EP0053719A1 - Procédé pour le décapage de surfaces métalliques - Google Patents

Procédé pour le décapage de surfaces métalliques Download PDF

Info

Publication number: EP0053719A1
Authority: EP; European Patent Office
Prior art keywords: solution; etching; copper; hydrogen peroxide; etching solution
Prior art date: 1980-12-10
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

Application number

EP81109230A

Other languages

German (de)

English (en)

Other versions

EP0053719B1 (fr

Inventor

Dieter C. Ing. Grad. Schmid

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Gebrueder Schmid GmbH and Co

Original Assignee

Gebrueder Schmid GmbH and Co

Priority date (The priority date 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 date listed.)

1980-12-10

Filing date

1981-10-29

Publication date

1982-06-16

Family has litigation

First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6118774&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0053719(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.

1981-10-29 Application filed by Gebrueder Schmid GmbH and Co filed Critical Gebrueder Schmid GmbH and Co

1982-06-16 Publication of EP0053719A1 publication Critical patent/EP0053719A1/fr

1987-09-09 Application granted granted Critical

1987-09-09 Publication of EP0053719B1 publication Critical patent/EP0053719B1/fr

Status Expired legal-status Critical Current

Links

238000005530 etching Methods 0.000 title claims abstract description 60
238000000034 method Methods 0.000 title claims abstract description 36
239000002184 metal Substances 0.000 title claims abstract description 9
229910052751 metal Inorganic materials 0.000 title claims abstract description 9
MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 30
229910052802 copper Inorganic materials 0.000 claims abstract description 18
239000010949 copper Substances 0.000 claims abstract description 18
RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 17
QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 8
229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 4
238000001816 cooling Methods 0.000 claims description 6
229910000365 copper sulfate Inorganic materials 0.000 claims description 6
ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
230000001376 precipitating effect Effects 0.000 claims description 3
239000000243 solution Substances 0.000 description 29
150000002978 peroxides Chemical class 0.000 description 18
239000007921 spray Substances 0.000 description 5
238000003421 catalytic decomposition reaction Methods 0.000 description 4
238000006243 chemical reaction Methods 0.000 description 4
239000000203 mixture Substances 0.000 description 4
239000007800 oxidant agent Substances 0.000 description 4
239000002253 acid Substances 0.000 description 3
239000000654 additive Substances 0.000 description 3
238000000354 decomposition reaction Methods 0.000 description 3
238000005868 electrolysis reaction Methods 0.000 description 3
239000000463 material Substances 0.000 description 3
VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
239000004922 lacquer Substances 0.000 description 2
229920002120 photoresistant polymer Polymers 0.000 description 2
239000000126 substance Substances 0.000 description 2
RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
229910019142 PO4 Inorganic materials 0.000 description 1
QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
239000003929 acidic solution Substances 0.000 description 1
ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
229910001870 ammonium persulfate Inorganic materials 0.000 description 1
230000015572 biosynthetic process Effects 0.000 description 1
239000003795 chemical substances by application Substances 0.000 description 1
230000008021 deposition Effects 0.000 description 1
230000018109 developmental process Effects 0.000 description 1
239000007789 gas Substances 0.000 description 1
230000020169 heat generation Effects 0.000 description 1
LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
239000007788 liquid Substances 0.000 description 1
150000002739 metals Chemical class 0.000 description 1
230000003647 oxidation Effects 0.000 description 1
238000007254 oxidation reaction Methods 0.000 description 1
235000021317 phosphate Nutrition 0.000 description 1
150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
YXJYBPXSEKMEEJ-UHFFFAOYSA-N phosphoric acid;sulfuric acid Chemical compound OP(O)(O)=O.OS(O)(=O)=O YXJYBPXSEKMEEJ-UHFFFAOYSA-N 0.000 description 1
238000001556 precipitation Methods 0.000 description 1
230000008929 regeneration Effects 0.000 description 1
238000011069 regeneration method Methods 0.000 description 1
238000007650 screen-printing Methods 0.000 description 1
238000011144 upstream manufacturing Methods 0.000 description 1
239000002351 wastewater Substances 0.000 description 1
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1

Images

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
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- 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
- C23F1/46—Regeneration of etching compositions

