U.S. patent number 3,929,678 [Application Number 05/493,953] was granted by the patent office on 1975-12-30 for detergent composition having enhanced particulate soil removal performance.
This patent grant is currently assigned to The Procter & Gamble Company. Invention is credited to Vincent Paul Heuring, Robert Gene Laughlin.
United States Patent |
3,929,678 |
Laughlin , et al. |
December 30, 1975 |
Detergent composition having enhanced particulate soil removal
performance
Abstract
Detergent compositions are disclosed incorporating combinations
of specified ethoxylated zwitterionic compounds with other types of
surfactants and with detergent builders to give enhanced
particulate soil removal.
Inventors: |
Laughlin; Robert Gene
(Cincinnati, OH), Heuring; Vincent Paul (Cincinnati,
OH) |
Assignee: |
The Procter & Gamble
Company (Cincinnati, OH)
|
Family
ID: |
25767502 |
Appl.
No.: |
05/493,953 |
Filed: |
August 1, 1974 |
Current U.S.
Class: |
510/349; 510/341;
510/340; 510/351; 510/355; 510/494; 510/441; 510/352; 510/350;
987/110 |
Current CPC
Class: |
C11D
1/886 (20130101); C11D 1/88 (20130101); C11D
1/94 (20130101); C11D 3/361 (20130101); C07F
9/54 (20130101) |
Current International
Class: |
C07F
9/00 (20060101); C07F 9/54 (20060101); C11D
1/94 (20060101); C11D 3/36 (20060101); C11D
1/88 (20060101); C11D 003/066 (); C11D
001/18 () |
Field of
Search: |
;252/526,527,545,DIG.11
;260/501.12 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
813,502 |
|
0000 |
|
BE |
|
2,009,802 |
|
Nov 1970 |
|
DT |
|
Primary Examiner: Welsh; John D.
Attorney, Agent or Firm: Witte; Richard C. Filcik; Julius P.
Wilson; Charles R.
Claims
What is claimed is:
1. A detergent composition comprising
A. 1 to 99% by weight of the composition of a compound having a
formula selected from the group consisting of ##EQU31## wherein
R.sub.1 is selected from the group consisting of straight and
branched chain C.sub.8 -C.sub.30 alkyl and alkenyl moieties and
alkaryl moieties in which the alkyl group has 10-24 carbon
atoms;
R.sub.2 is selected from the group consisting of straight and
branched chain C.sub.8 -C.sub.21 alkyl and alkenyl moieties,
alkaryl moieties in which the alkyl group has 6-16 carbon atoms,
and C.sub.1-4 alkyl and hydroxyalkyl moieties;
R.sub.3 is selected from the group consisting of straight and
branched chain C.sub.8 -C.sub.21 alkyl and alkenyl moieties,
alkaryl moieties in which the alkyl group has 6-16 carbon atoms,
C.sub.1-4 alkyl and hydroxyalkyl moieties and --(C.sub.2 H.sub.4
O).sub.x H wherein x has a value of about 3 to about 50;
R.sub.4 is selected from the group consisting of C.sub.1 -C.sub.8
alkylene, C.sub.3 -C.sub.8 alkenylene, 2-hydroxy propylene, 2- and
3-hydroxy butylene moieties and C.sub.1 -C.sub.4 alkarylene
moieties provided that where R.sub.3 is --(C.sub.2 H.sub.4 O).sub.x
H then R.sub.4 is --CH.sub.2 --CH.sub.2 --;
X.sup.- is an anion selected from the group consisting of sulfate
and sulfonate radicals; and
y has a value in the range of 2-100 provided that where R.sub.3 is
--(C.sub.2 H.sub.4 O).sub.x H then x + y .gtoreq. 10; and ##EQU32##
wherein R.sub.1 is selected from the group consisting of linear and
branched C.sub.8 -C.sub.30 alkyl and alkenyl radicals; R.sub.2 is
selected from the group consisting of linear and branched C.sub.8
-C.sub.30 alkyl and alkenyl radicals and C.sub.1 -C.sub.4 alkyl and
hydroxyalkyl radicals; X.sup.- is selected from the group
consisting of sulfate and sulfonate; y and x have values in the
range of 2-100 provided that y + x .gtoreq. 12; M is a cation
selected from the group consisting of alkali metal, ammonium and
alkanolammonium ions; and
B. 99 to 1% by weight of the composition of an organic
detergent.
2. A detergent composition according to claim 1 wherein the
detergent is selected from the group consisting of nonionic,
ampholytic, and zwitterionic surfactants and mixtures thereof.
3. A detergent composition according to claim 1 wherein the
zwitterionic compound has the formula: ##EQU33## wherein R.sub.1 is
selected from the group consisting of straight and branched chain
C.sub.16 -C.sub.22 alkyl and alkenyl moieties, R.sub.2 is a C.sub.1
-C.sub.3 alkyl group and x + y has a value in the range of
14-50.
4. A detergent composition according to claim 3 wherein R.sub.1 is
selected from the group consisting of straight and branched chain
C.sub.16-C.sub.18 alkyl and alkenyl moieties and x + y has a value
in the range of 15-25.
5. A detergent composition comprising
A. 1 - 99% by weight of the composition of a compound having the
formula ##EQU34## wherein R.sub.1, R.sub.2, and R.sub.3 are each
selected from the group consisting of branched and straight chain
C.sub.6 -C.sub.16 alkyl and alkenyl radicals;
R.sub.4 is selected from the group consisting of C.sub.1-4 alkylene
and 2-hydroxy propylene and 2- and 3-hydroxy butylene moieties and
alkarylene moieties in which the alkyl group contains from 1-4
carbon atoms; X is an anion selected from the group consisting of
sulfate and sulfonate radicals;
and y has an average value in the range of 6 to 100; and
B. 99 - 1% by weight of the composition of an organic detergent
selected from the group consisting of nonionic, ampholytic, and
zwitterionic surfactants and mixtures thereof.
6. A detergent composition according to claim 3 wherein y has a
value of at least 9.
7. A detergent composition comprising
A. 1 - 99% by weight of the composition of a compound having the
formula ##EQU35## wherein R.sub.1 and R.sub.2 are each selected
from the group consisting of branched and straight chain C.sub.6
-C.sub.21 alkyl and alkenyl radicals;
R.sub.3 is selected from the group consisting of C.sub.1 -C.sub.4
alkyl and hydroxyalkyl moieties;
R.sub.4 is selected from the group consisting of C.sub.1 -C.sub.4
alkylene and 2-hydroxy propylene and 2- and 3-hydroxy butylene
moieties, and alkarylene moieties in which the alkyl group contains
1-4 carbon atoms; X.sup.- is an anion selected from the group
consisting of sulfate and sulfonate radicals and
y has an average value in the range of 6 to 100; and
B. 99-1% by weight of the composition of an organic detergent
selected from the group consisting of nonionic, ampholytic, and
zwitterionic detergents and mixtures thereof.
8. A detergent composition according to claim 1 wherein the
compound has the formula: ##EQU36## wherein R.sub.1 is selected
from the group consisting of branched and straight chain C.sub.8
-C.sub.30 alkyl and alkenyl radicals; R.sub.2 and R.sub.3 are each
selected from the group consisting of C.sub.1 -C.sub.4 alkyl and
hydroxyalkyl moieties; R.sub.4 is selected from the group
consisting of C.sub.1 -C.sub.4 alkylene and 2-hydroxy propylene and
2- and 3-hydroxy butylene radicals and alkyarylene moieties in
which the alkylene group has 1 to 4 carbon atoms; and y has a value
of from about 6 to about 20.
9. A detergent composition according to claim 8 wherein R.sub.1 is
a C.sub.12 -C.sub.18 alkyl moiety; R.sub.2 and R.sub.3 are
independently selected from C.sub.1 -C.sub.3 alkyl and hydroxyalkyl
moieties; and y has a value from about 6 to 12.
10. A detergent composition comprising
A. 50 to 99% by weight of the composition of a compound having a
formoula selected from the group consisting of ##EQU37## wherein
R.sub.1 is selected from the group consisting of straight and
branched chain C.sub.8 -C.sub.30 alkyl and alkenyl moieties and
alkaryl moieties in which the alkyl group has 10-24 carbon
atoms;
R.sub.2 is selected from the group consisting of straight and
branched chain C.sub.8 -C.sub.21 alkyl and alkenyl moieties,
alkaryl moieties in which the alkyl group has 6-16 carbon atoms,
and C.sub.1-4 alkyl and hydroxyalkyl moieties;
R.sub.3 is selected from the group consisting of straight and
branched chain C.sub.8 -C.sub.21 alkyl and alkenyl moieties,
alkaryl moieties in which the alkyl group has 6-16 carbon atoms,
C.sub.1-4 alkyl and hydroxyalkyl moieties and --(C.sub.2 H.sub.4
O).sub.x H wherein x has a value of about 3 to about 50;
R.sub.4 is selected from the group consisting of C.sub.1 -C.sub.8
alkylene, C.sub.3 -C.sub.8 alkenylene, 2-hydroxy propylene and 2-
and 3-hydroxy butylene moieties and C.sub.1 -C.sub.4 alkarylene
moieties provided that where R.sub.3 is --(C.sub.2 H.sub.4 O).sub.x
H then R.sub.4 is --CH.sub.2 --CH.sub.2 --;
X.sup.- is an anion selected from the group consisting of sulfate
and sulfonate radicals; and
y has a value in the range of 2-100 provided that where R.sub.3 is
--(C.sub.2 H.sub.4 O).sub.x H then x + y .gtoreq. 10; and ##EQU38##
wherein R.sub.1 is selected from the group consisting of linear and
branched C.sub.8 -C.sub.30 alkyl and alkenyl radicals;
R.sub.2 is selected from the group consisting of linear and
branched C.sub.8 -C.sub.30 alkyl and alkenyl radicals and C.sub.1
-C.sub.4 alkyl and hydroxyalkyl radicals;
X.sup.- is selected from the group consisting of sulfate and
sulfonate;
y and x have values in the range of 2 to 100 provided that y + x
.gtoreq. 12;
M is a cation selected from the group consisting of alkali metal,
ammonium and alkanolammonium ions; and
B. 50 to 1% by weight of the composition of an anionic
detergent.
11. A detergent composition according to claim 10 wherein the
compounds has the formula ##EQU39## wherein R.sub.1 is selected
from the group consisting of branched and straight chain C.sub.8
-C.sub.30 alkyl and alkenyl radicals; R.sub.2 and R.sub.3 are each
selected from the group consisting of C.sub.1 -C.sub.4 alkyl and
hydroxyalkyl moieties; R.sub.4 is selected from the group
consisting of C.sub.1 -C.sub.4 alkylene and 2-hydroxy propylene and
2- and 3- hydroxy butylene radicals and alkarylene moieties in
which the alkylene group has 1 to 8 carbon atoms; and y has a value
from about 6 to about 20.
12. A detergent composition according to claim 11 wherein R.sub.1
is a C.sub.12 -C.sub.18 alkyl moiety; R.sub.2 and R.sub.3 are
independently selected from the group consisting of C.sub.1
-C.sub.3 alkyl and hydroxyalkyl moieties; R.sub.4 is selected from
C.sub.1 -C.sub.3 alkylene and hydroxyalkylene moieties; and y has a
value from about 6 to about 12.
13. A detergent composition according to claim 12 wherein the
anionic detergent is selected from the group consisting of alkali
and alkaline earth metal, ammonium and alkanol ammonium linear and
branched C.sub.10 -C.sub.14 alkyl benzene sufonates, C.sub.10
-C.sub.20 alpha-sulfo carboxylic acid salts and esters in which the
alkyl group has 1-8 carbon atoms, C.sub.10 -C.sub.20 alkane
sulfonates, C.sub.14 -C.sub.18 olefin sulfonates, C.sub.10
-C.sub.18 alkyl sulfates and condensation products thereof with
1-20 moles of ethylene oxide, and mixtures thereof.
14. A detergent composition according to claim 13 wherein the
anionic surfactant is incorporated in an intimate mixture with 5 to
50% by weight of the mixture of a material requiring more than 60
seconds for substantially complete dissolution or dispersion in an
aqueous medium at 100.degree.F.
15. A detergent composition according to claim 14 wherein the
material is an organic material selected from the group consisting
of polyethylene glycols of MWt greater than 1000, C.sub.12
-C.sub.18 fatty acid amides, C.sub.12 -C.sub.18 fatty acid
alkanolamides, C.sub.12 -C.sub.20 fatty acids and mixtures
thereof.
16. A detergent composition according to claim 14 wherein the
material is an inorganic hydratable salt.
17. A detergent composition according to claim 16 wherein the
hydratable salt is an alkali metal polyphosphate.
18. A detergent composition according to claim 14 wherein the
anionic surfactant is incorporated by coating with a material
requiring more than 60 seconds for substantially complete
dissolution or dispersion in an aqueous medium at 100.degree.F.
19. A detergent composition according to claim 18 wherein the
material is selected from the group consisting of polyethylene
glycols of MWt >1000.
20. A detergent composition according to claim 9 incorporating a
nonionic detergent selected from the group consisting of ethylene
oxide condensates of C.sub.8 -C.sub.20 branched and linear
aliphatic primary and secondary alcohols, alkyl phenols wherein the
alkyl group contains 6-12 carbon atoms, C.sub.10 -C.sub.22
aliphatic carboxylic acid esters in which the alkyl group has 1-8
carbon atoms, ethylene oxide-propylene oxide condensates.
21. A detergent composition according to claim 20 wherein the
nonionic detergent is a primary alcohol ethoxylate of the
formula
wherein R.sub.1 is a linear alkyl residue and R.sub.2 has the
formula CHR.sub.3 CH.sub.2 --; R.sub.3 being selected from the
group consisting of hydrogen and mixtures thereof with not more
than 40% by weight of C.sub.1-4 alkyl groups, wherein R.sub.1 and
R.sub.2 together form an alkyl residue having a mean chain length
in the range of 8-15 carbon atoms at least 65% by weight of said
residue having a chain length within .+-.1 carbon atoms of the
mean, wherein the average value of n lies between 3.5 and 6.5
provided that the total amount by weight of components in which n =
0 shall be not greater than 5% and the total amount by weight of
components in which n = 2-7 inclusive shall be not less than 63%,
based on the total weight of the ethoxylate and wherein the HLB of
the ethoxylate lies in the range of 9.5-11.5.
22. A detergent composition according to claim 9 wherein the
nonionic surfactant is a C.sub.10-15 alkyl, di-lower alkyl, or
hydroxy lower alkyl amine oxide.
23. A detergent composition according to claim 9 wherein the
zwitterionic surfactant is selected from the group consisting of
3-(N-C.sub.10-16 alkyl N,N-dimethylammonio)propane-1-sulfonate,
3-(N-C.sub.10-16 alkyl
N,N-dimethylammonio)-2-hydroxypropane-1-sulfonate, 3-(N-C.sub.10-15
alkyl benzyl,
N,N-dimethylammonio)-2-hydroxypropane-1-sulfonate.
24. A detergent composition comprising a mixture of (A) 5-95% by
weight of the mixture of a detergent builder and (B) 95-5% by
weight of the mixture of a combination consisting essentially of 5
to 95% by weight of the combination of a water soluble compound
having a formula selected from the group consisting of ##EQU40##
wherein R.sub.1 is selected from the group consisting of straight
and branched chain C.sub.8 -C.sub.30 alkyl and alkenyl moieties and
alkaryl moieties in which the alkyl group has 10-24 carbon
atoms;
R.sub.2 is selected from the group consisting of straight and
branched chain C.sub.8 -C.sub.21 alkyl and alkenyl moieties,
alkaryl moieties in which the alkyl group has 6-16 carbon atoms,
and C.sub.1-4 alkyl and hydroxyalkyl moieties;
R.sub.3 is selected from the group consisting of straight and
branched chain C.sub.8 -C.sub.21 alkyl and alkenyl moieties,
alkaryl moieties in which the alkyl group has 6-16 carbon atoms,
C.sub.1-4 alkyl and hydroxyalkyl moieties and --(C.sub.2 H.sub.4
O).sub.x H wherein x has a value of about 3 to about 50;
R.sub.4 is selected from the group consisting of C.sub.1 -C.sub.8
alkylene, C.sub.3 -C.sub.8 alkenylene, 2-hydroxy propylene and 2-
and 3- hydroxy butylene moieties and C.sub.1 -C.sub.4 alkarylene
moieties provided that where R.sub.3 is --(C.sub.2 H.sub.4 O).sub.x
H then R.sub.4 is --CH.sub.2 --CH.sub.2 --;
X.sup.- is an anion selected from the group consisting of sulfate
and sulfonate radicals; and
y has a value in the range of 2-100 provided that where R.sub.3 is
--(C.sub.3 H.sub.4 O).sub.x H then x + y .gtoreq.10; and ##EQU41##
wherein R.sub.1 is selected from the group consisting of linear and
branched C.sub.8 -C.sub.30 alkyl and alkenyl radicals;
R.sub.2 is selected from the group consisting of linear and
branched C.sub.8 -C.sub.30 alkyl and alkenyl radicals and C.sub.1
-C.sub.4 alkyl and hydroxyalkyl radicals;
x.sup.- is selected from the group consisting of sulfate and
sulfonate;
y and x have values in the range of 2 to 100 provided that y + x
.gtoreq. 12;
M is a cation selected from the group consisting of alkali metal,
ammonium and alkanolammonium ions and 95-5% by weight of the
combination of an organic detergent selected from the group
consisting of nonionic, zwitterionic, and ampholytic
detergents.
