U.S. patent number 3,856,695 [Application Number 05/350,393] was granted by the patent office on 1974-12-24 for solvent based detergent.
Invention is credited to Richard Geiss, Rolf Quarch.
United States Patent |
3,856,695 |
Geiss , et al. |
* December 24, 1974 |
SOLVENT BASED DETERGENT
Abstract
A solvent based detergent composition consisting essentially of
(A) 10-80% liquid aliphatic chlorinated hydrocarbon solvents, (B)
10-40% liquid aliphatic ketones and/or liquid aliphatic esters, (C)
6 to 50% water soluble liquid alkanols having two to five carbon
atoms and (D) 1-10% surface active agents.
Inventors: |
Geiss; Richard (8875 Offingens,
1 Donau, DT), Quarch; Rolf (7912 Weissenhorn,
DT) |
[*] Notice: |
The portion of the term of this patent
subsequent to June 5, 1990 has been disclaimed. |
Family
ID: |
25757764 |
Appl.
No.: |
05/350,393 |
Filed: |
April 12, 1973 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
60924 |
Aug 4, 1970 |
3737386 |
Jun 5, 1973 |
|
|
Foreign Application Priority Data
Current U.S.
Class: |
510/204; 510/240;
134/38; 252/71; 510/238; 510/366; 510/412; 510/414; 510/365 |
Current CPC
Class: |
C09D
9/005 (20130101); C11D 3/48 (20130101); C11D
3/43 (20130101); C23G 5/032 (20130101) |
Current International
Class: |
C09D
9/00 (20060101); C23G 5/00 (20060101); C11D
3/48 (20060101); C11D 3/43 (20060101); C23G
5/032 (20060101); C09d 009/04 () |
Field of
Search: |
;252/162,170,171
;134/38,40 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Schulz; William E.
Attorney, Agent or Firm: Littlepage, Quaintance, Murphy
& Dobyns
Parent Case Text
This application is a continuation in part of application 60,924,
filed Aug. 4, 1970 now U.S. Pat. No. 3,737,386, granted June 5,
1973.
Claims
What is claimed is:
1. A solvent-based detergent composition that is miscible with
water consisting essentially of
A. 10-80% by weight liquid aliphatic chlorinated hydrocarbons;
B. 10-40% by weight liquid lower aliphatic ketones and/or liquid
lower aliphatic esters;
C. 5-50% by weight water-soluble alkanols having two to five carbon
atoms and
D. 1-10% by weight of a detergent anionic or nonionic surface
active agents.
2. The composition of claim 1, consisting essentially of
A. 10-25% of said liquid aliphatic chlorinated hydrocarbons;
B. 25-40% of said liquid aliphatic ketones and/or said liquid
aliphatic esters;
C. 40-50% of said water-soluble alkanols, and
D. 1-10% of said surface active agents.
3. A detergent composition of claim 1, wherein said component
A. is methylene chloride, trichloroethylene or
perchloroethylene;
B. is methyl ethyl ketone or ethyl acetate
C. is isopropanol, propanol or butanol and
D. is an anionic surface active agent.
4. A detergent composition of claim 1 wherein said chlorinated
hydrocarbons are selected from the group consisting of
monochloromethane, trichloromethane, tetrachloromethane,
dichloroethane, trichloroethane and tetrachloroethane.
5. A detergent composition of claim 1 wherein said ketone (B) is
selected from the group consisting of diethyl ketone, methyl propyl
ketone and isomeric ethyl butyl ketones.
6. A detergent composition of claim 1, wherein said esters (B) are
selected from the group consisting of methyl acetate, propyl
acetates, butyl acetates, methyl propionates, ethyl propionates,
propyl propionates, butyl propionates, methyl butyrates, ethyl
butyrates, propyl butyrates and butyl butyrates.
7. A detergent composition of claim 1, wherein said alkanols (C)
are selected from the group consisting of ethanol and amyl
alcohols.
8. A detergent composition of claim 1, wherein (A) is methylene
chloride, (B) is ethyl acetate, (C) is isopropanol and (D) is a
sulphonate of coconut fat alcohols.
