JPWO2016171055A1 - Copper alloy material and method for producing the same - Google Patents
Copper alloy material and method for producing the same Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 51
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 78
- 150000001875 compounds Chemical class 0.000 claims abstract description 59
- 239000000463 material Substances 0.000 claims abstract description 22
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 238000000445 field-emission scanning electron microscopy Methods 0.000 claims abstract 3
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 16
- 238000000137 annealing Methods 0.000 claims description 15
- 238000005266 casting Methods 0.000 claims description 15
- 238000012545 processing Methods 0.000 claims description 11
- 238000000265 homogenisation Methods 0.000 claims description 10
- 238000005098 hot rolling Methods 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- 238000005097 cold rolling Methods 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 238000005452 bending Methods 0.000 abstract description 34
- 230000000694 effects Effects 0.000 description 18
- 230000007423 decrease Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000005096 rolling process Methods 0.000 description 8
- 229910009038 Sn—P Inorganic materials 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 230000000007 visual effect Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/02—Alloys based on copper with tin as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/04—Alloys based on copper with zinc as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/05—Alloys based on copper with manganese as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/08—Alloys based on copper with lead as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/10—Alloys based on copper with silicon as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
- B21B2003/005—Copper or its alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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- Materials Engineering (AREA)
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- Conductive Materials (AREA)
Abstract
本発明は、高強度、高導電率および良好な曲げ加工性に加えて、良好な耐熱性も兼ね備えた銅合金材料及びその製造方法を提供する。本発明の銅合金材料は、Ｎｉを０．０５〜１．２質量％、Ｐを０．０１〜０．１５質量％およびＳｎを０．０５〜２．５質量％含有し、残部がＣｕおよび不可避不純物からなる合金組成を有し、電解研磨後の材料表面をＦＥ−ＳＥＭで観察し、１μｍ×１μｍの視野面積当たり、粒子径が５〜３０ｎｍである化合物粒子の個数割合が２０個／μｍ２以上、粒子径が３０ｎｍ超えである化合物粒子の個数割合が１個／μｍ２以下であることを特徴とする。The present invention provides a copper alloy material having good heat resistance in addition to high strength, high electrical conductivity, and good bending workability, and a method for producing the same. The copper alloy material of the present invention contains 0.05 to 1.2% by mass of Ni, 0.01 to 0.15% by mass of P and 0.05 to 2.5% by mass of Sn, with the balance being Cu and An alloy composition composed of inevitable impurities, the surface of the material after electropolishing is observed with FE-SEM, and the number ratio of compound particles having a particle diameter of 5 to 30 nm per 1 μm × 1 μm viewing area is 20 / μm 2. As described above, the number ratio of the compound particles having a particle diameter exceeding 30 nm is 1 / μm 2 or less.
Description
本発明は、銅合金材料およびその製造方法に関し、特に、半導体装置に用いられるリードフレームをはじめとした電気電子部品に用いられる銅合金材料およびその製造方法に関する。 The present invention relates to a copper alloy material and a method for manufacturing the same, and more particularly to a copper alloy material used for electrical and electronic parts such as lead frames used in semiconductor devices and a method for manufacturing the same.
ＩＣやＬＳＩ等の半導体装置に用いられるリードフレームは、銅合金材料をプレス加工することで形成されるが、この際、材料中に加工歪が残留する。この加工歪が残留すると、後工程のエッチングを行う際、材料に反りが生じ、リードフレームのリードピン間隔の寸法精度が低下する。このため、通常、プレス加工後のリードフレームに４００〜４５０℃での熱処理を施して加工歪を除去するが、この熱処理の際に銅合金の結晶組織が再結晶化することによって、銅合金材料の強度が低下する傾向があることが知られている。そこで、リードフレームに使用される電子機器用銅合金材料には、前述の熱処理を施しても強度が低下しない特性（耐熱性）を具備することが必要とされる。 A lead frame used in a semiconductor device such as an IC or LSI is formed by pressing a copper alloy material. At this time, processing strain remains in the material. If this processing strain remains, the material is warped during the subsequent etching process, and the dimensional accuracy of the lead pin interval of the lead frame decreases. For this reason, the lead frame after press processing is usually subjected to heat treatment at 400 to 450 ° C. to remove the processing strain, and the crystal structure of the copper alloy is recrystallized during this heat treatment. It is known that the strength of the steel tends to decrease. Therefore, the copper alloy material for electronic equipment used for the lead frame is required to have a characteristic (heat resistance) that does not decrease the strength even when the heat treatment is performed.
またリードフレーム用銅合金材料には、小型化された部品に適用するための高強度と、部品の発熱を抑制するための高導電率とを具備することに加えて、部品成型の自由度を高めるための良好な曲げ加工性を兼ね備えていることも要求される。 In addition to having high strength for application to miniaturized parts and high conductivity for suppressing heat generation of parts, the copper alloy material for lead frames has a high degree of freedom in molding parts. It is also required to have good bending workability to enhance.
このような要求を満たす銅合金材料として、Ｃｕ−Ｎｉ−Ｓｎ−Ｐ系合金が広く提供されている。Ｃｕ−Ｎｉ−Ｓｎ−Ｐ系合金は、Ｎｉ−Ｐ系の化合物を析出させることで、高強度、高導電率および良好な曲げ加工性を兼ね備えることができる。 Cu-Ni-Sn-P-based alloys are widely provided as copper alloy materials that satisfy such requirements. The Cu—Ni—Sn—P based alloy can have both high strength, high electrical conductivity, and good bending workability by precipitating a Ni—P based compound.
特許文献１〜９では、析出物のサイズや分布を制御することで、引張強度、導電率、曲げ加工性に加え、ばね性、耐応力緩和特性、プレス加工性、耐食性、めっき性、半田濡れ性、耐マイグレーション性、熱間加工性といった様々な特性を兼ね備えることが検討されている。 In Patent Documents 1 to 9, by controlling the size and distribution of precipitates, in addition to tensile strength, electrical conductivity and bending workability, spring properties, stress relaxation resistance, press workability, corrosion resistance, plating properties, solder wetting It has been studied to combine various properties such as heat resistance, migration resistance, and hot workability.
Ｃｕ−Ｎｉ−Ｓｎ−Ｐ系合金は、高強度、高導電率および良好な曲げ加工性を兼ね備えた優れた合金系であるが、プレス加工後のリードフレームに施される４００〜４５０℃の熱処理に対する耐熱性は、十分とは言い難い。 Cu-Ni-Sn-P alloy is an excellent alloy system that has high strength, high electrical conductivity, and good bending workability, but heat treatment at 400 to 450 ° C. applied to the lead frame after press working. It is hard to say that the heat resistance against is sufficient.
特許文献１〜９ではいずれも、様々な材料特性の改良を試みてはいるものの、耐熱性の向上に着目したものではない。 Although all of Patent Documents 1 to 9 try to improve various material properties, they do not focus on improving heat resistance.
上記の事情に鑑み、本発明の目的は、高強度、高導電率および良好な曲げ加工性に加えて、さらに良好な耐熱性を兼ね備えた銅合金材料およびその製造方法を提供することにある。 In view of the above circumstances, an object of the present invention is to provide a copper alloy material having a good heat resistance in addition to a high strength, a high conductivity and a good bending workability, and a method for producing the same.
