the Ni-P compound precipitated in the aging treatment is reduced, thereby guiding Further, the strength of the alloy is lowered. Further, a compound such as Ni-PB or BP may remain in the product as an inclusion having a size of 5 to 5 μm, which causes cracks in the surface of the product, and cracking during plating. The defect in the application treatment is not preferable. Therefore, the B content of the alloy of the present invention is 〇·〇〇5% to 〇〇7%, preferably 0.007% to 0.060%. [Fe, Co, Mn, The amount of Ti and Zr], ~, ^, and any of them are easy to generate, and the compounds such as Fe_p, c〇_p, ip, Ti_p, /ρ are generated during melting or solidification, and When these compounds are precipitated in the aging treatment, the second phase particles of the second P system or the Ni-P-Mg system are reduced to cause a decrease in the strength of the alloy. Therefore, Fe, Mn, τ, and B are early or two kinds. The content of the yttrium is 0.05% or less, and the Γ 斗 & Γ Γ Γ Γ Γ 较佳 较佳 较佳 较佳 较佳 较佳 。 。 。 。 。 合金 合金 合金 合金 合金 合金 合金 合金 合金 合金 合金 合金 合金 合金 合金 合金 合金 合金 合金 合金 合金 合金 合金 合金 合金Exist

Cu reacts, and if it is in the alloy, it will hinder the deterioration of the properties of Ni and ρ compounds 10 200907077. The lower portion is preferably precipitated so that the degree of strength improvement is lowered, and the tube is added. Therefore, the niobium content of the alloy of the present invention is 〇.〇〇5〇% to 0.0030〇/〇 or less. [Sn, In amount; |

None of Sn and in can greatly reduce the electrical conductivity of the alloy, and mainly has the effect of improving the strength by solid solution strengthening. Therefore, if one or more of these metals are added as needed, if the content of the total amount of S...n is not $, the effect of improving the strength due to solid solution strengthening cannot be obtained, and on the other hand, even her county&gt;丄, work right 乂,, heart rate meter added 1.0〇 / 〇 or more, the alloy's electrical conductivity and bending workability will be significantly reduced. Therefore, it is preferable to add two or more kinds of S η τ θ &amp; mouth and Ιη I to 〜1.G%, preferably 0.05% to 0.8% in total. Furthermore, today, the main one is more than 70 in the present invention, and is not an inevitable impurity. [The size and area ratio of the second phase particles ci]

In the second phase particles of the present invention, precipitates, crystallized materials, and inclusions are included in the composition range of the present invention, and generally precipitates other than Ni_p-based precipitates or Chuan Ig-based precipitates are not precipitated, except for solid solution treatment. In addition to the middle and the aging treatment, the Ni_p system precipitates and the I: control 2 specific size. For other second phase particles, "crystals" (Ni_p, U Nl_P-〇-Mg, Cu_Ni-p-〇-B, Cu-Ni-P-〇-B-Mg) produced in the second and the casting k , Cu-S, exist: § such as emulsion or sulfide), but when the size of the crystallized compound or inclusion exceeds 100 nmq μηη, even if it is treated by solid solution 200907077, it can not control the cost invention. Therefore, the size of the range is such that the addition of the crystallized compound or the inclusions does not remain in the alloy, and the addition of p, B, etc. is suppressed in order to suppress the formation of inclusions. (Inclusions) are formed to lower the inclusions of the crucible. The area ratio ci of all the second phase particles in the sample which does not sufficiently reduce the crystallized or inclusions is less than 8〇%, which is beyond the present. When the long diameter of the second phase particles is 3 (11111) and the short diameter is b (nm), in the Ni-P copper alloy of the present invention, if the long diameter a is less than 2, the second When the phase grain I is subjected to a light rolling process with a processing strain η=2 or more in the final cold, the second phase particles are solid-dissolved in the copper to make the conductive It is not preferable. Here, 'the processing strain η is set to % when the thickness of the sheet before rolling, and the thickness of the sheet after rolling is set to t' is represented by η = Ιη (ν〇. The second phase particles having a long diameter &amp; 2 Å or more are hardly resolubilized even in the rolling process on the processing strain η... in the final cold rolling, and are more than ι 〇 (10) or more; The form exists and contributes to precipitation strengthening and