U.S. patent number 3,904,430 [Application Number 05/391,258] was granted by the patent office on 1975-09-09 for cleaning process using a non-azeotrope forming contaminated cleaning mixture.
This patent grant is currently assigned to Imperial Chemical Industries Limited. Invention is credited to James William Tipping, Bernard Patrick Whim.
United States Patent |
3,904,430 |
Tipping , et al. |
September 9, 1975 |
Cleaning process using a non-azeotrope forming contaminated
cleaning mixture
Abstract
Printed circuits are cleaned by passing them through a heated
non-azeotropic solvent mixture comprising a halogenated hydrocarbon
solvent preferably fluorochlorohydrocarbons containing two or three
carbon atoms and an auxiliary solvent such as n-butanol, alkoxy
alcohols, or cyclic ethers contained in a sump compartment and then
rinsing them in a similar body of a solvent mixture but containing
a lower proportion of the auxiliary solvent in a rinsing
compartment.
Inventors: |
Tipping; James William
(Runcorn, EN), Whim; Bernard Patrick (Runcorn,
EN) |
Assignee: |
Imperial Chemical Industries
Limited (London, EN)
|
Family
ID: |
10419909 |
Appl.
No.: |
05/391,258 |
Filed: |
August 24, 1973 |
Foreign Application Priority Data
|
|
|
|
|
Sep 7, 1972 [GB] |
|
|
41484/72 |
|
Current U.S.
Class: |
134/11; 134/12;
134/30; 134/38; 134/26; 134/31; 239/106; 510/175; 510/412 |
Current CPC
Class: |
C23G
5/02 (20130101); C11D 7/5018 (20130101); C11D
7/261 (20130101); C11D 7/28 (20130101); C11D
7/263 (20130101); C11D 7/267 (20130101) |
Current International
Class: |
C11D
7/50 (20060101); C23G 5/00 (20060101); C23G
5/02 (20060101); C11D 7/22 (20060101); C11D
7/28 (20060101); C11D 7/26 (20060101); B08b
007/04 (); B08b 003/00 () |
Field of
Search: |
;134/11,12,15,31,26,30,38 ;252/171 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
The Technology of Solvents and Plasticizers; Doolittle; pages
591-599, John Wiley & Sons, Inc.; New York, 1954..
|
Primary Examiner: Bashore; S. Leon
Assistant Examiner: Alvo; M. Steven
Attorney, Agent or Firm: Cushman, Darby & Cushman
Claims
What we claim is:
1. A method of cleaning a contaminated article which comprises
contacting the article with a first contaminated liquid mixture
which is heated to at least 30.degree.C., removing contamination
from the article and accumulating the removed contamination in the
first liquid mixture, said first liquid mixture containing a
fluorinated hydrocarbon solvent and an organic auxiliary solvent
which together form a non-azeotrope-forming mixture and wherein the
concentration of the auxiliary solvent in the mixture is at least
2.5 parts by weight per hundred parts of the fluorinated
hydrocarbon solvent, and subsequently rinsing the article with a
second liquid non-azeotrope-forming mixture containing the
fluorinated hydrocarbon solvent and a proportion of the auxiliary
solvent which is lower than that contained in the first liquid
mixture, but at least equal to 0.5% by weight of said second liquid
mixture.
2. A method as claimed in claim 1 in which there is introduced,
continuously or intermittently from an external source a supply of
the fluorinated hydrocarbon solvent or the auxiliary solvent in
quantities required to maintain the composition of the said first
and second liquid mixtures substantially constant.
3. A method as claimed in claim 2 in which the external source of
the fluorinated hydrocarbon solvent and the auxiliary solvent are
introduced into a sump compartment.
4. A method as claimed in claim 1 in which the second liquid
mixture is also heated.
5. A method as claimed in claim 1 which comprises immersing the
article in said first heated liquid mixture, said mixture being
contained in a sump compartment and subsequently passing the
article into said second liquid mixture in a rinsing compartment,
the first and second liquid mixtures having a common vapour
zone.
6. A method as claimed in claim 5 in which at least part of the
condensate from the vapour of the first and second liquid mixtures
is returned to the rinsing compartment containing the second liquid
mixture.