本発明者らは、リードフレームをはじめとした電気電子部品に用いられるＣｕ−Ｎｉ−Ｓｎ−Ｐ系合金について研究を行い、Ｎｉを０．０５〜１．２質量％、Ｐを０．０１〜０．１５質量％およびＳｎを０．０５〜２．５質量％含有する合金組成を有し、電解研磨後の材料表面をＦＥ−ＳＥＭで観察し、１μｍ×１μｍの視野面積当たり、粒子径が５〜３０ｎｍである化合物粒子の個数割合を２０個／μｍ２以上、粒子径が３０ｎｍ超えである化合物粒子の個数割合を１個／μｍ２以下とすることで、高強度、高導電率および良好な曲げ加工性を具備するだけではなく、さらに良好な耐熱性をも兼ね備えた銅合金材料が得られることを見出し、本発明を完成させるに至った。The present inventors have studied Cu—Ni—Sn—P based alloys used for electric and electronic parts including lead frames, and 0.05 to 1.2 mass% of Ni and 0.01 to 0.01% of P. It has an alloy composition containing 0.15% by mass and 0.05 to 2.5% by mass of Sn, and the surface of the material after electropolishing is observed with an FE-SEM. By setting the number ratio of the compound particles having a particle diameter of 5 to 30 nm to 20 particles / μm 2 or more and the number ratio of the compound particles having a particle diameter exceeding 30 nm to 1 particle / μm 2 or less, high strength, high conductivity and good The present inventors have found that a copper alloy material having not only excellent bending workability but also excellent heat resistance can be obtained, and the present invention has been completed.
すなわち、本発明の要旨構成は、以下のとおりである。
（１）Ｎｉを０．０５〜１．２質量％、Ｐを０．０１〜０．１５質量％およびＳｎを０．０５〜２．５質量％含有し、残部がＣｕおよび不可避不純物からなる合金組成を有し、電解研磨後の材料表面をＦＥ−ＳＥＭで観察し、１μｍ×１μｍの視野面積当たり、粒子径が５〜３０ｎｍである化合物粒子の個数割合が２０個／μｍ２以上、粒子径が３０ｎｍ超えである化合物粒子の個数割合が１個／μｍ２以下であることを特徴とする銅合金材料。That is, the gist configuration of the present invention is as follows.
(1) An alloy containing 0.05 to 1.2% by mass of Ni, 0.01 to 0.15% by mass of P and 0.05 to 2.5% by mass of Sn, with the balance being Cu and inevitable impurities The surface of the material after electropolishing having a composition is observed with an FE-SEM, and the ratio of the number of compound particles having a particle diameter of 5 to 30 nm per 1 μm × 1 μm visual field area is 20 particles / μm 2 or more. A copper alloy material, wherein the number ratio of the compound particles having a particle size exceeding 30 nm is 1 / μm 2 or less.
（２）Ｎｉを０．０５〜１．２質量％、Ｐを０．０１〜０．１５質量％およびＳｎを０．０５〜２．５質量％を含有し、さらにＦｅ、Ｚｎ、Ｐｂ、Ｓｉ、Ｍｇ、Ｚｒ、Ｃｒ、Ｔｉ、ＭｎおよびＣｏの中から選ばれる少なくとも１成分を含有し、Ｆｅが０．００１〜０．１質量％、Ｚｎが０．００１〜０．５質量％、Ｐｂが０．００１〜０．０５質量％、Ｓｉが０．００１〜０．１質量％、Ｍｇが０．００１〜０．３質量％、Ｚｒが０．００１〜０．１５質量％、Ｃｒが０．００１〜０．３質量％、Ｔｉが０．００１〜０．０５質量％、Ｍｎが０．００１〜０．２質量％およびＣｏが０．００１〜０．２質量％であり、かつＭｇ、Ｚｒ、Ｃｒ、Ｔｉ、ＭｎおよびＣｏを２以上含有する場合の合計含有量が０．００１〜０．５質量％であり、残部がＣｕおよび不可避不純物からなる合金組成を有し、電解研磨後の材料表面をＦＥ−ＳＥＭで観察し、１μｍ×１μｍの視野面積当たり、粒子径が５〜３０ｎｍである化合物粒子の個数割合が２０個／μｍ２以上、粒子径が３０ｎｍ超えである化合物粒子の個数割合が１個／μｍ２以下であることを特徴とする銅合金材料。(2) 0.05 to 1.2% by mass of Ni, 0.01 to 0.15% by mass of P and 0.05 to 2.5% by mass of Sn, and further Fe, Zn, Pb, Si , Mg, Zr, Cr, Ti, Mn and Co are contained, Fe is 0.001 to 0.1% by mass, Zn is 0.001 to 0.5% by mass, and Pb is 0.001 to 0.05 mass%, Si is 0.001 to 0.1 mass%, Mg is 0.001 to 0.3 mass%, Zr is 0.001 to 0.15 mass%, and Cr is 0.00. 001 to 0.3 mass%, Ti is 0.001 to 0.05 mass%, Mn is 0.001 to 0.2 mass%, Co is 0.001 to 0.2 mass%, and Mg, Zr , Cr, Ti, Mn and Co in the case of containing two or more, the total content is 0.001 to 0.5 mass%, the balance An alloy composition composed of Cu and inevitable impurities, the surface of the material after electropolishing is observed with an FE-SEM, and the number ratio of compound particles having a particle diameter of 5 to 30 nm per 1 μm × 1 μm viewing area is 20 / [mu] m 2 or more, the copper alloy material, wherein the ratio of the number of compound particles is a particle diameter of more than 30nm is one / [mu] m 2 or less.
（３）Ｓｎを０．０５〜０．５質量％含有し、引張強度が４００ＭＰａ以上、導電率が５０％ＩＡＣＳ以上であることを特徴とする上記（１）または（２）に記載の銅合金材料。 (3) The copper alloy according to (1) or (2) above, containing 0.05 to 0.5% by mass of Sn, having a tensile strength of 400 MPa or more and a conductivity of 50% IACS or more. material.
（４）Ｓｎを０．５質量％超え２．５質量％以下含有し、引張強度が５００ＭＰａ以上、導電率が２５％ＩＡＣＳ以上であることを特徴とする上記（１）または（２）に記載の銅合金材料。 (4) The content of Sn is more than 0.5% by mass and 2.5% by mass or less, the tensile strength is 500 MPa or more, and the conductivity is 25% IACS or more. Copper alloy material.
（５）下記（ａ）〜（ｅ）の工程を含むことを特徴とする上記（１）〜（４）のいずれか１項に記載された銅合金材料の製造方法。
（ａ）３００℃までの冷却速度を３０℃／分以上とする溶解鋳造工程。
（ｂ）５℃／分以上で昇温し、６００〜１０００℃で３０分〜１０時間保持する均質化熱処理工程。
（ｃ）３００℃までの冷却速度を３０℃／分以上とする熱間圧延工程。
（ｄ）加工率を８０％以上とする冷間圧延工程。
（ｅ）３５０〜６００℃で５秒〜１０時間保持する焼鈍工程。(5) The method for producing a copper alloy material described in any one of (1) to (4) above, comprising the following steps (a) to (e):
(A) A melt casting step in which the cooling rate to 300 ° C. is 30 ° C./min or more.
(B) A homogenization heat treatment step in which the temperature is raised at 5 ° C./min or more and held at 600 to 1000 ° C. for 30 minutes to 10 hours.
(C) A hot rolling step in which the cooling rate to 300 ° C. is 30 ° C./min or more.
(D) A cold rolling step in which the processing rate is 80% or more.
(E) An annealing step of holding at 350 to 600 ° C. for 5 seconds to 10 hours.