25. A detergent composition according to claim 24 wherein the
detergent builder is an inorganic builder, selected from the group
consisting of ammonium and alkali metal polyphosphates,
phosphonates, carbonates, bicarbonates, silicates, alumino
silicates, and sulfates.
26. A detergent composition according to claim 21 wherein the
detergent builder is an organic builder selected from the group
consisting of alkali metal nitrilotriacetates, citrates,
oxydisuccinates, carboxylmethoxysuccinates, polymaleates, and
copolymers of maleic anhydride with methyl vinyl ether or
ethylene.
27. A detergent composition comprising a mixture of (A) 5-95% by
weight of the mixture of a detergent builder and (B) 95-5% by
weight of the mixture of a combination consisting essentially of 50
to 95% by weight of the combination of a water soluble compound
having a formula selected from the group consisting of ##EQU42##
wherein R.sub.1 is selected from the group consisting of straight
and branched chain C.sub.8 -C.sub.30 alkyl and alkenyl moieties and
alkaryl moieties in which the alkyl group has 10-24 carbon
atoms;
R.sub.2 is selected from the group consisting of straight and
branched chain C.sub.8 -C.sub.21 alkyl and alkenyl moieties,
alkaryl moieties in which the alkyl group has 6-16 carbon atoms,
and C.sub.1-4 alkyl and hydroxyalkyl moieties;
R.sub.3 is selected from the group consisting of straight and
branched chain C.sub.8 -C.sub.21 alkyl and alkenyl moieties,
alkaryl moieties in which the alkyl group has 6-16 carbon atoms,
C.sub.1-4 alkyl and hydroxyalkyl moieties and --(C.sub.2 H.sub.4
O).sub.x H wherein x has a value of about 3 to about 50;
R.sub.4 is selected from the group consisting of C.sub.1 -C.sub.8
alkylene, C.sub.3 -C.sub.8 alkenylene, 2-hydroxy propylene and 2-
and 3-hydroxy butylene moieties and C.sub.1 -C.sub.4 alkarylene
moieties provided that where R.sub.3 is --(C.sub.2 H.sub.4 O).sub.x
H then R.sub.4 is --CH.sub.2 --CH.sub.2 --;
X.sup.- is an anionic selected from the group consisting of sulfate
and sulfonate radicals; and
y has a value in the range of 2-100 provided that where R.sub.3 is
--(C.sub.2 H.sub.4 O).sub.x H then x + y .gtoreq. 10; and ##EQU43##
wherein R.sub.1 is selected from the group consisting of linear and
branched C.sub.8 -C.sub.30 alkyl and alkenyl radicals;
R.sub.2 is selected from the group consisting of linear and
branched C.sub.8 -C.sub.30 alkyl and alkenyl radicals and C.sub.1
-C.sub.4 alkyl and hydroxyalkyl radicals;
X.sup.- is selected from the group consisting of sulfate and
sulfonate;
y and x have values in the range of 2 to 100 provided that y + x
.gtoreq.12;
M is a cation selected from the group consisting of alkali metal,
ammonium, and alkanolammonium ions and 5-50% by weight of the
combination of an anionic detergent.
28. A detergent composition according to claim 27 wherein the
detergent builder is an inorganic builder selected from the group
consisting of ammonium and alkali metal polyphosphates,
phosphonates, carbonates, bicarbonates, silicates, alumino
silicates and sulfates.
29. A detergent composition according to claim 28 wherein the
detergent builder is an organic builder selected from the group
consisting of alkali metal nitrilotriacetates, citrates,
oxydisuccinates, carboxylmethyloxysuccinates, and copolymers of
maleic anhydride with methyl vinyl ether or ethylene.
Description
BACKGROUND OF THE INVENTION
This invention relates to detergent compositions having improved
particulate soil removal capability. More particularly, this
invention relates to detergent compositions incorporating certain
ethoxylated compounds which provide unexpectedly good clay soil
removal.
Zwitterionic surfactants, i.e., those surface active compounds that
contain both positive and negative charge centers in the same
molecule while being electrically neutral, are known. For example,
U.S. Pat. Nos. 3,668,240 and 3,764,568 to Melvin A. Barbera, issued
respectively on June 6, 1972, and Oct. 9, 1973, disclose
zwitterionic surfactants having a 2, 3-butene moiety between the
charge centers. U.S. Pat. No. 3,332,875 to Adriaan Kessler and
Phillip Floyd Pflaumer also discloses mixtures of certain olefin
sulphonates with zwitterionic detergents in which the charge
centers are separated by a 2-hydroxy propane group. U.S. Pat. Nos.
3,452,066 and 2,781,390 to Hans S. Mannheimer, issued respectively
on June 24, 1969, and Feb. 12, 1957, outline a range of
zwitterionic surfactants which optionally may be substituted with a
wide variety of oxygen-containing groups between the positive and
negative charge centers. U.S. Pat. No. 3,769,311 to Leonard J.
Armstrong and Eldon de Vere Dawald issued Oct. 30, 1973, discloses
carboxylic compounds having ethylene oxide groups between the
charge centers but fails to recognize the effect of the various
structural parameters on the performance of the molecule in
removing soil, especially particulate soil.
In contrast, the present invention concerns detergent compositions
incorporating certain zwitterionic surfactants in a polyethenoxy
group of a size that permits not only adsorption of the molecule
from an aqueous system onto particulate and other soils, and the
subsequent removal of the soil by emulsification or dispersion but
also the continued maintenance of the removed soil in suspension in
the aqueous solution.
Some of these compounds are effective in the absence of
conventional detergent additives such as builders, surfactants etc.
and form the subject of the commonly assigned co-filed Applications
by Robert G. Laughlin, Eugene P. Gosselink, William A. Cilley, and
Vincent P. Heuring Ser. No. 493,951, filed Aug. 1, 1974 and Robert
G. Laughlin, Eugene P. Gosselink, and William A. Cilley Ser. No.
493,956, filed of even date, both Applications being entitled
"Detergent Compounds." The disclosures of both said Applications
are hereby incorporated herein by reference.
However, the present invention is directed to the discovery that a
wider range of zwitterionic compounds, of the type disclosed in the
above identified Applications, in combination with certain other
surfactant and detergent builder materials can provide unexpectedly
good particulate soil removal and also good oily soil removal from
hard surfaces and textile materials. The ethoxylated zwitterionic
compounds useful in the present invention possess an ability to
remove particulate soil that is independent of water hardness over
a very wide range or Ca.sup.+.sup.+ and Mg.sup.+.sup.+ levels.
Furthermore, this performance is relatively insensitive to
temperature changes in the range of 70.degree.-140.degree.F, the
normal range for domestic cleaning functions.
The importance of such a development is readily apparent as it
permits a high level of soil removal performance to be obtained
with a range of detergent formulations. Furthermore, the nature and
level of other components of the formulation can be controlled by
the selection of an ethoxylated zwitterionic material having the
appropriate level of performance.
Accordingly, it is an object of the present invention to provide
detergent compositions incorporating ethoxylated zwitterionic
compounds that have good particulate and oily soil removal
performance.
Another object of the present invention is the provision of
detergent compositions having improved particulate and oily soil
removal performance in both liquid and granular forms.
SUMMARY OF THE INVENTION
In its broadest aspect the present invention embraces a detergent
composition comprising:
A. 1 to 99% by weight of the composition of a water-soluble
compound having a formula selected from the group consisting of:
##EQU1## wherein R.sub.1 is selected from the group consisting of
straight and branched chain C.sub.8 -C.sub.30 alkyl and alkenyl
moieties and alkaryl moieties in which the alkyl group has 10-24
carbon atoms;
R.sub.2 is selected from the group consisting of straight and
branched chain C.sub.8 -C.sub.21 alkyl and alkenyl moieties,
alkaryl moieties in which the alkyl group has 6-16 carbon atoms,
and C.sub.1-4 alkyl and hydroxyalkyl moieties;
R.sub.3 is selected from the group consisting of straight and
branched chain C.sub.8 -C.sub.21 alkyl and alkenyl moieties,
alkaryl moieties in which the alkyl group has 6-16 carbon atoms,
C.sub.1-4 alkyl and hydroxyalkyl moieties and --(C.sub.2 H.sub.4
O).sub.x H wherein x has a value of about 3 to about 50;
R.sub.4 is selected from the group consisting of C.sub.1-8
alkylene, C.sub.3 -C.sub.8 alkenylene, 2-hydroxy C.sub.3 alkylene
and 2- and 3- hydroxy C.sub.4 alkylene moieties and C.sub.1
-C.sub.4 alkarylene moieties provided that where R.sub.3 is
--(C.sub.2 H.sub.4 O).sub.x H then R.sub.4 is --CH.sub.2 --CH.sub.2
--;
X.sup.- is an anion selected from the group consisting of sulfate
and sulfonate radicals;
and y has a value in the range of 2-100 provided that where R.sub.3
is --(C.sub.2 H.sub.4 O).sub.x H then x + y .gtoreq. 10. ##EQU2##
wherein R.sub.1 is selected from the group consisting of linear and
branched C.sub.8 -C.sub.30 alkyl and alkenyl radicals;
R.sub.2 is selected from the group consisting of linear and
branched C.sub.8 -C.sub.30 alkyl and alkenyl radicals and C.sub.1
-C.sub.4 alkyl and hydroxyalkyl radicals; X.sup.- is selected from
the group consisting of sulfate and sulfonate;
y and x have values in the range of 2-100 provided that y + x
.gtoreq. 12;
M is a cation selected from the group consisting of alkali metal,
ammonium and alkanolammonium ions.
B. 99 to 1% by weight of the composition of an organic detergent,
preferably selected from the group consisting of anionic, nonionic,
ampholytic, and zwitterionic detergents.
In the context of the present invention, ethoxylated zwitterionic
compounds having hydroxy substituents on the carbon atoms
immediately adjacent the nitrogen atom and/or X.sup.- moiety are
not preferred as they are unstable in water, especially at pH's
other than neutrality, and are extremely difficult to prepare
compared to other hydroxy substituted compounds.
Preferably, the ethoxylated zwitterionic compound is one of
either:
.omega.-(N-C.sub.16-18 alkyl,N-C.sub.1-3 alkyl,N- polyethenoxy
ammonio)-2-polyethenoxyethane-1-sulphonate wherein the total number
of ethylene oxide groups lies in the range 15-25
or
.omega.-(N-C.sub.12-18 alkyl,N,N-diC.sub.1 -C.sub.3
alkylammonio)-2-polyethenoxy ethane-1-sulphonate wherein the number
of ethylene oxide groups in the polyethenoxy chain is in the range
6-12.
DESCRIPTION OF THE DRAWING
The FIGURE illustrates the sudsing characteristics of a series of
blends of an ethoxylated zwitterionic compound (C.sub.16 EZ) and an
anionic cosurfactant (C.sub.11.8 LAS). The FIGURE constitutes a
plot of the suds height (in cms.) developed by the Recirculating
Suds Generator (R.S.G.) as a function of time (in minutes) for
C.sub.16 EZ alone, for blends of C.sub.16 EZ:C.sub.11.8 LAS of
19:1, 7:1, 3:1 and 1:1 by weight and for C.sub.11.8 LAS alone.
PERFORMANCE TESTING
In this specification the assessment of particulate and oily soil
removal performance both of detergent formulations of the invention
and of comparative formulations is carried out using the following
procedures.
a. Particulate soil removal testing
This is carried out in either an automatic mini washing machine
(AMW) having a capacity of 4,700 ml. and a cloth/liquor ratio of
1:30 or a Tergotometer having a capacity of 1,000 ml. and a
cloth/liquor ratio of 1:140. In both instances the machines are
fitted with horizonally rotating paddle agitators, the AMW having a
speed of 100 RPM, while the Tergotometer uses a speed of 80
RPM.
The AMW washing procedure involves a 12-minute wash cycle at
105.degree.F in 7 grains per U.S. gallon hard water (calculated as
CaCO.sub.3) using a 2:1 ratio of Ca:Mg salts. The first two minutes
of the cycle are used for product dissolution following which the
fabric load is added and washed for the remaining 10 minutes. A
5-minute rinse cycle then follows, 2 minutes of which is with
agitation, the remaining 3 minutes being a spin to remove excess
moisture. The fabrics are then tumble-dried prior to being
graded.
A similar washing procedure is used for the Tergotometer with the
exception that 5.5 grains/gallon water is employed having a 3:1
ratio of Ca:Mg salts (calculated as CaCO.sub.3). The wash is
followed by one rinse cycle of 3 minutes in 80.degree.F water of
the same hardness, level, and type as for the wash, after which the
swatches are machine-dried before being graded.
The fabric load for particulate soil removal testing comprises a
mixture of white cotton, polycotton (65% DACRON/35% cotton), and
polyester (KODEL) swatches which are stained with a standardized
illite clay soil. For the AMW, three 5 .times. 5 inch swatches of
each fabric are used in each load, while in the Tergotometer, three
21/2 .times. 21/2 inch swatches of each fabric type are
employed.
The results (expressed as relative clay removal index) for each
formulation represent a percentage of the whiteness value achieved
by a commercial synthetic detergent standard tested at the same
time under identical conditions. This standard formulation
hereinafter designated as A has the following composition by
weight:
Sodium C.sub.12 alkylbenzene sulphonate 7.55 Sodium Tallow alkyl
sulphate 9.25 Coconut alcohol + 6 mole EO 0.60 Diethanolamide 1.60
Sodium Tripolyphosphate 50.00 Sodium Silicate solids 5.90 Sodium
sulphate 14.20 Moisture 10.00 Miscellaneous 0.30 100.00
GRADING OF PERFORMANCE
Swatches are graded before and after washing on a Gardner Whiteness
meter reading the L, a, and b coordinates. Whiteness (W) is
calculated as: ##EQU3## Performance is determined by finding the
difference in whiteness (.DELTA.W) before and after washing as:
This is compared to the commercial Control Product A by calculating
.DELTA.W as a percentage of .DELTA.W given by the Control Product
in each batch.
The Relative Clay Removal Index = ##EQU4##
b. Grease and oil removal testing
Identical equipment and washing conditions are used to evaluate
grease and oil removal performance. The fabric load comprises a
mixture of green polycotton (65% DACRON/35% cotton) and polyester
(KODEL) swatches, four 21/2 .times. 21/2 inch swatches of each type
being used in the tergotometer. Two triglyceride stains, namely
bacon grease and vegetable oil, and two hydrocarbon-based stains,
namely dirty motor oil and simulated lipid soil are employed.
Following washing and drying, the swatches are graded visually on a
scale whose absolute values are described below:
5. Complete removal
4. Discernible stain remaining
3. Moderate amount of soil remaining
2. Large amount of soil remaining
1. Very large amount of soil remaining
0. No change, original amount of stain remaining
As in the particulate soil removal performance test, the results
are expressed as a percentage of the soil removal achieved by the
standard A under the same conditions.
SUDSING EVALUATION
In this Application, the evaluation of the sudsing characteristics
of detergent compositions is carried out using a Recirculating Suds
Generator.
This apparatus basically consists of a 1000 ml. graduated cylinder
which holds the bulk of the test solution and a circulating pump
which is connected to the base of the cylinder and which discharges
to an exit jet located in the cylinder above the level of the test
solution. The desired solution temperature is maintained by heating
tapes secured around tubing connecting the pump to the exit
jet.
In operation, approximately 200 ml. of test solution is placed in
the cylinder and continuously circulated at a selected temperature
within the range of 70.degree.-125.degree.F. The force of the
downward-directed solution from the exit jet onto the bulk of the
test solution in the graduated cylinder generates a level of suds
in the cylinder which is measured at one-minute intervals.
