EP0119262B1
EP0119262B1
EP0119262B1
J E u r o p European
a i s c h e Patent
s 0 1 1 9 2 6 2
Office ® Publication number:
B1
Office européen des brevets 1
The solution provides an extended life span for stripping of solder alloys or tin from base metals of
copper, nickel or copper alloys including substrates of printed circuit boards.
Brief description of the drawings
Other objects and many of the attendant advantages of this invention will be readily appreciated as the
same becomes better understood by reference to the following detailed description when considered in
connection with the accompanying drawings, in which like reference numerals designate like parts
throughout the figures thereof and where:
Figure 1 is an operational view of the solder stripping solution;
Figure 2A-2E is an operational view of steps of a SMOBC board having been stripped of solder or tin
in the stripper solution and the subsequent application of a solder mask in selected areas; and,
Figure 3A-3D is an operational view of steps of a printed circuit board and the process necessary for
applying the nickel-gold coating in the tab areas.
Sodium meta-nitrobenzene sulfonate is the preferred aromatic nitro compound, but any other water
soluble nitro-substituted aromatic compound is suitable. By example for illustrations only but not limiting,
o, m, and p-nitrochlorobenzenes; o, m, and p-nitrobenzene sulfonic acids; and o, m, and p-nitrobenzoic
acids and mixtures thereof are suitable. The preferred nitro-substituted aromatic compound used is
sodium meta-nitrobenzenesulfonate.
The use of nitric acid as the inorganic acid accelerates the reaction speed such that it doubles the
stripping rate of previously known stripping compositions of similar formulations. The white residue of tin
or lead salts left on the base metal surface is also removed by using nitric acid. Additionally, the use of nitric
acid instead of fluoboric, fluosilicic, or sulfamic greatly increases the stripping rate of the solution, but more
importantly removes the white residue left on the copper surface if nitric acid is not used. Nitric acid is the
preferred inorganic acid, but other acid such as fluoboric, fluosilicic, or sulfamic are suitable if the white
residue left by using these acids alone is removed by a secondary solution. As is known by those familiar
with fluoborate chemistry, boric acid should be present with fluoborate ion so as to negate the effect of free
fluoride if the fluoborate ion disassociates.
Ammonium fluoborate is the preferred source of ammonium and fluoborate ion. Other suitable
sources are common ammonium compounds such as ammonium nitrate, ammonium acetate, ammonium
halides, or ammonium hydroxide and sodium fluoborate, potassium fluoborate, or fluoboric acid.
Additionally, the introduction of ammonium ion causes the lead-tin alloy solder or tin being attacked to
remain in a white and unoxidized condition making it possible for only partial removal of such deposits.
Heretofore this partial removal and subsequent reactivation has not been possible. The addition of
ammonium ion as ammonium fluoborate also has the added benefit of increasing the amount of lead and
tin that can be dissolved before precipitation occurs.
Thiourea per se is the preferred thiourea, but other alkyl and aromatic thioureas are also suitable.
The presence of 3-hydroxyphenol stops the adverse effect of organo-tin compounds causing
premature stoppage of a useful stripping action thereby extending the life of such a stripping solution to be
measured in weeks/months instead of hours. 3-hydroxyphenol is the preferred hydroxyphenol but other
hydroxyphenols and/or their derivatives are suitable for use therein as so determined.
A preferred composition of the components for the solution 10 includes in an aqueous solution to one
liter of water the following:
Mode of operation
The solder stripping non-peroxide solution of the present invention is utilized to strip tin, or tin/lead
alloys for the like solder deposits from a copper substrate such as that laminated on a printed circuit board
or from any like surface particularly, the non-peroxide tin/lead solder removing solution is oriented towards
solder-mask-over-bare copper (SMOBC) printed circuit type boards or for subsequent nickel-gold tab
stripping. In mass production, the solution can be either sprayed onto the particular segment of the printed
circuit or, in the alternative, the end of the board can be dipped into a solution such as that illustrated in the
drawing. The solution strips the tin/lead alloy from the tabs of the printed circuit board until the copper
shows as a pink bright metal. There is no attack on the copper itself. The non-peroxide solder stripping
solution particularly lends itself to spraying as opposed to a dipping procedure. Upon the room
temperature, the solution is recommended for use at 30°C (85°F). Heating can be accomplished with a 316
stainless steel orteflon type heater and the solution can be utilized in a PVC, polyethylene or polypropylene
container. The shelf life of the solution is anticipated to be six months when stored at room temperature in
a cool dry area. Inherently, standard safety equipment is utilized as the solution contains acids as well as
oxidizers. The appearance of the solution is a straw yellow color with little or no odor.
