TW201536934A - Fe-P based copper alloy sheet excellent in strength, heat resistance and bendability - Google Patents
Fe-P based copper alloy sheet excellent in strength, heat resistance and bendability Download PDFInfo
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- TW201536934A TW201536934A TW103145001A TW103145001A TW201536934A TW 201536934 A TW201536934 A TW 201536934A TW 103145001 A TW103145001 A TW 103145001A TW 103145001 A TW103145001 A TW 103145001A TW 201536934 A TW201536934 A TW 201536934A
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 48
- 239000013078 crystal Substances 0.000 claims abstract description 50
- 239000002245 particle Substances 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 238000005096 rolling process Methods 0.000 claims abstract description 19
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 14
- 229910052718 tin Inorganic materials 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 238000001887 electron backscatter diffraction Methods 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 description 85
- 238000001556 precipitation Methods 0.000 description 42
- 239000002244 precipitate Substances 0.000 description 27
- 238000005098 hot rolling Methods 0.000 description 26
- 238000001953 recrystallisation Methods 0.000 description 20
- 238000001816 cooling Methods 0.000 description 18
- 238000005097 cold rolling Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 13
- 229910045601 alloy Inorganic materials 0.000 description 12
- 239000000956 alloy Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000007747 plating Methods 0.000 description 9
- 229910000679 solder Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000008439 repair process Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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- 238000009864 tensile test Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- 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
Abstract
Description
本發明是關於強度、耐熱性和撓曲加工性優異，適合作為半導體用引線框架、端子、連接器、匯流條等的電氣暨電子元件材料的Fe-P系銅合金板。 The present invention relates to an Fe-P-based copper alloy sheet which is excellent in strength, heat resistance, and flexural workability, and is suitable as an electric and electronic component material such as a lead frame for a semiconductor, a terminal, a connector, and a bus bar.
銅和銅基合金由於導電率暨熱傳導性非常高，所以能够適用於作為以引線框架為首的電氣暨電子元件用材料。 近年來，引線框架的薄型化、細引腳化、窄小間距化日益進展，一部分甚至達到厚度100μm以下的程度，這樣子就需要具有非常高的強度。 Since copper and copper-based alloys have very high electrical conductivity and thermal conductivity, they can be used as materials for electrical and electronic components including lead frames. In recent years, the thickness of the lead frame has been progressing in thinning, thinning, and narrow pitch, and some have reached a thickness of 100 μm or less, which requires a very high strength.
另外，在引線框架的製作中，會對於已將銅和銅基合金軋製成既定厚度的條材，實施衝壓加工、蝕刻處理之類的工序來予以加工成既定的形狀。在衝壓加工時，在用來消除衝壓所帶來的應變的應變消除工序中，以400℃以上的溫度進行加熱等，實施高溫加熱處理的情況也很多。此外，還會實施各種鍍敷處理、或者封裝加工中的晶片黏合和引線黏合、樹脂模塑等處理。 Further, in the production of the lead frame, a strip obtained by rolling copper and a copper-based alloy into a predetermined thickness is processed into a predetermined shape by a process such as press working or etching. At the time of the press working, in the strain eliminating step for eliminating the strain due to the press, the heating is performed at a temperature of 400 ° C or higher, and the high-temperature heat treatment is also performed. In addition, various plating treatments, or wafer bonding, wire bonding, and resin molding in the packaging process are performed.
因此，對於引線框架材料來說，不僅要求導電率、強 度(主要特性)，還要求耐衝壓性、耐熱性(加熱至高溫時的強度降低的程度)，此外還要求具有蝕刻性、各種鍍敷性、焊料密合性、氧化膜密合性、樹脂密合性、引線黏合性等(次要特性)。 Therefore, for the lead frame material, not only conductivity but also strength is required. The degree (main characteristics) also requires stamping resistance and heat resistance (degree of reduction in strength when heated to a high temperature), and also requires etching property, various plating properties, solder adhesion, oxide film adhesion, and resin. Adhesion, wire bonding, etc. (minor characteristics).
雖然沒有一種材料可以全部都充分地符合這些特性，但是，作為多引腳IC的引線框架材料，從特性、成本、容易取得的觀點考量，逐漸地集中在：以Cu-2.2質量%Fe-0.03質量%P-0.12質量%Zn為標準化學組成分的CDA合金194；以Cu-3.0質量%Ni-0.65質量%Si-0.15質量%Mg為標準化學組成分的CDA合金7025；以及以Cu-0.23質量%Cr-0.25質量%Sn-0.20質量%Zn為標準化學組成分的CDA合金18045。此處，所謂的CDA係指：美國銅開發協會。 Although none of the materials can fully meet these characteristics, as a lead frame material for multi-pin ICs, from the viewpoints of characteristics, cost, and easy availability, gradually concentrate on: Cu-2.2% by mass Fe-0.03 Mass %P-0.12% by mass Zn is a standard chemical composition of CDA alloy 194; Cu-3.0% by mass Ni-0.65 mass% Si-0.15 mass% Mg as a standard chemical composition of CDA alloy 7025; and Cu-0.23 Mass%Cr-0.25 mass% Sn-0.20 mass% Zn is a standard chemical composition of CDA alloy 18045. Here, the so-called CDA refers to: the American Copper Development Association.
在此，特別是在需要強度的多引腳IC的引線框架材料中，係使用強度最高的CDA合金7025(維氏硬度200Hv)。但是，該材料中因為大量含有會使氧化膜的密合性降低的Ni、Si，所以係有氧化膜的密合性變低的缺點。 Here, particularly in a lead frame material of a multi-pin IC requiring strength, the highest strength CDA alloy 7025 (Vickers hardness 200 Hv) is used. However, since this material contains a large amount of Ni and Si which lower the adhesion of the oxide film, the adhesion of the oxide film is lowered.
半導體裝置利用熱硬化性樹脂將半導體晶片封裝成一個封裝體的作法，從經濟性考量已經成為主流，重要的是保持封裝體的可靠性。封裝體的可靠性則是仰賴於模塑樹脂與引線框架的密合性。若是受到半導體裝置的組裝工序中的加熱過程的影響，而在引線框架表面形成密合性低的氧化膜的話，則模塑樹脂與引線框架的密合性會降低，將 封裝體安裝到印刷電路板安裝時，受到當時的加熱的影響，將會導致封裝體發生龜裂或剝離，而降低了封裝體的可靠性。 The semiconductor device uses a thermosetting resin to encapsulate a semiconductor wafer into a package, which has become a mainstream from an economical point of view, and it is important to maintain the reliability of the package. The reliability of the package depends on the adhesion of the molding resin to the lead frame. If an oxide film having low adhesion is formed on the surface of the lead frame due to the influence of the heating process in the assembly process of the semiconductor device, the adhesion between the molding resin and the lead frame is lowered. When the package is mounted on a printed circuit board, it is affected by the heating at that time, which will cause the package to crack or peel off, which reduces the reliability of the package.
因此，為了確保封裝體的可靠性，重要的條件是引線框架材料的氧化膜的密合性需要很高，但CDA合金7025的這種特性卻是很低。另外，CDA合金7025也有因蝕刻加工等而產生污物，而降低鍍敷層的密合性之類的問題，在價格上也偏高而難以採用的問題。 Therefore, in order to ensure the reliability of the package, it is important that the adhesion of the oxide film of the lead frame material is required to be high, but the characteristics of the CDA alloy 7025 are very low. In addition, the CDA alloy 7025 has a problem that dirt is generated by etching or the like, and the adhesion of the plating layer is lowered, which is expensive and difficult to adopt.
