U.S. patent number 3,887,497 [Application Number 05/341,383] was granted by the patent office on 1975-06-03 for liquid cleansing composition and method of producing.
Invention is credited to George B. Ulvild.
United States Patent |
3,887,497 |
Ulvild |
June 3, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
Liquid cleansing composition and method of producing
Abstract
A relatively stable, liquid cleansing composition containing (a)
an alkylbenzene sulfonic acid detergent surfactant, (b) an alkaline
builder or a builder which is a mineral acid or inorganic salt
thereof, (c) a normally liquid organic solvent, and (d) water. The
molar ratio of builder material to the detergent surfactant is from
0.01:1 to 3:1, the weight ratio of solvent to detergent surfactant
is within the range of 1:1 to 5:1 and water may be present in the
composition in amounts from about 4 to 80 weight percent.
Inventors: |
Ulvild; George B. (Corpus
Christi, TX) |
Family
ID: |
23337324 |
Appl.
No.: |
05/341,383 |
Filed: |
March 15, 1973 |
Current U.S.
Class: |
510/420; 134/2;
134/40; 510/365; 510/432; 510/480 |
Current CPC
Class: |
C11D
1/22 (20130101); C11D 3/43 (20130101) |
Current International
Class: |
C11D
1/02 (20060101); C11D 3/43 (20060101); C11D
1/22 (20060101); C11D 17/00 (20060101); C11d
003/065 (); C11d 003/08 (); C11d 003/10 () |
Field of
Search: |
;134/40
;252/526,527,529,539,139,143,144,156,545,546,548,158,159,558,559,525,DIG.14 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Sebastian; Leland A.
Attorney, Agent or Firm: Rice; Stewart N.
Claims
What is claimed is:
1. A one phase cleansing composition comprising (a) an anionic
detergent surfactant which is an alkylamine salt or an alkylolamine
salt of an alkylbenzene sulfonic acid, (b) a normally liquid
organic solvent, (c) water and (d) an alkaline builder material or
a builder material which is a mineral acid or a neutral or acidic
inorganic salt thereof, wherein in said composition the molar ratio
of said builder material to said detergent surfactant is within the
range of 0.01:1 to 3:1, wherein the weight ratio of said solvent to
said detergent surfactant is within the range of 1:1 to 5:1,
wherein said water is present in amounts of from about 4.0 to 80
weight per cent, and wherein the alkyl portion of said alkylbenzene
sulfonic acid contains substantially from 11 to 13 carbon
atoms.
2. The cleansing composition of claim 1 wherein said builder
material is an alkaline builder material, wherein said solvent is a
non-polar normally liquid hydrocarbon solvent, and wherein the
ratio of said alkaline builder material to said detergent
surfactant is within the range of 0.01:1 to 1:1.
3. The cleansing composition of claim 2 wherein said detergent
surfactant is a salt of a monoalkylamine containing 1 to 6 carbon
atoms.
4. The cleansing composition of claim 2 wherein said solvent is a
petroleum derived, substantially aliphatic hydrocarbon solvent
having a boiling range of about 300.degree.F to 550.degree.F and
having a neutralization number of 0.01 or below, and wherein said
water is present in amounts of 65 weight per cent or below.
5. The cleansing composition of claim 4 wherein said alkaline
builder material is selected from the group consisting of (i) the
inorganic alkali metal or ammonium phosphates, (ii) the inorganic
alkali metal or ammonium silicates, (iii) the inorganic alkali
metal or ammonium carbonates, (iv) the inorganic alkali metal or
ammonium borates, (v) ammonium hydroxide, (vi) the alkali metal
hydroxides, (vii) the alkaline salts of nitrilotriacetic acid,
(viii) the alkaline salts of the unsubstituted or hydroxy
substituted carboxylic acids, (ix) the alkylolamines, (x) the
alkylenepolyamines having the one or more of the hydrogens thereof
substituted with hydroxyalkyl groups and/or with
carboxyl-substituted alkyl groups or the alkali salts thereof
and/or with carboxyl groups or the alkali salts thereof, and (xi)
mixtures thereof.
6. The cleansing composition of claim 5 wherein the molar ratio of
said builder material to said detergent surfactant is within the
range of 0.04:1 to 0.55:1.
7. The cleansing compositions of claim 2 wherein said solvent is a
petroleum derived, substantially aliphatic hydrocarbon solvent
having a boiling range of about 300.degree.F to 550.degree.F and
having a neutralization number above 0.01 and below 0.04, and
wherein said water is present in amounts above 65 weight per
cent.
8. The cleansing composition of claim 7 wherein said alkaline
builder material is selected from the group consisting of (i) the
inorganic alkali metal or ammonium phosphates, (ii) the inorganic
alkali metal or ammonium silicates, (iii) the inorganic alkali
metal or ammonium carbonates, (iv) the inorganic alkali metal or
ammonium borates, (v) ammonium hydroxide, (vi) the alkali metal
hydroxides, (vii) the alkaline salts of nitrilotriacetic acid,
(viii) the alkaline salts of the unsubstituted or hydroxy
substituted carboxylic acids, (ix) the alkylolamines, (x) the
alkylenepolyamines having the one or more of the hydrogens thereof
substituted with hydroxyalkyl groups and/or with
carboxyl-substituted alkyl groups or the alkali salts thereof
and/or with carboxyl groups or the alkali salts thereof, and (xi)
mixtures thereof.
