JPH02225684A - Smut removing agent for copper or copper alloy and method for removing smut - Google Patents
Smut removing agent for copper or copper alloy and method for removing smutInfo
- Publication number
- JPH02225684A JPH02225684A JP4830289A JP4830289A JPH02225684A JP H02225684 A JPH02225684 A JP H02225684A JP 4830289 A JP4830289 A JP 4830289A JP 4830289 A JP4830289 A JP 4830289A JP H02225684 A JPH02225684 A JP H02225684A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- smut
- acid
- copper alloy
- soln
- 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
- 239000010949 copper Substances 0.000 title claims abstract description 41
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 39
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims description 20
- 239000002253 acid Substances 0.000 claims abstract description 15
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 8
- 230000007935 neutral effect Effects 0.000 claims abstract description 7
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000007513 acids Chemical class 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 150000003009 phosphonic acids Chemical class 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 abstract description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 abstract description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 abstract description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 abstract description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007654 immersion Methods 0.000 abstract description 2
- 239000011975 tartaric acid Substances 0.000 abstract description 2
- 235000002906 tartaric acid Nutrition 0.000 abstract description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 abstract 2
- 239000004471 Glycine Substances 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000003822 epoxy resin Substances 0.000 description 12
- 229920000647 polyepoxide Polymers 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 210000001525 retina Anatomy 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004381 surface treatment Methods 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/103—Other heavy metals copper or alloys of copper
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
【発明の詳細な説明】
髪皇上立■皿光互
本発明は、銅又は銅合金の表面に形成されたスマットの
除去剤及び該除去剤を用いたスマットの除去方法に関し
、更に詳述すると、プリント配線基板上の綱のスマット
を除去する場合などに好適なスマット除去剤及び除去方
法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an agent for removing smut formed on the surface of copper or copper alloy, and a method for removing smut using the agent. The present invention relates to a smut remover and a removal method suitable for removing smut from ropes on printed wiring boards.
の び が しようとする
近年、エレクトロニクス機器の高機能化、低コスト化の
中でプリント基板の高密度化が進むに伴い１図面に示し
たようなガラスエポキシ樹脂板１の内部に内層銅２，２
．外面に外層銅３．３をそれぞれ有し、スルーホール４
，４を形成した多層プリント基板が多用されるようにな
ってきている。In recent years, with the increasing functionality and cost reduction of electronics equipment, the density of printed circuit boards has become higher.As shown in Figure 1, an inner layer of copper 2, 2
．． Each has an outer layer copper 3.3 on the outer surface and a through hole 4.
, 4 are increasingly being used.
従来、このようなプリント基板を製造する方法として、
内部に内層銅を埋設したガラスエポキシ樹脂板の両面に
それぞれ一面に銅めっきを施したアルミニウム板を該銅
めっき層がガラスエポキシ樹脂板側になるように挾んだ
積層板を使用し、配線を形成する場合、アルミニウム板
を水酸化ナトリウム溶液により溶解除去してガラスエポ
キシ樹脂板上に銅めっき層を残し、次いでレジスト膜の
形成処理或いはフィルムラミネート処理、めっき処理、
エツチング処理などを行なってプリント回路板を得ると
いう方法が知られている。この銅めっき暦を形成したア
ルミニウム板でガラスエポキシ樹脂板を挾んだ積層板を
用いる方法は、所謂銅張積層板を用いる場合に比べて外
層網の厚さを薄くし得る利点があるものである。Conventionally, as a method for manufacturing such printed circuit boards,
Wiring is carried out using a laminate consisting of a glass epoxy resin plate with an inner layer of copper embedded inside, and an aluminum plate with copper plating on both sides, sandwiched between the copper plated layers facing the glass epoxy resin plate. When forming, the aluminum plate is dissolved and removed with a sodium hydroxide solution to leave a copper plating layer on the glass epoxy resin plate, and then resist film formation processing, film lamination processing, plating processing,
A method is known in which a printed circuit board is obtained by performing an etching process or the like. This method of using a laminate in which a glass epoxy resin plate is sandwiched between copper-plated aluminum plates has the advantage that the thickness of the outer layer can be made thinner than when using a so-called copper-clad laminate. be.
