Note: Descriptions are shown in the official language in which they were submitted.
1~2~
Technical Field
This invention relates to laundry detergent com~ositionS
containing no or low levels of phosphate materials,which exhibit
highly improved particulate soil removal capabilities. These
detergent compositions provide surprisingly effective clay soil
removal performance even in the absence of detergency builders.
Similar compositions which utilize mixtures of selected nonionic
surfactants and selected cationic surfactants and which give un-
expectedly good removal of greasy/oily and body soils are defined
in U. S. Patent 4,259,217 of A. P. Murphy, issued March 31, 1981.
_ckground Art
Nonionic surfactants are generally used in laundry de-
tergent 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 surfact-
ants have been included in detergent compositions for the pur-
pose of yielding a germicidal or santization 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 ditallowalkyl-
dimethylammonium chloride, are included in detergent compositions
for the purpose of yielding a fabric-softening benefit, as dis-
closed in U. S. Patent 3,607,763, Salmen et al, issued September
21, 1971; and U. S. Patent 3,64~,203, Lamberti et al, issued
February 22, 1972. Such components are also used to control
staticO 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, 1975. However, none
of these patents indicate that by the careful selection and com-
bination of certain nonionic and cationic surfactants, to achieve
-- 1
Z95~
specific nonionic:c~tionic su~f~ctant r~tios and reduced cationic
monomer concentrations, outstanding removal of particulate soils
may be obtained.
The compositions of the present invention have outstan-
ding cleaning 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 dramaticall~ 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 compositions additionally provide biodegradability
and excellent removal of greasy and oily soils, while also pro-
viding, in a single detergent product, particulate soil removal,
fabric softening, static control and dye transfer inhibition ben-
efits to the laundered fabrics. The cleaning performance, which
is superior to that previously demonstrated, is the 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 conjunction
with a carrier such as a substrate.
It is a further more specific object of this invention
to provide specific detergent compositions which yield e~cellent
Particulate soil removal and which are biodegradable.
- 2 -
3~
It i5 a still further specific object of this invention
to de~ine specific novel cationic surfactants which are biode-
gradable 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 com-
positions which yield both excellent particulate soil removal and
0 anti-redeposition properties.
It is yet another object of this invention to provide a
process for laundering fabrics which yields especially good par-
ticulate soil removal, using cationic and nonionic surfactant-
containing detergent compositions.
Disclosure of the Invention
The present invention relates to laundry detergent com-
positions, containing from 0 to about 20% phosphate materials,
which are especially beneficial for the removal of particulate
soils from fabrics and in preventing their redeposition back onto
the fabric surfaces, which comprise from about 5% to about 100%
of a surfactant mixture consisting essentially of:
(a) a biodegradable nonionic surfactant having the
formula R(OC2H4)nOH wherein R is a primary or secondary
alkyl chain of from about 8 to about 22 carbon atoms
and n is an average of from about 2 to about 12, having
an HLB of from about 5 to about 17;
(b) a cationic surfactant 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
l~Z~9~
o O R2 R2 ~
C-O-, -O-C-, -C-N-, -N-C-,
-C-N-, -N-C-, -O-, -O-C-O-, -O-C-N-, -N-C-O-,
and mixtures thereof, each R containing from about 8
to 2~ carbon atoms, and which may additionally contain
up to about 12 ethylene oxide groups, m is a number
from 1 to 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 R in a molecule being benzyl,
x is a number from 0 to 11, the remainder of any carbon
atom positions being filled by hydrogens, Y is selected
from the group consisting of
(1) --~ -- ,
\ ~ I
N - C-
(~) -C +
~ N - C -
(3) -P -
(4) -S -
(5) -N~- , wherein p is from 1 to 12,
(C2H4 ) p
(C2H4) P
(6) -N+~ , wherein each p is from 1 to 12,
~C2H4 ) p
(7) ~C ~ ~N~
C /
C ~ / , and
~ C\ ~C
(9) mixtures thereof;
L is 1 or 2~ the Y groups being separated by a moiety
selected from the group consisting of Rl and R2 analogs
having from 1 to about 22 carbon atoms and two free carbon
single bonds, when L is 2; Z is an anion in a number
to give electrical neutrality, and said cationic sur-
factant being at least water-dispersable in admixture
with said nonionic surfactant; and
(c) a fatty amide surfactant;
said composition having a pH of at least about 6.5 in the aqueous
laundry solution, the ratio of said nonionic to said cationic
surfactant being in the range of from about 1:1 to about 100:1,
and the ratio of the combined nonionic and cationic surfactants
to said amide surfactant being in the range of from about 5:1
to about 50:1.
The compositions of the present invention are formula-
ted 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
cleaning performance; preferably, they are alkaline in nature
when placed in the laundry solution and have a pH of greater than
about 7. ~t pH's lower than about 6.5, the overall cleaning per-
formance of the compositions tend to decrease. Particularly pre-
ferred compo5itions have a pH of greater than about 8 in the
: laundry solution, in order to improve the removal of body soil.
~ . 5 -
~2~
The compositions may be formulated so as to be free of
oily hydrocarbon materials, such as many dry cleaning solvents,
mineral oil, paraffin oil and kerosene, because these materials
(which are themselves oily in nature) load the washing liquor with
excessive oily material, thereby diminishing the cleaning effec-
tiveness of the compositions of the present invention.
The compositions may also be formulated such that thecationic 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.
The compositions of the present invention comprise, by
weight, from about 5 to 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 ratio stated It is preferred that the detergent compositions
contain at least about 1~ of the cationic component; otherwise
sufficient cationic surfactant may not be present in the wash
solution to provide the desired cleaning and conditioning results.