本発明によれば、Ｎｉを０．０５〜１．２質量％、Ｐを０．０１〜０．１５質量％およびＳｎを０．０５〜２．５質量％含有し、残部がＣｕおよび不可避不純物からなる合金組成を有し、電解研磨後の材料表面をＦＥ−ＳＥＭで観察し、１μｍ×１μｍの視野面積当たり、粒子径が５〜３０ｎｍである化合物粒子の個数割合を２０個／μｍ２以上、粒子径が３０ｎｍ超えである化合物粒子の個数割合を１個／μｍ２以下とすることにより、高強度、高導電率および良好な曲げ加工性に加えて、さらに良好な耐熱性を兼ね備えた銅合金材料の提供が可能になった。According to the present invention, 0.05 to 1.2% by mass of Ni, 0.01 to 0.15% by mass of P, and 0.05 to 2.5% by mass of Sn, with the balance being Cu and inevitable impurities The surface of the material after electropolishing is observed with an FE-SEM, and the number ratio of compound particles having a particle diameter of 5 to 30 nm per 1 μm × 1 μm visual field area is 20 / μm 2 or more. In addition to high strength, high electrical conductivity, and good bending workability, copper having better heat resistance can be obtained by setting the number ratio of compound particles having a particle diameter of more than 30 nm to 1 / μm 2 or less. It is now possible to provide alloy materials.
以下、本発明の銅合金材料の好ましい実施の態様について、詳細に説明する。
（銅合金材料の成分組成）
本発明の銅合金材料の基本組成は、Ｎｉを０．０５〜１．２質量％、Ｐを０．０１〜０．１５質量％およびＳｎを０．０５〜２．５質量％含有し、残部がＣｕおよび不可避不純物である。Hereinafter, preferred embodiments of the copper alloy material of the present invention will be described in detail.
(Component composition of copper alloy material)
The basic composition of the copper alloy material of the present invention contains 0.05 to 1.2% by mass of Ni, 0.01 to 0.15% by mass of P and 0.05 to 2.5% by mass of Sn, and the balance Are Cu and inevitable impurities.
［必須含有成分］
（Ｎｉ：０．０５〜１．２質量％）
Ｎｉは、母相に固溶し、またＰと化合物を形成することで、強度を増加させる元素である。また、Ｎｉは、Ｐと化合物を生成し、この生成物を析出させることで、導電率を高めるとともに耐熱性も向上させる効果を有している。しかしながら、Ｎｉ含有量が０．０５質量％未満では、その効果を十分に発揮することができず、また、１．２質量％超えでは、導電率が顕著に低下する。このため、Ｎｉ含有量は、０．０５〜１．２質量％とし、好ましくは０．１０〜１．００質量％、より好ましくは０．１０〜０．４０質量％とした。[Required ingredients]
(Ni: 0.05-1.2% by mass)
Ni is an element that increases the strength by forming a solid solution with the matrix and forming a compound with P. Ni has the effect of increasing the electrical conductivity and heat resistance by generating a compound with P and precipitating this product. However, if the Ni content is less than 0.05% by mass, the effect cannot be sufficiently exerted, and if it exceeds 1.2% by mass, the conductivity is significantly reduced. For this reason, Ni content was 0.05-1.2 mass%, Preferably it was 0.10-1.00 mass%, More preferably, it was 0.10-0.40 mass%.
（Ｐ：０．０１〜０．１５質量％）
Ｐは、Ｎｉと化合物を生成することで、強度の増加、導電率の上昇、および耐熱性の向上に寄与する元素である。しかしながら、Ｐ含有量が０．０１質量％未満では、その効果を十分に得られず、また、０．１５質量％超えだと、導電率の低下、粗大（例えば、粒子径が３０ｎｍ超え）な化合物粒子の生成による曲げ加工性の低下、微細（例えば、粒子径が５〜３０ｎｍ）な化合物の生成割合を減少させることによる耐熱性の低下、加工性の低下を引き起こす。このため、Ｐ含有量は、０．０１〜０．１５質量％とし、好ましくは０．０１〜０．１０質量％、より好ましくは０．０５〜０．１０質量％とした。(P: 0.01 to 0.15 mass%)
P is an element that contributes to an increase in strength, an increase in conductivity, and an improvement in heat resistance by forming a compound with Ni. However, if the P content is less than 0.01% by mass, the effect cannot be sufficiently obtained, and if it exceeds 0.15% by mass, the conductivity is lowered and coarse (for example, the particle diameter exceeds 30 nm). It causes a decrease in bending workability due to the formation of compound particles, a decrease in heat resistance and a decrease in workability due to a decrease in the generation ratio of fine compounds (for example, particle diameter of 5 to 30 nm). For this reason, P content was 0.01-0.15 mass%, Preferably it was 0.01-0.10 mass%, More preferably, it was 0.05-0.10 mass%.
（Ｓｎ：０．０５〜２．５質量％）
Ｓｎは、母相に固溶することで、強度の増加および耐熱性の向上に寄与する元素である。しかしながら、Ｓｎ含有量が０．０５質量％未満では、その効果を十分に得られず、また、２．５質量％超えだと、導電率の低下、熱間加工性の劣化を引き起こす。このため、Ｓｎ含有量は、０．０５〜２．５質量％とした。なお、引張強度と導電率のうち、特に導電率を重視する場合には、Ｓｎ含有量を０．０５〜０．５質量％に限定すれば、引張強度が４００ＭＰａ以上で、５０％ＩＡＣＳ以上の高導電率を具備することができる点で好ましく、また、特に引張強度を重視する場合には、Ｓｎ含有量を０．５質量％超え２．５質量％以下に限定すれば、２５％ＩＡＣＳ以上の導電率で、５００ＭＰａ以上の高引張強度を具備することができる点で好ましい。(Sn: 0.05 to 2.5% by mass)
Sn is an element that contributes to an increase in strength and an improvement in heat resistance by dissolving in the matrix. However, if the Sn content is less than 0.05% by mass, the effect cannot be sufficiently obtained, and if it exceeds 2.5% by mass, the electrical conductivity is lowered and the hot workability is deteriorated. For this reason, Sn content was 0.05-2.5 mass%. Of the tensile strength and electrical conductivity, particularly when electrical conductivity is important, if the Sn content is limited to 0.05 to 0.5% by mass, the tensile strength is 400 MPa or more and 50% IACS or more. It is preferable in that it can have a high electrical conductivity, and in particular, when the tensile strength is important, if the Sn content is limited to 0.5% by mass or more and 2.5% by mass or less, 25% IACS or more This is preferable in that it can have a high tensile strength of 500 MPa or more.
［任意添加成分］
本発明では、基本組成として、上述したＮｉ、ＰおよびＳｎを含有することを必須とするが、さらに任意添加成分として、Ｆｅ、Ｚｎ、Ｐｂ、Ｓｉ、Ｍｇ、Ｚｒ、Ｃｒ、Ｔｉ、ＭｎおよびＣｏの中から選ばれる少なくとも１成分を選択的に含有させてもよい。[Optional components]
In the present invention, it is essential to contain the above-described Ni, P and Sn as a basic composition, but as optional additional components, Fe, Zn, Pb, Si, Mg, Zr, Cr, Ti, Mn and Co At least one component selected from among them may be selectively contained.
