JPH02115383A - Oxygen-mixing etching method and spray-type etching device used therefor - Google Patents
Oxygen-mixing etching method and spray-type etching device used thereforInfo
- Publication number
- JPH02115383A JPH02115383A JP26553988A JP26553988A JPH02115383A JP H02115383 A JPH02115383 A JP H02115383A JP 26553988 A JP26553988 A JP 26553988A JP 26553988 A JP26553988 A JP 26553988A JP H02115383 A JPH02115383 A JP H02115383A
- Authority
- JP
- Japan
- Prior art keywords
- etching
- etchant
- spray
- oxygen
- copper
- 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.)
- Pending
Links
- 238000005530 etching Methods 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims description 25
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 30
- 229960003280 cupric chloride Drugs 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 238000005507 spraying Methods 0.000 claims abstract description 7
- 239000007921 spray Substances 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 20
- 239000010949 copper Substances 0.000 claims description 17
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 229910001882 dioxygen Inorganic materials 0.000 claims description 16
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000007789 gas Substances 0.000 abstract description 4
- 125000000129 anionic group Chemical group 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 abstract 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 abstract 1
- 229940112669 cuprous oxide Drugs 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 6
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229940045803 cuprous chloride Drugs 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/08—Apparatus, e.g. for photomechanical printing surfaces
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
- H05K3/068—Apparatus for etching printed circuits
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- ing And Chemical Polishing (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は酸素混合エツチング方法及びその方法に使用す
るスプレー式エツチング装置に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an oxygen mixed etching method and a spray type etching apparatus used in the method.
プリント配線基板、テープキャリア（ＴＡＢ）等の回路
形成用材料として用いられる銅板及び銅箔等をエツチン
グするエツチング方法では、エツチング液として塩化第
二鉄系水溶液、塩化第二銅系水溶液、過硫酸アンモニウ
ム系水溶液、亜塩素酸ナトリウム系水溶液等が使用可能
であるが、近年においては低価格で廃液処理が容易でか
つ溶解した金属の回収が容易であることから塩化第二鉄
系及び塩化第二銅系エツチング液の使用が増加している
。In the etching method for etching copper plates and copper foils used as materials for forming circuits such as printed wiring boards and tape carriers (TAB), ferric chloride-based aqueous solutions, cupric chloride-based aqueous solutions, and ammonium persulfate-based etching solutions are used. Aqueous solutions, sodium chlorite-based solutions, etc. can be used, but in recent years, ferric chloride-based and cupric chloride-based solutions have been used because they are inexpensive, easy to treat waste liquid, and easy to recover dissolved metals. The use of etching solutions is increasing.
従来、塩化第二銅系エツチング液を用いる銅のエツチン
グ方法としては、下記反応式（ａ）、（ハ）に示すよう
に、塩化第二銅が加工部材の構成材である銅と反応して
塩化第一銅スケールが形成され、次いで、該スケールが
塩酸及び過酸化水素との反応により溶解されることによ
って銅のエツチングを行うものが知られている。過酸化
水素はエツチング液を再生するために液中に調合されて
いる酸化剤である。Conventionally, as a copper etching method using a cupric chloride-based etching solution, as shown in reaction formulas (a) and (c) below, cupric chloride reacts with copper, which is a constituent material of the workpiece. It is known to etch copper by forming cuprous chloride scale, which is then dissolved by reaction with hydrochloric acid and hydrogen peroxide. Hydrogen peroxide is an oxidizing agent that is added to the etching solution to regenerate it.
Ｃｕ＋ＣｕＣｌ意→２ＣｕＣ１−・−・（ａＪ２ Ｃｕ
Ｃ１＋ ２ ＨＣＩ ＋Ｉｈ０ｘ−２ＣｕＣ１ｇ
＋ ２８ｚＯ−（ｂ）また上記エツチングを行うに当た
っては従来、エツチング液をスプレーノズルから噴出さ
せて加工部材に吹きつける一般のスプレー式エツチング
装置が使用されている。Cu+CuCl → 2CuC1−・−・(aJ2 Cu
C1+ 2 HCI +Ih0x-2CuC1g
+28zO-(b) Furthermore, in carrying out the above-mentioned etching, conventionally, a general spray type etching apparatus has been used in which an etching liquid is jetted from a spray nozzle onto the workpiece.