Further, preferred compositions do not contain more than about 10
of the cationic component, due to cost and commercial availabil-
ity 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, carhon atoms and n
is an avera~e of from about 2 to about 12, preferably from about
2 to about 7, and especially from about 4 to about 7. The non-
ionic surfactants .included within the present invention includebranched alcohol ethoxylates. The nonionics have an H~B (hydro-
philic-lipophilic balance) of from about 5 to about 17, preferably
-- 6 --
. .~
1~ Z~'~99
from about 6 to about 14 ! and especiall~ from about 10 to about
13.5. These nonionic surfactants are preferably com~ined with
less solu~le cationic materials (such as those having 2 or 3 long
alkyl chains~. ~here 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, rnc., 1~66, pp. 507-613.
Particularly preferred nonionic surfactants for use in
the compositions of the present invention include the condensa-
tion product of C10 alcohol with 3 moles of ethylene oxide, thecondensation product of coconut 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 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_15 alcohol with 7 moles
of ethylene oxide, 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, the condensation product
2a of C14 15 alcohol with 3 moles of ethylene oxide, the condensa-
ion product of C14_15 alcohol with 4 moles of ethylene oxide,
and the condensation product of C14 15 alcohol with 9 moles of
ethylene oxide. A preferred class of such surfactants are made
from substantially linear alcohols, such as those which u~ilize
oxoalcohols containing about 20% 2-methyl branched isomers, com-
mercially 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
3Q nonionic surfactant definition, or mixtures of nonionic surfac-
tants, some of which do not fall within the above nonionic sur-
factant definition, as long as at least one of the nonionic sur-
-- 7 --
~L2~3z~
factants contained in the mixtu.re falls within the above defin-
ition of the nonionic surfactants, and the ratio of that nonionic
surfactant to the cationic surfactant falls wit~in the required
nonionic/cationic ratio. Where the nonionic surfactant mixture
contains a nonion;c surfactant (:or surfactants) which falls out-
side of the above nonionic definition, the ratio of the surfact-
ant (or surfactants~ wtthin the above definition to that which
does not fall within the definition is preferably within the
range of from about 1:1 to about 5:1. Specific examples of sur-
1~ factant mixtures include a mixture of the condensation product of
Cl4 15 alcohol with 3 moles of ethylene oxide. "~eodol 45_3)"1
and the condensation product of C14 15 alcohol with 14 moles of
ethylene oxide "(Neodol 45_14)~2~ in a ratio of lower ethoxylate
nonionic to higher ethoxylate nonionic of from about 1:1 to about
3:1; a mixture of the condensation product of Cl0 alcohol with 3
moles of ethylene oxide together with the condensation product of
of secondary Cl5 alcohol with 9 moles of ethylene oxide "(Tergitol
15-S-9)"3, in a ratio of lower ethoxylate nonionic to higher ethoxy-
late nonionic of from about 1:1 to about 4:1; and a mixture of
"Neodol 45-3" and "Tergitol 15-S-9", in a ratio of lower ethoxy-
late nonionic to higher ethoxylate nonionic of from about l:l to
about 3~
Preferred nonionic surfactant mixtures contain alkyl
glyceryl ether compounds in addition to the required nonionic
surfactant. Particularly preferred are glyceryl ethers having
the formulae
R-OCH2-CIH-CH2OH and R-O(CH2~H2O~rlcH2cHcH2oH
OH OH
wherein R is an alkyl or alkenyl group of from about 8 to about
1. Trademark
2. "
3. "
-- 8 --
112~299
18, preferably about 8 to 12 caxbon atoms or an alkaryl group
having from about 5 to 14 carbons in the alkyl chain, and n 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 No. 1,081,574, K. L. Jones,
issued July 15, 1980; and U. S. Patent 4,098,713, K. L. Jones,
issued ~uly 4, 1'~78.
Other biodegrada~le 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 non-
ionic surfactants required in the present invention, to form use-
ful nonionic surfactant mixtures. Examples of such surfactants
are listed in U. S. Patent 3,717,630, Booth, issued February 20,
1~73, and U. S. Patent 3,332,880, Kessler et al, issued July 25,
1967. Nonlimiting examples of suita~le nonionic surfactants
which may be used in conjunction with the required nonionic sur-
factants include the condensation products of aliphatic 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
th~ condensation product of myristyl alcohol condensed with about
13 moles of ethylene oxide per mole of alcohol; and the condensa-
tion 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" containing
at least one nonionic surfactant falling ~ithin the definition of
nonionic surfactants useful in the present invention, as described
in Canadian Patent No. 1,059,865 of Collins, issued August 7,1979.
g
f~
Cationic Component
The cationic surfactants used in the compositions of
the present invention have 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 following group:
O O O R R O
a ~r, ~ o-, -o-c-, -c-~ N-C-,
O H H O O O H H O
~1 7 ~ tl
-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 12 ethoxy
groups. m is a number from 1 to 3. No more than one R ~roup
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 R is an alkyl or hydroxy-
alkyl group containing from 1 to 4 carbon atoms or a benzyl group
with no more than one R in a molecule being benzyl, and x is a
number from 0 to 11~ preferably from 0 to 6. The remainder of
any carbon atom positions on the Y group are filled by hydrogens.
Y is selected from the group consisting of:
(1) --~+_
\ ,/ I
/N - C-
(2) -C
N - C-
(3) -P -
(4) -S+-
-- 10 ~-
2~9
(5) 1 ~ , whercin p is from 1 to 12,
(C2H~O)pH
(C~4O)pH
(6) -N _ , whcrein each p is from 1 to 12,
(C2H4O)~H
.~,C \ ~,
t7) C +N
1 0 C
/c~ /
(8) N +N , and
C C \
; N
(9) mixtures thereof;
`` L is 1 or 2, with the ~ groups being separated by a moiety selec-
ted from R1 and R analogs (preferably alkylene or alkenylene)
having from 1 to about 2~ carbon atoms and two free carbon single
bonds when L is 2. Z is a water-soluble anion, such as a halide,
sulfate, methylsulfate, hydxoxide, or nitrate anion, particularly
preferred being chloride, bromide, iodide, sulfate or methyl
sulfate anions, in a number to give electrical neutrality of the
cationic component. 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 surfactant. The term
"water-dispersible" means that the cationic and nonionic surfac-
tants, as well as the anions discussed hereinafter, remain dis-
persed throughout the laundry solution during the washing process.Mixtures of the above~defined cationic materials may also be used
in the compositions of the present invention. Small amounts of
other cationic materials can be tolerated in such mixtures.