（Ｆｅ：０．００１〜０．１質量％）
Ｆｅは、Ｐと化合物を形成することで強度の増加、耐熱性の向上に寄与する元素であり、この効果を奏するには、Ｆｅ含有量を０．００１質量％以上とすることが好ましい。しかしながら、Ｆｅ含有量が０．１質量％よりも多いと、材料が磁性を帯びやすくなり、材料が磁性を帯びると、リードフレームにおける伝送信号の伝達特性が劣化する懸念がある。このため、Ｆｅ含有量は、０．００１〜０．１質量％とすることが好ましく、０．００１〜０．０５質量％がより好ましく、０．００１〜０．０１質量％がさらに好ましい。(Fe: 0.001 to 0.1% by mass)
Fe is an element that contributes to an increase in strength and an improvement in heat resistance by forming a compound with P. In order to achieve this effect, the Fe content is preferably 0.001% by mass or more. However, if the Fe content is more than 0.1% by mass, the material tends to be magnetized, and if the material is magnetized, the transmission characteristics of the transmission signal in the lead frame may be deteriorated. For this reason, it is preferable that Fe content shall be 0.001-0.1 mass%, 0.001-0.05 mass% is more preferable, 0.001-0.01 mass% is further more preferable.
（Ｚｎ：０．００１〜０．５質量％）
Ｚｎは、母相に固溶することで強度の増加、半田濡れ性の向上、めっき性の向上に寄与する元素であり、この効果を奏するには、Ｚｎ含有量を０．００１質量％以上とすることが好ましい。しかしながら、Ｚｎ含有量が０．５質量％より多いと、導電率が低下する傾向がある。このため、Ｚｎ含有量は、０．００１〜０．５質量％であることが好ましく、０．０１〜０．５質量％がより好ましく、０．１〜０．５質量％がさらに好ましい。(Zn: 0.001 to 0.5 mass%)
Zn is an element that contributes to an increase in strength, improvement in solder wettability, and improvement in plating properties by dissolving in the matrix phase. To achieve this effect, the Zn content is 0.001% by mass or more. It is preferable to do. However, when the Zn content is more than 0.5% by mass, the conductivity tends to decrease. For this reason, it is preferable that Zn content is 0.001-0.5 mass%, 0.01-0.5 mass% is more preferable, 0.1-0.5 mass% is further more preferable.
（Ｐｂ：０．００１〜０．０５質量％）
Ｐｂは、プレス加工性の向上に寄与する元素であり、この効果を奏するには、Ｐｂ含有量を０．００１質量％以上とすることが好ましい。しかしながら、Ｐｂ含有量を０．０５質量％よりも多くしても、効果の更なる向上は認められず、また、近年の環境保護の観点から、Ｐｂ含有量を極力抑えることが望ましい。このため、Ｐｂ含有量は０．００１〜０．０５質量％にすることが好ましく、０．００１〜０．０１質量％がより好ましい。(Pb: 0.001 to 0.05 mass%)
Pb is an element that contributes to the improvement of press workability. In order to achieve this effect, the Pb content is preferably 0.001% by mass or more. However, even if the Pb content is more than 0.05% by mass, no further improvement in the effect is observed, and it is desirable to suppress the Pb content as much as possible from the viewpoint of environmental protection in recent years. For this reason, it is preferable to make Pb content into 0.001-0.05 mass%, and 0.001-0.01 mass% is more preferable.
（Ｓｉ：０．００１〜０．１質量％）
Ｓｉは、強度の増加に寄与する元素であり、この効果を奏するには、Ｓｉ含有量を０．００１質量％以上とすることが好ましい。しかしながら、Ｓｉ含有量を０．１質量％よりも多くすると、導電率の低下や、粗大な化合物の生成による曲げ加工性の劣化が懸念される。このため、Ｓｉ含有量は、０．００１〜０．１質量％が好ましく、０．０１〜０．１質量％がより好ましい。(Si: 0.001 to 0.1% by mass)
Si is an element that contributes to an increase in strength. In order to achieve this effect, the Si content is preferably 0.001% by mass or more. However, when the Si content is more than 0.1% by mass, there is a concern that the electrical conductivity is lowered and the bending workability is deteriorated due to the generation of a coarse compound. For this reason, 0.001-0.1 mass% is preferable and Si content has more preferable 0.01-0.1 mass%.
（Ｍｇ：０．００１〜０．３質量％）
Ｍｇは、強度の増加や耐熱性の向上に寄与する元素である。また例えば電子部品のばね接点などにおいて、耐応力緩和特性の向上に寄与する。これらの効果を奏するには、Ｍｇ含有量を０．００１質量％以上とすることが好ましい。しかしながら、Ｍｇ含有量を０．３質量％よりも多くすると、導電率の低下や、鋳造時の介在物の形成が懸念される。このため、Ｍｇ含有量は、０．００１〜０．３質量％が好ましく、０．０１〜０．３質量％がより好ましい。(Mg: 0.001 to 0.3% by mass)
Mg is an element that contributes to an increase in strength and an improvement in heat resistance. Further, for example, it contributes to improvement of stress relaxation resistance in a spring contact of an electronic component. In order to achieve these effects, the Mg content is preferably 0.001% by mass or more. However, when the Mg content is more than 0.3% by mass, there is a concern that the electrical conductivity is lowered and inclusions are formed during casting. For this reason, 0.001-0.3 mass% is preferable and, as for Mg content, 0.01-0.3 mass% is more preferable.
（Ｚｒ：０．００１〜０．１５質量％）
Ｚｒは、強度の増加や耐熱性の向上に寄与する元素である。また例えば電子部品のばね接点などにおいて、耐応力緩和特性の向上に寄与する。これらの効果を奏するには、Ｚｒ含有量を０．００１質量％以上とすることが好ましい。しかしながら、Ｚｒ含有量を０．１５質量％よりも多くすると、導電率の低下や、熱間加工時の割れが懸念される。このため、Ｚｒ含有量は、０．００１〜０．１５質量％が好ましく、０．０１〜０．１質量％がより好ましい。(Zr: 0.001 to 0.15 mass%)
Zr is an element that contributes to an increase in strength and an improvement in heat resistance. Further, for example, it contributes to improvement of stress relaxation resistance in a spring contact of an electronic component. In order to achieve these effects, the Zr content is preferably 0.001% by mass or more. However, when the Zr content is more than 0.15% by mass, there is a concern about a decrease in conductivity and cracking during hot working. For this reason, 0.001-0.15 mass% is preferable and, as for Zr content, 0.01-0.1 mass% is more preferable.
（Ｃｒ：０．００１〜０．３質量％）
Ｃｒは、強度の増加や耐熱性の向上に寄与する元素であり、この効果を奏するには、Ｃｒ含有量を０．００１質量％以上とすることが好ましい。しかしながら、Ｃｒ含有量を０．３質量％よりも多くすると、鋳造時の晶出物の発生による曲げ加工性の低下が懸念される。このため、Ｃｒ含有量は、０．００１〜０．３質量％が好ましく、０．０１〜０．３質量％がより好ましい。(Cr: 0.001 to 0.3% by mass)
Cr is an element that contributes to an increase in strength and an improvement in heat resistance. In order to achieve this effect, the Cr content is preferably 0.001% by mass or more. However, when the Cr content is more than 0.3% by mass, there is a concern that bending workability may be lowered due to generation of crystallized substances during casting. For this reason, 0.001-0.3 mass% is preferable and Cr content has more preferable 0.01-0.3 mass%.
