Note: Descriptions are shown in the official language in which they were submitted.
5~ ~
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LAUNDRY DETERGENT COMPOSITIONS HAVING
ENHANCED PARTICULATE SOIL REMOVAL PERFORMANCE
Technical Field
This invention relates to laundry detergent compositionscontaining no or low levels of phosphate materials, which
exhibit highly improved particulate soil removal capabilities.
T~ese detergent compositions provide surprisingly effective -
clay soil removal performance even in the absence of deter-
gency builders. Similar compositions which utilize mixtures
of selected nonionic surfactants and selected cationic sur-
factants and which give unexpectedly good removal of greasy/
oily and body soils are defined in concurrently filed
Canadian Patent Application Serial No. 306,474, of Alan Pearce
Murphy.
~ac~groun~ Art
Nonionic surfactants are generally used in laundry
detergent compositions for their ability to remove greasy and
oily soils. Cationic surfactants have also been used in
detergent compositions, primarily to provide adjunct fabric
care benefits, and not for the purpose of cleaning. Certain
cationic surfactants have been included in detergent compo-
sitions for the purpose of yielding a germicidal or sanitiza-
tion benefit to washed surfaces; see, for example, U.S.
Patent 2,742,434, Kopp, issued April 17, 1956; U.S. Patent
3,539,520, Cantor et al, issued November 10, 1970; and U.S.
Patent 3,965,026, Lancz, issued June 22, 1976. Other cationic
surfactants, such as ditallowalkyldimethylammonium chloride,
are included in detergent compositions for the purpose of
yielding a fabric-softening benefit, as disclosed in U.S.
Patent 3,607,763, Salmen et al, issued September 21, 1971;
and U.S. Patent 3,644,203, Lamberti et al, issued February
22, 1972. Such components are also used to control static,
as well as soften laundered fabrics as, for example, in U.S.
Patent 3,951,879, Wixon, issued April 20, 1976; and U.S.
Patent 3,959,157, Inamorato, issued May 25, 1976.
How-
ever, none of these patents indicate that by the careful
selection and combination of certain nonionic and cationic
surfactants, to achieve specific nonionic:cationic surfactant
ratios and reduced cationic monomer concentrations, outstand-
$~
_ 3 _ 11~9754
,
ing removal of particulate soils may be obtained.
The compositions of the present invention have outstandingcleaning capabilities. In laundry tests, these compositions,
not containing any builder components, have been shown to
remove clay soils at least as well, and in some cases drama-
tically better, than fully-built conventional laundry detergent
compositions. In addition, the compositions inhibit the
transfer of dyes, soften and control static through the washing
and drying operations. Further, by selecting the preferred
cationic components defined in this application, the composi-
tions additionally provide biodegradability and excellent
removal of greasy and oily soils, while also providing, in a
single detergent product, particulate soil removal, fabric
softening, static control and dye transfer inhibition benefits
to the laundered fabrics. The cleaning performance, which is
superiox to that previously demonstrated, is ~he result of a
heretofore unrecognized cleaning potential of certain selected
cationic surfactants when used in the presence of certain
selected nonionic surfactants under the conditions specified
herein.
It is an object of this invention to provide laundry
detergent compositions which yield outstanding particulate
soil removal, and which also provide fabric softening, static
control and dye transfer inhibition benefits.
It is another object of this invention to provide laundry
detergent compositions, yielding excellent particulate soil
removal, which may be used in a variety of physical forms,
such as liquid, solid, paste, granular, powder, or in con-
junction with a carrier such as a substrate.
It is a further more specific object of this invention to
provide specific detergent compositions which yield excellent
particulate soil removal and which are biodegradable.
It is a still further specific object of this invention
to define specific novel cationic surfactants which are bio-
degradable and which yield excellent particulate and greasy
and oily soil removal performance, as well as fabric softening
and static control, in the cationic/nonionic surfactant
systems of the present invention.
It is another specific object of this invention to pro-
vide amide-containing cationic/nonionic surfactant-containing
_ 4 _ ~ ~9754
compositions which yield both excellent particulate soil re-
moval and anti-redeposition properties.
It is yet another object of this invention to provide a
process for laundering fabrics which yields especially good
particulate soil removal, using cationic and nonionic sur-
factant-containing detergent compositions.
Disclosure of the Invention
The present invention relates to laundry detergent compo-
sitions, containing from 0 to about 20% phosphate materials,
which are especially beneficial for the removal of particulate
soils from fabrics, having a pH of at least about 6.5 in the
aqueous laundry solution, and which are substantially free of
fatty acid polyglycol ether diester compounds, oily hydro-
carbon materials and cationic materials containing 13 or more
ethylene oxide groups, comprising from about 5 to about 100%,
by weight, of a surfactant mixture consisting essentially of
(a) a biodegradable nonionic having the formula
R(OC2H4)nOH
wherein R is a primary or secondary alkyl chain of
from 8 to about 22 carbon atoms and n is an average
of from about 2 to about 12, having an HLB of from
5 to about 17; and
(b) a cationic surfactant, free of hydrazinium groups,
having the formula
RmRxYLZ
wherein each Rl is an organic group containing a
straight or branched alkyl or alkenyl group
optionally substituted with up to three phenyl or
hydroxy groups and optionally interrupted by up to
four structures selected from the group consisting
of
1l 1l 11 R2 ~20 ~ H
H ~ 0 0 H H 0
~ c , o , -o-c-o-, -o-~ , -h-ll-o-,
and mixtures thereof, said Rl containing from
about 8 to 22 carbon atoms, and which may addi-
"i~
~ , .
111~9754
-- 5 --
~.
tionally contain up to 12 ethylene oxide groups; mis a number from 1 to 3, with no more than one Rl
in a molecule having a total of 16 or more carbon
atoms when m is 2, or more than 12 carbon atoms
when m is 3; each R2 is an alkyl or hydroxyalkyl
group containing from 1 to 4 carbon atoms or a benzyl
group, with no more than one R2 in a molecule being
benzyl; x is a number from O to 11, the remainder of
any carbon atom positions being filled by hydrogens;
Y is selected from the group consisting of:
N+-
I
/ N - C- -
(2) -C~ l
~ N - C -
l+
(3) -p _
(4) -S -
(S) - ~ - , wherein p is from 1 to 12,
(C2H40)pH
(lC2H4)pH
(6) -I+- , wherein each p is from 1 to 12,
(C2 40)pH
C
~C~ \~
,C~ /C~,
Cl
, \ ~ C\ , and
N
t9) mixtures thereof;
L is 1 or 2, the Y groups being separated by a
?~ moiety selected from Rl and R2 analogs having from
~L,
.
1~97S4
.,
1 to about 22 carbon atoms and 2 free carbon single
bonds when L is 2; Z is an anion in a number to give
electrical neutrality to the molecule; said cationic
surfactant being at least water-dispersible in ad-
mixture with said nonionic surfactant;
the ratio of said nonionic to said cationic surfactant being
in the range of from 5:1 to about 1:1. In preferred composi-
tions, the reduced cationic monomer concentration of said
surfactant mixture is from about 0.005 to about 0.2.
The compositions of the present invention are formulated
so as to have a pH of at least about 6.5 in the laundry solu-
tion at conventional usage concentrations in order to optimize
overall cleaning performance; preferably, they are alkaline in
nature (pH greater than about 7) when placed in the laundry
solution, and preferred compositions have a pH of at least
about 7.5. Some of the cationic/nonionic systems of the
present invention will attain optimum removal of greasy/oily
soils at higher pHs, while attaining optimum clay removal at
relatively lower pHs. In these systems, overall performance
may be enhanced by varying the pH of the wash solution during
the laundering process. Particularly preferred compositions
have a pH of at least about 8 in the laundry solution, in
order to improve the removal of body soil. In addition to the
alkaline laundry solution pH, these preferred compositions
should also have the ability to maintain a pH in the laundry
solution of from about 8 to 11 throughout the washing operation
(reserve alkalinity). Such a reserve alkalinity may be
obtained by incorporating compounds which buffer at pHs of
from about 8 to 11, such as monoethanolamine, diethanolamine
or triethanolamine.
The compositions are free of oily hydrocarbon materials,
such as mineral oil, paraffin oil and kerosene, because these
materials (which are themselves oily in nature) load the
washing liquor with excessive oily material, thereby diminish-
ing the cleaning effectiveness of the compositions of the
present invention.
The cationic component is free of hydrazinium groups due
to their relatively high toxicity level which makes them
unsuitable for use in the compositions of this invention.
. . :
'
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,.
The compositions of the present invention are substan-
tially free of fatty acid polyglycol ether diester compounds,
such as polyethylene glycol-600-dioleate or polyethylene
glycol-800-distearate. Such additives offer no advantage,
and possibly even result in a disadvantage, in terms of
achieving the particulate soil removal and fabric conditioning
benefits provided by the present invention.
Preferred compositions contain nonionic surfactant to
cationic surfactant ratios of from 5:1 to about 5:3, especially
from about 10:3 to 10:5, and particularly about 10:4. Compo-
sitions may also contain mixed nonionic systems. These mixed
nonionic systems may contain nonionic surfactants which fall
outside of the definition of the nonionic surfactant given
above (such as alcohol polyethoxylates having an average of
greater than 12 ethylene oxide groups per molecule) as long
as at least one of the nonionic surfactants in the mixture
falls within the required definition and the ratio of that non-
ionic surfactant to the cationic surfactant falls within the
required nonionic:cationic surfactant ratio. Preferred compo-
sitions may also contain fatty amide surfactants, in addition
to the cationic and nonionic components. These amide-containing
compositions yield excellent particulate soil removal, as well
as a particulate soil anti-redeposition benefit. Processes for
laundering fabrics with the compositions of the present
invention are also taught herein.
There is no sharp line of delineation in cleaning per-
formance between the compositions of the present invention and
those described in Canadian Patent Application No. 306,474 of
Alan P. Murphy, filed June 29, 1978, previously referred to herein
3D
when the ratio of nonionic to cationic sur-
factant is at or about 5:1. The cleaning benefits of both
inventions can be obtained when such ratios are used. The
particulate soil removal benefits of the present invention,
under typical American laundering conditions, are best
appreciated at ratios of nonionic to cationic surfactant which
C
~1~97S4
are in the range of about 1:1 to 5:1, particularly at about
10:4. Thus, a clear line of distinction is maintained between
the two inventions.
The compositions of the present invention comprise, by
weight, from about 5 to about 100%, particularly from about
10 to about 95%, and most preferably from about 20 to about
90%, of a mixture of the particularly defined nonionic and
cationic surfactants in the ratios stated. It is preferred
that the detergent compositions contain at least 1% of the
cationic component; otherwise, sufficient cationic surfactant
may not be present in the wash solution to provide the desired
cleaning results. In addition, preferred compositions con-
tain less than about 10% of the cationic component, due to
commercial availability and cost considerations.
Nonionic Component
The nonionic surfactants used in the compositions of the
present invention are biodegradable and have the formula
R(OC2H4)nOH
wherein R is a primary or secondary alkyl chain of from about
8 to about 22, preferably from about 10 to 18, carbon atoms
and n is an average of from about 2 to about 12, preferably
from about 2 to about 9, most preferably from about 2 to about
7, and especially from about 4 to about 7. The nonionic sur-
factants included within the present invention include
branched alcohol ethoxylates. The nonionics have an HLB
(hydrophilic-lipophilic balance) of from about 5 to about 17,
preferably from about 6 to about 14. Especially useful
particulate soil removal can be obtained with nonionic sur-
factants having HLBs of from about 10 to about 13.5. These
nonionic surfactants are preferably combined with less soluble
cationic materials (such as those having 2 or 3 long alkyl
chains). Where more soluble cationic materials are used,
nonionic surfactants of lower HLB may be equally as beneficial.