The yield of the non-peroxide solder stripping solution will dissolve 135-165 g/I (18-22 ounces per
gallon) of solder from a 20,32 !-1m (0.0008 inch) of tin/lead in approximately 90 seconds. The load factor can
be up to one foot squared/gallon.
Figure 1 illustrates a non-peroxide solder stripping solution in a suitable container 12 such as PVC,
polyethylene or polypropylene 12. A heater 14 such as a 316 stainless steel or Teflon@ type heater or the
like is utilized. A printed circuit board 16 having a dielectric substrate 18 such as G-10 glass epoxy or the like
includes an etched copper foil 20 thereon having a tin/lead solder plate coating 22. The one end of the
board 24 includes a plurality of circuit traces or tabs 26 which connect to the copper foil circuit.
While the solution lends itself to a dipping operation, the solution also lends itself just as well to a
spraying operation. The solution is clear and the work of stripping is easily visible to the naked eye. The
solution does not leave the solder black at the demarcation line and provides that on stripping the copper
appears pink and bright for the subsequent operation. No residue remains and is particularly useful in the
stripping of plated-through holes. Most importantly, there are no offensive odors given off during the
stripping process of the SMOBC. The stripper will dissolve 135-165 g/I (18-22 ounces per gallon) of
solder over a 20,32 µm (0.0008 inch) of tin/lead in approximately 90 seconds with a load factor up to one
foot squared per gallon. This is at slightly above room temperature at 30°C (85°F). but for reflowed solder a
temperature range of 35-38°C (95-100°F) is suggested. Lower temperatures will result in a corresponding
drop in strip rate. The particular advantage is that there is no significant attack on the base epoxy laminate
or the underlying copper no matter what length of immersion is undertaken. More importantly, the light
powdery residue typically left on the surface of the copper underlay by the prior art peroxide or
non-peroxide type strippers is not present and is absent from the non-peroxide solder stripper solution 10.
Figure 2A-2E is an operational view of steps of a SMOBC process stripped of solder or tin in the
stripper solution. Figure 2A shows the board prior to stripper and Figure 2B shows the copper etching.
Figure 2C shows the solution performing solder or tin stripping. Figure 2D shows the selective solder mark
application in selected areas. Figure 2E shows the areas where the solder mask is not applied and where
the areas are then covered with a layer of molten solder in a solder levelling application step. The solution
10 of the present invention strips in Figure 2C.
Figure 3A-3D is an operational view of steps of using the solder stripping solution on a printed circuit
board and the process necessary for applying a nickel-gold coating to the tabs. Figure 3A shows the PC
board, Figure 3B shows the copper etching, Figure 3C shows the stripping of solder or tin, and Figure 3D
shows the nickel or gold plating.
Specific Examples
Example 1
A 500 ml stripping solution is prepared by adding sodium m-nitrobenzenesulfonate, fluoboric acid, and
thiourea to water, the components being added in an amount to provide the following concentrations:
The resulting solution is divided into two 250 ml portions. The first of these portions, Solution A, is
composed of the above formulation. Solution B contains an added amount of 8 g/1 3-hydroxyphenol. To
both solutions three pieces of 2.54 cmx 12.7 cmxO.16 cm 1"x5"x.062" copper clad laminate which has been
plated with a thickness of 17.78 pm (0.0007") of solder alloy are immersed. Both Solutions A and B stripped
the solder from the copper clad laminate in approximately three minutes leaving only a light white residue.