另一方面，Fe-P系的CDA合金194，即使是作為最高強度等級的ESH，其強度仍很低，抗拉強度為550N/mm2左右，維氏硬度為160Hv左右。另外耐熱性也比較低，例如若以450℃加熱5分鐘左右，則軟化至只有原本強度的80%以下。但是，CDA合金194在衝壓性等的次要特性上並沒有重大的缺陷，氧化膜的密合性也優異，廉價且容易取得，因此被廣泛使用中。 On the other hand, the Fe-P-based CDA alloy 194 has a low strength even at the highest strength grade of ESH, and has a tensile strength of about 550 N/mm 2 and a Vickers hardness of about 160 Hv. Further, the heat resistance is also relatively low. For example, when heated at 450 ° C for about 5 minutes, it is softened to only 80% or less of the original strength. However, the CDA alloy 194 has no major defects in secondary characteristics such as punchability, and is excellent in adhesion of an oxide film, and is inexpensive and easy to obtain, and thus is widely used.
在專利文獻1中記述了藉由在Fe-P系銅合金中添加Mg和Sn，來使Fe-P系銅合金高強度化的作法。另外，在專利文獻2中，記述了藉由使結晶組織整粒化，而改善了衝壓性(衝孔加工性和撓曲加工性)的Fe-P系銅合金板。在專利文獻3中記述了藉由採取對於Fe-P系銅合金進行熱軋和冷軋後，加熱至950~1050℃，接著進行急冷至300℃以下的固溶處理等特定的製造方法，從而改善了Fe-P系銅合金板的強度和耐熱性。 Patent Document 1 describes a method of increasing the strength of an Fe—P-based copper alloy by adding Mg and Sn to an Fe—P-based copper alloy. Further, in Patent Document 2, an Fe-P-based copper alloy sheet having improved punchability (punchability and flexural workability) by granulating a crystal structure is described. Patent Document 3 describes a specific production method in which a Fe-P-based copper alloy is subjected to hot rolling and cold rolling, and then heated to 950 to 1050 ° C, followed by solid solution treatment to rapidly cool to 300 ° C or lower. The strength and heat resistance of the Fe-P based copper alloy sheet are improved.
專利文獻1：日本特開平4-41631號公報 Patent Document 1: Japanese Patent Laid-Open No. 4-41631
專利文獻2：日本特開2000-104131號公報 Patent Document 2: Japanese Laid-Open Patent Publication No. 2000-104131
專利文獻3：日本特開2012-57242號公報 Patent Document 3: Japanese Laid-Open Patent Publication No. 2012-57242
但是，專利文獻1的Fe-P系銅合金板雖然具有高強度，但耐熱性卻不夠充分，另外對於衝壓性則尚未進行檢討。專利文獻2的Fe-P系銅合金板雖然衝壓性優異，但是耐熱性卻不夠充分。專利文獻3的Fe-P系銅合金板雖然強度和耐熱性都優異，但對於衝壓性則尚未進行檢討。 However, the Fe-P-based copper alloy sheet of Patent Document 1 has high strength, but the heat resistance is insufficient, and the stampability is not yet reviewed. The Fe-P-based copper alloy sheet of Patent Document 2 is excellent in pressability, but is insufficient in heat resistance. The Fe-P-based copper alloy sheet of Patent Document 3 is excellent in both strength and heat resistance, but has not been reviewed for the stampability.
本發明是有鑑於Fe-P系銅合金板的這種現狀而進行開發完成的，其目的在於提供：一種具有高強度，耐熱性高，且衝壓性(特別是撓曲加工性)也優異的Fe-P系銅合金板。 The present invention has been developed in view of such a state of the art of an Fe-P-based copper alloy sheet, and an object thereof is to provide a high strength, high heat resistance, and excellent pressability (particularly, flexural workability). Fe-P based copper alloy sheet.
本發明的Fe-P系銅合金板的特徵為：該Fe-P系銅合金板的組成分，以質量%計，係含有Fe：1.6~2.6質量%；P：0.01~0.15質量%；Zn：0.01~1.0質量%；Sn和Mg的其中一種以上，且是0.2~0.5質量%；C：0.003質量%以下；Co、Si和Cr合計為0.05質量%以下；其餘部分由Cu和不可避免的雜質構成，以電子背向散射繞射法 (EBSD)觀察與輥軋方向平行並且與板面垂直的截面的 結晶組織時，以面積對各晶粒的當量圓直徑進行加權的加權平均值在10μm以下，導電率為50%IACS以上，維氏硬度為180Hv以上，當量圓直徑為10~40nm的Fe或Fe-P化合物的析出粒子的存在密度為20個/μm2以上。還有，在本發明中，“銅合金板”的這個用語係以包含銅合金條的意思來使用。 The Fe-P-based copper alloy sheet of the present invention is characterized in that the composition of the Fe-P-based copper alloy sheet contains, in mass%, Fe: 1.6 to 2.6% by mass; P: 0.01 to 0.15 mass%; Zn : 0.01 to 1.0% by mass; one or more of Sn and Mg, and 0.2 to 0.5% by mass; C: 0.003 mass% or less; Co, Si, and Cr in total of 0.05% by mass or less; the balance being Cu and inevitable When the crystal structure of the cross section parallel to the rolling direction and perpendicular to the plate surface is observed by electron backscatter diffraction (EBSD), the weighted average weighted by the area of the equivalent circle diameter of each crystal grain is 10 μm. Hereinafter, the conductivity of the precipitated particles of Fe or Fe-P compound having a conductivity of 50% IACS or more and a Vickers hardness of 180 Hv or more and an equivalent circle diameter of 10 to 40 nm is 20 / μm 2 or more. Further, in the present invention, the term "copper alloy sheet" is used in the sense of including a copper alloy strip.
根據本發明，能夠提供具有接近CDA合金7025的強度之強度暨耐熱性以及氧化膜的密合性優異的Fe-P系銅合金板。 According to the present invention, it is possible to provide an Fe-P-based copper alloy sheet having strength and heat resistance close to the strength of the CDA alloy 7025 and excellent adhesion of the oxide film.
第1圖(a)(b)(c)是實施例No.20、21、23的顯微鏡組織照片。 Fig. 1 (a), (b) and (c) are photographs of the microstructure of Examples Nos. 20, 21 and 23.
以下，對於本發明的Fe-P系銅合金板更具體地加以說明。 Hereinafter, the Fe-P-based copper alloy sheet of the present invention will be more specifically described.
Fe是有助於Fe-P系銅合金板的強度和耐熱性的提高，另外，具有抑制在熱軋中或再結晶熱處理中的結晶粒 生長的效果。Fe的含量低於1.6質量%的話，上述效果不充分。另一方面，若Fe的含量高於2.6質量%的話，則在熔化暨鑄造時，由於兩液相分離、結晶析出而生成粗大的Fe粒子(直徑數μm以上)，鍍敷性、蝕刻性會降低。因此，將Fe的含量設為1.6~2.6質量%，下限優選為1.7質量%，更優選為1.8質量%，上限優選為2.5質量%，更優選為2.4質量%。 Fe is useful for improving the strength and heat resistance of the Fe-P-based copper alloy sheet, and further, suppressing crystal grains in hot rolling or recrystallization heat treatment. The effect of growth. When the content of Fe is less than 1.6% by mass, the above effects are insufficient. On the other hand, when the content of Fe is more than 2.6 mass%, coarse Fe particles (having a diameter of several μm or more) are formed by the two liquid phase separation and crystallization during the melting and casting, and the plating property and the etching property are reduce. Therefore, the content of Fe is 1.6 to 2.6% by mass, the lower limit is preferably 1.7% by mass, more preferably 1.8% by mass, and the upper limit is preferably 2.5% by mass, and more preferably 2.4% by mass.