HLB is defined in detail in Nonionic Surfactants, by M. J.
Schick, Marcel Dekker, Inc., 1966, pp. 607-613,
~,
- :
.
~1~39~54
Particularly preferred nonionic surfactants for use in
the compositions of the present invention include the conden-
sation product of Clo alcohol with 3 moles of ethylene oxide,
the condensation product of coconut alcohol with 5 moles of
ethylene oxide, the condensation product of C12_13 alcohol
with ~.5 moles of ethylene oxide, the condensation product of
C12_13 alcohol with 3 moles of ethylene oxide, and the same
product which is stripped so as to remove the lower ethoxylate
and nonethoxylated fractions, the condensation product of
C14_1s alcohol with 7 moles of ethylene oxide, the condensa-
tion product of C12 alcohol with 5 moles of ethylene oxide,
the condensation product of C12_13 alcohol with 9 moles of
ethylene oxide, the condensation product of C14_1s alcohol
with 3 moles of ethylene oxide, the condensation product of
C14_15 alcohol with 4 moles of ethylene oxide, and the condensation
product of C14_1s alcohol with 9 moles of ethylene oxide. A
preferred class of such surfactants are made from sub-
stantially linear alcohols, such as those which utilize oxo-
alcohols containing about 20% 2-methyl branched isomers,
commercially available under the trademark Neodol, from Shell
Chemical Company.
The compositions of the present invention may also con-
tain mixtures of nonionic surfactants falling within the above
nonionic surfactant definition, or mixtures of nonionic sur-
factants, some of which do not fall within the above non-
ionic surfactant definition, as long as at least one of the
nonionic surfactants contained in the mixture falls within the
above definition of the nonionic surfactants, and the ratio of
that nonionic surfactant to the cationic surfactant falls
3~ within the required nonionic/cationic ratio. Where the non-
ionic surfactant mixture contains a nonionic surfactant (or
surfactants) which falls outside of the above nonionic defini-
tion, the ratio of the surfactant (or surfactants) within the
above definition to that which does not fall within the defi-
nition is preferably within the range of from about 1:1 to
about 5:1. Specific examples of surfactant mixtures include
a mixture of the condensation product of C14_15 alcohol with
3 moles of ethylene oxide (~Neodol 45_3~)* and the condensation
product of C14_1s alcohol with 14 moles of ethylene oxide
* TradOEk
- lo- 1~975~
("l~eodol 45-14")*, in a ratio of lower ~thoxylate nonionic to
higher ethoxylate nonionic of from about 1:1 to about 3:1; a
mixture of the condensation product of C10 alcohol with 3 .
moles of ethylene oxide together with the condensation pro-
duct of a secondary C15 alcohol with 9 moles of ethylene oxide
("Tergitol ls-S-9")** in a ratio of lower ethoxylate nonionic to
higher ethoxylat~ nonionic of from about 1:1 to about 4:1;
and a mixture of ~leodol 45-3" and "Tergitol 15-S 9", in a ratio
of lower ethoxylate nonionic to higher ethoxylate nonionic of
from about 1:1 to about 3:1.
Preferred nonionic surfactant mixtures contain alkyl
glyceryl ether compounds in addition to the required nonionic
surfactant. Particularly preferred are glyceryl ethers having
the formulae
f and R-O(CH2cH2O)ncH2fHcH2oH
OH OH
wherein R is an alkyl or alkenyl group of from about 8 to about
18, preferably about 8 to 12 carbon atoms or an alkaryl group
having from about 5 to 14 carbons in the alkyl chain, and n
~o is from 1 to about 6, together with the nonionic surfactant
component of the present invention, in a ratio of nonionic
surfactant to glyceryl ether of from about 1:1 to about 4:1,
particularly about 7:3. Glyceryl ethers of the type useful in
the present invention are disclosed in Canadian Patent~.
1,081,574 of Kenneth L Jones, issued July 15, 1980; and U.S.
Patent No. 4,098,713, Jones, issued July 4, 1978.
Other biodegradable nonionic surfactants well known in
the detergency arts may be used, in combination with one or
more of the nonionic surfactants falling within the definition
of nonionic surfactants required in the present invention, to
form useful nonionic surfactant mixtures. Examples of such
surfactants are listed in U.S. Patent 3,717,630, Booth, issued
February 20, 1973, and U.S. Patent 3,332,880, Kessler et al,
issued July 25, 1967,
Nonlimiting examples of suitable nonionic sur-
factants which may be used in conjunction with the required
* Trademark
** Trademark
- 11 - 11~97S4
nonionic surfactants include the condensation products of ali-
phatic alcohols with from about 13 to about 25 moles of
ethylene oxide. The alkyl chain of the aliphatic alcohol can
either be straight or branched, primary or secondary, and
generally contains from about 8 to about 22 carbon atoms.
Examples of such ethoxylated alcohols include the condensation
product of myristyl alcohol condensed with about 13 moles of
ethylene oxide per mole of alcohol; and the condensation
product of about 14 moles of ethylene oxide with coconut alcohol
(a mixture of fatty alcohols with alkyl chains varying in length
from 10 to 14 carbon atoms).
A preferred group of nonionic surfactants useful herein
comprises a mixture of "surfactant" and "cosurfactant", con-
taining at least one nonionic surfactant falling within the
definition of nonionic surfactants useful in the present inven-
tion, as described in Canadian Patent No. 1,059,86S
of Jerome H. Collins, granted August 7, 1979.
Cationic Component
The cationic surfactants used in the compositions of the
present invention have the formula
RlR2y z
wherein each Rl is an organic group containing a straight or
branched alkyl or alkenyl group optionally substituted with
up to three phenyl or hydroxy groups and optionally inter-
rupted by up to four structures selected from the following
group:
O O O R R2O
, -C-O-, -O-C-, _c_l_, -N-C-,
O H H O O O H H O
Il l l 11 11 11 1 1 11
-C-N-, -N-C-, -O-, -O-C-O-, -O-C-N-, -N-C-O-,
and mixtures thereof, and which contains from about 8 to 22
carbon atoms. The Rl groups may additionally contain up to
Ci
- 12 ~ 11~9754
.
12 ethoxy groups. m is a number from 1 to 3. No more than
one Rl group in a molecule can have 16 or more carbon atoms
when m is 2 or more than 12 carbon atoms when m is 3. Each R2
is an alkyl or hydroxyalkyl group containing from 1 to 4
carbon atoms or a benzyl group with no more than one R2 in a
molecule being benzyl, and x is a number from O to 11. Pre-
ferably from O to 6. The remainder of any carbon atom posi-
tions on the Y group are filled by hydrogens. Y is selected
from the group consisting of:
(1) -N+-
\ / ~
N - C -
/ t
(2) -~ I
N - C -
(3) -~+_
(4) -S -
~5) -N+- , wherein p is from 1 to 12,
( 2 4 )p
'f 2H4)pH
(6) -N - , wherein each p is from 1 to 12,
(C2H4)pH
I
(7) \C ~ \
/C;~ / C
(8) Nll I IN
C\ ~ C\ , and
(9) mixtures thereofi
. . ~
.~ . .
- 13 ~9754
L is 1 or 2, with the Y groups being separated by a moiety
selected from Rl and R2 analogs (preferably alkylene or
alkenylene~ having from 1 to about 22 carbon atoms and two
free carbon single bonds when L is 2. Z is a water-soluble
anion, such as a halide, sulfate, methylsulfate, hydroxide,
or nitrate anion, particularly preferred being chloride,
bromide, iodide, sulfate or methyl sulfate anions, in a
number to give electrical neutrality of the cationic com-
ponent. The specific cationic component to be included in a
given system depends to a large extent upon the particular
nonionic component to be included in the system, and is
selected such that it is at least water-dispersible, or
preferably water-soluble, when mixed with said nonionic sur-
factant. The term "water-dispersible" means that the cationic
and nonionic surfactants, as well as the anions discussed
hereinafter, remain dispersed throughout the laundry solution
during the washing process. Mixtures of the above-defined
cationic materials may also be used in the eompositions of
the present invention. Small amounts of other cationic
materials can be tolerated in such mixtures.
When used in combination with nonionic surfactants,
within the specific ratios and the preferred reduced cationic
monomer concentrations, defined hereinafter, these cationic
components provide excellent soil removal characteristics,
confer static control and fabric softening benefits to the
laundered fabrics, and inhibit the transfer of certain dyes
among the laundered fabrics in the wash solution. Preferred
cationic surfactants are those which have critlcal micelle
concentrations less than about 500 ppm.
In preferred cationic materials, L is equal to 1 and Y is
\ /1
,N - C -
-N - or -C ~
N - C -
or mixtures thereof. However, L may be 2 and, in that case,
the cationic component contains 2 cationic charge centers.
Other cationic materials which are useful in the compositions
.
.
~ - 14 ~ 9 754
of the present invention includ~ phosphonium and sulfonium
materials.
Where m is equal to 1, it is preferred that x is equal
to 3 and R2 is a methyl group. Preferred compositions of
this mono-long chain type include those in which Rl is a
C10 to C18 alkyl group. Particularly preferred compositions
of this class include C12 alkyl trimethylammonium halide, C14
alkyl trimethylammonium halide, coconutalkyl trimethylammonium
halide, tallowalkyl trimethylammonium halide, and C16 alkyl
trimethylammonium halide.
In order to be sufficiently water-soluble or wa~er-
dispersible, the cationic surfactant must satisfy the following
chain-length criteria. Where m is equal to 2, only one of the
Rl chains can be longer than 16 carbon atoms. Thus, ditallow-
dimethylammonium chloride and distearyldimethylammonium
chloride, which are used conventionally as fabric softeners
and static contrcl agents in detergent compositions, are not
included within the definition of the cationic components used
in the present invention. Preferred di-long chain cationics
of this type include those in which x is equal to 2 and R2 is
a methyl group. In this instance it is also preferred that
is a C10 to C14 alkyl group. Particularly preferred cationic
materials of this class include di-Clo alkyldimethylammonium
halide, di-C12 alkyldimethylammonium halide materials, and
dicoconutalkyl dimethylammonium halide.
Where m is equal to 3, only one of the Rl chains can be
greater than 12 carbon atoms in length. In this instance, it
is preferred that x is equal to 1 and that R2 is a methyl
group. In these compositions it is preferred that Rl is a
C8 to C12 alkyl group. Particularly preferred tri-long chain
cationics include trioctylalkylmethylammonium halide, and
tridecylalkylmethylammonium halide.
Another type of preferred cationic surfactant for use in
the compositions of the present invention are the alkoxylated
alkyl quaternaries. Examples of ethoxylated compounds are
given below:
~ ..
,
.' ' ' : ' ' ',
,
.:
11~9~
- 15 -
+l 3 H(OC H ) -T+ - (c H O) H Z~
R R
wherein each p is from 1 to 12, preferably from 1 to 10, most
preferably from 1 to 7, with the total ethylene oxide groups
in a molecule not exceeding about 12. Each R is a C10 to C20
alkyl group.
The compositions of the present invention are formulated
so as to be substantially free of ethoxylated cationic sur-
factants which contain an average of about 13 or more, and
especially more than about 10, moles of ethylene oxide per
mole of surfactant. These compounds tend to be relatively
nonbiodegradable, do not enhance the cleaning or fabric con-
ditioning benefits provided by the compositions and may, in
some circumstances, decrease the overall laundering perfor-
mance provided by them.