この種のエツチングでは、エツチング加工が常にスムー
ズに且つ一定条件で行われるように、塩化第二銅濃度（
通常、２Ｍ程度）、液温等を一定にしてエツチング液を
常に同じ状態に保持させることや、また過酸化水素を一
定に存在させることが必要である。これにより、銅表面
に形成された塩化第一銅スケールを２価の遊離銅イオン
として液中に円滑に溶出させることが可能となる。In this type of etching, the concentration of cupric chloride (
It is necessary to keep the etching solution in the same state at all times by keeping the temperature of the etching solution constant (usually about 2M), and to make hydrogen peroxide exist at a constant level. This allows the cuprous chloride scale formed on the copper surface to be smoothly eluted into the liquid as divalent free copper ions.
しかしながら上記従来のエンチング方法は、特に、過酸
化水素の酸化剤が不足したり或いは存在しない場合、塩
化第一銅スケールが塩素イオンと反応してアニオン錯体
を形成してエツチング液中に溶出可能であるものの、ア
ニオン錯体は銅／エッチャント界面において即座に形成
されるため該錯体が銅表面に物理的に吸着して活性表面
を被覆してしまい、その結果、金属光沢を発するような
りリーンなエツチング加工面が得られないという不具合
があった。このアニオン錯体の銅表面への付着は、銅の
自然電極電位が約０．２ Ｖ ｖｓ、 ＳＣＥであるた
め結局、銅表面が“正”に帯電していることにより起こ
る。However, in the above conventional etching method, especially when the oxidizing agent of hydrogen peroxide is insufficient or absent, cuprous chloride scale reacts with chloride ions to form anionic complexes that can be eluted into the etching solution. However, since anionic complexes form immediately at the copper/etchant interface, the complexes physically adsorb onto the copper surface and coat the active surface, resulting in a lean etching process with metallic luster. There was a problem that the surface could not be obtained. The adhesion of this anion complex to the copper surface occurs because the copper surface is "positively" charged since the natural electrode potential of copper is about 0.2 V vs. SCE.
上述のクリーンなエツチング加工面が得られないという
問題は、特にＴＡＢ用キャリアテープなどのように微細
なパターンを連続処理しなければならないエツチング、
即ち、エツチングすべきパターン面積が多く、溶解すべ
き金属銅量が多いエツチングにおいて多発していた。The above-mentioned problem of not being able to obtain a clean etched surface is particularly important for etching, which requires continuous processing of fine patterns such as carrier tape for TAB.
That is, this phenomenon occurred frequently in etching processes where the pattern area to be etched was large and the amount of metallic copper to be dissolved was large.
また、−従来のエツチング方法では酸化剤として過酸化
水素をエツチング液と調合して供給しているため、エツ
チング液中に溶けた銅（ＩＩ）イオンの触媒作用により
容易に自然分解を起こし、過剰な塩素ガスを発生し、そ
の酸素ガスが泡状となってエツチング液中に混入された
ままとなり、そしてエツチング液を循環させるためのポ
ンプに送られた際にはポンプ内に停留して蓄積されてし
まい、その結果、該ポンプが正常に作動せずエツチング
液の循環を良好に行えなくなる欠点があり、しかもスプ
レーノズルからのエツチング液噴出が均一にできない問
題が生じていた。In addition, - in conventional etching methods, hydrogen peroxide is mixed with the etching solution as an oxidant and supplied, so natural decomposition easily occurs due to the catalytic action of copper (II) ions dissolved in the etching solution, resulting in excessive Oxygen gas remains mixed in the etching solution in the form of bubbles, and when it is sent to the pump that circulates the etching solution, it remains and accumulates inside the pump. As a result, the pump does not operate normally and the etching liquid cannot be circulated properly, and furthermore, the etching liquid cannot be spouted uniformly from the spray nozzle.
