JPH0474837A - Rolled copper alloy foil for film carrier - Google Patents
Rolled copper alloy foil for film carrierInfo
- Publication number
- JPH0474837A JPH0474837A JP18595090A JP18595090A JPH0474837A JP H0474837 A JPH0474837 A JP H0474837A JP 18595090 A JP18595090 A JP 18595090A JP 18595090 A JP18595090 A JP 18595090A JP H0474837 A JPH0474837 A JP H0474837A
- Authority
- JP
- Japan
- Prior art keywords
- copper alloy
- precipitates
- foil
- rolled
- alloy foil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011888 foil Substances 0.000 title claims abstract description 72
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 60
- 239000002244 precipitate Substances 0.000 claims abstract description 35
- 239000010949 copper Substances 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 33
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 238000013508 migration Methods 0.000 abstract description 16
- 230000005012 migration Effects 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract 1
- 239000011889 copper foil Substances 0.000 description 24
- 239000002985 plastic film Substances 0.000 description 14
- 229920006255 plastic film Polymers 0.000 description 14
- 239000000969 carrier Substances 0.000 description 9
- 238000005096 rolling process Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000007547 defect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 235000013405 beer Nutrition 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000866 electrolytic etching Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、導電性、強度、耐熱性、耐マイグレーショ
ン性および絶縁性プラスチックフィルムに対する接着性
に優れ、かつ厚さの薄いＴＡＢ（Ｔａｐｅ Ａｕｔｏｍ
ａｔｅｄ Ｂｏｎｄｉｎｇ）に使われるフィルムキャリ
ア用圧延銅合金箔に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to a thin TAB (Tape Auto) which has excellent conductivity, strength, heat resistance, migration resistance, and adhesion to insulating plastic films, and is thin.
This invention relates to a rolled copper alloy foil for film carriers used in bonding.
一般に、ＴＡＢに使われるフィルムキャリア（以下、単
にフィルムキャリアという）用箔は、（１）導電性が優
れていること、
（２）厚さが薄いこと、
（３） ＴＡＢ製造工程中にリードの曲がりやインナ
リードの破断が起こらないだけの強度を有すること、
（４）ＴＡＢ製造工程中の加熱あるいは半田付けなどに
よってフィルムキャリアが軟化しないたけの耐熱性を有
すること、
（５）ある程度の高温、高湿度あるいは塵埃環境下にＴ
ＡＢがさらされても、リード間に短絡（マイグレーショ
ンが起こらない特性、すなわち耐マイグレーション性を
有すること、
（６）絶縁性プラスチックフィルムに対する接着性が優
れていること、
などの特性か要求されており、一般に、電気銅と同等の
純度を有する電解純銅箔あるいは電気銅を溶解、鋳造し
てスラブ（鋳塊）を作製し、熱処理と圧延加工とを繰り
返すことによって得られる圧延純銅箔が用いられており
（特開平２−１７０９５１号公報参照）、これらの電解
純銅箔および圧延純銅箔は、共に導電率が高いという特
徴をもっている。In general, foils for film carriers (hereinafter simply referred to as film carriers) used in TABs have (1) excellent conductivity, (2) thin thickness, and (3) poor conductivity during the TAB manufacturing process. (4) have sufficient heat resistance to prevent the film carrier from softening due to heating or soldering during the TAB manufacturing process; (5) a certain degree of high temperature and high temperature T under humid or dusty environment
Characteristics such as (6) excellent adhesion to insulating plastic films, and (6) excellent adhesion to insulating plastic films are required. In general, electrolytic pure copper foil having the same purity as electrolytic copper or rolled pure copper foil obtained by melting and casting electrolytic copper to create a slab (ingot) and repeating heat treatment and rolling processing is used. (Refer to Japanese Unexamined Patent Publication No. 2-170951), these electrolytic pure copper foils and rolled pure copper foils are both characterized by high electrical conductivity.
近年、ＬＳＩチップは、多ピン化およびファインパター
ン化の傾向にあり、さらに苛酷な条件および環境下で使
用される傾向にあるために、優れた導電率を有すること
は勿論のこと、より一層優れた強度、耐熱性、耐マイグ
レーション性および絶縁性プラスチックフィルムに対す
る接着性を有し、かつより厚さの薄いフィルムキャリア
用箔が求められていた。In recent years, LSI chips have tended to have more pins and finer patterns, and are also used under harsher conditions and environments. There has been a need for a thinner foil for film carriers that has superior strength, heat resistance, migration resistance, and adhesion to insulating plastic films.