9. The cleansing composition of claim 8 wherein the molar ratio of
said builder material to said detergent surfactant is within the
range of 0.04:1 to 0.55:1.
10. The cleansing composition of claim 6 wherein said detergent
surfactant is a salt of a monoalkylamine containing 1 to 6 carbon
atoms.
11. The cleansing composition of claim 9 wherein said detergent
surfactant is a salt of monoalkylamine containing 1 to 6 carbon
atoms.
12. The cleansing composition of claim 1 wherein said builder
material is an alkaline builder material selected from the group
consisting of (i) the inorganic alkali metal or ammonium
phosphates, (ii) the inorganic alkali metal or ammonium silicates,
(iii) the inorganic alkali metal or ammonium carbonates, (iv) the
inorganic alkali metal or ammonium borates, (v) ammonium hydroxide,
(vi) the alkali metal hydroxides, (vii) the alkaline salts of
nitrilotriacetic acid, (viii) the alkaline salts of the
unsubstituted or hydroxy substituted carboxylic acids, (ix) the
alkylolamines, (x) the alkylenepolyamines having the one or more of
the hydrogens thereof substituted with hydroxyalkyl groups and/or
with carboxyl-substituted alkyl groups or the alkali salts thereof
and/or with carboxyl groups or the alkali salts thereof, and (xi)
mixtures thereof.
13. The cleansing composition of claim 12 wherein said solvent is a
polar solvent, and wherein the ratio of said alkaline builder
material to said detergent surfactant is within the range of 0.01:1
to 1.5:1.
14. The cleansing composition of claim 13 wherein said polar
solvent is free of halogen atoms and is selected from the group
consisting of glycol ethers and cyclic ketones.
15. The cleansing compositon of claim 1 wherein said builder is a
builder material which is a mineral acid or a neutral or acidic
inorganic salt thereof.
16. The cleansing composition of claim 15 wherein said solvent is a
non-polar, petroleum derived, substantially aliphatic hydrocarbon
solvent having a boiling range of about 250.degree.F to
800.degree.F and having a neutralization number of 0.01 or below,
wherein said water is present in amounts of 65 weight per cent or
below, and wherein the molar ratio of said builder to detergent
surfactant is within the range of 0.04:1 to 0.70:1.
17. The cleansing composition of claim 15 wherein said solvent is a
non-polar petroleum derived, substantially aliphatic hydrocarbon
solvent having a boiling range of about 250.degree.F to
800.degree.F and having a neutralization number of within the range
of above 0.01 and below 0.04, wherein said water is present in
amounts of above 65 weight per cent, and wherein the molar ratio of
said builder to said detergent surfactant is within the range of
0.04:1 to 0.70:1.
18. The cleansing composition of claim 15 wherein said solvent is a
polar solvent and wherein the molar ratio of said builder to said
detergent surfactant is within the range of 0.04:1 to 2.7:1.
19. The cleansing compositon of claim 18 wherein said polar solvent
is free of halogen atoms and is selected from the group consisting
of glycol ethers and cyclic ketones, and wherein said detergent
surfactant is a salt of a monoalkylamine having 1 to 6 carbon
atoms.
20. The cleansing composition of claim 18 wherein said builder is a
mineral acid builder.
21. A method of producing a one phase cleansing composition
containing (a) an anionic detergent surfactant which is an
alkylamine salt or an alkylolamine salt of an alkylbenzene sulfonic
acid, (b) a normally liquid organic solvent, (c) water and (d) an
alkaline builder material or a builder material which is a mineral
acid or a neutral or acidic inorganic salt thereof, wherein in said
composition the molar ratio of said builder material to said
detergent surfactant is within the range of 0.01:1 to 3:1, wherein
the weight ratio of said solvent to said detergent surfactant is
within the range of 1:1 to 5:1, wherein said water is present in
amounts of from about 4.0 to 80 weight per cent, and wherein the
alkyl portion of said alkylbenzene sulfonic acid contains
substantially from 11 to 13 carbon atoms, which method comprises
the sequential steps of (1) firstly mixing together said organic
solvent and said detergent surfactant, (2) secondly adding to and
blending with the thus formed mixture of solvent and detergent
surfactant a concentrated solution of said builder material
dissolved in a portion of said water and (3) finally adding to and
blending the remaining portion of said water with the mixture
resulting from steps (1) and (2) above.
22. The method of claim 21 wherein said builder material is an
alkaline builder material and said solvent is a non-polar solvent.
Description
BACKGROUND OF THE INVENTION
The present invention relates to a new and useful liquid cleansing
composition, and to a method for producing such composition.
Three component liquid systems consisting of organic solvent,
certain alkylbenzene sulfonic acid detergent surfactants and
varying amounts of water offer possibilities for a wide range of
effective cleansing products. However use of such three component
liquid systems has heretofore been limited because of typically
undesirable storage characteristics and/or undesirable viscosity
characteristics. For example such systems frequently form
undesirable gels or suffer from liquid phase separation problems or
have hard to manage high viscosity characteristics at temperatures
below about 60.degree.F. In addition to other storage problems,
such three component liquid systems are quite corrosive to some
metals and adversely affect the condition of mild steel or tinplate
steel normally used in the industry for storage vessels. This is
due somewhat to the acid nature of the detergent surfactants.