本発明は上記の問題点に鑑みなされたもので、過酸化水
素を使用せずに常にクリーンなエツチング加工面が得ら
れ、エツチングを安定してスムーズに行うことができる
エンチング方法と、エツチング液循環のためのポンプ等
の機能を損ねることなく、液の均一な吹きつけ、液の円
滑な循環を行うことができる上記方法に使用するスプレ
ー式エツチング装置を提供することを目的とする。The present invention has been made in view of the above problems, and includes an etching method that can always obtain a clean etched surface without using hydrogen peroxide, and that can perform etching stably and smoothly, and an etching solution circulation method. It is an object of the present invention to provide a spray type etching device for use in the above-mentioned method, which can uniformly spray a liquid and circulate the liquid smoothly without impairing the functions of the pump and the like.
即ち、本発明は、
（１） 金属銅を塩化第二銅でエツチングするエツチ
ング方法において、塩化第二銅系エツチング液を加工部
材に吹きつける直前に該液中に酸素ガスを定量的に送り
込むことを特徴とする酸素混合エツチング方法。That is, the present invention provides the following features: (1) In an etching method of etching metallic copper with cupric chloride, oxygen gas is quantitatively fed into the cupric chloride-based etching liquid immediately before spraying the liquid onto the workpiece. An oxygen mixed etching method characterized by:
（２）塩化第二銅系エツチング液をスプレーノズルから
噴出させて加工部材に吹きつけるエツチング装置におい
て、上記スプレーノズルの吹出口側先端内部に酸素ガス
をエツチング液中に定量的に送り込む供給部を設けてな
ることを特徴とするスプレー式エツチング装置。(2) In an etching device that sprays a cupric chloride-based etching solution from a spray nozzle onto a workpiece, a supply section is provided inside the tip of the spray nozzle on the outlet side to quantitatively feed oxygen gas into the etching solution. A spray etching device characterized by comprising:
を要旨とするものである。The main points are as follows.
以下、本発明の実施例を図面に基づき説明する。 Embodiments of the present invention will be described below based on the drawings.
本発明の酸素混合エツチング方法は、塩化第二銅で金属
鋼をエツチングするに当たり、塩化第二銅系エツチング
液を加工部材に吹きつける直前に該液中に酸素ガスを定
量的に送り込むことを要点とするものである。In the oxygen mixed etching method of the present invention, when etching metal steel with cupric chloride, the key point is to quantitatively feed oxygen gas into the cupric chloride-based etching liquid immediately before spraying it onto the workpiece. That is.
酸素ガスを吹きつけ直前にエツチング液中に送り込むこ
とにより、酸素ガスが必要以上にエツチング液中に混入
した状態となる不具合を解消することができる。また酸
素ガスを定量的に送り込むとは、エツチング加工が円滑
に行われるために必要な酸素を所定量、一定して半強制
的に供給することをいい、これにより塩化第一銅スケー
ルを２価の銅イオンとして安定して溶出させることがで
きる。By sending oxygen gas into the etching solution immediately before spraying, it is possible to eliminate the problem of a state in which more oxygen gas than necessary is mixed into the etching solution. Furthermore, quantitatively feeding oxygen gas refers to supplying a predetermined amount of oxygen necessary for smooth etching processing in a constant semi-forced manner, thereby removing divalent cuprous chloride scale. It can be stably eluted as copper ions.
次に、上記の如き構成からなる酸素混合エツチング方法
に使用する本発明のスプレー式エツチング装置について
詳述する。Next, the spray type etching apparatus of the present invention used in the oxygen mixed etching method having the above-mentioned configuration will be described in detail.
第１図は本発明装置の一実施例を示すものであり、図中
１は装置枠体、２はエツチング液、３はエツチング液を
循環させるためのポンプ、４はエツチング液を移送する
ための配管、５はスプレーノズル、６は加工部材、７は
加工部材を搬送するためのコンベアをそれぞれ示す。FIG. 1 shows an embodiment of the apparatus of the present invention, in which 1 is an apparatus frame, 2 is an etching liquid, 3 is a pump for circulating the etching liquid, and 4 is for transferring the etching liquid. Piping, 5 is a spray nozzle, 6 is a workpiece, and 7 is a conveyor for transporting the workpiece.