DETAILED DESCRIPTION OF THE INVENTION
The compositions of the present invention contain two essential
components, namely the ethoxylated zwitterionic compound and a
surfactant compound. The zwitterionic and surfactant may be present
in a ratio of from 99:1 to 1:99 by weight, preferably 10:1 to 1:10
by weight, and most preferably 4:1 to 1:10 by weight depending on
the nature of the zwitterionic compound and the type of product to
be formulated. For example, a product intended for prewash
treatment of laundry to remove specific stains by direct
application to the fabric will be formulated to contain a lower
level of zwitterionic compound and different optional ingredients
than a product designed as a main wash detergent.
For use as a main wash detergent, the level of ethoxylated
zwitterionic compound in the product will lie in the range 5-35% by
weight, preferably 10-25%, and most preferably 15-20%, the level of
the surfactant compound being 0.5-15%, preferably 1-10%, and most
preferably 1-5% by weight. Such a main wash detergent can be
formulated as a conventional granule or as a liquid, paste, flake,
ribbon, noodle, pellet, or tablet. As will be shown hereinafter,
this formulation flexibility is due, at least in part, to the
ability of the zwitterionic surfactants of the present invention to
achieve satisfactory particulate soil removal performance
equivalent to that of commercial heavy duty laundry detergents when
used in blends with other surfactants.
ETHOXYLATED ZWITTERIONIC COMPOUNDS
Ethoxylated zwitterionic compounds useful in the present invention
may have one or other of the following formulae: ##EQU5##
a. Mono-long chain derivatives
In this derivative, R.sub.1 is a hydrocarbon moiety that can be a
straight or branched chain C.sub.8 -C.sub.30 alkyl or alkenyl group
or an alkaryl group in which the alkyl portion has 10-24 carbon
atoms; R.sub.2 and R.sub.3 are C.sub.1 -C.sub.4 alkyl or
hydroxyalkyl groups; R.sub.4 is a C.sub.1 -C.sub.8 alkylene,
C.sub.3 -C.sub.8 alkenylene or 2-hydroxy propylene or 2- or 3-
hydroxy butylene group or a C.sub.1 -C.sub.4 alkarylene group;
X.sup.- is a sulfonate or sulfate radical; and y has a value in the
range 2-100.
In this embodiment, preferred groups for R.sub.1 are C.sub.12
-C.sub.18 alkyl, particularly C.sub.14 -C.sub.16 alkyl, while
preferred groups for R.sub.2 and R.sub.3 are C.sub.1-3 alkyl and
C.sub.2-3 hydroxyalkyl, the most preferred groups being methyl- and
hydroxyethyl- radicals. The preferred range of values for y is
6-50, more preferably 6-25, and most preferably 9-12.
The synthesis of the above compounds can be achieved using readily
available commercial starting materials. One such synthetic route
is as follows. Sodium hydride is slowly and stoichiometrically
reacted (2:1 molar ratio) with polyethylene glycol in a solution of
tetrahydrofuran under an atmosphere of an inert gas, e.g., argon.
The reaction is carried out over a period of 4-10 hours in an ice
bath to cool the reaction, which is exothermic. The polyethylene
glycol used is the commercially available material comprising a
mixture of compounds having chain lengths from about 4 to about
100. The resultant product is the sodium salt represented by
wherein y can be, for example, 3, 21, 32, 67, or 99.
A stoichometric amount of tosyl chloride dissolved in
tetrahydrofuran is then added slowly to reaction product (I),
cooled in an ice bath, and the resultant mixture is stirred for 12
to 20 hours to form ##EQU6## i.e., the polyethylene glycol
ditosylate. Pyridine or other suitable base is added to the
mixture, and the solution is then poured into ice water and
acidified with HCl to a pH of about 2-3. The aqueous solution is
then extracted with chloroform, rinsed with water and the
chloroform extract is dried over sodium sulfate to give purified
polyethylene glycol ditosylate (II).
The ditosylate (II) is then reacted with a tertiary amine of the
structure ##EQU7## wherein R.sub.1, R.sub.2 and R.sub.3 are as
defined above. The reaction of (III) with (II) is conveniently
carried out neat, or with a suitable solvent as N,N-dimethyl
formamide or CH.sub.3 CN at temperatures of 80.degree. to about
100.degree.C to produce a mixture of ##EQU8## and
The mixture of (IV) and (V) is then dissolved in methanol and
refluxed from 20-40 hours with an aqueous solution of sodium
sulfite. The unreacted (V) and other ionic materials are removed by
contacting the above solution with a mixed bed ion exchange resin,
followed by filtration of the solution and evaporation of the
solvent to give, as the predominant zwitterionic product, ##EQU9##
Compound (VI) can optionally be further purified using the mixed
bed resin and tested for purity by thin layer chromatography.
It will be appreciated that zwitterionic compounds of the general
formula (VI) can be prepared using any of a variety of tertiary
amines (III). Moreover, zwitterionic compounds having any desired,
specific degree of ethoxylation (y) can be prepared by
fractionating the polyethylene glycol used in the reaction and
using the desired fraction in the synthesis scheme. Alternatively,
relatively narrowly defined distillation "cuts" of polyoxyethylene
glycol having any desired average degree of ethoxylation, and
containing individual compounds having differing degrees of
ethoxylation within the desired range, can be used in the reaction.
It will be further understood that sodium salt (I) can be reacted
with a variety of epoxy compounds (e.g., butylene epoxide) or
halohydrins (e.g., 6-chlorohexanol or 8-bromooctanol) to provide
zwitterionics having various R.sub.4 groups within the scope of
this invention.
A specific preparation of a mono-long chain ethoxylated
zwitterionic compound useful in the present invention was as
follows:
Preparation of 26-dimethyloctadecylammonio- 3,6,9,12,15,18,21,24
octaoxahexacosane-1-sulfonate
Preparation of Nonaethyleneglycol (A)
Under nitrogen, 46 grams (2 moles) of sodium pellets were added
cautiously to 2,664 ml (20 moles) of previously dried and distilled
triethyleneglycol. The temperature was kept below 100.degree.C.
After all the sodium had reacted, the temperature was adjusted to
100.degree.C and 187 grams (1 mole) of 1,2-bis-(2-chloroethoxy)
ethane was added in a slow stream. The mixture was heated overnight
at 100.degree.C (still under nitrogen) and then filtered hot to
remove most of the sodium chloride. Excess triethyleneglycol was
stripped under vacuum and the mixture was again filtered while hot.
The material was purified by molecular distillation and has a b.p.
of 170.degree.-175.degree.C at 0.001 mm.
Preparation of Nonaethyleneglycol ditosylate (B)
The nonaethyleneglycol (A), 300 grams, (0.72 moles) was dissolved
in 800 ml (10.3 moles) of dry pyridine and cooled to 0.degree.C.
Tosyl chloride (i.e., p-toluene-sulfonyl chloride, 420 grams, 2.2
moles) was added, with stirring, in small portions. After the
addition was complete, the temperature increased to 10.degree.C and
the clear reaction mixture became cloudy. The mixture was stirred
at 0.degree.-10.degree.C for an additional 3 hrs., then poured into
an equal volume of ice water and acidified to pH 2-3 with 6N HCl.
The aqueous solution was then extracted 3 times with CHCl.sub.3.
The CHCl.sub.3 was washed with water, sodium bicarbonate solution,
and again with water, then dried over anhydrous sodium sulfate.
Evaporation of the CHCl.sub.3 gave 520 grams of a slightly yellow
oil. Thin layer chromatography indicated an impurity which remained
at the origin. The oil was dissolved in warm benzene (40.degree.C)
and extracted with warm water to remove the polar impurity. The
benzene was dried filtered and concentrated to yield 423 grams of a
yellowish oil (B).
Preparation of dimethyloctadecyl-26-tosyloxy-3,6,9,12,15,18,21,24
octaoxahexacosylammonium tosylate (C)
The ditosylate (B) 86.7 grams (0.12 mole) and 35.8 grams of
distilled dimethyloctadecylamine were heated at reflux for 5 hrs.
in 400 ml of acetonitrile. The solvent was then removed to give 120
grams of a mixture consisting of the monoquaternary tosylate (C),
diquaternary ammonium byproduct (D) and some unreacted ditosylate
(B).
Preparation of 26-dimethyloctadecylammonio-3,6,9.12,15,18,21,24
octaoxahexacosane-1-sulfonate
The mixture of monoquat (C) and diquaternary ammonium byproduct (D)
prepared above was dissolved in 1 liter of methanol. Sodium sulfite
(100 grams, 0.79 mole) was added and the reaction mixture was
refluxed with stirring for 5 hours. Additional methanol was added
and the insoluble salts were filtered. The solvents were removed to
yield a solid product.
Purification
The above solid reaction product was dissolved in 1 liter of
methanol and stirred with 386 grams of a mixed bed (Rexyn 300 H-OH,
commercially available from the Fisher Scientific Co.) resin for 5
hours. The solution was then passed through a column of fresh resin
(350 grams of Rexyn 30C) at a rate of 2 liters per 7 hours. The
methanol solution was then concentrated to yield 31.8 grams of a
light yellow oil which was recrystallized from acetone to give a
white crystalline, hygroscopic product. This product was identified
as the title compound (E in the following schematic).
The following sequence sets forth the above procedure in
abbreviated form to clarify the structures of compounds prepared
thereby. In the sequence, the dimethyloctadecylamine can be
replaced by dimethylhexadecylamine, dimethylnonadecylamine,
dimethyleicosylamine, and dimethyldocosylamine, respectively, and
the corresponding compounds wherein R.sub.1 is C.sub.16, C.sub.19,
C.sub.20, and C.sub.22 are secured, respectively. ##EQU10##
b. Di-long chain derivatives
In this derivative, both R.sub.1 and R.sub.2 are hydrocarbon
moieties that can be straight or branched chain C.sub.6 -C.sub.21
alkyl or alkenyl groups; R.sub.3, R.sub.4, and X.sup.- are as in
(i) (a.) above and y has an average value in the range 6-100.
Preferably R.sub.1 and R.sub.2 are identical and comprise alkyl
groups each having 10 to 16 carbon atoms, most preferably alkyl
groups each having 10 to 24 carbon atoms. Preferred values for y
lie in the range 9 to 50, most preferably in the range 12 to
25.
A specific preparation of a di-long chain alkyl ethoxylated
zwitterionic compound useful in the present invention was as
follows:
Methylation of di-n-octylamine was accomplished by slowly mixing 50
grams of the secondary amine with, first, formic acid (30.03
grams), and then formaldehyde, at 0.degree.C. The reaction mixture
was kept at 80.degree.C for 24 hours, then adjusted to pH 8-9 with
10% NaOH solution. The resulting tertiary amine was extracted with
CHCl.sub.3 and dried over Na.sub.2 SO.sub.4. The tertiary amine
(25.6 grams, 0.10 mole) was then refluxed with 72 grams (0.10 mole)
of nonaethylene glycol ditosylate (compound B, prepared as in the
previous procedure) in acetonitrile for 6 hours. The solvent was
evaporated and the resulting mixture of mono- and diquaternary
compounds was dissolved in methanol and refluxed with 100 grams of
sodium sulfite (predissolved in water) for 16 hours. Excess sulfite
and other salts were filtered and the filtrate was stirred for 16
hours with 500 grams of a mixed bed resin (Rexyn 300). A second
treatment with fresh resin was necessary to remove all impurities.
The solvents were evaporated to complete dryness and the product,
22 grams of a light yellow viscous oil, was identified as ##EQU11##
or
26-dioctylmethylammonio-3,6,9,12,15,18,21,24-octaoxahexacosane-1-sulfonate
.
c. Tri-long chain derivatives
In this derivative, R.sub.1, R.sub.2, R.sub.3 are all hydrocarbon
moieties that can be straight or branched chain C.sub.6 -C.sub.16
alkyl or alkenyl groups; R.sub.4 and x are as in (i) (a.) and (b.)
above and y has a value in the range 6-100. Preferably R.sub.1,
R.sub.2, and R.sub.3 are each identical and each comprise an alkyl
group having 8-16 carbon atoms in the chain. Most preferably each
chain contains 8-12 carbon atoms. y has a preferred value in the
range 9-50, most preferably in the range 12-50.
A specific preparation of a tri-long chain alkyl ethoxylated
zwitterionic compound was as follows:
Tri-n-octylamine was distilled to insure purity and 42 grams of the
purified product (0.12 mole) was reacted with 87 grams (0.12 mole)
of the ditosylate of nonaethylene glycol (compound B in the
mono-long chain preparation) in dry N,N-dimethylformamide at
100.degree.C for 2 hours. The dimethylformamide was removed and the
mixture of mono- and diquaternary material was dissolved in
methanol. This mixture was refluxed for 16 hours with 100 grams of
NA.sub.2 SO.sub.3 predissolved in water. The insoluble salts were
filtered and the filtrate was stirred with 500 grams mixed bed
resin (Rexyn 300 H--OH) for 24 hours. An additional treatment with
500 grams fresh resin was used to further purify the product. Thin
layer chromatography still indicated an impurity, which was
subsequently removed by dissolving the product in H.sub.2 O,
acidifying to pH 4, and extracting with CHCl.sub.3. The CHCl.sub.3
extract was rinsed with sodium bicarbonate, dried and evaporated to
give a light yellow viscous oil, identified as ##EQU12## or
trioctylammonio-3,6,9,12,15,18,21,24-octaoxahexacosane-1-sulfonate.
##EQU13##
In this structure, R.sub.1 can be a linear or branched C.sub.8
-C.sub.30 alkyl or alkenyl group, preferably a C.sub.16-18 alkyl or
alkenyl group; R.sub.2 can also be a C.sub.8 -C.sub.30 alkyl or
alkenyl group or can be a C.sub.1 -C.sub.4 alkyl or hydroxyalkyl
group, preferably a methyl group; and X.sup.- can be a sulfonate or
sulfate radical.
The number of ethylene oxide groups in each chain can be from 1 to
100 but their sum should be greater than 10. Normally there will be
approximately the same number in each chain, the sum of the groups
in both chains preferably having a value in the range 12-50 and
most preferably in the range 12-25.
The preparation of zwitterionic compounds of this type is
accomplished using commercially available starting materials. A
typical starting material is marketed under the tradename Ethoquad,
by the Armak Company of the Armour Company. Ethoquad is a mixture
of quaternary ammonium compounds whose predominant component is a
di-ethoxylate of the structure ##EQU14## wherein y and x are each
non-zero integers whose average sum is, for example, 5, 10, 15, 50,
depending on the "cut" selected, and R.sub.1 and R.sub.2 are
C.sub.12 -C.sub.18 alkyl and C.sub.1 -C.sub.3 alkyl,
respectively.
In general terms, the compounds herein are prepared by dissolving
Ethoquad in pyridine or other suitable base and cooling the mixture
to a temperature of about 0.degree.C. Tosyl chloride is slowly
added to the Ethoquad mixture at a 1:1 stoichiometric ratio while
the reaction mixture is kept at about 0.degree.C-5.degree.C in an
ice bath. The mixture is then stirred for about 24 hours at
0.degree.C-5.degree.C. At the end of that time the reaction mixture
is poured into water and acidified to a pH of 2-3 with HCl.
The foregoing acidified reaction mixture is then extracted with
chloroform and the extract is rinsed first with sodium bicarbonate
solution, then with water; the extract is then dried over anhydrous
sodium sulfate. After evaporation of the chloroform extract, an
oily residue is obtained. This is the mono-tosylate ester of the
structure ##EQU15## wherein y and x are as above.
The foregoing tosylate ester is then dissolved in methanol and
refluxed for about 24 hours with about a 10 molar excess of sodium
sulfite predissolved in H.sub.2 O. The reaction mixture is cooled
and excess sodium sulfite and sodium tosylate are removed by
filtration. The filtrate is stirred with a mixed bed (anion-cation)
resin to purify the product. A second resin treatment can
optionally be used to remove substantially all traces of all
cationic and anionic impurities. The purified mono-sulfonate
corresponding to (I) above is recovered by evaporating the solvent.
The product can optionally be recrystallized from acetone.
##EQU16## where R.sub.1, R.sub.2, and X.sup.- are as in (ii) and y
and x each have a value in the range of 1-100 provided that the sum
of y + x .gtoreq. 10. Preferred values for the sum of y + x will
lie in the range 12-50 and most preferably in the range 15-25. The
cation M.sup.+ can be alkali metal, ammonium, and alkanolammonium,
e.g. ethanolammonium or methanolammonium but is most preferably
sodium.
The disulfonate (II) is prepared in the same manner as the
mono-sulfonate (I), but using excess tosyl chloride (about 3:1 mole
ratio, or greater) in the first step and a larger excess of sodium
sulfite (20:1 mole ratio) in the second step. If a cation, M, other
than sodium is desired in the final product, the corresponding
sulfite can be used in the second step. Alternatively, the sodium
form of compound (II) can be ion-exchanged in standard fashion to
any desired cation, M. The resin purification treatment is
unnecessary when preparing the disulfonate.