7. A method as claimed in claim 5 in which liquid mixture overflows
from said rinsing compartment to said sump compartment.
8. A method as claimed in claim 5 in which there is employed a
plurality of rinsing compartments.
9. A method according to claim 5 in which the fluorinated
hydrocarbon is 1,1,2-trichloro-1,2,2-trifluoroethane.
10. A method as claimed in claim 5 in which the auxiliary solvent
is n-butanol.
11. A method as claimed in claim 5 in which the auxiliary solvent
is an alkoxy alcohol.
12. A method as claimed in claim 11 in which the alkoxy alcohol is
2-ethoxy ethanol.
13. A method as claimed in claim 1 in which the first liquid
mixture contains at least five parts by weight of the auxiliary
solvent per hundred parts by weight of the total mixture.
14. A method as claimed in claim 13 in which the fluorinated
hydrocarbon solvent is a fluorochlorohydrocarbon.
15. A method as claimed in claim 14 in which the
fluorochlorohydrocarbon contains two or three carbon atoms.
16. A method as claimed in claim 15 in which the
fluorochlorohydrocarbon is
1,1,2-trichloro-1,2,2-trifluoroethane.
17. A method as claimed in claim 1 is which the auxiliary solvent
is n-butanol.
18. A method as claimed in claim 1 in which the auxiliary solvent
is an alkoxy alcohol.
19. A method as claimed in claim 18 in which the alkoxy alcohol is
2-methoxy ethanol.
20. A method as claimed in claim 18 in which the alkoxy alcohol is
2-ethoxy ethanol.
21. A method as claimed in claim 18 in which the alkoxy alcohol is
2-butoxy ethanol.
22. A method as claimed in claim 1 in which the auxiliary solvent
is a cyclic ether.
23. A method as claimed in claim 22 in which the cyclic ether is
1,4-dioxane.
24. A method as claimed in claim 3 in which the concentration of
the auxiliary solvent in the sump compartment is not greater than
90% by weight of the liquid mixture therein.
25. A method as claimed in claim 24 in which the concentration of
auxiliary solvent in the sump compartment is not greater than 70%
of the liquid mixture therein.
26. A method as claimed in claim 25 in which the concentration of
auxiliary solvent in the sump compartment is not greater than 40%
by weight of the liquid mixture therein.
27. A method as claimed in claim 1 in which the concentration of
auxiliary solvent in the second liquid mixture is in the range of
0.5 to 10% by weight of the second liquid mixture.
28. A method as claimed in claim 1 in which the auxiliary solvent
is n-butanol and the fluorinated hydrocarbon solvent is
1,1,2-trichloro-1,2,2-trifluoroethane and the concentration of
n-butanol in 1,1,2-trichloro-1,2,2-trifluoroethane employed in the
first liquid mixture in the sump compartment is 15to 25% by weight
with reference to the total liquid mixture.
29. A method as claimed in claim 28 in which the concentration of
n-butanol in said trichlorotrifluoroethane employed in the second
liquid mixture in the rinsing compartment is 1 to 1.5% by weight
with reference to the total liquid mixture.
30. A method as claimed in claim 1 in which the auxiliary solvent
is 1,4-dioxane and the fluorinated hydrocarbon solvent is
1,1,2-trichloro-1,2,2-trifluoroethane and the concentration of
1,4-dioxane in said trichlorotrifluoroethane employed in the first
liquid mixture in the sump compartment is 8 to 12% by weight with
reference to the total liquid mixture.
31. A method as claimed in claim 30 in which the concentration of
1,4-dioxane in said trichlorotrifluoroethane employed in the second
liquid mixture in the rinsing compartment is 2 to 4% by weight with
reference to the total liquid mixture.
32. A method as claimed in claim 1 wherein the temperature of the
first and second liquid mixtures is at least 30.degree.C and up to
the boiling point of the mixtures.
33. A method as claimed in claim 32 wherein the temperature of said
mixtures is at least 40.degree.C and up to the boiling point of the
mixtures.