The following formulations have been found to be especially
suitable for removing particulate soils, and providing fabric
softening, static control and dye transfer inhibition benefits,
in a conventional home laundering operation.
(a) Tallowalkyltrimethylammonium halide or methylsulfate,
such as chloride, together with a nonionic surfactant selected
from the condensation product of C12-C13 alcohol with 2 to 4
moles of ethylene oxide and the condensation product of C14-C15
alcohol with 3 to 6 moles of ethylene oxide, such as the
condensation product of C12 13 alcohol with 3 moles of
ethylene oxide, the condensation product of C14 15 alcohol
with ~ moles of ethylene oxide, or mixtures thereof, in a
nonionic:cationic ratio of from 5:1 to about 5~3.
(b) Tallowalkyltrimethylammonium halide or methylsulfate,
such as chloride, together with a nonionic surfactant selected
from the condensation product of C12-C13 alcohol with 5 to 7
moles of ethylene oxide and the condensation product of
C14-C15 alcohol with 5 to 8 moles of ethylene oxide, such as
the condensation product of C12 alcohol with 5 moles of
ethylene oxide, the condensation product of C12 13 alcohol
with 6.5 moles of ethylene oxide, the condensation product of
C14 15 alcohol with 7 moles of ethylene oxide, or mixtures
~A
~ .
- 16 _11~9754
thereof, in a nonionic:cationic ratio of from 5:1 to about
1:1, especially from 5:1 to about 4~1. Compositions which
exhibit both excellent particulate and greasy/oi~y soil removal
may be formulated by combining this cationic material with
the condensation product of C12-C13 alcohol with 4 to 10
moles of ethylene oxide or the condensation product of C14-
C15 alcohol with 6 to 10 moles of ethylene oxide, in nonionic:
cationic ratios of from 5:1 to about 1:1.
(c) Coconutalkyltrimethylammonium halide or methyl-
sulfate, such as chloride, together with a nonionic surfactant
selected from the condensation product of C12-C13 alcohol with
2 to 4 moles of ethylene oxide and the condensation product
of C14-C15 alcohol with 3 to 6 moles of ethylene oxide, such
as the condensation product of C12 13 alcohol with 3 moles of
ethylene oxide, the condensation product of C14 15 alcohol
with 4 moles of ethylene oxide, or mixtures thereof in a
nonionic:cationic ratio of from 5:1 to about 1:1.
(d) Coconutalkyltrimethylammonium halide or methyl-
sulfate, such as chloride, together with a nonionic surfactant
selected from the condensation product of C12-C13 alcohol with
5 to 7 moles of ethylene oxide and the condensation product
of C14-C15 alcohol with 5 to 8 moles of ethylene oxide, such
as the condensation product of C12 alcohol with 5 moles of
ethylene oxide, the condensation product of C12 13 alcohol
with 6.5 moles of ethylene oxide, the condensation product of
C14 15 alcohol with 7 moles of ethylene oxide, or mixtures
thereof, in a nonionic:cationic ratio of from 5:1 to about
1:1, especially about 3:1. Compositions which exhibit both
excellent particulate and greasy/oily soil removal may be
formulated by combining this cationic material with the
condensation product of C12-C13 alcohol with 4 to 10 moles
of ethylene oxide or the condensation product of C14-C15
alcohol with 6 to 10 moles of ethylene oxide, in nonionic:
cationic ratios of from 5:1 to about 1:1.
(e) A cationic surfactant of the formula
R2
l2 2 Z , wherein Rl, R2 and Z are as
R defined above,
!~j
. . .
,
i~9754
,
together with a nonionic surfactant selected from the con-
densation products of C12-C15 alcohols with 2 to 4 moles of
ethylene oxide, such as the condensation product of C12 13
alcohol with 3 moles of ethylene oxide, the condensation
product of C14 15 alcohol with 4 moles of ethylene oxide, or
mixtures thereof, in a nonionic:cationic ratio of from about
3:1 to about 1:1.
(f) A cationic surfactant of the formula
R2
Rl-~t-CH2- ~ Z~ , wherein Rl, R2 and Z are as
R defined above,
together with a nonionic surfactant selected from the con-
densation products of C12-C15 alcohols with 5 to 10 moles of
ethylene oxide, such as the condensation product of C12
alcohol with 5 moles of ethylene oxide, the condensation
product of C12 13 alcohol with 6.5 moles of ethylene oxide,
the condensation product of C14 15 alcohol with 7 moles of
ethylene oxide, or mixtures thereof, in a nonionic:cationic
ratio of from 5:1 to about 1:1.
(g) Dicoconutalkyldimethylammonium halide, or methyl-
sulfate such as chloride, together with a nonionic surfactant
selected from the condensation product of C12-C13 alcohol
with 4 to 8 moles of ethylene oxide or the condensation
product of C14-C15 alcohol with 4 to 8 moles of ethylene
oxide, such as the condensation product of C12 alcohol with 5
moles of ethylene oxide, the condensation product of C12 13
alcohol with 6.5 moles of ethylene oxide, the condensation
product of C14 15 alcohol with 7 moles of ethylene oxide, or
mixtures thereof,in a nonionic:cationic ratio of from 5:1 to
to about 1:1, especially from about 4:1 to about 2:1. Compo-
sitions which give both excellent particulate and greasy/oily
soil removal can be obtained by combining this cationic
surfactant with the condensation product of C12-C13 alcohol
with 6 to 10 moles of ethylene oxide in nonionic:cationic
ratios of from 5:1 to about 4:1.
(h) Tri-C12alkylmethylammonium halide or methylsulfate,
such as chloride, together with a nonionic surfactant selected
from the condensation product of C12-C13 alcohol with 6 to 10
~A~1
t.~,,j
- 18 - 11~97~
moles of ethylene oxide and the condensation product of
C14-C15 alcohol with 6 to 10 moles of ethylene oxide, such
as the condensation product of C12 13 alcohol with 6.5
moles of ethylene oxide, the condensation product of C12 13
alcohol with 9 moles of ethylene oxide, the condensation
product of C14 15 alcohol with 7 moles of ethylene oxide, the
condensation product of C14 15 alcohol with 9 moles of
ethylene oxide, or mixtures thereof, in a nonionic:cationic
ratio of from 5:1 to about 1:1, especially from 5:1 to about
5:3.
(i) Tri-C8 1Oalkylmethylammonium halide or methyl-
sulfate, such as chloride, together with a nonionic surfactant
selected from the condensation product of C12-C13 alcohol
with 5 to 10 moles of ethylene oxide, and the condensation
product of C14-C15 alcohol with 6 to 10 moles of ethylene
oxide, such as the condensation product of C12 alcohol with
5 moles of ethylene oxide, the condensation product of
C12 13 alcohol with 6.5 moles of ethylene oxide, the
condensation product of C12 13 alcohol with 9 moles of
ethylene oxide, the condensation product of C14 15 alcohol
with 7 moles of ethylene oxide, the condensation product of
C14 15 alcohol with 9 moles of ethylene oxide, or mixtures
thereof, in a nonionic:cationic ratio of from about 3:1 to
about 1:1.
A particularly preferred type of cationic component,
which is described in Canadian Patent Application Serial No.
306,517 of James C. Letton, filed June 29, 1978J
has the formula
R2_(zl)a_(R3)n~Z ~(CH2)m~~ -R X
wherein R1 is C1 to C4 alkyl or hydroxyalkyl; R2 is C5 to C30
straight or branched chain alkyl or alkenyl, alkyl phenyl, or
C
.
'' - ' ~ . -
- 19- ~1~9754
X R - N-(CH2)s- ; wherein s is from 0 to 5;
R
R is Cl to C20 alkylene or alkenylene; a is 0 or 1, n is 0
or l, and n is 1 when a is 1; m is from 1 to 5; zl and Z
are each selected from the group consisting of
O O O O H H O O H H O
Il 11 11 11 1 1 11 11 1 1 11
-C-O-, -O-C-, -O-, -O-C-O-, -C-N-, -N-C-, -O-C-N-, -N-C-O-
and wherein at least one of said groups is an ester, reverse
/D ester, amide or reverse amide; and X is an anion which makes
the compound at least water-dispersible, preferably selected
from the group consisting of halide, methyl sulfate, and
nitrate, preferably chloride, bromide, iodide, sulfate, or
methyl sulfate.
In addition to the advantages of the other cationic sur-
factants disclosed herein, this particular cationic component
is environmentally desirable, since it is biodegradable,
yielding environmentally acceptable compounds, both in terms
of its long alkyl fragment and its nitrogen-containing frag-
ment. These preferred cationic components are useful in
nonionic/cationic surfactant mixtures which have a ratio of
nonionic to cationic of from about 1:1 to about 100:1.
However, when used in the compositions of the present invention,
they are used in surfactant mixtures which have nonionic to
cationic ratios of from 5:1 to about 1:1, more preferably from
5:1 to about 5:3, particularly from about 10:3 to about 10:5,
most preferably about 10:4. In preferred compositions, the
ratios are selected such that the compositions have reduced
cationic monomer concentrations as specified herein. These
~c preferred cationic surfactants mav also be used in the
detergent systems defined in Canadian Patent Application Serial
No. 306,474 of Alan P. Murphy, filed June 29, 1978,
in nonionic to cationic ratios of 5.1:1 to
about 100:1, preferably from 5:1 to about 50:1, particularly
from about 6:1 to about 40:1, and most particularly from
about 6:1 to about 20:1. In formulating such compositions,
the nonionic/cationic surfactant mixture should have a cloud
C
1~97S~
- 20 -
point of from about 0 to about 95C, preferably from about 10
to about 65C, most preferably from about 20 to about 65C,
and in preferred compositions, the surfactant mixture has a
reduced cationic monomer concentration of from about 0.002 to
about 0.2, especially from about 0.002 to about 0.15, parti-
cularly from about 0.002 to about 0.08.
Where this type of biodegradable cationic surfactant is
used, it is preferred that the detergent compositions have a
pH of not greater than about 11, preferably less than about 10,
in the laundry solution, in order to minimize hydrolysis of
the cationic surfactant.
Particularly preferred cationic surfactants of this type
are the choline ester derivatives having the following formula:
2 1l f + 3
R -C-O-CH2CH2-N -CH3 X
CH3
as well as those wherein the ester linkage in the above
formula is replaced with a reverse ester, amide or reverse
amide linkage.
Particularly preferred examples of this type of cationic
surfactant include stearoyl choline ester quaternary ammonium
halides (R2 = C17 alkyl), palmitoyl choline ester quaternary
ammonium halides (R2 = C15 alkyl), myristoyl choline ester
quaternary ammonium halides (R2 = C13 alkyl), lauroyl choline
ester ammonium halides (R2 = Cll alkyl), and tallowyl choline
ester quaternary ammonium halides (R2 = C15-C17 alkyl).
Additional preferred cationic components of the choline
ester variety are given by the structural formulas below,
wherein p may be from 0 to 20.
O O CH
R2-O-C-(CH2)pC-O-CH2CH2-N -CH3 X
H3
CH O O CH
- ~l 3 11 11 1+3
X CH3- 1_CH2_CH2_0_C_(CH2)p-C-O CH2 CH2 7 CH3
H3 H3
,,"~,
- 21 ~ 9754
The preferred choline-derivative cationic substances,
discussed above, may be prepared by the direct esterification
of a fatty acid of the desired chain length with dimethyl-
aminoethanol, in the presence of an acid catalyst. The
reaction product is then quaternized with a methyl halide,
forming the desired cationic material. The choline-derived
cationic materials may also be prepared by the direct esteri-
fication of a long chain fatty acid of the desired chain
length together with 2-haloethanol, in the presence of an acid
catalyst material. The reaction product is then used to
quaternize trimethylamine, forming the desired cationic
component.
