Cleaning compositions containing selected hydrogen-containing fluorochlorohydrocarbons, selected surface-active agents, and optional amounts of water and/or ammonia.

BACKGROUND OF THE INVENTION 
This invention relates to compositions containing hydrogen-containing 
fluorochlorohydrocarbons, selected surface-active agents, and optionally 
water. 
Fully halogenated fluorochlorohydrocarbons are used as solvents in a number 
of different cleaning and drying applications, since they satisfactorily 
fulfill the high requirements for dissolving properties with regard to the 
impurities to be removed, optionally in conjunction with conventional 
co-solvents or other additives for cleaning and drying applications. 
However, the fully halogenated fluorochlorohydrocarbons are associated 
with the considerable disadvantage that they contribute to the dangerous 
decrease in the ozone content of the upper air layers of the earth's 
atmosphere. Because of these properties of the fully halogenated 
fluorochlorohydrocarbons which damage the environment, it is desirable to 
replace cleaning and drying compositions containing these fully 
halogenated fluorochlorohydrocarbons with alternative cleaning and drying 
compositions containing solvents which are less dubious in this respect. 
However, these solvents must fulfil a series of further requirements, 
particularly when they are to be used for cleaning or drying electronic 
components, printed circuits, sensitive equipment parts, precision 
equipment and protective circuits, such as for example fault current 
protected switches. The solvents thus should not damage the objects to be 
cleaned or to be dried, that is they should neither have a corrosive 
effect on metal parts nor should they attack plastic parts. 
These solvents should also be capable of forming stable water-in-oil 
emulsions with the other constituents of cleaning compositions, for 
example with surface active agents and especially with water, so that the 
compositions containing them can be stored for long periods of time prior 
to use, even at temperatures well below room temperature, without any 
danger of deterioration in the quality of the emulsion or of the emulsion 
breaking (i.e. demixing with formation of separate oil and aqueous 
phases). 
SUMMARY OF THE INVENTION 
It is the object of the present invention to provide new solvent cleaning 
compositions which avoid the use of potentially environmentally damaging 
fully halogenated fluorochlorohydrocarbons. 
Another object of the invention is to provide new solvent cleaning 
compositions which will not damage things to be cleaned or dried, nor have 
a corrosive effect on metal parts or attack plastic parts. 
A further object of the invention is to provide storage-stable compositions 
in the form of emulsions which are stable even at low temperatures, for 
example temperatures well below 0.degree. C. 
These and other objects of the invention are achieved by providing a 
cleaning composition consisting essentially of 
from 0.25 to 35 wt. % of at least one surface-active agent selected from 
the group consisting of ammonium salts of alkylbenzenesulfonates and 
mixtures of fatty acid alkanol amides and alkylphenol polyglycol ethers; 
at least 65 wt. % of at least one hydrogen-containing 
fluorochlorohydrocarbon selected from the group consisting of 
trichlorodifluoroethane, dichlorotrifluoroethane, dichloromonofluoroethane 
and dichloropentafluoropropane; 
from 0 to 34.75 wt. % water, and 
from 0 to 34.75 wt. % ammonia; 
the sum of the components being 100 wt. %. 
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS 
It has now been found that cleaning compositions containing 0.25 to 35 wt. 
% of a surface-active agent, which is selected from ammonium salts of 
alkylbenzenesulfonates and/or mixtures of fatty acid alkanol amides and 
alkylphenol polyglycol ethers, and at least 65 wt. % of one or more 
hydrogen-containing fluorochlorohydrocarbons, which are selected from 
trichlorodifluoroethane, dichlorotrifluoroethane, dichloromonofluoroethane 
and dichloropentafluoropropane, and optionally water and optionally 
ammonia, the sum of the components being 100 wt. %, are well suited for 
industrial cleaning and drying processes. 
In a preferred embodiment of the invention, the compositions of the 
invention are characterized in that they contain 0.5 to 5 wt. % of the 
surface-active agent relative to the total composition. 
As used herein the term "trichlorodifluoroethanes" refers to 
fluorochlorohydrocarbons corresponding to the empirical formula C.sub.2 
HCl.sub.3 F.sub.2 which carry a hydrogen atom. They therefore include the 
three incompletely halogenated isomeric fluorochlorohydrocarbons 
1,1,1-trichloro-2,2-difluoroethane (R122b), 
1,1,2-trichloro-2,2-difluoroethane (R122) and 
1,1,2-trichloro-1,2-difluoroethane (R122a). 