The sulfates of the type (I) and (II) are easily prepared by
reacting one of two moles of chlorosulfonic acid with the
Ethoquads, respectively. The same consideration with regard to
selection of cation M holds true for the sulfates as for the
sulfonates.
It will be appreciated that a variety of diethoxylated amino
starting materials can be employed in the foregoing reaction
scheme. For example, Ethoquad derivatives having variations in
groups R.sub.1 and R.sub.2 are commercially available, e.g.,
compounds wherein R.sub.1 is an average C.sub.12 cut. Moreover,
precursor compounds having varying sums of y and x (within the
recited range) can be selected according to the desires of the
user. Compounds wherein y and x are of approximately equal length,
the sum of y and x being from about 12 to about 25, most preferably
fom 15 to about 25, are especially useful herein.
It will be further appreciated that a variety of other starting
materials can be employed to prepare various di-ethoxylated
precursors of the present zwitterionic compounds. For example, the
Ethomeens (a tradename of a clas of compounds marketed by the Armak
Company, a division of the Armour Company) can be quaternized to
produce variations of the commercial Ethoquads. Thus, Ethomeens of
the general formula R--N(C.sub.2 H.sub.4 O).sub.x H(C.sub.2 H.sub.4
O).sub.y H, when R is alkyl, can be reacted with excess alkyl
iodide or hydroxy-substituted alkyl iodide (CH.sub.3 I, C.sub.2
H.sub.5 I, etc.) to produce a quaternary ammonium compound which
can be sulfated or sulfonated on one or both ethylene oxide groups
in the manner disclosed above.
It should be appreciated that mixtures of any of these zwitterionic
compounds in any proportions may be used in the compositions of the
present invention. Such mixtures may be produced intentionally by
blending individual species or may arise as a result of the choice
of feedstocks or as a result of the processing steps involved.
The ethoxylated zwitterionic compounds useful in the present
invention desirably display appreciable solubility in aqueous
media. A solubility in water at 25.degree.C of at least 50 ppm,
preferably more than 75 ppm appears to be necessary for
satisfactory particulate soil removal performance, but the
preferred materials have solubilities in water of 10-30% by
weight.
The second essential component of a composition in accordance with
the present invention is an organic detergent. This can be present
at a level of from 1-99% by weight of the composition, the actual
level being dependent on the end use of the composition and its
desired physical form.
A wide range of organic detergents can be mixed i.e. can be
considered compatible with the ethoxylated zwitterionic compounds
to form compositions useful in the present invention. In the
context of this invention "compatible" is defined as causing no
appeciable decrease in the ability of the ethoxylated zwitterionic
compound to remove and suspend particulate soil.
Classes of compatible detergents that can serve as cosurfactants
include the nonionic, zwitterionic, and ampholytic surfactants
which can be used in a broad range of proportions to the
ethoxylated zwitterionic compound. In contrast, most anionic
detergents do not enhance the particulate soil removal performance
of the ethoxylated zwitterionic compounds to the same extent,
especially on synthetic fibers, although delayed solubility of the
anionic surfactant improves the performance of the combination.
Amongst the cationic surfactants, only those having a
polyoxyalkylene function are compatible with the ethoxylated
zwitterionic compounds useful in the present invention.
NONIONIC SYNTHETIC DETERGENTS
Most commonly, nonionic surfactants are compounds produced by the
condensation of an alkylene oxide (hydrophilic in nature) with an
organic hydrophobic compound which is usually aliphatic or alkyl
aromatic in nature. The length of the hydrophilic or
polyoxyalkylene moiety which is condensed with any particular
hydrophobic compound can be readily adjusted to yield a
water-soluble compound having the desired degree of balance between
hydrophilic and hydrophobic elements. Another variety of nonionic
surfactant is the semi-polar nonionic typified by the amine oxides,
phosphine oxides, and sulfoxides.
Examples of suitable nonionic surfactants include:
1. The polyethylene oxide condensates of alkyl phenols. These
compounds include the condensation products of alkyl phenols having
an alkyl group containing from about 6 to 12 carbon atoms in either
a straight chain or branched chain configuration, with ethylene
oxide, the said ethylene oxide being present in amounts equal to 5
to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl
substituent in such compounds may be derived, for example, from
polymerized propylene, diisobutylene, octene, or nonene. Examples
of compounds of this type include nonyl phenol condensed with about
9.5 moles of ethylene oxide per mole of nonyl phenol, dodecyl
phenol condensed with about 12 moles of ethylene oxide per mole of
phenol, dinonyl phenol condensed with about 15 moles of ethylene
oxide per mole of phenol, di-isooctylphenol condensed with about 15
moles of ethylene oxide per mole of phenol. Commercially available
nonionic surfactants of this type include Igepal CO-610 marketed by
the GAF Corporation; and Triton X-45, X-114, X-100 and X-102, all
marketed by the Rohm and Haas Company.
2. The condensation products of aliphatic alcohols with ethylene
oxide. The alkyl chain of the aliphatic alcohol may either be
straight or branched and generally contains from about 8 to about
22 carbon atoms. Examples of such ethoxylated alcohols include the
condensation product of about 6 moles of ethylene oxide with 1 mole
of tridecanol, myristyl alcohol condensed with about 10 moles of
ethylene oxide per mole of myristyl alcohol, the condensation
product of ethylene oxide with coconut fatty alcohol wherein the
coconut alcohol is a mixture of fatty alcohols with alkyl chains
varying from 10 to 14 carbon atoms and wherein the condensate
contains about 6 moles of ethylene oxide per mole of alcohol, and
the condensation product of about 9 moles of ethylene oxide with
the above-described coconut alcohol. Examples of commercially
available nonionic surfactants of this type include Tergitol 15-S-9
marketed by the Union Carbide Corporation, Neodol 23-6.5 marketed
by the Shell Chemical Company and Kyro EOB marketed by The Procter
& Gamble Company. Preferred nonionic surfactants which, when
blended with the ethoxylated zwitterionic compounds, enhance their
particulate soil removal performance, are the primary alcohol
ethoxylates which are the subject of the commonly assigned
copending Application Ser. No. 453,464 of Jerome H. Collins
entitled "Detergent Compositions." This Application discloses a
grease and oil-removing composition that consists essentially of at
least one ethoxylate material consisting essentially of a mixture
of compounds having at least two levels of ethylene oxide addition
and having the formula
wherein R.sub.1 is a linear alkyl residue and R.sub.2 has the
formula
R.sub.3 being selected from the group consisting of hydrogen and
mixtures thereof with not more than 40% by weight of lower alkyl,
wherein R.sub.1 and R.sub.2 together form an alkyl residue having a
mean chain length in the range of 8-15 carbon atoms, at least 65%
by weight of said residue having a chain length within .+-. 1
carbon atoms of the mean, wherein 3.5 < n.sub.av < 6.5
provided that the total amount by weight of components in which n =
O shall be not greater than 5% and the total amount by weight of
components in which n = 2-7 inclusive shall be not less than 63%
based on the total weight of the, or each, said ethoxylate material
and the HLB of the or each said ethoxylate material shall lie in
the range 9.5-11.5, said composition being otherwise free of
nonionic surfactants having an HLB outside of this range.
Preferred embodiments of this invention utilize blends of primary
alcohols in which at least 90% and most preferably 95% by weight of
the alcohol has a chain length within .+-. 1 carbon atom of the
mean, wherein the amount of unethoxylated alcohol is less than 1%
by weight and wherein the amount of ethoxylated alcohols having 2-7
ethylene oxide groups is at least 70% by weight. Preferably
ethoxylates having a mean chain length of C.sub.12 and below
contain at least 55% by weight of material having 2-6 ethoxylate
groups while for ethoxylates having a chain length of C.sub.12 14
C.sub.13 at least 55% by weight of the material has 3-7 ethoxylate
groups. Ethoxylates having a chain length in the C.sub.14-15 range
preferably have at least 55% by weight of E.sub.3 -E.sub.8
material. In the preferred embodiments of the invention the HLB of
the ethoxylates are in the range 10.0-11.1.
3. The condensation products of ethylene oxide with a hydrophobic
base formed by the condensation of propylene oxide with propylene
glycol. The hydrophobic portion of these compounds has a molecular
weight of from about 1500 to 1800 and of course exhibits water
insolubility. The addition of polyoxyethylene moieties to this
hydrophobic portion tends to increase the water-solubility of the
molecule as a whole, and the liquid character of the product is
retained up to the point where the polyoxyethylene content is about
50% of the total weight of the condensation product. Examples of
compounds of this type include certain of the commercially
available Pluronic surfactants marketed by the Wyandotte Chemicals
Corporation.
4. The condensation products of ethylene oxide with the product
resulting from the reaction of propylene oxide and ethylene
diamine. The hydrophobic base of these products consists of the
reaction product of ethylene diamine and excess propylene oxide,
said base having a molecular weight of from about 2500 to about
3000. This base is condensed with ethylene oxide to the extent that
the condensation product contains from about 40 to about 80% by
weight of polyoxyethylene and has a molecular weight of from about
5,000 to about 11,000. Examples of this type of nonionic surfactant
include certain of the commercially available Tetronic compounds
marketed by the Wyandotte Chemicals Corporation.
5. Surfactants having the formula R.sup.1 R.sup.2 R.sup.3
N.fwdarw.O (amine oxide surfactants) wherein R.sup.1 is an alkyl
group containing from about 10 to about 18 carbon atoms, from 0 to
about 2 hydroxy groups and from 0 to about 5 ether linkages, there
being at least one moiety of R.sup.1 which is an alkyl group
containing from about 10 to about 18 carbon atoms and no ether
linkages, and each R.sup.2 and R.sup.3 is selected from the group
consisting of alkyl groups and hydroxyalkyl groups containing from
1 to about 3 carbon atoms;
Specific examples of amine oxide surfactants include:
dimethyldodecylamine oxide, dimethyltetradecylamine oxide,
ethylmethyltetradecylamine oxide, cetyldimethylamine oxide,
dimethylstearylamine oxide, cetylethylpropylamine oxide,
diethyldodecylamine oxide, diethyltetradecylamine oxide,
dipropyldodecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide,
bis-(2-hydroxyethyl)-3-dodecoxy-2-hydroxypropylamine oxide,
(2-hydroxypropyl)methyltetradecylamine oxide, dimethyloleylamine
oxide, dimethyl-(2-hydroxydodecyl)amine oxide, and the
corresponding decyl, hexadecyl and octadecyl homologs of the above
compounds. 6. Surfactants having the formula R.sup.1 R.sup.2
R.sup.3 P.fwdarw. O (phosphine oxide surfactants) wherein R.sup.1
is an alkyl group containing from about 10 to about 28 carbon
atoms, from 0 to about 2 hydroxy groups and from 0 to about 5 ether
linkages, there being at least one moiety of R' which is an alkyl
group containing from about 10 to about 18 carbon atoms and no
ether linkages, and each R.sup.2 and R.sup.3 is selected from the
group consisting of alkyl groups and hydroxyalkyl groups containing
from 1 to about 3 carbon atoms.
Specific examples of the phosphine oxide detergents include:
dimethyldodecylphosphine oxide, dimethyltetradecylphosphine oxide,
ethylmethyltetradecylphosphine oxide, cetyldimethylphosphine oxide,
dimethylstearylphosphine oxide, cetylethylpropylphosphine oxide,
diethyldodecylphosphine oxide, diethyltetradecylphosphine oxide,
dipropyldodecylphosphine oxide, dipropyldodecylphosphine oxide,
bis-(hydroxymethyl)dodecylphosphine oxide,
bis-(2-hydroxyethyl)dodecylphosphine oxide,
(2-hydroxypropyl)methyltetradecylphosphine oxide,
dimethyloleylphosphine oxide, and
dimethyl-(2-hydroxydodecyl)phosphine oxide and the corresponding
decyl, hexadecyl, and octadecyl homologs of the above
compounds.
7. Surfactants having the formula: ##EQU17## (sulfoxide
surfactants) wherein R.sup.1 is an alkyl group containing from
about 10 to about 18 carbon atoms, from 0 to about 5 ether linkages
and from 0 to about 2 hydroxyl substituents, at least one moiety of
R.sup.1 being an alkyl group containing no ether linkages and
containing from about 10 to about 18 carbon atoms, and wherein
R.sup.2 is an alkyl group containing from 1 to 3 carbon atoms and
from zero to two hydroxyl groups. Specific examples of sulfoxide
surfactants include octadecyl methyl sulfoxide, dodecyl methyl
sulfoxide, tetradecyl methyl sulfoxide, 3-hydroxytridecyl methyl
sulfoxide, 3-methoxytridecyl methyl sulfoxide,
3-hydroxy-4-dodecoxybutyl methyl sulfoxide, octadecyl
2-hydroxyethyl sulfoxide, and dodecylethyl sulfoxide.
Table 1 illustrates the clay soil removal performance of mixtures
of ethoxylated zwitterionic compounds and various nonionic
surfactants. Experimental Run 1 shows that the C.sub.16 ethoxylated
zwitterionic material alone at a level of 250 ppm in water closely
approaches the cleaning performance of the fully formulated control
product A on polyester and polycotton fabrics and achieves a major
proportion of the control product performance on cotton.
Experimental Run 2 shows that an appreciable proportion of this
performance is retained at half the level of the ethoxylated
zwitterionic compound. The addition of 125 ppm of several different
nonionic cosurfactants in Runs 3, 5, 7, and 9 to the C.sub.16
ethoxylated zwitterionic material enables the performance at 250
ppm to be approached and even exceeded, the extent of the recovery
being dependent on the cosurfactant type. It can also be seen that
the addition of sodium tripolyphosphate to these systems, while
providing an additional benefit in one or two instances, does not
give an overall advantage. While the reason for this is not fully
understood, it is believed that the lack of benefit is a function
of the ability of the better ethoxylated zwitterionic compounds, of
which the C.sub.16 compound is an example, to remove soil in the
presence of free mineral hardness ion.
Experimental Runs 11-20 inclusive record similar data for the
C.sub.14 ethoxylated compound which, as Runs 11 and 12 demonstrate,
is not as effective a material on its own as the C.sub.16
ethoxylated compound. However, Runs 13, 15, 17, and 19 again show
that the performance of the C.sub.14 ethoxylated compound at 125
ppm can be improved by the addition of various nonionic
surfactants, the improvement being seen over all fabric types and
in almost every instance providing performance that exceeds that
for the C.sub.14 material at 250 ppm. Addition of sodium
tripolyphosphate at 250 ppm leads to a further performance
improvement which is not inconsistent with the theory that the
benefit that can be derived from detergent builders in compositions
of the present invention is related to the particulate soil removal
performance of the ethoxylated zwitterionic materials.
Table V is a presentation of the grease and oil removal performance
achieved by detergent compositions of the present invention. Runs 4
and 5 show respectively combinations of 125 p.p.m. C.sub.16
ethoxylated zwitterionic compound of Table 1 with 125 ppm of Neodol
45 E7 and with 125 ppm of C.sub.11-15 secondary alcohol ethoxylate
(Tergitol 15-S-9 marketed by Union Carbide Corporation). Runs 11
and 12 give the same data for the C.sub.14 ethoxylated zwitterionic
of Table 1. For both C.sub.14 and C.sub.16 ethoxylated zwitterionic
compounds advantages can be seen on polyester fabric for the
combinations relative to the performance of the ethoxylated
zwitterionic compound alone at 250 ppm.
Thus for compositions of nonionic surfactants with ethoxylated
zwitterionic materials useful in the present invention, it can be
seen that for ethoxylated zwitterionics having good particulate
soil removal performance, nonionic surfactants can be used to
reduce the level of ethoxylated zwitterionic necessary to achieve a
given level of performance. For ethoxylated zwitterionics not
having such good particulate soil removal performance, the level of
performance can be raised by the addition of nonionic surfactants
and builders.
TABLE I
__________________________________________________________________________
CLAY SOIL REMOVAL OF ETHOXYLATED ZWITTERIONIC COMPOUNDS IN
COMBINATION WITH NONIONIC SURFACTANTS Conditions: 10 Minute
Tergotometer Wash in 7 grain/gal. Mineral Hardness (2:1 Ca:Mg) at
105.degree.F RELATIVE ETHOXYLATED LEVEL LEVEL LEVEL CLAY REMOVAL
INDEX ZWITTERIONIC PPM IN PPM IN BUILDER PPM IN POLY- POLY- NO.