Another type of novel, particularly preferred cationic
material, described in Canadian Patent Application Serial No.
306,517 of James C. Letton, filed June 29, 1978,
has the formula
lR2 Rll
R3-o ~(CH)n~ y~(Zl)a~(R4)t~Z ~(CH2)m~NI -Rl X
Rl
In the formula, each R is a Cl to C4 alkyl or hydroxyalkyl
group, preferably a methyl group. Each R2 is either hydrogen
or Cl to C3 alkyl, preferably hydrogen. R3 is a C4 to C30
straight or branched chain alkyl, alkenyl, alkyl phenyl, or
alkyl benzyl group, preferably a C8 to Clg alkyl group, most
preferably a C12 alkyl group. R is a Cl to C10 alkylene or
alkenylene group. n is from 2 to 4, preferably 2; y is from
1 to 20, preferably from about 1 to 10, most preferably about
7; a may be 0 or 1, and t may be 0 or 1, but t must be 1
when a is l; and m is from 1 to 5, preferably 2. z2 is selected
from the group consisting of:
O O O O H H O O H H O
Il 11 11 11 1 1 11 11 1 1 11
-~-O-, -C-, -O-, -O-C-O-, -C-N-, -N-C-, -O-C-N-, -N-C-O-
zl is selected from the group consisting of:
~s
9759~
- 22 -
O O O ~ H O H O
-C-O-, -C-~ -C-N-, l C , -N-~C-O-
and wherein at least one of said zl and 32 groups is selected
from the group consisting of ester, reverse ester, amide and
reverse amide. X is an anion which will make the compound at
least water-dispersible, and is selected from the group con-
sisting of halides, methyl sulfate, and nitrate, particularly
chloride, bromide, iodide, sulfate, and methyl sulfate.
Mixtures of the above structures can also be used.
'~ These novel cationic surfactants may be used in nonionic/
cationic surfactant mixtures in a ratio of nonionic component
to cationic component of from about 1:1 to about 100:1. When
these surfactants are used in the compositions of the present
invention they are used in nonionic to cationic ratios of
from 5:1 to about 1:1, more preferably from 5:1 to about 5:3,
particularly from about 10:3 to about 10:5, especially about
10:4, and preferably have ratios which yield reduced cationic
monomer concentrations within the range given herein. They
may be also used ; n the nonionic/cationic surfactant mixtures
disclosed in Canadian Application Serial 21o. 306,474,
Murphy, filed June 29, 1978, wherein the ratio of nonionic com~onent to
cationic component would be from 5.1:1 to about 100:1, pre-
ferably from 5.1:1 to about 50:1, particularly from about 6:1
to about 40:1, and most particularly from about 6:1 to about
20:1. In formulating such compositions, the nonionic/cationic
surfactant mixture should have a cloud point of from about 0
to about 95C, preferably from about 10 to about 65C, most
preferably from about 20 to about 65C, and the surfactant
mixture preferably has a reduced cationic monomer concentra-
tion of from ahout 0.002 to about 0.2, especially from about
0.002 to about 0.15, particularly from about 0.002 to about
0.08.
These surfactants, when used in the compositions of the
present invention, yield excellent particulate soil, body
soil, and grease and oil soil removal. In addition, the
detergent compositions control static and soften the fabrics
laundered therewith, and inhibit the transfer of certain dyes
in the washing solution. Further, these novel cationic sur-
i ~
- 23 _ ~1~97s4
,,
factants are environmentally desirable, since both their long
chain alkyl fragments and their nitrogen fragments are bio-
degradable, in that they degrade to yield environmentally
acceptable compounds. Where this type of biodegradable
cationic surfactant is used, it is preferred that the detergent
compositions have a pH of not greater than about 11, preferably
less than about 10, in the laundry solution, in order to
minimize hydrolysis of the cationic surfactant.
Preferred embodiments of this type of cationic component
are the esters in which Rl is a methyl group and z2 is an
ester or reverse ester group, particular formulas of which
are given below, in which t is 0 or 1 and y is from 1 to 20.
2 2) Y tCH2) t-3_0_CH2_CH2_ 1 +-CH X~
O CH
R3-o (CH2CH2) y-C-CH2-1+-CH3 X
CH3
CH 3 O CH
R3-O ~1HCH2O) _C_CH2_N_CH3 X
H3
CH3 O CH
R3-o(lHCH20) -(CH2)t-C-O-CH2-CH2-1 -CH3 X
O O CH
2 2)y C (CH2)t-C-O-CH2CH2-N+-CH3 X~
~
.
!
- 24 ~ 97S4
,
O H H O CH
R3-o (CH2CH20) y --C-C=C-C-O-CH2CH2-N+-CH3 X
CH3
O CH
R3-o (CH2CH2CH2CH20) y~C~CH2 1 CH3
CH3
O CH
R3-o(CH2CH2CH2CH2o)y~(CH2)t C O CH2C 2 1 3
CH3
The preferred derivatives, described above, may be
prepared by the reaction of a long chain alkyl polyalkoxy
(preferably polyethoxy) carboxylate, having an alkyl chain
of desired length, with oxalyl chloride, to form the corres-
ponding acid chloride. The acid chloride is then reacted with
dimethylaminoethanol to form the appropriate amine ester,
which is then quaternized with a methyl halide to form the
desired choline ester compound. Another way of preparing
these compounds is by the direct esterification of the
appropriate long chain ethoxylated carboxylic acid together
with 2-haloethanol or dimethyl aminoethanol, in the presence
of heat and an acid catalyst. The reaction product formed
is then quaternized with methylhalide or used to quaternize
trimethylamine to form the desired choline ester compound.
As a guide in formulating compositions which deliver
excellent particulate soil removal, the reduced cationic
monomer concentration may be used. Thus, the nonionic and
cationic components, defined above, may be combined into a
surfactant mixture which has a ratio corresponding to a
reduced cationic monomer concentration (CR) of from about
0~005 to about 0.2, preferably from about 0.008 to about
0.15, particularly from about 0.01 to about 0.1. A CR value
within this range will yield a composition which exhibits
optimum particulate soil removal performance. Where the non-
ionic and cationic components used are pure, the more narrow
CR ranges are preferred. In a preferred method of preparing
.:
-.
:
- 25 ~ 9~54
the compositions of the present invention, the nonionic and
cationic surfactants are intimately and completely mixed
together prior to the addition of any additional components to
the mixture. This intimate premixing of the nonionic and
cationic components enhances performance of the compositions.
An approximation of the CR of a surfactant mixture is
obtained by dividing the concentration of the cationic sur-
factant monomer in the laundry solution by the critical micelle
concentration (CMC) of the surfactant. As used in this
application, CMC's are determined at 105F in water containing
7 grains/gallon of mixed hardness, unless otherwise stated.
For purposes of this application, CR is calculated according
to the equations given below.
The concept of reduced monomer concentration is derived
from the discussion in Clint, J. Chem. Soc. Far. Trans., I,
71, 1327 (1975), in the
context of an ideal solution, and is based on the following
quadratic equation (equation (ll) in Clint):
(cml)2[C2 - l] + cml(C-c2 ~ cl) - aCcl =
wherein in the above and the following equations:
C = total analytical surfactant concentration in the
solution (moles/l.) = sum of the cationic and
nonionic concentrations = Cl ~ C2 (wherein "l"
denotes nonionic surfactant and "2" denotes
cationic surfactant)
cl = critical micelle concentration (CMC) of nonionic
surfactant (moles/l.)
C2 = critical micelle concentration of cationic sur-
factant (moles/l.)
= total mole fraction of nonionic surfactant in the
solution = Cl/(Cl ~ C2)
~ = a constant based upon the heat of mixing = -2.8
cml = nonionic monomer concentration
~'
- 26 - ~ 9~54
c2m . cationic monomer concentration
e = base of Napierian logarithm system = 2.71828
x = mole fraction of the nonionic surfactant in the
micelle at concentration C
fl = nonionic activity coefficient in the mixed micelle =
e~(l-x)2
f2 = cationic activity coefficient in the mixed micelle =
* *
~ = f2C2 ~ flCl
CR = reduced cationic monomer concentration
Ml = molecular weight of nonionic surfactant
M2 = molecular weight of cationic surfactant
W = total analytical surfactant concentration in the
solution (ppm) = sum of the cationic and nonionic
concentrations (ppm) ~ Wl+W2 (wherein "1" denotes
nonionic surfactant and "2" denotes cationic
surfactant)
Y ~ weight fraction of nonionic surfactant in the
composition
The above equation is solved for the nonionic monomer
concentration by taking its positive root (equation (12) in
Clint).
m {-(C-(c2-cl))+ ~(C-(c2-cl))2 ~ 4~C(c2-cl)] 1/2
Cl =
2( 2 - 1)
c;
By modifying this equation based on the assumptions of
a regular, rather than an ideal, solution, the CR range for
optimum performance was derived from the following equation:
~ 2
x = -(C-O ~ (C-a) ~ 4~C~ (1)
~.
- ~ ~
.
~ ' .
- 27 ~ 9754
,,
For a given cleaning test for a nonionic/cationic system,
x was found by inserting the values known from the test (i.e.,
* *
cl, c2, a, C and ~) into equation (1) and solving iteratively
for x, such that the error in x is less than 0.001. This
procedure was repeated for a large number of such tests, over
varying usage conditions. The x values obtained were then
used to solve for the cationic monomer concentrations using
the following equation:
cm2 = (1-x)f2c2 (2)
The CR value was then calculated using equation (3).
CR = c2/c2 (3)
The CR values obtained cover a large number of combina-
tions and ratios of various nonionic and cationic surfactants,
at various concentrations and temperatures, which have been
evaluated for their ability to clean greasy/oily soils. The
examination of the resulting data revealed that for a given
system the optimum cleaning of greasy/oily soils was found
at a CR value of from about 0.002 to about 0.2.
This range of CR (i.e., 0.002 to 0.2) can then be used
to determine the range of optimum nonionic/cationic ratios
for any given combination of nonionic surfactant and cationic
surfactant, for the desired wash concentration within the
overall wash concentration range of from 100 parts per
million (ppm) to 10,000 ppm of surfactant. This calculation
is carried out in the following manner, where ~, CR, cl, C2,
Ml and M2 are known for a given nonionic-cationic surfactant
pair.
(a) for a given nonionic surfactant, cationic surfactant,
and for each end of the CR range, solve for x using
the equation
(l-x)e~ = CR
by standard numerical iterative techniques to an
error in x of less than 0.001;
.~.
~1~97S~
- 28 -
~,
(b) find the range of Y from the equation
Y ~1--X) _ x (1--Y) = 1000 [x (x-l)~
using 100 ppm and 10,000 ppm as the boundary
values for W, for each end of the CR range;
(c) the nonionic/cationic ratio (NCR) range for optimum
performance is then within the range obtained by
substituting the boundary values for Y into the
formula
NCR = Y
1--Y
Put another way, steps (b) and (c) may be combined into
a single equation which may be solved directly for the NCR.
NCR Y (1000/W)~ M2(x-1)
(1000/W)~ I 1
The above procedure is relevant only to wash solution
concentrations above the critical micelle concentration of
the nonionic/cationic mixture. For concentrations which are
as high as about five times the critical micelle concentra-
tion, CR is essentially independent of concentration. This
means that for conventional laundry usage concentrations
(e.g., 100 ppm to 10,000 ppm, and especially from about 250
ppm to about 3,000 ppm), the CR of most commercial cationic/
nonionic surfactant mixtures (wherein the cationic component
has a CMC of less than about 100 ppm, measured at 105F
water containing 7 grain/gallon of mixed calcium and magnesium
hardness) will be independent of the actual usage concentra-
tion, so that using a concentration of about 1,000 ppm in
the above calculation will be a satisfactory approximation
for the entire range. As used herein, if a concentration
range is not specified, the 1,000 ppm CR is meant.