しかしなから、従来からフィルムキャリア用箔として使
用されている電解純銅箔および圧延純銅箔は、共に導電
率は優れているものの、強度、耐熱性および耐マイグレ
ーション性については十分に満足できるものではなく、
また上記電解純銅箔は最大表面粗さか４−以上あるので
絶縁性プラスチックフィルムに対する接着性は優れてい
るものの逆に、エツチングにより高い精度のファインパ
ターンを得るには問題となり、一方、圧延純銅箔は十分
に薄くすることができるものの表面が平滑すぎて絶縁性
プラスチックフィルムに対する接着強度が得られないと
いう問題点があった。However, although electrolytic pure copper foil and rolled pure copper foil, which have traditionally been used as foils for film carriers, have excellent conductivity, they are not fully satisfactory in terms of strength, heat resistance, and migration resistance. ,
Furthermore, since the electrolytic pure copper foil has a maximum surface roughness of 4- or more, it has excellent adhesion to insulating plastic films, but on the other hand, it poses a problem in obtaining fine patterns with high precision through etching.On the other hand, rolled pure copper foil Although it can be made sufficiently thin, there is a problem in that the surface is too smooth and adhesive strength to the insulating plastic film cannot be obtained.
そこで、本発明者等は、導電性、強度、耐熱性、および
耐マイグレーション性に優れ、さらに絶縁性プラスチッ
クフィルムに対する接着性が優れた極めて薄いフィルム
キャリア用銅合金箔を開発すべく研究を行った結果、
（１） Ｚ ｒ ： ０．００５〜０．２３重量％
、酸素： ０．００２０重量％以下、
を含有し、残りかＣｕおよび不可避不純物からなる組成
を有する銅合金、または、
Ｚｒ ： ０．００５〜０．２３重量％、Ｍｇ ：
０．００１〜０．０２重量％、酸素： （１，０（１
２０重量９６以下、を含有し、残りがＣｕおよび不可避
不純物からなる組成を有する銅合金は、その組織中に存
在するＺｒを含む析出物総量の９０容量％以上が最大粒
径＝３−未満の微細な析出物（ここで最大粒径とは、個
々の析出物粒の径の最大のものをいう）で占める、
（２）上記銅合金を圧延して得られた圧延銅合金箔は、
９０％ｌＡＣ３以上の導電率があり、上記電解純銅箔お
よび圧延純銅箔に比べて、強度、耐熱性および耐マイグ
レーション性が一層優れている、（３）上記銅合金を圧
延して得られた圧延銅合金箔を酸、アルカリ等による化
学的処理または電気化学的処理すると、上記圧延銅合金
箔の表面には銅合金素地中に含まれる析出物か残存突出
し、または脱落して窪みが形成されて、表面に凹凸か形
成されるので、絶縁性プラスチックフィルムに対する接
着性がより安定、強固になる。Therefore, the present inventors conducted research to develop an extremely thin copper alloy foil for film carriers that has excellent conductivity, strength, heat resistance, and migration resistance, and also has excellent adhesion to insulating plastic films. Results: (1) Zr: 0.005-0.23% by weight
, oxygen: 0.0020% by weight or less, and the remainder consisting of Cu and unavoidable impurities, or Zr: 0.005 to 0.23% by weight, Mg:
0.001-0.02% by weight, oxygen: (1,0(1
20% by weight or less, and the remainder is Cu and unavoidable impurities. (2) The rolled copper alloy foil obtained by rolling the above copper alloy is
(3) A rolled product obtained by rolling the above-mentioned copper alloy, which has an electrical conductivity of 90%lAC3 or more and has superior strength, heat resistance, and migration resistance compared to the electrolytic pure copper foil and the rolled pure copper foil. When copper alloy foil is chemically or electrochemically treated with acid, alkali, etc., the precipitates contained in the copper alloy base protrude or fall off and form depressions on the surface of the rolled copper alloy foil. Since the surface is uneven, the adhesion to the insulating plastic film becomes more stable and strong.
という知見を得たのである。We obtained this knowledge.