COMPOUND SOLUTION COSURFACTANT SOLUTION TYPE SOLUTION COTTON COTTON
ESTER
__________________________________________________________________________
1 N--C.sub.16 H.sub.33 N,N--bisCH.sub.3 250 -- -- -- -- 75 96 95
(C.sub.2 H.sub.4 O).sub.8 CH.sub.2 CH.sub.2 SO.sub.3 2 " 125 -- --
-- -- 62 88 77 3 " 125 Neodol 45-7* 125 -- -- 91 91 86 4 " 125 "
125 STP 250 80 100 71 5 " 125 Stripped C.sub.10 E.sub.3 ** 125 --
-- 87 91 74 6 " 125 " 125 STP 250 96 116 98 7 " 125 CnE.sub.6 ***
125 -- -- 85 89 86 8 " 125 " 125 STP 250 80 100 71 9 " 125 Ethomeen
18/60**** 125 -- -- 78 96 80 10 " 125 " 125 STP 250 90 113 88 11
N--C.sub.14 H.sub.29 N,N--bisCH.sub.3 250 -- -- -- -- 53 69 46
(C.sub.2 H.sub.4 O).sub.8 CH.sub.2 CH.sub.2 SO.sub.3 12 " 125 -- --
-- -- 41 52 24 13 " 125 Neodol 45-7* 125 -- -- 68 81 51 14 " 125 "
125 STP 250 78 98 94 15 " 125 Stripped C.sub.10 E.sub.3 ** 125 --
-- 57 92 52 16 " 125 " 125 STP 250 78 98 94 17 " 125 CnE.sub.6 ***
125 -- -- 74 84 49 18 " 125 " 125 STP 250 80 93 59 19 " 125
Ethomeen 18/60**** 125 -- -- 73 89 43 20 " 125 " 125 STP 250 68 86
55 21 Formulation A 1400 -- -- -- -- 100 100 100
__________________________________________________________________________
*Neodol 45-7 is a linear primary C.sub.14.sub.-15 alcohol
containing 15% 2-methyl branching condensed with an average of
seven moles of ethylene oxide per mole of alcohol, marketed by
Shell Chemical Company. **Stripped C.sub.10 E.sub.3 is a linear
primary C.sub.10 alcohol condensed with approximately 3 moles of
ethylene oxide per mole of alcoho and then stripped to remove at
least 95% of the unethoxylated alcohol and a proportion of the
monoethoxylate, so as to leave a condensate having a mean of 4
moles ethylene oxide per mole of alcohol. ***Middle cut coconut
alcohol condensed with an average of 6 moles of ethylene oxide per
mole of alcohol. ****Ethomeen 18/60 is a tertiary C.sub.18 amine
having 2 ethoxy side chains directly attached to the nitrogen atom
and containing a total of 5 ethylene oxide groups.
TABLE V
__________________________________________________________________________
GREASE AND OIL REMOVAL OF ETHOXYLATED ZWITTERIONICS IN COMBINATION
WITH OTHER SURFACTANTS Conditions: 10 Minute Tergotometer Wash at
100.degree.F in 5.5 grains/gal. Mineral Hardness (Ca:Mg = 3:1)
RELATIVE ETHOXYLATED LEVEL LEVEL LEVEL SOIL REMOVAL INDEX
ZWITTERIONIC PPM IN PPM IN BUILDER PPM IN POLYCOTTON POLYESTER NO.
COMPOUND SOLUTION COSURFACTANT SOLUTION TYPE SOLUTION TG HG TG HC
__________________________________________________________________________
1 N--C.sub.16 H.sub.33 N,N--bisCH.sub.3 (CH.sub.2 CH.sub.2 O).sub.8
CH.sub.2 CH.sub.2 SO.sub.3 250 -- -- -- -- 91 132 75 102 2 " 125
125 -- -- 88 157 91 110 3 " 125 C.sub.16 -C.sub.18 alkyl 125 -- --
59 100 35 21 (EO).sub.6 OSO.sub. 3 Na 4 " 125 C.sub.14 -C.sub.15
primary alcohol condensed with 7 moles ethylene oxide 125 -- -- 62
83 91 126 5 " 125 C.sub.11 -C.sub.15 secondary alcohol condensed
with 9 moles ethylene oxide 125 -- -- 100 136 86 109 6 " 125
3(N--C.sub.16 H.sub.33 N,N--dimethyl ammonio)propane-1-sulphonate
125 -- -- 80 58 111 126 7 " 125 3(N--C.sub.14.8 alkyl N,N-dimethyl
ammonio)2-hydroxypropane-1-sulphonate 125 -- -- 78 163 75 127 8
N--C.sub.14 H.sub.29 N,N--bisCH.sub.3 (CH.sub.2 CH.sub.2 O).sub.8
CH.sub.2 CH.sub.2 SO.sub.3 250 -- -- -- -- 100 75 80 99 9 " 125 125
-- -- 88 107 118 135 10 " 125 C.sub.16 -C.sub.18 alkyl 125 -- -- 55
120 43 36 (EO).sub.6 OSO.sub.3 Na 11 " 125 C.sub.14 -C.sub.15
primary alcohol condensed with 7 moles ethylene oxide 125 -- -- 50
58 89 129 12 " 125 C.sub.11 -C.sub.15 secondary alcohol condensed
with 3 moles ethylene oxide 125 -- -- 57 36 79 116 13 " 125
3(N--C.sub.16 H.sub.33 N,N--dimethyl ammonio)propane-1-sulphonate
125 -- -- 120 42 124 131 14 " 125 3(N--C.sub.14.8 alkyl
N,N-dimethyl ammonio)-2-hydroxypropane-1-sulphonate 125 -- -- 47 88
112 133
__________________________________________________________________________
AMPHOLYTIC SYNTHETIC DETERGENTS
Ampholytic synthetic detergents can be broadly described as
derivatives of aliphatic or aliphatic derivatives of heterocyclic
secondary and tertiary amines in which the aliphatic radical may be
straight chain or branched and wherein one of the aliphatic
substituents contains from about 8 to 18 carbon atoms and at least
one contains an anionic water-solubilizing group, e.g., carboxy,
sulfonate, sulfato. Examples of compounds falling within this
definition are sodium 3-(dodecylamino)propionate, sodium
3-(dodecylamino)propane-1-sulfonate, sodium 2-(dodecylamino)ethyl
sulfate, sodium 2-(dimethylamino)octadecanoate, disodium
3-(N-carboxymethyldodecylamino)propane-1-sulfonate, disodium
octadecyl-iminodiacetate, sodium
1-carboxymethyl-2-undecylimidazole, and sodium
N,N-bis(2-hydroxyethyl)-2-sulfato-3-dodecoxypropylamine. Sodium
3-(dodecylamino)propane-1-sulfonate is preferred.
ZWITTERIONIC SYNTHETIC DETERGENTS
Zwitterionic surfactants can be broadly described as derivatives of
secondary and tertiary amines, derivatives of heterocyclic
secondary and tertiary amines, or derivatives of quaternary
ammonium, quaternary phosphonium or tertiary sulfonium compounds.
The cationic atom in the quaternary compound can be part of a
heterocyclic ring. In all of these compounds there is at least one
aliphatic group, straight chain or branched, containing from about
3 to 18 carbon atoms and at least one aliphatic substituent
containing an anionic water-solubilizing group, e.g., carboxy,
sulfonate, sulfate, phosphate, or phosphonate. Examples of various
classes of zwitterionic surfactants operable herein are described
as follows:
1. Compounds corresponding to the general formula ##EQU18## wherein
R.sub.1 is alkyl, alkenyl or a hydroxyalkyl containing from about 8
to about 18 carbon atoms and containing if desired up to about 10
ethylene oxide moieties and/or a glyceryl moiety; Y.sub.1 is
nitrogen, phosphorus or sulfur, R.sub.2 is C.sub.1 -C.sub.3 alkyl
or a C.sub.2 -C.sub.3 .beta.- or .gamma.-monohydroxy alkyl
containing 1 to 3 carbon atoms; x is 1 when Y.sub.1 is S, 2 when
Y.sub.1 is N or P; R.sub.3 is C.sub.1 -C.sub.4 alkylene or
2-hydroxy-, 3-propylene or 2- or 3-hydroxy butylene containing from
1 to about 5 carbon atoms; and Z is a carboxy, sulfonate, sulfate,
phosphate or phosphonate group. Examples of this class of
zwitterionic surfactants include
3-(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate;
3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate;
N,N-dimethyl-N-dodecylammonio acetate;
3-(N,N-dimethyl-N-dodecylammonio)propionate;
2-(N,N-dimethyl-N-octadecylammonio)ethyl sulfate; 3
-(P,P-dimethyl-P-dodecylphosphonio)propane-1-sulfonate;
2-(S-methyl-S-tert-hexadecylsulfonio)ethane-1-sulfonate;
3-(S-methyl-S-dodecylsulfonio)propionate;
4-(S-methyl-S-tetradecylsulfonio)butyrate;
3-(N,N-dimethyl-N-4-dodecenylammonio)propane-1-sulfonate;
3-(N,N-dimethyl-N-2-diethoxyhexadecylammonio)propyl hydrogen
phosphate; and
3-(N,N-dimethyl-N-4-glyceryldodecylammonio)propionate.
Preferred compounds of this class from a commercial standpoint are
3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate;
3-(N,N-dimethyl-N-alkylammonio)-2-hydroxypropane-1-sulfonate, the
alkyl group being derived from tallow fatty alcohol;
3-(N,N-dimethyl-N-hexadecylammonio)propane-1-suffonate;
3-(N,N-dimethyl-N-tetradecylammonio)propane-1-sulfonate;
3-(N,N-dimethyl-N-alkylammonio)-2-hydroxypropane-1-sulfonate, the
alkyl group being derived from the middle cut of coconut fatty
alcohol;
3-(N,N-dimethyldodecylammonio)-2-hydroxypropane-1-sulfonate;
4-(N,N-dimethyl-tetradecylammonio)butane-1-sulfonate;
4-(N,N-dimethyl-N-hexadecylammonio)butane-1-sulfonate;
4-(N,N-dimethyl-hexadecylammonio)butyrate;
6-(N,N-dimethyl-N-octadecylammonio)hexanoate;
3-(N,N-dimethyl-N-eicosylammonio)-3-methylpropane-1-sulfonate; and
6-(N,N-dimethyl-N-hexadecylammonio)hexanoate.
Means for preparing many of the surfactant compounds of this class
are described in U.S. Pat. Nos. 2,129,264, 2,774,786, 2,813,898,
2,828,332 and 3,529,521 and; German Pat. No. 1,018,421 all
incorporated herein by reference.
2. Compounds having the general formula: ##EQU19## wherein R.sub.4
is an alkyl, cycloalkyl, aryl, aralkyl or alkaryl group containing
from 10 to 20 carbon atoms; M is a bivalent radical selected from
the group consisting of aminocarbonyl, carbonylamino, carbonyloxy,
oxycarbonyloxy, aminocarbonylamino, the corresponding thio
groupings and substituted amino derivatives; R.sub.5 and R.sub.8
are alkylene groups containing from 1 to 12 carbon atoms; R.sub.6
is alkyl or hydroxyalkyl containing from 1 to 10 carbon atoms;
R.sub.7 is selected from the group consisting of R.sub.6 groups
R.sub.4 --M--R.sub.5.sup.-, and --R.sub.8 COOMe wherein R.sub.4,
R.sub.5, R.sub.6 and R.sub.8 are as defined above and Me is a
monovalent salt-forming cation. Compounds of the type include
N,N-bis(oleylamidopropyl)-N-methyl-N-carboxymethylammonium betaine;
N,N-bis(stearamidopropyl)-N-methyl-N-carboxymethylammonium betaine;
N-(stearamidopropyl)-N-dimethyl-N-carboxymethylammonium betaine;
N,N-bis(oleylamidopropyl)-N-(2-hydroxyethyl)-N-carboxymethylammonium
betaine; and
N-N-bis-(stearamidopropyl)-N-(2-hydroxyethyl)-N-carboxymethylammonium
betaine. Zwitterionic surfactants of this type are prepared in
accordance with methods described in U.S. Pat. No. 3,265,719 and
DAS 1,018,421.
3. Compounds having the general formula: ##EQU20## wherein R.sub.9
is an alkyl group, R.sub.10 is a hydrogen atom or an alkyl group,
the total number of carbon atoms in R.sub.9 and R.sub.10 being from
8 to 16 and ##EQU21## represents a quaternary ammonio group in
which each group R.sub.11, R.sub.12, and R.sub.13 is an alkyl or
hydroxyalkyl group or the groups R.sub.11, R.sub.12, and R.sub.13
are conjoined in a heterocyclic ring
and n is 1 or 2. Examples of suitable zwitterionic surfactants of
this type include the .gamma. and .delta. hexadecyl pyridino
sulphobetaines, the .gamma. and .delta. hexadecyl .gamma.-picolino
sulphobetaines, the .gamma. and .delta. tetradecyl pyridino
sulphobetaines and the hexadecyl trimethylammonio sulphobetaines.
Preparation of such zwitterionic surfactants is described in
British patent specification No. 1,277,200.
4. Compounds having the general formula ##EQU22## wherein R.sub.14
is an alkarylmethylene group containing from about 8 to 24 carbon
atoms in the alkyl chain; R.sub.15 is selected from the group
consisting of R.sub.14 groups and alkyl and hydroxyalkyl groups
containg from 1 to 7 carbon atoms; R.sub.16 is alkyl or
hydroxyalkyl containing from 1 to 7 carbon atoms; R.sub.17 is
alkylene or hydroxyalkylene containing from 1 to 7 carbon atoms and
Z.sub.1 is selected from the group consisting of sulfonate, carboxy
and sulfate. Examples of zwitterionic surfactants of this type
include
3-(N-4-n-dodecylbenzyl-N,N-dimethylammonio)propane-1-sulfonate;
4-(N-4-n-dodecylbenzyl-N,N-dimethylammonio)butane-1-sulfonate;
3-(N-4-n-hexadecylbenzyl-N,N-dimethylammmonio)propane-1-sulfonate;
3-(N-4-n-dodecylbenzyl-N,N-dimethylammonio)propionate;
4-(N-4-n-hexadecylbenzyl-N,N-dimethylammonio)butyrate;
3-(N-4-n-tetradecylbenzyl-N,N-dimethylammonio)propane-1-sulfate;
3-(N-4-n-dodecylbenzyl-N,N-dimethylammonio)-2-hydroxypropane-1-sulfonate;
3-[N,N-di(4-n-dodecylbenzyl)-N-methylammonio]propane-1-sulfonate;
4-[N,N-di(4-n-hexadecylbenzyl)-N-methylammonio]butyrate; and
3-[N,N-di(4-n-tetradecylbenzyl)-N-methylammonio]-2-hydroxypropane-1-sulfon
ate.
Zwitterionic surfactants of this type as well as methods for their
preparation are described in U.S. Pat. Nos. 2,697,116; 2,697,656
and 2,669,991 and Canadian Pat. No. 883,864, all incorporated
herein by reference.
5. Compounds having the general formula: ##EQU23## wherein R.sub.18
is an alkylphenyl, cycloalkylphenyl or alkenylphenyl group
containing from 8 to 20 carbon atoms, in the alkyl, cycloalkyl or
alkenyl moiety; R.sub.19 and R.sub.20 are each aliphatic groups
containing from 1 to 5 carbon atoms; R.sub.21 and R.sub.22 are each
hydrogen atoms, hydroxyl groups or aliphatic groups containing from
1 to 3 carbon atoms and R.sub.23 is an alkylene group containing
from 2 to 4 carbon atoms.
Examples of zwitterionic surfactants of this type include
3-(N-dodecylphenyl- N,N-dimethylammonio)propane-1-sulfonate;
4-(N-hexadecylphenyl-N,N-dimethylammonio)butane-1-sulfonate; and
3-(N-dodecylphenyl-N,N-dimethylammonio)-2-hydroxypropane-1-sulfonate.
Compounds of this type are described more fully in British Pat.
Nos. 970,883 and 1,046,252, incorporated herein by reference.
Of all the above-described types of zwitterionic surfactants,
preferred compounds include
3(N,N-dimethyl-N-alkylammonio)-propane-1-sulfonate and
3(N,N-dimethyl-N-alkylammonio)-2-hydroxypropane-1-sulfonate wherein
in both compounds the alkyl group averages 14.8 carbon atoms in
length; 3(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate;
3(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate;
3-(N-dodecylbenzyl-N,N-dimethylammonio)-propane-1-sulfonate;
3-(N-dodecylbenzyl-N,N,dimethylammonio)-2-hydroxypropane-1-sulfonate;
N-dodecylbenzyl-N,N-dimethylammonio acetate;
3-(N-dodecylbenzyl-N,N-dimethylammonio)propionate;
6-(N-dodecylbenzyl-N,N-dimethylammonio)hexanoate; and
N,N-dimethyl-N-hexadecylammonio acetate.