P除了作為去氧劑有幫助以外，還形成Fe-P化合物的析出粒子，使Fe-P系銅合金板的強度和耐熱性提高。 另外，P具有抑制在熱軋中或再結晶熱處理中的結晶粒生長的效果。P的含量低於0.01質量%的話，上述效果不充分。另一方面，若P的含量高於0.15質量%的話，則導電率降低，並且氧化膜的密合性會降低。因此，將P的含量設為0.01~0.15質量%，下限優選為0.015質量%，更優選為0.02質量%，上限優選為0.13質量%，更優選為0.10質量%。 In addition to being helpful as an oxygen scavenger, P forms precipitated particles of an Fe-P compound to improve the strength and heat resistance of the Fe-P-based copper alloy sheet. Further, P has an effect of suppressing the growth of crystal grains in hot rolling or recrystallization heat treatment. When the content of P is less than 0.01% by mass, the above effects are insufficient. On the other hand, when the content of P is more than 0.15% by mass, the electrical conductivity is lowered and the adhesion of the oxide film is lowered. Therefore, the content of P is 0.01 to 0.15 mass%, the lower limit is preferably 0.015 mass%, more preferably 0.02 mass%, and the upper limit is preferably 0.13 mass%, and more preferably 0.10 mass%.
Zn使Fe-P系銅合金板的焊料耐熱剝離性、氧化膜的密合性提高。Zn的含量低於0.01質量%的話，其效果不充分，另一方面，若高於1.0質量%的話，則導電率降低。因此，將Zn的含量設為0.01~1.0質量%，下限優選為0.02質量%，更優選為0.05質量%，上限優選為0.8質量%，更優選為0.5質量%。 Zn improves the solder heat-resistant peelability of the Fe-P-based copper alloy sheet and the adhesion of the oxide film. When the content of Zn is less than 0.01% by mass, the effect is insufficient. On the other hand, when the content is more than 1.0% by mass, the electrical conductivity is lowered. Therefore, the content of Zn is 0.01 to 1.0% by mass, the lower limit is preferably 0.02% by mass, more preferably 0.05% by mass, and the upper limit is preferably 0.8% by mass, and more preferably 0.5% by mass.
Sn和Mg在母材中固溶，具有使Fe-P系銅合金板的強度和耐熱性提高的效果，可添加Sn和Mg的其中一種 以上(Sn或Mg的一種或其二者)。Sn和Mg的其中一種以上的含量低於0.2質量%的話，上述效果不充分，無法達到維氏硬度180Hv以上。另一方面，若Sn和Mg的其中一種以上的含量高於0.5質量%的話，則導電率降低，並且氧化膜的密合性降低。因此，將Sn和Mg的其中一種以上的含量設為0.2~0.5質量%，下限優選為0.25質量%，更優選為0.3質量%，上限優選為0.45質量%，更優選為0.40質量%。 Sn and Mg are solid-solved in the base material, and have an effect of improving the strength and heat resistance of the Fe-P-based copper alloy sheet, and one of Sn and Mg may be added. Above (one or both of Sn or Mg). When the content of one or more of Sn and Mg is less than 0.2% by mass, the above effects are insufficient, and the Vickers hardness of 180 Hv or more cannot be achieved. On the other hand, when the content of one or more of Sn and Mg is more than 0.5% by mass, the electrical conductivity is lowered and the adhesion of the oxide film is lowered. Therefore, the content of one or more of Sn and Mg is 0.2 to 0.5% by mass, the lower limit is preferably 0.25 mass%, more preferably 0.3 mass%, and the upper limit is preferably 0.45% by mass, and more preferably 0.40 mass%.
在Fe-P系銅合金中，若作為不可避免的雜質的C的含量高於0.003質量%的話，或者同樣作為不可避免的雜質的Co、Si和Cr的含量的合計高於0.05質量%的話，則因兩液相分離、結晶析出所造成的粗大的Fe粒子很容易生成。因此，Fe-P系銅合金的強度和耐熱性會降低，另外，鍍敷性、蝕刻性也會降低。因此，將C含量設為0.003質量%以下，將Co、Si和Cr的合計含量設為0.05質量%以下。此外，也有在進行熔化暨鑄造時，基於抗氧化等之目的而被散佈在金屬熔液表面的木炭、石墨粒和石墨鑄模等的原因，而有導致C含量超過限度被混入的情況。在這種情況下，為了減少C含量，係可採用下列的作法，例如：使用C含量少的Fe原料；減少木炭、石墨粒的散佈量；增大木炭、石墨粒的尺寸而減少與熔液的接觸面積；改變所使用的鑄模等。 In the Fe-P-based copper alloy, when the content of C as an unavoidable impurity is more than 0.003 mass%, or the total content of Co, Si, and Cr as an unavoidable impurity is more than 0.05% by mass, The coarse Fe particles due to the separation of the two liquid phases and the precipitation of crystals are easily formed. Therefore, the strength and heat resistance of the Fe-P-based copper alloy are lowered, and the plating property and the etching property are also lowered. Therefore, the C content is set to 0.003 mass% or less, and the total content of Co, Si, and Cr is set to 0.05 mass% or less. In addition, there are cases in which charcoal, graphite particles, and graphite molds which are scattered on the surface of the molten metal for the purpose of oxidation resistance and the like are subjected to melting and casting, and the C content may exceed the limit. In this case, in order to reduce the C content, the following methods may be employed, for example, using Fe raw materials having a small C content; reducing the amount of charcoal and graphite particles dispersed; increasing the size of charcoal and graphite particles to reduce the melt Contact area; change the mold used, etc.
以電子背向散射繞射法(Electron Back Scatter Diffraction；EBSD)觀察Fe-P系銅合金板之與輥軋方向平行並且與板面垂直的截面的結晶組織(結晶粒界條件：方位差值5°以上)，求得觀察面的全部結晶粒的當量圓直徑，以面積對各結晶粒的當量圓直徑進行加權而求得加權平均值，在本發明中將其作為平均結晶粒直徑。作為平均結晶粒直徑之所以取其加權平均值，是因為像Fe-P系銅合金板這種的係有粗大粒與微細粒混合的情況下，若僅僅取相加平均值的話，則得出的晶粒直徑小得超出實際情況。若該平均結晶粒直徑高於10μm的話，則撓曲加工性、衝孔加工性會降低，並且強度、耐熱性也會降低。因此，將平均結晶粒直徑設為10μm以下，優選為8μm以下，更優選為6μm以下。平均結晶粒直徑越小越好，下限值不需要特別限制，但根據後述的製造方法能夠使之微細化至3μm左右。 The crystal structure of the section of the Fe-P-based copper alloy sheet parallel to the rolling direction and perpendicular to the sheet surface was observed by Electron Back Scatter Diffraction (EBSD) (crystal grain boundary condition: azimuth difference value 5 Above °), the equivalent circle diameter of all the crystal grains of the observation surface is obtained, and the weighted average value is obtained by weighting the equivalent circle diameter of each crystal grain by the area, and is used as the average crystal grain diameter in the present invention. The weighted average value of the average crystal grain diameter is obtained because, when a coarse particle and a fine particle are mixed like a Fe-P-based copper alloy plate, if only the average value is added, it is obtained. The grain size is small enough to exceed the actual situation. When the average crystal grain diameter is more than 10 μm, the flexural workability and the punching workability are lowered, and the strength and heat resistance are also lowered. Therefore, the average crystal grain diameter is 10 μm or less, preferably 8 μm or less, and more preferably 6 μm or less. The smaller the average crystal grain diameter, the better, and the lower limit is not particularly limited. However, it can be made fine to about 3 μm according to the production method described later.