1~2:3Z~
When used in comblnation with nonionic surfactants,
within the specific ratios and the preferred reduced cationic
monomer concentrations, defined hereinafter, these cationic com-
ponents provide excellent soil removal characteristics, confer
static control and fabr~c softening benefits to the laundered
fabrics, and inhibit the transfer of certain dyes among the
laundered fabrics in ~he wash solution. Preferred cationic sur-
factants are those which have critical micelle concentrations
less than about 500 ppm.
In preferred cationic materials, L is equal to 1 and Y
is
\ / !
C--
-~- or -C ~ I
~ N _ ~ _
or mixtures thereof. However, L may be 2 and~ in that case, the
cationic component contains 2 ca~tionic charge centers. Other
cationic materials which are useful in the compositions of the
present invention include phosphonium and sulfonium materials.
;; 20 Where m is equal to 1, it is preferred that x is equal
to 3 and R is a methyl groupO Preferred compositions of this
mono-long chain type include those in which Rl is a C10 to Cl~
alkyl group. Particularly preferred compositions of this class
include C12 alkyl trimethylammonium halide, C14 alkyl trimethyl-
ammonium halide, coconutalkyl trimethylammonium halide, tallow-
alkyl trimethylammonium halide, and C16 alkyl trimethylammonium
halide.
In order to be sufficiently water-soluble or water-
dispersible, the cationic surfactant must satisfy the following
chain-length criteria. Where m is equal to 2, only one of the
R chains can be longer than 16 carbon atoms. Thus, ditallow-
dimethylammonium chloride and distearyldimethylammonium chloride,
- 12 -
~2~Z99
which are used conventionally as. fahric softeners and static
control agents in detergent compositions, are not included within
the definition of the cationic components used in t~e present
invention. Preferred di-long chain cationics of this type in-
clude those in ~hich x is equal to 2 and R is a methyl group.
In this instance it is also preferred that Rl is a C10 to C14
alkyl group. Particularly preferred cationic materials of this
class include di-Clo alkyldimethylammonium halide, di-C12 alkyl-
dimethylammonium halide materials, and dicoconutalkyl dimethyl-
lQ ammonium halide.
Where m is equal to 3, only one of the Rl chains can begreater than 12 carbon atoms in length. In this instance, it is
pre~erred 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 tridecylalkylmethyl-
ammonium halide.
~ nother 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:
CIH3 CH3
Z R-tN-(C2H4O)pH H(OC H ) -N~-(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 surfactants
whic~ contain an average of about 13 or more, and especially more
than about lQ~ moles of ethylene oxide per mole of surfactant.
; - 13 -
~'
1~ Z~ 9
These compounds tend to be xelatively nonbiodegradable, do not
enhance the cleaning or fabr.ic conditioning benefits provided
by the compositions and may, in some circumstances, decrease the
overall laundering performance provided by them.
The following formulations have been found to be es-
pecially suita~le for removing particulate soils, and provid~ng
fabric softening, static control and dye transfer inhibition ben-
efits, in a conventional home laundering operation.
(a) Tallowalkyltrimethylammonium halide or methyl-
sulfate, such as chloride, together with a nonionic surfactant
selected fxom 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 the 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 5:3.
(b) Tallowalkyltrimethylammonium halide or methylsul-
fate, such as chloride, together with a nonionic surfactant sel-
ected 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 conden-
sation 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 from 5:1 to about 4:1. Com-
positions which exhibit both excellent particulate and greasy/oily
soild removal may be formulated by combining this cationic ma-
terial 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 a nonionic:
cationic ratios of from 5:1 to about 1:1.
. - 14 -
~12~
(c) Coconutalkyltrimethylammonium halide or methyl-
sulfate, such as chloride, together with a nonionic surfac-
tant selected from the condensation product of C12-C13 alc o
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 surfac-
tant 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 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 particu-
late and greasy/oily 50il removal may be formulated by combin-
ing this cationic material with the condensation product of
C12-C 3 aicohol 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
R -N -CH2 - ~ Z ' wherein R , R and Z
R are as defined above,
l~LZ929~
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 cat onic surfactant of the formula
R -N -CH2- ~ Z , wherein R , R and Z are
¦2 as 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::L to about 1:1.
(g) Dicoconutalkyldimethylammonium halide, or methyl-
sulfate, such as chloride, together with a nonionic surfac-
tant selected from the condensation product of C12-C13
alcohol with 4 to 8 moles of ethylene oxide or the conden-
sation 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 about 1:1, especially from about 4:1 to about 2:1. Composi-
tions which give both excellent particulate and greasy/oily
-16-
,,,
112~$'3
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-C12 alkylmethylammonium halide or methylsul-
fate, such as chloride, together with a nonionic surfactant
selected from the condensation product of C12-C13 alcohol
with 6 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 13 alcohol
with 6.5 moles of ethylene oxide, the condensation product
of C12 13 alcohol with 9 moles of ethylene oxide, the con-
densation 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 methylsulfate,
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 ethyl-
ene 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 condensa-
tion product of C14_15 alcohol with 7 moles of ethylene oxide,
the condensation product of C14 lS 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,
-17-
~i
~29~99
which is described in U.S. Patent No. 4,260,529 of James C.