processing strengthening. The second phase particles with length = 2 or more are more likely to change before and after the drying, and the long diameter a before rolling is more than 5 〇 nm ::: In the case of the second phase particle of 5〇_, the public 々pq卩- τ I brother 2 phase particle is large, and thus it is impossible to obtain analysis (four) and processing reinforcement. The long diameter a and the short diameter b are the long diameters of all and a few 2a $ 2 phase particles, and the long diameter and the short diameter are perpendicular to the dryness parallel to the pro-rolling direction and are cut off before the final cold rolling. Alloy strip, material cross-sectional image 12 200907077 All of the measurement is performed using an image analysis device. The second phase particles having a length of 5 (10) or more according to the above description, the present invention The preferred size of the second phase particles of Ni_p yttrium copper, which is the final cold yield of gold, and the long diameter a of the lanthanum system are 2 〇 nm~5 〇 _. Further, if the ratio of Ni_p is expressed by a/b Then, when a/b Zhao milk "the second phase particles in the main gold", if the final cold rolling is performed with η=2 or more, the second phase particles are lowered. Therefore, the final cooling loss is achieved. The front side 攸 and the conductivity ^ 2 phase particle line transverse ratio a / b is preferably 1 to 5, more preferably 1 to 3. In order to prevent the strength and electrical conductivity from decreasing, after the final cold rolling of the copper alloy The second phase grain invention... and ^ is a bu. The a is 10 nm to 50 nm. In order to make the Ni_p-based particles of the present invention, the second phase a_, before the final cold rolling of gold, is nm~5〇nm and the aspect ratio is a/b4.丨 卜 卜 将 时 时 时 时 前 前 前 前 前 时 时 时 时 时 时 时 时 时 时 时 时 时 时 时 时 时 时 时 时 时 时 时 时 时 时 时 时 时 时 时 时 时 时 时 时 时Make appropriate adjustments. Preferably, the processing strain of the most κ cold rolling is η== 〇·7~ΐ 4 or so. 'However, it is difficult to make all the second virgins of the second phase particles in the above a and a / b ί ::, so the long diameter ... and the aspect ratio a / b example (face / circumference of the second phase The ratio (t) of the particles (4) to all of the second phase particles is important. In addition, "all second phase particles" mean that all long diameter a is 5 nm or more and U is the second phase. (1) The second phase particles. Therefore, if the total area of the upper squamron (A) is equal to the sum of the area of all the 帛2-phase particles in the alloy of ^^^^^ before the final lyophilization, the area ratio is 13 200907077 ci, the area ratio C1 of the present invention is 80% or more. The area ratio Cl in the Ni-P-based copper alloy is not full, and refers to the second phase particle of a exceeding 50 nm or less than 2 〇 (10) The second phase particles may be present in a large amount. For example, when a a second phase particle of more than 5 Å or a peak produced by melting and casting, the sW seat, the Ό日日化When there is a large amount of 1 〇 granules which are not left in the state of solid solution in the heating or solution treatment before hot rolling, the strength is improved:

For the 20 to 50 nm fine 篦 八 &amp; micro and young 2 phase pullers have a large dispersion interval, so it is impossible to obtain the required strength by the hardening of the rolling and tempering. On the other hand, the second phase particles of a less than 20 nm are re-dissolved by the rolling process, so that the electrical conductivity is remarkably lowered. In the Ni-P-Mg-based copper alloy of the present invention, the following two kinds of second phase particles can be produced before the final cold rolling, and have a large aspect ratio of a/b = 2 to 5 Å, and are needle-shaped and/or Or fibrous second phase particles (B,) and second phase particles (c,) having a/b less than 2 grains. By making the strain of the rolling process before the aging treatment less than 0_4, preferably less than 〇., the needle-shaped and fibrous second phase particles (Β') are formed, and the processing before the aging treatment is performed. The strain η is 〇·4 or more, and the granular second phase particles (C,) are formed. If the rolling processing degree before the aging treatment is η -0.4 or so, the second phase particles (Β') and the second phase particles (c,) are mixed to some extent, and if the