34. A method as claimed in claim 33 wherein the liquid mixtures
have 1,1,2-trichloro-1,2,2-trifluoroethane as the fluorinated
hydrocarbon solvent and the temperature of such mixtures is in the
range 45.degree.C to 50.degree.C.
35. A method as claimed in claim 1 in which the contaminated
article is contacted with said first liquid mixture, withdrawn to a
vapour zone above said first liquid mixture and rinsed with said
second liquid mixture which is obtained by condensation of vapors
from the vapor zone.
36. A method as claimed in claim 35 in which the article is
immersed in said first liquid mixture, withdrawn through and out of
said vapor zone, allowed to cool above the vapour zone but within a
cleaning vessel containing the liquid mixtures and then returned to
said vapour zone where it is rinsed by said second liquid mixture
derived by condensation of vapours from said vapour zone on to said
cooled article.
37. A method as claimed in claim 1 wherein said first and second
liquid mixtures are in compartments separate from each other and
not possessing a common vapor zone, and vapours from above said
first liquid mixture are condensed and returned to the second
liquid mixture.
Description
This invention relates to a method of cleaning contaminated
articles and apparatus therefor.
Contaminated articles, especially printed circuits, on which may be
mounted components containing polymeric insulations and markings
and having rosin-based soldering fluxes attached thereto do require
cleaning. Such articles may be treated with halogenated hydrocarbon
solvents especially fluorochlorohydrocarbon solvents such as for
instance 1,1,2-trichloro-1,2,2-trifluoroethane in association with
auxiliary solvents. In particular the articles may be treated with
azeotropic mixtures of the solvents or with mixtures capable of
forming an azeotrope. It is usual to employ azeotropic mixtures at
the boil. Azeotropic mixtures of the primary solvent with an
auxiliary solvent are useful for some purposes but such mixtures
may not contain sufficient of the auxiliary solvent to remove the
fluxes effectively. Azeotrope-forming mixtures comprising a mixture
of the primary solvent with a high concentration of the auxiliary
solvent well above that of the azeotrope or mixtures of solvents
not containing such an azeotrope might be expected to solve the
problem and these are utilised at a relatively cold temperature,
that is, near to ambient temperature, e.g., 20.degree.C or less. If
desired such treatment may be followed by then bringing the article
into contact with a clean cold mixture of the primary solvent and
the auxiliary solvent in a separate tank, or by then bringing the
article into contact with a liquid produced from a body of the
liquid mixture by evaporation and condensation of the vapour the
article being within a vapour zone and allowing the liquid to drain
off the article. In such methods there may be quite serious loss of
solvent due to an adhering layer of cold solvent on articles
withdrawn from the plant and/or in that in certain applications a
sufficiently high degree of removal of flux from the contaminated
article may still not be effected.
Cleaning plants for treating contaminated articles may comprise a
liquor tank in which the articles are immersed, the liquor tank
being provided with an overflow to a sump tank. This latter tank
contains a relatively small amount of liquor which is held at the
boil and the purpose of the sump is not to bring the articles into
contact with the liquor but to collect dirty solvent. Vapour above
the level of the liquor is condensed and returned to the liquor
tank thereby ensuring the presence of clean solvent in the liquor
tank while impure solvent overflows to the sump. The articles are
withdrawn from the liquor tank then through a vapour zone and
finally out of the plant. Use of hot or boiling solvent mixtures
containing high concentrations of auxiliary solvents of higher
boiling point than the primary solvent in both tanks of such plants
would not be effective inasmuch as there is depletion of the
auxiliary solvent from the liquor tank and increase of auxiliary
solvent in the sump. The system is therefore not stable and will
not do the cleaning job required of it.
We now provide a method of cleaning contaminated articles which is
quite distinct from what has been previously used, which permits
effective cleaning of contaminated articles at elevated
temperatures and which is stable.
