Note: Descriptions are shown in the official language in which they were submitted.
DETERGENT COMPOSITTO~S
Victor F. Rodriguez
and
Brandon H. Wiers
5Technical Field
.
This in~ention relates to detergent compositions
containing a nonionic/cationic surfactant mixture and,
as an impro~7ed builder mixture, a combination of alumino-
silicate and polycarboxylate builder materials. These com-
10 positions deliver excellent particula~e soil removal perfor-
mance and greasy/oily soil xemoval benefits, along with
- fabric softening, static control, color fidelity and dye
transfer inhibition benefits. Compositions which utilize
mixtures of selected nonionic and cationic surfactants,
15 but without the particular builders describe~ herein, are
defined in U.S. Patent No. 4,222,905 of Cockrell, issued
September 16, 1980; U.S. Patent No. 4,259,217 of A.P. Murphy,
issued March 31, 1981; and Canadian Patent Application No.
323,240, A.P. Murphy, filed March 12, 1979.
E~ackground Art
_
The property possessed by bui]der materials c~f improving
detergency levels of soaps and synt:~etic detergents is
lcnown. Such builders permit the at:tainment Oe better cleaning
25 per Eor~nance than is possible when so-called unbuilt compo-
~;itions are used. ~Iowever, the behavior and mechanisms by
which builders perfonn their function are only partially
understood. It i~ known that good builders must be able
to sequestex most of the calcium and/or magnesium ions in
30 the wash water since these ions are detrimental to the
detergency process. However, it is difficult to predict
which compounds possess useful combinations o~ builder
properties because of the complex
nature of detergency and the countless factors which con-
35 tribute both to overall perEormance results and therequirements of environmental acceptability~
Sodium tripolyphosphate (STP) has been found to be a
highly efficient cleaning and detergent builder and this
compound has been widely used for decades in cleaning and
.. . ~ r~
.
~3:~9~
- 2 -
detergent formu]ati s. However, because of the recent
emphasis on removing phosphates from detergent and cleaning
compositions, suitable replacements for phosphate builders,
which would deliver effective cleaning performance and be
environmentally acceptable, are being sought. Inorganic
builders other than STP are generally not satisfactsry for
use as a builder in detergent formulations because of their
poor build6r ~roperties. Sodium aluminosilicates, commonly
known as zeolites, have been proposed for use in detergent
formulations since they are able to soften water by removing
calcium ions; but they are not very effective in removing
magnesium ions from water.
It has also xecently been taught that by combining
~pecific types of cationic surfactants with a narrowly
defined range of alcohol ethoxyla~e type nonionic sur-
factants, within defined nonionic:cationic ratios, simple,
unbuilt detergent compositions which deliver good _le~ning
performance and fabric care benefits, can be formulated.
(See e.g., U.S. Patent 4,259,217, Murphy; U.S. Patent 4,222,905,
Cockrell, and Canadian Patent Appl:ication No. 323,240, of
A.P. Murphy, previously referred to). These unbuilt detergent
compositions, although generally.~qui~alent to fully built
phosphate compositions known in the art, still are capable
of further improvement.
Thus, it-can be seen that there is a need for new
detergent compositions with cleaning properties superior or
equivalent to phosphate-built detergents, but which do not
contain phosphates, and which achieve environmental accept-
ability by being readily biodegradable. Now, according to
the present invention, there is provided new detergsnt
compositions with a cationic/nonionic surfactant mixture
and, as an improved builder mixture, a combination of
aluminosilicate and polycarboxylate builder materials.
These compositions provide cleaning performance superior to
that of phosphate-built compositions and also provide other
fabric care benefits, such as softening and sta-tic control~
~3~
,. .
-- 3 --
Summary of the_Invention
The present invention encompasses a detergent compo-
sition, which contains from 0 to about 5~ phosphate
materials, comprising:
S (a) .from about 1% to about 95% of a suractant mixture
consisting essentially of: -
(i) a nonionic surfactan~ having an HLB of from
about 5 to about 17; and
(ii) a c~.tionic surfactant, having the formula
~ ~ ~LZ
wherein each R is an organic group contai.ning a
straight or branched alkyl or alkenyl group
optionally substituted with up to 3 phenyl or
hydroxy groups and optionally interrupted by up to
4 structures selected from the group consisting of
O O R2 R O
~3 c o o c -C-N-, -N-C-,
O H H O O O H H O
-C-N-, -N-C-, -O-, -O-C-0-, -O-C-N-,. -N-C-O-
,
and mixtures thereof~ each Rl containing from
i about 8 to about 22 carbon atoms, and which
may ~dditionally contain up to about 20
~: . ethy~ene oxide groups; m is a number from 1
to 3; each R is an alkyl or hydroxy alkyl
group containing from 1 to 4 earbon atoms or
a benzyl group, with no more than one R in a
molecule being benzyl; x is xom 0 to 11, the
remainder of any carbon atom positions being
filled by hydrogens; Y is selected from the
group consisting of
N~ ,
, " - Fr' 'l
\/ I
M - C
(2) -C
~ N - C - ,
I+
: ~3) _p
(~3 -S~ ,
- (5) -N~ , wherein p is from 1 to 1
(C2H4)pH
5C2H40) H
(6) -~ - , wherein each p is from 1 to 12,
(C2H40) p
(C H O) H
- - ~7) -N -(C2H40)pH, wherein each p is ~rom 1 ~o 12,
)pH ;
C
\ ~ \"~ '
, ~8) C ~N -
u
C~ ~ C
C
~3
C
(9~ N
. ~C C , and
N
(10) 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 one to about twenty-two carbon
atoms and 2 free carbon single bonds when ~ is 2; Z is
an anion in a number sufficient to yi~e electrical
neutrality to the molecule, said cationic surfactant
being at least water-disperslble in admixt~re with said
r~
-
, .
! - 5 -
nonionic sufactant;
wherein the ratio of said nonionic surfactant to said cati-
onic surfactant is from about 1:1 to about 100:1; and
(b) from about 5gO to about 99% of a detergency
builder mixture consisting essentially of:
~i3 a water-insoluble aluminosilicate material
selected from the group consisting of:
(1) Zeolites A, X, or P~B), or mi~tures
thereof, having a particle size diameter
of from about 0.01 microns to about 25
microns and containing at least 10%
water of ~ydration;
(2) amorphous hydrated aluminosilicate
material o the empirical ormula:
M (zAlO ySiO )
wherein M is sodium, potassium, ammon-
i~um~ z is from about 0.5 to abou~ 2, y
is 1, said material having a particle
~i size diameter of less than about 100
i - 20 -- microns, a magnesium ion exchange
capacity of at least about 50 milligrams
equivalents of CaCO3 hardness per gram
- of anhydrous aluminosilicate, and a Mg
exchange rate of at least about 1
grain/gallon/minute~gram/gallon; and
- (3) mi~tures thereof; and
(ii) a polycarboxylate builder material;
whexein the weight ratio of the aluminosilicate
material to the polycarboxylate material is from
about l:lQ to about 10:1.
D~sclosure of the Invention
_
This invention comprises the discovery of an improved
builder mixture ~or use in detergent compositions con-
taining selected nonionic/cationic surfactant mixtures.
The builder mixture, a combination of aluminosilica~e and
polycarboxylate builder materials, delivers excellent par-
ticulate soil remo~al performance and greasy/oily soil
removal benefits. These compositions also provide fabric
softening, static control, color fidelity and dye transfer
_._, ......................................... .~ r~'!
31 ~3~
. ~
inhibition benefits. The detergent compositions are
particulaxly good in 10-40C water, especially when the
particle size diameter of the aluminosilicate material is
from about 0.5 to about 2 microns.
The essential elements in the detergent composition of
this invention are:a nonionic~cationic surfactant mixture,
and a mixture of aluminosilicate and polycarboxylate builder
materials.
Surfactant Mixture
The compositions of the present invention comprise,
by weight, from about 1 to about 95%, preferably from
about 15 to about 60~, and most preferably from about 20 to
about 50%, of a mixture of particularly defined nonionic
and cationic surfactants, defined hereinafter, within ratios
of nonionic to cationic surfactant of from about 1:1 to
about 100:1, preferably from about 1:1 to about 50:1, and
more preferably from about 3:1 to about 40:1. Optimum
removal of greasy/oily soils is generally obtained with
nonionic:cationic surfactant ratios of from about 5:1 to
about 20:1; while optimum removal of particulate soils is
obtained with compositions having nonionic:cationic sur-
factant ratios of from about 2:1 to about 9:1, especially
from about 3:1 to about 6.5:1, most especially rom about
3.5:1 to about 5.5:1, with these ratios being particularly
effectiYe where the cationic surfactant used is of the di-
long chain variety disclosed and claimed in Canadian Patent
Application No. 323,240 of A.P. Murphy, filed March 12, 1979.