Definitions

the invention relates to a method for etching metal surfaces, in particular printed circuits, as specified in the preamble of claim 1.
etching with copper chloride and regeneration with hydrochloric acid / hydrogen peroxide or chlorine gas are known.
etching is generally carried out using ammoniacal-alkaline etching agents; iron-III chloride or ammonium persulfate is also used in special cases.
the copper sulfate formed in this reaction is more suitable than copper chloride for further use. There is also the possibility of creating a closed cycle without waste water problems within the etching process and of recovering the etched copper.
the copper is preferably removed electrolytically from the etching solution.
the copper is removed from the etching solution by cooling the etching solution and thereby precipitating copper sulfate.
etching solution and the hydrogen peroxide are sprayed separately onto the circuit to be etched.
any contact between the peroxide and the etched-off copper in the etching solution is reliably avoided before the substances meet in the reaction area.
the etching process of the printed circuit boards, which are coated with copper, a lacquer, photoresist material or metal resist such as lead tin, between guide rollers 1 in the horizontal direction takes place in the interior of a housing 2, which has a collecting container 3 for the etching solution dripping from the printed circuit boards below the feed path of the printed circuit boards.
the printed circuit boards are inserted along the feed path formed by the guide rollers 1 into the housing 2 and leave it again on the opposite side.
stations for pretreatment and stations for post-treatment of the printed circuit boards are connected upstream or downstream of the etching housing.
the hydrogen peroxide is added to the etching solution only shortly before it is applied to the circuit to be etched or even only during the application, in an amount which is sufficient for the respective etching process, but which is so it is small that after the etching process, the solution dripping from the circuit contains essentially no more peroxide.
the amount of peroxide added is relatively easy to adjust and regulate.
This method has the advantage that catalytic decomposition of the peroxide in the etching solution collected after the etching process can no longer take place since there is practically no peroxide in this etching solution.
the etching solution can therefore be pumped back into a storage tank in a manner known per se and used again for a new etching process. Nevertheless, the etching process proceeds in the desired manner, because in the reaction area, i.e. on the circuit, the required amount of peroxide is added to the etching solution, so that the desired decomposition of the peroxide, oxidation of the metal and etching of the copper take place here.
the etched copper is at least partially removed from the etching solution after each etching process.
sulfuric acid phosphoric acid can also be used, in which case corresponding phosphates are formed.
This etchant can be fed directly to the collecting container 11 and applied again to the printed circuit boards by means of the pump 12 with the addition of the appropriate amount of the peroxide.
This procedure also has the advantage that the etching solution supplied to the collecting container 11 contains little copper, so that when this low-copper etching solution is mixed with peroxide from the storage container, the catalytic decomposition of the peroxide is reduced. It is quite possible To apply the etching solution to the printed circuit boards, there are spray nozzles 4 and 5 above and below the feed path, from which the etching solution can be sprayed against the printed circuit board.
the etching solution collected in the collecting container 3 is fed by means of a suitable pump 6 via a line 7 either to an electrolysis vessel 8 or to a cooling station 9. After passing through the electrolysis vessel or the cooling station, a pump 10 conveys the etching solution into a collecting container 11.
the etching solution is fed from this collecting container 11 to the spray nozzles 4 and 5 via a line 13 by means of a pump 12.
this is fed from a storage container for oxidizing agent separated from the collecting container 11 by means of a pump 15 to the line 13, so that a mixture of the etching solution and the oxidizing agent is sprayed onto the printed circuit boards through the spray nozzles. It is also possible to spray the oxidizing agent evenly through separate nozzles.
the oxidizing agent in the storage container 14 is hydrogen peroxide.
the acid gets onto the circuit boards together with the hydrogen peroxide.
the etching process there follows the following formulas: Lich to produce the mixture of etching solution and peroxide shortly before it is applied to the printed circuit boards and sprayed through common nozzles.