本発明のスプレー式エツチング装置は、第２図に示すよ
うにスプレーノズル５の吹出口８側の先端内部に酸素ガ
スをエツチング液中に送り込む供給部９を設けた構成を
有する。上記供給部９をノズル５の先端内部に設けるこ
とにより酸素ガスをエツチング液の噴出直前に該液中に
送り込むことができる。As shown in FIG. 2, the spray type etching apparatus of the present invention has a configuration in which a supply section 9 for feeding oxygen gas into the etching solution is provided inside the tip of the spray nozzle 5 on the outlet 8 side. By providing the supply section 9 inside the tip of the nozzle 5, oxygen gas can be fed into the etching liquid immediately before it is ejected.
供給部９は例えば、第２図の示す如きガス排出孔１０を
穿設してなるキャピラリー１１にて構成され、ノズル先
端内部の所定位置に挿入設置されている。The supply section 9 is composed of, for example, a capillary 11 having a gas discharge hole 10 as shown in FIG. 2, and is inserted into a predetermined position inside the nozzle tip.
キャピラリー１１は特に図示しないが酸素ガスボンベ等
に適宜接続されている。キャピラリーはエツチング液（
特に塩酸等）に腐食されない塩化ビニル樹脂、チタン等
の材質にて形成したり、また多孔質ガラス（ポーラスバ
イコール）などを使用してもよい。Although not particularly shown, the capillary 11 is appropriately connected to an oxygen gas cylinder or the like. The capillary is etched with etching liquid (
In particular, it may be made of a material such as vinyl chloride resin or titanium that is not corroded by hydrochloric acid (hydrochloric acid, etc.), or may be made of porous glass (porous Vycor).
本発明装置はスプレーノズル５からエンチング液２を加
工部材６に吹きつける際、第２図に示すように供給部９
から酸素ガス（実線矢印）がエツチング液（点線矢印）
中に定量的に送り込まれる。When spraying the etching liquid 2 onto the workpiece 6 from the spray nozzle 5, the apparatus of the present invention uses a supply section 9 as shown in FIG.
Oxygen gas (solid line arrow) flows from the etching liquid (dotted line arrow)
Quantitatively sent inside.
吹きつけ後のエツチング液２は回収され、ポンプ３にて
再び配管４を通してノズル５に移送されて循環使用され
る。The etching liquid 2 after being sprayed is recovered and transferred to the nozzle 5 through the piping 4 again by the pump 3 for circulation.
本発明に使用される加工部材は、銅板、銅箔等を基材の
片面又は両面に積層した素材からなり、その金属銅が存
在する表面にレジス）ｌｉｔ！ｆ１２が形成されたもの
である。本発明装置によるエツチング液の吹きつけ終了
後は、水洗工程等の後工程へ移送される。The processed member used in the present invention is made of a material in which a copper plate, copper foil, etc. is laminated on one or both sides of a base material, and there is a resist on the surface where metallic copper is present. f12 is formed. After the etching solution is sprayed by the apparatus of the present invention, the material is transferred to a subsequent process such as a water washing process.
次に、具体的実施例を挙げて本発明を更に詳細に説明す
る。Next, the present invention will be explained in more detail by giving specific examples.
実施例１
長さ２０ｍのポリイミド製キャリアフィルム上に圧延銅
箔をラミネートした構造からなり、該銅箔上に微細パタ
ーンのリード線形成用レジスト層を形成してなる加工部
材を、本発明装置を用いて連続のエツチング加工を行い
、微細パターンのリード線を形成した。エツチング液は
所定の濃度、ｐＨに調整した塩化第二銅水溶液を使用し
、酸素ガスはその混合量を事前に試験片のエツチングを
行い、顕微鏡にてスケールの発泡状態を確認しながらス
ケールが認められなくなるまで混合量を増加させる方法
によって決定してから供給した。Example 1 A workpiece consisting of a rolled copper foil laminated on a polyimide carrier film with a length of 20 m, and a resist layer for forming a fine pattern of lead wires formed on the copper foil, was processed using the apparatus of the present invention. Using this method, continuous etching was performed to form lead wires with fine patterns. The etching solution used was a cupric chloride aqueous solution adjusted to the specified concentration and pH, and the amount of oxygen gas mixed was etched on the test piece in advance, and the scale was confirmed while checking the foaming state of the scale using a microscope. The mixing amount was determined by increasing the mixing amount until it became no longer available.