Fe或Fe-P化合物的析出粒子之中的當量圓直徑為10~40nm的析出粒子，會將結晶粒的重排予以釘軋固定下來而使Fe-P系銅合金板的強度和耐熱性提高。但若該析出粒子的存在密度低於20個/μm2的話，則能夠進行釘軋固定作用的析出粒子太少，強度和耐熱性的提高就不夠充分。因此，將當量圓直徑為10~40nm的Fe或Fe-P化合物的析出粒子的存在密度設為20個/μm2以上，優選為25 個/μm2以上，更優選為30個/μm2以上。其存在密度越大越好，上限值不需要特別限定，如果是在本發明的組成分範圍之內，則藉由後述的製造方法，能夠將密度提升至40個/μm2左右。 The precipitated particles having an equivalent circle diameter of 10 to 40 nm among the precipitated particles of Fe or Fe-P compound are subjected to pinning and fixing the rearrangement of the crystal grains to improve the strength and heat resistance of the Fe-P-based copper alloy sheet. . However, when the density of the precipitated particles is less than 20 / μm 2 , too few precipitated particles capable of performing pinning fixation are insufficient, and the improvement in strength and heat resistance is insufficient. Therefore, the presence density of the precipitated particles of the Fe or Fe-P compound having an equivalent circle diameter of 10 to 40 nm is 20 pieces/μm 2 or more, preferably 25 pieces/μm 2 or more, and more preferably 30 pieces/μm 2 or more. . The upper limit is not particularly limited, and if it is within the composition range of the present invention, the density can be increased to about 40/μm 2 by the production method described later.
本發明的製造方法如下。 The manufacturing method of the present invention is as follows.
首先，鑄塊是藉由使用通常的坩堝型熔爐等，來進行熔化原料，成分調整之後，再向一般的金屬鑄模、碳鑄模等之中澆注熔液而製造出來的。 First, the ingot is produced by melting a raw material by using a usual crucible furnace or the like, and then adjusting the composition, and then pouring a molten metal into a general metal mold, a carbon mold, or the like.
其次，將鑄塊加熱至850~1050℃的溫度，以軋製加工率50%以上進行熱軋，熱軋的結束溫度為750℃以上。 熱軋後的冷卻，是利用水冷等，以10℃/秒以上的冷卻速度，對於從熱軋結束溫度(=冷卻開始溫度)至少到300℃的範圍進行急速冷卻。 Next, the ingot is heated to a temperature of 850 to 1050 ° C, and hot rolling is performed at a rolling reduction ratio of 50% or more, and the hot rolling end temperature is 750 ° C or higher. The cooling after the hot rolling is rapid cooling at a cooling rate of 10 ° C /sec or more by a water cooling or the like in a range from at least a hot rolling end temperature (= cooling start temperature) to at least 300 ° C.
熱軋的加熱溫度低於850℃的話，Fe、Fe-P化合物析出並粗大化，因此這部分Fe、P將會被消耗，經析出熱處理而析出的微細的Fe、Fe-P化合物將會減少，製品的強度、耐熱性會降低。另一方面，若高於1050℃的話，則接近熔點，因此會發生熱軋裂紋。另外，氧化會加劇，因實施熱軋而導致氧化物被捲入，變成缺陷殘留在製品銅合金板中。因此，將熱軋的加熱溫度設為850~1050℃，優選為870~1030℃，更優選為890~1010℃。 When the heating temperature of hot rolling is lower than 850 ° C, Fe and Fe-P compounds are precipitated and coarsened, so that Fe and P will be consumed, and fine Fe and Fe-P compounds precipitated by precipitation heat treatment will be reduced. The strength and heat resistance of the product will decrease. On the other hand, if it is higher than 1050 ° C, the melting point is approached, so hot rolling cracking occurs. Further, the oxidation is intensified, and the oxide is caused to be caught by the hot rolling, and the defects remain in the copper alloy sheet of the product. Therefore, the heating temperature of hot rolling is 850 to 1050 ° C, preferably 870 to 1030 ° C, and more preferably 890 to 1010 ° C.
若熱軋的軋製加工率比50%小的話，則不引起再結 晶，有鑄造組織殘存的可能性。因此，將熱軋的軋製加工率設為50%以上，優選為60%以上，更優選為70%以上。 If the rolling reduction rate of hot rolling is less than 50%, it will not cause re-knotting. Crystal, there is the possibility of casting tissue remaining. Therefore, the rolling reduction ratio of hot rolling is 50% or more, preferably 60% or more, and more preferably 70% or more.
若熱軋的結束溫度低於750℃的話，則Fe、Fe-P化合物的析出量增加並粗大化，因此在析出熱處理中析出的微細的Fe、Fe-P化合物將會減少，製品銅合金板的強度和耐熱性會降低。另外，若熱軋的結束溫度低於750℃的話，則製品銅合金板的平均晶粒直徑會變大。這被認為是由於粗大化的Fe、Fe-P化合物在再結晶熱處理時成為再結晶的起點，促進再結晶。因此，將熱軋的結束溫度設為750℃以上，優選為770℃以上，更優選為790℃以上。 When the end temperature of hot rolling is less than 750 ° C, the precipitation amount of Fe and Fe-P compound increases and coarsens, so that fine Fe and Fe-P compounds precipitated during precipitation heat treatment are reduced, and the product copper alloy sheet is reduced. The strength and heat resistance are lowered. Further, if the end temperature of hot rolling is lower than 750 ° C, the average crystal grain diameter of the product copper alloy sheet becomes large. This is considered to be because the coarsened Fe and Fe-P compounds become the starting point of recrystallization during recrystallization heat treatment and promote recrystallization. Therefore, the temperature at which the hot rolling is completed is 750 ° C or higher, preferably 770 ° C or higher, and more preferably 790 ° C or higher.
熱軋後的冷卻速度，若在從熱軋結束溫度至300℃的範圍內低於10℃/秒的話，則冷卻中也有Fe、Fe-P化合物析出並粗大化，因此在析出熱處理中析出的微細的Fe、Fe-P化合物將會減少，製品銅合金板的強度和耐熱性會降低。因此，將熱軋後的冷卻速度設為10℃/秒以上，優選為20℃/秒以上，更優選為30℃/秒以上。熱軋材冷卻達到300℃後，不需要急冷。 When the cooling rate after the hot rolling is less than 10 ° C / sec in the range from the hot rolling end temperature to 300 ° C, Fe and Fe-P compounds are precipitated and coarsened during cooling, so that they are precipitated during the precipitation heat treatment. The fine Fe and Fe-P compounds will be reduced, and the strength and heat resistance of the product copper alloy sheet will be lowered. Therefore, the cooling rate after hot rolling is 10 ° C /sec or more, preferably 20 ° C / sec or more, and more preferably 30 ° C / sec or more. After the hot rolled material is cooled to 300 ° C, no quenching is required.
其後，除去熱軋材的氧化鏽皮，進行冷軋。為了在後續進行的再結晶熱處理中獲得均勻的再結晶組織，將冷軋的軋製加工率設為50%以上，優選為60%以上，更優選為70%以上。 Thereafter, the scale of the hot-rolled material is removed and cold rolling is performed. In order to obtain a uniform recrystallized structure in the subsequent recrystallization heat treatment, the rolling reduction ratio of the cold rolling is 50% or more, preferably 60% or more, and more preferably 70% or more.