Clay soil removal performance results for combinations of the
ethoxylated zwitterionic compounds of the present invention with
other zwitterionic surfactants are shown in Table II. Experimental
Runs 1 and 2 reproduce the Table 1 results at 250 ppm and 125 ppm
for the C.sub.14 ethoxylated zwitterionic compound on its own while
Runs 3 and 10 provide the same data for the C.sub.16 material.
The data shows that for both C.sub.14 and C.sub.16 ethoxylated
zwitterionics, combination with other zwitterionic cosurfactants
results in an improvement in performance which is further enhanced
by the addition of a builder (sodium tripolyphosphate).
Performance results for the C.sub.16 APS cosurfactant at 125 ppm
together with a three-component builder combination are shown in
Run 19, while Runs 23 and 24 respectively show the performance of
250 ppm of a single chain length C.sub.16 APS and a C.sub.16
average chain length APS both built with a sodium carbonate-sodium
silicate system.
It will be seen that the C.sub.16 ethoxylated zwitterionic material
on its own at 250 ppm is as good as the C.sub.16 APS material at
125 ppm with 1000 ppm of builder and better than C.sub.16 APS at
250 ppm with 400 ppm of builder, on both cotton and polyester
fabrics.
Grease and oil removal data for combinations of the C.sub.14 and
C.sub.16 ethoxylated zwitterionic compounds with zwitterionic
cosurfactants are shown in Table V, Runs 6 and 7 (C.sub.16) and 13
and 14 (C.sub.14). Advantages are again apparent for the
combinations in removing both triglyceride and hydrocarbon stains
from polyester fabrics although the results for polycotton are more
variable.
TABLE II
__________________________________________________________________________
CLAY SOIL REMOVAL OF ETHOXYLATED ZWITTERIONIC COMPOUNDS IN
COMBINATION WITH ZWITTERIONIC SURFACTANTS Conditions: 10 Minute
Tergotometer Wash in 7 grains/gal. Mineral Hardness (2:1 Ca:Mg) at
105.degree.F Cosurfactants were 3-(N-alkyl N,N-dimethyl
ammonio)propane-1-sulphonate(AP S) and 3-(N-alkyl N,N-dimethyl
ammonio)-2-hydroxy propane-1-sulphonate(HAP S) RELATIVE ETHOXYLATED
LEVEL LEVEL LEVEL CLAY REMOVAL INDEX ZWITTERIONIC PPM IN PPM IN
BUILDER PPM IN POLY- POLY- NO. COMPOUND SOLUTION COSURFACTANT
SOLUTION TYPE SOLUTION COTTON COTTON ESTER
__________________________________________________________________________
1 N--C.sub.14 H.sub.29 N,N--bisCH.sub.3 (C.sub.2 H.sub.4 O).sub.8
CH.sub.2 CH.sub.2 SO.sub.3 250 -- -- -- -- 53 69 46 2 " 125 -- --
-- -- 41 52 24 3 " 125 C.sub.14 APS 125 -- -- 79 84 80 4 " 125 "
125 STP 250 94 102 101 5 " 125 C.sub.16 APS 125 -- -- 77 91 89 6 "
125 " 125 STP 250 96 105 103 7 " 125 C.sub.14.8 HAPS 125 -- -- 81
90 77 8 " 125 " 125 STP 250 112 101 107 9 N--C.sub.16 H.sub.33
N,N--bisCH.sub.3 (C.sub.2 H.sub.4 O).sub.8 CH.sub.2 CH.sub.2
SO.sub.3 250 -- -- -- -- 75 96 95 10 " 125 -- -- -- -- 62 88 77 11
- 125 C.sub.14 APS 125 -- -- 84 84 90 12 " 125 " 125 STP 250 114
100 105 13 " 125 C.sub.16 APS 125 -- -- 92 88 94 14 " 125 " 125 STP
250 110 99 104 15 " 125 C.sub.14.8 HAPS 125 -- -- 86 90 80 16 " 125
" 125 STP 250 106 97 103 17 N--C.sub.18 H.sub.37 N,N--bisCH.sub.3
(C.sub.2 H.sub.4 O).sub.8 CH.sub.2 CH.sub.2 SO.sub.3 125 C.sub.16
APS 125 Alumino- 108 -- 104 silicate* 600 Na.sub.2 CO.sub.3 200
Na.sub.2 SiO.sub.3 ** 200 18 " 63 " 63 " 600 94 -- 106 " 200 " 200
19 " 0 " 125 " 600 76 -- 96 " 200 " 200 20 " 125 " 125 Na.sub.2
CO.sub.3 200 86 -- 106 Na.sub.2 SiO.sub.3 ** 200 21 " 25 " 225 "
200 81 -- 94 " 200 22 " 13 " 237 " 200 81 -- 90 " 200 23 " 0 "
250/pure " 200 65 87 51 " 200 24 " 0 " 250/avge " 200 70 -- 84 200
__________________________________________________________________________
*The Aluminosilicate builder used had the formula Na.sub.12
[(AlO.sub.2).sub.12 (SiO.sub.2).sub.12 ] . 27H.sub.2 O **SiO.sub.2
: Na.sub.2 O ratio = 3.2:1
ANIONIC DETERGENTS
This class of detergents includes ordinary alkali metal soaps such
as the sodium, potassium, ammonium and alkylolamminium salts of
higher fatty acids containing from about eight to about 24 carbon
atoms and preferably from about 10 to about 20 carbon atoms.
Suitable fatty acids can be obtained from natural sources such as,
for instance, from plant or animal esters (e.g., palm oil, coconut
oil, babassu oil, soybean oil, caster oil, tallow, whale and fish
oils, grease, lard, and mixtures thereof). The fatty acids also can
be synthetically prepared (e.g., by the oxidation of petroleum, or
by hydrogenation of carbon monoxide by the Fischer-Tropsch
process). Resin acids are suitable such as rosin and those resin
acids in tall oil. Napthenic acids are also suitable. Sodium and
potassium soaps can be made by direct saponification of the fats
and oils or by the neutralization of the free fatty acids which are
prepared in a separate manufacturing process. Particularly useful
are the sodium and potassium salts of the mixtures of fatty acids
derived from coconut oil and tallow, i.e., sodium or potassium
tallow and coconut soap.
Anionic synthetic detergents include water-soluble salts,
particularly the alkali metal salts, of organic sulfuric reaction
products having in their molecular structure an alkyl group
containing from about 8 to about 22 carbon atoms and a moiety
selected from the group consisting of sulfonic acid and sulfuric
acid ester moieties. (Included in the term alkyl is the alkyl
portion of higher acyl moieties.) Examples of this group of
synthetic detergents are the sodium and potassium alkyl sulfates,
especially those obtained by sulfating the higher alcohols (C.sub.8
-C.sub.18 carbon atoms) produced by reducing the glycerides of
tallow or coconut oil; sodium and potassium alkyl benzene
sulfonates, in which the alkyl group contains from about 9 to about
20 carbon atoms in straight-chain or branched-chain configuration,
e.g. those of the type described in U.S. Pat. Nos. 2,220,099 and
2,477,383 (especially valuable are linear straight chain alkyl
benzene sulfonates in which the average of the alkyl groups is
about 11.8 carbon atoms and commonly abbreviated as C.sub.11.8
LAS); sodium alkyl glyceryl ether sulfonates, especially those
ethers of higher alcohols derived from tallow and coconut oil;
sodium coconut oil fatty acid monoglyceride sulfonates and
sulfates.
Anionic phosphate surfactants are also useful in the present
invention. These are surface active materials having substantial
detergent capability in which the anionic solubilizing group
connecting hydrophobic moieties is an oxy acid of phosphorus. The
more common solubilizing groups, of course, are --SO.sub.4 H and
--SO.sub.3 H. Alkyl phosphate esters such as (R--O).sub.2 PO.sub.2
H and ROPO.sub.3 H.sub.2 in which R represents an alkyl chain
containing from about 8 to about 20 carbon atoms are useful
herein.
These phosphate esters can be modified by including in the molecule
from one to about 40 alkylene oxide units, e.g., ethylene oxide
units. Formulae for these modified phosphate anionic detergents are
##EQU24## or ##EQU25## in which R represents an alkyl group
containing from about 8 to 20 carbon atoms, or an alkylphenyl group
in which the alkyl group contains from about 8 to 20 carbon atoms,
and M represents a soluble cation such as hydrogen, sodium,
potassium, ammonium or substituted ammonium; and in which n is an
integer from 1 to about 40.
Another class of suitable anionic organic detergents particularly
useful in this invention includes salts of
2-acyloxyalkane-1-sulfonic acids exemplified by the reaction
product of fatty acids esterified with isethionic acid and
neutralized with sodium hydroxide where, for example, the fatty
acids are derived from coconut oil. These salts have the formula
##EQU26## where R.sub.1 is alkyl of about 9 to about 23 carbon
atoms (forming with the two carbon atoms an alkane group); R.sub.2
is alkyl of 1 to about 8 carbon atoms; and M is a water-soluble
cation.
The water-soluble cation, M, in the hereinbefore described
structural formula can be, for example, an alkali metal cation
(e.g., sodium, potassium, lithium), ammonium or
substituted-ammonium cation. Specific examples of substituted
ammonium cations include methyl-, dimethyl-, and trimethyl-
ammonium cations and quaternary ammonium cations such as
tetramethyl-ammonium and dimethyl piperidinium cations and those
derived from alkylamines such as ethylamine, diethylamine,
triethylamine, mixtures thereof, and the like.
Specific examples of beta-acyloxy-alkane-1-sulfonates, or
alternatively 2-acyloxy-alkane-1-sulfonates, useful herein include
the sodium salt of 2-acetoxy-tridecane-1-sulfonic acid; the
potassium salt of 2-propionyloxy-tetradecane-1-sulfonic acid; the
lithium salt of 2-butanoyloxy-tetradecane-1-sulfonic acid; the
sodium salt of 2-pentanoyloxy-pentadecane-1-sulfonic acid; the
sodium salt of 2-acetoxy-hexadecane-1-sulfonic acid; the potassium
salt of 2-octanoyloxy-tetradecane-1-sulfonic acid; the sodium salt
of 2-acetoxy-heptadecane-1-sulfonic acid; the lithium salt of
2-acetoxy-octadecane-1-sulfonic acid; the potassium salt of
2-acetoxy-nonadecane-1-sulfonic acid; the sodium salt of
2-acetoxy-uncosane-1-sulfonic acid; the sodium salt of
2-propionyloxy-docosane-1-sulfonic acid; the isomers thereof.
Preferred beta-acyloxy-alkane-1-sulfonate salts herein are the
alkali metal salts of beta-acetoxy-alkane-1-sulfonic acids
corresponding to the above formula wherein R.sub.1 is an alkyl of
about 12 to about 16 carbon atoms, these salts being preferred from
the standpoints of their excellent cleaning properties and ready
availability.
Typical examples of the above described beta-acetoxy
alkanesulfonates are described in the literature: Belgium Pat. No.
650,323 issued July 9, 1963, discloses the preparation of certain
2-acyloxy alkanesulfonic acids. Similarly, U.S. Pat. Nos. 2,094,451
issued Sept. 28, 1937, to Guenther et al. and 2,086,215 issued July
6, 1937 to DeGroote disclose certain salts of beta-acetoxy
alkanesulfonic acids. These references are hereby incorporated by
reference.
Another preferred class of anionic detergent compounds herein, both
by virtue of superior cleaning properties and low sensitivity to
water hardness (Ca++ and Mg++ ions) are the alkylated
.alpha.-sulfocarboxylates, containing about 10 to about 23 carbon
atoms, and having the formula: ##EQU27## wherein R is C.sub.8 to
C.sub.20 alkyl, M is a water-soluble cation as hereinbefore
disclosed, preferably sodium ion, and R' is either short chain
length alkyl, e.g., methyl, ethyl, propyl, and butyl or medium
chain length alkyl, e.g., hexyl, heptyl, octyl, and nonyl. In the
latter case, i.e. the medium chain length esters, the total number
of carbon atoms should ideally be in the range 18-20 for optimum
performance. These compounds are prepared by the esterification of
.alpha.-sulfonated carboxylic acids, which are commercially
available, using standard techniques. Specific examples of the
alkylated .alpha.-sulfocarboxylates preferred for use herein
include:
a. Short chain length esters
ammonium methyl-.alpha.-sulfopalmitate,
triethanolammonium ethyl-.alpha.-sulfostearate,
sodium methyl-.alpha.-sulfopalmitate,
sodium ethyl-.alpha.-sulfopalmitate,
sodium butyl-.alpha.-sulfostearate,
potassium methyl-.alpha.-sulfolaurate,
lithium methyl-.alpha.-sulfolaurate,
as well as mixtures thereof.
b. Medium chain length esters
sodium hexyl-.alpha.-sulphomyristate
potassium octyl-.alpha.-sulpholaurate
ammonium methyl-hexyl-.alpha.-sulpholaurate
and mixtures thereof.
A preferred class of anionic organic detergents are the
.beta.-alkyloxy alkane sulfonates. These compounds have the
following formula: ##EQU28## where R.sub.1 is a straight chain
alkyl group having from 6 to 20 carbon atoms, R.sub.2 is a lower
alkyl group having from 1 (preferred) to 3 carbon atoms, and M is a
water-soluble cation as hereinbefore described.
Specific examples of .beta.-alkyloxy alkane sulfonates, or
alternatively 2-alkyloxy-alkane-1-sulfonates, having low hardness
(calcium ion) sensitivity useful herein to provide superior
cleaning levels under household washing conditions include:
potassium-.beta.-methoxydecanesulfonate,
sodium 2-methoxytridecanesulfonate,
potassium 2-ethoxytetradecylsulfonate,
sodium 2-isopropoxyhexadecylsulfonate,
lithium 2-t-butoxytetradecylsulfonate,
sodium .beta.-methoxyoctadecylsulfonate, and
ammonium .beta.-n-propoxydodecylsulfonate.
Another suitable class of anionic surfactants are the water-soluble
salts of the organic, sulfuric acid reaction products of the
general formula
wherein R.sub.1 is chosen from the group consisting of a straight
or branched chain, saturated aliphatic hydrocarbon radical having
from 8 to 24, preferably 12 to 18, carbon atoms; and M is a cation.
Important examples are the salts of an organic sulfuric acid
reaction product of a hydrocarbon of the methane series, including
iso-, neo-, meso-, and n-paraffins, having 8 to 24 carbon atoms,
preferably 12 to 18 carbon atoms and a sulfonating agent e.g.
SO.sub.3, H.sub.2 SO.sub.4, oleum, obtained according to known
sulfonation methods, including bleaching and hydrolysis. Preferred
are alkali metal and ammonium sulfonated C.sub.12-18
n-paraffins.
Other synthetic anionic detergents useful herein are alkyl ether
sulfates. These materials have the formula RO(C.sub.2 H.sub.4
O).sub.x SO.sub.3 M wherein R is alkyl or alkenyl of about 10 to
about 20 carbon atoms, x is 1 to 30, and M is a water-soluble
cation as defined hereinbefore. The alkyl ether sulfates useful in
the present invention are condensation products of ethylene oxide
and monohydric alcohols having about 10 to about 20 carbon atoms.
Preferably, R has 14 to 18 carbon atoms. The alcohols can be
derived from fats, e.g., coconut oil or tallow, or can be
synthetic. Lauryl alcohol and straight chain alcohols derived from
tallow are preferred herein. Such alcohols are reacted with 1 to
30, and especially 6, molar proportions of ethylene oxide and the
resulting mixture of molecular species, having, for example, an
average of 6 moles of ethylene oxide per mole of alcohol, is
sulfated and neutralized.
Specific examples of alkyl ether sulfates of the present invention
are sodium coconut alkyl triethylene glycol ether sulfate; lithium
tallow alkyl triethylene glycol ether sulfate; and sodium tallow
alky hexaoxyethylene sulfate. Highly preferred alkyl ether
sulphates are those comprising a mixture of individual compounds,
said mixture having an average alkyl chain length of from about 12
to 16 carbon atoms and an average degree of ethoxylation of from
about 1 to 4 moles of ethylene oxide. Such a mixture also comprises
from about 0 to 20% by weight C.sub.12-13 compounds; from 60 to
100% by weight of C.sub.14-15-16 compounds; from about 0 to 20% by
weight of C.sub.17-18-19 compounds; from about 3 to 30% by weight
of compounds having a degree of ethoxylation of 0; from about 45 to
90% by weight of compounds having a degree of ethoxylation of from
1 to 4; from about 10 to 25% by weight of compounds having a degree
of ethoxylation of from 4 to 8; and from about 0.1 to 15% by weight
of compounds having a degree of ethoxylation greater than 8.