processing strain is less than 〇4, the diameter is large. The part is the second phase particle (Β'), and if the processing strain is 〇·4 or more, it is mostly the second phase particle (C,). In the Ni-P-Mg-based copper alloy of the present invention, the second phase particles having a short diameter b of less than 10 nm before the final cold rolling are subjected to a processing strain η = 2 or more; 200907077 The second phase particles are destroyed, decomposed, and solid-dissolved in the copper, so that the electrical conductivity is lowered, which is not preferable. On the other hand, the second phase particles having a short diameter of 1 〇 or more before the final lyophilization are less likely to be solid-solved even in the rolling process with a processing strain η=2 or more, and the second phase particles having a diameter of 10 nm or more. The form exists 'and thus contributes to precipitation strengthening and processing reinforcement. In particular, the second phase particles having a short diameter b of 20 nm or more have a small change in size before and after the stick, and the 帛2 phase particles are less likely to be destroyed by cold drying and solid solution. On the other hand, the long diameter a before the roll is more than 5 〇 nm and the short diameter exceeds h. The second phase particles retain their size even after the light rolling, but the volume of each second phase is larger. Therefore, in the copper alloy The dispersion interval of the second phase particles is excessively large, and it is difficult to obtain precipitation strengthening and processing strengthening. According to the above description, the second phase particles before the final cold rolling of the Ni_p_Mg-based copper alloy in the present invention means that the aspect ratio _ is Μ. : In addition to the second phase particles (9) having a short diameter Μ1, the first particle (6) having an aspect ratio a/b of less than 2 and a major axis 3 of 2 〇 to 5 〇 nm is included. To make the Ni of the present invention -P-Mg-based steel alloy is a second-phase particle (B) having a short diameter of 1 〇 to 25 (10) and an aspect ratio of 2 (9) before the final cold-rolling, and the processing of the second phase before the aging treatment is ==圭: Not full ο.1' and the temperature and time during the aging treatment are adjusted. X, in order to make the second phase particles before the final cold rolling of the Ni_p_Mg copper alloy of the present invention have a long diameter a 2〇~5〇i 9 ^ m and the aspect ratio a/b is full of the second phase particles (C)', so that the processing before the aging treatment is 4 or more, preferably about h5' and the aging treatment; Make appropriate adjustments. R Brewing and time 15 200907077 However, 'it is difficult to make Νί-Ρ μ / _ _Mg copper alloy in the family has the first son in the above a and a / b * Du * 0 second phase of the grain In the case of Kaijia, the total of the second phase particles is important for all the second "() with a long diameter a of 5 nm or more. Therefore, if the ratio of the second phase particles of the upper phase is χΐ. D , the total area of the second phase particles (B) and (C) is the same as that of the Ni-P-Mg copper alloy. The ratio of the two-phase particle sum is set to the area ratio 夂¢ 夂¢ 7 bar ~, the product sheep C2 'the area ratio of the invention C2 $ _ or more. When the area ratio C2 is less than 80%, it means that a super... and... Any of the second phase particles having a length of more than 25 nm, the phase particles having a long diameter a of less than 2 Å, the second phase particles having a short diameter b of less than 1 〇 nm, and the second phase particles having an aspect ratio of 50 More often, for example, when the first phase particles of more than 50 nm and the short diameter b exceeds 25 nm, or the crystals produced when the casting is melted, the crystallized material is not subjected to hot rolling or solution treatment: When there are many Ni_p_Mg-based particles (junctions) of _ nm or more, the fine second-phase particles (B) and/or the size of the present invention which contribute to the improvement of the strength are improved. Or the amount of (c) is small, and the dispersion interval of the second phase particles is increased. Therefore, the processing by the rolling process cannot be performed, and the required strength is further obtained. a second phase particle of less than 20 nm or a diameter of b less than 1 〇 