再結晶熱處理是用以形成微細的再結晶晶粒的熱處理，以加熱溫度為550~900℃左右保持1秒~10分鐘的程度。加熱溫度低於550℃的話，難以發生再結晶，若高 於900℃的話，則再結晶晶粒粗大化。因此，將加熱溫度設為550~900℃，優選為570~880℃，更優選為590~860℃左右。保持時間可以根據加熱溫度來做適當的選擇為1秒~10分鐘程度的短時間。若保持時間低於1秒的話，則難以再結晶。若保持時間高於10分鐘的話，則再結晶晶粒粗大化，製品銅合金板的平均晶粒直徑會變大。 另外，Fe、Fe-P化合物的析出量增加並粗大化，因此在其後的析出熱處理中析出的微細的Fe、Fe-P化合物將會減少。因此，將保持時間設為1秒~10分鐘，優選為2秒~5分鐘，更優選為5秒~2分鐘左右。 The recrystallization heat treatment is a heat treatment for forming fine recrystallized grains, and is maintained at a heating temperature of about 550 to 900 ° C for about 1 second to 10 minutes. When the heating temperature is lower than 550 ° C, recrystallization is difficult to occur, if high At 900 ° C, the recrystallized grains are coarsened. Therefore, the heating temperature is 550 to 900 ° C, preferably 570 to 880 ° C, and more preferably about 590 to 860 ° C. The holding time can be appropriately selected according to the heating temperature to a short time of about 1 second to 10 minutes. If the holding time is less than 1 second, it is difficult to recrystallize. If the holding time is longer than 10 minutes, the recrystallized grains are coarsened, and the average crystal grain diameter of the product copper alloy sheet becomes large. Further, since the precipitation amount of the Fe and Fe-P compounds is increased and coarsened, the fine Fe and Fe-P compounds precipitated in the subsequent precipitation heat treatment are reduced. Therefore, the holding time is set to 1 second to 10 minutes, preferably 2 seconds to 5 minutes, and more preferably 5 seconds to 2 minutes.
另外，再結晶熱處理的加熱速度在300℃以上的範圍為1℃/秒以上。該加熱速度低於1℃/秒時，加熱中發生Fe、Fe-P化合物的析出，得不到微細的再結晶晶粒。這被認為是由於加熱中析出的Fe和Fe-P化合物伴隨溫度的上升而粗大化，其成為再結晶的起點，促進再結晶。另外，因為加熱中發生Fe、Fe-P化合物的析出並粗大化，所以在析出熱處理中析出的微細的Fe、Fe-P化合物減少。因此，再結晶熱處理的加熱速度為1℃/秒以上，優選為2℃/秒以上，更優選為5℃/秒以上。 Further, the heating rate of the recrystallization heat treatment is in the range of 300 ° C or more and 1 ° C / sec or more. When the heating rate is lower than 1 ° C / sec, precipitation of Fe and Fe-P compounds occurs during heating, and fine recrystallized grains are not obtained. This is considered to be because the Fe and Fe-P compounds precipitated during heating are coarsened with an increase in temperature, which is a starting point of recrystallization and promotes recrystallization. Further, since Fe and Fe-P compounds are precipitated and coarsened during heating, the fine Fe and Fe-P compounds precipitated during the precipitation heat treatment are reduced. Therefore, the heating rate of the recrystallization heat treatment is 1 ° C /sec or more, preferably 2 ° C / sec or more, and more preferably 5 ° C / sec or more.
此外，將再結晶熱處理後的冷卻速度，在從加熱溫度到300℃的範圍中係設為5℃/秒以上。該溫度範圍的冷卻速度低於5℃/秒的話，冷卻中將發生Fe、Fe-P化合物的析出並粗大化，因此在析出熱處理中析出的微細的Fe、Fe-P化合物將會減少。因此，將再結晶熱處理後的冷卻速 度設為5℃/秒以上，優選為10℃/秒以上，更優選為20℃/秒以上。 Further, the cooling rate after the recrystallization heat treatment is set to 5 ° C /sec or more in the range from the heating temperature to 300 ° C. When the cooling rate in the temperature range is less than 5 ° C / sec, the Fe and Fe-P compounds are precipitated and coarsened during cooling, so that the fine Fe and Fe-P compounds precipitated during the precipitation heat treatment are reduced. Therefore, the cooling rate after recrystallization heat treatment The degree is set to 5 ° C /sec or more, preferably 10 ° C / sec or more, and more preferably 20 ° C / sec or more.
再結晶熱處理之後，進行或不進行冷軋，進行析出熱處理。析出熱處理是用以大量生成微細的(當量圓直徑為10~40nm的)Fe、Fe-P化合物的析出物的熱處理，雖然不進行冷軋也會生成析出物，但藉由進行冷軋，可以使析出物高效率地析出，進一步提高強度。 After the recrystallization heat treatment, the precipitation heat treatment is performed with or without cold rolling. The precipitation heat treatment is a heat treatment for producing a large amount of fine precipitates of Fe and Fe-P compounds having an equivalent circle diameter of 10 to 40 nm, and precipitates are formed even without cold rolling, but by cold rolling, The precipitate is precipitated efficiently, and the strength is further increased.
析出熱處理以加熱溫度300~600℃的程度保持0.5~30小時的程度。加熱溫度低於300℃的話，析出量少，若高於600℃的話，則析出物容易粗大化。因此，將加熱溫度設為300~600℃，優選為320~580℃，更優選為340~560℃。保持時間可以根據加熱溫度來做適當的選擇為0.5~30小時左右的時間。保持時間低於0.5小時的話，析出容易不充分，若高於30小時的話，則對降低生產性的影響將會變大。因此，將保持時間設為0.5~30小時，優選為1~25小時，更優選為1.5~20小時左右。 The precipitation heat treatment is maintained at a heating temperature of 300 to 600 ° C for 0.5 to 30 hours. When the heating temperature is lower than 300 ° C, the amount of precipitation is small, and when it is higher than 600 ° C, the precipitate is likely to be coarsened. Therefore, the heating temperature is set to 300 to 600 ° C, preferably 320 to 580 ° C, and more preferably 340 to 560 ° C. The holding time can be appropriately selected according to the heating temperature for about 0.5 to 30 hours. When the holding time is less than 0.5 hours, precipitation is likely to be insufficient, and if it is higher than 30 hours, the effect on productivity reduction will become large. Therefore, the holding time is set to 0.5 to 30 hours, preferably 1 to 25 hours, and more preferably about 1.5 to 20 hours.
還有，為了進一步提高強度，是反覆進行多次析出熱處理為宜。進行多次的析出熱處理時，需要在析出熱處理之間進行冷軋。藉由這種冷軋而在銅合金板材中形成作為Fe、Fe-P化合物的析出點的部分，可在其後的析出熱處理中新形成析出物。若進行多次析出熱處理，則析出物的密度增加，能夠提高強度。進行多次析出熱處理時，需要以析出熱處理後的硬度在第2次比第1次高，第3次比第2次高，析出熱處理的次數越多越高的方式，適當選擇析出 熱處理條件(溫度、時間)和析出熱處理間的冷軋加工率。亦即，選定的條件是，藉由第2次以後的析出熱處理，除了在此之前就已經存在的析出物以外，還會新形成當量圓直徑為10~40nm的析出物的條件。具體來說，可以考慮例如：越重複析出熱處理的次數，越使析出熱處理的溫度降低的方式。析出熱處理後的硬度，在即使重複析出熱處理多次也不變高或反而變低時，則析出物粗大化，微細的析出物的密度並沒有增加。 Further, in order to further increase the strength, it is preferred to carry out a plurality of precipitation heat treatments in multiple steps. When performing a plurality of precipitation heat treatments, it is necessary to perform cold rolling between the precipitation heat treatments. By forming such a portion as a precipitation point of Fe and Fe-P compound in the copper alloy sheet material by such cold rolling, precipitates can be newly formed in the subsequent precipitation heat treatment. When a plurality of precipitation heat treatments are performed, the density of the precipitates increases, and the strength can be improved. When the precipitation heat treatment is performed a plurality of times, it is necessary to appropriately select the precipitation so that the hardness after the precipitation heat treatment is higher than the first time, the third time is higher than the second time, and the number of precipitation heat treatments is higher. The cold rolling processing ratio between the heat treatment conditions (temperature, time) and the precipitation heat treatment. In other words, the conditions for the selection of the precipitates having an equivalent circle diameter of 10 to 40 nm are newly formed by the precipitation heat treatment after the second and subsequent stages in addition to the precipitates which have existed before. Specifically, for example, the manner in which the temperature of the precipitation heat treatment is lowered is repeated as the number of times of the precipitation heat treatment is repeated. When the hardness after the heat treatment is precipitated and the temperature is not high or reversed even if the precipitation heat treatment is repeated a plurality of times, the precipitates are coarsened, and the density of the fine precipitates does not increase.