9. A detergent composition of claim 1, wherein (A) is methylene
chloride, (B) is methyl propyl ketone, (C) is propanol and (D) is
ammonium salt of sulphuric acid ester of lauryl alcohol.
10. A detergent composition of claim 1, wherein (A) is methylene
chloride, (B) is diethyl ketone and ethyl acetate, (C) is butanol
and (D) is moneethanolamine salt of the sulphonated coconut fatty
alcohols ether.
11. A detergent composition of claim 1, wherein (A) is methylene
chloride, (B) is methyl ethyl ketone and propyl acetate, (C) is
ethanol and (D) is triethanolamine salt of the lauryl alcohol
sulphuric acid ester.
12. A detergent composition of claim 1, wherein (A) is methylene
chloride, (B) is methyl ethyl ketone and ethyl acetate, (C) is
isopropanol and (D) is sodium lauryl sulphate.
13. A detergent composition of claim 1, which also contains 1-10%
of a liquid hydrocarbon fraction having a boiling point of
120.degree. to 180.degree. C.
14. Cleaning surfaces soiled with oils, fats, tars, resins,
asphaltenes, pitches, varnishes, paints or mechanical impurities
with the composition of claim 1.
Description
The invention relates to industrial detergents based on a
combination of organic solvents in admixture with cleansing
intensifiers.
It has long been known to utilize a number of different mixtures of
solvents for industrial cleaning, in particular combinations of
trichloroethylene or perchloroethylene in admixture with benzenes
or aromatics such as benzene, toluene and xylene. In general these
substances are used for removing fat and varnish.
For several cleaning processes, however, detergents of the known
prior art have proved to be insufficient, particularly for cleaning
construction units, e.g. tiles in service stations, tunnels,
railway stations and similar buildings, soiled concrete areas and
other cemented surfaces.
The dirt on walls and floors of such buildings consists of tars,
greases, oils, rosins, resins, asphaltenes, set paints and
varnishes as well as of mechanical impurities.
It is impossible to solve such dirt accumulations and wash them
away with water immediately without a long residence time and
without applying mechanical power such as scrubbing and rubbing.
The same is true with soiled tools, e.g. brushes, etc.
Accordingly, it is an aim of the present invention to provide a
detergent composition comprising in combination several solvents
which can be applied even at high levels of impurity, i.e., which
exhibit good solving properties and which make it possible to wash
away the lubricants composed of dirt (tars, greases, oils, rosins,
resins, etc.).
The new detergents are organic liquid or solvent mixtures which can
be mixed with water and consist of:
A. 10-80%, preferably 10-25%, by weight liquid aliphatic
chlorinated hydrocarbons;
B. 10-40%, preferably 25-40%, by weight liquid lower aliphatic
ketones and/or liquid lower aliphatic esters;
C. 5-50%, preferably 40-50%, by weight water-soluble liquid
alkanols having 2-5 carbon atoms; and
D. 1-10% by weight of a detergent anionic or nonionic surface
active agent.
These compositions may also contain
E. 1-10%, preferably 5-7%, by weight liquid hydrocarbon fraction
having a boiling point of 120.degree. to 180.degree. C.
As a result of practical experiments the preferred percentages of
the components, A, B, C, and D in the compositions according to the
invention are considered optimal. From the economic point of view
they are also optimal. A reduction of A would cause a longer
cleaning time and a reduction of the synergetic effect which means
a reduction of the detregency power of the composition.
The percentage of A can be increased from 25-80% by weight which
causes an increase of the detergency power, especially if methylene
chloride is used.
The combined percentage of B and C can be reduced only to 25% by
weight without reducing the detergency power as well. If the
percentage of B and C is increased to more than 75 -80% the
detergency power is diminished, too.
The percentage of component D should remain within the limits of
1-10% by weight. Smaller amounts reduce the wetting and emulsifying
power far too much, whereas using higher amounts produce no
additional benefits.