この発明は、かかる知見にもとづいてなされたものであ
って、
Ｚｒ ： ０．００５〜０．２３重量％、酸素： ０
．００２０重量％以下、
を含有し、残りがＣｕおよび不可避不純物からなる銅合
金組成、または、
Ｚｒ ： ０．００５〜０．２３重量％、Ｍｇ ：
０．０（１１−０，０２重量％、酸素： ０．００２０
重量％以下、
を含有し、残りがＣｕおよび不可避不純物からなる銅合
金組成、および最大粒径＝３μｓ未満の大きさの析出物
が析出物総量の９０容量％以上存在する組織からなる圧
延銅合金箔であって、上記圧延銅合金箔の表面は、上記
析出物が残存突出している突起および上記析出物か化学
処理中に脱落して生した窪みからなる凹凸を有するフィ
ルムキャリア用圧延銅合金箔に特徴を合するものである
。This invention was made based on this knowledge, and includes: Zr: 0.005 to 0.23% by weight, oxygen: 0
．． 0020% by weight or less, with the remainder consisting of Cu and inevitable impurities, or Zr: 0.005 to 0.23% by weight, Mg:
0.0 (11-0.02% by weight, oxygen: 0.0020
% by weight or less, with the remainder consisting of Cu and unavoidable impurities, and a rolled copper alloy having a structure in which precipitates with a maximum grain size of less than 3 μs exist in 90% by volume or more of the total amount of precipitates. The surface of the rolled copper alloy foil for a film carrier has an uneven surface consisting of protrusions where the precipitates remain and protrude and depressions formed by the precipitates falling off during chemical treatment. It matches the characteristics of
この発明のフィルムキャリア用圧延銅合金箔は、特にＺ
ｒを０．００５〜０．０２３重量％含有し、かつ酸素含
有量を可及的に少なくした銅合金箔を用いることにより
、フィルムキャリア用箔に要求される所望の特性が一層
向上し、圧延により製造されるので極めて薄くかつ平滑
にすることができるだけでなく、この圧延銅合金箔の表
面を化学処理（ここで化学処理とは、通常のエツチング
処理、電解エツチング処理なとを指す）することにより
、微細な析出物が圧延銅合金箔の表面に残存突出したり
上記析出物が脱落したりして、表面に凹凸が形成され、
この凹凸が絶縁性プラスチックフィルムに対する接着性
を向上させるものである。The rolled copper alloy foil for film carrier of this invention is particularly suitable for Z
By using a copper alloy foil containing 0.005 to 0.023% by weight of r and with as low an oxygen content as possible, the desired properties required for film carrier foils are further improved, and rolling Not only can it be made extremely thin and smooth, but the surface of this rolled copper alloy foil can also be chemically treated (here, chemical treatment refers to ordinary etching treatment, electrolytic etching treatment, etc.). As a result, fine precipitates remain on the surface of the rolled copper alloy foil and protrude, or the above precipitates fall off, forming unevenness on the surface.
This unevenness improves the adhesion to the insulating plastic film.
従来から使用されている圧延純銅箔も、厚さを極めて薄
くすることができるが、上記圧延純銅箔は、化学処理し
ても析出物か存在しないので表面に所望の凹凸を形成す
ることかできないために絶縁性プラスチックフィルムに
対する接着性は改善されない。The rolled pure copper foil that has been used in the past can also be made extremely thin, but the rolled pure copper foil does not have any precipitates even if it is chemically treated, so it is not possible to form the desired unevenness on the surface. Therefore, the adhesion to insulating plastic films is not improved.
上記最大粒径二３節未満の析出物か析出物総量の９０容
２％以上存在するような銅合金は、市販の高純度電気銅
を原料とし、通常の低周波溝型溶解炉を用いて還元性雰
囲気中にて酸素含有量を低目に抑えた無酸素銅に溶解し
、さらにこの溶湯を還元性雰囲気であるいは黒鉛で覆い
ながら酸素の侵入を阻止し、ＺｒまたはＺｒおよび〜１
ｇを所定量添加して銅合金溶湯を調製し、この溶湯を酸
素の侵入を阻止した雰囲気にて水冷鋳型に鋳込んた後５
００℃までの冷却速度を３℃／秒〜３０℃／秒の所定の
範囲内で急速冷却することにより製造することができる
。このようにして得られた銅合金の鋳塊は、さらに７５
０℃〜９７０℃の範囲内の所定の圧延開始温度にて熱間
圧延、水冷され、ついで冷間圧延と焼鈍とを交互に繰り
返し行ない、最終的に圧延のままおよび１００℃〜５５
０℃の範囲内の所定温度保持の条件で焼鈍を施すことに
より圧延銅合金箔に加工される。Copper alloys containing precipitates with a maximum grain size of less than 23 nodes or more than 2% by volume of the total amount of precipitates are produced using commercially available high-purity electrolytic copper as raw material and using a normal low-frequency groove-type melting furnace. Zr or Zr and ~1
A predetermined amount of copper alloy is added to prepare a molten copper alloy, and this molten metal is poured into a water-cooled mold in an atmosphere that prevents oxygen from entering.
It can be produced by rapid cooling to 00°C at a cooling rate within a predetermined range of 3°C/sec to 30°C/sec. The copper alloy ingot obtained in this way has an additional 75
Hot rolled at a predetermined rolling start temperature within the range of 0°C to 970°C, water cooled, then cold rolled and annealed alternately, and finally as rolled and at 100°C to 55°C.
It is processed into a rolled copper alloy foil by annealing it under the condition of maintaining a predetermined temperature within the range of 0°C.
つぎに、この発明のフィルムキャリア用圧延銅合金箔の
成分組成、析出物の大きさ、および表面凹凸を上記の如
く限定した理由について説明する。Next, the reason why the composition, size of precipitates, and surface irregularities of the rolled copper alloy foil for film carrier of the present invention are limited as described above will be explained.