The compositions of the present inYentiOn are prefer-
ably formulated so as to have a pH of at least about 7 in
the laundry solution, at conventional usage concentrations,
in order to optimi2e their o~erall cleaning performance, to
aid in their manufacturina and pro~essing, and to minimize
the possibility of washing machine corrosion. Alkalinity
sources, such as potassium hydroxide, potassium carbonate,
potassium bicarbonate, sodium hydroxide, sodium carbonate,
and sodium bicarbonate, may be included in the compositions
for this purpose. So~e of the cationic/nonionic systems of
.~33L~
-- 7
the presen-t invention may attain optimum removal of greasy/
oily soils at higher pHs, while attaining optimum partic-
ulate removal at relatively lower pHs. In these systems,
overall performance may b~ enhanced by varying the pH of the
5 wash solution during the laundering proces~. Particularly
preferred compositions have a pH of at least about 8 in the
laundry solution in order to optimize the removal of greasy/
oily and body soils. In addition to the higher pH in the
laundry solution, these preferred compositions should also
10 have the ability to maintain a pH in the laundry solution of
from about 8 to 11 throughout the washing operation ~reserve
c alkalinity). Such a reserve alkalinity may be obtained by
incorporating compounds which buffer at pHs of from about 8
to 11, such as monoethanolamine, diethanolamine, and tri-
15 ethanolamine.
Preferred compositions of the present invention are
also essentially.free of oily hydrocarbon materials and
solvents, such as mineral oil, para~fin oil and kerosene,
since these materials, which are themselves oily by nature,
20 load the washing liquor with excessive oily material,
thereby diminishing the clean.ing effèctiveness of the
compositions themselves.
Nonionic Component
-
Nonionic surfactants, having H~Bs of from about 5 to
~5 about 17, preferably from about 8O5 to about 14, more
pre~erably from about 10 to about 13.5, which are conven-
tionally used in detergent compositions, may be used in the
compositions of the present invention. Such surfactants
include the condensation product of 1 mole of a saturated or
30 unsaturated, straight or branched chain carboxylic acid
having from about 10 to about 18 carbon atoms with ~rom
about 5 to about 50 moles of alkylene (particularly ethylere)
oxide; the condensation product of 1 mole of saturated or
unsaturated, straight or branched chain alcohol having from
about 10 to about 24 carbon atoms with from about 5 to about
50 moles of alkylene (especially ethylene) oxide; poly-
ethylene glycols having a molecular weight of from about 400
to about 30,000; and the condensation product of 1 mole of
., .. . ~, . .
~ r 7
~3~
alkyl phenol wherein the alkyl chain contains from a~out 8
to a~out 18 carbon atoms with from about 4 to about 50 moles
of alkylene (especially ethylene) oxide. Further disclosure
of nonionic surfactants useful in the present invention is
found in U.S. Patent 3,862,058, Nirschl and Gloss, issued
January 21, 1975,
Preferred nonionic surfactants for use in the composi-
tions of the present invention, because of their excellent
biodegradability and performance characteristics, have the
formula RtoC2H4)noH, wherein R is a primaxy or secondary,
straight or branched alkyl chain containing an average of
from about 8 to about 22, preferably from about 10 to about
20, carbon atoms, and n is an average of from about 2 to
about 12, preferably from a~out 2 to about 9, especially
from about 2 to about 7. ~here di-long chain cationic
m~terials are used in the compositions of the present
invention, it is especially preferred that the R group in
the nonionic surfactant contain from about 10 to about 16
carbon atoms. The nonionic suractants described herein have
an ~LB (hydrophilic-lipop}lilic ba.lance) of from about 5 to
~bout 17, preerably from about 8.5 to about 14, and most
preferably from about 10 to about 13.5. HLB, an indicator
of a surfactants hydrophilic or lipophilic nature, is
defined in detail in Non onic Surfactants, by Mo J~ Schick,
Marcel Dekker, Inc., 1976, pp. 607,613.
Preferred nonionic surfac~an~s for use in the present
invention include the condensation product of C10 alcoh~l with 3
moles of ethylene oxide, the condensation product o coconut
: 3V alcohol with 5 or 7 moles of ethylene oxide, the co~densation
product of tallow alcohol wi~h 6, 9, or 11 moles of ethylene
oxide, the condensation product of.secondary C15 alcohol with
5 or 9 moles of ethylene oxide, the condensation product of
C12_13 alcohol with 3, 4, 5, 6.5, or 9 moles of ethylene
oxide, the condensation product of Cl~ 15 alcohol with 7 or
9 moles of ethylene oxide, the condensation product of C12
alcohol wit~ 5 moles of ethylene cxide, the condensation
`. 3L~31$~
product of Cl4-15 alcohol with 3, 4, 5, 7, or 5 moles of
ethylene oxide, and mixtures thereof.
A preferred class of surfactants utilizes alcohols
which contain about 20% of 2-methyl branched isomers, and
are commercially available under the trade mark "Neodol", from
the Shell Chemical Company. Particularly preferred nonionic
surfactants for use in the compositions of the present
invention include the condensation p-oduct of ClO alcohol
with 3 moles of ethylene oxide, the condensation product of
Cl2 13 alcohol with about 3 moles of ethylene oxide, and the
same product which is stripped to remove substantially all
lower ethoxylate and nonethoxylated fractions, the conden-
sation product of Cl4_l5 alcohol with 7 moles of ethylene
oxide, the condensation product of Cl~ 13 alcohol with 6~5
moles of ethylene oxide, the condensation product of Cl2
alcohol with 5 moles of ethylene oxide, the condensation
product of coconut alcohol with 5 moles of ethylene oxide,
the condensatiQn ~x~ct of C12_13 alcoho:Lwith 9 moles of ethylene
oxide, the condensation product of Cl4 15 alcohol with 3
moles of ethylene oxide, the condensation product of Cl~ 15
alcohol with 4 moles o ethylene oxide, the condensation
product of C14 15 alcohol with 9 moles of ethylene oxide,
: and mixtures thereofO
~ Where optimum particulate soil removal performance is
; 25 sought, it is preferred ~hat cationic surfactants used are
of the di-lon~ chain variety and that the nonionic sur-
factant be selected from the group consisting of the con~
densation product of Cl4 15 alcohol with 2.25 moles of
ethylene oxide, the condensation product of Cl4 15 alcohol
- 30 with 7 moles of ethylene oxide, the condensation product of
Cl2 15 alcohol with 7 moles of ethylene oxide, the con-
densation product of C12 15 alcohol with 9 moles of ethylene
oxide, the condensation product of Cl2_l3 alcohol wi
moles of ethylene oxide, and the same product which is
stripped so as to remove lower ethoxylate and nonethoxylated
fractions, the condensation product o Cg 11 alcohol with 8
moles of ethylene ~oxide, which is stripped so as to remove
_............................................................ . r-
.
9~
- ln ~
lower ethoxylate and nonethoxylated fractions, the con-
densation product of coconut alcohol with 5 moles of ethylene
oxide, the condensation product of coconut alcohol with 6
moles of ethylene oxide, -the condensation produc~ of tallow
alcohol with 9 moles of ethylene oxide, and mixtures thereof.
The compositions of the present invention may contain
mixtures of nonionic surfactants falling within the above
preferred nonicnic surfactant,deinition, such as a mixture
of the condensation product of C12 13 alcohol with 6.5 moles
of ethylene oxide with the condensation product of C14 15
alcohol with 7 moles of ethylene oxide, in a ratio o~ from
i about 4:1 to about 1:4. The present invention may also
contain mixtures of nonionic surfactants r some o~ which do
I not fall within the above preferred nonionic surfactant
definition (such as alcohol ethoxylates having an average of
greater than about 12 ethylene oxide groups per molecule),
~ and in such mixtures it i5 preferred that at leas~ one of
- the nonionic surfactants contained in the mixture falls
' ' within'the above preferred nonionic surfactant definition
and that this preferred nonionic surfactant (or mixture of
surfactants) be included in an amount such that it falls
i within the nonionic/cationic ratio range required herein.
- - ~here the nonionic surfactant mixture contains a non}onic
surfactant (or surfactants) which falls outside of the above
preferred nonionic surfactant definition, it is preferable
that the ratio of the surfactant (or surfactants) within the
definition to those outside the definition be within the
- xange of from about 1:1 to about 10:1.
In addition to the required nonionic surfactant,
preferred nonionic surfactant mixtures also contain alkyl
glyceryl ethers. Particularly preferred are glyceryl ethers
having the formulae: .