Preferred use is made of mixtures of components of the above groups
consisting of
A. methylene chloride, trichloroethylene, and
perchloroethylene;
B. methyl ethyl ketone and ethyl acetate;
C. isopropanol, propanol and butanol;
D. an anionic surface active agent; and
E. a benzene fraction.
Additionally, the following substances individually or in admixture
with other representatives of the same groups may be used as
components of the groups consisting of
A. as chlorinated hydrocarbons: monochloromethane, trichloroethane
and tetrachloromethane, 1,1 - and 1,2-dichloromethanes, 1,1,1 and
1,1,2-trichloroethanes, and 1,1,1,2- and
1,1,2,2-tetrachloroethanes;
B. as esters: methyl acetate, propyl acetates and butyl acetates,
as well as the corresponding propionates and butyrates including
ethyl esters;
as ketones: diethyl, methyl propyl and isomeric ethyl butyl
ketones. The esters and ketones are completely interchangeable and
they preferably have 3-8 carbon atoms;
C. as alkanols: ethanol and amyl alcohols;
D. as anionic surface active agents: sulphates and ether sulphates
and sulfonates of fatty alcohols and fatty acids alkyl sulphonates,
aryl alkyl sulphonates and alkyl aryl sulphonates, ethylene oxide
adducts, e.g. sodium lauryl sulphates, lauryl alcohol surfurce acid
ester and triethyanolamine salts of ether sulphates of fat
alcohols; and as nonionic surface active agents: nonionic
detergents having polyoxyethylene hydrophilic groups and oil
soluble fatty acid, alcohol, amide or amine groups.
They produce above all a high degree of detergency and make it
possible that the treated areas can be washed clean with water.
In order to prove the efficiency of the composition of the
invention comparative tests were conducted using compositions which
did not contain chlorinated hydrocarbons or the surface active
substances. However, these test compositions produced insufficient
cleaning results.
All amounts of the ingredients listed in the following examples are
by weight. With the compositions of the test examples 1 and 2 and
the examples 1 to 7 pottery tiles were cleaned which had been
soiled successively with the substances a to e listed below in the
Test comparison report and which had then been submitted to the
ageing process described in that report.
Test 1: Test compositions without surface active substances.
The test compositions had the following ingredients:
A. 10% methylene chloride 20% methyl ethyl ketone 20% ethyl acetate
50% isopropanol B. 70% methylene chloride 10% methyl ethyl ketone
15% ethyl acetate 5% isopropanol
In the absence of a surface active substance the lubricants formed
by dirt and solvent from the test composition could not be washed
away with water from the soiled areas or could not be washed away
completely. Dirt stripes remained which could be removed only after
various applications of the solvent while rubbing or by means of
other mechanical powers.
Test 2: Test composition without a chlorinated hydrocarbon.
The mixture had the following ingredients:
A. 25% methyl ethyl ketone 25% ethyl acetate 40% isopropanol 10% of
an anionic surface active substance. B. 45% methyl ethyl ketone 25%
ethyl acetate 25% isopropanol 5% of an anionic surface active
agent.
In the absence of a chlorinated hydrocarbon the mixture of solvents
required a prolonged residence time to remove the dirt lubricant,
i.e., the total cleaning of 1 m.sup.2 of soiled area required more
than 3 minutes time and the application of mechanical power. Thus,
it can be stated that the detergency power is rather high but that
the dirt lubricant solving time is far too long, especially in view
of the great areas to be cleaned.
Further tests showed that aliphatic, lower ketones, from which
acetone is known as a solvent for certain resins, exhibit a much
stronger and quicker solving efficiency for resins in admixture
with the other ingredients (A), (B), and (D) than individual
ketones. This synergetic effect was very much surprising and
unpresumable.
Example 1 ______________________________________ A mixture
consisting of the following ingredients was examined: 25% methylene
chloride 25% ethyl acetate 40% isopropanol 10% of a sulphonate of
coconut fat alcohols. ______________________________________
The tiles to be cleaned were soiled with the above-mentioned
lubricant forming dirt composition and submitted to an ageing
process of one year. By means of a cleaning cloth soaked with the
above-mentioned detergent an area of tiles of 1 m.sup.2 was cleaned
and rinsed with water in 30 sec. time. This detergency power of 30
seconds could be considered as very good.