After two hours, three more pieces of solder plated copper clad laminate were immersed. The solder on the
pieces immersed in Solution A turned a very deep black-yellow color with the solder only being somewhat
removed after 15 minutes. The pieces immersed in Solution B stripped in approximately three minutes with
only the same light white residue being left on the surface of the copper, this residue being easily wiped off.
Solutions A and B were covered and twelve days later more solder plated samples were immersed.
The results were exactly the same as described as for two hours after the introduction of solder alloy into
the solution.
Example 2
A 1000 ml stripping solution is prepared by adding sodium m-nitrobenzenesulfonate, fluoboric acid
and thiourea to water, the components being added in an amount to provide the following concentrations:
The resulting solution is divided into four 250 ml portions. Solution C is composed of the above
formulations with an added 32 ml/I of a 492 g/I solution of a lead fluoborate concentrate. Solution D is
composed of the above formulation with an added 50 ml/I of a 328 g/I stannous fluoborate concentrate.
Solution E is composed of the above formulation with an added 8 g/I of 3-hydroxyphenol and 32 ml/I of a
lead fluoborate concentrate. Solution F is composed of the above formulation with an added 8 g/I of
3-hydroxyphenol and 50 ml/I of a 328 g/I stannous fluoborate concentrate.
The four portions, after mixing were allowed to sit for two hours. After two hours a 2.54 cmx12.7
cmxO.16 cm (1"x5"x.062") piece of solder plated to at thickness of 17.78 11m (0.0007") copper clad laminate
was immersed.
Those samples immersed in Solutions C, E and F were stripped of their solder coating in approximately
three minutes with only a light white residue left on the surface. The solder on the sample immersed in
Solution D turned a very deep black-yellow color with the solder only being somewhat removed after 15
minutes.
Example 3
A 500 ml stripping solution is prepared by adding sodium m-nitrobenzenesulfonate, fluoboric acid,
thiourea, and 3-hydroxyphenol to water, the components being added in an amount to provide the
following concentrations:
The resulting solution is divided into two 250 ml portions. The first of these portions, Solution G, is
composed of the above formulation. Solution H contains an added 9 percent of concentration nitric acid.
To both solutions, three pieces of a 2.54 cmx12.7 cm (1"x5") copper clad laminate which was solder
plated to a thickness of 17.78 µm (0.0007") was immersed. The pieces immersed in Solution G were solder
stripped in approximately three minutes with only a light white residue being left on the copper surface.
The pieces immersed in Solution H were solder stripped in 1-1/2 minutes with no evidence of a
residue of any kind left on the copper surface.
Example 4
A 300 ml stripping solution is prepared by adding sodium m-nitrobenzenesulfonate, thiourea, nitric
acid, and 3-hydroxyphenol to water, the components being added in an amount to provide the following
concentrations:
Example 5
A 300 ml stripping solution is prepared by adding sodium m-nitrobenzenesulfonate, nitric acid and
thiourea to water, the components being added in an amount to provide the following concentrations:
The resulting solution is divided into two 150 ml portions. The first of these portions, Solution L, is
composed of the above formulations. Solution M contains an added amount of 8 g/I 3-hydroxyphenol.
To both solutions three pieces of 2.54 cmx12.7 cmxO.16 cm (1"x5"x.062") copper clad laminate which
has been plated with a thickness of 12.7 pm (0.0005") of tin are immersed. Both Solutions L and M stripped
the tin from the copper clad laminate in approximately 5 minutes leaving only a light white residue. After
three hours, three more pieces of tin plated copper clad laminate were immersed in both solutions. The tin
on the pieces immersed in Solution L turned a deep gray-yellow color with the tin not completely removed
after 20 minutes. The tin on the pieces immersed in Solution M stripped in approximately 5 minutes leaving
only a light white residue.