R-0CH2CH-CH2OH and R-O(CH2CH2O)ncH2cHcH2OH
QH OH
wherein R is an alkyl or alkenyl group of from about 8 to
35 about 18, preferably from about 8 to 12~ carbon atoms or an
alkaryl group having from about 5 to 14 carbon atoms in the
alkyl chain, and n is from 1 to about 6. These compounds
may be used together with the nonionic surfactant component
of the present invention, in a ratio o nonionic surfactant
to glyceryl ether of from about 1:1 to abou~ 4:1, partic-
S ularly about 7:3. Glyceryl ethers of the type useful in thepresent invention are disclosed in U.S. Patent 4,09~,713,
Jones, issued July 4, 1978, and U.S. Patent No. 4,206,070
of Jones, granted June 3, 1980.
Another preferred group of nonionic surfactants useful
herein comprises a mixture of "surfactant" and "co-sur-
factant", containing at least one nonionic surfactant
~alling within the definition of the nonionic surfactants
preferred herein, as described in Canadian Patent No.
1,059,865 of Jerome H. Collins, granted August 7, 1979.
Cationic Component
The cationic surfactants used in the compositions of
~ the present in~ention have the formula RlR2~LZ wherein each
R is an oxganic group containing ZL $traight or branched
aIkyl or alkenyl group optionally substituted with up to
three phenyl or hydroxyl groups, and optionally interrupted
by up to four structures selected from the group consisting
of:
O O O R~ R2O
Il 1~ 11 1 1 ~ :.
~t c o o c -C-N-, -N-C-,
O H H O O g H H O
Il ~ i 11 11 11 1 1 11
-C-N-, -N-C-, -O-, -O-C-O-, -O-C-N-. -N-C-O-,
and mixtures thereof~ and which contains from about 8 to 22
carbon atoms, and which may additionally contain up to 20
ethylene oxide groups, and m is a number from 1 to 3~ R2 is
an alkyl or hydroxy alkyl group containiny from 1 to 4
carbon atoms, or a benzyl group with no more than one R2 in
~ 12 -
a molecule being benzyl, and x is a number from 0 to 11,
preferably from 0 to 6. The remainder of any carbon
positions on the ~ group are ~illed by hydrogens. Y is
selected from the group consisting of:
(l) -N+- ,
~ N - C-
(2) -C~
N - C -
I
(3) -p~_
~4) -S -
.
(5) -N+- , wherein p is from 1 to 12,
(C2H~O)pH
(C~H40)pH
~6) -N - , wherein each p is from l to 12,
(~2H40) H
. .
C~H40~pH
(7) -N -(C2H40)pH, wherein each p is from l to 12,
(C2~40)pH
C \ /
~8) ~C
C
C
/ ~/
(9) N +N t and
C C
N
~,, i
~3~
13 -
~10) mixtures t~ereof;
; L is 1 or 2~ with the Y groups being separated by a moiety
selected from the group consisting of Rl and R2 analogs
(preferably alkylene or alkenylene~ having from one to about
twenty-two calbon atoms and 2 ~ree carbon single bonds when
L is 2. Z is a water-soluble anion such as halide, methyl
! sulfate, sulfate, or nitrate anion, particularly preferre~ I
! anions being chloride, bromide, iodide, sulfate, or methyl
sulfate, in a number to give electrical neutrality of the
j 10 cationic component.
~ The particular cationic component to be included in a
! given system depends to a large extent upon the particular
¦ nonionic componen-t to be used; it is selected such that it
is at least water-dispersible when mixed with the nonionic
1 15 surfactant. The cationic surfactant is chosen, in light of
t the paxticulax nonionic surfactant used, in order to satisfy
the cloud point requirements of the detergent composition,
discussed below. Mixtures of these cationic materials may
also be used in the compositions of the present invention.
20 Preferred cationic surfactants are those having critical
micelle concentrations of less than about 500 ppm,
especially less than about 100 ppm.
In preferred cationic materials, L is equal to 1, p is
from 1 to 12, pre~erably from 1 to 10, and Y is
C ~ H4~)p~
- C ~C2H4)p~ (C2H4O)pH
or mixtures thereo~. However, L may be equal to two r
thereby yielding cationic components containing two cationic
charge cen-ters. An example of a di-cationic component is
given below:
Z CH3 1 3
C18H35 I CH2-CH2-CH2-N -CH3
CH3 CH3
.
1~31L~9Z
- 14 -
Other cationic materials which are useful in the compo-
sitions of the present invention include phosphonium and
sulfonium materials.
Additional cationic surfactants useful in the compo-
S sitions herein are disclosed in U.S. Paten~ No. 4,259,217
Murphy, issued March 31, 1981.
A particularly preferred type of cationic component,
which is described in U.S. Patent No~ 4,260,529, Letton,
granted April 7, 1981.
R2-(Zl)a~(R3)n-Z2-(CH2)m-N~-Rl X
Rl :
wherein Rl is Cl to C4 alkyl ox hydroxyalkyl; R2 is C5 to
C30 straight or branched chain alkyl, alkenyl, alkylbenzyl
or alkyl phenyl, or
1 + 1
X R - N-(CH2)s- ; wherein s is from ~ to 5;
11
R 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; Z and Z
are each selected from the group consisting of
O O O O Q H H O O H H O
-C-, -C-O-, -O-C-, -O-, -O-C 0-, -C-N-, -N-C-, -O-~-W~, -N-C-O-,
and wherein at least one of said zl or z2 groups i5
O O O H H O
-c-o, -o--, -C-N-, or -N-~-;
and X is an anion which makes the compound at least water-
dispersible, preferably selected from the group consisting
. . . j.
.
. ~
~3~
- 15 - .
of halide, methyl sulfate, sul~ate, and nitrate, more ~'
preferably chloride, bromide, iodide, methyl sulfate and
sulfate.
Particularly preferred cationic surfactants o this t:
type are the choline ester derivatives having the following
formula: ~
O CH ~-
R2-C-O-CH2CH2-N~-CH3 X
CH3
~ J
as well as those compounds in which the -C-0- linkase in the
¦ above formula is replaced with
O O H H O
1~ p t - t 11 -
-O-C, -C-N-, or -N-C-.
¦ Particularly preferred examples of this type of cat~
I ionic surfactant include stearoyl choline ester quaternary
¦ ammoni~um halides (R2 = C17 alkyl), palmitoyl choline ester
. quaternary ammonium halides ~R = C15 alkyl), myristoyl
choline ester quaternary ammonium halides ~R = Cll alkyl~,
and tallowyl chGline ester quaternary ammonium halides tR~ =
C~-C17 alkyl).
Additional preferred cationic components of the choline
ester variety are given by the structural formulas below,
wherein p mày be fro~ 0 to 20.
O O CH
R -o-~-(cH2)p-c-o-cH2cH2-~-cH3 X
CH3
X CH3-~ -C~2-CH2-O-C-(CH2)p-C-O-C~-CH2-~ -CH3 X
~H3 C~3
. ... ~
~3~
~ 1 6 -- ,
The preferred choline-derivative cationic substances,
discussed above, may be prepared by the direct esterifi-
cation of a fatty acid of the desired chain length with
dimethylaminoethanol, 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 o~ a long chain fatty acid of the
desired chain length together with 2-haloethanol, in the
presence of an acid catalyst material~ The reaction product
is then used to quaternize trimethylamine, forming the
desired cationic component.
Another type o~ novel, particularly prefexred cationic
material, described in U.S. Patent No. 4,228,042, Letton,
granted October 14, 1980 has the formula:
R Rl
R3-o~(CH)no]y-(Zl)a~ R4)'t-Z2-(C~12)m-N -Rl X
In the abo~e formula, each Rl is a~ Ci to C4 alkyL or
hydroxyalkyl group, preerably a m~st~yl group. Each R2 is
either hydrogen or Cl to C3 al~yl, preferably hydrogen. R
is a C4 to C30 straight or branched chain alXyl or alkenyl,
prefera~ly a C8 to C18 alkyl group, most prefera~ly a C12
alkyl group. R4 is a Cl to C10 alkylene or a~kenylene
group. n is from 2 to 4, preferably 2; y is from 1 to 20,
2S preferably from about 1 to 10, most preferably about 7; a
- may be 0 or 1, and t may be 0 or 1, but t is 1 when a is 1;
and m is from 1 to S, preferably 2. Z is selected from the
group consisting o
~ IT p O H H o ~ ~
-O-C-, -C-O-, -C-, ~O-, -O-C-O-, -C-N-, -N~C-, -O-C-N-,
u o O O H
-N C-O-; zl is -C- or -C-N-; and at least one of zl
and z2 groups is selected from the group consisting of
~13 3 ~
- ~7 -
O O O H H O
Il ~I 11 ~ l 11
-O-C-, -C-O~, -C-N-, -N-C-. X is an anion which makes the
compound at least water dispersible, and is selected from
the group consisting of halides, methyl sulfate, sulfate,
and nitrate, particularly chloride, bromide iodide, methyl
sulfate and sulfate. Mixtures of the above structures can
also be used.