As used herein the term "dichlorotrifluoroethanes" refers to 
fluorochlorohydrocarbons corresponding to the empirical formula C.sub.2 
HCl.sub.2 F.sub.3 which carry a hydrogen atom. They therefore include the 
three non-fully halogenated isomeric fluorochlorohydrocarbons 
1,1-dichloro-2,2,2-trifluoroethane (R123), 
1,2-dichloro-1,1,2-trifluoroethane (R123a), and 
1,1-dichloro-1,2,2-trifluoroethane (R123b). 
As used herein the term "dichloromonofluoroethanes" refers to the three 
fluorochlorohydrocarbons corresponding to the empirical formula C.sub.2 
H.sub.3 Cl.sub.2 F which carry three hydrogen atoms. They therefore 
include the three non-fully halogenated isomeric fluorochlorohydrocarbons 
1,2-dichloro-1-fluoroethane (R141), 1,1-dichloro-2-fluoroethane (R141a) 
and 1,1-dichloro-1-fluoroethane (R141b). 
As used herein the term "dichloropentafluoropropanes" refers to the 
fluorochlorohydrocarbons corresponding to the empirical formula C.sub.3 
HCl.sub.2 F.sub.5 which carry a hydrogen atom. In particular they include 
the incompletely halogenated isomeric fluorochlorohydrocarbons 
1,2-dichloro-1,1,2,3,3-pentafluoropropane, 
2,3-dichloro-1,1,1,2,3-pentafluoropropane, 
1,1-dichloro-2,2,3,3,3-pentafluoropropane (=3,3-dichloro- 
1,1,1,2,2-pentafluoropropane), 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 
1,1-dichloro-1,2,2,3,3-pentafluoropropane, 
1,2-dichloro-1,1,3,3,3-pentafluoropropane, and 
1,1-dichloro-1,2,3,3,3-pentafluoropropane. Preferred 
dichloropentafluoropropanes are 1,1-dichloro-2,2,3,3,3-pentafluoropropane 
(R225ca) and 1,3-dichloro-1,1,2,2,3-pentafluoropropane (R225cb). 
The compositions of the invention may also contain the aforementioned 
hydrogen-containing fluorochlorohydrocarbons mixed with one another and/or 
as an isomeric mixture. In particular, the compositions advantageously 
contain hydrogen-containing fluorochlorohydrocarbons selected from the 
group consisting of the dichlorotrifluoroethanes, the 
dichloromonofluoroethanes, and mixtures thereof. Compositions which 
contain the dichlorotrifluoroethane isomer 
1,1-dichloro-2,2,2-trifluoroethane (R123) or the dichloromonofluoroethane 
isomer 1,1-dichloro-1-fluoroethane (R141b), or a mixture thereof, are 
especially preferred. However, compositions containing other isomers, 
particularly dichlorotrifluoroethane or dichloromonofluoroethane, i.e. 
1,2-dichloro-1,1,2-trifluoroethane (R123a), 
1,1-dichloro-1,2,2-trifluoroethane (R123b), 1,2-dichloro-1-fluoroethane 
(R141) and 1,1-dichloro-2-fluoroethane (R141a), are also highly suitable. 
In one variant of the invention, the cleaning compositions contain a 
mixture of fatty acid alkanol amide and alkylphenol polyglycol ether as 
the surface-active agent. Suitable fatty acid alkanol amides include, for 
example N-alkylated fatty acid amides corresponding to the formula R.sup.1 
--CO--N(R.sup.2)--(CH.sub.2).sub.n --OH, which can be obtained by reacting 
alkanol amines with fatty acids, fatty acid methyl esters or fatty acid 
glycerides, wherein R.sup.1 represents a saturated or unsaturated fatty 
acid radical, R.sup.2 represents hydrogen in monoalkanol amides or 
--(CH.sub.2).sub.n --OH in fatty acid dialkanol amides, and n denotes an 
integer from 1 to 6, but preferably the number 2. Fatty acid dialkanol 
amides are particularly preferred, especially fatty acid diethanol amides 
in which the group R.sup.1 is the fatty acid radical of lauric acid, 
myristic acid, palmitic acid, stearic acid, or oleic acid and optionally 
also a fatty acid radical of the coconut fatty acids. Suitable alkylphenol 
polyglycol ethers include, for example, those containing medium chain 
alkyl radicals, i.e. those having the C8 to C12 alkyl radicals octyl, 
nonyl, decyl, undecyl or dodecyl, and having 5 to 8 ethylene oxide units. 