By way of example, the optimum ratio for grease/oil
removal for Composition A of Example I, herein, given CR, is
' '
. .
- :~9 - 11~97S4
,~
calculated below. For this system, the following values
are either known or selected as indicated:
W = 1,000 ppm (selected as representative of usage
conditions)
cl = 1.967 x 10 ppm
C2 = 2.1875 x 10 5 ppm
= -2.8
~1 = 406.7
M2 = 320
CR ~ 0.0073 (selected for optimum greasy/oily soil
removal performance, but could be any value
between 0.002 and 0.2)
Substituting the values for ~ and CR into equation (a):
(1 X)e-2.8x , 0,0073.
Solving iteratively for x, it is found that x - 0.922.
Using this value for x, it is found that
fl - 0.983
f2 = 0.0925
~ = (0.0925) (2.1875 x 10 ) - (0.983) (1.967 x
_ 10 5) = -1.73 x 10 5
Substituting these values into equation (b), it is
found that:
y(l-0 922) 0.922(1-Y) = 11O (0.922) (0.922-1) (-1.73x10
Y = 0.93~
Substituting this value for Y into equation (c), the
nonionic/cationic ratio is determined.
1 0.938
It will be noted that this ratio corresponds to the
ratio actually found in Example I, Composition A.
p~..
11~9~7S4
- 30 -
.
In addition to these reduced cationic monomer criteria,
the nonionic/cationic surfactant mixture may also satisfy the
specific cloud point requirements, given below. In addition
to outstanding particulate soil detergency, these preferred
compositions will be optimized for the removal of greasy/oily
soils. Thus, in preferred compositions, the cloud point of
the nonionic/cationic mixture (and in preferred embodiments
the nonionic/cationic mixture plus any electrolytes present
in the composition) falls between about 0 and about 95C,
preferably between about 10 and about 65C, more preferably
between about 20 and about 65C, especially between about 30
and about 50C. For cold water detergency, the surfactant
mixture should have a cloud point between about 0 and about
25C. The fact that a composition has a cloud point within
these temperature ranges assures that the composition can be
utilized under laundry temperature conditions to achieve out-
standing removal of greasy/oily soils~ If a composition does
not have a cloud point within the temperature range specified,
it will not yield the outstanding cleaning of the present
invention. The compositions will exhibit their best grease/
oil removal performance when the temperature of the wash
solution in which they are used falls within about 20C, pre-
ferably within about 15C, and most preferably within about
10C, of the cloud point of the nonionic/cationic surfactant
mixture. Put another way, the laundry solution temperature
range in which the preferred compositions deliver optimum
grease/oil removal lies between the cloud point temperature
of the system in the absence of the cationic component, and
about 30C, preferably about 25C, most preferably about 20C,
above that cloud point temperature.
As used herein, the term "cloud point" means the tempera-
ture at which a graph which plots the light scattering inten-
sity of the composition versus wash solution temperature
begins to sharply increase to its maximum value, under the
following experimental conditions:
The light scattering intensity is measured using a Model
VM-12397 Photogoniodiffusometer, manufactured by Societe~
Francaise d'instruments de controle et d'analyses, France
~.
- 31 -
11~97~g'
(the instrument being hereinafter referred to as (SOFICA).
The SOFICA sample cell and its lid are washed with hot
acetone and allowed to dry. The surfactant mixture is made
and put into solution with distilled water at a concentration
of 1000 ppm. Approxima8ely a 15 ml. sample of the solution is
placed into the sample cell, using a syringe with a 0.2
nucleopore filter. The syringe needle passes through the
sample cell lid, so that the cell interior is not exposed to
atmospheric dust. The sample is kept in a variable tempera-
ture bath, and both the bath and the sample are subject to
constant stirring. The bath temperature is heated using the
SOFICA's heater and cooled by the addition of ice (heating
rate 1C/minute); the temperature of the sample is determined
by the temperature of the bath. The light scattering intensity
of the sample is then determined at various temperatures, using
a green filter and no polarizer in the SOFICA.
Fatty Amide Component
In particular preferred embodiments of the present
invention the nonionic surfactant/cationic surfactant mixture
additionally contains from about 2 to about 25%, preferably
from about 2 to about 16%, and most preferably from about 3
to about 10%, of a fatty amide surfactant. Any nonionic
surfactant conventionally used in detergent compositions;
however, preferred compositions contain the nonionic surfactants
defined above, in order to maximize the cleaning benefit
obtained. These amide surfactants may be used in nonionic/
cationic surfactant mixtures having nonionic:cationic ratios
of from about 1:1 to about 100:1. When they are used in the
compositions of the present invention, the mixtures have
nonionic:cationic ratios of from 5:1 to abaut l:l, preferably
from 5:1 to about 5:3, more preferably about 10:3 to about
10:5, particularly about 10:4. In nonionic/cationic systems,
the ratio of the total cationic and nonionic components to
the amide component in the composition is in the range of
from 5:1 to about 50:1, preferably from about 8:1 to 25:1.
When these compositions are formulated in accordance with the
ratio and the preferred reduced cationic monomer concentration
limits given herein, they result in excellent particulate soil
removal performance, as well as improved soil anti-redeposition
,A
- 32 ~1~9754
characteristics, and the develoPment is described i~ ~rS~
Patent No. 4,228,044 of C.M. Cambre, issued
October L4, 1980.
Amides useful in these preferred compositions include,
but are not limited to, carboxylic acid amides, sulfonic
acid amides, phosphonic acid amides, and boronic acid amides.
Preferred amides include those having the formulae:
~o o R R2
Rl-C-N Rl_S_N/
\ R2 O ~ R
wherein Rl is a C8-C20 alkyl, alkenyl, alkyl phenyl or alkyl
benzyl group, preferably C10-C18 alkyl, and most preferably
Cll alkyl; and each R2 is hydrogen, or Cl-C8 alkyl or hydroxy-
alkyl, preferably hydrogen. Specific examples of thesecompositions include a mixture of stearoyl choline bromide
(present in the washing solution at 120 parts per million),
the condensation product of coconut alcohol with 5 moles of
ethylene oxide (present in the wash solution at about 357
parts per million), and a mid-cut coconùt alkyl ammonia amide
(Rl=coconut alkyl and R2 is hydrogen; present in the wash
solution at about 50 parts per million); and a mixture of
stearoyl choline bromide (100 ppm); the condensation product
of coconut alcohol with 5 moles of ethylene oxide (357 ppm),
and lauramide (Rl = Cll and R2 is hydrogen; at 45 ppm).
These amides may also be used in the surfactant mixtures
described in Canadian Patent Application Serial No. 306,474
of A.P. Murphy, filed June 29, 1978
to about 100:1, preferably from 5.1:1 to about 50:1, parti-
cularly from about 6:1 to about 40:1, and most particularly
from about 6:1 to about 20:1. In forming such compositions,
which are optimized for the removal of greasy/oily soils,
the nonionic/cationic surfactant mixture should have a cloud
point of from about 0 to about 95C, preferably from about
i ~
L~
- 33 -
11~97~4
10 to about 65C, especially from about 20 to about 65C,
and the surfactant mixture preferably has a ratio which
corresponds to a reduced cationic monomer concentration of
from about 0.002 to about 0.2, especially from about 0.002
to about 0.15, particularly from about 0.002 to about 0.08.
Additional Components
While the compositions of the present invention may con-
tain additive materials conventionally used in detergent
compositions, the amount,of anion-producing materials, and
hence anions, which will make the particular cationic sur-
factant used in the compositions non-water dispersible should
be minimized. Whether a particular anion constitutes an
"interfering anion" depends upon the physical and chemical
properties (such as structure and dissociation constant) of
the particular anions and cationic surfactants used in a
given composition. It is preferred that anionic materials
be contained in amounts sufficiently small such that not
more than about 10 molar percent, preferably not more than
about 5 molar percent, of the cationic surfactant contained
in the laundry solution, is complexed by the anionic material.
Such a complexing of the anionic material with the cationic
surfactant decreases the overall cleaning and fabric con-
ditioning performance of the composition.
Suitable anionic materials may be selected based on
their strength of complexation with the cationic material
included in the composition tas indicated by their dissocia-
tion constant). Thus, when an anionic material has a dis-
sociation constant of at least about lxlO 3 (such as sodium
toluene sulfonate), it may be contained in an amount up to
about 40%, by weight, of the cationic surfactant; where the
anionic material has a dissociation constant of at least
about lxlO 5, but less than about lxlO 3, it may be contained
in an amount up to about 15%, by weight, of the cationic
surfactant; and where the anionic material has a dissociation
constant of less than about lxlO 5, (such as sodium Cll 8
linear alkylbenzene sulfonate), it should be contained only
in amounts up to about 10%, by weight, of the cationic
surfactant.
i~... .
11~97~9~
- 34 -
It is preferred, in order to minimize the effects of
interfering anions, that the compositions of the present
invention be substantially free of phosphate, polyphosphate,
silicate, and polycarboxylate builder anions, carboxymethyl
cellulose, and anionic surfactants; particularly preferred
are those which are substantially free of phosphate, poly-
phosphate, and carboxymethyl cellulose materials. The compo-
sitions of the present invention contain from 0 to about 20
of phosphate materials; and, even though they contain no or
low levels of phosphate materials, exhibit an outstanding
level of particulate soil removal. It is preferred that the
compositions be substantially free of phosphate materials
both for performance and environmental reasons.
The compositions of the present invention may also
contain additional ingredients generally found in laundry
detergent compositions, consistent with the restrictions on
interfering anions, stated above, at their conventional art-
established levels. Very low levels (i.e., from about 1 to
about 15%) of electrolytes, such a perborates, phosphates,
polyphosphonates, carbonates or sulfates, may have a bene-
ficial effect on cleaning performance.
The compositions of the present invention may contain
up to about 15%, preferably up to about 5%, and most pre-
ferably from about .1 to 2%, of a suds suppressor component.
Typical suds suppressors include long chain fatty acids,
such as those described in U.S. Patent 2,954,347, issued
September 27, 1960, St. John, and combinations of certain
nonionics therewith, as disclosed in U.S. Patent 2,954,348,
issued September 27, 1960, Schwoeppe,
Other suds suppressor
components useful in the compositions of the present inven-
tion include, but are not limited to those described below.
Preferred suds suppressing additives are described in
U.S. Patent 3,933,672, issued January 20, 1976, Bartolotta
et al., relative to a
silicone suds controlling agent. The silicone material can
be represented by alkylated polysiloxane materials such as
silica aerogels and xerogels and hydrophobic silicas of
f~
.
.
~1~975~
- 35 -
various types. The silicone material can be described as a
siloxane having the formula:
- ~710~
R'
wherein x is from about 20 to about 2,000, and R and R' are
each alkyl or aryl groups, especially methyl, ethyl, propyl,
butyl and phenyl. The polydimethylsiloxanes (R and R' are
methyl) having a molecular weight within the range of from
about 200 to about 200,000, and higher, are all useful as
suds controlling agents. Additional suitable silicone
materials wherein the side chain groups R and R' are alkyl,
aryl, or mixed alkyl and aryl hydrocarbyl groups exhibit
useful suds controlling properties. Examples of the like
ingredients include diethyl-, dipropyl-, dibutyl-, methyl-
ethyl-, phenylmethyl-polysiloxanes and the like. Additional
useful silicone suds controlling agents can be represented by
a mixture of an alkylated siloxane, as referred to herein-
before, and solid silica. Such mixtures are prepared by
affixing the silicone to the surface of the solid silica.