しかしながら、アルミニウム板を水酸化ナトリウム溶液
で溶解除去した場合は、網上にスマットが形成され易い
、この場合、アルミニウム板の溶解除去液として酸性液
を使用すればスマットの形成量は少なくなる。しかし、
Ｒとガラスエポキシ樹脂とを接着する場合、その接着性
を向上させるため、銅の表面に黒色酸化銅処理を行なっ
て銅の表面に緻密な酸化膜を形成することが通常行なわ
れており、この酸化膜は酸によって侵され易いため、酸
性液を使用してアルミニウム板を溶解すると、酸性液が
スルーホールから銅とガラスエポキシ樹脂との接着界面
に侵入して酸化膜を溶解し。However, when the aluminum plate is dissolved and removed with a sodium hydroxide solution, smut is likely to be formed on the screen. In this case, if an acidic solution is used as the solution for dissolving and removing the aluminum plate, the amount of smut formed will be reduced. but,
When adhering R and glass epoxy resin, in order to improve the adhesion, the copper surface is usually treated with black copper oxide to form a dense oxide film on the copper surface. The oxide film is easily attacked by acid, so when an acidic liquid is used to dissolve the aluminum plate, the acidic liquid enters the adhesive interface between the copper and glass epoxy resin through the through holes and dissolves the oxide film.
接着性を阻害する場合がある。このため、酸性液は使用
し難く、従ってスマット形成が多くなるが、水酸化ナト
リウム溶液を使用してアルミニウム板を溶解することが
行なわれている。May inhibit adhesion. For this reason, it is difficult to use acidic liquids, which results in increased smut formation, but sodium hydroxide solution is used to dissolve the aluminum plate.
この網上のスマットは、Ｃｕ及びＣｕ中に不純物として
含まれる金属元素の水酸化物、ｌ！１化物やＳｉｏ、な
どからなるものであるが、従来この飼」−のスマットを
除去する方法としては、超音波洗浄やブラッシングによ
り機械的に除去するか、又は過硫酸ソーダ＋硫酸、過酸
化水素水十硫酸、塩酸。The smut on this network is composed of Cu and the hydroxides of metal elements contained in Cu as impurities, l! Conventional methods for removing smut include mechanically using ultrasonic cleaning or brushing, or using sodium persulfate + sulfuric acid or hydrogen peroxide. Water, decasulphuric acid, hydrochloric acid.
塩酸＋塩化第２銅等の酸性洗浄液に浸漬する方法が採用
されている。しかし、超音波洗浄やブラッシングといっ
た機械的洗浄法では微小領域のスマットが除去しきれな
い場合があり、また複雑な機械設備を必要とし、製造工
程も複雑になるという問題がある。一方、酸性洗浄液に
浸漬する方法は良好な洗浄は行なわれるものの、上述し
たように内層銅及び外層網とガラスエポキシ樹脂との界
面から酸が侵入し、上記黒色酸化銅処理により形成した
銅表面の酸化膜が侵され、銅とガラスエポキシ樹脂との
接着性が阻害される場合がある。A method of immersing in an acidic cleaning solution such as hydrochloric acid + cupric chloride is adopted. However, mechanical cleaning methods such as ultrasonic cleaning and brushing may not be able to completely remove smut in minute areas, and they also require complicated mechanical equipment, which complicates the manufacturing process. On the other hand, although the method of immersing in an acidic cleaning solution performs good cleaning, as mentioned above, acid enters from the interface between the inner layer copper, the outer layer network, and the glass epoxy resin, and the copper surface formed by the black copper oxide treatment is The oxide film may be attacked and the adhesion between copper and glass epoxy resin may be impaired.