Where pa.ii~ulate soil removal is to be optimized, it
is preferred that the cationic surfactants used are of the
di-long chain quaternaxy D onium type, having two chains
which contain an average o from about 12 to about 22,
preferably from about 16 to about 18 carbon atoms. The
remaining groups, if any, attach to the quaternary nitrogen
atom, are preferably Cl to ~4 alkyl or hydroxyalkyl groups.
Although it is preferred that the long chains be alkyl
groups, these chains may contain hetero atoms or other
linkages, such as hydroxy groups, double or triple carbon-
carbon bonds, and ester, amide, or ether linkages, as long
as each chain falls with the preferred carbon atom ran~es
given above. Cationic surfactants of this type are
disclosed in Canadian Patent Application Serial No. 323,240
of A.P. Murphy, filed March 12, 1989. Preferred cationic
surfactants are those having the formulae:
3 f~N - CH2
~4 N+ R2 X~ or Rl-c ¦
R N - CH
R~ ~3
wherein the Rl and R2 groups contain an average of xom
about 16 to about 22 carbon a~oms, preferably i5 alkyl
groups, and most preferably contain an average of from about
16 to about 18 carbon atoms, R3 and R4 are Cl to C~ alkyl or
hydroxyalkyl groups, and X is any ~ompatible anion~ partic-
ularly one selected from the group consisting of halide,hydroxide, m~thyl sulfate, or acetate anions.
~3~
- 18 -
Preferred cationic surfactants include ditallowalkyl-
dimethyl (or diethyl or dihydroxyethylj ammonium chloride,
ditallowalkyldimethylammonium methyl sulfate, dihexadecyl-
alkyl (C16) (also known as distearyl), dimethyl (or diethyl,
5 or dihydroxyethyl) ammonium chloride, dioctadecylalkyl (C18)
dimethylammonium chloride, dieicosylalkyl ~C20) dimethyl-
ammonium chloride, methyl~ tallowalkylamiao ethyl (2)
tallowalkylimidazolinium methyl sulfate (commercially
available as ~;A~iso~t 475 from Ashland Chemical Company), or
mixtures of those surfactants. Particularly preferred
cationic surfactants are ditallowalkyldimethylammonium
chloride, ditallowalkyldLmethylammonium methyl sulfate,
methyl(l)tallowalkylamidoe~hyl(2)tallowalkylimidazolinium
methyl sulfate, and mixtures o~ those sur~actants, with
ditallowalkyldimethylammonium chloride being especially
preferred.
Another particularly useful class of cationic sur-
factant is that in which the two long chains of the cationic
surfactant contain a significant amount of unsaturation,
such as where at least about 20~, preferably at least about
30~, of the long chain contain at l~ast one double bondO
Compounds of this type have the fo~mula
..
R3
R4_N+_R2 ~-
Rl
wherein Rl and R contain an average of Erom about 16 to
about 22 (most preferably from about 16 to about 18) carbon
atoms, and at least about 20% of these chains contain at
least one double bond; R3 and R4 are Cl to C4 alkyl or
hydroxyalkyl groups, and X is any compatible anion, partic-
ularly one selected from the group consisting of halide,
hydroxide, methyl sulfate, or acetate anions. Thus, for
example, a preferred cationic surfactant is di-partially
hydrogenated tallow dimethylammonium halide (especially
chloride or methyl sulfate), which is also known as disoftered-
tallowalkyldi.~nethylammonium halide. A commercially available
*Trademark
..
..
-- 19 --
compound of this type is Adogen ~70, sold by Ashland Chemical
Company, wherein about 30% of the tallow chains are oleyl in
character. Compositions made with these cationics showed
several significant advantages over those made with more
conventional cationics (such ditallowalkyldimethyl~nonium
chloride), particularly those compositions show improved
particulate soil removal, especially at low wash temperatures,
improved static control, and remain in a stable single phase
at temperature~ down to about 40F.
Utilizing the nonionic and cationic components, defined
above, preferred compositions of the present invention may
be formulated using the guidance provided by the reduced
monomer concentration of the cationic component ~CR) in the
laundry solution. Specifically, the selection of a CR value
for a given nonionic and cationic surfactant pair will
determine the ratio in which to combine those surfactants.
A given nonionic~cationic surfactant pair will ~ive its best
particulate or grease~oil removal performance when it is
formulated to have a CR value which falls within the ranges
defined herein. The reduced monomer concentration of a
surfactant is obtained by dividing th~e concentration of the
surfactant monomer present in the laundr~ solution by the
critical micelle concentration (CMC) of that sur~actant As
used in this application, CMCs are aetermined at 105F in
water containing 7 grains/gallon of mixed ~2 1; ~a M
hardness, unless otherwise stated.
The concept of reduced cationic monomer concentration
is explained in detail in U.S. Patent No. 4,259,217,
Murphy, granted March 31, 1981; Tamamushi and Tamaki,
Proceedings o~ the Second International Congress of Surface
Activity, III, 449, Academic Press, Inc. (1957); and Clint,
J. Chem. Soc~ ~ar. Trans., I, 71, 1327 ~lg75)
The reduced cationic
monomer concentration of the nonionic/ cationic surfactant
~5 mixture is defined by equations (a) through (c), below~ In
systems where grease/oil removal i5 to be optimized it is
preferred that the CR value of the nonionic/cationic sur-
: factant mixture be in the range of from about 0.002 to abou~
*Trademark
_. . r-
- 20 -
0.2, especially from about 0.002 to about 0.15/ most pre-
ferably from about 0.002 to abou-t 0~08. In compositions
wherein the particulate,soil removal capabilities are to be
optimized, it is preferred that the nonionic/cationic
surfactant mixture have a CR of from 0.005 to about 0.2,
especially from about 0.008 to about 0.15, most preferably
from about 0.01 to about 0.1. It is in the area of overlap
(i.e., CR equals about 0.005 to about 0.2) of these CR
ranges that th~ compositions of the present invention yield
bo~h optimum particulate and greasy/oily soil removal.
In the following equations these abbreviations are
used:
Cl = critical micelle concentration o nonionic
: surfactant (moles per liter~
15 C2 critical micelle concentration o cationic
surfactant (moles per liter)
= a-,constant based upon the heat of mixing = -
2.8
e = base, of Napierian logarithm system 3
2.71828
x = mole fraction of the n~onionic surfactant in
the micelle at concentration C
f = nonionic activit~2coeficient in the mixed
' ' 1 micelle = e~ X)
f2 ~ cationic acti~ity coefficient in the mixed
' micelle = e
~ = f2C2 -flCl
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
Y - weight fraction of nonionic surfactant in the
composition
~here a desired CR value or range is selected, and ~,
Cl ~ C2 , Ml and M~ are known for given nonionic/cationic
surfactant pair, the corresponding nonionic:cationic ratios(s)
-: is calculated as follows:
,. ' ' I
~3
- 21 -
~a) fox a given nonionic surfactant, cationic sur-
factant, and for each end of the CR ran~e desired,
solve for x using the equation
x2
~l-x~ R
by standard numerical iterative techniques to an
error in x of less than OoO01;
~b) find the range of Y from the equation
---- -- = [X (X~
Ml M2 W
using 100 ppm and 10,000 ppm as the boundary
values for W, for each end of the desixed C~
range;
(c) the nonionic/cationic ratio(s) (NCR) corresponding
to the CR value or range selected is then obtained
~ by substituting the boundary values for Y into the
~ormula
. NCR _ lYy
In addition to these reduced cationic monomer concen-
tration criteria, compositions which give the best per-
formance on greasy/oily soils also satisfy specific cloud
~ 20 point requirements, given below, and detailed in U.S. Patent
: No. 4,~59,217r Murphy, granted March 31, 1981.
Thus, these pxeferred
compositions have nonionic/cationic mixtures which exhibit a
cloud point between about 10C and 70C, more preferably
- 25 between about 20C and 70C, especially between about 30~C
and!about 50~C. The compositions will exhibit their best
grease/oil xemoval performance when the temperaturP of the
wash solution in which they are used falls within about
20C, preferably within about 15C, and most prefexably
within about 10C, of the cloud point of the nonionic/
cationic surfactant mixture .