接著進行最終的冷軋，精製成既定的強度和板厚。在最終冷軋之後，也可以進行低溫退火(也稱為消除應力退火)。隨著半導體裝置的小型化、高集成化而來的引線框架的微細配線化，對於銅合金板的平整度和減小內部應力的品質要求也日益提高，低溫退火對於提昇這些品質是有效的。 The final cold rolling is then carried out to achieve a given strength and thickness. After the final cold rolling, low temperature annealing (also known as stress relief annealing) can also be performed. With the miniaturization and high integration of the semiconductor device, the wire frame is finely wired, and the requirements for the flatness of the copper alloy plate and the quality of the internal stress are also increasing. Low-temperature annealing is effective for improving these qualities.
在高頻爐中熔煉銅合金原料之後進行成分調整，以碳鑄模鑄錠(冷卻方法為水冷)，得到厚度50mm、寬度180mm、長度100mm的鑄塊。將製得的Fe-P系銅合金的化學組成分顯示在表1中。還有，表1所示的Fe-P系銅合金除了表1所示的元素以外，還含有不可避免的雜質，其中Ti、Zr、Be、V、Nb、Mo、W、Mg總量為0.01質量%以下，B、Na、S、Ca、As、Se、Cd、In、Sb、Pb、Bi、MM(混合稀土合金)總量為0.005質量%以下。這些 元素極為少量，對本發明的Fe-P系銅合金板的特性不造成影響。 After the copper alloy raw material was smelted in a high-frequency furnace, the composition was adjusted, and the carbon ingot was cast (the cooling method was water-cooled) to obtain an ingot having a thickness of 50 mm, a width of 180 mm, and a length of 100 mm. The chemical composition of the obtained Fe-P-based copper alloy is shown in Table 1. Further, the Fe-P-based copper alloy shown in Table 1 contains inevitable impurities in addition to the elements shown in Table 1, in which the total amount of Ti, Zr, Be, V, Nb, Mo, W, and Mg is 0.01. The mass% or less, the total amount of B, Na, S, Ca, As, Se, Cd, In, Sb, Pb, Bi, MM (mixed rare earth alloy) is 0.005 mass% or less. These ones The element is extremely small, and does not affect the characteristics of the Fe-P-based copper alloy sheet of the present invention.
接著，將各鑄塊以950℃加熱1小時後，熱軋至厚度18mm，熱軋後每一個都進行水冷。熱軋的結束溫度(冷 卻開始溫度)，No.1~23、25~28係設為750℃以上，只有No.24是低於750℃。No.24因為延長了通過輥軋機之間的時間，所以熱軋的結束溫度變低。在熱軋後進行的水冷的冷卻速度全部為10℃/秒以上。 Next, each of the ingots was heated at 950 ° C for 1 hour, then hot rolled to a thickness of 18 mm, and each of the ingots was subjected to water cooling after hot rolling. End temperature of hot rolling (cold However, the temperature was started. No. 1 to 23 and 25 to 28 were set to 750 ° C or higher, and only No. 24 was lower than 750 ° C. Since No. 24 lengthened the time between passing through the rolling mill, the end temperature of hot rolling became low. The cooling rate of the water cooling performed after the hot rolling was all 10 ° C /sec or more.
對於No.1~28的熱軋板的兩面，進行端面車削以除去氧化鏽皮，達到厚度16mm後，進行冷軋、再結晶熱處理、析出熱處理、最終冷軋和消除應力退火，製得厚度0.15mm的Fe-P系銅合金板。還有，析出熱處理的次數，No.1~10、13~25、28都進行一次。No.11、12、26、27則進行兩次析出熱處理，第一次析出熱處理後以60%的加工率進行冷軋。 For both sides of the hot-rolled sheet No. 1 to 28, face turning was performed to remove scale, and after reaching a thickness of 16 mm, cold rolling, recrystallization heat treatment, precipitation heat treatment, final cold rolling, and stress relief annealing were performed to obtain a thickness of 0.15. Mm Fe-P copper alloy plate. Further, the number of times of the precipitation heat treatment was once performed in Nos. 1 to 10, 13 to 25, and 28. No. 11, 12, 26, and 27 were subjected to two precipitation heat treatments, and after the first precipitation heat treatment, cold rolling was performed at a processing rate of 60%.
熱軋結束溫度、再結晶熱處理、析出熱處理和最終冷軋的軋製率的工序條件顯示在表2中。 The process conditions of the hot rolling end temperature, the recrystallization heat treatment, the precipitation heat treatment, and the final cold rolling rolling rate are shown in Table 2.
將製得的Fe-P系銅合金板作為試樣，按下述要點進行測定平均結晶粒直徑、析出物密度、抗拉強度、加熱前後的硬度、導電率、W撓曲性、焊料耐熱剝離性、氧化膜密合性。其結果顯示在表3中。另外，以光學顯微鏡(倍率：500倍)觀察所得到的Fe-P系銅合金板的表面，調查有無因兩液相分離、結晶析出而發生的粗大Fe粒子。關於觀察到粗大Fe粒子的No.20、21、23，其顯微鏡組織照片顯示在圖1中。稍深的灰色的粒子是粗大Fe粒子。 The obtained Fe-P-based copper alloy sheet was used as a sample, and the average crystal grain diameter, the precipitate density, the tensile strength, the hardness before and after heating, the electrical conductivity, the W flexibility, and the solder heat-resistant peeling were measured according to the following points. Properties, oxide film adhesion. The results are shown in Table 3. Further, the surface of the obtained Fe-P-based copper alloy sheet was observed with an optical microscope (magnification: 500 times), and the presence or absence of coarse Fe particles which were caused by separation of two liquid phases and precipitation of crystals was examined. Regarding No. 20, 21, and 23 in which coarse Fe particles were observed, a photomicrograph of the microstructure was shown in Fig. 1. The slightly darker gray particles are coarse Fe particles.
以電子背向散射繞射法(EBSD)觀察試樣之與輥軋方向平行並且與板面垂直的截面的結晶組織，對於以結晶粒界條件為方位差值5°以上的條件來進行過解析後的全部結晶粒，以當量圓直徑進行數值化，以面積對各結晶粒的當量圓直徑進行加權而求得加權平均值，以此作為試樣的平均結晶粒直徑。因此，平均結晶粒直徑由下式計算。 The crystal structure of the cross section of the sample parallel to the rolling direction and perpendicular to the plate surface was observed by an electron backscatter diffraction method (EBSD), and the crystal grain boundary condition was analyzed under the condition that the crystal grain boundary condition was 5° or more. All the crystal grains after that were quantified by the equivalent circle diameter, and the weighted average value was obtained by weighting the equivalent circle diameter of each crystal grain as the average crystal grain diameter of the sample. Therefore, the average crystal grain diameter is calculated by the following formula.