Letton, granted April 7, 1981, has the formula
Rl
R2 _ (Zl)a-(R )n~Z ~(CH2)m~N -R X
R
wherein Rl is Cl to C4 alkyl or hydroxyalkyl; R2 is C5 to
C30 straight or branched chain alkyl or alkenyl, alkyl
phenyl, or
Rl
X R - N-(CH2)S-; wherein s is frGm 0 to 5;
Rl
R3 is Cl to C20 alkylene or alkenylene; a is 0 or 1, n is 0
or 1, and n is 1 when a is 1; m is from 1 to 5; zl and
z2 are each selected from the group consisting of
R ~ H H 1~
-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
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 nit-
: rate, preferably chloride, bromide, iodide, sulfate, or
methyl sulfate.
In addition to the advantages of the other cationicsurfactants disclosed herein, this particular cationic
component is environmentally desirable, since it is bio-
degradable, yielding environmentally acceptable compounds,
both in terms of its long alkyl fragment and its nitrogen-
containing fragment. 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
-- s; ~
Z~9
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 concentra-
tions as specified herein. These preferred cationic surfact-
ants may also be used in the detergent systems defined in
U.S. Patent No. 4,259,217 of A.P. Murphy, issued March 31,
1981, 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 point of from
about 0 to about 95C, preferably from about 10 to about
70C, most preferably from about 20 to about 70C, 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, particularly
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: CH
0 1 3
R -C-0-CH2CH2-N -CH3 X
'i I
CH3
.,
. --19--
..
.,
ll~g~
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 o~ 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 tallowvl choline
ester quaternary ammonium halides (R = C15-C17 alkyl).
Additional preferred cationic components of the choline
ester variety are given by the structural formulas below, where-
in p may be from 0 to 20.
O O CH3
Z 11 11 1 +
R -O-C-(CH2)pC-O-CH2-N -CH3 X
CH3
IH3 1 IH3
X~ CH +N-CH -CH2-O-C-(C~2)p-C O CH2 2 1 3
CH3 CH3
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 dimethylamino-
ethanol, 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 esterification 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 quaterni~e t_i-
methylamine, forming the desired cationic component.
-20-
Another type of novel, particularly preferred cationicmaterial, described in U.S. Patent No. 4,228,042 of J.C.Letton
issued October 14, 1980, has the formula
R2 Rl
R -O[(CH)nO]y~(Zl)a~~R )t-Z -(CH2)m-N -R X
Rl
In the formula, each Rl is a Cl to C4 alkyl or hydroxy-
alkyl group, preferably a methyl group. Each R2 is either
hydrogen or C1 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 C18 alkyl
group, most preferably a C12 alkyl group. R4 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 OE 1; and t may be 0 or 1,
but t must be 1 when a is 1; and m is from 1 to 5, preferably
2. z2 is selected from the group consisting of:
O O O O ~ H O O H H O
Il 11 11 11 1 1 11 11 1 1 il
-C-O-, -C-, -O-, -O-C-O-, -C-N-, -N-C-, ~O-C-N-, -N-C-O- ;
zl is selected from the group consisting of:
O O O H H O H O
l! 11 ll I 1 11 1 11
-C-O-, -C-, -C-N-, -N-C-, -N-C-O-
and wherein at least one of said zl and z2 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 consisting 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/
-21-
,
112~
cationic surfactant mixtures in a ratio of nonionic component
to cationic component of from about 1:1 to a~out 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 concentration within the range given herein. They
may be also used in the nonionic/cationic surfactant mixtures
disclosed in U.S. Patent ~,259,217 of Murphy, issued March 31,
1981, wherein the ratio of nonionic component to cationic
component would be from 5.1:1 to about 100:1, preferably 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 form-
ulating 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 70C, most preferably
from about 20 to about 70C, and the surfactant mixture pre-
ferably has a reduced cationic monomer concentration of from
- 20 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.
These surfactants, when used in the compositions of
the present .invention, yield excellent particulate soil, body
soil, and grease and oily 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
surfactants are environmentally desirable, since both their
long chain alkyl fragments and their nitrogen fragments are
biodegradable, in that they degrade to yield environmentally
acceptable compounds. Where this type of biodegradable
-22-
. ~
2g9
cationic surfactant is used, it is preferred that the deter-
gent compositions have a pH of not greater than about 11, pre-
ferably 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.
~' C~3 -
R -~(CII CH~O)~ `T''2)t-C-(~-c~l2-c~l2-~l -Ci13'`
C~3
O CH
R -o(C~12CH2O)~ C-C}12-N -C113 X
CH3
ICH3 IC 3
R3_o(CHCH2O)y-C~CH2 I C 3 X
CE13
3 l IC~13
R -O(CHCH O) -(CH2) -C-O-CH2-CH2-N -CH3 X
c~3
o O CH3
R O( 2CH2O).t, ( 2)t 2 2 , 3
C~3
o El H O Cll
ll I I 1~ 1 3
R -O(CH2CH2O)y~C~c=c~c-o-cll2cH2-L~ -C~T3 Y~
c~3
-23-
~!~
~12~99
O CH
R -o(CH2CH2cH2cH2O)y-c-cH2-~ -CH3 X
R3-o(CH2 CH2CH2CH2O)y~(CH2)t C O-CH2C~12 1 3
The preferred derivatives, described above, may be pre-
pared by the reaction of a long chain alkyl polyalkoxy (pre-
ferably polyethoxy) carboxylate, having an alkyl chain of
desired length, with oxalyl chloride, to form the correspond-
ing 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 com-
pounds 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 mono-
mer 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 nonionic and cationic com-
-24-
ponents used are pure, the more narrow CR ranges are preferred.In a preferred method of preparing 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 per-
formance of the compositions.
An approximation of the CR of a surfactant mixture is
obtained by dividing the concentration of the cationic surfac-
tant monomer in the laundry solution by the critical micelleconcentration (CMC) of the surfactant. As used in the applica-
tion, 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, in a
single component system, as a quantity which normalizes the
extent of adsorption of a surfactant onto a fabric surface
(the critical element in the removal of greasy/oily soils) is
discussed in Tamamushi and Tamaki, Proceedings of the Second
International Congress of Surface Activity, III, 449 Academic
_.