Additional examples of anionic synthetic detergents which come
within the terms of the present invention are the reaction product
of fatty acids esterified with isethionic acid and neutralized with
sodium hydroxide where, for example, the fatty acids are derived
from coconut oil; sodium or potassium salts of fatty acid amides of
methyl tauride in which the fatty acids, for example, are derived
from coconut oil. Other anionic synthetic detergents of this
variety are set forth in U.S. Pat. Nos. 2,486,921; 2,486,922; and
2,396,278.
Additional examples of anionic synthetic detergents, which come
within the terms of the present invention, are the compounds which
contain two anionic functional groups. These are referred to as
di-anionic detergents. Suitable dianionic detergents are the
disulfonates, disulfates, or mixtures thereof which may be
represented by the following formulae:
where R is an acyclic aliphatic hydrocarbyl group having 15 to 20
carbon atoms and M is a water-solubilizing cation, for example, the
C.sub.15 to C.sub.20 disodium 1,2-alkyldisulfates, C.sub.15 to
C.sub.20 dipotassium-1,2-alkyldisulfonates or disulfates, disodium
1,9-hexadecyl disulfates, C.sub.15 to C.sub.20
disodium-1,2-alkyldisulfonates, disodium 1,9-stearyldisulfates and
6,10-octadecyldisulfates.
The aliphatic portion of the disulfates or disulfonates is
generally substantially linear, thereby imparting desirable
biodegradable properties to the detergent compound.
The water-solubilizing cations include the customary cations known
in the detergent art, i.e., the alkali metals, and the ammonium
cations, as well as other metals in group IIA, IIB, IIIA, IVA and
IVB of the Periodic Table except for boron. The preferred
water-solubilizing cations are sodium or potassium. These dianionic
detergents are more fully described in British Pat. No. 1,151,392
which is hereby incorporated by reference.
Still other anionic synthetic detergents include the class
designated as succinamates. This class includes such surface active
agents as disodium N-octadecylsulfosuccinamate; tetrasodium
N-(1,2-dicarboxyethyl)-N-octadecylsulfo-succinamate; diamyl ester
of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic
acid; dioctyl esters of sodium sulfosuccinic acid.
Other suitable anionic detergents utilizable herein are olefin
sulfonates having about 12 to about 24 carbon atoms. The term
"olefin sulfonates" is used herein to mean compounds which can be
produced by the sulfonation of .alpha.-olefins by means of
uncomplexed sulfur trioxide, followed by neutralization of the acid
reaction mixture in conditions such that any sultones which have
been formed in the reaction are hydrolyzed to give the
corresponding hydroxy-alkanesulfonates. The sulfur trioxide can be
liquid or gaseous, and is usually, but not necessarily, diluted by
inert diluents, for example by liquid SO.sub.2, chlorinated
hydrocarbons, etc., when used in the liquid form, or by air,
nitrogen, gaseous SO.sub.2, etc., when used in the gaseous
form.
The .alpha.-olefins from which the olefin sulfonates are derived
are mono-olefins having 12 to 24 carbon atoms, preferably 14 to 16
carbon atoms. Preferably, they are straight chain olefins. Examples
of suitable 1-olefins include 1-dodecene; 1-tetradecene;
1-hexadecene; 1-octadecene; 1-eicosene and 1-tetracosene.
In addition to the true alkene sulfonates and a proportion of
hydroxy-alkanesulfonates, the olefin sulfonates can contain minor
amounts of other materials, such as alkene disulfonates depending
upon the reaction conditions, proportion of reactants, the nature
of the starting olefins and impurities in the olefin stock and side
reactions during the sulfonation process.
A specific .alpha.-olefin sulfonate mixture of the above type is
described more fully in the U.S. Pat. No. 3,332,880 of Phillip F.
Pflaumer and Adrian Kessler, issued July 25, 1967, titled
"Detergent Composition", the disclosure of which is incorporated
herein by reference.
In Table II A-D clay soil removal results are given for
combinations of ethoxylated zwitterionic compounds and anionic
surfactants. Experimental Runs 1, 2, 33, and 34 represent
comparative results for the C.sub.16 and C.sub.14 ethoxylated
zwitterionic compounds respectively at levels of 250 and 125 ppm.
Experimental Runs 3-14 inclusive also give comparative results for
various anionic surfactants and, with the exception of the alkyl
ether sulphate, these materials all show very poor clay soil
removal when used alone in water.
Runs 35-40 inclusive demonstrate the effect of various anionic
cosurfactants on the performance of the C.sub.14 ethoxylated
zwitterionic compound, both with and without builder at a level of
125 ppm each (i.e. a 1:1 ratio) of the C.sub.14 compound and
cosurfactant. It can be seen that for ethoxylated zwitterionic
compounds having mediocre particulate soil removal performance
addition of anionic cosurfactants provides a benefit but that
incorporation of builder gives little further improvement.
Runs 15-32 and 41-88 demonstrate the effect of various anionic
cosurfactants on the performance of the C.sub.16 ethoxylated
zwitterionic compound in the presence and absence of builder. Runs
15-32 show that, at 125 ppm each of C.sub.16 compound and anionic
cosurfactant in the absence of builder, particulate soil removal
performance of the ethoxylated zwitterionic compound is depressed.
It is restored, in varying degrees, by either delaying the solution
of the anionic cosurfactant (Runs 16, 19, 22, 25, 28, and 31) which
produces a marked effect on the performance on polyester fabrics,
or by adding builder to the system, which shows a benefit for the
more hydrophilic cotton-containing fabrics.
Runs 41-58 duplicate Runs 15-32 except that the level of C.sub.16
ethoxylated zwitterionic compound is at 250 ppm in solution, i.e. a
ratio of C.sub.16 compound to anionic cosurfactant of 2:1. It can
be seen that the depressive effect of the anionic surfactant is
less evident, particularly for the composition containing sodium
stearate. Furthermore, the effect of either delaying cosurfactant
solution, or of adding builder, is to appreciably improve
performance and in certain specific instances, to equal the
performance attained by 250 ppm C.sub.16 ethoxylated zwitterionic
compound on its own.
Runs 59-88 provide further evidence of the extent to which anionic
surfactants inhibit the particulate soil removal performance of the
ethoxylated zwitterionic compounds of the present invention. A
reduction in performance is still apparent at a ratio of
ethoxylated zwitterionic to anionic cosurfactant of 4:1, the
exception again being sodium stearate, but is much less noticeable
at a ratio of 9:1, the addition of builder providing a benefit in
each instance. At an ethoxylated zwitterionic compound level of 300
ppm in solution and with 25 ppm cosurfactant (12:1 ratio)
substantially no diminution in particulate soil removal performance
is seen.
As noted above, the results show the sequential dissolution of
first the ethoxylated zwitterionic and then the anionic
cosurfactant serves to minimize the adverse effect of the latter on
the clay removal performance of the former. Such sequential
dissolution can be achieved by any one of a number of known
methods, e.g., by coating, granulation, or agglomeration of the
anionic with other conventional detergent components such as
C.sub.12-20 fatty acids, c.sub.12-18 fatty acid amides and alkanol
amides, high molecular weight (i.e. MWt>1000) polyethylene
glycols, hydratable inorganic builder salts such as alkali metal
polyphosphates, and porous siliceous materials such as those sold
under the Trade Name "Zeosyl" by J. M. Huber Corporation.
Conveniently, the diluent component is incorporated at a level of 5
to 50%, preferably 10 to 25%, by weight of the mixture of anionic
surfactant plus diluent so as to effect a delay of at least 60
seconds in the complete dissolution or dispersion of the mixture in
an aqueous medium at 100.degree.F.
Similarly, microencapsulation using, e.g., hydrolysed gelatin,
agar, or polyvinyl alcohol wall materials can be employed where low
levels of anionic material are desired. Techniques for
microencapsulating materials, including detergent components, are
well known in the art. A typical disclosure of such techniques is
given in Kirk-Othmer Encyclopedia of Chemical Technology, 2nd
edition, 13, pp. 436-456, published in 1967 by John Wiley &
Sons, Inc. This disclosure is incorporated herein by reference.
TABLE IIIA
__________________________________________________________________________
CLAY SOIL REMOVAL OF ETHOXYLATED ZWITTERIONIC COMPOUNDS IN
COMBINATION WITH ANIONIC SURFACTANTS Conditions: 10 Minute
Tergotometer Wash at 105.degree.F in 5.5 grains/gal. Mineral
Hardness (Ca:Mg = 3:1) RELATIVE ETHOXYLATED LEVEL LEVEL LEVEL CLAY
REMOVAL INDEX ZWITTERIONIC PPM IN PPM IN BUILDER PPM IN POLY- POLY-
No. COMPOUND SOLUTION COSURFACTANT SOLUTION TYPE SOLUTION COTTON
COTTON ESTER
__________________________________________________________________________
1 N--C.sub.16 H.sub.33 N,N--bisCH.sub.3 (C.sub.2 H.sub.4 O).sub.8
CH.sub.2 CH.sub.2 SO.sub.3 250 -- -- -- -- 90 92 95 2 " 125 -- --
-- -- 69 88 93 3 -- -- 125 -- -- 23 64 20 4 -- -- " 250 -- -- 41 69
21 5 -- -- C.sub.16.sub.-18 alkyl 125 -- -- 32 32 27 OSO.sub.3 Na 6
-- -- " 250 -- -- 36 33 31 7 -- -- C.sub.16 -C.sub.18 alkyl 125 --
-- 71 71 45 (EO).sub.6 OSO.sub.3 Na 8 -- -- " 250 -- -- 84 79 51 9
-- -- Na stearate 125 -- -- 30 40 30 10 -- -- " 250 -- -- 30 43 34
11 -- -- C.sub.14 -C.sub.16 alkane 125 -- -- 60 63 46 SO.sub.3 Na
12 -- -- " 250 -- -- 64 63 46 13 -- -- Na Hexyl .alpha.-sulpho 125
-- -- 35 55 34 Laurate 14 -- -- " 250 -- -- 35 60 32 15 N--C.sub.16
H.sub.33 N,N--bisCH.sub.3 125 125 -- -- 39 81 34 (C.sub.2 H.sub.4
O).sub.8 CH.sub.2 CH.sub.2 SO.sub.3 16 " 125 " 125* -- -- 64 71 78
17 " 125 " 125 STP 250 52 79 35 18 " 125 C.sub.16 -C.sub.18 alkyl
125 -- -- 38 60 30 OSO.sub.3 Na 19 " 125 " 125* -- -- 61 67 77 20 "
125 " 125 STP 250 48 74 36 21 " 125 C.sub.16 -C.sub.18 alkyl 125 --
-- 38 65 31 (EO).sub.6 OSO.sub.3 Na 22 " 125 " 125* -- -- 66 65 72
23 " 125 " 125 STP 250 52 78 37 24 " 125 Na stearate 125 -- -- 43
85 72 25 " 125 " 125* -- -- 77 78 93 26 " 125 " 125 STP 250 61 96
89 27 " 125 C.sub. 14 -C.sub.16 alkane 125 -- -- 53 68 37 SO.sub.3
Na 28 " 125 " 125* -- -- 69 83 78 29 " 125 " 125 STP 250 55 69 37
30 " 125 Na Hexyl .alpha.-sulpho 125 -- -- 53 68 34 Laurate 31 "
125 " 125* -- -- 55 78 78 32 " 125 " 125 STP 250 55 73 40
__________________________________________________________________________
*Introduced 2 minutes after ethoxylated zwitterionic compound
contacted with fabrics.
TABLE IIIB
__________________________________________________________________________
CLAY SOIL REMOVAL OF ETHOXYLATED ZWITTERIONIC COMPOUNDS IN
COMBINATION WITH ANIONIC SURFACTANTS Conditions: 10 Minute
Tergotometer Wash in 7 grains/gal. Mineral Hardness (2:1 Ca:Mg) at
105.degree.F RELATIVE ETHOXYLATED LEVEL LEVEL LEVEL CLAY REMOVAL
INDEX ZWITTERIONIC PPM IN PPM IN BUILDER PPM IN POLY- POLY- NO.
COMPOUND SOLUTION COSURFACTANT SOLUTION TYPE SOLUTION COTTON COTTON
ESTER
__________________________________________________________________________
33 N--C.sub.14 H.sub.29 N,N--bisCH.sub.3 250 -- -- -- -- 53 69 46
(C.sub.2 H.sub.4 O).sub.8 CH.sub.2 CH.sub.2 SO.sub.3 34 " 125 -- --
-- -- 41 52 24 35 " 125 125 -- -- 69 89 38 36 " 125 " 125 STP 250
68 73 37 37 " 125 C.sub.16.sub.-18 alkyl 125 -- -- 65 70 34
(EO).sub.6 OSO.sub.3 Na 38 " 125 " 125 STP 250 77 75 40 39 " 125 Na
stearate 125 -- -- 44 57 31 40 " 125 " 125 STP 250 72 62 24
__________________________________________________________________________
TABLE IIIC
__________________________________________________________________________
CLAY SOIL REMOVAL OF ETHOXYLATED ZWITTERIONIC COMPOUNDS IN
COMBINATION WITH ANIONIC SURFACTANTS Conditions: 10 Minute
Tergotometer Wash at 105.degree.F in 5.5 grains/gal. Mineral
Hardness (Ca:Mg = 3:1) RELATIVE ETHOXYLATED LEVEL LEVEL LEVEL CLAY
REMOVAL INDEX ZWITTERIONIC PPM IN PPM IN BUILDER PPM IN POLY- POLY-
NO. COMPOUND SOLUTION COSURFACTANT SOLUTION TYPE SOLUTION COTTON
COTTON ESTER
__________________________________________________________________________
41 N--C.sub.16 H.sub.33 N,N--bisCH.sub.3 250 125 -- -- 68 53 37
(C.sub.2 H.sub.4 O).sub.8 CH.sub.2 CH.sub.2 SO.sub.3 42 " 250 "
125* -- -- 89 82 100 43 " 250 " 125 STP 250 63 68 47 44 " 250
C.sub.16 -C.sub.18 alkyl 125 -- -- 60 67 31 OSO.sub.3 Na 45 " 250 "
125* -- -- 75 82 91 46 " 250 " 125 STP 250 77 74 42 47 " 250
C.sub.16 -C.sub.18 alkyl 125 -- -- 30 68 42 (EO).sub.6 OSO.sub.3 Na
48 " 250 " 125* -- -- 113 83 62 49 " 250 " 125 STP 250 46 79 61 50
" 250 Na stearate 125 -- -- 84 92 95 51 " 250 " 125* -- -- 95 92 96
52 " 250 " 125 STP 250 105 103 99 53 " 250 C.sub.14 -C.sub.16
alkane 125 -- -- 62 69 34 SO.sub.3 Na 54 " 250 " 125 -- -- 95 92 96
55 " 250 "125 STP 250 55 31 87 56 " 250 Na Hexyl .alpha.-sulpho 125
-- -- 67 73 36 Laurate 57 " 250 " 125* -- -- 75 89 89 58 " 250 "
125 STP 63 78 35
__________________________________________________________________________
*Introduced 2 minutes after ethoxylated zwitterionic compound
contacted with fabrics. TABLE IIID
__________________________________________________________________________
CLAY SOIL REMOVAL OF ETHOXYLATED ZWITTERIONIC COMPOUNDS IN
COMBINATIN WITH ANIONIC SURFACTANTS Conditions: 10 Minute
Tergotometer Wash at 105.degree.F in 5.5 grains/gal. Mineral
Hardness (Ca:Mg = 3:1) RELATIVE ETHOXYLATED LEVEL LEVEL LEVEL CLAY
REMOVAL INDEX SWITTERIONIC PPM IN PPM IN BUILDER PPM IN POLY- POLY-
NO. COMPOUND SOLUTION COSURFACTANT SOLUTION TYPE SOLUTION COTTON
COTTON ESTER
__________________________________________________________________________
59 N--C.sub.16 H.sub.33 N,N--bisCH.sub.3 (CH.sub.2 CH.sub.2
O).sub.8 CH.sub.2 CH.sub.2 SO.sub.3 200 50 -- -- 44 79 36 60 " 200
" 50 STP 250 71 60 62 61 " 225 " 25 -- -- 52 82 59 62 " 225 " 25
STP 250 93 97 96 63 " 300 " 25 -- -- 91 90 96 64 " 200 C.sub.16
-C.sub.18 alkyl 50 -- -- 54 68 32 OSO.sub.3 Na 65 " 200 " 50 STP
250 59 71 34 66 " 225 " 25 -- -- 70 81 64 67 " 225 " 25 STP 250 86
94 92 68 " 300 " 25 -- -- 88 88 96 69 " 200 C.sub.16 -C.sub.18
alkyl 50 -- -- 59 72 39 (EO).sub.6 OSO.sub.3 Na 70 " 200 " 50 STP
250 63 67 42 71 " 225 " 25 -- -- 71 83 73 72 " 225 " 25 STP 250 82
88 96 73 " 300 " 25 -- -- 88 g3 95 74 N--C.sub.16 H.sub.33
N,N--bisCH.sub.3 (CH.sub.2 CH.sub.2 O).sub.8 CH.sub.2 CH.sub.2
SO.sub.3 200 Na stearate 50 -- -- 89 87 91 75 " 200 " 50 STP 250 92
99 99 76 " 225 " 25 -- -- 94 89 93 77 " 225 " 25 STP 250 101 100
101 78 " 300 " 25 -- -- 88 90 96 79 " 200 C.sub.14 -C.sub.16 alkane
50 -- -- 70 72 36 SO.sub.3 Na 80 " 200 " 50 STP 250 71 63 42 81 "
225 " 25 -- -- 75 76 45 82 " 225 " 25 STP 250 84 78 73 83 " 300 "
25 -- -- 93 83 96 84 " 200 Na Hexyl .alpha.-sulpho 50 -- -- 50 71
42 Laurate 85 " 200 " 50 STP 250 50 79 41 86 " 225 " 25 -- -- 61 82
74 87 " 225 " 25 STP 250 70 94 79 88 " 300 " 25 -- -- 70 90 91
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Grease and oil removal data are shown in Table V for combinations
of C.sub.11.8 LAS and C.sub.16-18 alkyl E.sub.6 S respectively with
both C.sub.16 and C.sub.14 ethoxylated zwitterionic compounds, and
it can be seen that C.sub.11.8 LAS provides performance advantages
relative to the control product. In contrast, the ethoxylated
sulphate surfactant serves to inhibit grease and oil removal.