A similar very good (30 seconds or less) detergency power was
exhibited by the following combinations according to example 2 to
5.
Example 2 ______________________________________ 25% methylene
chloride 25% methyl propyl ketone 40% propanol 10% ammonium salt of
the sulphuric acid ester of lauryl alcohol.
______________________________________
Example 3 ______________________________________ 25% methylene
chloride 12.5% diethyl ketone 12.5% ethyl acetate 40% butanol 10%
monoethyanolamine salt of the sulphonated coconut fatty alcohols
ether. ______________________________________
Example 4 ______________________________________ 10% methylene
chloride 20% methyl ethyl ketone 20% propyl acetate 40% ethanol 10%
triethyanolamine salt of the lauryl alcohol sulphuric acid ester.
______________________________________
Example 5 ______________________________________ 10% methylene
chloride 20% methyl ethyl ketone 20% ethyl acetate 40% isopropanol
10% sodium lauryl sulphate.
______________________________________
Example 6 ______________________________________ 70% methylene
chloride 15% ethyl acetate 6% isopropanol 4% of a sulphonate of
coconut fat alcohols 5% bezin of Kp. 130-150.degree.C.
______________________________________
Example 7 ______________________________________ 65% methylene
chloride 19% methyl propyl ketone 12% propanol 4% ammonium salt of
the sulphuric acid ester of lauryl alcohol.
______________________________________
Example 8 ______________________________________ 75% methylene
chloride 7% diethyl ketone 10% ethyl acetate 5% butanol 3%
monoethanolamine salt of the sulphonated coconut fatty alcohols
ether. ______________________________________
Example 9 ______________________________________ 60% methylene
chloride 8% methyl ethyl ketone 13% propyl acetate 15% ethnaol 4%
triethanolamine salt of the lauryl alcohol sulphuric acid ester.
______________________________________
Example 10 ______________________________________ 80% methylene
chloride 3% methyl ethyl ketone 10% ethyl acetate 5% isopropanol 2%
sodium lauryl sulphate. ______________________________________
The results obtained in Examples 1 to 10 could be considered as
very good: the joints of the cleaned tiles did not show any changes
and the lustre of the tiles remained unchanged. The expression
"very good" at the end of the examples 1 to 10 means that in the
very short time of 30 seconds, the dirt had been soaked completely
without any residue and could be washed away with water. The known
prior art cleaning agents, however, are not able to solve analogous
dirts consisting at the same time of lignite tar, motor oil
recovered from waist oils and fats, and resins. The maximum
allowable vapor concentration (in ppm or b/m.sup.3) of the
detergent according to the invention is so high that they can be
used without any operating safety risk.
In the following examples 11 to 14 the detergency power of
combinations including perchloroethylene or trichloroethylene were
examined. For this end methylene chloride from the composition
according to example 5 was substituted by perchloroethylene or
trichloroethylene. This composition required a longer residence
time, the detergency power of the mixture, however, can be
considered as good.
Example 11 ______________________________________ A mixture with
the following ingredients: 10% trichloroethylene 20% methyl ethyl
ketone 20% ethyl acetate 40% isopropanol 10% sodium lauryl sulphate
______________________________________
showed a good detergency power; required, however, a much longer
residence time than the compositions including methylene chloride
according to the examples 1 to 10.
Similar compositions which had the following ingredients showed the
same results:
Example 12 ______________________________________ 10%
perchloroethylene 20% methyl ethyl ketone 20% ethyl acetate 40%
isopropanol 10% sodium lauryl
______________________________________
Example 13 ______________________________________ 70%
trichloroethylene 6% methyl ethyl ketone 9% ethyl acetate 8%
isopropanol 4% sodium lauryl sulphate 3% benzin of Kp.