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)
ing And Chemical Polishing (AREA)
Manufacturing Of Printed Circuit Boards (AREA)

EP81109230A 1980-12-10 1981-10-29 Procédé pour le décapage de surfaces métalliques Expired EP0053719B1 (fr)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
DE3046477		1980-12-10
DE19803046477 DE3046477A1 (de)	1980-12-10	1980-12-10	"verfahren zum aetzen von metalloberflaechen"

Publications (2)

Publication Number	Publication Date
EP0053719A1 true EP0053719A1 (fr)	1982-06-16
EP0053719B1 EP0053719B1 (fr)	1987-09-09

Family

ID=6118774

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP81109230A Expired EP0053719B1 (fr)	1980-12-10	1981-10-29	Procédé pour le décapage de surfaces métalliques

Country Status (2)

Country	Link
EP (1)	EP0053719B1 (fr)
DE (2)	DE3046477A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
EP0222347A3 (fr) *	1985-11-11	1988-11-30	HANS HÖLLMÜLLER MASCHINENBAU GMBH & CO.	Procédé et appareil pour le décapage de pièces composées au moins partiellement de métal, de préférence de cuivre
EP0222348A3 (fr) *	1985-11-11	1989-01-25	HANS HÖLLMÜLLER MASCHINENBAU GMBH & CO.	Appareil de décapage de pièces composées au moins partiellement de métal, de préférence de cuivre
WO1993010280A1 (fr) *	1991-11-13	1993-05-27	Hughes Aircraft Company	Procede et dispositif de decontamination
US5244000A (en) *	1991-11-13	1993-09-14	Hughes Aircraft Company	Method and system for removing contaminants
WO1997016379A1 (fr) *	1995-10-30	1997-05-09	Chemasol Spol.S.R.O.	Procede de production de monohydrate de sulfate cuivrique
EP0885985A1 (fr) *	1997-05-05	1998-12-23	Akzo Nobel N.V.	Procédé de traitement d'un métal
RU2131484C1 (ru) *	1997-05-05	1999-06-10	Акцо Нобель Н.В.	Способ обработки металла
US5958147A (en) *	1997-05-05	1999-09-28	Akzo Nobel N.V.	Method of treating a metal
DE102017128630A1 (de) *	2017-12-01	2019-06-19	Wen Yao Chang	Leiterplatte mit einem siliziumsubstrat und fertigungsverfahren dafür

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
DE4206626A1 (de) *	1992-03-03	1993-09-09	Heidelberger Druckmasch Ag	Verfahren zur verringerung von dublieren beim anlaufen einer bogendruckmaschine
DE4402788A1 (de) *	1994-01-31	1995-08-10	Emil Krechen Industrievertretu	Verfahren zum Abtragen von Metallen
DE102013112045A1 (de)	2013-10-31	2015-04-30	Holger Manfred Schmid	Vorrichtung und Verfahren zur Bearbeitung von metallischen Oberflächen mit einer Ätzflüssigkeit

Citations (5)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
GB1176892A (en) *	1965-04-28	1970-01-07	Fmc Corp	Reactivation of Etching Solutions
DE1906304A1 (de) *	1969-02-08	1970-09-03	Wiederhold Fa Hermann	Verfahren und Vorrichtung zum kontinuierlichen AEtzen
US3756957A (en) *	1971-03-15	1973-09-04	Furukawa Electric Co Ltd	Solutions for chemical dissolution treatment of metallic materials
DE2358683A1 (de) *	1973-11-24	1975-06-05	Kalman Von Dipl Phys Soos	Verfahren zum beizen und aetzen von metallen
FR2392100A1 (fr) *	1977-05-27	1978-12-22	Alfachimici Spa	Solution acide pour corrosion selective du cuivre

1980
- 1980-12-10 DE DE19803046477 patent/DE3046477A1/de not_active Withdrawn
1981
- 1981-10-29 DE DE8181109230T patent/DE3176426D1/de not_active Expired
- 1981-10-29 EP EP81109230A patent/EP0053719B1/fr not_active Expired

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
GB1176892A (en) *	1965-04-28	1970-01-07	Fmc Corp	Reactivation of Etching Solutions
DE1906304A1 (de) *	1969-02-08	1970-09-03	Wiederhold Fa Hermann	Verfahren und Vorrichtung zum kontinuierlichen AEtzen
US3756957A (en) *	1971-03-15	1973-09-04	Furukawa Electric Co Ltd	Solutions for chemical dissolution treatment of metallic materials
DE2358683A1 (de) *	1973-11-24	1975-06-05	Kalman Von Dipl Phys Soos	Verfahren zum beizen und aetzen von metallen
FR2392100A1 (fr) *	1977-05-27	1978-12-22	Alfachimici Spa	Solution acide pour corrosion selective du cuivre