The effect of anionic cosurfactants on the sudsing characteristics
of the ethoxylated zwitterionic compounds of the present invention
is illustrated in the Figure in which the suds heights developed by
the Recirculating Suds Generator (RSG) are plotted for different
blends of C.sub.16 ethoxylated zwitterionic compound and sodium
C.sub.11.8 linear alkyl benzene sulphonate over a 10-minute time
interval. It can be seen that an appreciable fraction of the
sudsing performance achieved by 100% C.sub.11.8 LAS is given by
blends in which the level of C.sub.11.8 LAS is as low as 5%, the
sudsing performance increasing with increasing C.sub.11.8 LAS
level.
Thus anionic surfactants can be incorporated in detergent
compositions in accordance with the present invention although they
should not exceed 50% by weight of the ethoxylated
zwitterionic-cosurfactant mixture if the desirable particulate soil
removal properties of the ethoxylated zwitterionic compound are to
be retained. Alkali metal salts of aliphatic carboxylic acids can
be incorporated at these levels without special formulation
precautions but most anionic cosurfactant levels in excess of 20%
of the mixture, more preferably in excess of 10% of the mixture,
require incorporation in a manner that will delay the cosurfactant
solubility.
CATIONIC DETERGENTS
Only those cationic detergents having a hydrophilic grouping with
the molecule have been found to be compatible with the ethoxylated
zwitterionic compounds useful in the present invention.
Thus compounds of the class ##EQU29## can be employed where R.sub.1
is a C.sub.12 -C.sub.18 linear or branched alkyl or alkenyl group
R.sub.2 and R.sub.3 are C.sub.1 -C.sub.4 alkyl or hydroxy alkyl
groups, p has a value in the range 3-50, and X.sup.- is a
compatible anion such as chloride, bromide, iodide, sulphate,
methosulphate acetate or phosphate.
Similarly, compounds having the structure ##EQU30## where R.sub.1,
R.sub.2, and X are as previously defined and wherein the sum of m+n
has a value in the range 3-50 can also be combined satisfactorily
with the ethoxylated zwitterionics useful in the present invention.
Compounds of the above type are available under the trade name
"Ethoquad" from the Armour Chemical Company.
The effect of cationic cosurfactants on the clay soil removal
performance of ethoxylated zwitterionic compounds of the present
invention is shown in Table IV. It can clearly be seen that the
C.sub.16 trimethyl quaternary has an adverse effect on clay soil
removal which is mitigated by the addition of a builder whereas the
C.sub.18 ethoxylated quaternary cosurfactant enhances performance.
This effect can be seen for both the C.sub.14 and C.sub.16
ethoxylated zwitterionic compounds and characterizes a general
tendency for quaternary cosurfactants having hydrophilic structural
components to have beneficial effects on the particulate soil
removal performance of the ethoxylated zwitterionic compounds while
for quaternary cosurfactants not having hydrophilic structural
components, the reverse effect is seen.
TABLE IV
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CLAY SOIL REMOVAL OF ETHOXYLATED ZWITTERIONIC COMPOUNDS IN
COMBINATION WITH CATIONIC SURFACTANTS Conditions: 10 Minute
Tergotometer Wash in 7 grains/gal. Mineral Hardness (2:1 Ca:Mg) at
105.degree.F RELATIVE ETHOXYLATED LEVEL LEVEL LEVEL CLAY REMOVAL
INDEX ZWITTERIONIC PPM IN PPM IN BUILDER PPM IN POLY- POLY- NO.
COMPOUND SOLUTION COSURFACTANT SOLUTION TYPE SOLUTION COTTON COTTON
ESTER
__________________________________________________________________________
1 N--C.sub.16 H.sub.33 N,N--bisCH.sub.3 (CH.sub.2 CH.sub.2 O).sub.8
CH.sub.2 CH.sub.2 SO.sub.3 250 -- -- -- -- 75 96 95 2 " 125 -- --
-- -- 68 88 77 3 " 125 [C.sub.16 H.sub.33 (CH.sub.3).sub.3 ] 125 --
-- 26 63 28 N.sup.+ Br.sup.- 4 " 125 " 125 STP 250 90 84 61 5 " 125
C.sub.18 alkyl di- 125 -- -- 88 93 96 polyethenoxy Ammonium
Bromide* 6 " 125 " 125 STP 250 98 108 104 7 N--C.sub.14 H.sub.29
N,N--bisCH.sub.3 250 -- -- -- -- 53 69 46 (CH.sub.2 CH.sub.2
O).sub.8 CH.sub.2 CH.sub.2 SO.sub.3 8 " 125 -- -- -- -- 41 52 24 9
" 125 [C.sub.16 H.sub.33 (CH.sub.3).sub.3 ] 125 -- -- 15 46 13
N.sup.+ Br.sup.- 10 " 125 " 125 STP 250 46 60 26 11 " 125 C.sub.18
alkyl di- 125 -- -- 71 82 61 polyethenonxy Ammonium Bromide* 12 "
125 " 125 STP 250 71 89 70
__________________________________________________________________________
*Total No. of ethylene oxide groups per mole = 50.
OPTIONAL COMPONENTS
In addition to the ethoxylated zwitterionic compound and the
organic surfactant, the detergent compositions may also contain
other ingredients conventionally employed in such products. The
principal optional component is an inorganic or organic detergent
builder to assist in mineral hardness control which may be used at
levels between 1 and 99% by weight of the detergent composition,
preferably between 10 and 75% and most preferably between 25 and
60%.
Suitable inorganic builders include the alkali metal polyphosphates
(including the pyrophosphates and glassy high polymeric phosphates)
phosphonates, carbonates, sesquicarbonates, bicarbonates, borates,
silicates, sulphates, and aluminosilicates.
Aluminosilicate builder salts found to be useful in the present
invention have the general formula:
wherein z and y are integers of at least 6, the molar ratio of z to
y is in the range from 1.0 to about 0.5 and x is an integer from
about 15 to about 15 to about 264. Such aluminosilicates also
should have a particle size diameter in the range 0.1 to 100
microns, a calcium ion exchange capacity of at least about 200
milligram equivalent/gram and a calcium ion exchange rate of at
least about 2 grains/U.S. gallon/minute/gram. Detergent
compositions incorporating aluminosilicate builder salts of this
type are disclosed in the commonly assigned copending application
Ser. No. 450,266 of Corkill, Madison, and Burns filed Mar. 11,
1974, which disclosure is incorporated herein by reference.
Suitable organic builders include alkali metal salts of ethylene
diamine tetraacetic acid, nitrilotriacetic acid, citric acid,
oxydisuccinic acid, carboxy methoxysuccinic acid, polymaleic acid,
benzene hexa- and penta-carboxylic acid, 1,3,5-trihydroxy benzene
2,4,6-trisulphonic acid and copolymers of maleic anhydride with
ethylene or methyl vinyl ether. Examples of these and similar
organic builders are set forth in U.S. Pat. No. 3,308,067 issued
Mar. 7, 1967, to Francis L. Diehl, the disclosures of which are
hereby incorporated by reference. The commonly assigned cofiled
Application, Ser. No. 493,952, of Robert G. Laughlin and Robert L.
Stewart, now U.S. Pat. No. 3,925,262, entitled Detergent
Compositions discloses combinations of the above mentioned
detergent builder salts with ethoxylated zwitterionic compounds,
and this disclosure is incorporated herein by reference.
Another optional ingredient that may be incorporated is an enzyme
for removal of protein-based or carbohydrate-based stains. Enzymes
for removing protein-based stains are proteolytic in nature such as
those sold under the trade names "Alcalase" and "Esterase" by Novo
Industries A/S. Denmark or under the trade names "Maxatase" and "AZ
Protease" by Gist-Brocades N.V. The Netherlands. These materials
are normally incorporated at levels of up to 1% by weight,
preferably 0.25 to 0.75% by weight, and are preferably coated or
prilled with inert additives to minimize dust formation and improve
storage stability. A wide range of enzyme materials and means for
their incorporation into synthetic detergent granules is disclosed
in U.S. Pat. No. 3,553,139 issued on Jan. 5, 1971, to McCarty,
Roald, DeOude, Blomeyer, and Cracco which disclosure is hereby
incorporated by reference.
A further ingredient that may be incorporated to improve product
performance is a bleaching agent of the halogen of
oxygen-containing type. Examples of the hypohalite bleach type
include trichloro isocyanuric acid and the sodium and potassium
dichloroisocyanurates and N-chloro and N-bromo alkane
sulphonamides. Such materials are normally added at 0.5-10% by
weight of the finished product, preferably 1-5% by weight.
Examples of oxygen-containing bleaches include sodium perborate,
sodium percarbonate, and potassium non-opersulphate that are
incorporated at levels of 5-30%, preferably 10-25% by weight of the
final product. The inclusion of organic bleach activators such as
phthalic anhydride, tetra acetyl ethylene diamine, tetra acetyl
methylene diamine or tetra acetyl glycouril lead to the in situ
production during the washing process of the corresponding organic
peroxy acids which have enhanced low temperature bleaching
performance. Activators of this type are normally used with sodium
perborate, at usage levels of 5-15 % by weight of the final
product.
Materials to boost or modify the sudsing pattern of the
compositions of the present invention may also be included.
Examples of suds boosters include coconut and tallow mono- and
di-alkanolamides, particularly ethanolamides and C.sub.12-15 alkyl
di-lower alkyl amine oxides. Typical suds depressors include long
chain fatty acids such as those disclosed in U.S. Pat. No.
2,954,347 issued Sept. 27, 1960, to Wayne St. John and combinations
of certain nonionics therewith as disclosed in U.S. Pat. No.
2,954,348 issued Sept. 27, 1960, to Eugene Schwoeppe, both
disclosures being incorporated herein by reference.
Other optional ingredients in granular products include hydrotropes
and anticaking additives such as salts of lower alkyaryl sulphonic
acids, salts of .alpha.-sulphosuccinic acid, and
.alpha.-sulphobenzoic acid, and urea, normally utilized at levels
of 0.5 to 5% by weight of the final product, preferably at levels
of 1-3% by weight. C.sub.12 -C.sub.18 alkyl acid phosphates and
their condensation products with ethylene oxide may also be
incorporated at similar levels for control of crutcher mix
viscosity. Antiredeposition agents such as carboxymethyl cellulose,
hydroxyethyl cellulose, and their derivatives may also be
incorporated.
Anti-tarnish and anti-corrosion agents, perfume and colour may also
be included, the last ingredient being conveniently added either as
a general colour or in the form of a speckle applied to a separate
granule fraction of the entire formulation or to a granulate of one
or more of the ingredients.
The pH of detergent formulations in accordance with the present
invention can lie anywhere within the range 5-12 but is preferably
chosen to fall within the range 8.0 -10.5 as this provides a slight
particulate soil removal benefit on synthetic fabrics. However, the
use of specific optional components such as enzymes may require the
selection of a product pH that will permit optimum functioning of
the component concerned.
Granular formulations embodying the compositions of the present
invention may be formed by any of the conventional techniques i.e.,
by slurrying the individual components in water and then atomizing
and spray-drying the resultant mixture, or by pan or drum
granulation of the components.
Liquid formulations embodying the compositions of the present
invention may contain builders or may be unbuilt. If the
compositions are unbuilt, they will conventionally contain
approximately 30-50% total surfactant, from 1-10% of an organic
base such as mono, di, or tri-alkanolamine, a solubilization system
such as alkali metal halide and a lower primary alcohol such as
ethanol or isopropanol and approximately 30-40% water. Such
compositions will normally be homogeneous single phase liquids of
low viscosity (approximately 100-150 centipoises at
75.degree.F).
Built liquid detergent compositions may also be single phase
liquids provided that the builder can be solubilized in the mixture
at its level of use. Such liquids conventionally contain 10-25%
total surfactant, 10-20% builder which may be organic or inorganic,
5-10% of a hydrotrope system and 50-60% of water. Liquids of this
type also have low viscosity (100-150 c.p.s. at 75.degree.F). Built
liquid detergents incorporating components that form heterogeneous
mixtures or levels of builder that cannot be completely dissolved
can also embody the compositions of the present invention. Such
liquids conventionally employ viscosity modifiers to produce
systems having plastic shear characteristics to maintain stable
dispersions and to prevent phase separation or solid
settlement.
The following examples serve to illustrate the present
invention:
EXAMPLE I
A granular detergent composition was made up having the following
composition:
.OMEGA.-(N-octadecyl-N,N-dimethylammonio)-
2-octaethenoxy-ethane-1-sulphonate 9.3% 3-(N-myristyl
N,N-dimethylammonio)prpane- 1-sulphonate 9.3% Na.sub.12 (SiO.sub.2
:AlO.sub.2).sub.12 15H.sub.2 O 51.8% Na.sub.2 CO.sub.3 14.8% Sodium
Silicate (SiO.sub.2 :Na.sub.2 O=3.2:1) 14.8% 100.0%
The composition was dissolved in water having a mineral hardness of
7 grains/U.S. gallon (Ca:Mg = 2:1) to give a 0.12% solution and was
then used in a Tergotometer to give a 10 minute wash at
105.degree.F to a mixture of cotton, polycotton, and polyester
cloth swatches, employing the Test Procedure previously described.
A similar wash using Control Product A at a level of 1400 ppm in
solution was also carried out, and the particulate soil removal
given by the composition expressed as a percentage of the
performance of the control product was:
Cotton Polycotton Polyester 110 102 108
EXAMPLE II
Liquid laundry detergents were made up having the following
compositions:
P Q R S T ______________________________________ C.sub.14.sub.-14
alcohol with 7 moles ethylene oxide 33.0 33.0 33.0 33.0 33.0
C.sub.11.8 linear alkyl benzene sulphonate 23.0 23.0 -- -- --
Triethanolamine 3.0 3.0 3.0 3.0 3.0 KCL 2.5 2.5 -- -- -- Ethanol
5.0 15.0 15.0 15.0 15.0 N-octadecyl N,N- dimethyl ammonio-2- -- --
-- 2.0 5.0 octaethenoxy-ethane- 1-sulphonate Water to 100 ------ to
100 ---- ----.fwdarw. ______________________________________
Each composition was used to pretreat a 5 inch square knitted
polyester swatch presoiled with a clay solution prior to the latter
being washed. In each pretreatment, three drops of the composition
were applied to a 1 inch square cut out from the swatch, and this
cut out and the remainder of the swatch were then given a 10 minute
wash at 105.degree.F in a Tergotometer using water having 7
grains/gallon hardness (Ca/Mg = 2:1). The wash, rinse, and dry
cycles were as hereinbefore described in the standard
procedure.
The swatches and cut outs were then graded visually for particulate
soil removal. Compositions P and Q showed no pretreatment benefit
on the respective cut outs and little if any clay soil removal from
the swatches. Composition R achieved discernible clay removal from
the swatch and a visible benefit for pretreatment. Compositions S
and T also showed some clay removal from the swatches but the areas
of the cut outs which had been pretreated were restored to their
original condition before clay soiling.
* * * * *