（ａ） Ｚｒ
Ｚｒ成分には、析出物を形成することによって、導電率
を大幅に低下させることなく、強度および耐熱性を向上
させる作用および耐マイグレーション性を向上させる作
用があるが、その含有量が０．００５重量％未満では所
望の効果が得られず、一方その含有量が０．２３％を越
えると、熱間圧延性が悪くなり、製造上問題が起るとと
もに、最大粒径＝３虜を越える大きな析出物が形成され
やすくなり、大きな析出物の銅合金を圧延して箔にする
と疵等の表面欠陥が生じやすくなり、さらに導電率も９
０％ＩＡＣＳ以上を確保することが困難になることから
、その含有量を０．００５〜０．２３重量％と定めた。(a) Zr The Zr component has the effect of improving strength and heat resistance and improving migration resistance without significantly reducing conductivity by forming precipitates, but its content is If the content is less than 0.005% by weight, the desired effect will not be obtained, while if the content exceeds 0.23%, hot rolling properties will deteriorate, production problems will occur, and the maximum grain size = 3 Large precipitates that are larger than the capacitance are likely to form, and when copper alloys with large precipitates are rolled into foil, surface defects such as scratches are likely to occur, and the conductivity is also 9.
Since it would be difficult to secure 0% IACS or more, the content was determined to be 0.005 to 0.23% by weight.
（ｂ） Ｍｇ
Ｍｇ成分には、Ｃｕ合金箔の強度を高めるとともに耐マ
イグレーション性をなお一層向上させる作用があるが、
その含有量かｏ、ｏｏｔ重量％未満では所望の効果か得
られず、一方その含有量か０．０２重量％を越えると、
鋳塊への酸化物の巻込みか起こりやすくなり、箔に製造
した状態で疵等の表面欠陥が生じやすくなるとともに９
０％ＩＡＣＳ以上の導電率を確保することが困難になる
ことから、その含有量をｏ、ｏｏｉ〜０，０２重量％と
定めた。(b) Mg The Mg component has the effect of increasing the strength of the Cu alloy foil and further improving the migration resistance.
If the content is less than 0.02% by weight, the desired effect cannot be obtained, while if the content exceeds 0.02% by weight,
Oxides are more likely to be entrained in the ingot, and surface defects such as scratches are more likely to occur when the foil is manufactured.
Since it would be difficult to ensure a conductivity of 0% IACS or higher, the content was determined to be from o,ooi to 0.02% by weight.
（ｃ）酸 素
酸素含有量は可能な限り少ない方がよいが、その含有量
か０．００２０重量％を越えると鋳塊へのＭｇあるいは
Ｚｒの酸化物の巻き込みが起こりやすくなるとともにＺ
ｒを含む析出物の粗大化が起こり、箔に製造した状態で
疵等の表面欠陥が生じやすくなるために、酸素含有量は
０．００２０重量％以下と定めた。(c) Oxygen It is better to keep the oxygen content as low as possible, but if the oxygen content exceeds 0.0020% by weight, Mg or Zr oxides are likely to be incorporated into the ingot, and Zr
The oxygen content was set at 0.0020% by weight or less because the precipitates containing r tend to coarsen and surface defects such as scratches occur easily in the foil produced.
（ｄ）析出物
Ｚｒを含む析出物の存在は、高い導電率の確保、強度お
よび耐熱性の向上にとって必要なものであるか、最大粒
径か３μｓ以上の析出物の占める比率か１０８ｊｉ％を
越える程度に粗大な析出物か多く存在すると、強度向上
に対する寄与か小さくなるとともに、圧延加工による銅
合金箔製造にも疵等が発生して困難が生し、さらにエツ
チングによりファインパターンを得る上からも悪い影響
が出てくるようになることから、析出物総量の９０容量
％以上が最大粒径二３μｓ未満の微細な析出物で占めら
れるように定めた。(d) Is the presence of precipitates containing precipitates Zr necessary to ensure high conductivity, improve strength and heat resistance? If there are many coarse precipitates present, the contribution to strength improvement will be small, and it will be difficult to manufacture copper alloy foil by rolling due to the occurrence of defects, and furthermore, it will be difficult to obtain fine patterns by etching. Since this would also have an adverse effect, it was determined that 90% by volume or more of the total amount of precipitates was occupied by fine precipitates with a maximum particle size of less than 23 μs.
つぎに、この発明のフィルムキャリア用圧延銅合金箔に
ついて、実施例により具体的に説明する。Next, the rolled copper alloy foil for film carriers of the present invention will be specifically explained with reference to Examples.