~. . , r~
'
~ ~ 3~
- 22 -
As used herein, the term "cloud point" means -~he
temperature at which a graph plotting the light scattering t
intensity of the composition versus wash solution temper-
ature begins to sharply increase to its maximum value, under
5 the following experimental conditions: j
Il The light scattering intensity is measured using a
j Model VM-12397 Photogoniodiffusometer, manufac~ure~ by
Societe Francaise A I instruments de controle ek a 'analyses,
France (the instrument being hereinafter referred to as
10 (SOFICA). The SOFICA sample cell and its lid are washed
with hot acetone and allowed to dry. The surfactant mixture
is made and put into solution with distilled water at a
concentration of 1000 ppm. Approximately a 15 ml. sample of
the solution is placed into the sample cell, using a syringe
15 with a 0.2~ nucleopore filter. The syringe needle passes
through the sample cell lld, so that the cell interior is
not expoc!ed to atmospheric dust. The sample is kept in a
variable temperature bath, and both the bath and the sample
are subject to constant stirring. The bath temperature is
~ heated using the SOFICA's heater and cooled by the addition
; of ice (heating rate 1C/minute); the temperature of the
sample is determined by the t~peratuxe o~ the bath. The
light scattering (90 angle intensity of the sample is then
determined at various temperatures, using a green filter and
25 no polarizer in the SOFICA.
Builder Mixture
The detergent compositlons herein contain from abou~ 5
to about 99%, preferably from about 20% to about 60%~ by
weight of a detergency builder mixture. The builder mix~ure
3~ consists essentially of:
(i) a water-insoluble aluminosilicate material se-
lected from the group consisting of
(1~ Zeolites A, X, or P~B), or mixtures thereof,
having a particle size diameter of from about
On Ol microns to about 25 microns and contain-
ing at least 10% water of hydration, and
(2) amorphous h~drated aluminosilicàte makerial
~ T
~;3
-- 23 --
of the empirical fonmulao
Mz~zAlO2 ySiO2)
wherein M is sodium, potassium, ammonium, z
is from about n. 5 to about 2, y is 1, said
material having a particle size dia~,eter of
less than about 100 microns, a magnesium ion
exchange capacity of a. least about 50
milligrams equivalents of CaC03 hardness per
gram of anhydrous aluminosilica~e, and a Mg~t
exchange rate of at least about 1 grain/
gallon/minute~gram~gallon, and
(3) mixture.~ thereof; and
(ii) a polycarboxylate builder material;
wherein.the weight ratio of the aluminosilicate mater~
~al to the polycarboxylate materia~ is from about 1:10
to about 10~
Preferably, the weight ratio of the aluminosilicate
material to the polycarboxylate material is from about 1:4
to about 4:1, more preferably from about 1:~ to about 2:1.
Preferably, the aluminosilicate materials for use
herein are those commonly known as Zèolites A, X, and P(B~.
The zeolites should contain at least 10% water of hydration
~nd should have a particle siæe diameter of from abou~ 0.
microns to about 25 microns, preerably rom about 0~1
microns to about 10 microns, more prefexably from about 0.5
microns to about 2 microns. Aluminosilicate materials are
more fully descri~ed in U.S. Patent 4,096,081, Phenicie et
al~ issued June 20, 1978,
The amor- .
phous aluminosilicate materials suitable or use herein are
fully described in U.S. Patent No. 4,180,485, Llenado,
granted December 25, 1979.
~xamples of suitable polycarboxylate builder materials
for use herein are (1) water-soluble aminopolycarboxylates~
,, .
~13~9
-- 2~ --
e.g., sodium and potassium ethylenediaminetetraacetates, (2
the water-soluble salts of phytic acid, e.g., sodium and
potassium phyta~es, disclosed in U.S. Patent No. 2,739,942,
Eckey, issued March 2~, 1956,
(3j the polycarboxylate materials described in
U.S. Patent 3,364,103; and (4) water-soluble salts of
polycarboxylate polymers and copolymers as described in U.S.
Patent No. 3,308,067, Diehl, issued March 7, 1967,
A useful detergent builder which may be employed in the
present invention comprises a water-soluble salt of a
polymeric aliphatic polycarboxylic acid having the following
structural relationships as to the position of the carboxy-
late groups and possessing the following prescribed physiGal
charactexistics: (a3 a minimum molecular weight of about 350
calculated as to the acid form; (b1 an equivalent weight of
about 50 ,o about 80 calculat~d as to acid form; (c) at
least 45 mole percent o~ the monomeric species having at
least two carboxyl radicals separated from each other by not
more than two carbon atoms; (d) the site of attachment of
the polymer chain of any carboxyl-containing radical being
separated by not more than three carbon atoms along the
polymer chain from the site of attachment of the next
carboxyl-containing radical. Spec:ific examples of the
above-described builders include polymers of itaconic acid,
aconitic acid, maleic acid, mesaconic acid, fumaric acid,
methylene malonic acid and citraconic acid and copol~mers
with themselves.
In addition, other builders which can be used satis-
factorily include water-soluble salts, especially the sodium
and potassium salts, of mellitic acid, citric acid, pyro-
mellitic acid, benzene pentacarboxylic acid, oxydiacetic
acid~ carboxymethyloxysuccini acid, carboxymethyloxymalonic
acid, cis-cyclohexanehexacarboxylic acid9 cis-cyclopenta-
netetracarboxylic acid and oxydisuccinic acid.
It is to be understood that while the alkali metalsalts of the foregoing inorganic and organic polyvalent
anionic builder salts are preferred ~or use herein from an
.. .
~31~9;2
- 25 -
economic standpoint, the ammonium, alkanolammonium, e.g.,
triethanolammonium, diethanolammonium, and the like,
water-soluble salts of any of the foregoing builder anions
are also useful herein.
Other suitable polycarboxylates for use herein are ~he
polyacetal carboxylates fully described in U.S. Patent
4,144t226, issued March 13, 1979 to Crutchfield et al, and
U.S. Patent 4,146,495, issued March 27, 1979 to Crutchfield
et al,
These polyacetal carboxylates can be prepared by
bringing together under polymeriæation conditions an ester
of glyoxylic acid ~nd a pol~merization initiator. The
resulting polyacetal carboxylate ester is then attached to
chemically stable end groups to stabilize the polyacetal
carboxylate against rapid depolymerization in alkaline
solution, cor.verted to the ccrresponding salt, and added to
a surfactant. Copending Canadian Patent Application Serial
No. 345,728, Rodriguez et al, filed February 15, 1980,
~0 discloses a builder system containing
these polyacetal carboxylates along with aluminosilicate
b~ilder materials, for use in detergent compositions, which
preferably contain nonionic/cationic surfactants.
Preferred polycarboxylate builders for use in the
present invention are sodium or potassium nitrilotriacetate
or citrate, or mixtures thereof. The compositions of this
invention contain from 0 to about 5% phosphate materials,
and are preferably substantially free of phosphate materials.
~dditional Components
In particularly pr~ferred embodiments oE the present
invention, the detergent compositions additionally contain
from about 2 to about 25%, preferably from about ~ 'o about
16~, and most preferably from about 2 to about 10% o~ A
~atty amide surfactant, such as ammonia amides (e.g.,
coconutalkyl ammonia amide, diethanol amides, and ethoxy-
lated amides~. In relation to the nonionic/ cationic
surfactant system, the ratio of the cationic/ nonionic
mixture to the amide component in the composition is in the
~3~2
-- 26 --
range of from about 5:1 to about 50:1, preferably from about
8:1 to about 25:1. The addition of the amide component
results in a composition which exhibits improved anti-
redeposition of both clay and greasy/oily soils. This
development is described in greater detail in U.S. Patent
No. 4,228,044, Cambre, granted October 14, 1980.
Preferred amides are
C~-C20 monoethdnol amides, ~8-C20 diethanol amides, and
amides having the formula
O H
19 R-C-N-CH2C~20CH2CH2H ~
wherein R is a C8-C20 alkyl group, and mixtures thereof.
Particularly preferred amides are those where the alkyl
group contains from about 10 to about 16 carbon atoms, such
as coconut alkyl monoethanol or diethanol amide. Such
compounds are commercially available under the trademarks
'~uperamide GR,"from Onyx Chemical Co., Jersey City, N.J~,
"Superamide F-3"from Ryco, Inc., Conshohocken, Pa., and
"Gafamide CDD-518,"available from GAF Corp., New York, N.Y.
These amide components may also be added in small
amountsr i.e., from about 2~ to about 5~, to act as suds
modifiers. Specifically, they tend to boost the sudsing in
an active system which exhibits reLatively low sudsing, an~
depress the sudsing in an active system which exhibits
relatively high sudsing.
The compositions o~ the present inven~ion may also
contain addi~ional ingredients generally found in laundry
detergent compositions, at their conventional art-establi~hed
levels, as long as these ingredients are compatible with the
nonionic and cationic components required herein. For
example, the compositions may contain up to about 15%,
preferably up to about 5%, and most pre~erably rom about
O.001 to about 2~, of a suds suppressor component. Typical
suds suppressors useful in the compositions of the present
invention include, but are not limited to, those described
below.