本発明は、上記事情に鑑みなされたもので、銅表面のス
マットを良好かつ簡単に除去することができ、しかもプ
リント基板の銅表面のスマットを除去する場合に、外、
内層銅の黒色酸化銅処理部を侵すことがない中性乃至ア
ルカリ性の銅のスマット除去剤及びスマット除去方法を
提供することを目的とする。The present invention has been made in view of the above circumstances, and it is possible to effectively and easily remove smut on a copper surface, and when removing smut on a copper surface of a printed circuit board,
It is an object of the present invention to provide a neutral to alkaline copper smut removal agent and a smut removal method that do not attack the black copper oxide treated portion of the inner copper layer.
を するための手 及び作
本発明者は、上記目的を達成するため、鋭意検討を行な
った結果、銅表面をオキシカルボン酸。In order to achieve the above object, the inventors of the present invention conducted intensive studies and found that the copper surface was coated with oxycarboxylic acid.
アミノカルボン酸及びホスホン酸から選ばれる酸のアン
モニウム塩の１種又は２種以上の混合物を含む中性乃至
アルカリ性水溶液で処理することにより、網上のスマッ
トを良好に除去することができることを見い出し１本発
明を完成したものである。Finding 1: Smut on a screen can be effectively removed by treatment with a neutral to alkaline aqueous solution containing one or a mixture of two or more ammonium salts of acids selected from aminocarboxylic acids and phosphonic acids. This completes the present invention.
以下、本発明につき、更に詳しく説明する。The present invention will be explained in more detail below.
本発明の綱のスマット除去剤は、オキシカルボン酸、ア
ミノカルボン酸及びホスホン酸から選ばれる酸のアンモ
ニウム塩の１種又は２種以」―を含有する中性乃至アル
カリ性水溶液からなるものである。The smut remover of the present invention consists of a neutral to alkaline aqueous solution containing one or more ammonium salts of acids selected from oxycarboxylic acids, aminocarboxylic acids, and phosphonic acids.
ここで、上記オキシカルボン酸としては、酒石酸、クエ
ン酸、リンゴ酸等が挙げられ、アミノカルボン酸として
は、エチレンジアミンテトラ酢酸（ＥＤＴＡ）、ヒドロ
キシエチルエチレンジアミントリ酢酸（ＨＥＤＴＡ）、
ニトリロトリ酢酸（ＮＴＡ）。Here, examples of the oxycarboxylic acid include tartaric acid, citric acid, malic acid, etc., and examples of the aminocarboxylic acid include ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA),
Nitrilotriacetic acid (NTA).
グリシン等が挙げられ、ホスホン酸としては、１−ヒド
ロキシエチリデン−１，１−ジホスホン酸、アミノトリ
（メチレンホスホン酸）等を挙げることができ、これら
のアンモニウム塩の１種又は２種以上の混合物の中性乃
至アルカリ性水溶液がスマット除去剤として使用される
。なお、これらアンモニウム塩の濃度は２０〜１００ｇ
／Ｑ、特に３０〜６０ ｇ ／ Ｑとすることが好まし
く、２０ｇ／Ｑ未満であると洗浄効率が悪く、処理時間
が長くなり、一方１００ ｇ ／ Ｑを超えても特に効
果の向上は見られず、コストメリットが生じない。Examples of the phosphonic acid include 1-hydroxyethylidene-1,1-diphosphonic acid and aminotri(methylenephosphonic acid). A neutral to alkaline aqueous solution is used as the smut remover. The concentration of these ammonium salts is 20 to 100 g.
/Q, especially 30 to 60 g/Q is preferable; if it is less than 20 g/Q, the cleaning efficiency will be poor and the processing time will become long, while if it exceeds 100 g/Q, no particular improvement in the effect will be observed. Therefore, there is no cost advantage.
また、このスマット除去剤は通常アンモニウム塩の形の
ものを水に溶解して得られるが、酸のままで水に溶解し
、アンモニア水で中和して用いることもできる。なお、
好適なメイは７〜１２、より好ましくは８〜９である。Further, this smut remover is usually obtained by dissolving an ammonium salt in water, but it can also be used by dissolving it in water as an acid and neutralizing it with aqueous ammonia. In addition,
A suitable number is 7-12, more preferably 8-9.