エツチングが終了した加工部材のエツチング加工面を電
子顕微鏡で観察したところ、表面状態が橿めて平滑であ
り、しかもエッチ精度が高いリードが形成されているこ
とがｎ認された。またＸ線マイクロアナライザー（ＸＭ
Ａ）によるエンチング加工面の元素分析を行った。その
結果を第３図に示す。When the etched surface of the workpiece after etching was observed under an electron microscope, it was found that the surface was smooth and that leads with high etching accuracy were formed. In addition, the X-ray microanalyzer (XM
Elemental analysis of the etched surface according to A) was conducted. The results are shown in FIG.
第３図から明らかなように塩素原子に帰属されるスペク
トルは観測されなかった。尚、図中に於けるＣｕＬＳＣ
ｕｋα、Ｃｕｋβはそれぞれ銅の特性Ｘ線におけるし殻
線、Ｋ殻α線、Ｋ殻β線を示している。As is clear from FIG. 3, no spectrum attributed to chlorine atoms was observed. In addition, CuLSC in the figure
ukα and Cukβ respectively indicate the plasma line, K shell α line, and K shell β line in the characteristic X-ray of copper.
比較例１
実施例１と同様の加工部材を、従来の如く過酸化水素を
エツチング液に調合して行うスプレー式エツチング装置
を用いてエツチング加工を行い、微細パターンのリード
線を形成した。Comparative Example 1 A workpiece similar to that of Example 1 was etched using a conventional spray etching device that mixes hydrogen peroxide with an etching solution to form lead wires with a fine pattern.
このエツチング加工面を実施例１と同じく電子顕微鏡で
観察したところ、表面に結晶状の析出物が数多く付着し
ており、これは塩酸やアンモニア等の洗浄処理を施して
も完全に離脱させることができなかった。また実施例１
と同様の元素分析を行い、その結果を第４図に示す。第
４図から明らかなように塩素原子に帰属されるスペクト
ル（Ｃ！にα）が観測され、上記析出物が塩化物である
ことが裏付けられた。When this etched surface was observed using an electron microscope as in Example 1, it was found that many crystalline precipitates were attached to the surface, which could not be completely removed even by cleaning with hydrochloric acid, ammonia, etc. could not. Also, Example 1
Elemental analysis similar to that was performed and the results are shown in FIG. As is clear from FIG. 4, a spectrum (α in C!) attributed to a chlorine atom was observed, confirming that the precipitate was a chloride.
以上説明したように、本発明のエツチング方法とエツチ
ング装置によれば酸素ガスが定量的にエツチング液に供
給されるため、アニオン錯体等を形成することなく円滑
に塩化第一銅スケールを２価の銅イオンとして溶解させ
ることができ、その結果、クリーンなエツチング加工面
が得られるエツチングをスムーズに且つ安定して行うこ
とが可能となる。この効果は特に、キャリアテープ、プ
リント配線板等における微細パターンエツチングを連続
して行う場合に十二分に発揮される。As explained above, according to the etching method and etching apparatus of the present invention, oxygen gas is quantitatively supplied to the etching solution, so that cuprous chloride scale can be smoothly converted into divalent form without forming anion complexes. It can be dissolved as copper ions, and as a result, it becomes possible to perform etching smoothly and stably to obtain a clean etched surface. This effect is particularly fully exhibited when fine pattern etching on carrier tapes, printed wiring boards, etc. is performed continuously.
また、エツチング液に供給される酸素ガスは該液の吹き
つけ直前に送りこまれるため、エツチングにおける溶解
反応に使用されない不用なガスはエツチング液吹きつけ
と同時に大気中に放出され、その結果、循環させて使用
するエツチング液中に混入されることがないため、過酸
化水素を使用してした従来のようなポンプの機能を損ね
るという問題は生じる虞れがなく、安定したエツチング
液の循環、吹きつけ等を行うことができる。In addition, since the oxygen gas supplied to the etching solution is sent just before the etching solution is sprayed, unnecessary gas that is not used in the dissolution reaction during etching is released into the atmosphere at the same time as the etching solution is sprayed, and as a result, it is circulated. Since it is not mixed into the etching solution used in the etching process, there is no risk of impairing the functionality of conventional pumps that use hydrogen peroxide, and stable etching solution circulation and spraying are possible. etc. can be done.