120-140.degree.C. ______________________________________
Example 14 ______________________________________ 75%
perchloroethylene 7% methyl ethyl ketone 10% ethyl acetate 5%
isopropanol 3% sodium lauryl sulphate
______________________________________
Finally compositions with considerably changing concentrations of
the ingredients were examined, i.e., compositions with a
considerably higher or lower amount of methylene chloride, methyl
ethyl ketone, ethyl aceate, surface active substances and alcohols
according to examples 1 to 10. It was observed that within a great
range dirt lubricant solubility is to be called good or very good,
but that the residence time of the lubricants soaked by the solvent
increases with a decreasing amount of methylene chloride, whereas
the wettability of the dirty places increases with a rising amount
of surface active substances.
TEST COMPARISON REPORT
In the following manner the superiority of the detergent
compositions of the invention in comparison with the known
detergents of comparable mixture was proved in the preceding and in
the following comparative examples. On 1 m.sup.2 pottery tiles were
subsequently spread 250.sup.g each of
a. varnish of a polyacrylic resin
b. a mixed styrene butadiene polymer
c. a dispersion of polyvinyl acetate
d. lignite tar
e. motor oil recovered from waist oils and fat,
and submitted to an ageing process, comprising the following steps:
for 12 hours the tiles were dryed by infrared light and aerated and
then for 12 hours submitted to a relative humidity of 65% at
20.degree. C. The prepared tiles were then treated with each 250 g
of the detergent in the composition of the invention and of the
fluid detergent known from the German published Pat. application
No. 1,200,460. In the examples which follow, after 5 minutes time,
we tried to remove the impurities with water. Out of the known
detergents were applied those of example 1 (with
perchloroethylene), 2 and 6 of the German published Pat. No.
1,200,460.
The composition of Example 1 of the German patent contains 80 parts
by weight of carbon tetrachloride or perchloroethylene and 20 parts
by weight of a 80% technical alkyl benzene acid, neutralized with
15 parts by weight of crude pyridine.
The composition of Example 2 of the German patent contains 2320
parts by weight of perchloroethylene, 100 parts by weight of a
sulfated polyglycol ether of fat alcohol and 660 parts by weight of
the above-mentioned alkylbenzene sulfonic acid neutralized with 330
parts by weight of crude pyridine and 165 parts by weight of
morpholine.
The composition of Example 6 of the German patent contains 2,600
parts by weight of perchloroethylene, 1,000 parts by weight of
decylphenolepolyglycolether and 390 parts by weight of a 80%
dibutylnaphtalenesulfonic acid, which was neutralized with 100
parts by weight of pyridine.
These compositions were capable of solving only oils (e) and tars
(d); only these tars and fats could be removed in the form of
aqueous emulsions; varnishes, e.g. resins (a), (b) and (c)
remained; however, unchanged and could not be removed. For
comparison the following mixtures in the composition of the
invention were applied:
1) 800 g perchloroethylene 80 g methylene chloride 40 g methyl
ethyl ketone 30 g isopropanol 200 g sodium lauryl sulphate. 2) 25%
by weight of methylene chloride 25% by weight of ethyl acetate 40%
by weight of isopropanol 10% by weight of sodium lauryl sulphate.
3) 15.5% by weight of methylene chloride 37.5% by weight of
butanone 40% by weight of isopropanol 7% by weight of sodium lauryl
sulphate. 4) 12% by weight of methylene chloride 25% by weight of
methyl ethyl ketone 50% by weight of isopropanol 13% by weight of
sodium lauryl sulphate.
In the four cases all inpurities spread on the tiles could be
solved quickly and removed easily with water.
The same results were obtained when cleaning spatulas, brushes,
etc. soiled with oil, tar, paint and varnish. In most of the cases
there was required a residence time of only 1 minute; set residues
of resin, varnish and paint required depending on the hardening
rate a longer residence time. The detergents of the German Pat. No.
1,200,460 and liquid hydrocarbon-based cleansing agents proved to
be insufficient.
Therefore it can be seen that in general the known detergents which
were used for comparison are effective at solving oil and fat but
have no or only minor solving efficiency to solve varnish, paint
and resin. In contrast the detergents of the present invention
varnish, paint and resin easily. Thus, the detergents of the
present invention are universal cleaning agents.
* * * * *