Press, Inc. (1957). The equations below extend this concept
of reduced monomer concentration to multi-component systems,
utilizing surfactant monomer concentrations. The concept of
surfactant 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 (II) in Clint):
*
(clm) 2[ 2 _ 1] + cml(C-c2 + cl) - ~ Ccl = 0
-25-
. . .
112~?9
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
"1" denotes nonionic surfactant and "2" denotes
cationic surfactant)
cl = critical micelle concentration (CMC) of nonionic
surfactant (moles/l.)
C2 = critical micelle concentration of cationic
surfactant (moles/l.)
x = total mole fraction of nonionic surfactant
in the solution = Cl/(Cl + C2)
~ = a constant based upon the heat of mixing =-2.8
clm = nonionic monomer concentration
c2m = cationic monomer concentration
e = base of Mapierian logarithm system = 2.71828
x = mole fraction of the nonionic surfactant
in the micelle at concentration C
fl = nonionic activity coefficient in the mixed
20 micelle = e~ (1-x)2
f2 = cationic activity coefficient in the mixed
micelle = e~x
~ = 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~
-26-
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).
cm = {_(C-(c2-cl))+[~C-(c2-cl) )2 ~ 4~C(c2-cl)]l/2}
-- .... . _ .
*
C2
j 2( * -1)
Cl
By modifying this equation based on the assumptions
of a regular, rather than an ideall solution, the CR range
for optimum performance was derived from the following
equation:
-(C-~) + ~(C-~) + 4~C~ (1)
x = 2h
For a given cleaning test for a nonionic/cationic
systeml x was found by inserting the values known from the
* *
test (i.e., cll c2l ~ , C and ~ ) into equation (1) and
solving iteratively for xl such that the error in x is less
, than O.001. This procedure was repeated for a large number
of such testsl over varying usage conditions. The x values
obtained were then used to solve for the cationic monomer
concentrations using the following equation:
c2m = (1-X)f2C2 (2)
The CR value was then calculated using equation (3).
R 2/ 2 (3)
The CR values obtained cover a large number of com~ina-
tions and ratios of various nonionic and cationic surfactants
' at various conce~trations and temperaturesl which have been
' evaluated for their ability to clean greasy/oily soils. The
,,: .
-27-
.. ..
:
~9~g~
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 over-
all 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 sur-
factant, and for each end of the CR range, solve
for x using the equztion
(l-x)e3 x = C
By standard numerical iterative techniques to
an error in x of less than 0.001;
(b) find the range of Y from the equation
Y(l-x) x(l-Y) 1000
Ml - - = [x (x-l)~ ]
using 100 ppm and 10,000 ppm as the boundary
values for W, fox 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
Put another way, steps ~b) and (c) may be combined
into a single equation which may be solved directly for
the NCR.
-28-
~'
NCR = X = (lOOC/W)~ + M2-T--1)
_Y (10-Oa/~)~ +
xMl
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 con-
centration, CR is essentially independent of concentration.
This means that or 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 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 or Composition A (palmitoylalkyl trimethylammonium
chloride plus the condensation product of C12 alcohol with
5 moles of ethylene oxide) of Example I, described in U.S.
Patent No. 4,259,217 of A.P. Murphy, issued March 31, 1981,
given CR, is 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 5ppm
c2- 2.1875 x 10 5ppm
~= -2.8
-29-
.;,
11~3~t
Ml = 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):
(l-x)e-2.8x2 = 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 5) - (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) _ 032202(1-Y) 1OOO (0.922) (0.922-1) (~.73 x
10-5)
Y = 0.938
Substituting this value for Y into equation (c), the
nonionic/cationic ratio is determined.
NCR =1 o:9388 = 15.1
It will be noted that this ratio corresponds to the
ratio actually found in Example I, Composition A.
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
,. .
-30-
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 70C, more prefer-
ably between about 20 and about 7QC, 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 outstanding greasy/oily soil cleaning within
that temperature range. 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, 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 temper-
ature at which a graph which plots the light scattering intensity
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
.~,
9~
Francoise d'instruments de controle et d'analyses, France
(the instrument being hereinafter referred to as (SOFICA).
The SOFICA s~mple 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. Appro~imately 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 ~he
sample cell lid, so that the cell interior is not exposed
to atmospheric dust. The sample is kept in a variable temp~
erature 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 (heat-
ing rate 1C/minute); the temperature of the sample is deter-
mined by the temperature of the bath. The light scattering
intensity of the sample is then determined at various temp-
eratures, 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;
may be used in these compositions; however, preferred compo-
sitions contain the nonionic surfactants defined above, in
order to maximize the cleaning benefit obtained. These
amide surfactants may be used ~n nonionic/cationic surfactant
mixtures having nonionic:cationic ratios of from about 1:1
3Q to about 100:2. When they are used in the compositions of
th~ present invention, the mixtures have nonionic:cationic
-32-
99
ratios of from 5:1 to about 1:1, 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-redeposi-
tion characteristics.
Amides useful in these preferred compositions include,
but not limited to, carboxylic acid amides, sulfonic acid
amides, phosphonic acid amides, and boronic acid amides.