本発明のスマットの除去方法は、上記除去剤で銅又は銅
合金表面を処理するものであるが、その処理方法として
は、特に限定されないが、銅又は銅合金を含む被処理物
を上記スマット除去剤中に浸漬する方法やスプレー法な
どが好適に採用され、この場合液温は３０〜８０℃、特
に４０〜６０℃とすることが好ましく、また処理時間は
スマッ１−の程度にもよるが通常２〜１０分、はとんど
は５分程度で十分である。The method for removing smut of the present invention is to treat the surface of copper or copper alloy with the above-mentioned removing agent, but the treatment method is not particularly limited, but the method for removing smut from the object containing copper or copper alloy is as follows. Methods such as immersion in the agent or spray method are preferably adopted, and in this case, the liquid temperature is preferably 30 to 80°C, particularly 40 to 60°C, and the treatment time depends on the degree of smearing. Usually 2 to 10 minutes, usually about 5 minutes is sufficient.
なお、本発明のスマット除去剤及び除去方法は、プリン
ト配線基板上の銅のスマット除去に好適に利用されるほ
か、例えば、銅や銅合金にめっき等の表面処理を施す場
合の前処理として行なわれるスマット除去にも利用する
ことができ、その他網や銅合金上のスマットを除去する
方法として広く使用し得るものである。The smut removal agent and removal method of the present invention can be suitably used to remove smut from copper on printed wiring boards, and can also be used, for example, as a pretreatment when surface treatment such as plating is applied to copper or copper alloys. It can also be used to remove smut from other surfaces such as nets and copper alloys.
又皿朶刀１
本発明の銅又は銅合金のスマット除去剤及び該除去剤を
用いたスマット除去方法によれば、銅又は銅合金表面に
付着したスマットを良好かつ簡単に除去することができ
、しかもプリント基板の飼上のスマット除去に採用した
場合には、外、内層銅の黒色酸化銅処理部を侵すことな
く、また洗浄後のレジスト、フィルムラミネート、エツ
チング等に何らの影響も与えないものである。Further, according to the copper or copper alloy smut removal agent and the smut removal method using the copper or copper alloy smut removal method of the present invention, smut attached to the surface of copper or copper alloy can be effectively and easily removed. Furthermore, when used to remove smut from printed circuit boards, it does not attack the black oxide copper treated areas of the outer and inner copper layers, nor does it have any effect on the resist, film lamination, etching, etc. after cleaning. It is.
以下、実施例及び比較例を示し１本発明を具体的に説明
するが、本発明は下記実施例に＠限されるものではない
。EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
一面側に飼めっきを施し、更にその表面を黒色酸化銅処
理したアルミニウム抜のめっき処理側の面で内部に黒色
酸化銅処理を施した内ＮＩ銅が埋設さ九たガラスエポキ
シ樹脂板を挾み込んで接着することにより、アルミニウ
ムーガラスエポキシ樹脂板を作製した。One side is plated, and the surface is treated with black copper oxide, and the plated side without aluminum is coated with black copper oxide and NI copper is embedded inside.A glass epoxy resin plate is sandwiched between the plates. An aluminum-glass epoxy resin plate was produced by bonding the aluminum and glass together.
次に、このアルミニウムーガラスエポキシ樹脂板の適宜
箇所にスルーホールを形成した後、５０ｇ／Ｑの水酸化
ナトリウム溶液（７０℃）中に浸漬して表面のアルミニ
ウムを溶解除去した。その後第１表に示した各種のスマ
ット除去剤を用いてスマット除去処理を行ない、水洗後
乾燥させ、スマット除去状態を目視により判定した。結
果を第１表に示す。Next, after forming through holes at appropriate locations on this aluminum-glass epoxy resin plate, it was immersed in a 50 g/Q sodium hydroxide solution (70°C) to dissolve and remove the aluminum on the surface. Thereafter, smut removal treatment was performed using various smut removal agents shown in Table 1, washed with water and dried, and the state of smut removal was visually determined. The results are shown in Table 1.