（Ｔｉ：０．００１〜０．０５質量％）
Ｔｉは、強度の増加や耐熱性の向上に寄与する元素である。また例えば電子部品のばね接点などにおいて、耐応力緩和特性の向上に寄与する。これらの効果を奏するには、Ｔｉ含有量を０．００１質量％以上とすることが好ましい。しかしながら、Ｔｉ含有量を０．０５質量％よりも多くすると、導電率の低下や、鋳塊表面の鋳肌異常が懸念される。このため、Ｔｉ含有量は、０．００１〜０．０５質量％が好ましく、０．０１〜０．０５質量％がより好ましい。(Ti: 0.001 to 0.05 mass%)
Ti is an element that contributes to an increase in strength and an improvement in heat resistance. Further, for example, it contributes to improvement of stress relaxation resistance in a spring contact of an electronic component. In order to achieve these effects, the Ti content is preferably 0.001% by mass or more. However, if the Ti content is more than 0.05% by mass, there is a concern about a decrease in electrical conductivity or abnormal casting surface on the ingot surface. For this reason, 0.001-0.05 mass% is preferable, and Ti content is more preferable 0.01-0.05 mass%.
（Ｍｎ：０．００１〜０．２質量％）
Ｍｎは、強度の増加や耐熱性の向上、熱間加工性の向上に寄与する元素であり、この効果を奏するには、Ｍｎ含有量を０．００１質量％以上とすることが好ましい。しかしながら、Ｍｎ含有量を０．２質量％よりも多くすると、導電率の低下が懸念される。このため、Ｍｎ含有量は、０．００１〜０．２質量％が好ましく、０．０１〜０．２質量％がより好ましい。(Mn: 0.001 to 0.2% by mass)
Mn is an element that contributes to an increase in strength, heat resistance, and hot workability. To achieve this effect, the Mn content is preferably 0.001% by mass or more. However, when the Mn content is more than 0.2% by mass, there is a concern that the electrical conductivity is lowered. For this reason, 0.001-0.2 mass% is preferable and, as for Mn content, 0.01-0.2 mass% is more preferable.
（Ｃｏ：０．００１〜０．２質量％）
Ｃｏは、強度の増加や熱間加工性の向上に寄与する元素であり、この効果を奏するには、Ｃｏ含有量を０．００１質量％以上とすることが好ましい。しかしながら、Ｃｏ含有量を０．２質量％よりも多くすると、導電率の低下が懸念される。このため、Ｃｏ含有量は、０．００１〜０．２質量％が好ましく、０．０１〜０．２質量％がより好ましい。(Co: 0.001 to 0.2% by mass)
Co is an element that contributes to an increase in strength and an improvement in hot workability. In order to achieve this effect, the Co content is preferably 0.001% by mass or more. However, if the Co content is more than 0.2% by mass, there is a concern that the electrical conductivity will decrease. For this reason, 0.001-0.2 mass% of Co content is preferable, and 0.01-0.2 mass% is more preferable.
（Ｍｇ、Ｚｒ、Ｃｒ、Ｔｉ、ＭｎおよびＣｏを２以上含有する場合の合計含有量：０．００１〜０．５質量％）
Ｍｇ、Ｚｒ、Ｃｒ、Ｔｉ、ＭｎおよびＣｏは、Ｐと化合物を形成することで、強度の増加、耐熱性の向上に寄与する。これらの元素の添加量は０．００１〜０．５質量％が好ましく、０．０１〜０．５質量％がより好ましく、０．１〜０．５質量％がさらに好ましい。０．５質量％より大きい場合、導電率の低下、粗大な化合物形成による曲げ加工性の低下が懸念される。(Total content when containing two or more of Mg, Zr, Cr, Ti, Mn and Co: 0.001 to 0.5% by mass)
Mg, Zr, Cr, Ti, Mn and Co contribute to an increase in strength and an improvement in heat resistance by forming a compound with P. The amount of these elements added is preferably 0.001 to 0.5 mass%, more preferably 0.01 to 0.5 mass%, and still more preferably 0.1 to 0.5 mass%. When it is larger than 0.5% by mass, there is a concern about decrease in conductivity and decrease in bending workability due to the formation of a coarse compound.
（化合物粒子）
本発明においては、電解研磨後の材料表面をＦＥ−ＳＥＭで観察し、１μｍ×１μｍの視野面積当たり、粒子径が５〜３０ｎｍである化合物粒子の個数割合を２０個／μｍ２以上、粒子径が３０ｎｍ超えである化合物粒子の個数割合を１個／μｍ２以下とすることで、高強度、高導電率および良好な曲げ加工性に加えて、良好な耐熱性をも兼ね備えた銅合金材料を得ることができる。ここでいう「化合物粒子」とは、鋳造時に形成される介在物や晶出物、鋳造凝固後に形成される析出物の総称である。また、化合物粒子の粒子径は、長径の長さを意味する。１μｍ×１μｍの視野面積当たり、粒子径が５〜３０ｎｍである微細な化合物粒子の個数割合が２０個／μｍ２以上であるとき、微細な化合物粒子により十分なピン止め効果が得られることで再結晶が抑制され、良好な耐熱性が得られる。一方、微細な化合物粒子の個数割合が２０個／μｍ２より少ない場合には良好な耐熱性が得られない。また、粒子径が３０ｎｍ超えである粗大な化合物粒子の個数割合が１個／μｍ２以下とすることで、良好な曲げ加工性が得られる。粗大な化合物粒子の個数割合が１個／μｍ２を超えると、粗大な化合物粒子が破壊の起点となって、曲げ加工性が顕著に劣化する。さらにこのとき、粗大な化合物粒子が多く形成されると、微細な化合物粒子の個数割合が減少する傾向があるため、耐熱性も悪化するおそれもある。従来、化合物粒子の分散状態は、透過型電子顕微鏡（ＴＥＭ）を用いて観察し、視野中の個数や面積率で表現されることが多いが、それらの数値は試験片の厚さに依存する。しかしながら、ＴＥＭ用に作製される試験片の厚さを一様に揃えることは困難であり、加えて、同じ試験片で測定したとしても、測定回によってやや異なる結果になる可能性もある。このため、本発明では、試験片の厚さに因らない電界放射型走査電子顕微鏡（ＦＥ−ＳＥＭ）を用いて化合物粒子の個数割合を評価した。(Compound particles)
In the present invention, the material surface after electropolishing is observed with an FE-SEM, and the number ratio of compound particles having a particle diameter of 5 to 30 nm per 1 μm × 1 μm visual field area is 20 particles / μm 2 or more. By setting the number ratio of the compound particles having a particle size exceeding 30 nm to 1 / μm 2 or less, a copper alloy material having good heat resistance in addition to high strength, high conductivity, and good bending workability is obtained. Can be obtained. The term “compound particles” as used herein is a general term for inclusions and crystallization products formed during casting and precipitates formed after casting solidification. The particle diameter of the compound particles means the length of the major axis. When the number ratio of fine compound particles having a particle diameter of 5 to 30 nm per 1 μm × 1 μm visual field area is 20 particles / μm 2 or more, a sufficient pinning effect can be obtained by the fine compound particles. Crystals are suppressed and good heat resistance is obtained. On the other hand, when the number ratio of fine compound particles is less than 20 / μm 2, good heat resistance cannot be obtained. Moreover, favorable bending workability is obtained because the number ratio of the coarse compound particle | grains whose particle diameter exceeds 30 nm shall be 1 piece / micrometer < 2 > or less. When the number ratio of the coarse compound particles exceeds 1 / μm 2 , the coarse compound particles serve as a starting point of fracture, and the bending workability is remarkably deteriorated. Further, at this time, if a large number of coarse compound particles are formed, the number ratio of fine compound particles tends to decrease, so that heat resistance may be deteriorated. Conventionally, the dispersion state of compound particles is often observed with a transmission electron microscope (TEM) and is often expressed by the number and area ratio in the field of view, but these values depend on the thickness of the test piece. . However, it is difficult to make the thickness of the test pieces prepared for TEM uniform. In addition, even if the same test piece is used for measurement, there is a possibility that the results will be slightly different depending on the measurement time. For this reason, in this invention, the number ratio of the compound particle was evaluated using the field emission scanning electron microscope (FE-SEM) which does not depend on the thickness of a test piece.