In a preferred embodiment of this variant of the invention, the cleaning 
compositions contain a mixture of oleic acid diethanol amide and 
nonylphenol polyglycol ethers with 7 to 8 ethylene oxide units. Cleaning 
compositions in which the oleic acid diethanol amide and the nonylphenol 
polyglycol ethers are present in the weight ratio 5:1, are particularly 
preferred in this case. 
Suitable alkylbenzenesulfonates include, for example, those containing 
medium chain alkyl radicals, i.e. those with the C8 to C12 alkyl radicals 
octyl, nonyl, decyl, undecyl or dodecyl. The cleaning compositions of the 
invention may contain ammonium salts of the alkylbenzenesulfonates with, 
for example, the following amines having 2 to 6 C atoms: diethylamine, 
n-propylamine, isopropylamine, diisopropylamine, n-butylamine, 
isobutylamine, tert.-butylamine, and cyclohexylamine. In a preferred 
embodiment of this variant of the invention, the cleaning compositions 
contain isopropylammonium dodecylbenzenesulfonate as an 
alkylbenzenesulfonate ammonium salt. 
The compositions of the invention described above are very well suited for 
removing grease and oil impurities and for drying surfaces. In order to 
assist in the removal of water-soluble impurities, it is advantageous to 
incorporate a suitable additive for this purpose in the compositions of 
the invention which comprise a surface-active agent and a 
hydrogen-containing fluorochlorohydrocarbon. One advantageous variant of 
the invention therefore relates to compositions of the aforementioned type 
which contain a certain amount of water as a further component, in 
addition to the aforementioned surface-active agents and 
hydrogen-containing fluorochlorohydrocarbons. The water portion is very 
well tolerated by the compositions of the invention, i.e. stable 
water-in-oil emulsions are formed without diminishing the advantages of 
the compositions, for example by the emulsion separating into two phases 
(water phase and oil phase) or reverting to an oil-in-water emulsion. In 
this respect very advantageous cleaning compositions according to the 
invention in the form of a water-in-oil emulsion are characterized by 
containing 0.5 to 5 wt. % of the surface-active agent, 80 to 99 wt. % of 
one of the fluorochlorohydrocarbons dichlorotrifluoroethane or 
dichloromonofluoroethane, and 0.5 to 15 wt. % of water, the sum of the 
components being 100 wt. %. 
In one preferred embodiment of this variant of the invention, the cleaning 
composition exists in the form of a water-in-oil emulsion and is 
characterized by containing 2 to 3 wt. % of the surface-active agent, 88 
to 96 wt. % of one of the hydrogen-containing fluorochlorohydrocarbons 
dichlorotrifluoroethane or dichloromonofluoroethane, and 2 to 9 wt. % 
water. 
The ammonium salts of alkylbenzenesulfonates in particular are used as 
surface-active agents for the compositions of the invention which exist in 
the form of a water-in-oil emulsion. A most particularly preferred 
alkylbenzenesulfonate ammonium salt for this is isopropylammonium 
dodecylbenzenesulfonate. 
In one particularly advantageous embodiment of the cleaning compositions of 
the invention which exist in the form of a water-in-oil emulsion, the 
compositions are characterized by also containing 0.01 to 2 wt. % of 
ammonia at the expense of the proportion by weight of the 
hydrogen-containing fluorochlorohydrocarbon; accordingly, compositions of 
this type contain 78 to 98.99 wt. %, preferably 86 to 95.99 wt. %, of 
hydrogen-containing fluorochlorohydrocarbons, whereas the other 
components, such as surface-active agent and water, are present in the 
amounts given above for compositions in the form of water-in-oil 
emulsions. 
Depending on the water content, the compositions of the invention are clear 
solutions or emulsions at room temperature to which known additives can be 
added. One group of known additives is stabilizers. This group includes 
those compounds which prevent undesirable reactions between components of 
the composition or with other reactants, such as for example air-oxygen, 
metal, water and the like. Examples of known stabilizers include 
nitroalkanes, in particular nitromethane and nitroethane, alkylene oxides, 
in particular butylene oxide, or branched alkynols, such as for example 
2-methyl-but-3-yn-2-ol. These stabilizers may be used alone or in 
combination with one another. Amounts of stabilizer ranging from 0.01 to 5 
wt. %, preferably 0.05 to 1 wt. %, relative to the total mixture are very 
suitable. Other suitable additives include known corrosion inhibitors, 
non-ionic or ionic emulsifiers, dyes, and the like. 
The compositions of the invention have numerous applications in the 
cleaning and/or drying sector. In these known processes the object to be 
cleaned is immersed in one or more stages in an optionally heated liquid 
cleaning mixture or sprayed with the cleaning mixture. The cleaning effect 
may also be increased for less sensitive objects to be cleaned by suitable 
measures, such as for example ultrasound and/or stirring, and/or by 
mechanical effects, such as, for example, brushing. 