Preferred amides include those having the formulae:
O R2 R -S- ~
\ R2 O/ 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
hydroxyalkyl, preferably hydrogen. Specific examples of
these compositions 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 coconut alkyl
ammonia amide (Rl=coconut alkyl and R2 is hydrogeni 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
-33-
9~'g~
(357 ppm), and lauramide (Rl = Cll and R2 is hydrogen; at45 ppml. These amides may also be used in the surfactant
mixtures described in U.S. Patent No. 4,259,217 of A.P. Murphy,
issued March 31, 1981,which have nonionic:cationic ratios of
from 5.1:1 to about 100:1, preferably from 5.1:1 to about
50:1, particularly from about 6:1 to about 40:1, and most par-
ticularly from about 6:1 to about 20:1. In forming such com-
positions, 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 10 to about 70C, especially from about 20 to about 70C,
and the surfactant mixture preferably has a ratio which corres-
ponds 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 contain
additive materials conventionally used in detergent compositions
the amount of anion-producing materials, and hence anions which
will make the particular cationic surfactant used in the com-
positions 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. Su~h a complexing of the anionic material with the
cationic surfactant decreases the overall cleaning and fabric
-34-
1~2~32~9
conditioning performance of the composition.
Suitable anionic materials may be selected based on
their strength of complexation with the cationic material
included in the composition (as indicated by their dissoci-
ation constant). Thus, ~hen an anionic material has a
dissociation constant of at least about lxlO 3 (such as
sodium toluene sulfonate), it may be contained in an amount
up to about 40%, hy weight, of the cationic surfactant;
~here 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.
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
compositions of the present invention contain from 0 to about
20% of phosphatç 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
-35-
1:~292~9
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 as perborates, phosphates, polyphosphonates,
carbonates or sulfates, may have a beneficial effect on clean-
ing 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 various types. The silicone material can be
described as a siloxane having the formula:
~ R ~
t sio~
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
-36-
~L~2~2~
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-, phenyl-
methyl-polysiloxanes and the like. Additional useful silicone
suds controlling agents can be represented by a mi~ture of an
alkylated siloxane, as referred to hereinbefore, 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 silianated
(most preferably trimethylsilanated) silica having a particle
size in the range from about 10 millimicrons to 20 millimicrons
and a specific surface of 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-emulsify-
ing silicone suds suppressors, described in Canadian Patent
No. 1,085,697 of Gault et al, issued September 16, 1980. An
example of such a compound is 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
*Trademark
-37-
. . .
~2$~
100 represent additional examples of a preferred suds regulat-
ing 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
surfactants Preferred microcrystalline waxes have a metling
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 microcrystalline petro-
latum waxes; Fischer-Tropsch and oxidized Fisher-Tropsch waxes;
ozokerite; ceresin; montan wax; beeswax; candelilla; and car-
nauba wax.
Alkyl phosphate esters represent an additional preferred
suds suppressant for use herein. These preferred phosphate
esters are predominantly monostearyl phosphate which, in add-
ition thereto, can contain di- and tristearyl phosphates and
monooleyl phosphates, which can contain di- and trioleyl phos-
phates.
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., monostearyl
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 conven-
tional 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.
-38-
:-.
1~2~3Z99
However, because of the numerous and diverse performance ad-
vantages 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 manufac-
tured 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 such articles are described in U.S. Patent No. 4,170,565,
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 specifically 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 of any addition-
al 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.
-39-
~2;~
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 pre-
ferred 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
17H3s C O-CH2CH2-N -CH3 Br
. 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 stear-
oyl 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,
-40-
~L~23299
at a nonionic:cationic ratio of about 10:4, a thick pasteproduct is formed. If t~e same components are mixed together
at about 25C, the mixture remains a liquid, which is much
less desirable for use in making substrate articles. Sub-
stantially 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 U~S. Patent No. 4,259,
217 of A.P. Murphy, issued March 31, 1981, nonionic:cationic
ratios of from 5.1:1 to about loa 1, preferably from 5.1:1
to about 50:1, 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 (pre-
ferably 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
-41-
~3 ~9Z~9
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 adsorp~ion 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 com-
positions of t~le present invention are used in a laundry
solution, a threshold 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 detergent composition in the laundry solution, nonionic
surfactant to cationic surfactant ratios of from 5:1, to about
1:1 are necessary in order to provide this threshold concentra-
tion in the laundry solution. In washing processes which
utilize higher concentrations of detergent composition, such
as European washing processes, it is possible to use higher
nonionic surfactant to cationic surfactant ratios, while still
attaining the necessary cationic threshold concentration.
Under these European washing conditions it is possible to
obtain excellent particulate soil removal, in addition to
r outstanding greasy and oily soil and body soil removal,
using the nonionic surfactant to cationic suxfactant ratios
of from 5.1:1 to about 100:1 defined in U.S. Patent No. 4,259,
217 of A.P. Murphy, issued March 31, 1981.
All percentages, parts, and ratios used herein are by
weight unless otherwise specified.
~ The following nonlimiting examples illustrate the com-
i positions and the method o- the present invention.