1. Aqueous solution for the removal of tin or tin-lead alloy solder from a copper or nickel base, said
solution comprising:
a) 20-150 g/I of a nitro-substituted aromatic compound;
b) 0.1-30 g/I of a thiourea selected from thiourea per se, an alkyl thiourea or an aromatic thiourea;
c) 0.1-400 g/I of an inorganic acid; and
d) 0.1-50.0 g/I of a hydroxyphenol providing extended life to the stripping solution.
2. Solution of claim 1 where the organic acid is selected from fluoboric acid, fluosilicic acid, sulfamic
acid and nitric acid.
3. Solution of claim 1 where the inorganic acid comprises nitric acid.
4. Solution of anyone of claims 1 to 3 which also contains an ammonium ion of the formulation NH4X in
the range of 0.1-300 g/I, X being an ion consisting of nitrate, fluoborate, acetate, halogen, or hydroxide.
5. Solution of anyone of claims 1 to 3, which also contains a fluoborate ion of the formulation RBF4 in
the range of 0.1-300 g/I, R being a cation consisting of a hydrogen, ammonium, sodium or potassium ion.
6. Solution of anyone of claim 1 to 5 which also contains boric acid in the range of 2-60 g/I.
7. Non-peroxide solder stripper solution comprising:
a) nitro-substituted aromatic compound of 20-150 g/I;
b) fluoborate compound of 0.1-300 g/I;
c) hydroxyphenol of 0.1-50 g/I;
d) ammonium compound of 0.1-300 g/I;
e) inorganic acid of 0.1-400 g/I;
f) thiourea of 0.1-30 g/I;
g) boric acid of 2-60 g/I; and
h) water to one liter.
8. Solution of anyone of claim 1 to 7, wherein said nitrosubstituted aromatic compound is collected
from o, m, or p-nitrochlorobenzenes, o, m, or p-nitrobenzene sulfonic acids, and o, m, or p-nitrobenzoic
acids.
9. Solution of claim 8, comprising sodium meta-nitrobenzenesulfonate.
10. Solution of claim 7, wherein said ammonium compound is selected from ammonium nitrate,
ammonium halides, ammonium acetate, or ammonium hydroxide in combination with sodium fluoborate,
potassium fluoborate, or fluoboric acid.
11. Solution of claim 10 comprising ammonium fluoborate.
12. Solution of anyone of claim 1 to 7, wherein said hydroxyphenol comprises 3-hydroxyphenol.
13. Solution of claim 8, wherein said inorganic acid is selected from fluoboric acid, fluosilic, sulfamic,
or nitric acid.
14. Solution of claim 8 comprising nitric acid.
15. Solution of claim 8, wherein said thiourea is selected from alkyl and aromatic thiourea.
16. Non-peroxide solder stripping solution comprising:
a) sodium m-nitrobenzenesulfonate of 80 g/I;
b) fluoboric acid-48% of 276 g/I;
c) boric acid of 8 g/I;
d) 3-hydroxyphenol of 8 g/I;
e) ammonium nitrate of 36 g/I;
f) nitric acid 42° Be of 90 ml/I;
g) thiourea of 14 g/I; and
h) to one liter of water.
17. Use of the solution of claim 16 for stripping solder or tin in an SMOBC process.
18. Use of the solution of claim 16 for stripping solder or tin from printed circuit boards in a nickel-gold
process.
1. Wässrige Lösung zur Entfernung von Zinn- oder Zinn-Blei-Legierungslot aus einer Kupfer- oder
Nickelgrundlage, wobei die Lösung umfaßt:
a) 20 bis 150 g/I einer nitrosubstituierten aromatischen Verbindung,
b) 0,1 bis 30 g/I eines Thioharnstoffs, gewählt aus Thioharnstoff, einem Alkylthioharnstoff oder einem
aromatischen Thioharnstoff,
c) 0,1 bis 400 g/I einer anorganischen Säure und
d) 0,1 bis 50,0 g/I eines Hydroxyphenols, das der Abstreiflösung eine verlängerte Haltbarkeit verleiht.
2. Lösung nach Anspruch 1, worin die anorganische Säure aus Fluorborsäure, Fluorkieselsäure,
Sulfaminsäure und Salpetersäure gewählt wird.