According to the present invention we provide a method of cleaning
a contaminated article in a system which comprises using a solvent
mixture comprising a halogenated hydrocarbon solvent and an
auxiliary solvent which does not form an azeotrope with said
halogenated hydrocarbon solvent wherein the article is contacted
with a first heated liquid mixture comprising the halogenated
hydrocarbon solvent and a proportion of the auxiliary solvent which
is at least 2.5 parts by weight per hundred parts by weight of the
halogenated hydrocarbon solvent, and the article is subsequently
rinsed with a second liquid mixture containing a lower proportion
of the auxiliary solvent than is contained in the first liquid
mixture.
Preferably there is introduced into the cleaning system,
continuously or intermittently from an external source, a supply of
the halogenated hydrocarbon solvent and/or the auxiliary solvent in
quantities required to maintain the composition of the said first
and second liquid mixtures substantially constant.
Preferably in any method of carrying out the process of the
invention the second liquid mixture is allso heated.
It is preferred that at least part and preferably all of the
condensate from the vapour of the first and second liquid mixtures
be returned to a vessel (the rinsing compartment) containing the
second liquid mixture, the latter overflowing to a vessel
containing the first liquid mixture.
According to a preferred method of carrying out the process of the
invention we provide a method of cleaning a contaminated article
which comprises immersing the article in said first heated liquid
mixture, said mixture being contained in a sump compartment of a
cleaning system, and subsequently passing the article into said
second liquid mixture in a rinsing compartment of said system, the
first and second liquid mixtures having a common vapour zone.
Preferably the second liquid mixture is also heated. This second
liquid mixture is in equilibrium with the vapour in the vapour zone
above the sump and rinsing compartments and with the said mixture
in the sump compartment. A plurality of rinsing compartments may be
employed if desired.
Suitably the appropriate proportion of the halogenated hydrocarbon
solvent and the auxiliary solvent is introduced continuously or
intermittently into the sump and/or rinsing compartments of the
cleaning system.
In said preferred form of carrying out the present process at least
part, and preferably all, of the liquid obtained by condensation of
vapours from the common vapour zone is returned to the rinsing
compartment. Most suitably it is also arranged that liquid mixture
overflows from the rinsing compartment and passes to the sump
compartment.
Preferably the first headed liquid mixture contains at least five
parts by weight of the auxiliary solvent per hundred parts by
weight of the total mixture.
Of the halogenated hydrocarbons which may be used in the present
process there may be mentioned fluorochlorohydrocarbons especially
those containing two or three carbon atoms, for example
1,1,2,2-tetrachloro-1,2-difluoroethane.
1,1,2-trichloro-1,2,2-trifluoroethane gives especially good
results.
Examples of auxiliary solvents which can be employed in association
with the halogenated hydrocarbon include alcohols (which do not
form azeotropes with the halogenated hydrocarbon solvent), for
example, n-butanol; alkoxy alcohols for example 2-methoxy ethanol,
2-ethoxy ethanol and 2-butoxy ethanol; and cyclic ethers, for
example 1,4-dioxane. The non-azeotropic solvent mixtures used in
the present process are those which do not have the capability of
forming an azeotrope as for example they do not include mixtures of
1,1,2-trichloro-1,2,2-trifluoroethane having a high concentration
of isopropyl alcohol which on fractionation give an azeotrope of
said trichlorotrifluoroethane and a small proportion of isopropyl
alcohol.
In the sump compartment when using for example
1,1,2-trichloro-1,2,2-trifluoroethane the concentration of the
auxiliary solvent is suitably not greater than 90% by weight of the
liquid mixture therein. It is preferred that said concentration of
auxiliary solvent is not greater than 70% and it is particularly
preferred that this concentration is not greater than 40% by weight
of the liquid mixture in the sump compartment.
The concentration of the auxiliary solvent in the rinsing tank is
different from that of the liquid mixture in the sump compartment.
The liquid mixture in the rinsing compartment, once stable
conditions are established, has a concentration of the auxiliary
solvent in the primary halogenated hydrocarbon solvent which
generally corresponds to 0.5 to 10% by weight of the said liquid
mixture. In operating the present process, with supply from an
external source of said primary and auxiliary solvent, this second
liquid mixture is in equilibrium with the first liquid mixture in
the sump compartment and with the vapour in the common vapour zone,
that is, the composition of said second liquid mixture is
substantially constant while that in the sump compartment and the
vapour in the common vapour zone remain substantially constant.