, -42-
.,
llZ~3~
_XAMPLE 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
commercially 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 com-
position of the present invention, having the following formul-
ation:
Component % by Weight
Dicoconutalkyl dimethyl- 19
ammonium bromide
Condensation product of C 4 5 48
alcohol with 7 moles ofl
ethylene oxide (Neodol 45-7)
HLB-11.5
Sodium chloride 33
CR- 0.0815
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 contained 7 grains per gallon of mixed calcium
and magnesium hardness, and the laundering operation lasted
for 10 minutes at 100 F (38 C). 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 re-
- *Trademar~
-43-
~2,f~g
flectance readings of the individual swatches. A higher re-
flectance 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 62.0
Hunter Whiteness Vnits. These data demonstrate the outstand-
ing clay soil removal performance of the unbuilt compositions
of the present invention, which equaled the performance pro-
vided by the conventional built, brightener-containing deter-
gent 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 solution 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 hromide, tri-C10 alkyl methylammonium c~oride, or
the cationic s~factants listed below:
HOH4C2-N -C2H4OH Cl
C12H25
~ -~4-
1~2
N-CH2
.~
C12H25 C \ ¦ Cl
N -CH
/ \
CH3 C12H25
CIH3
C18H37-N -CH2- ~ Cl
i
CH3
O CH
li 1 3
C16H33-C-O-cH2cH2 N CH3 Br
I
C 3
O o CH3
1~ 11 1
C H --C-cH2cH2-c--cH2cH2 1 3 Br
CH3
O IH3
lOH21 O(CH2CH2O)lo~C~CH2~N -CH3 Cl
CH3
Substantially similar cleaning results are also
ohtained where the cationic surfactant used above is
replaced by a mixture of dicoconutalkyl dimethyl-
ammonium bromide (A) together with C12 alkyl trimethyl-
ammonium chloride (B) in a ratio of A:B of about
4:1, 3:1, 2:1, 1:1, 1:2, or 1:4, a mixture of
-45-
~,
l~Z~3~99
O CE~
ll 1 3
C17H35-C-O-cH2cH2 N C 3 Br (C)
CH3
together with di-Cl~ 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 of C, above, together with
O CH3
C H -O-(CH2C~2O)7 CH2-C O CH2 2 3 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 condensa-
tion 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 unethoxy-
lated 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. A 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
: -46-
l~lZ~ 9
higher ethoxylate nonionic of about 2:1, or the mixture of the
condensation product of coconut alcohol wit~ 5 moles of
ethylene oxide together with an alkyl glyceryl ether having
the structural formula:
C12H25-0CH2ClH C~2
OH
in a ratio of alcohol ethoxylate to glyceryl ether of about
7:3.
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 addi-
tion 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 compo-
sition, optimized for grease and oil removal, having for form-
ulation given below, at its recommended usage level.
-47-
~2~ 9
Component % by Weight
"Neodol 45-7" 15.0
Mg Linear alkyl benzene31.3
sulfonate
Triethanolamine 3.5
Ethanol 6.5
Coconut alkyl fatty acid1.0
Water 41.8
Brightener and minorsBalance to 100
(brighteners, 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
11 ICH3
12 25 ( 2cH2o)7-cH2-c-o-cH2~H2-N+-cH Cl-
CH3
Condensation product of C12_13 71.4
alcohol with 3 moles of
ethylene oxide, stripped to
remove lower ethoxylate and
unethoxylated fractions
("~eodol 23-3T)"
The detergent composition of the present invention has
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
-48-
9~
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 fa~ric ty~es)
Bacon Dirty
Grease Morcor Oil
Liquid laundry composition 58.2 45.5
lQ 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 pre~ent 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 ethy-
lene 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 the above composition is 10:3, 20:7, 10:5, 20:11, 5:3, 5:4,
or 1:1.
-49-
~L~2~Z99
Similar results are also obtained where the cationic
surfactant, used above, is replaced by one of the following
surfactants:
+
C14H2~-O(CH2CH2O)7-CH2-C-O-CH2CH2-N -CH3 Br
I
CH3
O CH
ll 1 3
C12H25-O(CH2CH2O)g-CH2-C-O-CH2-O-CH2CH2-N -CH3 Br
CH3
o CH
ll 1 3
lOH21 O(CH2CH2O)lo~C~CH2~N -CH3 Cl
CH3
O H H O CH
~ 3
C13H27-O(CH2CH2O)8-C-C=C-C O CH2CH2 1 3 Cl
CH3
O CH
(C~I2CH2C~2CH2O)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 (HLB=10.5) together
with one of the preferred cationic surfactants of the present
invention having the formula:
O CH
ll 1 3
C H -C-O CH2CH2-N -CH Cl
CH3
-5~-
~L2~9
in a ratio of nonionic surfactant to cationic surfactant of
about 10:4 (CR 0.071). This detergent composition had a pH
in the wash solution of about 8.5, and was used in the washing
solution at a concentration of about 500 ppm. A second deter-
gent composition of the present invention was formula~ed by
combining the same nonionic and cationic surfactants in the
same ratio as above. The composition also contained mono-
ethanolamine as an alkalinity source, in an amount such that
the monoethanolamine was present at about 30 ppm in the wash-
ing solution when the entire composition was used at a concentra
tion of about 530 ppm. The pH of the second detergent com-
position 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 dat~ demonstrate that improved soil removal per-
formance i3 obtained by the use of cationic/nonionic detergent
compositions having a higher alkalinity such as that obtained
-51-
, :
1~2~299
by the inclusion of monoethanolamine.
Substantially similar results are obtained when other
sources of alkalinity, such as sodium hydroxide, sodium carbon-
ate, triethanolamine, and sodium silicate, are used, in com-
parable amounts, in place of or in com~ination with the mono-
ethanolamine.
Similar results are also obtained where the nonionic
component 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 ~ moles of ethylene oxide,
the condensation product of cocon~lt 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 conden-
sation product of C12_13 alcohol with 3 moles of ethylene oxide
stripped so as to remove the lower ethoxylate and unethoxylated
fràctions.
Excellent cleaning results are also obtained where the
detergent compositions used contain nonionic to cationic sur-
factant 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 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 ~:1, or a
mixture of the condensation product of coconut alcohol with
5 moles of ethylene oxide together with an al~ylglyceryl ether
having the formula:
~ . .