It is thus the object of the present invention to provide a new and
useful liquid cleansing composition containing certain alkylbenzene
sulfonic acid type detergents, water and an organic solvent which
has desirable storage characteristics. It is another object of the
present invention to provide such a cleansing composition which is
less corrosive than those known in the prior art. It is a further
object of the present invention to provide a cleansing composition
containing such ingredients which have improved cleansing
properties. It is another object of the present invention to
provide a method for producing such a cleansing composition.
Additional objects will become apparent from the following
description of the present invention.
SUMMARY OF THE INVENTION
These and other objects are accomplished by the present invention
which in one of its aspects is a cleansing composition comprising
(a) an anionic detergent surfactant which is an alkylamine salt or
an alkylolamine salt of an alkylbenzene sulfonic acid (b) a
normally liquid organic solvent (c) water and (d) a builder
material which is an alkaline builder, a mineral acid builder or an
inorganic, neutral or acidic, mineral acid salt builder, wherein in
said composition the molar ratio of said builder material to said
detergent surfactant is within the range of 0.01:1 to 3:1, wherein
the weight ratio of said solvent to said detergent surfactant is
within the range of 1:1 to 5:1, and wherein said water is present
in amounts of from about 4.0 to 80 weight percent. In another of
its aspects the present invention is a method of producing the
foregoing described cleansing composition, which method comprises
the sequential steps of (1) firstly mixing together said organic
solvent and said detergent surfactant, (2) secondly adding to and
blending with the thus formed mixture of solvent and detergent
surfactant a concentrated solution of said builder material
dissolved in a portion of said water and (3) finally adding to and
blending the remaining portion of said water with the mixture
resulting from steps (1) and (2) above.
DETAILED DESCRIPTION OF THE INVENTION
As can be seen from the foregoing summary, the present invention
resides in the addition of a builder material in specific amounts
to the three component systems of the prior art. That an alkaline
builder material or mineral acid (or salt thereof) builder can be
successfully incorporated into a balanced one phase liquid system
of water, organic solvent, and alkylbenzene sulfonic acid type
detergent is indeed surprising since addition of electrolytes
generally effects phase separation in such liquid systems.
The detergent surfactants that may be used in the present invention
are those alkylamine or alkylolamine salts of alkylbenzene sulfonic
acids. These anionic detergent surfactants are well known in the
industry. For best results the alkyl portion of the alkylbenzene
sulfonic acid or salt contains at least 3 carbon atoms, for example
8 to 16 carbon atoms, however it is preferred that such alkyl
portion contains from 11 to 13 carbon atoms with 12 carbon atoms
being most preferable. In other words the salts of dodecylbenzene
sulfonic acid are most preferable as detergent surfactants for use
in the present invention. As between the alkylamine salts and the
alkylolamine salts the alkylamine salts are preferred, with the
monalkylamine salts being most preferable. By "monoalkylamine" is
meant those primary amines having a single alkyl group such as
methyl amine, ethyl amine, isopropyl amine, n-propyl amine, n-butyl
amine, isobutyl amine, and n-hexyl amine. The salts of
monoalkylamines of 1 to 6 carbon atoms are preferred. The most
preferred salt of an alkylbenzene sulfonic acid for use as the
detergent surfactant in the present invention is the monoisopropyl
amine salt. Alkylolamine salts include those salts of amines having
at least one hydroxyalkyl group. Of the alkylolamine salts those of
monoalkylolaimes are most preferable, the term monoalkylolamine
being used to refer to a primary amine having a single
hydroxyalkyl, (sometimes referred to as alkylol or alkanol) group
substituent. Specific alkylolamines include monoethanol amine,
diethanolamine and monoisopropanolamine. The salts of alkylolamines
containing 1 to 6 carbon atoms are preferred.
The normally liquid organic solvents useful in the present
invention include both polar and non-polar solvents although the
non-polar hydrocarbon solvents are preferred. By the term "normally
liquid" is meant liquid at 65.degree.F and atmospheric pressure. Of
the polar solvents the most useful are those free of halogen atoms,
especially those halogen-free polar solvents selected from the
group consisting of glycol ethers and cyclic ketones. The preferred
gylcol ethers, are thos of 2-12 carbon atoms of the formula R.sub.1
--O--R--OH wherein R.sub.1 is an alkyl or hydroxyalkyl group and
where R is an alkylene group, such as 2 -methoxy ethanol,
diethylene glycol, 2-butoxy ethanol, and 5-ethoxy-1-pentanol. The
cyclic ketones may be either carbocyclic or heterocyclic such as
N-methyl-2-pyrrolidone and cyclohexanone. The non-polar hydrocarbon
solvents useful in the present invention are preferably those
normally liquid, substantially aliphatic hydrocarbon solvents
having boiling ranges within the range of 250.degree. to
800.degree.F, preferably in the range of 300.degree. to
550.degree.F although the aromatic hydrocarbons may also be used.