The concentration of the auxiliary solvent in the halogenated
hydrocarbon solvent in the sump and rinsing compartments will also
differ according to the particular auxiliary solvent used. Thus
when using 1,1,2-trichloro1,2,2-trifluoroethane as the primary
solvent useful results can be obtained, for example, when using a
concentration of 15 to 25% by weight of n-butanol (auxiliary
solvent) with reference to the total liquid mixture in the sump
compartment and 1 to 1.5% by weight n-butanol in the rinse
compartment, both liquids being at the boil. In a similar way there
may be usefully employed a concentration of 8 to 12% by weight
1,4-dioxane in the sump compartment and 2 to 4% by weight
1,4-dioxane in the rinse comparting, both liquid being employed at
the boil.
The external source of halogenated hydrocarbon solvent and
auxiliary solvent supplied to the system will vary according to the
particular solvents employed. The two solvents may be introduced
separately into the sump and/or rinsing compartments or a preformed
mixture of the solvents can be employed. The amount of said
solvents introduced into the system is preferably that required to
maintain the level constant in the sump compartment.
The solvent mixtures in the sump and rinsing compartments are held
at a temperature greater than ambient temperature (the latter in
some climates being 20.degree.C). Usually the mixtures are held at
a temperature of at least 30.degree.C and preferably at least
40.degree.C. More preferably the solvent mixtures are held at the
boiling point which in the case of mixtures using
1,1,2-trichloro1,2,2-trifluoroethane as the primary solvent are
often in the range 45.degree.C to 50.degree.C or higher.
The procedure of immersing the contaminated article in said heated
liquid mixture (which does not form an azeotrope) in the sump
compartment of a cleaning system alone or in association with the
further immersion in said heated liquid mixture in the rinsing
compartment is inter alia an unusual feature of the present
process.
Other solvents or additives can be added to the solvent
compositions used in the present process if it is desired to modify
their cleaning or solvent power. Suitable additives include
cationic, anionic, and non-ionic detergents. Water may also be
added in some circumstances, particularly when the compositions
include a detergent but this is not essential.
It is usually unnecessary to use stabilisers in the solvent
mixtures. However it is possible that stabilisers may be desirable
under corrosive conditions, for example those conditions in which
the solvent mixtures come into contact with light metals for
example zinc and aluminium.
The present process is useful in a wide range of applications for
cleaning contaminated articles including removal of tenacious
soldering fluxes from electrical equipment. In particular it is
useful for removing fluxes from equipment carried on a plastic or
resin substrate while not damaging the boards or components
thereon.
In another method of carrying out the process of the invention a
contaminated article is contacted with said first heated liquid
mixture in a cleaning system having one compartment (sump
compartment), the article is withdrawn to the vapour zone above
said compartment and therein is rinsed with said second liquid
mixture which is first obtained by condensation of vapours from
said vapour zone. In a modification of that process the
contaminated article after immersion in said first heated liquid
mixture is withdrawn through and out of said vapour zone, allowed
to cool above the vapour zone but within the cleaning vessel and is
then returned to said vapour zone where it is rinsed by said second
liquid mixture derived by direct condensation of vapours from said
vapour zone on to said cooled article.
In another variant of the present process the first and second
liquid mixtures are in compartments separate from each other and
not possessing a common vapour zone, condensed liquid from vapour
above said first heated mixture being returned to the second heated
mixture.
One suitable type of apparatus which can be used in the present
process is shown in the accompanying drawing (FIG. 1), which
represents a schematic view in vertical cross section and are not
to scale. In the drawing, a vessel 1 is divided into a sump
compartment 2 and a rinse compartment 4 separated by wall 3. Sump
compartment 2 contains a body of the first mixture (which does not
form an azeotrope) of sufficient depth for the contaminated
articles to be immersed therein, and is provided with heater 5.