Preferred silicone-type suds suppressing additives are
described in U.S. Patent 3,933,672, issued January 20, 1976,
,.3~ ~3Z
-- 27 ~
Bartolotta et al. The
silicone material can be represented by alkylated poly-
siloxane materials such as silica aerogels and xerogels and
hydrophobic silicas of various types. The silicone material
can be described as a siloxane having the ~ormula:
~ ~'~ .
~ ~ )x
~ 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. Polydimethylsiloxanes tR and R' are
methyl, having a molecular weight within the range of from
about 200 to about 200,000, and higher, are al:l useful as
suds controlling agents. Ad~itional suitable silicone
materials wherein the side chain g~oups R and R' are alkyl,
aryl, ox mixed alkyl and aryl hydrocarbyl groups exhibit
useful Suas controlling properties. Examples of suc~
ingredients include diethyl-, dipropyl~, dibutyl-, methyl-
e~hyl- t phenylmethyl-polysiloxanes and the like. Additional
useful silicone suds controlllng agents can be represented
by a mixture of an alkyla~ed siloxane, as re~erred 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 silanated (most praferably trimethyl-
silanated) silica having a particle size ~n the range from
about 10 millimicrons to 20 millimicrons and a specific
surface area above about 50 m2~gm intimately admixed with
dimethyl silicone ~luid having a molecular weight in the
range from about 5G0 to about 200,000 at a weight ratio of
silicone to silanated silica of from about lY~l to about
1:2. The silicone suds suppressing agent is advantageously
~eleasably incorporated in a water~soluble or water~
dispersible, substantially non-surface-active, detergent-
impermPable carrier.
.. . - r
,
3~ 2
- 28 -
Particularly useful suds supp~essors are t~e self-
emulsifying silicone suds suppressors, described in U.S.
Patent 4,075,118~ Gault et al, issued Februar~ 21, 197B,
An example of such a
compound is DB-544," commercially available from Pow Corning,
which contains a siloxane/glycol copolymex together with
solid silica and a siloxane resin.
Microc-ys alline waxes having a meltin~ point ~n the
xange from 35C-115C and a saponification value of less
than 100 represent additional examples of a prefer~ed suds
regulating component for use in the subject compositions,
and are described in detail in U.S. Patent ~0S6J481~ Tate,
issued November 1, 1~77,
The microcrystalline waxes are substantially water-insoluble,
but are water-dispersible in the presence of or~anic sur-
factants. Preferred microcrystalline waxes have a meltin~
. .
~` point from about 65C to 100C, a molecular ~eigh~ in the
range ~rom 400-1,000; and a penetration value of at least 6,
measured at 77F by ASTM-D1321. ',uitable examples of the
above waxes include: microcrysta]line and oxidized micro-
crystalline petrolatum waxes; Fischer-Tropsch an~ oxidized
Fischer~Tropsch waxes; ozokerite; ceresin; montan wax;
; beeswax; candelilla; an~ carnauba wax.
- Alkyl phosphate esters rep~esent an addition~l pre-
~5 ferred suds suppressant for use herein. These preferred
phosphate esters are predominantly monostearyl p~osphate
which, in addition thereto, can contain di- and tristearyl
phosphates and mo~o-oleyl phosphates, which can contain di-
and trioleyl phosphates.
The alkyl phosphate esters frequently contain some
trialkyl phosphate. Accordingly, a preferred phosphate
ester can contain, in addition to the monoalkyl ester, e.g.
monostearyl phosphate, up to about 50 ~o~e percen~ of
dialkyl phosphate and up to about 5 mole percen~ o~ ~rialkyl
phosphate
Other adjunct components which may be included in the
compositions of the present invention, in their con~entional
art-established levels for use ~i.e., from about 0 to about
*Trademark
. _. - !
~..3~
~ 29 -
40%), include semi-polar nonionic (such as amine oxides),
anionic, zwitterlonic and ampholytic cosurfactants; deter-
gency builders; bleaching a~ents; bleach activatoxs; soil
release agents (particularly copolymers of ethylene tere-
phthalate and polyethylene oxide terephthalate, such as
"Milease r sold by ICI, United States, as disclosed in U.S.Patent 4,132,6~0, Nicol, issued ~anuary 2, 1979
soil suspending agents;
corrosion inhibitors; dyes; fillers; optical brighteners;
germicides; pH adjusting agents~ alkalinity sources; hydro-
tropes; enzymes, enzyme-stabilizing agents; perfumes;
solvents; carriers; suds modifiers7 opaci~iers; and the
like. However, because o~ the numerous and diverse per-
~ormance advantages of the present inVention, certain
conventional componentsl such as cosurfactants and other
detergency builders, as well as fabric softening and static
control agen~s, will not generally be necessary in a par~
ticulax foxmulatlon, giving the compositions of the present
invention a potenti~l cost advantage over conventional
detergent/ softener compositions. I~ fact, ~ecause tha
compositions of the present invention give such outstanding
ciay removal performance across the range of water hardness
conditions, for environmental reasons the compositions of
the present invention contain less than about 5% phosphate
materials. Preferred compositions are substantially or
totally free of such phosphate materials, without decreasing
the perormance of the compositions. Preferred compositions
of the present invention are also substantially free of
carboxymethylcellulose in order to optimize the clay removal
performance of the system. Finally~ while the compositions
of the present invention may contain anionic materials, such
as anionic surfactants and hydrotropes ~e.g., alkali metal
toluene sulfonates), it is preferred that particular anionic
materials be contained in amounts sufficiently small such
that not more than about 10~, pre~erably not mor~ than about
5%, of the cationic surfactant, contained in the laundry
solution, is complexed by the anionic material. Such a
complexing of the anionic material with the cationic
*Trademark
r
L3L3~ Z
-- 30 --
surfactant, decreases the overall cleaning and fabric
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 dissociation constant).
Thus, when an anionic mat~rial has a dissociation constant
of at least about l x 10 (such as sodium toluene sul-
fonate), it may be contained in an amoun~ up to about 40%,
by weight, of the cationic surfactant; where the anionic
material has a dissociation constant of at least about l x
10 5, but less than about l x 10 3, it may be contained in
an amount up to about 15~, b~ weight, of the cationic
surfactant; and where the anionic material has a dissoci-
ation constant of less than about l x lQ 5 (such as sodium
Cll 8 linear alkylbenzene sulfonate), it may be contained
only in amounts up to about 10%, by weight, of the cationic
surfactant. Preferred compositions are subs`tantially free
of such anionic materials.
Examples of cosurfactants and detergency builders which
; 20 may be used in the compositions of the present invention are
found in U.S. Patent No. ~,717,630, Boo~h, issued February
20, 1973, and U.S. Patent No. 4,259,217 of A.P. Murphy,
issued March 31, 1981. However, these components, partic-
; 25 ularly the anionic surfactants, should be checked with the
particular nonionic/cationic surfac~ant system chosen, and
used in an amount, so as to be certain that they will be
compatible with the nonionic/cationic surfac~ant system.
The compositions of the present invention may be
produced in a variety of forms, includin~ liqui~, solid,
granular, paste, powder or substrate compositions. ~re-
ferred substrate articles may be formulated according to
U.S. Patent No. 4,170,565 of Flesher et al granted
October 9, 1979. In
a particularly preferred embodiment, the compositions of the
present invention are formulated as liquids and contain up
to about 20~ of a lower alkyl (Cl to C4~ alcohol, partic-
ularly ethanol. Liquid compositions containing lower levels
~ ., - ~
~31~9~
- 31 -
of such alcohols (i.e., about 7 to 12~) tend to exhibit less
phase separation than compositions containing higher alcohol
levels. Granular compositions herein may also contain up to
! about 15~ by weight of alkali metal silicates, especially
sodium silicate (2.0 ratio), to increase flowability and
physical stability of the granules.
¦ The compositions of the present invention are used in
¦ the laundering process ~y fonning an aqueous solution
containing from about 0.01 (100 parts per million) to abou~
0.3~ (3,000 parts per million), preferably from about 0.02
to about 0.2%, and most preferably from about 0.03 to about
0.15%, of the detergent compositions defined herein, 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 outstanding
particulate and greasy/oily soil removal, togethex with
fabric softening, static control, colox fidelity, and dye
~ transfer inhibition benefits, without requiring the use of
; any of the other conventionally used fabric softening
; 20 and static control laundry additives~
; All percentages, parts, and ratios used herein are by
weight unless otherwise specified.
The following nonlimiting examples illustrate the
compositions of the present invention.