The compositions of the invention are suitable for cleaning and/or drying 
elastomers, metal, plastic and glass parts or surfaces, and for textile 
cleaning (dry cleaning). The cleaning compositions of the invention are 
also particularly suitable for cleaning electronic components, printed 
circuits, sensitive equipment parts, precision equipment and protective 
circuits, such as for example fault current protected switches. The high 
requirements for cleaning these objects are satisfactorily fulfilled by 
the cleaning compositions of the invention. 
The cleaning compositions of the invention may also be used, for example, 
for cleaning small parts or bulk material, or for removing grease or 
fingerprints from electronic components, for example from silicon wafers. 
Ammonia-containing compositions are also well suited to removing oxidized 
surface layers from metal parts, for example from precision parts made of 
copper. 
The present invention surprisingly results in formation of water-in-oil 
emulsions which exhibit very good storage stability even at temperatures 
significantly below 0.degree. C. This assures that the emulsions can be 
suitably stored prior to use, as frequently occurs with such compositions, 
without any danger of formation of separate phases or deterioration in the 
quality of the emulsion which would adversely affect its usefulness, even 
in cool weather or in refrigerated storage areas.

The following examples are intended to illustrate the invention in further 
detail without limiting its scope. Unless otherwise stated, percentages 
always refer to percent by weight. The abbreviations used in the examples 
denote: 
R122=1,1,2-trichloro-2,2-difluoroethane 
R123=1,1-dichloro-2,2,2-trifluoroethane 
R141b=1,1-dichloro-1-fluoroethane 
R225=dichloropentafluoropropane (isomeric mixture of R225ca and R225cb in 
the weight ratio 20:80) 
R225ca=1,1-dichloro-2,2,3,3,3-pentafluoropropane 
R225cb=1,3-dichloro-1,1,2,2,3-pentafluoropropane 
IDS=isopropylammonium dodecylbenzenesulfonate 
ODA/NPE=oleic acid diethanol amide/nonylphenol polyglycol ether (5:1) 
EXAMPLE 1: 
Cleaning of glass lenses, aluminum plates and silicon slices 
Cleaning tests with glass lenses, aluminum plates and silicon slices, which 
were contaminated with fingerprints, oil and/or grease, were carried out 
in a commercially available 4-chamber cleaning apparatus. The cleaning 
compositions, cleaning conditions and cleaning results are listed in Table 
1. 
TABLE 1 
__________________________________________________________________________ 
Cleaning results from Example 1 
No. 
Compositions for bath 1 
Cleaning conditions 
Material Result 
__________________________________________________________________________ 
1.1 
R123 emulsion: 
4-bath: a) glass lenses 
+ + 
5.0% IDS 1) 3 min. ultrasound (emulsion) 
b) aluminum plates 
15.0% water 2) 1 min. immersed boiling (R123) 
c) silicon slices 
+ + 
80.0% R123 3) 1 min. ultrasound (R123) 
4) 1 min. steam degreasing (R123) 
+ + 
1.2 
R141b emulsion: 
4-bath: a) glass lenses 
+ + 
2.0% IDS 1) 3 min. ultrasound (emulsion) 
b) aluminum plates 
4.0% water 2) 1 min. immersed boiling (R141b) 
c) silicon slices 
+ + 
94.0% R141b 3) 1 min. ultrasound (R141b) 
4) 1 min. steam degreasing (R141b) 
+ + 
1.3 
R123/R141b emulsion: 
4-bath: (R123 or R141b) 
a) glass lenses 
+ + 
1) 3 min. ultrasound (emulsion) 
b) aluminum plates 
3.0% IDS 2) 1 min. immersed boiling (*) 
c) silicon slices 
+ + 
8.0% water 3) 1 min. ultrasound (*) 
44.5% R123 4) 1 min. steam degreasing (*) 
+ + 
44.5% R141b 
V1 R123 4-bath: a) glass lenses 
poor 
1) 3 min. ultrasound (R123) 
b) aluminum plates 
2) 1 min. immersed boiling (R123) 
c) silicon slices 
poor 
3) 1 min. ultrasound (R123) 
4) 1 min. steam degreasing (R123) 
poor 
V2 R123 4-bath: a) glass lenses 
poor 
1) 3 min. ultrasound (R141b) 
b) aluminum plates 
2) 1 min. immersed boiling (R141b) 
c) silicon slices 
poor 
3) 1 min. ultrasound (R141b) 
4) 1 min. steam degreasing (R141b) 
poor 
__________________________________________________________________________ 
A very good cleaning effect was achieved in the cases marked "++" in the 
"Result" column. The cleaned glass lenses, aluminum plates and silicon 
slices were perfectly clean and completely free of oil, grease and 
fingerprints when cleaned with emulsions Nos. 1.1 to 1.3 of the invention. 