nm is re-dissolved by rolling, so that the desired conductivity is obtained by a thermal method. The Ni-P-Mg-based copper alloy of the present invention is Before the aging treatment and finally cold rolling, in order to make the second phase particles (B) and the second phase particles (the total sum of the bismuth and the total area of all the second phase particles in the copper alloy account for 8% or more (area ratio C 2 ) It is preferable to set the rolling strain η before the aging treatment to 〇~丨.5 left 16 200907077 right 'and adjust the temperature and time during the aging treatment appropriately. The above requirements of the present invention are satisfied. Cu_Ni p everyone

Wl-P alloy or Cu-Ni-P-

Mg-based alloys can be suitably selected from ingot casting, hot rolling, solution treatment, intermediate cold rolling, aging treatment, final cold rolling, stress relief annealing (10) ess relieving anneaUng, etc., which are used by the industry in the process of education. It is manufactured by heating temperature, time, cooling rate, and affinity ratio. For example, according to (1) dazzle, casting, (7) hot rolling, (3) oxide scale (〇xide coffee (4) removal, (4) cold rolling (thickness adjustment), (5) solution treatment, (6) cold rolling, (7) Aging treatment, (8) surface cleaning treatment (grinding or pickling), (9) cold rolling (final), (丨〇) stress relief annealing sequence 'repeated or omitted part of the process to manufacture. For area ratio C1 or C2 The above-mentioned "rolling processing before aging treatment" in the adjustment is equivalent to the above (6). Further, the processing strain η = 前 before the aging treatment corresponds to the omission of (6). The second phase particle of the present invention The evaluation is based on (7) the material after the aging treatment is used as a sample. [Examples] j_Model I _ I will use electrolytic copper or oxygen-free copper (0Xygen_free copper) as the main raw material' Nickel (Ni), 15% p_Cu master alloy, 2/〇 B-Cu (B), tin (Sn), indium (In), 10% Fe-Cu (Fe), 10% c〇- Cu(Co), 25% Mn-Cu(Mn), titanium sponge (Ti) and sponge strontium (Zr) are used as auxiliary materials in the high-frequency melting furnace to melt under vacuum or argon atmosphere. Spinning of 5x45x90 mm. Perform hot rolling test of the key. The ingots which are not cracked during hot rolling are in the order of hot rolling and solution treatment, aging treatment, intermediate cold rolling, aging treatment, final cold rolling and stress relief annealing. 200907077 .! 5 mm flat plate. Take the obtained plate for "strength" and "conductivity" evaluation. Apply 'to obtain a test piece with a thickness of 015 for testing, and enter the sample π to make electrolytic copper. Or oxygen-free steel as the main raw material, nickel (Ni), 15% P-Cu master alloy, 1%% Mg Cu master alloy (he, the mother of the river)

Fe-Cu master alloy (Fe), 10% gold (B), tin (Sn), indium (In), 〇% 匚〇 (: 11 mother alloy ((: 〇), 25%] ^ 11 -&lt;:11 master alloy (river 11), titanium sponge (1^) and sponge enamel (Zr) as auxiliary materials, dissolved in a high-frequency melting furnace under vacuum or argon gas, 'molding into 45x45x90 In the same manner as the above sample 1, the hot rolling test of the ingot was carried out, and the ingot which did not cause cracks in the hot rolling was applied to a flat plate having a thickness of 0.5 μm, and the test was conducted to evaluate the "strength" and "conductivity". Rate. Compared with hot workability, the hot workability is evaluated by the heat of the heat.

Three hot rolling tests were performed up to this point. It was confirmed by visual inspection that the crack on the surface and the edge of the sample after hot rolling was marked as "cracked", and the case where the surface and the edge were smooth without cracks was marked as "no crack." In the present invention, the term "excellent hot workability" refers to the case of "no crack" in the above evaluation. The "strength of physical property evaluation" was measured by the tensile test according to JIS Z 2241 using No. 13 and B test pieces, and the tensile strength was measured. In the present invention, the high strength in the so-called Cu-Ni-P alloy refers to 18 200907077