The most readily available are those derived from petroleum
fractions such as kerosene, naphtha, mineral spirits, (Stoddard
solvent), no. 2 diesel fuel and the like. Kerosene and no. 2 diesel
fuel are generally the preferred solvents as compositions
containing such do the least harm to painted surfaces. When the
storage characteristics of a cleansing composition prepared using a
petroleum-derived non-polar solvent are of concern, it has been
unexpectedly discovered that the neutralization number of the
non-polar solvent is quite material. As is well known in crude
petroleums there are a great many organic compounds present in very
small amounts which can be neutralized with strong alkalis such as
sodium hydroxide or potassium hydroxide and these are sometimes
called saponifiable materials. A great many of these saponifiable
materials are naphthenic acids consisting primarily of mono or
dicyclic monocarboxylic acids such as methylcyclohexane
monocarboxylic acid. Although not all of the saponifiable
materials, and not even all of the naphthenic acids, have been
identified several of them can and usually do distill over in
refined petroleum cuts boiling from 250.degree. to 850.degree.F,
particularly kerosene. Due to modern refining methods many types of
the saponifiable materials are eliminated by other than
distillation however the naphthenic acids usually remain in the
final products in amounts of from 10 to 200 p.p.m. depending on the
source of crude, refining method, etc. The most convenient method
for measuring the presence of naphthenic acids and other
saponifiables is as a neutralization equivalent against potassium
hydroxide such as by ASTM-D974-64 test method. This latter method
gives a "neutralization number" which is actually the miliigrams of
potassium hydroxide required to neutralize the saponifiables in one
gram of non-polar solvent. As pointed out above the neutralization
number of a petroleum-derived non-polar solvent is quite material
in that it has been discovered that the neutralization number
should be above 0.01 but not exceeding 0.04 when the water content
of the cleansing composition is above 65% while the neutralization
number should be 0.01 or below when the water content of the
cleansing composition is 65% or below. For example if a cleansing
composition containing 30% of water were prepared with a kerosene
solvent having a neutralization number of 0.015 then the cleansing
composition would most likely separate into two phases after only a
short period of time, while if a kerosene with a neutralization
number of 0.008 had been used the cleansing composition would have
remained homogenous for a long period of time--even in excess of 1
year in many cases. Conversely if one were to prepare a cleansing
composition containing 75% water with a kerosene solvent having a
neutralization number of 0.008 then such would most likely separate
into two phases after about 3 hours, while if a kerosene of 0.015
neutralization number had been used then the cleansing composition
would have remained stable for a much longer period of time.
The builders useful in the present invention may vary widely and
are well known in the industry with the alkaline builders being
preferred. Both inorganic builders as well as the organic chelating
agent builders may be utilized. Included among the types of
alkaline builders which may be utilized in the present invention
are those selected from the group consisting of the invention are
those selected from the group consisting of the inorganic alkali
metal or ammonium phosphates, silicates, carbonates or borates,
ammonium hydroxide, the alkali metal hydroxides, the alkaline salts
of nitrilotriacetic acid, the alkaline salts of the unsubstituted
or hydroxysubstituted carboxylic acids, the alkylolamines, and the
alkylenepolyamines having one or more of the amino hydrogens
thereof substituted with hydroxyalkyl groups and/or carboxyalkyl
groups or the alkali salts thereof and/or with carboxyl groups or
the salts thereof. Mixtures of the foregoing may also be used. By
the term "alkali metal" as used herein and in the claims is meant
lithium, sodium, potassium, rubidium and cesium.
The inorganic alkali metal or ammonium phosphates that may be used
include the orthophosphates as well as the condensed or complex
phosphates. Specific orthophoshates include monosodium phosphate,
monoammonium phosphates, disodium phosphate, and trisodium
phosphate. Condensed or complex phosphates that may be used are
tetrasodium pyrophosphate, tetrapotassium pyrophosphate, disodium
acid pyrophosphate, sodium hexametaphosphate, sodium
tetraphosphate, and pentasodium tripolyphosphate.
The inorganic alkali metal or ammonium silicate builders that may
be used include sodium metasilicate, sodium silicate, potassium
silicate, sodium sequisilicate, and sodium orthosilicate.
Inorganic alkali metal or ammonium borate builders useful in the
present invention include sodium metaborate, sodium tetraborate
(including the anhydrous, pentahydrate and the decahydrate),
potssium tetraborate, potassium pentaborate, and sodium
perborate.
Useful inorganic alkali metal or ammonium corbonate builders
include anhydrous sodium carbonate, sodium sesquicarbonate, and
sodium bicarbonate. The useful alkali metal hydroxides include
sodium hydroxide, potassium hydroxide and lithium hydroxide with
sodium hydroxide the most preferable among the hydroxides.
The builders comprising alkaline salts of nitrilotriacetic acid
include the sodium salt of nitriloacetic acid as well as the
potassium salt thereof. The unsubstituted and hydroxyl substituted
carboxylic acids, the salts of which may be used, include glycolic
acid, citric acid, formic acid, acetic acid, butyric acid, oxalic
acid, malonic acid, succinic acid, diglycolic acid, glutaric acid,
tartaric acid and gluconic acid. For example, sodium gluconate and
disodium oxydiacetate are specific utilizable salts.