第１図は本発明装置の一例を示す概略図、第２図はスプ
レーノズルの一例を示す一部断面図、第３図は実施例１
で行ったエツチング加工面の元素分析結果を示すＸＭＡ
スペクトル分布図、第４図は比較例１で行ったエツチン
グ加工面の元素分析結果を示すＸＭＡスペクトル分布図
である。
２・・エツチング液
５・・スプレーノズル
６・・加工部材
８・・吹出口
９・・供給部
第 １
図
第 ３ 図
２θ
第 ２ 図
第 ４
図
８・秋出口
９・・・供給部
手続補正書（自発）
昭和６３年特許願第２６５５３９号
２発明の名称
酸素混合エツチング方法及びその方法に使用するスプレ
ー式エツチング装置
３、補正をする者
事件との関係 特許出願人
住所 東京都新宿区市谷加賀町−丁目１番１号名称 （
２８９）大日本印刷株式会社
代表者北島義俊
４、代理人 〒１０１
住所 東京都千代田区岩本町２−１０−２５、補正命令
の日付
自発補正
６、補正の対象
明細書の発明の詳細な説明の欄
７、補正の内容Fig. 1 is a schematic diagram showing an example of the device of the present invention, Fig. 2 is a partial sectional view showing an example of a spray nozzle, and Fig. 3 is a schematic diagram showing an example of the spray nozzle.
XMA showing the results of elemental analysis of the etched surface
Spectrum distribution diagram, FIG. 4 is an XMA spectrum distribution diagram showing the results of elemental analysis of the etched surface performed in Comparative Example 1. 2...Etching liquid 5...Spray nozzle 6...Working member 8...Blowout port 9...Supply section Fig. 1 Fig. 3 Fig. 2θ Fig. 2 Fig. 4 Fig. 8 Autumn outlet 9...Supply section procedure correction 1986 Patent Application No. 265539 2 Name of the invention Oxygen mixed etching method and spray type etching device used in the method 3 Relationship with the case of the person making the amendment Patent applicant address Kaga Ichigaya, Shinjuku-ku, Tokyo Town-chome 1-1 name (
289) Dainippon Printing Co., Ltd. Representative Yoshitoshi Kitajima 4, Agent 101 Address 2-10-25 Iwamoto-cho, Chiyoda-ku, Tokyo Date of amendment order Voluntary amendment 6 Detailed description of the invention in the specification subject to amendment Column 7, Contents of amendment
Claims (2)
方法において、塩化第二銅系エッチング液を加工部材に
吹きつける直前に該液中に酸素ガスを定量的に送り込む
ことを特徴とする酸素混合エッチング方法。(1) In the etching method of etching metallic copper with cupric chloride, oxygen mixing is characterized by quantitatively feeding oxygen gas into the cupric chloride-based etching liquid immediately before spraying the liquid onto the workpiece. Etching method.
噴出させて加工部材に吹きつけるエッチング装置におい
て、上記スプレーノズルの吹出口側先端内部に酸素ガス
をエッチング液中に定量的に送り込む供給部を設けてな
ることを特徴とするスプレー式エッチング装置。(2) In an etching device that sprays a cupric chloride-based etching solution from a spray nozzle onto a workpiece, a supply unit is provided inside the tip of the spray nozzle on the outlet side to quantitatively feed oxygen gas into the etching solution. A spray etching device characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26553988A JPH02115383A (en) | 1988-10-21 | 1988-10-21 | Oxygen-mixing etching method and spray-type etching device used therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26553988A JPH02115383A (en) | 1988-10-21 | 1988-10-21 | Oxygen-mixing etching method and spray-type etching device used therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02115383A true JPH02115383A (en) | 1990-04-27 |
Family
ID=17418530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26553988A Pending JPH02115383A (en) | 1988-10-21 | 1988-10-21 | Oxygen-mixing etching method and spray-type etching device used therefor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02115383A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05214565A (en) * | 1991-10-18 | 1993-08-24 | Internatl Business Mach Corp <Ibm> | Process for etching lowly reactive material in the presence of higher reactive material |
-
1988
- 1988-10-21 JP JP26553988A patent/JPH02115383A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05214565A (en) * | 1991-10-18 | 1993-08-24 | Internatl Business Mach Corp <Ibm> | Process for etching lowly reactive material in the presence of higher reactive material |
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