通常の低周波溝型溶解炉を用い、高純度電気銅を原料と
して還元性雰囲気中で溶解して純銅溶湯を製造し、さら
にこの純銅溶湯を黒鉛で覆いなからＺｒ、またはＺｒお
よびＭｇを添加し、第１表に示される組成の銅合金溶湯
を製造し、この銅合金溶湯をＡｒガス雰囲気下で水冷鋳
型に鋳込み、５００℃までの冷却速度＝ｌＯ℃／秒で急
速冷却し、厚さ：５０ｍ１Ｘ幅：ｌＯＯｍＩＩＸ長さ：
２００ｍｍの寸法を有する鋳塊に鋳造した。この鋳塊
をさらに８５０℃の圧延開始温度に加熱し、この温度で
熱間圧延を施して厚さ：１１ｍｍの熱延板とし、ついて
水冷し、上記水冷した熱延板の上下両面をＣｏｍａづつ
面側して厚さ：９關とし、この面側した熱延板を通常の
条件にて冷間圧延と焼鈍とを交互に繰り返し行ない、最
終的に厚さ：１．８ｕｍの圧延銅合金箔を製造した。こ
の圧延銅合金箔をさらに温度：３００〜５００℃の範囲
内の所定の温度で２０分間保持の条件で焼鈍したのち、
この焼鈍した圧延銅合金箔を、塩 酸 ＋ＩＯ容
量容量
環化第二鉄：５容量％、
水 ：８５容量％、
の水溶液に３分間浸肩し、表面化学処理を行なった後、
水洗、乾燥し、第１表に示される本発明圧延銅合金箔１
〜９および比較圧延銅合金箔１〜４を製造した。Using an ordinary low-frequency groove-type melting furnace, high-purity electrolytic copper is melted as a raw material in a reducing atmosphere to produce pure copper molten metal, and then Zr or Zr and Mg is added to this pure copper molten metal without covering it with graphite. Then, a molten copper alloy having the composition shown in Table 1 was produced, and this molten copper alloy was cast into a water-cooled mold under an Ar gas atmosphere, and rapidly cooled at a cooling rate of 10°C/sec to 500°C. :50m1X Width:lOOmIIX Length:
An ingot with dimensions of 200 mm was cast. This ingot was further heated to a rolling start temperature of 850°C, hot-rolled at this temperature to form a hot-rolled plate with a thickness of 11 mm, and then water-cooled. The face-faced hot-rolled sheet was made to have a thickness of 9 mm, and the face-faced hot-rolled sheet was alternately cold-rolled and annealed under normal conditions, and finally a rolled copper alloy foil with a thickness of 1.8 um was obtained. was manufactured. This rolled copper alloy foil is further annealed at a predetermined temperature within the range of 300 to 500°C for 20 minutes, and then
This annealed rolled copper alloy foil was immersed in an aqueous solution of hydrochloric acid + IO ferric cyclization: 5% by volume, water: 85% by volume for 3 minutes to perform surface chemical treatment.
Washed with water, dried and rolled copper alloy foil of the present invention shown in Table 1 1
-9 and comparative rolled copper alloy foils 1-4 were manufactured.
さらに、通常市販されている厚さ１ｍｍの無酸素銅につ
いて、通常の条件にて冷間圧延と焼鈍とを交互に繰り返
し行ない、最終的に厚さ： １８％Ｍｌの圧延純銅箔を
製造した。この圧延純銅箔をさらに温度：１８０℃に２
０分間保持の条件で焼鈍し、上記と同様に表面化学処理
して従来圧延純銅箔を用意した。Further, commercially available oxygen-free copper with a thickness of 1 mm was alternately cold-rolled and annealed under normal conditions to finally produce a rolled pure copper foil with a thickness of 18% Ml. This rolled pure copper foil is further heated to 180℃ for 2
A conventionally rolled pure copper foil was prepared by annealing under the condition of holding for 0 minutes and carrying out the surface chemical treatment in the same manner as above.
これら表面化学処理した本発明圧延銅合金箔１〜９、比
較圧延銅合金箔１〜４および従来圧延純銅箔について、
その表面を光学顕微鏡により観察したところ、本発明圧
延銅合金箔１〜９および比較圧延銅合金箔１〜４の表面
には析出物の突起および析出物が脱落して生じた窪みか
見られたが、従来圧延純銅箔の表面にはかかる突起およ
び窪みはほとんど見られなかった。Regarding the surface chemically treated rolled copper alloy foils 1 to 9 of the present invention, comparative rolled copper alloy foils 1 to 4, and conventional rolled pure copper foil,
When the surfaces of the rolled copper alloy foils 1 to 9 of the present invention and comparative rolled copper alloy foils 1 to 4 were observed using an optical microscope, protrusions of precipitates and depressions caused by falling off of the precipitates were observed on the surfaces of rolled copper alloy foils 1 to 9 of the present invention and comparison rolled copper alloy foils 1 to 4. However, such protrusions and depressions have rarely been seen on the surface of conventional rolled pure copper foils.