Alkylolamines useful in the present invention include primary,
secondary and tertiary amines wherein at least one amino-hydrogen
is substituted with an hydroxyalkyl group. These are generally of
the formula NR.sub.1 R.sub.2 R.sub.3 wherein R.sub.1 is a hydroxy
alkyl group and R.sub.2 and R.sub.3 may be either hydrogen, alkyl,
or hydroxylkyl. Most preferably the alkylolamines used have from 1
to 10 carbon atoms. Specific alkylolamines includes
monoethanolamine, diethanolamine, triethanolamine,
monoisopropanolamine, triisopropanolamine, morpholine,
2-amino-2-methyl-1-propanol, diethyl-aminoethanol, and
diglycolamine. Also useful are the alkaline builders which are
alkylenepolyamines having one or more of the amino hydrogens
substituted with an hydroxy alkyl group and/or a carboxyalkyl group
or alkali metal salt thereof and/or a carboxyl group or alkali
metal salt thereof. This class of builders preferably contains from
6 to 25 carbon atoms. Examples include ethylenediamine tetraacetic
acid and its tetrasodium salt, diethylenetriamine penetaacetic
acid, and N-hydroxy-ethylenediamine triacetic acid,
N-betahydroxypropyl ethylenediamine, and the trisodium salt of
N,N,N'-tris betahydroxypropyl-N'-1,2,3
tricarboxyisopropyl-ethylenediamine. Although the alkaline builders
are preferred in the present invention the builders which are
mineral acids or the neutral and acidic inorganic salts thereof may
also be used. Specific examples include orthophosphoric acid,
sulfuric acid, hydrochloric acid, sodium sulfate, magnesium
sulfate, and sodium chloride.
It has been found that the cleansing compositions of the present
invention are best accomplished by blending the ingredients in a
particular sequence in order to avoid flocculation, gelling or
lumping. Namely, it is preferred to form the cleansing compositions
by first blending together in a suitable blending vessel all of the
solvent and all of the detergent surfactant to be used. Either the
solvent can be added to the detergent surfactant or vice-versa; or
the solvent and surfactant may be added simultaneously. Next in the
sequence of steps is the addition to the solvent-surfactant mixture
of a concentrated aqueous solution of the builder material. Such
concentrated aqueous solution is formed by dissolving all of the
builder material to be utilized in a minimum amount of the water
which is to be present in the finished cleansing composition. Most
preferably the amount of water utilized in forming the concentrated
aqueous builder solution is only that amount required to completely
dissolve the builder at the temperatures involved, however
satisfactory results are obtained with concentrated aqueous
solutions wherein the water is present in amount of from 1.0 to 2.0
times the amount required for complete dissolution at the
temperatures involved. In this respect, the temperatures to be
maintained in all phases of the blending of components so as to
form the cleansing composition should be at least 45.degree.F and
generally not above 135.degree.F, although preferably the
temperatures are within the range of 65.degree.F to
120.degree.F.
After blending the concentrated aqueous solution of builder
material with the mixture of solvent and detergent surfactant, the
final step involves the mere addition and blending of the remaining
portion of water to be used in the cleansing composition which was
not used in forming the concentrated aqueous solution of builder
material. Undesirable results occur when the foregoing mixing
sequence is not followed. For example if water alone is added to
the mixture of synthetic detergent and solvent without the builder
present, considerable gelling or thickening is encountered soon
after introduction of the water begins which requires a great
amount of agitation over undesirably long length of time to "thin
out." If all the water and solvent are first mixed and the
detergent surfactant then added, a thick, unmanageable suspension
results. A similar thick, unmanageable suspension also results if
all the builder material dissolved in all the water is first placed
in the blending tank and then either the solvent or the synthetic
detergent, or a mixture of the latter, is then added. Further,
suitable results are not obtained by first mixing the detergent
surfactant and the builder (regardless of whether the builder is a
solid or a liquid) since these two usually will not uniformly mix,
and further addition of the solvent and/or the water results in
flocculation, gelling or lumping. It has also been unexpectedly
found that where alkali metal or ammonium carbonates are to be
utilized as builders, then the preferred blending procedure gives
products with longer storage stability. The foregoing preferred
blending procedure is especially applicable when using non-polar
solvents as they present the most problems of gel formation
although it is also preferred for polar solvents as well.
The best use for the cleansing compositions of the present
invention is in application where they are used to loosen soil,
dirt and grease from hard surfaces and then wash away with water.
The cleansing compositions generally fall into three classes --
light duty general maintenance cleaners, medium duty degreasers and
heavy duty degreasers -- with the main difference in the three
classes being in the amount of water present. Generally speaking
the light duty cleaners have present from about 65 to 80 weight
percent water, the medium duty degreasers from about 40 to 65
weight percent water and the heavy duty degreasers from about 4 to
40 weight percent water. Of course other factors than water
concentration are to be considered in selecting a cleansing
composition for a particular job since the choice of a builder and
solvent also affects cleansing characteristics. The light duty
general maintenance cleaners can be used to remove thin films of
grease, pigment stains, general dirt, waxes, and/or metallic
oxides. The medium duty degreasers are generally used to remove
grease deposits which range up to about 0.10 inches in thickness
with the heavy duty degreasers being used for thicker deposits
which are usually harder crusted.
In preparing a cleansing composition of the present invention, the
molar ratio of builder material to detergent surfactant must be
maintained within critical ranges. Generally such molar ratio will
be within the range of 0.01:1 to 3:1 however the preferred ratio
for any particular cleansing composition will vary according to the
nature of the solvent, surfactant and builder being used. When a
non-polar solvent and an alkaline builder are being used the molar
ratio of builder to surfactant is preferably 0.01:1 to 1:1,
especially 0.04:1 to 0.55:1. When a non-polar solvent and a mineral
acid or a neutral or acidic mineral acid salt builder is utilized,
the molar ratio of builder to surfactant is preferably within the
range of 0.01:1 to 1:1, especially 0.04:1 to 0.70:1. When utilizing
a polar solvent and an alkaline builder such molar ratio is
preferably within the range of 0.01:1 to 1.5:1, especially 0.04:1
to 0.90:1. When utilizing a polar solvent and a mineral acid or a
neutral or acidic salt builder, the molar ratio of builder to
surfactant is preferably within the range of 0.01:1 to 3.0:1,
especially 0.04:1 to 2.7:1 .