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
EP0222347A3 (fr) *	1985-11-11	1988-11-30	HANS HÖLLMÜLLER MASCHINENBAU GMBH & CO.	Procédé et appareil pour le décapage de pièces composées au moins partiellement de métal, de préférence de cuivre
EP0222348A3 (fr) *	1985-11-11	1989-01-25	HANS HÖLLMÜLLER MASCHINENBAU GMBH & CO.	Appareil de décapage de pièces composées au moins partiellement de métal, de préférence de cuivre
WO1993010280A1 (fr) *	1991-11-13	1993-05-27	Hughes Aircraft Company	Procede et dispositif de decontamination
US5244000A (en) *	1991-11-13	1993-09-14	Hughes Aircraft Company	Method and system for removing contaminants
AU651253B2 (en) *	1991-11-13	1994-07-14	Raytheon Company	Method and system for removing contaminants
WO1997016379A1 (fr) *	1995-10-30	1997-05-09	Chemasol Spol.S.R.O.	Procede de production de monohydrate de sulfate cuivrique
EP0885985A1 (fr) *	1997-05-05	1998-12-23	Akzo Nobel N.V.	Procédé de traitement d'un métal
RU2131484C1 (ru) *	1997-05-05	1999-06-10	Акцо Нобель Н.В.	Способ обработки металла
US5958147A (en) *	1997-05-05	1999-09-28	Akzo Nobel N.V.	Method of treating a metal
DE102017128630A1 (de) *	2017-12-01	2019-06-19	Wen Yao Chang	Leiterplatte mit einem siliziumsubstrat und fertigungsverfahren dafür

Also Published As

Publication number	Publication date
DE3176426D1 (en)	1987-10-22
DE3046477A1 (de)	1982-07-08
EP0053719B1 (fr)	1987-09-09

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1982-04-16	PUAI	Public reference made under article 153(3) epc to a published international application that has entered the european phase	Free format text: ORIGINAL CODE: 0009012
1982-06-16	AK	Designated contracting states	Designated state(s): BE CH DE FR GB LU NL SE
1982-07-28	17P	Request for examination filed	Effective date: 19820514
1987-07-25	GRAA	(expected) grant	Free format text: ORIGINAL CODE: 0009210
1987-08-19	RAP1	Party data changed (applicant data changed or rights of an application transferred)	Owner name: GEBR. SCHMID GMBH & CO.
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1988-08-03	26	Opposition filed	Opponent name: HANS HOELLMUELLER MASCHINENBAU GMBH & CO. Effective date: 19880608
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Publication	Publication Date	Title
DE2537757A1 (de)	1976-03-11	Verfahren zum regenerieren einer aetzloesung
EP0053719B1 (fr)	1987-09-09	Procédé pour le décapage de surfaces métalliques
DE2730322C3 (de)	1982-04-29	Verfahren zum Regenerieren stromlos arbeitender Abscheidungsbäder
DE1496808A1 (de)	1970-09-10	Verfahren zur elektrolytischen Entfernung von Zunder oder einer Walzhaut von Metalloberflaechen
DE69219063T2 (de)	1997-11-20	Verfahren zum Regenerieren von Ätzmitteln
DE2306524A1 (de)	1973-08-23	Verfahren zur wiedergewinnung von geloestem metall aus einer aetzloesung unter regenerierung derselben
EP0222347A2 (fr)	1987-05-20	Procédé et appareil pour le décapage de pièces composées au moins partiellement de métal, de préférence de cuivre
DE3208124A1 (de)	1983-09-08	Stripper
DE4241080C1 (de)	1994-02-17	Verfahren zur Überführung von Kupfer aus kupferhaltigen Abwässern in die verbrauchte Kupferchlorid-Ätze aus der Leiterplattenfertigung
DE3506825C2 (fr)	1987-11-12
DE1496906A1 (de)	1970-10-01	Verfahren zum elektrolytischen Entzundern von Eisen und Stahl
DE2943399C2 (de)	1983-12-08	Verfahren und Zusammensetzung zur galvanischen Abscheidung von Palladium
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