,
- 32 -
EXAMoeLE _
Identical clay-soiled cotton, polyester~cotton, and
polyester swatches were washed in aqueous solutions having
dissolved therein: 500 parts per million (ppm) of a sur-
factant mixture containing 4.5 parts of the nonionic sux-
factant C12 13 E6 5 (condensation product o C12 13 alcohol
with 6.5 mole~ of ethylene oxide, commercially available
as Neodol 23-6.~'from Shell Chemical Company) and 1 part
of the cationic surfactanttdihydrogenated tallowalkyl di-
methylammonium chloride); 600 ppm of the builder or buildermixture listed below; and 87 ppm of monoethanol amine.
~he swatches were washed for lO'minutes in a miniature ,
agitator containing 1-1/2 gallons of washing liquor at
100F and artificial water hardness (2 moles Ca~ to 1
mole Mg~+) at levels of 2, 7 and 1~ grains per gallon.
The swatches comprised approximate:Ly 4% by weight of the
washing liquor. After washing, the swatches were spun ary
and rinsed with 1-1/2 gallons of water, at lOO~F, having
the same water hardness as that of the water they were
washed in. The swatches were then dried in a miniature
electric dryer. A Hunter Reflectometer was used to obtain
` a~reflectance reading (in Hunter Whi'teness Units) for each
of the laundered swatchesn A higher reflectance reading
indicates greater cleaning effectiveness. The results
were as foll`ows: , . ... .
Fabric Water''Hardness' Hunter Whiteness Units
, .. . . .. . .
Solution_Containing 600 p;~ Sodium Citrate
Cotton2 gr./gal. 20.37 ~ 2.69
~ 7 gr./gal. 18.59 ~ 1.40
..12 gr./gal. 11.50 ~ 1.19
Polycotton2 gr.~gal. 63.47 ~ 2.13
n 7 gr./gal. 62.17 ~ 0.31
"12 gr./gal. 55.85 ~ 0~59
Polyester2 gr./galO 74.35 -~ 1.05
~ 7 gr.Jgal. 72.65 ~ 1.13
"12 gr./gal. 70.75 ~ 1.05
*Trademark
113~B$~2
- 33 -
Solution Containing 600 ppm Sodium Nitrilotriacetate
Cot~on2 gr.~gal. 27.88 f 1,49
"7 gr.~gal. 24.71 + 1.26
"12 gr./gal. 15O84 ~ 1.68
Polycotton 2 gr./gal. 65.35 ~ 1.91
7 gr./gal. 63~55 _ 0.~2
"12 gr./gal. 58.35 + 0.84
Polyester 2 gx./gal. 81.14 1.34
"7 gr./gal. 80.38 ~ 0.48
"12 gr./gal. 75.95 ~ 1.17
Solution Containing 600 ppm Po-lyacetal Carboxylate*
Cotton2 gr./gal. 28.60 ~ 0.30
7 gx./gal. 24.98 ~ 0.69
"12 gr./gal. 15.94 ~ 0.96
15 Polyco~ton 2 gr~/gal. 59.86 ~ 1.34
gr./yal. 56.5~ + 3.07
"12 gr./gal. 50.08 + 3.12
Polyester 2 gr./gal. 70.06 ~ 0.83
"7 gr./gal. 61.55 + 0.81
~ `12 gr./gal. 4~45 + 2.04
Solution Containing 600 ppm Sodium Mellitate
Cotton2 gr./gal~ 21.82 ~ 0.39
"7 gr./gal. 16.2~ + 2.Ç3
"12 gr./gal. 14.72 ~ 1.17
25 pOlycotton 2 gr./gal. 62.43 0.37
n7 gr./gal. 56.50 ~ 0.67
" ~12 gr./gal. 59.41 + 1.00
Polyester 2 gr./gal. 74.00 ~ 1.84
. . n .7 gr./gal. 73.64 + 0.18
"12 gr./gal. 65.46 ~ 1.23
Solution Cont:aining 600 ppm Zeolite ~**
Cotton2 gr.~gal~ 17.35 ~ 2.51 -~
-7 gr./gal. 11.43 ~ 1~37
~12 gr./gal. 7.57 ~ 1.90
* 1,
CH3CH2 I -C - O CH-OCH2CH3;n = 86 (average)
CH3 COONa ~ CH3
Hydrated, particle dîameter 1-10 microns ~same through-
out this Example) r
~13~
34
Polycotton2 gr./gal. 55.54 ~ 1.34
7 gr./gal. 48.37 + 1.43
" 12 gr./gal. 57.94 ~ 0.75
Polyester2 gr./gal. 71.65 ~ 0.86
" 7 gr./gal. 71.~0 ~ 0.76
" 12 gr./gal. 69.17 ~ 1.53
.
~ S~lution Containing 600 ppm Zeolite X***
_.
Cotton2 gr.~gal. 19.02 ~ 1.50
" 7 gr./gal. 14.77 + 2.04
" 12 gr./gal. 14.29 ~ 1.21
Polycotton2 gr./gal, 54.73 ~ 1.09
" 7 gr./gal. 50.89 ~ 4~47
" 12 gr.~gal. 59.41 ~ 1.34
~ ~ - - Polyester2 gr.~gal. 71.9~ ~ 0.98
; 15 - 7 gr./gal. 71.32 ~ 1.36
n 12 gr./gal. 70.~9 ~ 0~72
Solution Containing 30-0 ppm Zeolite A and
300 ppm Sodium Nitrilotriace-tate
` i - Cotton2 gr.~gal. 31.82 + 0.96
~` 20 " 7 gr./gal. 29.40 ~ 0.6~
12 gr./gal. 24.84 ~ 1.89
P~olycotton2 gr./gal. 67.24 t 0.47
'" 7 gr./gal. 66.85 + 1.57
" 12 gx./gal. ~2.88 + 1.07
- 2`5 Polyester -2 gr./gal. ~2.84 ~ 1.32
7 gr./gal. ~0.81 ~ 1~34
12 gr./gal. 77.67 ~ 0.58
Solution Containinq 300 ppm Zeolite A and
300 ppm Sodium Citrate
Cotton 2 gr./gal. 27.66 ~ 0.80
~ 7 gr./~al. 26.80 ~ 1.41
" ~ 12 gr./gal. 21.96 ~ 0.47
Polycotton 2 gr./gal. 64.~0 ~ 0.67
" 7 grO/gal. 52.68 ~ 0.37
" 12 gr./gal. 61.31 ~ 1 48
***
Hydrated, particle diameter 1~10 microns
.
_ .......
~3~
' -35 - -
Polyester2 gr.jgal. 78.11 f 0.55
"7 gr./gal. 77.65 ~ 2.31
"12 gr./gal. 74.28 ~ 0.68
Solution Contain'ing 300 ppm Ze ~ ite A and
; 5 300 ppm Polyacetal Carboxylate
Cotton2 gr./gal. 37.57 ~ 1.30
"7 gr./gal. 33.48 ~ 0.55
. n12 gr./gal. 25.66 ~ 1.37
Polycotton2 gr./gal. 67.09 + 1.20
~7 gr./gal. 63.54 ~ 0.44
' "12 gr./gal. 58.37 ~ 0.80
Polyester2 gr./gal. 70.09 ~ 1.52
"7 gr./gal. 68.89 ~ 1.32
"12 gr./gal. 64.87 ~ 1.23
. .....
15 ' Sol~tion Containing 300 ppm Zeolite' A and
300 'ppm ~Sod'ium Mëllitate
Cotton 2 gr./gal. 28.04 ~ 2.07
. n. . 7 gr./gal. 27.26 ~ 0~58
" 12 gr./gal. 24.7% ~ 0.21
20Polycotton2 gr./gal. 63.74 ~ 0.84
" , , 7 gr./gal. 60.61 ~ 2.09
- ' " ' ' 12 gr./gal. 59.35 ~ 1~71
Polyester2 gr./gal. , 74.88 ~ 0.51
" 7 gr./gal. 71.34 ~ 1.75
25" 12 gr./gal. 66.S5 ~ 3O25
Solution Containing 150 ppm Zeolite A and
- - 450 ppm Sodium Nitrilotriacetate
! Cotton 2 gr./gal. 30.91 ~ 1.49
~ 7 gr./gal. 28.34 + 1.33
i 30 ~ gr.~gal. - 13.73 1~24
Polycot-ton -2 gr./gal. 67.80 ~ 0.35
, 7 gr./gal. 60.98 ~ 2
12 gr./gal. 55.23 ~ 1.22
Polyester 2 gr./gal. 84.22 ~ 0.98
" ' 7 gr./gal. 82.11 ~ 0~68
'~ 12 gr./gal. 77.47 -~ 0.43
.
_ . . ,_.. . . ..