The following examples serve to illustrate but not to limit the
present inventon. All ratios, parts and percentages are by weight
unless otherwise specified.
Several cleansing compositions were prepared in accordance with the
present invention and the composition of each is hereafter set
forth. The water utilized in each cleansing composition was soft
water containing less than one grain hardness per gallon, and the
detergent surfactant utilized in each composition was the
monoisopropylamine salt of dodecylbenzenesulfonic acid.
COMPOSITION A
An excellent medium duty cleaner composition found to be useful in
cleansing is as follows: Soft water 62.5% Detergent surfactant 9.0
Kerosene, neut. no. 0.009 27.0 Potassium tetraborate.4H.sub.2 O
1.5
The molar ratio of builder to surfactant in this composition is
0.209:1. This composition was prepared by placing 2700 pounds of
the kerosene in a 1500 gallon stainless steel mixing tank fitted
with a mechanical propeller type stirrer and then slowly adding 900
pounds of the surfactant thereto with mechanical stirring. After
addition of the surfactant was complete, a concentrated solution of
the potassium tetraborate was formed by dissolving 150 pounds of
such in about 1000 pounds of water and then such concentrated
solution slowly added to the mixing tank with stirring. As the
final step, 5,250 pounds of water was added fairly fast with
stirring. The temperature in all the mixing steps was maintained at
about 77.degree.F. This composition could be stored in mild steel
containers.
COMPOSITION B
An excellent heavy duty cleansing composition was prepared
utilizing the following ingredients:
Soft water 25.00% Detergent surfactant 18.00 Trisodium
phosphate.12H.sub.2 O 3.00 Kerosene, neut. no. 0.009 54.00
This composition is suitable for storage in mild steel. The molar
ratio of builder to surfactant is 0.168:1.
COMPOSITION C
Another excellent heavy-duty cleansing composition was prepared
from the following ingredients:
Soft water 16.31% Detergent surfactant 20.60 Sodium
metasilicate.5H.sub.2 O 1.29 Kerosene, neut. no. 0.009 61.80
The molar ratio of builder to surfactant was 0.113:1. This
composition may be stored in mild steel.
COMPOSITION D
A medium duty cleansing composition was preapred from the following
ingredients:
Soft water 50.50% Detergent surfactant 12.10 Sodium carbonate 1.10
Kerosene, neut. no. 0.009 36.30
The molar ratio of builder to surfactant was 0.329:1. This
composition may be stored in mild steel.
COMPOSITION E
A light duty cleansing composition was prepared from the following
ingredients:
Soft water 75.00% Detergent surfactant 6.00 NTA, trisodium
salt.H.sub.2 O 1.00 Kerosene, neut. no. 0.015 18.00
The molar ratio of builder to surfactant was 0.233:1. NTA is the
abbreviation for nitrilotriacetic acid. This composition may be
stored in mild steel. In the above composition the trilithium salt
or a mixed alkali metal salt of NTA could be used.
COMPOSITION F
A heavy duty cleansing composition was prepared from the following
ingredients:
Soft water 5.10% Detergent surfactant 23.40 Sodium hydroxide 1.30
Kerosene, neut. no. 0.009 70.20
The molar ratio of builder to surfactant was 0.533:1. This
composition may be stored in mild steel.
COMPOSITION G
A heavy duty cleansing composition was prepared from the following
ingredients:
Soft water 10.33% Detergent surfactant 21.96 Ammonium hydroxide
1.83 Kerosene, neut. no. 0.009 65.88
The molar ratio of builder to surfactant was 0.912:1. The
composition could be stored in mild steel.
COMPOSITION H
A heavy duty cleansing composition was prepared from the following
ingredients:
Soft water 41.78% Detergent surfactant 14.20 Sodium gluconate 1.42
Kerosene, neut. no. 0.009 42.60
The molar ratio of builder to surfactant was 0.176:1. Storage of
this composition in other than a mild-steel container is
recommended.
COMPOSITION I
A light duty cleansing composition was prepared from the following
ingredients:
Soft water 70.33% Detergent surfactant 7.30 Sodium acetate.3H.sub.2
O 0.47 Kerosene, neut. no. 0.015 21.90
The molar ratio of builder to surfactant was 0.182:1. Storage of
this composition in other than a mild steel container is
recommended.
COMPOSITION J
A light duty cleansing composition was prepared from the following
ingredient:
Soft water 75.10% Detergent surfactant 6.10 Dilithium oxydiacetate
0.50 Kerosene, neut. no. 0.009 18.30
The molar ratio of builder to surfactant was 0.215:1. Storage of
this composition in mild steel is not recommended.
COMPOSITION K
A medium duty cleansing composition was prepared from the following
ingredients:
Soft water 48.15% Detergent surfactant 12.75 Disodium oxydiacetate
0.85 Kerosene, neut. no. 0.015 38.25
The molar ratio of builder to surfactant was 0.144:1. Storage of
this composition in mild steel is not recommended.
COMPOSITION L
A light duty cleansing composition was prepared from the following
ingredients:
Soft water 71.94% Detergent surfactant 6.90 Triethanol amine 0.46
Kerosene, neut. no. 0.015 20.70
The molar ratio of builder to surfactant was 0.171:1. This
composition may be stored in mild steel containers.