The good results obtained in the cleaning test with compositions according 
to the invention are in distinct contrast to the results obtained in 
comparative tests V1 and V2 in which only pure solvent without 
surface-active agent was used. 
EXAMPLE 2: 
Cleaning of copper precision parts 
Copper precision parts, which had an oxidized surface layer, were cleaned 
analogously to Example 1 in a commercially available 4-chamber cleaning 
apparatus. Emulsions with added ammonia were used for cleaning. The 
cleaning compositions, cleaning conditions and cleaning results are shown 
in the following Table 2. 
TABLE 2 
______________________________________ 
Cleaning result from Example 2 
Composition 
No. for bath 1 Cleaning conditions 
Material 
Result 
______________________________________ 
2.1 R123 emulsion: 
4-bath: Copper + + 
2.5% IDS 1) 3 min. ultrasound 
precision 
(emulsion) parts, 
6.0% water 2) 1 min. immersed 
surface- 
boiling (R123) oxidized 
0.2% ammonia 
3) 1 min. ultrasound 
(R123) 
91.3% R123 4) 1 min. steam 
degreasing (R123) 
______________________________________ 
A very good cleaning effect ("++") was achieved. The oxidized surface layer 
was completely removed and the cleaned metal surface had a particularly 
good metal gloss. 
EXAMPLE 3: 
Cleaning of bulk material and counter mechanisms 
Cleaning tests were carried out with bulk material (transistor caps) to 
remove drawing oils and with counter mechanisms for removing oils 
contaminated with resins, in a commercially available three-chamber 
cleaning apparatus. The cleaning compositions, cleaning conditions and 
cleaning results are shown in the following Table 3. 
TABLE 3 
______________________________________ 
Cleaning results from Example 3 
Compositions Cleaning 
No. for bath 1 conditions Material 
Result 
______________________________________ 
3.1 65.0% R123 3-bath: Electronic 
+ + 
35.0% 1) 3 min. counters 
ODA/NPE ultrasound 
2) 1 min. 
ultrasound (R123) 
3) 1 min. steam 
degreasing (R123) 
3.2 95.0% R141b 3-bath: Transistor 
+ + 
5.0% 1) 3 min. caps (bulk 
ODA/NPE ultrasound material) 
2) 1 min. 
ultrasound 
(R141b) 
3) 1 min. steam 
degreasing 
(R141b) 
3.3 65.0% R225 3-bath: Electronic 
+ + 
35.0% 1) 3 min. counters 
ODA/NPE ultrasound 
2) 1 min. 
ultrasound (R225) 
3) 1 min. steam 
degreasing (R225) 
3.4 95.0% R122 3-bath: Transistor 
+ + 
5.0% ODA/NPE 1) 3 min. caps (bulk 
ultrasound material) 
2) 1 min. 
ultrasound (R122) 
3) 1 min. steam 
degreasing (R122) 
______________________________________ 
A very good cleaning effect was achieved in the cases marked "++" in the 
"Result" column. In each case, the object to be cleaned or the bulk 
material to be cleaned was perfectly clean after the treatment. 
EXAMPLE 4: 
Drying of silicon slices 
Drying tests on silicon slices moist with water were carried out in a 
commercially available 4-chamber drying apparatus. The drying 
compositions, drying conditions and drying results are shown in the 
following Table 4. 
TABLE 4 
______________________________________ 
Drying result from Example 4 
Composition 
No. for bath 1 Drying conditions 
Material 
Result 
______________________________________ 
4.1 97.0% R141b 
4-bath: Silicon 
+ + 
3.0% IDS 1) 1 min. immersed 
slices 
boiling 
2) 1 min. immersed 
boiling (R141b) 
3) 1 min. immersed 
boiling (R141b) 
4) 1 min. steam 
chamber (R141b) 
______________________________________ 
A very good drying effect ("++") was achieved. The silicon slices to be 
dried were perfectly dry after the treatment. 
The foregoing description and examples have been set forth merely to 
illustrate the invention and are not intended to be limiting. Since 
modifications of the described embodiments incorporating the spirit and 
substance of the invention may occur to persons skilled in the art, the 
scope of the invention should be construed to include all variations 
falling within the ambit of the appended claims and equivalents thereof.