（銅合金材料の製造方法）
次に、本発明の銅合金材料の製造方法について説明する。
本発明の銅合金材料は、通常、溶解鋳造→均質化熱処理→熱間圧延→冷間圧延→焼鈍→仕上げ圧延を行うことで製造される。各工程の間に、必要に応じて、面削、バフ研磨、酸洗、脱脂等を適宜行っても良い。また、冷間圧延と焼鈍は、複数回繰り返し行なっても良く、さらに仕上げ圧延後に低温焼鈍を施しても良い。本発明の製造方法においては、溶解鋳造、均質化熱処理および熱間圧延で粗大な化合物粒子を極力生成させず、その後の冷間圧延および焼鈍で微細な析出物を多く生成させることが重要である。本発明の製造方法は、従来と同程度の工程数でありながら、それぞれの工程条件を適切に調整することで、材料特性の向上を実現することができる。(Method for producing copper alloy material)
Next, the manufacturing method of the copper alloy material of this invention is demonstrated.
The copper alloy material of the present invention is usually produced by performing melt casting → homogenization heat treatment → hot rolling → cold rolling → annealing → finish rolling. Between each process, you may perform chamfering, buffing, pickling, degreasing, etc. suitably as needed. Moreover, cold rolling and annealing may be repeated a plurality of times, and low temperature annealing may be performed after finish rolling. In the production method of the present invention, it is important not to produce coarse compound particles as much as possible by melt casting, homogenization heat treatment and hot rolling, but to produce many fine precipitates by subsequent cold rolling and annealing. . Although the manufacturing method of the present invention has the same number of steps as the conventional method, the material characteristics can be improved by appropriately adjusting each process condition.
＜溶解鋳造＞
溶解鋳造は、一般的な方法で実施すれば良いが、本発明では、鋳造時、３００℃までの冷却を、３０℃／分以上の冷却速度で行なうことが、冷却時の晶出や析出を抑制し、粗大な化合物粒子の生成を抑制する点で好ましい。前記冷却速度が３０℃／分よりも小さいと、冷却時の晶出や析出を十分に抑制することができず、粗大な化合物粒子が生成しやすくなる傾向があるからである。<Melting casting>
Melting casting may be carried out by a general method, but in the present invention, cooling to 300 ° C. at the time of casting is performed at a cooling rate of 30 ° C./min or more, so that crystallization and precipitation at the time of cooling are performed. It is preferable in that it suppresses the formation of coarse compound particles. This is because if the cooling rate is lower than 30 ° C./min, crystallization and precipitation during cooling cannot be sufficiently suppressed, and coarse compound particles tend to be generated.
＜均質化熱処理＞
均質化熱処理は、溶解鋳造で生成された粗大な化合物粒子を母相に固溶させ、溶体化状態とするために実施する。均質化熱処理は、６００〜１０００℃で３０分〜１０時間保持することが好ましい。従来、均質化熱処理の昇温速度は重要視されていなかったが、本発明では、規定する材料組織を得るために、特に昇温速度を、５℃／分以上、好ましくは１０℃／分以上に制御することが必要である。昇温速度が５℃／分より小さいと、昇温時に溶解鋳造で形成された粗大な化合物粒子が成長し、その後の均質化熱処理で粗大な化合物粒子を、母相に十分に溶かしきることができずに残存しやすくなって、最終特性で曲げ加工性を劣化させるからである。また、微細な化合物粒子の個数割合も減少するため、耐熱性も悪化する。保持温度が６００℃未満および保持時間が３０分未満の少なくとも一方を満たす場合には、母相に固溶し切れなかった粗大な化合物粒子が残存しやすくなって、最終特性で曲げ加工性は劣化する恐れがあり、また、保持温度が１０００℃超えの場合には、続く熱間圧延工程において、熱間加工割れが生じる恐れがあるからである。なお、保持時間は、溶体化の効果の飽和や、実際の製造における時間制約の観点から、上限を１０時間とすることが好ましい。<Homogenization heat treatment>
The homogenization heat treatment is carried out in order to make the coarse compound particles produced by the melt casting form a solid solution in the matrix phase to obtain a solution state. The homogenization heat treatment is preferably held at 600 to 1000 ° C. for 30 minutes to 10 hours. Conventionally, the heating rate of the homogenization heat treatment has not been regarded as important, but in the present invention, in order to obtain the specified material structure, the heating rate is particularly 5 ° C./min or more, preferably 10 ° C./min or more. It is necessary to control. If the rate of temperature increase is less than 5 ° C./min, coarse compound particles formed by dissolution casting grow at the time of temperature rise, and the coarse compound particles can be sufficiently dissolved in the parent phase by the subsequent homogenization heat treatment. This is because it is difficult to remain and the bending workability is deteriorated with the final characteristics. In addition, the number ratio of fine compound particles is reduced, so that the heat resistance is also deteriorated. When at least one of the holding temperature of less than 600 ° C. and the holding time of less than 30 minutes is satisfied, coarse compound particles that cannot be completely dissolved in the matrix phase are likely to remain, and the bending properties are deteriorated in the final characteristics. This is because, when the holding temperature exceeds 1000 ° C., hot working cracks may occur in the subsequent hot rolling process. The upper limit of the retention time is preferably 10 hours from the viewpoint of saturation of the effect of solution treatment and time constraints in actual production.
＜熱間圧延＞
熱間圧延は、５５０〜９５０℃で実施することが好ましい。本発明では、特に、３００℃までの冷却速度を３０℃／分以上とすることが必要である。３００℃までの冷却速度が３０℃／分より小さいと、冷却中に粗大な化合物粒子が析出しやすくなって、最終特性に悪影響を及ぼすからである。<Hot rolling>
The hot rolling is preferably performed at 550 to 950 ° C. In the present invention, in particular, the cooling rate up to 300 ° C. needs to be 30 ° C./min or more. This is because if the cooling rate to 300 ° C. is smaller than 30 ° C./min, coarse compound particles are likely to precipitate during cooling, which adversely affects the final characteristics.
＜冷間圧延＞
熱間圧延後の冷間圧延は、８０％以上の加工率で実施することが好ましい。加工率が８０％未満だと、材料内に均一にひずみが導入されず、後の焼鈍で微細な化合物粒子が析出する際、材料内で析出状態に差が出る恐れがあるからである。<Cold rolling>
The cold rolling after hot rolling is preferably performed at a processing rate of 80% or more. When the processing rate is less than 80%, strain is not uniformly introduced into the material, and when fine compound particles are precipitated by subsequent annealing, there is a possibility that a difference in the precipitation state occurs in the material.
＜焼鈍＞
焼鈍は、３５０〜６００℃で５秒〜１０時間保持するのが好ましい。前記の範囲よりも低温短時間だと、微細な化合物粒子の析出が不十分で、強度および導電率の低下が懸念され、また、前記の範囲よりも高温長時間だと、粗大な化合物粒子が析出し、曲げ加工性の劣化や耐熱性の悪化が懸念されるからである。<Annealing>
The annealing is preferably held at 350 to 600 ° C. for 5 seconds to 10 hours. If the temperature is lower than the above range for a short time, the precipitation of fine compound particles is insufficient, and there is a concern that the strength and conductivity are lowered. If the temperature is higher than the above range for a long time, coarse compound particles are produced. This is because there is a concern about precipitation and deterioration of bending workability and heat resistance.