A preferred silicone suds controlling agent is represented
by a hydrophobic silanated (most preferably trimethylsilana~ed)
silica having a particle size in the range from about 10
millimicrons to 20 millimicrons and a specific surface are
above about 50 m2/gm. intimately admixed with dimethyl
silicone fluid having a molecular weight in the range from
about 500 to about 200,000 at a weight ratio of silicone to
silanated silica of from about 19:1 to about 1:2. The silicone
suds suppressing agent is advantageously releasably incorporated
in a water-soluble or water-dispersible, substantially non-
surface-active detergent-impermeable carrier.
Particularly useful suds suppressors are the self-
emulsifying s~licone suds suppressors, described in
Canadian Patentl~o. 1,085,697, T.W. Gault and E.J. McGuire, Jr.,
granted September 16, 1980.
~,C
.
~ 1~9754
- 36 -
An
example of such a compound i5 "DB-544"~ commercially available
from Dow Corning, which contains a siloxane/glycol copolymer
together with solid silica and a siloxane resin.
Microcrystalline waxes having a melting point in the
range from 35C-115C and a saponification value of less than
100 represent additional examples of a preferred suds regu-
lating component for use in the subject compositions, such
waxes are described in U.S. Patent 4,056,481, Tate, issued
November 1, 1977, The
microcrystalline waxes are substantially water-insoluble,
but are water-dispersible in the presence of organic sur-
factants. Preferred microcrystalline waxes have a melting
point from about 65C to 100C, a molecular weight in the
range from 400-1,000; and a penetration value of at least 6,
measured at 77F by ASTM-D1321. Suitable examples of the
above waxes include: microcrystalline and oxidized micro-
crystalline petrolatum waxes; Fischer-Tropsch and oxidized
Fisher-Tropsch waxes; ozokerite; ceresin; montan wax;
beeswax; candelilla; and carnauba wax.
Alkyl phosphate esters represent an additional preferred
suds suppressant for use herein. These preferred phosphate
esters are predominantly monostearyl phosphate which, in
addition thereto, can contain di- and tristearyl phosphates
and monooleyl phosphates, which can contain di- and trioleyl
phosphates.
The alkyl phosphate esters frequently contain some tri-
alkyl phosphate. Accordingly, a preferred phosphate ester
can contain, in addition to the monoalkyl ester, e.g. mono-
stearyl phosphate, up to about 50 mole percent of dialkyl
phosphate and up to about 5 mole percent of trialkyl phosphate.
Other compatible adjunct components which may be included
in the compositions of the present invention, in their con-
ventional art-established levels of use, include bleaching
agents, bleach activators, soil suspending agents~ corrosion
inhibitors, dyes, fillers, optical brighteners~ germicides,
pH adjusting agents, enzymes, enzyme stabilizing agents,
perfumes, fabric softening components, static control agents,
and the like. However, because of the numerous and diverse
* Trademark
'~ ~
. . ~ ' ' '
,
' .
97~4
- 37 -
performance advantages of the compositions of the present
invention, many components, such as static control agents,
fabric softening agents and germicides, will not usually be
necessary.
The compositions of the present invention may be manu-
factured and used in a variety of physical forms, such as
solid, powder, granular, paste, or liquid. The compositions
are particularly well-suited for incorporation into substrate
articles for use in the home laundering process. Examples of
s~ch articles are described in U.S. Patent 4,170,565 of
Flesher et al, issued October 9, 1979; U.S. Patent No.
4,095,946, Jones et al, issued June 20, 1978;
U.S. Patent No. 4,118,525, Jones, issued October 3, 1978;
and U.S. Patent No. 4,113,630, Hagner et al, issued
September 12, 1978.
These articles consist of a water-insoluble substrate which
releasably incorporates an effective amount, preferably from
about 3 to 120 grams, particularly from about 20 to 80 grams,
of the detergent compositions of the present invention. A
particularly preferred substrate article incorporates a
bleaching component and a bleach activator on the substrate,
together with the nonionic/cationic surfactant mixture.
In a particularly preferred method of making the
detergent compositions of the present invention, the specifi-
cally defined nonionic and cationic surfactants, present in
ratios from about 1:1 to about 100:1, are intimately and
completely mixed at a temperature of from about 25C to about
95C, preferably from about 40C to about 90C, prior to the
addition o any additional components. By using this process,
the components are taken from their original liquid or powder
form and are made into a thick paste, which is ideally suited
for use in the substrate articles, described above.
~ 3,
, ~ ,..
' ~' :
:~ : ' . ;
11.~97~4
- 38 -
When this process is used to make the compositions of
the present invention, the components are present in non-
ionic:cationic ratios of from 5:1 to about 1:1, preferably
from 5:1 to about 5:3, and more preferably from about 10:3
to-about 10~5, and are formed into mixtures which satisfy the
reduced cationic monomer concentration requirements, herein.
In one particularly preferred embodiment of this process, the
components are intimately mixed together at a temperature of
about 25C. In this embodiment, it is preferred that the
anion contained in the cationic surfactant be bromide. Thus,
when stearoyl choline bromide, a powder having the following
formula,
O CH
ll 1 3
C17 35 2 2 1 3
CH3
is intimately mixed at a temperature of about 25C with the
condensation product of C12 alcohol with 5 moles of ethylene
oxide, a liquid, at a nonionic:cationic ratio of about 10:4,
a thick paste product is formed. Substantially similar
results are obtained when the nonionic surfactant is the
condensation product of coconut alcohol with 5 moles of
ethylene oxide.
In another particularly preferred embodiment of this
process, the components are intimately mixed together at a
temperature of at least about 65C. In this embodiment, it is
preferred that the anion contained in the cationic surfactant
be chloride. Thus, when stearoyl choline chloride, a powder,
is intimately mixed at a temperature of about 80C with the
condensation product of C12 alcohol with 5 moles of ethylene
oxide, a liquid, at a nonionic:cationic ratio of about 10:4,
a thick paste product is formed. If the same components are
mixed together at about 25C, the mixture remains a liquid,
which is much less desirable for use in making substrate
articles. Substantially similar results are obtained when
the nonionic surfactant is the condensation product of coconut
alcohol with 5 moles of ethylene oxide. Where this process
is used in making the compositions described in Canadian
Patent Application No. 306,474, Murphy, filed
June 29, 1978,
11~97~4
- 39 -
nonionic:cationic ratios
of from 5.1:1 to about 100:1, preferably from 5.1:1 to about
S0:1, more preferably from about 6:1 to about 40:1, and
most preferably from about 6:1 to about 20:1, are used, in
accordance with the cloud point and the preferred reduced
cationic monomer concentration definitions, stated therein.
The compositions of the present invention are used in
the laundering process by forming an aqueous solution
(preferably one having a temperature of from about 10 to
about 50C) containing from about 0.01 (100 parts per million)
to 0.3% (3,000 ppm), preferably from about 0.02 to 0.2%,
and most preferably from about 0.03 to about 0.15%, of the
nonionic/cationic detergent mixture, and agitating the
soiled fabrics in that solution. The fabrics are then rinsed
and dried. When used in this manner, the compositions of the
present invention yield exceptionally good particulate soil
removal performance. Further, the compositions also provide
fabric softening, static control, and dye transfer inhibition
benefits to the fabrics laundered therewith.
Although not intending to be bound by theory, it is
believed that the clay removal mechanism is as follows. At
the optimum nonionic:cationic ratio, as defined by the reduced
cationic monomer concentration, the cationic surfactant
adsorbs onto the clay soil (negatively-charged) in a mono-
layer, neutralizing the charge. This neutralized charge
results in a hydrophobic surface which increases the adsorption
of the nonionic surfactant onto the clay surface. The clay
soil is then easily removed by the agitation.
It has been found that when the nonionic/cationic compo-
sitions of the present invention are used in a laundry solution,
a threshhold concentration of at least about 50, preferably
about 100, most preferably about 150, parts per million on
the cationic component must be present in the laundry solution
in order to give the particulate soil removal benefit. Under
conventional United States laundry conditions, which generally
utilize from about 150 to 1500 parts per million of a deter-
gent composition in the laundry solution, nonionic surfactant
. ~
' '
~1~9~4
- 40 -
to cationic surfactant ratios of from 5:1 to about 1:1 are
necessary in order to provide this threshhold concentration
in the laundry solution. In washing processes which utilize
higher concentrations of detergent composition, such as Euro-
pean washing processes, it is possible to use higher nonionic
surfactant to cationic surfactant ratios, while still attaining
the necessary cationic threshhold concentration. Under these
European washing conditions it is possible to obtain excellent
particulate soil removal, in addition to outstanding greasy
,o and oily soil and body soil removal, using the nonionic
surfactant to cationic surfactant ratios of from 5.1:1 to
about 100:1 defined in concurrently filed Canadian Patent Appli-
cation Serial No. 306,474 of A.P. Murphy.
All percentages, parts, and ratios used herein are by
weight unless otherwise specified.
The following nonlimiting examples illustrate the compo~
sitions and the method of the present invention.
EXAMPLE I
Identical cotton, polyester/cotton, and polyester
swatches were stained with a clay-in-water suspension and
three stained swatches of each fabric type were washed in a
one gallon washing machine, which simulates the action of a
commercial washing machine, using two different detergent
compositions. One set of swatches was laundered using the
commerciall~ available built, brightener-containing laundry
detergent"Tide"*,marketed by The Procter & Gamble Company, at
the equivalent of its recommended 1-1/4 cup usage level.
The second set of swatches was laundered in a detergent
3~ composition of the present invention, having the following
formulation.
Component % by Weight
Dicoconutalkyl dimethylammonium
bromide 19
Condensation product of C14 15
alcohol with 7 moles of ethylene
oxide ("Neodol 45-7~)** HLB=11 5 48
Sodium chloride 33
C * Trademark CR = 0.0815
** Trademark
)9~4
41
This detergent composition, having a nonionic:cationic
ratio of about 10:4, was used in the aqueous laundering
solution at a concentration of about 500 ppm, and had a pH
in the laundry solution of about 6.5. The wash water con-
tained 7 grains per gallon of mixed calcium and magnesium
hardness, and the laundering operation lasted for 10 minutes
at 100F (38C). A Hunter Reflectometer was then used to
obtain a reflectance reading for each of the laundered
swatches. The cleaning effectiveness of the particular
treatment was determined by averaging the reflectance readings
of the individual swatches. A higher reflectance reading
indicates greater cleaning effectiveness.
This procedure was repeated twice for each of the two
detergent compositions and the reflectance readings were
averaged for the two runs. The conventional built phosphate
granular detergent yielded fabrics having an average of 63.1
Hunter Whiteness Units, while the detergent composition of the
present invention yielded fabrics having a value of 62.~
Hunter Whiteness Units. These data demonstrate the outstanding
clay soil removal performance of the unbuilt compositions of
the present invention, which equaled the performance pro-
vided by the conventional built, brightener-containing
detergent composition.
Substantially similar cleaning results are obtained where
the detergent composition of the present invention does not
contain the sodium chloride component, indicating that for the
particular detergent composition defined above, sodium chloride
does not contribute "interfering anions" to the laundry solu-
tion of the disclosed detergent compositions.