The tensile strength in the above evaluation is 650 MPa or more, and the high strength in the so-called Cu_Ni_p_M alloy means that the tensile strength is 750 MPa or more. "Electrical conductivity" is measured by the 4-terminal method using the 4-terminal method and expressed by γ % IACS. In the present invention, the term "high conductivity" means that the conductivity is 45% IACS or more in the above evaluation. The tortuous processability was evaluated in a 90 degree W bending test. The test is performed according to CES-M0002-6, using R_ (M mm fixture to perform 90 degree bending processing with a load of '^.) The evaluation of the bending portion uses optics: Micromirrors observe the condition of the central mountain surface, which will cause cracks. Marker: The main one is X', the wrinkle is marked as △, the good one is marked as 〇: the fine is perpendicular to the rolling direction (Good way) ef crankshaft ~? Xiangjiao's commentator is parallel to the rolling direction and Cut the final cold milk S gold bar perpendicularly to the thickness 'Using a scanning electron microscope and penetrating type 1. Viewing the second phase of the cross section; 5 to 5 〇 时, 50 立 立The size of the particles is 2, and the field of view of about 10,000 to 700,000 times (about 1.4 &gt;&lt;10丨〇~2.0&gt;&lt;1〇1〇nm) is taken, and the spring 箆? When the size is 1〇〇~2_(10), the red to 100,000 times of the field of view (about 1.0X1013~2〇x1〇13 photos. For the photographed "" 1G nm), the company's Congcai, the image analysis The device (limited to 5(4) and above 2/r) is determined for all the long diameters a. The long diameter a, the short diameter b, and the area of the head are just long. a is (10) or more of 5 nm or more, and the average ata of the long diameter of the second phase particles and the short-diameter flat 19 200907077 =bta and the average aspect ratio obtained according to the above are randomly selected among all the 4-mesh coarses. As the long diameter a, the short diameter b, and the aspect ratio a/^, the long diameter a is 10 nm to 5 〇 nm and the aspect ratio a/b is the second of the 5, and the total area of the particles (4) is relative to the self Ni_p copper. The ratio of the total area of all the 2nd phase 2 particles selected in the alloy sample work is set to the area ratio Cl (°/〇). = Again, the following conditions are confirmed: by final cold rolling (normal processing) In the strain η X, Νι Ρ copper alloy sample, the second phase particles having a long diameter or less, or the second phase particles having a long diameter but exceeding an aspect ratio of 5, are solid solution 'but 2 〇 nm m aspect ratio is The second phase particles of 5 retain their long diameter, short diameter, and aspect ratio even after final cold rolling. Moreover, since the second phase particles exceeding 200 nm are not solid-solved, the second phase particles after the final cold rolling The area ratio C1 is also almost unchanged. The aspect ratio a/b is 2 to 50 and the short diameter μ 1〇 to 25 is the second «sub (8) area and the aspect ratio a/b is less than 2 and the long diameter a The ratio of the sum of the areas of the second phase particles (C) of the 2nd to 5th coffee grains to the sum of the area of all the (10) second phase particles selected from the self-made copper alloy sample 并 is expressed as an area. The rate C2 (%). Again and again 'confirmed that the final diameter of the second phase particles in the Nl_p_Mg-based copper alloy sample was 20 nm or shorter by the final cold rolling (normally processing strain η 2 or more). The second phase particles having a diameter b of less than 1 〇 are solid-solved and fail to be observed. However, the second phase particles having a short diameter b of 1 〇 nm or more retain their long diameter, short diameter, and aspect ratio after the final cold slab. . Further, the area ratio C2 of the 帛2-phase particles hardly changed after the final cold rolling. 200907077 For the copper alloy sample i of the composition shown in Table 1, the examples and comparative examples of the Ni-P based copper alloy of the present invention are also shown. In the alloy examples 1 to 9 of the present invention, no crack occurred during hot rolling, and the strength and electrical conductivity were excellent. On the other hand, when the results of Comparative Examples 1 to 27 were examined, it was found that in Comparative Examples 10 to 13, since the amount of b or b was not added to a predetermined amount, cracks occurred during hot rolling. In Comparative Example 14, the total amount of addition of Sn and In exceeded 1.0%, and in Comparative Example 15, the total amount of addition amount of Sn exceeded ι.0 〇 / ο , so the