平均結晶粒直徑=(a1×d1+…+aN×dN)/A Average crystal grain diameter = (a1 × d1 + ... + aN × dN) / A
其中，ai：各結晶粒的面積 Where ai: the area of each crystal grain
di：各結晶粒的直徑 Di: diameter of each crystal grain
A：N個的晶粒的面積之總和。 A: the sum of the areas of the N crystal grains.
使用15萬倍的透射型電子顯微鏡觀察試樣的組織，測定粒徑為10nm以上且40nm以下的析出粒子的個數，計算每單位面積中的個數(個/μm2)，將其作為析出物密度。 The microstructure of the sample was observed using a transmission electron microscope of 150,000 times, and the number of precipitated particles having a particle diameter of 10 nm or more and 40 nm or less was measured, and the number per unit area (number/μm 2 ) was calculated and used as a precipitate. Material density.
由試樣製作出：將縱長方向設成與輥軋方向平行的日本工業規格JIS-5號測試片，依據日本工業規格JISZ2241的基準進行拉伸試驗，來進行測定。 A sample of Japanese Industrial Standard JIS-5, which has a longitudinal direction parallel to the rolling direction, was prepared from the sample, and was subjected to a tensile test in accordance with the Japanese Industrial Standard JIS Z2241 for measurement.
使用微型維氏硬度計施加4.9N的載荷，測定從試樣 採取的測試片的加熱前的硬度和以550℃加熱1分鐘後的硬度。接著，計算加熱後/加熱前硬度比。加熱前的硬度在180Hv以上為良好，加熱後/加熱前硬度比在0.90以上評判為良好。 A load of 4.9 N was applied using a micro Vickers hardness tester to measure the sample from the sample. The hardness of the test piece before heating and the hardness after heating at 550 ° C for 1 minute. Next, the hardness ratio after heating/heating was calculated. The hardness before heating was preferably 180 Hv or more, and the hardness after heating/pre-heating was judged to be good at 0.90 or more.
將試樣藉由銑削加工製作成：寬10mm×長300mm的狹條狀的測試片，利用雙電橋式電阻測定裝置測定其電阻，利用平均截面積法進行計算。在本發明中，將導電率50%IACS以上評判為良好。 The sample was produced by milling into a strip-shaped test piece having a width of 10 mm and a length of 300 mm, and the electric resistance was measured by a double bridge type resistance measuring device, and the calculation was performed by the average cross-sectional area method. In the present invention, the conductivity of 50% IACS or more was judged to be good.
對於從試樣採取的寬10mm的L.D.和T.D.測試片，依據JCBA-T307的規定，進行W撓曲(R/t=1)，觀察撓曲部的外觀而進行評判。在L.D.和T.D.測試片任何一片中，有發生裂紋的評判為×(不良)，發生表面粗糙的評判為△(不良)，裂紋或表面粗糙均未發生的評判為○(良好)。還有，所謂的L.D.(Londitudinal to Rolling Direction)測試片，係指：其長度方向是與輥軋方向平行，而撓曲線係與輥軋方向垂直的測試片，所謂的T.D.(Transverse to Rolling Direction)測試片，係指：其長度方向是與輥軋方向垂直，而撓曲線係與輥軋方向平行的測試片。 The L.D. and T.D. test pieces having a width of 10 mm taken from the sample were subjected to W deflection (R/t = 1) in accordance with the regulations of JCBA-T307, and the appearance of the bent portion was observed to judge. In any of the L.D. and T.D. test pieces, the evaluation of cracking was × (bad), the evaluation of surface roughness was Δ (bad), and the evaluation of crack or surface roughness was ○ (good). In addition, the so-called LD (Londitudinal to Rolling Direction) test piece refers to a test piece whose longitudinal direction is parallel to the rolling direction and whose deflection curve is perpendicular to the rolling direction, so-called TD (Transverse to Rolling Direction). The test piece refers to a test piece whose longitudinal direction is perpendicular to the rolling direction and whose deflection curve is parallel to the rolling direction.
在從試樣採取的狹條狀的測試片上塗布弱活性助焊劑，在保持於245℃的焊浴(Sn-3%Ag-0.5%Cu)中浸漬5秒鐘後，以150℃的烤爐加熱1000小時之後，對於該測試片施加180°撓曲和撓曲回復加工，在撓曲回復加工部貼上透明的修補膠帶後再予以撕下，根據有無焊料附著在修補膠帶上，來觀察加工部的焊料是否剝離。在修補膠帶上附著有剝離片，表示係發生了剝離，所以評判為×(不良)，沒有附著剝離片的，表示係未發生剝離，所以評判為○(良好)。 A weakly active flux was applied to the strip-shaped test piece taken from the sample, and immersed in a solder bath (Sn-3% Ag-0.5% Cu) maintained at 245 ° C for 5 seconds, and then baked at 150 ° C. After heating for 1000 hours, 180° deflection and flexural recovery processing was applied to the test piece, and a transparent repair tape was attached to the flexure recovery processing portion, and then peeled off, and the solder was attached to the repair tape to observe the processing. Whether the solder of the part is peeled off. When the peeling sheet was adhered to the repair tape, the peeling was observed, so that it was judged as × (bad), and the peeling sheet was not attached, indicating that peeling did not occur, so it was judged as ○ (good).
氧化膜密合性係以氧化膜密合保持溫度來進行評判。對於試樣進行鹼性陰極電解清洗後，再進行水洗→酸洗(10%硫酸)→水洗→乾燥之後，在大氣中以各種溫度加熱5分鐘，使用加熱後的試樣，利用膠帶來進行剝離試驗。加熱溫度係以每相隔10℃做增量變化，將未發生氧化膜的剝離的最高溫度作為氧化膜密合保持溫度。將氧化膜密合保持溫度在300℃以上者，視為良好。鹼性陰極電解清洗以液溫為60℃，陰極電流密度為5A/dm2，時間為30秒鐘的條件來進行。清洗液是以氫氧化鈉為主成分(40%)，另外含有磷酸鹽、矽酸鹽、碳酸鹽、表面活性劑，以50g/L的濃度溶解了具有代表性之市售的鹼性陰極電解清洗用藥劑的水溶液。利用膠帶來進行的剝離試驗， 係以黏貼上市售的膠帶(住友3M公司製造的修補膠帶)之後，予以撕下的方法來進行的。 The oxide film adhesion was evaluated by the temperature at which the oxide film was kept in close contact with each other. After the sample was subjected to alkaline cathodic electrolysis cleaning, it was further washed with water, pickled (acidified with 10% sulfuric acid), washed with water, dried, and then heated in the air at various temperatures for 5 minutes, and the sample was heated and peeled off using a tape. test. The heating temperature was changed in increments of 10 ° C per phase, and the highest temperature at which peeling of the oxide film did not occur was taken as the oxide film adhesion holding temperature. It is considered to be good if the oxide film is adhered and kept at a temperature of 300 ° C or higher. The alkaline cathode electrolytic cleaning was carried out under the conditions of a liquid temperature of 60 ° C, a cathode current density of 5 A/dm 2 and a time of 30 seconds. The cleaning solution is based on sodium hydroxide (40%), and contains phosphate, citrate, carbonate, and surfactant. It dissolves a representative commercially available alkaline cathode electrolysis at a concentration of 50g/L. An aqueous solution of the cleaning agent. The peeling test by the tape was carried out by sticking the tape which was sold on the market (the repair tape manufactured by Sumitomo 3M Co., Ltd.) and then peeling it off.