〈判定〉 ◎；スマット全く残らず。<judgement> ◎; No smut remains at all.
０；スマット僅かに残る。0: Slight amount of smut remains.
Δ；スマット少し取れる。Δ; A little smut can be removed.
×；スマット取れず。×; Smut could not be removed.
なお、上記比較例３の３６％塩酸を用いて処理したプリ
ント基板は黒色酸化網膜が侵されていることが認められ
た。一方、実施例のものは黒色酸化網膜を侵すことのな
いものであった。In addition, it was observed that the black oxidized retina of the printed circuit board treated with 36% hydrochloric acid in Comparative Example 3 was attacked. On the other hand, those of Examples did not attack the black oxidized retina.
図面は、ガラスエポキシ銅張積層プリント配線基板を示
す断面図である。
■・・・ガラスエポキシ樹脂板 ２・・・内 層 銅３
・・・外 層 銅 ４・・・スルーホール出
願人 上 村 工 業 株式会社
代理人 弁理士 小 島 隆 司The drawing is a sectional view showing a glass epoxy copper-clad laminated printed wiring board. ■...Glass epoxy resin plate 2...Inner layer copper 3
...Outer layer copper 4...Through hole Applicant Uemura Kogyo Co., Ltd. Agent Patent attorney Takashi Kojima
Claims (2)
酸から選ばれる酸のアンモニウム塩の１種又は２種以上
を含有する中性乃至アルカリ性水溶液からなる銅又は銅
合金のスマット除去剤。1. A smut remover for copper or copper alloys comprising a neutral to alkaline aqueous solution containing one or more ammonium salts of acids selected from oxycarboxylic acids, aminocarboxylic acids, and phosphonic acids.
を処理することを特徴とする銅又は銅合金のスマット除
去方法。2. A method for removing smut from copper or copper alloy, comprising treating the surface of copper or copper alloy with the smut removal agent according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4830289A JPH02225684A (en) | 1989-02-27 | 1989-02-27 | Smut removing agent for copper or copper alloy and method for removing smut |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4830289A JPH02225684A (en) | 1989-02-27 | 1989-02-27 | Smut removing agent for copper or copper alloy and method for removing smut |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02225684A true JPH02225684A (en) | 1990-09-07 |
Family
ID=12799638
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4830289A Pending JPH02225684A (en) | 1989-02-27 | 1989-02-27 | Smut removing agent for copper or copper alloy and method for removing smut |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02225684A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992016017A1 (en) * | 1991-02-28 | 1992-09-17 | Mitsubishi Gas Chemical Company, Inc. | Cleaning liquid for semiconductor substrate |
| WO2003002688A1 (en) * | 2001-06-29 | 2003-01-09 | Ashland Inc. | Process for removing contaminant from a surface and composition useful therefor |
-
1989
- 1989-02-27 JP JP4830289A patent/JPH02225684A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992016017A1 (en) * | 1991-02-28 | 1992-09-17 | Mitsubishi Gas Chemical Company, Inc. | Cleaning liquid for semiconductor substrate |
| US5302311A (en) * | 1991-02-28 | 1994-04-12 | Mitsubishi Gas Chemical Company, Inc. | Cleaning solution of semiconductor substrate |
| WO2003002688A1 (en) * | 2001-06-29 | 2003-01-09 | Ashland Inc. | Process for removing contaminant from a surface and composition useful therefor |
| KR100804353B1 (en) * | 2001-06-29 | 2008-02-15 | 에어 프로덕츠 앤드 케미칼스, 인코오포레이티드 | Process for Removing Contaminant from a Surface and Composition Useful Therefor |
| US7524801B2 (en) | 2001-06-29 | 2009-04-28 | Air Products And Chemicals, Inc. | Process for removing contaminant from a surface and composition useful therefor |
| US7700534B2 (en) | 2001-06-29 | 2010-04-20 | Air Products And Chemicals, Inc. | Process for removing contaminant from a surface and composition useful therefor description |
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