3. Lösung nach Anspruch 1, worin die anorganische Säure Salpetersäure umfaßt.
4. Lösung nach einem der Ansprüche 1 bis 3, die ebenfalls ein Ammoniumion der Formel NH4X im
Bereich von 0,1 bis 300 g/I enthält, wobei X ein Nitrat, Fluorborat, Acetat, Halogen oder Hydroxid ist.
5. Lösung nach einem der Ansprüche 1 bis 3, die ebenfalls ein Fluorboration der Formel RBF4 im
Bereich von 0,1 bis 300 g/I enthält, wobei R ein Kation, gewählt aus einem Wasserstoff-, Ammonium-,
Natrium- oder Kaliumion, ist.
6. Lösung nach einem der Ansprüche 1 bis 5, die ebenfalls Borsäure im Bereich von 2 bis 60 g/I enthält.
7. Lotabstreiflösung, die kein Peroxid enthält, umfassend: -
a) 20 bis 150 g/l einer nitrosubstituierten aromatischen Verbindung,
b) 0,1 bis 300 g/I einer Fluorboratverbindung,
c) 0,1 bis 50 g/I Hydroxyphenol,
d) 0,1 bis 300 g/I einer Ammoniumverbindung,
e) 0,1 bis 400 g/I einer anorganischen Säure,
f) 0,1 bis 30 g/I Thioharnstoff,
g) 2 bis 60 g/I Borsäure und
h) Wasser in einer Menge bis zu einem Liter.
8. Lösung nach einem der Ansprüche 1 bis 7, worin die nitrosubstituierte aromatische Verbindung aus
o-, m-, oder p-Nitrochlorbenzolen, o-, m-, oder p-Nitrobenzolsulfonsäure und o-, m-, oder p-Nitrobenzo-
esäure gewählt wird.
9. Lösung nach Anspruch 8, die Natriummetanitrobenzolsulfonat umfaßt.
10. Lösung nach Anspruch 7, worin die Ammoniumverbindung aus Ammoniumnitrat, Ammonium-
halogeniden, Ammoniumacetat oder Ammoniumhydroxid in Kombination mit Natriumfluorborat, Kalium-
fluorborat oder Fluorborsäure gewählt wird.
11. Lösung nach Anspruch 10, die Ammoniumfluorborat umfaßt.
12. Lösung nach einem der Ansprüche 1 bis 7, worin das Hydroxyphenol 3-Hydroxyphenol umfaßt.
13. Lösung nach Anspruch 8, worin die anorganische Säure aus Fluorborsäure, Fluorkieselsäure,
Sulfaminsäure oder Salpetersäure gewählt wird.
14. Lösung nach Anspruch 8, die Salpetersäure umfaßt.
15. Lösung nach Anspruch 8, worin der Thioharnstoff aus Alkyl- und aromatischem Thioharnstoff
gewählt wird.
16. Lotabstreiflösung, die kein Peroxid enthält, umfassend:
a) 80 g/I Natrium-m-Nitrobenzolsulfonat,
b) 276 g/I 48 %ige Fluorborsäure,
c) 8 g/I Borsäure,
d) 8 g/I 3-Hydroxyphenol,
e) 36 g/l Ammoniumnitrat,
f) 90 ml/l Salpetersäure (42° Be),
g) 14 g/I Thioharnstoff und
h) bis zu einem Liter Wasser.
17. Verwendung der Lösung nach Anspruch 16 zum Abstreifen von Lot oder Zinn in einem
SMOBC-Verfahren (Lot-Maske nach bloßem Kupfer-Verfahren).
18. Verwendung der Lösung nach Anspruch 16 zum Abstreifen von Lot oder Zinn aus gedruckten
Schaltungen in einem Nickel-Gold-Verfahren;
1. Solution aqueuse pour l'élimination d'une soudure à l'étain ou d'alliage à l'étain d'un support de
cuivre ou de nickel, ladite solution comprenant:
a) 20 à 150 g/I d'un composé aromatique nitrosubstitué;
b) 0,1 à 30 g/I d'une thiourée sélectionnée parmi la thiourée elle-même, une alkyl thiourée et une
thiourée aromatique;
c) 0,1 à 400 g/I d'un acide inorganique; et
d) 0,1 à 50,0 g/I d'un hydroxyphénol permettant d'accroître la longévité de la solution de dépouillage.