發明例No.1~13，銅合金的組成分落在本發明的規定範圍內，熱軋的結束溫度高達750℃以上，再結晶熱處 理的加熱、冷卻速度大，並且是高溫短時間的保持條件。 因此，平均結晶粒直徑小，析出物密度高，具有高強度(包括維氏硬度)和耐熱性、良好的撓曲性、焊料耐熱剝離性以及氧化膜密合性。 Inventive Examples No. 1 to 13, the composition of the copper alloy falls within the prescribed range of the present invention, and the end temperature of the hot rolling is as high as 750 ° C or higher, and the recrystallization heat is The heating and cooling rate are large, and it is a high temperature and short-time holding condition. Therefore, the average crystal grain diameter is small, the precipitate density is high, and it has high strength (including Vickers hardness), heat resistance, good flexibility, solder heat-resistant peelability, and oxide film adhesion.
其中No.11、12，進行兩次析出熱處理，將析出熱處理之間的冷軋加工率設為60%，與化學組成分大致相同的發明例No.1相比，平均結晶粒直徑更小，析出物密度更高，強度更高。 Among them, No. 11 and 12 were subjected to two precipitation heat treatments, and the cold rolling processing ratio between the precipitation heat treatments was 60%, and the average crystal grain diameter was smaller than that of Invention Example No. 1 in which the chemical composition was substantially the same. The precipitate has a higher density and a higher strength.
另一方面，No.14因為P的含量多，落在本發明的規定範圍外，所以導電率低，氧化膜密合性差。 On the other hand, since No. 14 has a large content of P and falls outside the predetermined range of the present invention, the electrical conductivity is low and the adhesion of the oxide film is poor.
No.15因為P的含量少，落在本發明的規定範圍外，所以結晶粒直徑大，析出物密度低，強度(特別是維氏硬度)和耐熱性低，撓曲性差。 Since No. 15 has a small content of P and falls outside the predetermined range of the present invention, the crystal grain diameter is large, the precipitate density is low, the strength (especially Vickers hardness) and heat resistance are low, and the flexibility is poor.
No.16平均結晶粒直徑小，析出物密度高，具有高強度、耐熱性、撓曲性。但是，因為Zn的含量少，落在本發明的規定範圍外，所以焊料耐熱剝離性差。 No. 16 has a small average crystal grain diameter and a high density of precipitates, and has high strength, heat resistance, and flexibility. However, since the content of Zn is small and falls outside the predetermined range of the present invention, the solder heat-resistant peeling property is inferior.
No.17平均結晶粒直徑小，析出物密度高，具有高強度、耐熱性、撓曲性。但是，Zn的含量多，落在本發明的規定範圍外，因此導電率低。 No. 17 has a small average crystal grain diameter and a high density of precipitates, and has high strength, heat resistance, and flexibility. However, since the content of Zn is large and falls outside the prescribed range of the present invention, the electrical conductivity is low.
No.18因為Sn與Mg的合計含量少，落在本發明的規定範圍外，所以雖然平均結晶粒直徑小，析出物密度也高，但強度和耐熱性低。 Since No. 18 has a small total content of Sn and Mg and falls outside the predetermined range of the present invention, the average crystal grain diameter is small and the precipitate density is high, but the strength and heat resistance are low.
No.19因為Sn和Mg的合計含量多，落在本發明的規定範圍外，所以導電率低，氧化膜密合性差。 In No. 19, since the total content of Sn and Mg is large and falls outside the predetermined range of the present invention, the electrical conductivity is low and the adhesion of the oxide film is poor.
No.20因為C的含量多，落在本發明的規定範圍外，所以如第1圖(a)所示，粗大Fe粒子大量生成，進行Ag等的鍍敷時容易生成突起和未鍍敷部等，可推測其鍍敷性低。另外，No.20平均結晶粒直徑大，析出物密度低，與組成分類似的No.2相比，強度和耐熱性低，撓曲性差。 Since No. 20 has a large content of C and falls outside the predetermined range of the present invention, as shown in Fig. 1(a), coarse Fe particles are formed in a large amount, and when plating such as Ag is performed, protrusions and unplated portions are easily formed. Etc., it is presumed that the plating property is low. Further, No. 20 has a large average crystal grain diameter and a low precipitate density, and has lower strength and heat resistance than that of No. 2 having a compositional component, and is inferior in flexibility.
No.21因為Co、Si、Cr的合計含量多，落在本發明的規定範圍外，所以如第1圖(b)所示，粗大Fe粒子大量生成，可推測其鍍敷性低。另外，No.21平均結晶粒直徑大，析出物密度低，與組成分類似的No.2相比，強度和耐熱性低，撓曲性差。 In the case of No. 21, since the total content of Co, Si, and Cr is large, it falls outside the predetermined range of the present invention. Therefore, as shown in Fig. 1(b), coarse Fe particles are formed in a large amount, and it is presumed that the plating property is low. Further, No. 21 has a large average crystal grain diameter and a low precipitate density, and has lower strength and heat resistance than that of No. 2 having a compositional component, and is inferior in flexibility.
No.22因為Fe的含量少，落在本發明的規定範圍外，所以平均結晶粒直徑大，析出物密度低，強度和耐熱性低，撓曲性差。 Since No. 22 has a small content of Fe and falls outside the predetermined range of the present invention, the average crystal grain diameter is large, the precipitate density is low, the strength and heat resistance are low, and the flexibility is poor.
No.23平均結晶粒直徑小，析出物密度高，具有高強度、耐熱性、撓曲性。但是，Fe的含量多，落在本發明的規定範圍外，因此如第1圖(c)所示，粗大Fe粒子大量生成，可推測其鍍敷性低。 No. 23 has a small average crystal grain diameter and a high density of precipitates, and has high strength, heat resistance, and flexibility. However, since the content of Fe is large and falls outside the predetermined range of the present invention, as shown in Fig. 1(c), coarse Fe particles are formed in a large amount, and it is presumed that the plating property is low.
No.24因為熱軋的結束溫度低，為低於750℃，因此，平均晶粒直徑大，析出物密度低，強度和耐熱性低，撓曲性差。 No. 24 is lower than 750 ° C because the end temperature of hot rolling is low. Therefore, the average crystal grain diameter is large, the precipitate density is low, the strength and heat resistance are low, and the flexibility is poor.
No.25因為再結晶熱處理的加熱暨冷卻速度小，並且是在較低溫下長時間的保持條件，所以平均結晶粒直徑大，析出物密度低，強度和耐熱性低，撓曲性差。 No. 25 has a small heating and cooling rate of the recrystallization heat treatment and is maintained at a relatively low temperature for a long period of time. Therefore, the average crystal grain diameter is large, the precipitate density is low, the strength and heat resistance are low, and the flexibility is poor.
No.26因為第二次析出熱處理的溫度與第一次相同，所以與相同組成分下除了析出熱處理以外的工序條件類似的No.12相比，析出物密度和強度(含維氏硬度)降低。 In No. 26, since the temperature of the second precipitation heat treatment is the same as that of the first time, the density and strength (including Vickers hardness) of the precipitate are lowered as compared with No. 12 in which the process conditions other than the precipitation heat treatment are similar. .
No.27因為第二次析出熱處理的溫度更高，所以與相同組成分下除了析出熱處理以外的工序條件類似的No.12相比，析出物密度、強度(含維氏硬度)和耐熱性降低。另外，平均結晶粒直徑大，撓曲性差。 In No. 27, since the temperature of the second precipitation heat treatment was higher, the precipitate density, the strength (including Vickers hardness), and the heat resistance were lower than those of No. 12 in which the same processing conditions except the precipitation heat treatment were carried out. . Further, the average crystal grain diameter is large and the flexibility is poor.
No.28因為再結晶熱處理的保持溫度高，所以平均結晶粒直徑大，強度(特別是維氏硬度)低，撓曲性差。 Since No. 28 has a high holding temperature of the recrystallization heat treatment, the average crystal grain diameter is large, the strength (especially Vickers hardness) is low, and the flexibility is poor.
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