electrical conductivity decreased. In Comparative Example i6, since Ni/P is relatively high and is out of range, the solid solution amount of Ni increases and the electrical conductivity decreases, and since the amount of the second phase particles is small, the strength is also low. In Comparative Example 7, since the Ni/p ratio was lower than the appropriate composition ratio, the solid solution amount of P increased and the electrical conductivity decreased. In Comparative Example 18, since the addition amount of Ni and P was lower than the range specified in the present invention, the strength was low. In Comparative Example 19, since the amount of Ni was higher than the predetermined range of the present invention, in Comparative Example 20, since the amount of P was higher than the predetermined range of the present invention, the electrical conductivity was lowered. In Comparative Example 21, since the content of cerium exceeds 〇 5 〇 %, an oxide of Cu-P-0 is generated during melting, so that the amount of the second phase particles is reduced, the strength is lowered, and the bending workability is deteriorated. In Comparative Example 22, since the content of B is higher than the predetermined range of the present invention, Ni_p_B, BP, or the like is formed during melting and casting, and crystallization is performed, so that the amount of the second phase particles is reduced, the strength and electrical conductivity are lowered, and the bending is performed. The workability is also degraded. In Comparative Examples 23 and 24, since the contents of Fe, Cu'Mn'Ti, and Zr were higher than the range of the present invention, the halogens formed a compound with P, and thus the amount of the second phase particles was reduced and the strength was low. . In the case of the second phase, since the average long diameter of the second phase particles is higher than that of the present invention 21 200907077, it is impossible to use cold rolling to increase the strength. The comparative example 26盥97 士叨5叨5 is not pregnant. In the case of H, since the average length of the second phase particles is lower than the average diameter of the present invention and the aspect ratio of Comparative Example 2 exceeds the specified range of the present invention, the second phase particles will be solidified in the cold drying. Dissolved, so the conductivity is low. 22 Conductivity% IACS 53.2 46.2 48.5 47.7 46.5 45.2 46.5 47.2 46.4 ※ ※ 31.2 32.5 34.4 38.8 62.5 2 m 30.1 ! 45.2 38.9 i 44.2 37.7 32.9 Tensile strength (Mpa) 1 652 1 V) 〇〇745 770 832 , 850 1 810 770 1 828 ※ ※ ※ ※ m 00 842 584 JN Vi ο Ό S r- 630 I JQ 562 602 i 720 Ό Γ-» Bending workability〇〇〇〇〇〇〇〇〇 ※ ※ ※ XX 〇〇〇〇Ο &lt;1 &lt;1 〇〇〇〇〇Second phase particle area ratio C(%) 00 «Ti Ον (N Os ON On ΓΛ 00 0C CTN ΙΛ&gt; σν ON ※ ※ ※ Ss (N 〇\ 〇〇ON ON 00 g On Os ο 〇〇in aspect ratio a/b »T) Γη »Τ) (N - 二〇※ ※ — - rn &lt;N p ρ ίΝ 二ίΝ fS m· ΛΛ CS mean length a (nm) m fN ΓΛ 0'S (N r- Pi 〇※ ※ ※ &lt;N ON &lt;N \D Os ο ΓΟ CO 00 § V) Hot rolling processability Crack no crack no crack no crack no crack no crack no crack no crack no crack 1 crack 1 1 crack 1 1 crack 1 _ dance crack no crack no crack no crack 1 no crack no No crack, no crack, no crack, no crack, no crack, no crack, no crack, total (wt%) Fe+Co+Mn +Ti+Zr less than 0.01 1 less than 0.01 less than 0.01; less than 0.01 i 0.01 Not full 〇.〇1 1 0.05 0.04 0.04 1Not full 〇.〇1 I Less than 0.01 Less than 0.01 1 Not full 〇.〇1 I Less than 0.01 1 Not full o.oi I 1Unfilled o.oi 1 1 under full o.oi 1 1 under full o.oi 1 1 under full o.oi 1 less than 0.01 ! under 0.01 less than 0.01 0.33 0.42 ! under 0.01 less than 0.01 1 under full o.oi Sn+In not Full o.oi 1 less than 0.01 1 less than 0.01 0.21 0.50 0.46 less than 0.01 less than 0.01 ! 0.32 less than 0.01 less than 0.01 0.75 0.65 1.55 less than 0.01 less than o.oi 1 less than 0.01 less than 0.01 less than 0.01 Less than 0.01 1 under full o.oi less than 0.01 less than 0.01 0.51 0.51 0.51 composition ratio Ni/P 〇\ 七 — 卜 — Γ 4 ID m rr — inch · inch · inch · rn rr (N TJ·· Γ-; · Ο) ^r &lt;N inch · 12.5 — inch · — r&gt;; chemical composition (wt%) 3 剩余 remaining part remaining Γ remaining part I 1 remaining part 1 1 remaining part 1 1 remaining part 1 1 remaining part 1 Remaining part 1 remaining part 1 1 remaining part 1 1 remaining part 1 1 remaining part 1 remaining part Γ remaining part 1 1 remaining part 1 1 remaining part I p remaining part 1 Γ remaining part 1 Γ remaining part 1 1 remaining part 1 1 remaining Part 1 Remaining part I Γ Remaining part 1 1 Remaining part 1 ! Remaining part of remaining part 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.020 0.001 0.001 0.001 0.001 0.001 0.001 ! o.ooi 0.001 0.001 0.140 丨0.001 0.001 O.ooi 0.001 0.001 0.001 0.001 0.010 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 1 o.ooi I o.ooi 0.001 0.160 0.001 0.001 | o.ooi c 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.020 0.010 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.120 0.001 0.001 | o.ooi 0.001 0.001 0. 