＜仕上げ圧延＞
仕上げ圧延の加工率は特に限定されるものではないが、良好な曲げ加工性を得るため、６０％以下とすることが好ましい。<Finish rolling>
The processing rate of finish rolling is not particularly limited, but is preferably 60% or less in order to obtain good bending workability.
＜低温焼鈍＞
仕上げ圧延後に、２５０〜４００℃で２秒〜５時間の低温焼鈍を実施しても良い。低温焼鈍により、材料のばね性や耐応力緩和特性を向上させることができる。前記の範囲よりも低温短時間だと、低温焼鈍の効果が得られない恐れがあり、また、前記の範囲よりも高温長時間だと、微細な化合物粒子が粗大に成長し、曲げ加工性や耐熱性に悪影響を及ぼす恐れがあるからである。また材料の再結晶が進行し、所望の強度が得られなくなる恐れがある。<Low temperature annealing>
After the finish rolling, low temperature annealing at 250 to 400 ° C. for 2 seconds to 5 hours may be performed. By low temperature annealing, the spring property and stress relaxation resistance of the material can be improved. If the temperature is lower than the above range for a short time, the effect of low temperature annealing may not be obtained, and if the temperature is higher than the above range for a long time, fine compound particles grow coarsely, This is because the heat resistance may be adversely affected. In addition, recrystallization of the material may proceed, and a desired strength may not be obtained.
本発明の銅合金材料は、所定の合金組成を有するＣｕ−Ｎｉ−Ｓｎ−Ｐ系銅合金中の化合物粒子のサイズと量を制御することで、高強度、高導電率および良好な曲げ加工性に加えて、さらに耐熱性も兼ね備えることができる。このため、本発明の銅合金材料は、リードフレームをはじめとした電気電子部品に用いるのに好適である。 The copper alloy material of the present invention controls the size and amount of compound particles in a Cu—Ni—Sn—P-based copper alloy having a predetermined alloy composition, thereby providing high strength, high conductivity, and good bending workability. In addition, it can also have heat resistance. For this reason, the copper alloy material of the present invention is suitable for use in electrical and electronic parts such as lead frames.
以下、本発明を実施例に基づきさらに詳細に説明するが、本発明はそれらに限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to them.
（実施例１〜２６および比較例１〜２２）
以下に、実施例に基づき本発明をさらに詳細に説明するが、本発明はこれに限定されるものではない。(Examples 1-26 and Comparative Examples 1-22)
Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.
合金成分を溶解し、３００℃まで３０℃／分以上の冷却速度で冷却しながら鋳造して、表１に示す成分組成を有する鋳塊を作製した後、表２に示す昇温速度で昇温し、６００〜１０００℃で３０分から１０時間保持する均質化熱処理を施し、次いで熱間圧延を実施した。熱間圧延後に、表２に示す３００℃までの冷却速度で冷却し、その後、面削により表面酸化層を除去し、８０％以上の加工率で冷間圧延を実施した。更にその後、３５０〜６００℃で５秒〜１０時間焼鈍を実施し、次いで仕上げ圧延を６０％以下の加工率で施し、最後に２５０〜４００℃で２秒〜５時間の低温焼鈍を行い、板厚０．５ｍｍの銅合金材料を製造した。 After melting the alloy components and casting to 300 ° C. while cooling at a cooling rate of 30 ° C./min or more to produce an ingot having the component composition shown in Table 1, the temperature is increased at the temperature rising rate shown in Table 2. Then, a homogenization heat treatment was performed at 600 to 1000 ° C. for 30 minutes to 10 hours, and then hot rolling was performed. After hot rolling, it was cooled at a cooling rate up to 300 ° C. shown in Table 2, and then the surface oxide layer was removed by face milling, and cold rolling was performed at a processing rate of 80% or more. Thereafter, annealing is performed at 350 to 600 ° C. for 5 seconds to 10 hours, then finish rolling is performed at a processing rate of 60% or less, and finally low temperature annealing is performed at 250 to 400 ° C. for 2 seconds to 5 hours, A copper alloy material having a thickness of 0.5 mm was produced.
このようにして製造した供試材について、下記の評価を実施した。 The following evaluation was performed on the specimens thus produced.
（組織観察）
製造した各銅合金材料（供試材）から採取した試験片（サイズ：２０ｍｍ×２０ｍｍ）の表面２０μｍをリン酸系水溶液で電解研磨した後、ＦＥ−ＳＥＭにより、材料表面を１００００〜１０００００倍で観察した。観察は１μｍ×１μｍの範囲を任意に３視野観察し、その視野範囲内に存在する、粒子径が５〜３０ｎｍの微細な化合物粒子の個数と、粒子径が３０ｎｍ超えの粗大な化合物粒子の個数を計測した。その後、計測した個数を、１μｍ×１μｍ（１μｍ２）の視野面積当たりの個数割合に換算した。換算した個数割合は四捨五入して、微細な化合物粒子に関しては整数で示し、また、粗大な化合物粒子に関しては小数点第二位の数字までを示した。(Tissue observation)
After electropolishing a surface 20 μm of a test piece (size: 20 mm × 20 mm) collected from each manufactured copper alloy material (test material) with a phosphoric acid aqueous solution, the surface of the material is 10000 to 100,000 times by FE-SEM. Observed. Observation is performed by observing three fields of view of 1 μm × 1 μm arbitrarily, and the number of fine compound particles having a particle diameter of 5 to 30 nm and the number of coarse compound particles having a particle diameter exceeding 30 nm are present in the field of view. Was measured. Thereafter, the measured number was converted into a number ratio per visual field area of 1 μm × 1 μm (1 μm 2 ). The converted number ratio was rounded off, and the fine compound particles were shown as integers, and the coarse compound particles were shown up to the second decimal place.
（引張強度の測定）
引張強度は、各供試材から、ＪＩＳ Ｚ２２４１：２０１１の附属書Ｂに規定されている５号試験片を、圧延平行方向に沿って切り出して３本採取し、ＪＩＳ Ｚ２２４１：２０１１に規定された「金属材料引張試験方法」に準じて３本測定した。それらの引張強度の平均値を表２に示す。(Measurement of tensile strength)
Tensile strength was specified in JIS Z2241: 2011 by extracting three specimens of No. 5 specified in Annex B of JIS Z2241: 2011 along the rolling parallel direction. Three samples were measured according to “Metal material tensile test method”. Table 2 shows the average values of the tensile strengths.
（導電率の測定）
２０℃（±０．５℃）に保たれた恒温漕中で、四端子法により比抵抗値を計測し、計測した比抵抗値から導電率を算出した。なお、端子間距離は１００ｍｍとした。(Measurement of conductivity)
In a constant temperature bath maintained at 20 ° C. (± 0.5 ° C.), the specific resistance value was measured by the four probe method, and the conductivity was calculated from the measured specific resistance value. In addition, the distance between terminals was 100 mm.