さらに、本発明圧延銅合金箔１〜９、比較圧延銅合金箔
１〜４および従来圧延純銅箔について、下記の方法で試
験および測定を行ない、それらの結果を第１表に示した
。Further, the rolled copper alloy foils 1 to 9 of the present invention, the comparative rolled copper alloy foils 1 to 4, and the conventional rolled pure copper foil were tested and measured in the following manner, and the results are shown in Table 1.
（１）析出物の大きさ測定
表面化学処理する前の各種銅合金箔について、りん酸−
水による電解研磨および塩化第二鉄による腐食を行なっ
た後、光学顕微鏡により析出物の大きさを観察した。析
出物の大きさの評価は、析出物総量の９０９６以上か３
虜未満の大きさになっているかどうかという観点から評
価し、評価か困難な場合は、任意の１０視野について倍
率１０００倍で写真を撮り評価の参考とした。その結果
を第１表に示した。(1) Measurement of the size of precipitates For various copper alloy foils before surface chemical treatment, phosphoric acid
After electropolishing with water and corrosion with ferric chloride, the size of the precipitates was observed using an optical microscope. Evaluation of the size of precipitates is 9096 or more of the total amount of precipitates or 3
Evaluation was made from the viewpoint of whether or not the size was smaller than that of a captive. If evaluation was difficult, photographs were taken at a magnification of 1000 times for any 10 fields of view and used as a reference for evaluation. The results are shown in Table 1.
（２）引張試験
第１表に示された各種銅合金箔および純銅箔を圧延方向
に平行に採取したＪＩ５５号試験片と同じ寸法の試験片
を用いて引張試験し、引張強さおよび伸びを測定して箔
の強度を評価した。(2) Tensile test The various copper alloy foils and pure copper foils shown in Table 1 were subjected to a tensile test using a test piece of the same size as the JI No. 55 test piece taken parallel to the rolling direction to determine the tensile strength and elongation. Measurements were taken to evaluate the strength of the foil.
（３）軟化温度測定
上記引張試験で作製した試験片をＡｒガス雰囲気下の種
々の温度でｌｈｒの焼鈍を行なった後、弓張試験し、引
張強さが初期の引張強さの値の８０％に減少した温度を
もって軟化温度とし、この温度を求めて耐熱性を評価し
た。(3) Softening temperature measurement The test pieces prepared in the above tensile test were annealed for 1hr at various temperatures in an Ar gas atmosphere, then subjected to a bow tension test, and the tensile strength was 80% of the initial tensile strength value. The temperature at which the temperature decreased was defined as the softening temperature, and this temperature was determined to evaluate the heat resistance.
（４）導電率測定
ＪＩＳ ＨＯ５０５に定める＃１定方法により各種銅合
金箔および純銅箔の導電率を測定した。(4) Conductivity measurement The conductivity of various copper alloy foils and pure copper foils was measured using the #1 standard method defined in JIS HO505.
（５） ビール強度測定
各種銅合金箔および純銅箔を幅：ｌＯｍｍｘ長さ：１０
０ｍ１１の寸法に採取して第１図に示されるビール強度
測定用試験箔片２を作製し、この試験箔片２を接着剤を
用いてポリイミドフィルム１に加熱圧着し、ついて第１
図に示されるように試験箔片２の一端を９０°方向に毎
分５０ｍｍの速さで引張り、その時の荷重をビール強度
（ｋｇｆ／ｃｍ）として測定し、絶縁性プラスチックフ
ィルムに対する接着性を評価した。(5) Beer strength measurement Various copper alloy foils and pure copper foils Width: lOmm x Length: 10
A test foil piece 2 for beer strength measurement as shown in FIG.
As shown in the figure, one end of the test foil piece 2 was pulled in a 90° direction at a speed of 50 mm per minute, the load at that time was measured as beer strength (kgf/cm), and the adhesion to the insulating plastic film was evaluated. did.
（６〉 耐マイグレーション性の測定各種銅合金箔お
よび純銅箔を幅：ｌＯ＋ｎＸ長さ２５０ｍｍの寸法に採
取して採取箔片とし、この採取箔片を接着剤を用いてポ
リイミドフィルムの表面に加熱圧着し、つづいてポリイ
ミドフィルム上の採取箔片の中央を極間距離：１＋ｎｍ
となるようにエツチングにより分離し、分離された採取
箔ハを第２図に示されるような電気回路に接続した。第
２図において、４は定電圧直流電源、５は抵抗、６は電
流計、７は電圧計、８は恒温・恒湿槽、１はポリイミド
フィルム、３は採取箔片である。(6) Measurement of migration resistance Various copper alloy foils and pure copper foils were sampled into pieces with a width of lO+n x length of 250 mm, and the sampled foil pieces were heat-pressed onto the surface of a polyimide film using an adhesive. Then, place the center of the sampled foil piece on the polyimide film at a distance of 1+nm.