~2~9
C12H25-OCH,~CH--CH20H
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:
~ N CH2
14 29 C \ ¦ Br
N+ - CH2
14 29
O CH3
C16H33-C-O-cH2cH2 N CH3 Cl
; C12H25 ~ C~CH2CH2~C ~ CH2CH2-N~ -CH3 Cl
CH3
.~
-53-
CH O O CH
1 3 ~ 3
Br CH3- N-cH2cH2-o-c-(cH2)l2-c-o-cH2cH2-N+-cH3 Br
CH3 CH3
Il i +
ClOH21 O(CH2CH2O)lo~C~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
Cl7H35-C-O-c~2cH2 N 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 so as to contain the same nonionic and cationic
components in the same ratio, but which additionally contained
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 5Q ppm when the composition
was used at a concentration of S00 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
-54-
1~L2~3Z~S~
one gallon washing machine which simulates the action of a
commercial washing machine, using each of the above two deter-
gent 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 100~ (38C), containing 6.5 grains per
gallon of mixed calcium and magnesium hardness. After washing
the cloths in the respective 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 excel-
lent. In addition, the first composition, containing only
the nonionic and cationic components, yielded terry cloths hav-
ing 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 Whiteness
Units. These data demonstrate the improved soil antiredepo-
sition 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 con-
centration of amide in the washing solution is about 80 ppm,
75 ppm, 65 ppmr 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:
o R2 R2
R -C-N or R -S-N
\ R2 O~ O \ 2
,,
-55-
1~2~Z~9
wherein Rl is C8 alkyl, Cl0 alkyl, C12 Y ~ 13
Cl5 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 condensation
product of coconut alcohol with 6 moles of ethylene oxide, the
condensation product of coconut alcohol with 7 moles of ethy-
lene oxide, the condensation product of C12 13 alcohol with
6.5 moles of ethylene oxide, the condensatiQn product of
C14 15 alcohol with 7 moles of ethylene oxide, or the conden~sa-
t on product of Cl2_l3 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 b~ 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 2 1 2
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
-56-
~.
2~9
COmponent of the above compositions is replaced by C12 alkyl
trimethylammonium chloride, C14 alkyl trimethylammonium chloride
di-Clo alkyl dim~thylammonium bromide, di-C12 alkyl dimethyl-
ammonium ~romide, tri-C8 alkyl methylammonium chloride, or
tri-C10 alkyl methylammonium ~romide.
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 8Q50 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 of about 80C,
to form a thick paste, and then adding the remaining components.
Component W
O CH
ll 1 3
C17H35 C -CH2cH2-N -CH3 Cl 24.6
I
CH3
Condensation product of 61.6
- coconut alcohol with S
moles of ethylene oxide
C12_16 alkyl fatty acid 8.6
ammonia amide
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
50 as to enclose the composition. This article has a pH in
the laundry solution of a~out 9.5, and provides a convenient
method for introducing the aompositions of the present
. ~ .
1~2.9;~
invention into the laundering solution, as well as providing
excellent cleaning performance.
A substrate article may also ~e made by coating one
side of an ll" x 11" sheet of melt-blown polypropylene, having
a thickness of about 29 mils, a ~asis weight of about 58.5
grams per sq. yd., and an air permea~ility 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
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 form~llated by mixing to-
sether the following components in the stated proportions.
Component Weight %
O CH
1 3
Cl2H25-o(cH2cH2o)7-cH2-c-o-cH2cH2-N+-cH3 Cl 14.3
CH3
Condensation product of coconut 35.7
alcohol with 5 moles of
ethylene oxide
Monoethanolamine 45.0
Lauramide 4.0
Minors (suds suppressor,perfume 1.0
~rightener, etc.)
CR=0.026
-58-
112g~
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/oil~ soils, as well as exhibiting good antiredeposition
properties.
EXAMæLE 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 dimethylamonium 14.3
bromide
Condensation product of coconut 35.7
alcohol with 5 moles of
ethylene oxide
Sodium bicarbonate 45.0
C12_16 alkyl fatty acid ammonia 4.0
amide
Minors (suds suppressor, perfume, 1.0
etc.)
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-
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
is prepared as follows.
-59-
O CH3
Il I
C12H 5-0 (CH C~I O) --CH --C--O--CH CH --N~--CH Cl
I
CH3
44 Grams of an anhydrous sodium alkyl ethoxy acetate,
having the formula given below and prepared by the azeotropic
removal of water from "Sandopan DTC Gel"*(Sandoz Chemical),
were dissolved in lO0 ml. of methylene chloride at room tem-
perature.
o
Cl2H25-O(cH2cH2o)7cH2 Na
1~.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 producer were then dissoved
in lO0 ml. of methylene chloride, in a two neck reaction
vessel, equipped with a reflux condenser and dropping funnel.
12.2 Grams of N, N-dimethylaminoethanol were then added drop-
wise 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 allow-
ed to stir overnight at ambient temperature. The methyl chlor-
ide solution was then washed with an aqueous base solution,
following by two water washesO The separated organic layer
was dried over sodium sulfate, and then stripped under vacuum
to yield about 39 grams of amine ester corresponding to the
*Trademark
-60-
~Z~99
sodium alkyl ethoxy ecetate compound described above.
37 Grams of this amine ester compound were then placed in
a round ~ottom 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 mixture was
left standing overnight and was then stripped under vacuum,
yielding 43 grams of the desired choline ester cationic sur-
factant having the formula given above.
This cationic surfactant, when used in the detergent com-
positions described herein, yields outstanding particulate soil
removal, as well as excellent greasy and oily soil and body soil
removal, in addition to providing static control, fabric soften-
ing, 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.
0 CH
ll 1 3
17H3s C 0-CH2CH2_N -CH3 Cl
CH3
200 Grams o~ stearic acid, 138 grams of N,N-dimethylamino-
ethanol, 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. The reaction
mixture was cooled to room temperature and then washed with a
dilute calcium hydroxide solution, following by three water
washes. The solution was then dried over sodium sulfate and
-61-
'~'
~lZ~
stripped under vacuum, yielding an amine ester.
The reaction product formed above was dissolved in 1000 ml.
of 80/20 acetone/methylene chloride solvent. Methyl chloride
was bubbled into the solution, which thickened as the quaternary
ammoniu~ ester began to precipitate out of solution. The re-
action 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 vacuum oven, yielding 185 grams of the desired
lQ stearoyl choline ester cationic surfactant.
This biodegradable cationic surfactant, when used in the
detergent compositions defined herein, yields excellent par-
ticulate soil removal performance, as well as fabric softening,
static control and dye transfer inhibition benefits to fabrics
laundered with those compositions.
-62-