COMPOSITION M
A light duty cleansing composition was prepared from the following
ingredients:
Soft water 75.06% Detergent surfactant 6.02 Ethylenediamine
tetraacetic acid, tetrasodium salt 0.86 Kerosene, neut. no. 0.015
18.06
The molar ratio of builder to surfactant was 0.144:1. Storage of
this composition may be in mild steel containers.
COMPOSITION N
A light duty cleansing composition was prepared from the following
ingredients:
Soft water 66.88% Detergent surfactant 8.16 Disodium
succinate.6H.sub.2 O 0.48 Kerosene, neut. no. 0.015 24.48
The molar ratio of builder to surfactant was 0.0836:1. Storage of
this composition in mild steel is not recommended.
COMPOSITION O
A light duty cleansing composition was prepared from the following
ingredients:
Soft water 75.00% Detergent surfactant 6.00 Sulfuric acid builder
1.00 Kerosene, neut. no. 0.015 18.00
The molar ratio of builder to surfactant was 0.652:1. Storage of
this composition in mild steel is not recommended.
COMPOSITION P
A light duty cleansing composition was prepared from the following
ingredients:
Soft water 74.00% Detergent surfactant 6.00 NTA, trisodium
salt.H.sub.2 O 2.00 2-Butoxy ethanol 18.00
The molar ratio of builder to surfactant was 0.465:1. This
composition may be stored in mild steel.
COMPOSITION Q
A light duty cleansing composition was prepared from the following
ingredients:
Soft water 74.22% Detergent surfactant 5.95 NTA, trisodium
salt.H.sub.2 O 1.98 N-methyl-2-pyrrolidone 17.85
The molar ratio of builder to surfactant was 0.464:1. This
composition may be stored in mild steel.
COMPOSITION R
A heavy duty cleansing composition was prepared from the following
ingredients:
Soft water 30.27% Detergent surfactant 16.87 Trisodium
phosphate.12H.sub.2 O 2.25 140.degree.F flash naphtha, neut. no.
0.007 50.61
The molar ratio of builder to surfactant was 0.135:1. The flash
naphtha was predominately aliphatic. Storage of this composition
may be in mild steel.
COMPOSITION S
A light duty cleansing composition was prepared from the following
ingredients:
Soft water 72.46% Detergent surfactant 6.80 NTA, trisodium
salt.H.sub.2 O 0.34 Mineral spirits, neut. no. 0.012 20.40
The molar ratio of builder to surfactant was 0.0697:1. The mineral
spirits utilized were petroleum refined, substantially aliphatic
hydrocarbons. Storage of this composition may be in mild steel.
COMPOSITION T
A heavy duty cleansing composition was preapred from the following
ingredients:
Soft water 8.60% Detergent surfactant 24.23 Triethanolamine 2.60
Heavy aromatic naphtha, neut. no. 0.020 64.57
The molar ratio of builder to surfactant was 0.276:1. This
composition may be stored in mild steel containers.
COMPOSITION U
A heavy duty cleansing composition was prepared from the following
ingredients:
Soft water 35.42% Detergent surfactant 15.80 Trisodium salt of
N,N,N'-tris betahydroxypropyl-N'-1,2,3 tri- carboxy
isopropyl-ethylenediamine 1.38 Kerosene, neut. no. 0.009 47.40
The molar ratio of builder to surfactant was 0.0706:1. This
composition has excellent rinseability characteristics. Storage in
mild steel is however not recommended.
COMPOSITION V
A light duty cleansing composition was prepared from the following
ingredients:
Soft water 75.00% Detergent surfactant 6.00 Sodium citrate.2H.sub.2
O 1.00 Kerosene, neut. no. 0.015 18.00
The molar ratio of builder to surfactant was 0.217:1. Storage of
this composition in mild steel is not recommended.
COMPOSITION W
A light duty cleansing composition was prepared from the following
ingredients:
Soft water 74.92% Detergent surfactant 6.08 Sodium sulfate 0.76
Kerosene, neut. no. 0.015 18.24
The molar ratio of builder to surfactant was 0.338:1. Storage of
this composition in mold steel is not recommended.
COMPOSITION X
A heavy duty cleansing composition was prepared from the following
ingredients:
Soft water 37.15% Detergent surfactant 15.60 Magnesium
sulfate.7H.sub.2 O 0.45 Kerosene, neut. no. 0.009 46.80
The molar ratio of builder to surfactant was 0.0449:1. Storage of
this composition in mild steel is not recommended.
In order to illustrate the cleansing properties of the compositions
of the present invention several runs were made in each of which a
flat test panel coated with white enamel paint was placed in a
horizontal position in a basin and then a test grease evenly
applied to the upper surface of the test panel. Different panels
were utilized for each run although they were identical to each
other. After the test grease was applied it was allowed to dry for
24 hours and then an amount of cleansing composition was placed in
the basin so as to be a uniform depth over the panels. The soiled
test panels were allowed to soak in the cleansing composition until
it appeared that the grease deposits had been dissolved and fluxed,
and the time required for such noted. The test panels were then
flushed with sufficient constant pressure tap water (eleven grains
hardness per gallon) to emulsify and rinse away the test grease and
cleansing composition as completely as practicable, and the amount
of flush water so required as well as the condition of the test
panel was noted. All tests were carried out inside a building in
open air at about 75.degree.F, 75% relative humidity and no wind
velocity.