Substantially similar results are also obtained where
the cationic surfactant used in the above composition is
replaced by C12 alkyl trimethylammonium chloride, C14 alkyl
trimethylammonium bromide, di-Clo alkyl dimethylammonium
chloride, di-C12 alkyl dimethylammonium chloride, tri-C8 alkyl
methylammonium bromide, tri-C10 alkyl methylammonium chloride,
or the cationic surfactants listed below:
.~
.
9754
-
- 42 -
f 3
HOH4C2-7~-C ~ OH C1-
C12H25
~N-CH2
12H25 C \ ¦ Cl
N -CH
3 C12H25
ICH3
C18H37-N~-CH ~ Cl
CH3
O CH
16H33 C O CH2CH2-e -CH3 Br
O O CH
~ 3
C H -O-C-CH2CH2-C-O-CH2CH2 1 3 Br
CH3
3 f 3
Substantially similar cleaning results are also obtained
where the cationic surfactant used above is replaced by a
mixture of dicoconutalkyl dimethylammonium bromide (A)
together with C12 alkyl trimethylammonium chloride (B) in a
ratio of A:B of about 4:1, 3:1, 2:1, 1:1, 1:2, or 1:4; a mix-
ture of
O CH
ll 1 3
17H3s C O CH2CH2-~ -CH3 Br (C)
CH3
together with di-Clo alkyl dimethylammonium chloride (D) in a
ratio of C:D of about 5:1, 3:1, 1:1, 1:3 or 1:5; or a mixture
~ '.
~ .
.' ~ .
11t~9754
- 43 -
of C, above, together with
O CH
ll 1 3
Cl2H25-(cH2cH2o)7-cH2-c-o-cH2cH2-N -CH3 Cl (E)
CH3
in a ratio of C:E of about 7:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4,
or 1:7.
Essentially similar results are also obtained where the
nonionic component of the above composition is replaced with
the condensation product of C10 alcohol with 3 moles of
ethylene oxide (HLB=9), the condensation product of coconut
alcohol with 5 moles of ethylene oxide, the condensation
product of coconut alcohol with 7 moles of ethylene oxide
(HLB.12.8), the condensation product of C12 13 alcohol with
6.5 moles of ethylene oxide (HLB=12), the condensation
product of C12_13 alcohol with 3 moles of ethylene oxide
(HLB~7.9), and the same product which is stripped so as to
remove unethoxylated and lower ethoxylate fractions, the
condensation product of C12 alcohol with 5 moles of ethylene
oxide, the condensation product of C12_13 alcohol with 9
moles of ethylene oxide, and the condensation product of
C14 15 alcohol with 3, 4 or 9 moles of ethylene oxide.
mixture of the condensation product of C14 15 alcohol with
3 moles of ethylene oxide together with the condensation
product of C14 15 alcohol with 7 moles of ethylene oxide in
a ratio of lower ethoxylate nonionic to higher ethoxylate
nonionic of about 2:1, or the mixture of the condensation
product of coconut alcohol with 5 moles of ethylene oxide
together with an alkyl glyceryl ether having the structural
formula:
C12H25-OCH2ICH CH20H
OH
in a ratio of alcohol ethoxylate to glyceryl ether of about
7:3.
`,A
~ . .
. ~
; ~ ' ' ~
'
- 44 -
Results substantially equivalent to those obtained above
are also obtained where the detergent composition has a ratio
of nonionic surfactant to cationic surfactant of 1:1, 10:3,
5 3, 10:5, or 5:1.
Substantially similar results are also obtained where the
detergent composition is formulated, such as by the addition
of monoethanolamine, to have a pH in the laundry solution of
about 7, 8, 8.5, 9 or 10.
EXAMPLE II
Identical cotton, polyester/cotton, and polyester swatches
were stained with bacon grease and dirty motor oil and were
aged for about 24 hours. The swatches were then washed in a
one gallon washing machine, which simulates the action of a
commercial washing machine, using two different detergent
compositions. The first group of swatches was washed using
a heavy-duty liquid laundry detergent composition, optimized
for grease and oil removal, having the formulation given below,
at its recommended usage level.
Component % by Weight
Neodol 45-7 15.0
Mg Linear alkyl benzene sulfonate 31.3
Triethanolamine 3.5
Ethanol 6.5
Coconut alkyl fatty acid 1.0
Water 41.8
Brightener and minors Balance to 100
(brlghteners, perfume, etc.)
The second group of swatches was washed in a laundry
detergent composition of the present invention having the
following formulation:
Component % by Weight
O CH
C12H25-(CH2CH2O)7-CH2-C-O CH2CH2 1 3 28.6
CH3
Condensation product of C12_13 alcohol 71.4
with 3 moles of ethylene oxide,
stripped to remove lower ethoxylate and
unethoxylated fractions "(Neodol 23-3T)" *
C
~ * Trademark
9754
- 45 -
The detergent composition of the present invention had
a ratio of nonionic surfactant to cationic surfactant of
about 10:4 and was used in the aqueous laundering solution at
a concentration of about 500 ppm, having a pH in the laundry
solution of about 6.5. The fabrics were washed for about 10
minutes in water having a temperature of about 100F (38C),
containing 7 grains per gallon of mixed calcium and magnesium
hardness. The percentage stain removal for each swatch was
calculated using light reflectance readings, obtained on a
Gardner color measurement device, taken before and after the
washing process. The average percent stain removal for each
of the detergent compositions tested is summarized in the
table below:
Average ~ Stain
Removal (across
3 fabric types)
Bacon Dirty
Grease Motor Oil
Liquid laundry composition 58.2 45.5
Nonionic/cationic mixture 58.8 57.5
These data demonstrate the effective grease and oil
removal obtained using the preferred cationic components in
the detergent compositions of the present invention. The
detergent composition of the present invention, as formulated
above, also yields excellent particulate soil removal per-
formance, and gives fabric softening, static control and dye
transfer inhibition benefits to fabrics laundered therewith.
Substantially similar results are obtained where the
nonionic component of the above composition is replaced by
the condensation product of C10 alcohol with 3 moles of
ethylene oxide, the condensation product of C12 alcohol with
5 moles of ethylene oxide (HLB=ll), the condensation product
of coconut alcohol with 5 moles of ethylene oxide, the con-
densation product of coconut alcohol with 7 moles of ethylene
oxide, the condensation product of C12_13 alcohol with 6-
moles of ethylene oxide, or the condensation product of C14 15
alcohol with 7 moles of ethylene oxide.
Substantially similar results are also obtained when the
ratio of nonionic surfactant to cationic surfactant used in
` ~ `
' ~'~j
9~
- 46 -
the above composition is 10:3, 20:7, 10:5, 20:11, 5:3, 5:4,
or 1:1.
Similar results are also obtained where the cationic
surfactant, used above, is replaced by one of the following
surfactants:
O CH
Il ~ 3
C14H29-(CH2CH2O)7-CH2-C-O-CH2CH2-N -CH3 Br
CH3
O CH
12 25 ( 2CH2O)g-CH2-C-O~CH2CH2-N -CH Br
O CH
10 21 C~CH2CH2O)lo~C~CH2~N -CH3 Cl-
CH3
O H H O CH
~ 3
C13H27-O(CH2CH2O) -C-C=C-C-O-CH CH -N -CH Cl
CH3
O CH
(CH2CH2CH2CH2O)7-C-CH2-N+-CH3 Br
CH3
EXAMPLE III
A detergent composition of the present invention was
formulated by combining the condensation product of coconut
alcohol with 5 moles of ethylene oxide (HL~=10.5) together
with one of the preferred cationic surfactants of the
present invention having the formula:
0 CH
C17H35-C-c-cH2cH2- +-CH3 Cl
in a ratio of nonionic surfactant to cationic surfactant of
about 10:4 (CR,0.071). This detergent composition had a pH
~'
.1
1~97~;~
- 47 -
in the wash solution of about 8.5, and was used in the
washing solution at a concentration of about 500 ppm. A
second detergent composition of the present invention was
formulated by combining the same nonionic and cationic sur-
factants in the same ratio as above. The composition also
contained monoethanolamine as an alkalinity source, in an
amount such that the monoethanolamine was present at about
30 ppm in the washing solution when the entire composition
was used at a concentration of about 530 ppm. The pH of the
second detergent composition in the laundry solution was
about 9.3.
Identical polyester/cotton blend swatches were stained
with a mixture of soil collected from air conditioning
filters and a mineral oil/olive oil/oleic acid blend. The
stained swatches were then washed using each of the above two
detergent compositions in a one gallon washing machine which
simulates the action of a commercial washing machine. The
washing operation was carried out for 10 minutes using water
having a temperature of about 100F (38C) and containing
7 grains per gallon of mixed calcium and magnesium hardness.
The soil removal performance was calculated by using the
weight removal percentage, averaged across the three stained
swatches washed in each composition. Both compositions gave
excellent soil removal performance. However, the cationic/
nonionic mixture containing monoethanolamine and having the
higher alkalinity had a soil removal of about 73%, while the
lower pH cationic/nonionic mixture had a soil removal of
about 50~. These data demonstrate that improved soil removal
performance is obtained by the use of cationic/nonionic
detergent compositions having a higher alkalinity such as
that obtained by the inclusion of monoethanolamine.
Substantially similar results are obtained when other
sources of alkalinity, such as sodium hydroxide, sodium
carbonate, triethanolamine, and sodium silicate, are used,
in comparable amounts, in place of or in combination with the
monoethanolamine.
Similar results are also obtained where the nonionic com-
,.~ j
.
.
- - . : : . .
-
.
11~9754
" ~
- 48 - .
ponent used above is replaced by the condensation product of
C10 alcohol with 3 moles of ethylene oxide, the condensation
product of coconut alcohol with 6 moles of ethylene oxide, the
condensation product of coconut alcohol with 7 moles of ethylene
oxide, the condensation product of C12_13 alcohol with 6-5
moles of ethylene oxide, the condensation product of C14 15
alcohol with 7 moles of ethylene oxide, or the condensation
product of C12_13 alcohol with 3 moles of ethylene oxide
stripped so as to remove the lower ethoxylate and unethoxylated
fractions.
Excellent cleaning results are also obtained where the
detergent compositions used contain nonionic to cationic
surfactant ratios of about 5:1, 4:1, 10:3, 20:7, 20:9, 2:1,
5:3, or 1:1.
Excellent cleaning results are also obtained where the
nonionic component is replaced by a mixture of the condensa-
tion product of C14_15 alcohol with 3 moles of ethylene oxide
together with the condensation product of C14 15 alcohol with
7 moles of ethylene oxide, in a ratio of lower ethoxylate
nonionic to higher ethoxylate nonionic of about 2:1; or a
mixture of the condensation product of coconut alcohol with
5 moles of ethylene oxide together with an alkylglyceryl
ether having the formula:
C12H25-OCH2CH-CH2OH
OH
in a ratio of alcohol ethoxylate to glyceryl ether of about
7:3.
Substantially similar cleaning results are also obtained
where the cationic component is replaced by C12 alkyl tri~
methylammonium chloride, C14 alkyl trimethylammonium bromide,
di-Clo alkyl dimethylammonium bromide, di-C12 alkyl dimethyl-
ammonium chloride, tri-C8 alkyl methylammonium bromide, tri-
C10 alkyl methylammonium chloride, or cationic components
having the formulae given below:
~ .