~36 -
j - Solution Containing 150 ppm Zeolite A and
450 ppm Sodlum Citrate
Cotton 2 gr./gal. 25.22 ~ 3.07
" 7 gr./gal. 21.15 + 0.92
" 12 gr./gal. 15.56 ~ 2.12
Polycot~on 2 gr./gal. 63.63 + 1.31
" 7 gr./gal. 62.62 ~ 1.72
~ r./gal. 57.27 + 2.42
Polyester 2 gr./gal. 81.75 ~ 0.86
~ 7 gr./gal. 78.1} ~ 1.02
" 12 gr./gal. 71.82 ~ 1.33
Solution Containing 150 ppm Zeolite ~ and
450 ppm Polyacetal Carboxylate*
Cotton 2 gr./gal. 28.44 + 0.80
" 7 gr./gal. 25.25 + 0.08
" 12 gr./gal. 1~.31 + 1.18
I Polycotton 2 gr.~gal. 60.36 ~ 1,7~
i " 7 gr./~al. 57.30 ~ 0.~2
i - n ~ 12 gr./gal. S0.83 ~ 0.57
Polyester 2 gr./gal. 7?.51 -~ 1.26
7 gr./gal. 73.85 + 0.2~
~" 12 gr./gal. 67.35 ~ 1.05
Solution Containinq 150 ppm Zeolite A and
45-0 ppm Sodium l~lellitate
Cotton -2 gr.fgal. 23.65 0.75
" 7 gr./gal. 17.28 ~ 1.15
; ~ " 12 gr./gal. 14.52 + 2.64
Polycotton 2 gr./gal. 59.13 + l.g2
- " 7 gr./gal. 56.82 + 2.96
" 12 gr./gal. 54.92 + 1.66
Polyester 2 gr./gal. 76.37 + 1.48
gr./gal. 75.73 + 0.99
. . - n - l~ gr./gal. 76.80 + 0.~2
- These results clearly demonstrate that syner~istic
cleaning perormance was provided by the combination of
the aluminosilicate and polycarboxylate builder materials.
Substantially better overall cleaning was provided, at the
. -37 -
same total builder level in otherwise identical composi-
tions, by the detergent.composition containing the builder
mixture than was provided by the detergent compositions
containing only the individual builders.
Substantially similar cleaning results are obtained when
the cationic surfactant is replaced, in whole or in part, by
ditallowalkyldimethylammo~lium methyl sulfa-~e, ditallow-
alkyldimethylammonium iodide, dihexadecylalkyldimethyl-
ammonium rhloride~ dihexadecylalkyldihydroxylethylammonium
. 10 methyl sulfate, dioctadecylalkyldimethyla~monium chloride,
dieicosylalkyl methyl ethyl ammonium chloride, dieicosyl-
alkyl dimethylammonium bromide, methyl (1) tallowalkyl amido
. ethyl (2) tallowalkyl imidazolinium methyl sulfate, or
mixtures of these surfactants.
Substantially similar results are also obtained where
the nonionic su-rfactant in Composition A i~ replacedj in
whole or in part, by the condensation product o C14_15
alcohol with 2.25 moles of ethylene oxide; the condensation
product of C14 15 alcohol with 7 moles of ethylene oxide;
the condensation product of C'12 15 alcohol with 9 moles of
ethylene oxide; the condensation product of C12 13 alcohol
with 6.5 moles of ethylene oxide, which is stripped so as to
remove lower ethoxylate and nonethoxylated fractions; the
~ condensation product of coconut alcohol with 5 moles o~
. 25 ethylene oxide; the condensation product of coconut alcohol
with 6 moles of e~hylene oxide; the condensation product of
C12 15 alcohol with 7 moles of ethylene oxide; the conden- -
sation product of tallow alcohol with 9 moles of ethylene
oxide; a 1:1 by weight mixture of the condensation product
of C12 15 alcohol with 7 moles of ethylene oxide and the
condensation product of Cl~ 15 alcohol with 7 moles or
ethylene oxide; and other mixtures of those surfactants.
Excellent cleaning results are also obtained where
the ratio of nonionic surfactant to cationic sura~tant used
is about 2:1, 3:1, 3.5:1, 5:1, 6:1 or 9:1.
Cleaning benefits are also obtained when the weight
ratio of the aluminosilicate material to the polycarboxy-
late material is from about 1:10 to about 10:1, especially
~ F -I
3~3~ Z
-~8
when from about 1:4 to about 4:1. At aluminosilicate/poly-
carboxylate ratios above 1, the cleaning advantages are most
readily apparent at high water hardness levels, such as
above 7 grains/gallon.
Similar synergistic cleanin~ effects are obtained when
the aluminosilicate material is any hydrated Zeolite A, X or
PtB), having a particle size diameter of from about 0.01
microns to about 25 microns, especiall- Crom about 0.1
microns to about 10 microns.
5ubstantially similar cleaning performance is obtained
when the number of segments (n) in the polyacetal carboxy-
late builder averages at least 4, but especially when n
averages between 10 and 200.
EXAMPLE II
The following detergent composition was produced:
Component Wt.f%
~ihydrogenated tallowalkyl7~65
dimethylammonium chloride
~12-13 E6 5 34.45
Monoethanol amine 7.3
Polyacetal carboxylate 25.25
Hydrated Zeolite A (particle - ~5.25
diametex 1-10 microns~
lCondensation product of ~12 13 alcohol with 6.5 moles
of ethylene oxide, commercially available as Neodol 23-
6.5 from Shell Chemical Company.
This composition delivered excellent particulate soil
removal perfarmance, as demonstrated in Example I. Further,
the composition provided greasy/oily soil removal ~enefits.
EX~MPLE III
The following deteryent composition was produced~
Component ` Wt.~
Dihydrogenated tallowalkyl7.65
dimethylammonium chloride
C12-13 E6 5 34~45
Monoethanol amine 7.3
Sodium nitrilotriacetate 25.2S
Hydrated Zeolite A (particle 25.25
diameter 1-10 microns)
A
~ 9~
- 39 -
lCondensation product of C12 13 alcohol with 6.5 moles
of ethylene oxide, commercially available as Neodol 23-
6.5 from Shell Chemical Company.
This composition delivered excellent particulate soil
removal performance, as demonstrated in Example I. Further,
the composition provided greasy/oily soil removal benefits.
EX~MPLE IV
The following detergent composition is produced:
Component W~.~%
C12_13(EO)6.5 12.0
Cl~_ls(EO)7 0 12.0
Ditallow dimethylammonium 4.8
chloride
- Ethanol lo o
Polyacetal carboxylate 10.0
Hydrated Zeolite A 10.0
(particle diameter 1-10 microns)
Miscellaneous (includes pcrfume, 0.37
brightener, dye)
Water Balance
.... . ..
EXAMPLE V
The following detergent composi~ion is produced;
Component Wt./%
C12_13(EO~6.5 12.0
C14_15(EO)6 5 12.0
, Ditallow-dimethylammonium 4.8
' chloride
Ethanol 10.0
Sodium nitrilotriacetate 10.0
Hydxated Zeolite A ~particle 10.
diameter 1-10 microns)
Miscellaneous (include perfume, 0.37
brightener dye)
Water Balance
EXAMPLE VI
The following detergent composition is produced:
Component Wt.
C12_13(EO)6 5 12.0
C14_ls(EO)7 0 12.0
Ditallow dimethylammonium 4.8
chloride
~ ~3~
- 40 -
Ethanol 10.0
Sodium citrate . 1~.0
Hydrated Zeolite A 10.0
(particle diameter 1~10 microns)
Miscellaneous (includes perfume, 0O37
brightener, dye)
Water Balance
EXA~LE VII
The following detergent composition is produced:
Component Wt.~%
C12-13 (E)6.5
Ditallow dimethylammonium chloride 7.0
Hydrated Zeolite A (particle 25~0
diameter 1-10 microns) .
Sodium nitrilotriacetate 25.0
Sodium silicate ~2.0 ratio) ~.0
Miscellaneous (includes perfwme r Balance
brightener, dye! and moisture) ~ . -
EXAMPL~. VIII
The following detergent composition is producea:
I Component Wt./6
_13(E)6.5 ~ 30.0
Ditallow dimethylammoniwm chloride 7.0
~ Hydrated Zeolite B (particle 25.0
diameter 1-10 microns)
Sodium citrate 25.0
Sodium silicate (2.0 ratio) 5.0
Miscellaneous (includes per~ume, Balance
brightener, dye, and moisture)
EXAMPLE IX
The followin~ detergent composition i5 produced:
Component Wt./~
C~2_13(Eo)6.5 30~0
Ditallow dimethylammonium chloride .7.0
Hydrated Zeolite B (particle 25.0
diameter 1-10 microns)
Polyacetal carboxylate 25.0
Sodium silicate (2.0 ratio) 8~0
Miscellaneous (includes perfume, Balance
brightener, dye, a~d moisture)
. .~. ~ !