2. Solution selon la revendication 1 dans laquelle l'acide organique est sélectionné parmi l'acide
fluoborique, l'acide fluosilicique, l'acide sulfamique et l'acide nitrique.
3. Solution selon la revendication 1 dans laquelle l'acide inorganique comprend de l'acide nitrique.
4. Solution selon l'une quelconque des revendications 1 à 3 contenant également un ion d'ammonium
de la formule NH4X dans une proportion se situant de 0,1 à 300 g/I, X représentant un ion constitué de
nitrate, fluoborate, acétate, halogène ou hydroxyde.
5. Solution selon l'une quelconque des revendications 1 à 3, qui contient également un ion de
fluoborate de la formule RBF4 dans la proportion de 0,1 à 300 g/l, R étant un cation constitué par un ion
d'hydrogène, d'ammonium, de sodium ou de potassium.
6. Solution selon l'une quelconque des revendications 1 à 5, contenant également de l'acide borique
dans une proportion de 2 à 60 g/I.
7. Solution de dépouillage de soudure sans peroxyde comprenant:
a) 20 à 150 g/I de composé aromatique nitrosubstitué;
b) 0,1 à 300 g/I de composé de fluoborate;
c) 0,1 à 50 g/I d'hydroxyphénol;
d) 0,1 à 300 g/I de composé d'ammonium;
e) 0,1 à 400 g/I d'acide inorganique;
f) 0,1 à 30 g/I de thiourée;
g) 2 à 60 g/I d'acide borique; et
h) une quantité suffisante d'eau pour 1 litre.
8. Solution selon l'une quelconque des revendications 1 à 7, dans laquelle le composé aromatique
nitro-substitué est sélectionné parmi les nitrochlorobenzènes o, m, ou p, les acides nitrobenzène
sulfoniques o, m, ou p, et les acides nitrobenzoïques o, m, ou p.
9. Solution selon la revendication 8, comprenant du méta-nitrobenzène-sulfonate de sodium.
10. Solution selon la revendication 7, dans laquelle ledit composé d'ammonium est sélectionné parmi
le nitrate d'ammonium, les halogénures d'ammonium, l'acétate d'ammonium, ou l'hydroxyde
d'ammonium combiné à du fluoborate sodium, du fluoborate de potassium, ou de l'acide fluoborique.
11. Solution selon la revendication 10 comprenant du fluoborate d'ammonium.
12. Solution selon l'une quelconque des revendications 1 à 7, dans laquelle l'hydroxyphénol comprend
du 3-hydroxyphénol.
13. Solution selon la revendication 8, dans laquelle ledit acide inorganique est sélectionné parmi les
acides fluoborique, fluosilique, sulfamique ou nitrique.
14. Solution selon la revendication 8 comprenant de l'acide nitrique.
15. Solution selon la revendication 8, dans laquelle ladite thiourée est sélectionnée parmi les alkyl
thiourées et les thiourées aromatiques.
16. Solution de dépouillage de soudure sans peroxyde, comprenant:
a) 80 g/I de m-nitrobenzène-sulfonate de sodium;
b) 276 g/I d'acide fluoborique-48%;
c) 8 g/I d'acide borique;
d) 8 g/I de 3-hydroxyphénol;
e) 36 g/I de nitrate d'ammonium;
f) 90 ml/I d'acide nitrique 42° Be;
g) 14 g/I de thiourée; et
h) une quantité suffisante d'eau pour 1 litre.
17. Utilisation de la solution selon la revendication 16 pour le dépouillage de soudure ou d'étain selon
un procédé SMOBC.
18. Utilisation de la solution selon la revendication 16 pour le dépouillage de soudure ou d'étain sur
des cartes de circuits imprimés selon un procédé nickel-or.