The sampled foils were separated by etching so as to be as follows, and the separated sampled foils were connected to an electric circuit as shown in FIG. In FIG. 2, 4 is a constant voltage DC power supply, 5 is a resistor, 6 is an ammeter, 7 is a voltmeter, 8 is a constant temperature/humidity bath, 1 is a polyimide film, and 3 is a sampling foil piece.
エツチングにより分離された採取箔片３の一方を正極に
、もう一方の採取箔片３を負極に接続し、１００Ｖの電
圧を印加し、かつ電極間の電流を２ｆｆｌＡ以下になる
ように調整し、温度：４０℃、湿度：９８％の恒温・恒
湿１８に２４時間暴露した。上記暴露後の採取箔片３，
３の中央部２０ｍ＋＊の範囲を光学顕微鏡により観察し
、採取箔片３，３に腐食およびＣｕの樹枝状成長の全く
生じないものを耐マイグレーション外大いにあり（○印
で示す）、腐食およびＣｕの樹枝状成長が少し生じてい
るものを耐マイグレーション性あり（△印で示す）、腐
食およびＣｕの樹枝状成長が全域に生じているものを耐
マイグレーション性全くなしく×印で示す）と区別して
評価した。One of the sampling foil pieces 3 separated by etching is connected to the positive electrode and the other sampling foil piece 3 is connected to the negative electrode, a voltage of 100V is applied, and the current between the electrodes is adjusted to be 2fflA or less, It was exposed to constant temperature and humidity 18 for 24 hours at a temperature of 40° C. and a humidity of 98%. Collected foil piece 3 after the above exposure,
An optical microscope was used to observe a 20m+* area in the central part of 3, and there were some specimens with no corrosion or dendritic growth of Cu on the sampled foil pieces 3 and 3, which were outside of the migration resistance (indicated by a circle), indicating corrosion and Cu. Those with a small amount of dendritic growth are classified as having migration resistance (indicated by a △ mark), and those in which corrosion and dendritic growth of Cu occur over the entire area are classified as having no migration resistance (indicated by an x mark). They were evaluated separately.
（７）箔の表面正常性測定
表面化学処理した後の各種銅合金箔について、光学顕微
鏡を用いて、倍率５０倍にて、幅３０ｍｍ、長さ：２ｍ
の範囲にわたって信頼性のあるバターを描くことのでき
ない程度の大きな疵等の表面欠陥の有無を調べ、その結
果を第１表に示した。(7) Measurement of surface normality of foils Various copper alloy foils after surface chemical treatment were measured using an optical microscope at 50x magnification, width: 30 mm, length: 2 m.
The presence or absence of surface defects such as large scratches that made it impossible to reliably draw butter over a range of 100 to 100 mm was examined, and the results are shown in Table 1.
第１表に示される結果から、本発明圧延銅合金箔１〜９
は、従来圧延純銅箔に比べて導電率か３〜１１％ｌＡＣ
３の範囲で減少するか、引張強さおよび伸びか大きいこ
とから強度が優れており、軟化温度が高いことから耐熱
性か優れており、ビール強度が大きいことから絶縁性プ
ラスチックフィルムとの接着性が優れており、さらにＣ
ｕの樹枝状成長が見られないことから耐マイグレーショ
ン性か優れていることかわかる。From the results shown in Table 1, the rolled copper alloy foils 1 to 9 of the present invention
has a conductivity of 3 to 11% lAC compared to conventional rolled pure copper foil.
It has excellent strength because it has a high tensile strength and elongation, and it has excellent heat resistance because it has a high softening temperature, and it has good adhesiveness with insulating plastic films because it has a high beer strength. is excellent, and C
It can be seen that the migration resistance is excellent because no dendritic growth of u was observed.
しかし、この発明の条件から外れた比較圧延銅合金箔１
〜４（第１表において、この発明の条件から外れている
値に※印を付して示した）は、上記強度、耐熱性、絶縁
性プラスチックフィルムに対する接着性および耐マイグ
レーション性のうちいずれかの特性か劣り、大きな析比
物か存在する銅合金を圧延して得られた箔の表面には大
きな表面欠陥か発生することがわかる。However, comparative rolled copper alloy foil 1 which deviates from the conditions of this invention
~4 (in Table 1, values outside the conditions of this invention are marked with *) are any of the above strength, heat resistance, adhesion to insulating plastic film, and migration resistance. It can be seen that large surface defects occur on the surface of foils obtained by rolling copper alloys with inferior properties and large grains.