11~P9754
- 49 -
~ N - CH2
14 29 \ ~ ¦ Br
N - CH2
CH
14H29
O CH
ll 1 3
C16H33-C-O-cH2cH2 I CH3 Cl
CH3
Cl2H2s-o-c-cH2cH2-c-o-cH2cH2-N -CH3 Cl
CH3
Br CH3-~N-CH2CH2-o-C-(CH2)l2-3-o-cH2cH2-t -CH3 Br
CH3 CH3
O CH
lOH21 (CH2CH2) lO-~-CH2-N+-CH3 Cl-
CH3
EXAMPLE IV
A detergent composition of the present invention was
formulated by combining the condensation product of coconut
alcohol with 5 moles of ethylene oxide together with the
cationic surfactant having the formula:
O CH
17 35 0 CH2CH2 I CH3 Cl
CH3
such that the ratio of nonionic surfactant to cationic sur-
factant was about 10:4. The detergent composition was used
in the laundry solution at a concentration of about 500 ppm.
A second detergent composition of the present invention was
formulated SQ as to contain the same nonionic and cationic
components in the same ratio, but which additionally contained
~j
. .
.
.
- -, .
- ~ ' : ', '
11~9~
- 50 -
a C12 16 alkyl fatty acid ammonia amide, present in an
amount such that the amide component would be present in
the washing solution at a concentration of 50 ppm when the
composition was used at a concentration of 500 ppm. This
composition had a pH in the laundry solution of about 8.4.
Nine swatches (3 cotton, 3 polyester, and 3 polyester/cotton
blend), were stained with a clay-in-water suspension and
were washed in a one gallon washing machine which simulates
the action of a commercial washing machine, using each of
the above two detergent compositions. Two 11" x 11" 100%
cotton terry cloths, with loop construction, were added to
each washing machine as redeposition sites for the soil
removed from the stained swatches. The washing process was
carried out for 10 minutes in water of about 100F (38C),
containing 6.5 grains per gallon of mixed calcium and
magnesium hardness. After washing the cloths in the respec-
tive test treatments and subsequently drying them, the
reflectance of the terry cloths were read using a Hunter
Reflectometer. The cleaning performance of both detergent
compositions on the stained swatches was excellent. In
addition, the first composition, containing only the nonionic
and cationic components, yielded terry cloths having a
reflectance of 53 Hunter Whiteness Units, while the second
composition, which additionally contained the amide component,
yielded terry cloths having a reflectance of 71 Hunter White-
ness Units. These data demonstrate the improved soil anti-
redeposition properties which are obtained by the inclusion
of an amide component in the cationic/nonionic detergent
compositions of the present invention.
Substantially similar results are obtained where the
amide component is present in such an amount such that the
concentration of amide in the washing solution is about 80
ppm, 75 ppm, 65 ppm, 55 ppm, 40 ppm, or 30 ppm. Similar
results are also obtained where the amide component used
above is replaced by amides having the formula:
C; ~R2 R2
R -~-N orR -S-N /
\R2 8 O R
~ . A ~ . ,
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wherein R is C8 alkyl, C10 alkyl, C12 alkyl, C13 alkyl, C15
alkyl or C17 alkyl, and R2 is hydrogen, methyl, ethyl,
propyl, or hydroxymethyl.
Excellent results are also obtained where the nonionic
surfactant used above is replaced by the condensation product
of C10 alcohol with 3 moles of ethylene oxide, the condensa-
tion product of coconut alcohol with 6 moles of ethylene
oxide, the condensation product of coconut alcohol with 7
moles of ethylene oxide, the condensation product of C12 13
alcohol with 6.5 moles of ethylene oxide, the condensation
product of C14 15 alcohol with 7 moles of ethylene oxide, or
the condensation product of C12 13 alcohol with 3 moles of
ethylene oxide stripped so as to remove nonethoxylated and
lower ethoxylate fractions. Excellent results are also
obtained wherein the nonionic component is replaced by a
mixture of the condensation product of C10 alcohol with 3
moles of ethylene oxide together with the condensation
product of a secondary C15 alcohol with 9 moles of ethylene
oxide, in a ratio of lower ethoxylate nonionic to higher
ethoxylate nonionic of about 3:1; or the mixture of the
condensation product of coconut alcohol with 5 moles of
ethylene oxide together with an alkyl glyceryl ether having
the formula:
12 25 2jCH CH2OH
OH
wherein the ratio of nonionic surfactant to glyceryl ether
is about 3:1.
Substantially similar results are also obtained wherein
the ratio of nonionic surfactant to cationic surfactant in
the above compositions is 5:1, 10:3, 20:7, 20:9, 2:1, 5:3,
or 1:1.
Excellent results are also obtained where the cationic
component of the above compositions is replaced by C12 alkyl
trimethylammonium chloride, C14 alkyl trimethylammonium
chloride, di-Clo alkyl dimethylammonium bromide, di-C12 alkyl
dimethylammoni~um bromide, tri-C8 alkyl methylammonium chloride,
or tri-C10 alkyl methylammoni~,l bromide.
~`
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11~9754
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EXAMPLE V
A substrate article, for use in the automatic laundering
operation, is made by coating one side of an 8" x 11" sheet
of a Scott 8050 Industrial Towel, having an air permeability
of about 130 cu. ft./min./sq. ft., a basis weight of about
77.5 grams per sq. yd., and a thickness of 44 mils, with
about 50 grams of a composition having the formulation given
below. The composition is made by intimately mixing the
nonionic and cationic surfactants together, at a temperature
o about 80C, to form a thick paste, and then adding the
remaining components.
Component Weight %
O CH
17H35 C O-CH2CH2-l -CH8 Cl 24.6
Condensation product of coconut alcohol
with 5 moles of ethylene oxide 61.6
C12 16 alkyl fatty acid ammonia amide 8.6
Monoethanolamine 5.2
CR=0.057
An identical sheet of the paper towel is placed on top
of the coated original sheet, and the edges are sewn together
so as to enclose the composition. This article has a pH in
the laundry solution of about 9.5, and provides a convenient
method for introducing the compositions of the present
invention into the laundering solution, as well as providing
excellent cleaning performance.
A substrate article may also be made by coating one side
of an 11" x 11" sheet of melt-blown polypropylene, having a
thickness of about 29 mils, a basis weight of about 58.5
grams per sq. yd., and an air permeability of about 66 cu.ft./
min./sq. ft., with about 60 grams of the detergent composition
described above, placing an identical substrate sheet over
the coated sheet, and heat-sealing together the edges of the
two substrates, enclosing the detergent composition within the
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article.
Similar articles may be manufactured wherein the cationic
surfactant is stearoyl choline bromide. In this case, the
cationic and nonionic surfactants are intimately mixed at a
temperature of about 25C, to form a thick paste, and the
remaining components are added.
EXAMPLE VI
A heavy-duty liquid laundry detergent composition, having
the formula given below, is formulated by mixing together the
following components in the stated proportions.
Component Weight
O CH
ll 1 3
C12H25-(CH2CH2)7-CH2-C- CH2CH2 1 3 14.3
CH3
Condensation product of coconut alcohol
with 5 moles of ethylene oxide 35.7
Monoethanolamine 45.0
Lauramide 4.0
Minors (suds suppressor, perfume
brightener, etc.) 1.0
CR=0.026
This product, when used in an automatic laundering
operation at a concentration of about .05%, has a pH of
about 9.5 and provides excellent removal of both particulate
and greasy/oily soils, as well as exhibiting good anti-
redeposition properties.
EXAMPLE VII
A solid particulate detergent composition of the present
invention, having the formulation given below, is made by
mixing together the following components.
Component Weight %
Dicoconut alkyl dimethylammonium bromide 14.3
Condensation product of coconut alcohol
with 5 moles of ethylene oxide 35.7
.1
' ' ` . . '
, - ' ll~g75~
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Component Weight %
Sodium bicarbonate 45.0
C12 16 alkyl fatty acid ammonia amide 4.0
Minors (suds suppressor, perfume, etc.) 1.0
CR=0.0466
This product, when used in an automatic laundering
operation, at conventional usage concentrations, has a pH
of about 10, and provides excellent particulate soil
removal. It is to be noted that as to the detergent compo-
J~ sition, defined above, bicarbonate anions do not constitute
"interfering anions" (i.e., excellent performance is obtained
even when such anions are present in the laundry solution).
EXAMPLE VIII
A cationic surfactant having the formula given below isprepared as follows: CH3
Cl2H25-(cH2cH2o)7-cH2-c-o-cH2cH2 ~ 3
CH3
44 Grams of an anhydrous sodium alkyl ethoxy acetate,
having the formula given below and prepared by the azeotropic
removal of water from~6andopan DTC~el (Sandoz Chemical),
were dissolved in 100 ml. of methylene chloride at room
temperature.
C12H25-O(cH2cH2o)7cH2 Na
18.8 Grams of oxalyl chloride were added rapidly to the
solution and the reaction mixture was left standing overnight.
The solvent and the excess oxalyl chloride were then removed
from the mixture by vacuum distillation, yielding the acid
chloride corresponding to the sodium alkyl ethoxy acetate
shown above.
40 Grams of the acid chloride product were then dissolved
in 100 ml. of methylene chloride, in a two neck reaction vessel,
equipped with a reflux condenser and dropping funnel. 12.2
f~
~ * Trademark
97~4
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Grams of N,N-dimethylaminoethanol were then added dropwise
from the dropping funnel into the reaction mixture, at a
rate such that the reaction heated to a boil. The reaction
was stirred at reflux during the addition step, and was
allowed to stir overnight at ambient temperature. The methyl
chloride solution was then washed with an aqueous base
solution, followed by two water washes. The separated
organic layer was dried over sodium sulfate, and then stripped
under vacuum to yield about 39 grams of amine ester corres-
ponding to the sodium alkyl ethoxy acetate compound described
above.
37 Grams of this amine ester compound were then placed
in a round bottom flask, equipped with a reflux condenser and
a dropping funnel. An excess of iodomethane was added rapidly
to the amine ester, causing the reaction mixture to boil
during the addition. After the reaction subsided, the mix-
ture was left standing overnight and was then stripped under
vacuum, yielding 43 grams of the desired choline ester
cationic surfactant having the formula given above.
This cationic surfactant, when used in the detergent
compositions described herein, yields outstanding particulate
soil removal, as well as excellent greasy and oily soil and bcdy soil
removal, in addition to providing static control, fabric
softening, and dye transfer inhibition benefits to fabrics
laundered with the compositions.
EXAMPLE IX
A stearic acid choline ester cationic surfactant, having
the formula given below, was prepared in the following manner.
O CH3
17H35 C O-CH2CH2 -N -CH3 Cl
CH3
200 Grams of stearic acid, 138 grams of N,N-dimethyl-
aminoethanol, 6 grams of concentrated sulfuric acid and 2000
ml. of benzene were combined in a flask equipped with a
Dean-Stark water trap and a reflux condenser. The mixture
was stirred at reflux, through the water trap, for four days,
during which time the theoretical amount of water had collected.
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The reaction mixture was cooled to room temperature and then
washed with a dilute calcium hydroxide solution, followed
by three water washes. The solution was then dried over
sodium sulfate and stripped under vacuum, yielding an amine
ester.
The reaction product formed above was dissolved in lO00
ml. of 80/20 acetone/methylene chloride solvent. Methyl
chloride was bubbled into the solution, which thickened as
the quaternary ammonium ester began to precipitate out of
solution. The reaction mixture was saturated with methyl
chloride and then allowed to stand overnight. The white,
crystalline solid product was isolated by vacuum filtration,
washed with acetone, and then dried in a uacuum oven,
yielding 185 grams of the desired stearoyl choline ester
cationic surfactant.
This biodegradable cationic surfactant, when used in
the detergent compositions defined herein, yields excellent
particulate soil removal performance, as well as fabric
softening, static control and dye transfer inhibition bene-
fits to fabrics laundered with those compositions.
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