Rinse compartment 4 adjacent to the sump compartment 2 is provided
with heater 6 and contains a volume of the second liquid mixture as
hereinbefore described, of composition different from that in the
sump compartment 2. Vapour zone 7 communicates with both sump and
rinsing compartments 2 and 4. Cooling coil 8 is fitted in the
vapour zone 7 to condense vapour, together with trough 9. The
latter is for collection of condensed liquor and pipe 10 is for
return of condensate to rinsing compartment 4. A cold line 11 is
attached to the outside of the vessel, through which a cooling
medium can be passed to provide extra cooling. An inlet 12 may be
provided for feeding a supply from an external source of a mixture
of primary and auxiliary solvents as hereinbefore described; it is
shown in the drawing as leading into the sump compartment 2, but it
can be placed so as to feed into the system at any convenient
point. Means (not detailed) are also provided to transport the
contaminated articles through the apparatus, the track of the
articles being represented by the line beginning at the entry point
13 and leading through sump compartment 2, vapour zone 7 and
rinsing compartment 4 and ending at exit point 14.
In operation, the solvent mixtures in both compartments 2 and 4 are
heated and the vapours from the mix in the vapour zone 7, condense
on the cooling coil 8 and flow back as liquid into rinsing
compartment 4, from which excess liquid flows over wall 3 into the
sump compartment 2. This continuing flow of liquid and vapour
maintains a clean rinsing liquid in compartment 4 and ensures that
the dirt and contamination accumulate in compartment 2, from which
it may be removed in any convenient manner, for example by
periodically removing all or part of the dirty liquid. The levels
of liquid are maintained by adding fresh solvent mixture, as
required, to make up for any amounts thus removed.
The present invention includes with its scope an apparatus which
comprises a vessel having a sump compartment provided with a
heating device and a volume of a first non-azeotrope forming liquid
mixture as hereinbefore described of depth sufficient to immerse
the contaminated articles, a rinsing compartment or compartments
adjacent to the sump compartment provided with a heating device or
devices and containing a volume of liquid as hereinbefore described
and being different from that in the sump compartment, said rinsing
compartment being adapted to permit overflow of liquid into the
sump compartment, a vapour zone communicating with both sump and
rinsing compartments, cooling means adapted to permit condensation
of vapour above the sump and rinsing compartments and means adapted
to return condensed liquor to the rinsing compartment or
compartments.
The following Examples illustrate but do not limit the
invention.
EXAMPLE 1
The material to be cleaned consisted of printed circuit boards
consisting of resin-bonded paper boards on which adhered a deposit
of flux. The flux coating had been produced by applying one brush
stroke of flux to the board, followed by 2 minutes drying at
70.degree.C, dip-soldering for 5 seconds at 250.degree.C, followed
by a 15-minute wait. The flux was an activated rosin-based fluxes
available commercially under the Trade Mark Zeva C4.
The method of cleaning was as previously described and involved
dipping the contaminated articles in the sump compartment of a
cleaning plant for a period of one minute followed by immersion in
an adjoining rinsing compartment for ten seconds. The solvent
mixture in the sump consisted of
1,1,2-trichloro-1,2,2-trifluoroethane containing 14.8% by weight of
n-butanol. The mixture in the rinsing tank consisted of 98.8% by
weight of said trichlorotrifluoroethane and 1.2% by weight of
n-butanol. Both liquids were maintained at the boil. Vapour above
the liquid levels was condensed by cooling coils and condensate was
returned to the rinsing tank. A mixture of said
trichlorotrifluoroethane containing 8.4% by weight n-butanol was
required to maintain the composition and level of the liquids in
the sump and rinsing compartments.
All traces of flux residues were removed by this treatment without
damaging the boards.
Example 2
In this Example the solvent mixtures for treating printed circuit
boards were as follows:
i. Sump: 1,1,2-trichloro-1,2,2-trifluoroethane containing 9.3% by
weight of 1,4-dioxane,
ii. Rinse: 97.3% by weight of said trichlorofluoroethane and 2.7%
by weight 1,4-dioxane,
iii. the mixture required to maintain the composition and level of
liquids in the sump and rinsing compartment consisted of said
trichlorotrifluoroethane containing 9.8% 1,4-dioxane.
All traces of flux residues (as described in Example 1) were
removed by this treatment without damaging the boards.
* * * * *