二の発明のフィルムキャリア用圧延銅合金箔は、従来か
ら使用されている圧延純銅箔に比べて、耐マイグレーシ
ョン性に優れているところから、ファインパターン化の
要求に対しても十分に対処することかでき、強度、耐熱
性、絶縁性プラスチックフィルムとの接着性等に優れて
いるので苛酷な条件および環境下にあっても十分に使用
することのできるフィルムキャリア用圧延銅合金箔とし
て提供することかでき、これを用いて（＝転性の高いＬ
ＳＩを製造することかできる。The rolled copper alloy foil for film carriers of the second invention has superior migration resistance compared to conventionally used rolled pure copper foils, and therefore satisfactorily meets the demands for fine patterning. To provide a rolled copper alloy foil for film carriers that can be used satisfactorily even under harsh conditions and environments because it has excellent properties such as hardness, strength, heat resistance, and adhesion to insulating plastic films. This can be used (=L with high convertibility)
It is possible to manufacture SI.
第１図は、ビール強度の７１Ｐ１定状態を示す斜視図、
第２図は、耐マイグレーション性を測定するための装置
の配線図である。
１：ポリイミドフィルム、
２：試験箔片、 ３：採取箔片、４：定電圧直
流電源、 ５：抵 抗、６：電流計、 ７
：電圧計、８、恒温・恒湿槽。
補正の内容
平成
２年
８月
９２日FIG. 1 is a perspective view showing the 71P1 constant state of beer strength;
FIG. 2 is a wiring diagram of an apparatus for measuring migration resistance. 1: Polyimide film, 2: Test foil piece, 3: Sampling foil piece, 4: Constant voltage DC power supply, 5: Resistor, 6: Ammeter, 7
: Voltmeter, 8, constant temperature/humidity chamber. Contents of amendment August 92, 1990
Claims (2)
００２０重量％以下、 を含有し、残りが銅および不可避不純物からなる組成、
および最大粒径：３μｍ未満の大きさの析出物が析出物
総量の９０容量％以上存在する組織からなる圧延銅合金
箔であって、上記圧延銅合金箔の表面は、上記析出物が
残存突出している突起および上記析出物が化学処理中に
脱落して生じた窪みからなる凹凸を有する、 ことを特徴とするフィルムキャリア用圧延銅合金箔。(1) Zr: 0.005-0.23% by weight, oxygen: 0.
0020% by weight or less, the remainder consisting of copper and unavoidable impurities,
and a rolled copper alloy foil having a structure in which precipitates with a maximum grain size of less than 3 μm exist in 90% by volume or more of the total amount of precipitates, wherein the surface of the rolled copper alloy foil has a surface where the precipitates remain protruding. 1. A rolled copper alloy foil for a film carrier, characterized in that the foil has unevenness consisting of protrusions and depressions formed by falling off of the precipitates during chemical treatment.
００１〜０．０２重量％、 酸素：０．００２０重量％以下、 を含有し、残りが銅および不可避不純物からなる組成で
あることを特徴とする請求項１記載のフィルムキャリア
用圧延銅合金箔。(2) Zr: 0.005-0.23% by weight, Mg: 0.
2. The rolled copper alloy foil for a film carrier according to claim 1, wherein the rolled copper alloy foil contains: 0.001 to 0.02% by weight, and 0.0020% by weight or less of oxygen, with the remainder consisting of copper and unavoidable impurities.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2185950A JP2977870B2 (en) | 1990-07-13 | 1990-07-13 | Rolled copper alloy foil for film carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2185950A JP2977870B2 (en) | 1990-07-13 | 1990-07-13 | Rolled copper alloy foil for film carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0474837A true JPH0474837A (en) | 1992-03-10 |
| JP2977870B2 JP2977870B2 (en) | 1999-11-15 |
Family
ID=16179718
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2185950A Expired - Lifetime JP2977870B2 (en) | 1990-07-13 | 1990-07-13 | Rolled copper alloy foil for film carrier |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2977870B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003013156A (en) * | 2001-07-04 | 2003-01-15 | Nippon Mining & Metals Co Ltd | Copper alloy foil for laminate |
| EP1630239A1 (en) | 2004-08-30 | 2006-03-01 | Dowa Mining Co., Ltd. | Copper alloy and method of manufacturing the same |
| US9777348B2 (en) | 2004-03-29 | 2017-10-03 | Akihisa Inoue | Copper alloy and copper alloy manufacturing method |
-
1990
- 1990-07-13 JP JP2185950A patent/JP2977870B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003013156A (en) * | 2001-07-04 | 2003-01-15 | Nippon Mining & Metals Co Ltd | Copper alloy foil for laminate |
| US9777348B2 (en) | 2004-03-29 | 2017-10-03 | Akihisa Inoue | Copper alloy and copper alloy manufacturing method |
| EP1630239A1 (en) | 2004-08-30 | 2006-03-01 | Dowa Mining Co., Ltd. | Copper alloy and method of manufacturing the same |
| US7563408B2 (en) | 2004-08-30 | 2009-07-21 | Dowa Metaltech Co., Ltd. | Copper alloy and method of manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2977870B2 (en) | 1999-11-15 |
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