（曲げ加工性）
ＪＣＢＡ Ｔ３０７：２００７に基づき、曲げ試験を実施した。板幅１０ｍｍの試験片を、曲げ軸が圧延方向と垂直になる方向（Ｇ．Ｗ．方向）及び平行になる方向（Ｂ．Ｗ．方向）に対してそれぞれ内側曲げ半径０．５ｍｍで、曲げ角度９０°のＷ曲げを行った。リードフレームをはじめとする電気電子部品においては、Ｇ．Ｗ．方向とＢ．Ｗ．方向の両方向の曲げ加工が想定されるため、曲げ後の曲げ部頂点の表面を光学顕微鏡により観察し、Ｇ．Ｗ．方向とＢ．Ｗ．方向のいずれも割れの発生していなかったものを曲げ加工性良好（Ａ）、発生していたものを曲げ加工性不良（Ｄ）として評価した。その評価結果を表２に示す。(Bending workability)
A bending test was performed based on JCBA T307: 2007. A test piece having a plate width of 10 mm was bent with an inner bending radius of 0.5 mm with respect to a direction (GW direction) and a direction (BW direction) in which the bending axis was perpendicular to the rolling direction. W-bending was performed at an angle of 90 °. For electrical and electronic parts such as lead frames, G. W. Direction and B. W. Since the bending process in both directions is assumed, the surface of the apex of the bent part after bending is observed with an optical microscope. W. Direction and B. W. Those in which no crack occurred in any of the directions were evaluated as good bending workability (A) and those in which cracking occurred were evaluated as poor bending workability (D). The evaluation results are shown in Table 2.
（耐熱性）
耐熱性は、４５０℃に昇温した塩浴中に試験片を投入し、５分間経過後に取出し水冷する熱処理を施し、熱処理後の硬さを、熱処理前の硬さで除した値が０．８以上である場合を耐熱性良好（Ａ）、０．８未満であったものを耐熱性不良（Ｄ）として評価した。その評価結果を表２に示す。なお、硬さは、ＪＩＳ Ｚ ２２４４：２００９に規定されるビッカース硬さ試験−試験方法に基づき測定した。また、熱処理後の材料は、塩浴と接触した表面に皮膜が形成されていたため、酸洗で除去した後に硬さを測定した。(Heat-resistant)
The heat resistance is a value obtained by putting a test piece in a salt bath heated to 450 ° C., performing a heat treatment of taking out after 5 minutes and cooling with water and dividing the hardness after the heat treatment by the hardness before the heat treatment. The case of 8 or more was evaluated as good heat resistance (A), and the case of less than 0.8 was evaluated as heat resistance defect (D). The evaluation results are shown in Table 2. In addition, hardness was measured based on the Vickers hardness test-test method prescribed | regulated to JISZ2244: 2009. Moreover, since the film after the heat treatment had a film formed on the surface in contact with the salt bath, the hardness was measured after removing it by pickling.
表１および表２に示す結果から、Ｓｎ濃度が０．０５〜０．５質量％の範囲である実施例１〜１３はいずれも、引張強度が４３２〜４９２ＭＰａと４００ＭＰａ以上であり、導電率が５０〜７７％ＩＡＣＳと５０％ＩＡＣＳ以上であり、良好な曲げ加工性（Ａ）と良好な耐熱性（Ａ）が得られている。これに対して、表１に示した成分組成が本発明の範囲外である比較例１〜９ならびに表２に示した製造条件が本発明の範囲外である比較例１０および１１はいずれも、引張強度、導電率、曲げ加工性、耐熱性および製造性の少なくとも１つが劣っていた。 From the results shown in Table 1 and Table 2, in Examples 1 to 13 where the Sn concentration is in the range of 0.05 to 0.5% by mass, the tensile strength is 432 to 492 MPa and 400 MPa or more, and the conductivity is 50 to 77% IACS and 50% IACS or more, and good bending workability (A) and good heat resistance (A) are obtained. On the other hand, Comparative Examples 1 to 9 in which the component compositions shown in Table 1 are outside the scope of the present invention and Comparative Examples 10 and 11 in which the production conditions shown in Table 2 are outside the scope of the present invention, At least one of tensile strength, electrical conductivity, bending workability, heat resistance and manufacturability was inferior.
また、Ｓｎ濃度が０．５質量％超え２．５質量％以下の範囲である実施例１４〜２６はいずれも、引張強度が５１２〜５９３ＭＰａと５００ＭＰａ以上であり、導電率が２７〜３８％ＩＡＣＳと２５％ＩＡＣＳ以上であり、良好な曲げ加工性（Ａ）と良好な耐熱性（Ａ）が得られている。これに対して、表１に示した成分組成が本発明の範囲外である比較例１２〜２０ならびに表２に示した製造条件が本発明の範囲外である比較例２１および２２はいずれも、引張強度、導電率、曲げ加工性、耐熱性および製造性の少なくとも１つが劣っていた。 In Examples 14 to 26 where the Sn concentration is in the range of more than 0.5 mass% and less than or equal to 2.5 mass%, the tensile strength is 512 to 593 MPa and 500 MPa or more, and the conductivity is 27 to 38% IACS. 25% IACS or more, and good bending workability (A) and good heat resistance (A) are obtained. On the other hand, Comparative Examples 12 to 20 in which the component composition shown in Table 1 is outside the scope of the present invention and Comparative Examples 21 and 22 in which the production conditions shown in Table 2 are outside the scope of the present invention, At least one of tensile strength, electrical conductivity, bending workability, heat resistance and manufacturability was inferior.
また、図１および図２は、それぞれ実施例１４と比較例２２の銅合金材料の電解研磨後の表面を、ＦＥ−ＳＥＭにより観察したときのＳＥＭ写真を示したものである。図１に示す実施例１４の銅合金材料では、微細な化合物粒子が分散しているのに対し、図２に示す比較例２２の銅合金材料では、化合物粒子が粗大となっているのがわかる。 FIG. 1 and FIG. 2 show SEM photographs when the surfaces after electrolytic polishing of the copper alloy materials of Example 14 and Comparative Example 22 are observed by FE-SEM. In the copper alloy material of Example 14 shown in FIG. 1, fine compound particles are dispersed, whereas in the copper alloy material of Comparative Example 22 shown in FIG. 2, the compound particles are coarse. .
本発明によれば、高強度、高導電率および良好な曲げ加工性に加えて、さらに良好な耐熱性を兼ね備えた銅合金材料の提供が可能になった。本発明の銅合金材料は、特に、半導体装置に用いられるリードフレームをはじめとした電気電子部品に用いられるのに好適である。
According to the present invention, it has become possible to provide a copper alloy material having not only high strength, high conductivity, and good bending workability, but also good heat resistance. The copper alloy material of the present invention is particularly suitable for use in electrical and electronic parts such as lead frames used in semiconductor devices.
Claims (5)
（ａ）３００℃までの冷却速度を３０℃／分以上とする溶解鋳造工程。
（ｂ）５℃／分以上で昇温し、６００〜１０００℃で３０分〜１０時間保持する均質化熱処理工程。
（ｃ）３００℃までの冷却速度を３０℃／分以上とする熱間圧延工程。
（ｄ）加工率を８０％以上とする冷間圧延工程。
（ｅ）３５０〜６００℃で５秒〜１０時間保持する焼鈍工程。
The method for producing a copper alloy material according to claim 1, comprising the following steps (a) to (e):
(A) A melt casting step in which the cooling rate to 300 ° C. is 30 ° C./min or more.
(B) A homogenization heat treatment step in which the temperature is raised at 5 ° C./min or more and held at 600 to 1000 ° C. for 30 minutes to 10 hours.
(C) A hot rolling step in which the cooling rate to 300 ° C. is 30 ° C./min or more.
(D) A cold rolling step in which the processing rate is 80% or more.
(E) An annealing step of holding at 350 to 600 ° C. for 5 seconds to 10 hours.
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