001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 I 0.001 | 0.001 0.001 0.11 0.001 0.001 1 o.ooi | o.ooi £ 0.001 0.001 0.001 0.001 0.001 0.001 0.05 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 1 o.ooi 0.001 0.120 0.001 1 o.ooi 0.001 | o.ooi 〇0.0012 0.0018 0.0020 0.0030 0.0031 •n S 〇d 0.0015 0.0012 0.0021 •Λ S 〇d 0.0032 0.0021 0.0030 0.0022 0.0027 0.0025 0.0018 0.0015 0.0020 | 0.0019 0.0040 0.0020 0.0027 ! 0.0019 0.0019 | 0.0019 £ 0.001 0.001 0.001 0.50 0.22 0.001 0.001 0.001 0.001 0.001 0.42 0.001 0.670 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.21 0.001 0.240 0.001 0.001 0.320 0.001 0.001 0.330 0.650 0.850 1.550 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.220 0.001 0.510 0.510 0.510 m 0.035 1 0.041 0.025 0.031 0.030 0.028 1 0.021 0.033 0.040 0.001 0.003 0.001 0.001 ! 0.041 0.035 0.035 0.040 0.033 0.042 0.051 0.034 0.085 0.036 0.025 丨0.031 0.031 | 0.031 D- 0.15 0.19 0.17 0.19 0.18 0.16 0.16 0.15 0.16 :0.20 0.21 0.15 ! 0.17 0.17 0.18 0.12 0.23 0.08 0.12 0.35 0.13 | 0.14 0.15 0.16 0.18 0.18 | 0.18 2 0.61 0.93 0.75 0.87 0.85 0.83 0.72 0.72 0.75 0.88 0.92 0.65 0.72 "0.80 0.85 0.95 0.55 1 0.33 1.50 ;0.60 ! 0.66 | 0.70 0.77 0.75 0.85 0.85 0.85 〇2: One &lt;N inch V5 〇〇 〇〇 ON 〇二CO 00 On V» 舡 舡佬球铖味赛^长^,※”*-^ 200907077 The results of the evaluation of the hot rolling workability, the second phase particles and the characteristics of the copper alloy sample n of the composition shown in Table 2 are also explained. Examples and comparative examples of the Ni-P-Mg-based copper alloy of the present invention. If it is in the range of ^ 2〇1250 and b - 1〇~25 and a/b= 2~50, it corresponds to the second phase particle (B)' if it is at a=20~50 and b=1〇~50 And in the range of a/b=丨~2, it corresponds to the second phase particle. In Examples 28 to 38 of the alloy of the present invention, cracks were not generated during hot rolling, and excellent strength and electrical conductivity were obtained. On the other hand, when the results of Comparative Examples 39 to 进行 were examined, in Comparative Examples 39 to 43, since the amount of B or B was not added to a predetermined amount, cracks occurred during hot rolling. In Comparative Example 44, since the total amount of addition with In exceeded 丨.0%, in Comparative Example 45, since the total amount of addition of Sn exceeded 1.0%, the electrical conductivity was lowered and the bending workability was deteriorated. In Comparative Example 46, since the amount of Mg added was higher than the range specified in the present invention, cracks occurred in hot rolling. In Comparative Example 47, since the addition amount of Mg was lower than the predetermined range of the present invention, the strength was lower than that of the inventive example 29 having the same chemical composition other than Mg. In Comparative Example 48, since the Ni/P ratio was lower than the range specified in the present invention, the amount of solid solution of P increased and the conductivity was low. In Comparative Example 49, since the addition amount of Ni and P was lower than the range of the present invention, the strength was low. In Comparative Example 50, since the amount of Ni and the ratio of Ni/P exceeded the predetermined range of the present invention, the electrical conductivity was lowered. In Comparative Example 51, since the amount of P was higher than the range specified in the present invention, and the Ni/P ratio exceeded the range of the present invention, cracks occurred during hot rolling. In Comparative Example 52, since the content of cerium exceeded 〇.