EXAMPLE 1
The cleansing characteristics of Composition B above as well as a
control composition was tested according to the foregoing
procedure. The control composition was practically identical to
Composition B except that the builder was left out. The test grease
utilized was a clean SAE-90 gear lubricant and such was applied in
a thickness of 0.15 inch or a total of 20 pounds per panel. Using
26 pounds of cleansing composition in each run about 20 minutes was
required of both Composition B and the control composition to flux
the test grease, however only 195 pounds of flush water was needed
for Composition B while 290 pounds of flush water was required for
the control. Also the pressure of the flush water required for the
control was 30 p.s.i.g. as opped to 20 p.s.i.g. for Composition B.
In both runs it appeared that 100% of the test grease had been
removed from the panels and that there was no soil redeposition. In
neither run did there appear to be any paint stripping.
EXAMPLE 2
The cleansing characteristics of Composition E above as well as a
control composition was tested according to the foregoing
procedure. The control composition was practically identical to
Composition E except that the builder was deleted. The test grease
utilized was about 11% SAE-90 gear lubricant, 81% scrapings from
inside an automobile engine crankcase and 8% dirty oil removed from
an automobile engine crankcase. The test grease was applied to the
panels and a thickness of 0.03 inch or a total weight of 0.001
pound per panel. Utilizing about 4.5 pounds of cleaner in each run,
Composition E required about 60 minutes fluxing time while the
control required about 75 minutes. Composition E required 50 pounds
of flush water at 20 p.s.i.g. while the control required 125 pounds
at 30 p.s.i.g. It appeared that Composition E removed 100% of the
test grease with a no soil redeposition taking place, while the
control composition removed slightly less than all of the test
grease and some soil redeposition occurred as several film spots
were noted. No paint stripping was observed in either run.
EXAMPLE 3
The cleansing characteristics of Composition P above as well as a
control composition was tested according to the foregoing
procedure. The control composition was practically identical to
Composition P except that the builder was deleted. The test grease
utilized was about 28% SAE-90 gear lubricant, 5% dirty axle grease,
11% printer's ink, and 56% clay. The test grease was applied to the
panels and a thickness of 0.005 inch or a total weight of 0.75
pound per panel. Utilizing about 10.5 pounds of cleaner in each
run, Composition P required only about 45 minutes fluxing time
while the control required about 75 minutes. Composition P required
65 pounds of flush water at 15 p.s.i.g. while the control required
95 pounds at 20 p.s.i.g. It appeared that both Composition P and
the control removed 100% of the test grease and no soil
redeposition was observed in either run. There was some slight
blistering of paint in both of the runs.
In order to test the storage stability of various cleansing
compositions and their corrosion of mild steel, several cleansing
compositions were placed in a DOT-17E-20/18 guage mild steel drums
and the drums stoppered. The cleansing compositions were stored in
the drums for 1 year with the temperature varying between about
60.degree.F and 90.degree.F during that time. The cleansing
compositions were frequently observed during the year. It was
observed that cleansing Composition B was very slightly turbid
after 1 year but otherwise clean and useable. The drum lining was
essentially uncorroded there being only about two or three tiny
rust spots along one of the seams. On the contrary the control
composition analogous to Composition B (see Example 1 above) was
moderately turbid after two months storage with some evidence of
very fine rust particles in suspension. At 3.5 months the control
composition was very turbid and rusty appearing and the drum lining
was extensively etched and pitted with several large flakes of
rusted steel on the bottom of the drum. At the end of 1 year the
control composition analogous to Composition B had corroded four
pin-hole leaks in the drum where the bottom joined the sides.
The storage and corrosion characteristics of Composition E and its
un-built control were also observed for 1 year with results very
similar to that of Composition B and its un-built control. That is
Composition E was stable at the end of one year with very little
corrosion observed while the un-built control analogous to
Composition E showed strong corrosion after 3 months. Furthermore
the un-built control analogous to Composition E separated into two
ligquid phases after about 4 months.
In order to illustrate the materiality of the neutralization number
of non-polar solvent utilized in forming a cleansing composition,
two cleansing compositions were prepared containing 75.00% soft
water, 6.10% of the monoisopropylamine salt of dodecylbenzene
sulfonic acid, 0.60% monoammonium phosphate, and 18.30% kerosene.
However in one of the compositions the kerosene had a
neutralization number of 0.009 while in the other the kerosene had
a neutralization number of 0.013. The cleansing composition
utilizing the kerosene having a neutralization number of 0.009
separated into two liquid phases after about 3 hours time at
60.degree.F to 90.degree.F while the composition utilizing the
kerosene with the neutralization number of 0.013 remained
homogeneous for at least one year at 60.degree.F to 105.degree.F.
Similar tests have shown that where the water is present in the
cleansing composition in amounts of less than 65% that the
neutralization number of the kerosene should be 0.01 or below in
order to prevent phase separation. It is pointed out that the
amount of saponifiable materials in a non-polar solvent has an
effect both when using acidic builders, neutral builders and
alkaline builders however by far the greatest advantage is obtained
when alkaline builders are being utilized.
The compositions herein described find their main use as cleansing
compositions, but are also useful as oil spill dispersents to be
poured upon oil slicks on water. They are also suitable wetting
agents which may be added to strong acid or alkali solutions used
in descaling or derusting operations as well as in oil and gas well
operations to dissolve formations or loosen sludge.
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