〇5〇〇/0, an oxide of Cu-PO was formed during melting, so that the amount of the second phase particles was reduced, the strength and the conductivity of 24 200907077 were lowered, and bending was performed. Sex also deteriorated. In Comparative Example 53, since the content of B is higher than the range specified in the present invention, Ni-PB or BP 会 is formed during melting and casting, and b ^ ^ ! is formed at the 廿, and then the amount of the second phase particles is obtained. The reduction, the strength and the electrical conductivity are lowered, and the bending workability is also deteriorated. In Comparative Examples 54 to 57, it was due to Fe, Co, Mn, Ti, and Zr! The total content of the above species is higher than the predetermined range of the present invention, so that the second phase particles are reduced, and the crystals of the Fe, Co, Mn, Ti, Zr and P or the second phase particles are coarsely formed, and the second phase particles are The evaluation results are outside the scope of the present invention, and thus the strength is lowered. In Comparative Example 5, the electric conductivity was lowered because the short diameter b of the second phase particles was lower than the range of the present invention. In Comparative Example 5, "the short diameter b of the second phase particles was higher than the range specified in the present invention, so the strength was low. In Comparative Example 6, since the major axis a and the minor axis b of the second phase particles are lower than the predetermined range of the present invention, the strength and electrical conductivity are low. In Comparative Examples 61 and 62, since the major axis a and the minor axis b of the second phase particles were higher than the predetermined range of the present invention, the degree of strength increase due to cold rolling was small, and the strength was low. 25 2 907 [2] 377 rsj in 赛Ον »^4 «Τί σ; 一卜οΜ 00 00 m — ο is »r&gt;&lt;Ν m ※ inchΌ vS r*l Ό Η m CS ο (Ν « η &lt;Ν ro ν&gt; Ρϊ i 卜 SO Γ-· Η ν&gt;=&quot;· 〇\ m •η »Τί Tensile strength (Mpa) v*&gt;v~&gt; 00 〇〇00 ο m 00 ο s 00 ν*&gt; 00 j^· ο 00 m ※ ※ ※ ※ «Λ οο S 00 ※ ο ο ν 〇 & ※ ※ & Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν S &gt;r&gt; Bending workability 〇〇〇0 〇〇〇〇〇〇〇※ ※ ※ ※ &lt;] &lt;] ※ 〇〇〇ο ※ &lt;] &lt;1 0 ο 0 0 0 〇〇〇〇 Area ratio C (%) 00 〇ΓΛ ΟΝ m On »Τ) σν 00 os § Ό Ο in ON 〇\ 00 ※ ※ ※ ※ ※ &gt;*〇ON m Os ※ οο ο ο V* ON m 00 ※ 〇ο «Τϊ ΓΟ ο Ο Ο ο Ο aJ 屮^13⁄4 S — (Ν二V» Ρ: ※ ※ ※ ※ cn ※ fS rs II ※ &lt;Ν (Ν rn ιη fS 00 V) mm (Ν ^r two mr 1 Correct (N 姊^ ε' ir&gt; (N (Ν mm 00 m Os ΟΟ (Ν &lt;N &lt;N ※ ※ ※ ※ ※ s ※ fS ΟΝ fS &lt;N 00 ※ 〇Μ 00 Ό 沄§ οο ο (Ν 00 ο ρ&gt;· ^ £ O ΜΊ IT) οο ο ο S Ό 沄Ό Ρ; m Ο Ό ※ ※ ※ m ※ in Γ&lt;Ί ※ ON *τ&gt; 00 οο ΟΟ 00 in (Ν S ο Os 卜 s heat Rollability 1 Cracks 1 1 Cracks 1 1 Cracks 1 1 Cracks 1 1 Cracks 1 1 Cracks 1 Disc 碡墉 0. 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Claims (1)

200907077 X. Shenyi Patent Standard: -1.- High-strength and high-conductivity copper alloy with excellent hot workability, i with Ni: 0.50〇/o^.00〇/o, P; 0.10〇/〇^25 〇/〇, content ratio of A to P Ni/p ·· 4.0~5.5, and B: G.嶋% edge 〇7(4), 〇: 0.0050% or less, Fe, 2: total 〇. 〇5 % or less The composition of the mass is characterized in that: Co' Mn, Ti, and Zr are more than the above species, and the remainder is composed of Cu and unavoidable impurities for the second phase particles, &amp; Λ 乂 is a, short When the diameter is b, the second phase particles (4) having a long diameter a of 2 〇 nm to 5 〇 nm and an aspect ratio of ^ are compared with all the second parts included in the copper alloy. The sum of the area of the phase particles accounts for 8 G% or more, and the conductivity is 45% IACS or more. 2. A high-strength, high-conductivity copper alloy excellent in hot workability, which contains Ni: 〇_5〇%~1〇〇%, p: 〇1〇%~Ο- by mass ratio. , Mg : 0.01 to 0.20%, content ratio of Ni to p Ni/p : 4 〇 〜 5 $, and, B Co, Μη, Ti, 0-005%~〇·〇7〇〇/. 〇: 〇〇〇5〇% or less, the content of one or more of Zr is 〇〇5% or less in total, and the remainder is composed of Cu and unavoidable impurities, and is characterized by: having a final cold rolling The second phase particle (B) having a front short diameter b of 1 〇 to 25 nm and an aspect ratio a/b of 2 to 50, the second phase particle (B) and the long diameter &amp; nm nm to 50 nm and an aspect ratio The total of the second phase particles (c) having a/b less than 2 is 纟8〇% or more with respect to the total area of all the second phase particles contained in the copper alloy, and the electric conductivity is 45% iACS or more. 3. For example, the high-strength, high-conductivity copper alloy excellent in hot workability of the second item of the second item is contained in the 'Sn and In', and the total amount of the above-mentioned Sn and In is 28 200907077 0.01% to 1.0%. XI. Schema: