Technical Field
[0001] This invention relates to laundry detergent compositions which exhibit highly improved
greasy and oily soil and body soil removal capabilities. The compositions may be free
of phosphate; alternatively, they may contain low levels of phosphate materials but
not amounts in excess of about 20% by weight. These detergent compositions provide
an unexpectedly high level of greasy and oily soil (such as motor oil, triolein, animal
fat and lipstick) removal; they also provide excellent removal of particulate soils,
especially clay soils, as well as fabric care benefits, such as fabric softening,
static control, and dye transfer inhibition.
Backaround Art
[0002] Nonionic surfactants are generally included in laundry detergent compositions for
their ability to attack greasy and oily soils. Cationic surfactants are also used
in detergent compositions primarily to'provide adjunct fabric
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0001)
selected nonionic surfactants in accordance with the cloud point and reduced cationic
monomer concentration requirements specified herein.
[0003] It is an object of this invention to provide laundry detergent compositions which
yield outstanding greasy and oily soil and body soil removal.
[0004] It is another object of this invention to provide laundry detergent compositions
which have excellent particulate soil removal performance and fabric conditioning
benefits, in addition to outstanding greasy and oily soil and body soil removal performance,
in the presence or absence of builder components.
[0005] It is a further object of this invention to provide - detergent compositions which
may be used in a variety of physical forms, such as liquid, paste, granular, solid,
powder, or in conjunction with a carrier such as a substrate.
[0006] It is a still further object of this invention to provide a process for laundering
fabrics to remove greasy and oily soil and body soil, as well as particulate soil,
using cationic and nonionic surfactant-containing detergent compositions.
Disclosure of the Invention
[0007] The present invention relates to phosphate-free laundry detergent compositions or,
alternatively, compositions which contain levels of phosphate which are no greater
than about 20%, by weight, that comprise from about 5 to 100%, by weight, of a surfactant
mixture consisting essentially of:
(a) a biodegradable ncnionic surfactant having the formula R(CC2H4)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, and having an HLB of from about
5 to about 17; and
(b) a cationic surfactant, free of hydrazinium groups, having the formula R1mR2xYLZ wherein each R1 is an organic group containing a straight or branched alkyl or alkenyl group opticnally
substituted
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0002)
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0003)
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0004)
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0005)
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0006)
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0007)
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0008)
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0009)
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0010)
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0011)
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0012)
wherein each p is from 1 to 12,
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0013)
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0014)
, and
(9) mixtures thereof,
L is 1 or 2, the Y groups being separated by
a moiety selected from the group consisting
of R and R2 analogs having from one to about twenty-two carbon atoms and 2 free carbon single
bonds when L is 2, Z is an anion in a number sufficient to dive electrical neutrality,
said cationic surfactant being at least water-dispersible in with said nonionic surfactant;
said composition having a pH of at least 6.5 in the aqueous laundry solution, and
being substantially free of oily hydrocarbon materials and caticnic materials containing
about 13 or more ethylene oxide groups, the ratio of said nonionic to said cationic
surfactant being in the range of from 5.1·1 to about 100:1, and the "cloud point",
as described hereinafter, of said surfactant mixture being from about 0 to about 95°C.
Preferred compositions are those in which the reduced cationic monomer concentration
of said surfactant mixture is from about 0.002 to about 0.2.Preferred cationic surfactants are water soluble and have. a critical micelle concentration
(CMC) of greater than 10 pp
m. The conventional fabric softening cationic materials having two alkyl chains each
of about 18 carbon atoms are substantially insoluble and may not form the sole cationic
component of compositions of the present invention.
[0008] The compositions of the present invention are formulated so as to have a pH of at
least 6.5
[0009] Preferred compositions may contain mixed cationic and/or mixed nonionic surfactant
systems. The cationic surfactants should all be within the definition of the cationic
surfactants set forth above although small amounts of other cationic materials can
be tolerated. The mixed nonionic surfactant systems may contain nonionic surfactants-
which fall outside of the definition given above (such as alcohol ethoxylates having
an average of greater than 12 ethylene oxide groups per molecule) as long as at least
one of the nonionic surfactants in the mixture falls within the definition of the
nonionic surfactants, and that nonionic surfactant is included in an amount so as
to fall within the required ratio of nonicnic to cationic surfactants. When the nonionic
surfactant mixture contains a nonionic surfac- 'tant (or surfactants) which falls
outside of the definition of nonionic surfactants, the ratio of the surfactant (or
surfactants) within the above definition to that which does not fall within the definition
preferably is in the range of from about 1:1 to about 5:1.
[0010] 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 ratios 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 availability considarations.
[0011] Compositions of the present invention may contain up to about 60% of an electrolyte
(althoagh low levels of from about 1 to 20% are preferred), such as a detergency builder,
as well as other adjunct components conventionally found in laundry detergent components,
as more fully
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0016)
[0012] The primary use of the compositions of the present invention is in conventional home
laundry operations. The compositions may also be used for other detegenay purposes,
including the pretreatment of greasy and oily soots and in industrial laundry operations.
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0018)
of ethylene oxide, a
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0019)
alcohol polyethoxylate containing an average of 5 moles of ethylene oxide, a C
10 alcohol polyethoxylate containing an average of 4 moles of ethylene oxide, a C
14 alcohol polyethoxylate containing an average
[0013] of 4 moles of ethylene oxide. This last surfactant is particularly useful for cold
water laundering of fabrics. Preferred nonionic surfactants useful in the compositions
of the present invertion include a C
10 alcohol polyethoxylate containing an average of 3 moles of ethylene oxide, a C
12-13 alcohol polyethoxylate containing an average of 3 moles of ethylene oxide, and the
same product which is stripped to remove substantially all lower ethoxylate and nonethoxylated
fractions, a C
14-15 alcohol polyethoxylate containing an average of 7 moles of ethylene oxide, a C
12-13 alcohol polyehoxylate containing an average of 6.5 moles of ethylene oxide, a C
12 alcohol polyethoxylate containing an average of 5 moles of ethylene oxide, a coconut
alcohol polyethoxylate containing an average of 5 moles of ethylene oxide, a C
12-13 alcohol polyethoxylate containing an average of 3 moles of ethylene oxide, a C
14-15 alcohol polyethoxylate containing an average of 3 moles of ethylene oxide, a C
14-15 alcohol polyethoxylate containing an average of 4 moles of ethylene oxide, and a
C
14-15 alcohol polyethoxylate containing an average of 9 moles of ethylene oxide.
[0014] Specific examples of nonionic surfactant mixtures in which both components are within
the definition of the nonionic comnonent include: a mixture of a alcohol nonionic
component include: a mixture of a C
14-15 alcohol polyethoxylate containing an average of 3 moles of ethylene oxide (Neodol
45-3) and a C
14-15 alcohol polyethoxylate containing an average of 7 moles of ethylene oxide (Neodol
45-7), in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of from
about 1:1 to about 3:1, a mixture of a C
10 alcohol polyethoxylate containing an average of 3 moles of ethylene oxide together
with a secondary C
15 alcohol polyethoxylate containing an average of 9 moles of ethylene oxide (Tergitol
15-S-9), in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of
from about 1:1 to about 4:1; and a mixture of Neodol 45-3 and Tergitol 15-S-3, in
a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of from about 1:1
to about 3:1.
[0015] Preferred nonicnic surfactant mixtures contain alkyl glyceryl ether compounds in
addition to the required nonionic surfactant. Especially preferred glyceryl ethers
have the formulae
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0020)
wherein R is an alkyl or alkenyl group of from about 3 to about 18, preferably 3 to
12, carbon atoms or an alkaryl group having from about 5 to 14 carbon atoms in the
alkyl chain, and R is from 1 to about 5. These materials are used in compositions
with the nonionic surfactant component of the present invention in the ratio of nonionic
surfactont to glyceryl ether of from about 1:1 to about
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0021)
portioularly about 7:3.
[0016] Preferred compositions of the preset invention are substantially free of fatry acid
polyglycol ether di-aster compounds, such as polyethylene glycol-600-dioleate or polyethylene.
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0022)
such additives offer no advantage, and
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0023)
oven result in a disadvantage in terms of achieving
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0024)
removal and fabric conditioning potential of the present invention.
[0017] Other nonionic surfactants well known in the detergency arts may be used, in combination
with one or more of the nonionic surfactants falling within the definition of nonionic
surfactants useful in the present invention, to form useful nonionic surfactant mixtures.
Examples of such . surfactants are listed in U.S. Patent 3,717,630, Booth, issued
February 20, 1973-, and U.S. Patent 3,332,180, Kessler et al, issued July 25, 1967,
each of which is incorporated herein by reference. Nonlimiting examples of suitable
nonionic surfactants which may be used in conjunction with. the required nonionic
surfactants defined above include the condensation products of aliphatic alcohols
with ethylene oxide, which differ in terms of alkyl or ethylene oxide chain length
(e.g., more than twelve ethylene oxide groups.per molecule) so as to fall outside
the definition, given above.
[0018] These supplemental nonionic surfactants may also be of the semi-polar type, including
water-soluble amine oxides containing one alkyl moiety of from about 10 to 28 carbon
atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl
groups. A preferred amine oxide is C
12-14 alkyl dimethyl amine oxide. In addition to their surface-active properties, these
compounds may also be included, in amounts of from about 3 to about 20% of the composition,
so as to modify the sudsing properties of the detergent compositions, to make them
compatible with parti- cular types of laundering conditions. Other semi-polar surfactants
include water-soluble phosphine oxides containing one alkyl moiety of about 10 to
28 carbon atoms and two moieties selected from the group consisting of alkyl groups
and hydroxyalkyl groups containing from about 1 to 3 carbon atoms, and water-soluble
sulfoxides containing one alkyl moiety of from about 10 to 28 carbon atoms and a moiety
selected from the group consisting of alkyl and hydroxyalkyl moieties of from 1 to
3 carbon atoms.
Cationic Component
[0019] The cationic surfactants used in the compositions of the present invention have the
formula R
1mR
2XY
LZ -as hereinbefore defined.
[0020] The particular cationic component to be included in a given system depends to a.large
extent upon the particular nonionic component to be used; it is selected such that
it is at least water-dispersible when mixed with the nonionic surfactant. The cationic
surfactant is chosen, in light of the particular 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. Preferred cationic surfactants are those having critical micelle concentrations
of less than about 500 ppm, especially less than about 100 ppm.
[0021] In preferred cationic materials, L is equal to 1, p is from 1 to 12, preferably from
1 to 10, and Y is
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0025)
or mixtures thereof. However, L may be equal to two, there by yielding cationic components
containing two cationic charge centers. An example of a di-cationic component is given
below: alkanolamine, prefernbly monoethanolamine, as an alkalinity source and to increase
body soil removal. For example, coconutalkyl trimethylammohium chloride may be combined
with the condensation product of C
12 alcohol with 5 moles of ethylene oxide, the condensation product of C
12-13 alcohol with 5.3 moles of ethylene oxide, or mixtures thereof, in nonionic cationic
ratios of from 5. 1:1 to about 20:1, especially 5.1:1 to about 9:1. In another composition,
coconutalkyl trimethylammonium chloride is combined with the condensation product
of C
14-15 alcohol with 7 moles of ethylene oxide, in nonionic:cationic ratios of from 5.1:1
to about 15:1.
[0022] Another preferred composition utilizes cationic surfactants of the formula
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0026)
, wherein R
1, R
2 and Z are as defined above, in combinationwith the condensation product C
12-C
13 alconols with 5 to 10 moles of ethylene oxide or the condensation product of C
14-C
15 alcohol with 5 to 10 moles of ethylene oxide, such as the condensation praduct of
C
12 alcohol with 5 moles of ethylene oxide, the condensation prodnot of C
12-13 alcchol with 5.5 moles of ethylene oxide, the condensation product of C
14-15 alcchol with 7 moles of ethylene oxide, and mixtures thereof, in nonionic:cationic
ratios of from 5. 1:1 to about 15:1, partioularly about 7:1.
[0023] There m is equal to 2 it is preferred that x is equal to 2, and that R
2 is a methyl group. In this Instance R
1 must not have more than 14 carbon atoms. A preferred cationic meterial of this class
is dicoconutalkyl
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0027)
dimethylammonium holide.
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0028)
Other cationic materials which are useful in the compo- sitions of the present invention
include phosphonium and sulfonium materials.
[0024] In preferred cationic materials, described above, where m is equal to 1, it is preferred
that x is equal to 3, and R
2 is a methyl group. Preferred compositions of this mono-long chain type include those
in which R is a C
10 to C
18 alkyl group. Particularly preferred components of this class include C
16 (
palmitylalkyl) trimethylammonium halide, tallowalkyl trimethylammonium halide and coconutalkyl
trimethylammonium halide. In preferred systems, tallowalkyl trimethylammonium or coconutalkyl
trimethyammonium materials are combined with a nonionic surfactant selected from the
condensation prouducts of C
12-C
13 alcohol with 4 to 10 moles of ethylene oxide or the condensation product of C
14-C
15 alcohol with 6 to 10 moles of ethylene oxide, such as the condensation product of
C
12 alcohol with 5 moles of ethylene oxide, the condensation product of C
12-13 alcohol with 6.5 moles of ethylene oxide, the condensation product of C
14-15 alcohol with 7 moles of ethylene oxide, or mixtures thereof, in nonionic: cationic
ratios of from 5.1:1 to about 30:1, particularly from about 7:1 to about 20:1, most
preferably about 10:1. In addition to outstanding grease/oil removal, excellent particulate
removal is obtained using the condensation product of C
12-C
13 alcohol with 2 to 4 moles of ethylene oxide or the condensation product of C
14-C
15 alcohol with 3-6 moles of ethylene oxide, in nonionic/cationic ratios of from 5.1:1
to about 10:1. These compositions may also contain up to about 15% of Preferred compounds
of this type
utilize dicoconutalkyl dimethylammonium halide together with the condensation product
of C
12-C
13 alcohol with 6 to 10 moles of ethylene oxide or the condensation product of C
14-C
15 alcohol with 5 to 9 moles of ethylene oxide, such as the condensation product of
C
12-13 alcohol with 6.5 moles of ethylene oxide, the condensation product of C
14-15 alcohol with 7 moles of ethylene oxide, and mixtures thereof, in nonionic:cationic
ratios of from 5.1:1 to about 15:1, especially from about 6:1 to about 12:1. Outstanding
removal of particulate soils, in addition to excellent greasy/oily soil removal, may
be obtained using the condensation product of C
12-C
13 alcohol with 4 to 8 moles of ethylene oxide or the condensation product of C
14-C
15 alcohol with 4 to 8 moles of ethylene oxide, in nonionic/cationic ratios of 5.1:1
to about 15:1.
[0025] Where tri-long chain materials are used (m=3), it is preferred that x is equal to
1 and that R
2 is a methyl group. In these compositions
R1 is a C8 to C11 alkyl group. Particularly preferred tri-long chain cationic materials include trioctylalkyl
(C8) methyl ammonium halide and tridecylalkyl (C10) methyl ammonium halide.
[0026] Another type of preferred cationic surfactant for use
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0029)
the compositions of the present invention are the alkoxy-
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0030)
alkyl quaternaries. Examples of such compounds are
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0031)
below:
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0032)
wherein each p is from 1 to 12, preferably from 1 to 10 with the total ethylene oxide
groups in a molecule not exceeding about 13), and each R is a C
10 to C
20 alkyl group. It is preferred that these compounds contain no more than a total of
about 10, preferably no more than about 7, ethylene oxide groups in order to obtain
the best removal of greasy and oily soils.
[0027] ![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0033)
compositions of the present invention.
[0028] A particular preferred type of cationic component, has the formula :
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0034)
wherein R
1 is C
1 to C
4 alkyl or hydroxyalkyl; R
2 is C
5 to C
30 straight or branched chain alkyl, alkenyl, alkyl phenyl, or
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0035)
wherein s is from 0 to 5; R is C
1 to C
20 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
1 and Z
2 are each selected from the group consisting of
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0036)
and wherein at least one of saia 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, sulfate, and nitrate,
more preferably chloride, bromide, iodide, methyl sulfate and sulfate.
[0029] In addition to the advantages of the other cationic surfactants disclosed herein-,
this particular cationic component.is environmentally desirable, since it is biodegradable,
yielding environmentally acceptable compounds, both in terms of its long alkyl chain
and its nitrogen-
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0037)
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 ubout 100:1. However,
when used in the compositions of the present invention they are used in surfactant
mixtures which have nonionic to cationic surfactant ratios of from 5.1:1 to about
100:1, partioularly from 5.1:1 to about 50:1, most preferably from about 6:1 to 40:1,
especially from about 6:1 to about 20:1.
[0030] Particularly preferred cationic surfactants of this type are the choline ester derivatives
having the following formula:
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0038)
of well as those compounds in which the ester linkage in the above formula is replaced
with a reverse ester, amide or reverse amide lindage.
[0031] Particularly preferred examples of this type of cat-
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0039)
surfactant include stearoyl choline ester quaternary
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0040)
halides R
2 = C
27 alkyl), palmitoyl choline ester
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0041)
ammonium halides (R
2 =C
25 alkyl), myristoyl
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0042)
quaternary ammonium halides (R
2 = C
11 alkyl),
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0043)
choline ester quaternary ammonium halides (R
2 =
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0044)
alkyl).
[0032] Additional preferred cationic components of the choline
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0045)
variety are given by the struetural formulas below,
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0046)
may be from 0 to 20
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0048)
[0033] 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 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 of a long chain fatty
acid of the desired chain length together with 2-haloethanol, in the presence of an
acid catalyst material. The reaction product is then used to quaternize trimethylamine,
forming the desired cationic component.
[0034] Another type of novel, particularly preferred cationic material has the formula :
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0049)
In the above formula, each R
1 is a C
1 to C
4 alkyl or hydroxyalkyl group, preferably a methyl group. Each R
2 is either hydrogen or C
1 to C
3 alkyl, preferably hydrogen. R
3 is a C
4 to C
30 straight or branched chain alkyl, alkenyl, or alkylbenzyl group, preferably a 4
8 to C
18 alkyl group, most preferably a C
12 alkyl group. R is a C
1 to C
10 alkylene or alkenylene group. n is from 2 to 4, preferably 2; y is from 1 to 20,
preferably from about 1 to 10, most preferably about 7; a may be 0 or I, and t may
be 0 or 1, but t is 1 when a is 1; and m is from 1 to 5, preferably 2. Z
2 is selected from the group consisting
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0050)
Z
1 is selected from the group consisting of:
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0051)
and at least one of Z
1 and Z
- groups is selected from the group consisting of ester, reverse ester, amide or reverse
amide. 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.
[0035] These surfactants, when used in the compositions of the present invention, yield
excellent particulate soil, body soil, and greasy and oily soil removal. In addition,
the detergent compositions control static and soften fabrics laundered therewith,
and inhibit the transfer of dyes in the wash solution. Further, these novel cationic
surfactants are environmentally desirable, since both their long chain alkyl segments
and their nitrogen segments are biodegradable.
[0037] The preferred derivatives, described above, may be prepared by the reaction of a
long chain alkyl
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0060)
(preferably polyethoxy) carboxylate, having an alkyl chain of desired length, with
oxalyl chloride,
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0061)
form the corresponding acid chloride. The acid chloride
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0062)
then reacted with dimethylaminoethanol to form the
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0063)
amine ester, which is then quaternized with a methyl halide to form the desired ester
compound. Another way of preparing these compounds is by the direct
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0064)
of the appropriate long chain ethoxylated rboxylic acid together with 2-haloethanol
or dimethyl
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0065)
in the presence of heat and an acid catalyst. ceaction product formed is then guaternized
with
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0066)
or used to quaternize trimethylamine to form
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0067)
desired ester compound.
Formulation Criteria
[0038] Utilising the nonionic and cationic components,
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0068)
above, preferred compositions of the present Anvention are formulated using the guidance
provided by the reduced Monomer Concentration (C
R) of the cationic
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0069)
the laundry solution. Specificaly, the
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0070)
of a C
R value for a given nonionic and cationic
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0071)
will determine the ratio in which to combine thoss surfactants. The Reduced Monomer
Concentration
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0072)
is obtained bu dividing the concentration
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0073)
monomer present in the aundry solution
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0074)
micelle concentration (CUC) of the umfactuat. As used in this application, VMC's are
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0075)
at 105°F in water containing 7 grains/gallon
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0076)
hardness, unless otherxise stated. The
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0077)
monomer concentration of the ronionic/
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0078)
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0079)
surfactant mixture is defined by equetions (1) through (3), given below. The nonionic/cationic
surfactant mixtures preferred in the present invention are those haying reduced monomer
concentrations in the range of from about 0.002 to about 0.2, preferably from about
0.002 to about 0.15, and most preferably from about 0.002 to about 0.08.. As nonionic
and cationic components of greater purity are utilized, the narrower C
R ranges become more preferred.
[0039] ![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0080)
Proceedings of the Second Internetional Congress of Surface Activity, III, 449, Academic
Press, Inc. (1957). The equatios 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), incorporated herein by reference, in the context
of an ideal solution, and is based on the following quadratic equation (equation (11)
in Clint):
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0081)
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 = C1 - C2 (wherein "1'' denotes nonionic surfactant and "2" denotes cationic surfactant)
c*1 = critical micelle concentration (CMC) of nonionic surfactant (moles/l.)
c*2 = critical micelle concentration of cationic surfactant (moles/l.)
α = total mole fraction of nonionic surfactant in the solution = C1/(C1 + C2)
3 = a constant base upon the heat of mixing = -2.3
cm1 = nonionio monomer concentration
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0082)
cm2 = cationic monomer concentration
e = base of Napierian logarithm system = 2.71828
x = mole fraction of the nonionic surfactant in the micelle at concentration C .
f1 = nonionic activity coefficient in the- mixed micelle = eB(1-x)2
f2 = cationic activity coefficient in the mixed micelle = eBx2
◁ = f2c*2 - f1c*1
CR = reduced cationic monomer concentration
M1 = 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) = W1+W2 (wnerein "1'' denotes nonionic surfactant and "2" denotes cationic surfactant)
Y = weight fraction of nonionic surfactant in the composition
[0040] The above equation is solved for the nonionic monomer concentration by taking its
positive root (equation (12) in Clint).
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0083)
[0041] By modifying this equation based on the assumptions of a regular, rather than an
ideal, solution, the C
R range for optimum performance was derived from the following equation:
[0042] ![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0084)
[0043] For a given cleaning test for a nonionic/cationic system, x was found by inserting
the values known from the teah (i.e., c*
1, c*
2, α, C and β) into equation (1) and colving iteratively for x, such that the error
in x is less than 0.001. This procedure was repeated for a large number of such tests,
over varying usage conditions. The x vaiues obtained were then used to solve for the
cationic
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0085)
concentrations using the following equation:
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0086)
[0044] The C
R value was then calculated using equation (3).
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0087)
[0045] The C
R values obtained cover a large number of combinations and ratios of various nonionic
and cationic surfactants, at various concentrations and temperatures, which have been
evaluated for their ability to clean greasy/oily soils. The examination of the resulting
data revealed that for a given system the optimum cleaning of greasy/oily soils was
found at a C
R value of from about 0.002 to about 0.2.
[0046] This range of C
R (i.e., 0.002 to 0.2) can then be used to determine the range of optimum nonionic/cationic
ratios for any given combination of nonionic surfactant and cationic surfactant, for
the desired wash concentration within the overall wash concentration range of from
100 ' parts per million (ppm) to 10,000 ppm of surfactant. This calculation is carried
out in the following manner, where β, C
R c*
1, c*
1 M
1 and M
2 are known for a given nonionic/ cationic surfactant pair:
(a) for a given nonionic surfactant, cationic surfactant, and for each end of the
CR range, solve for x using the equation
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0088)
by standard numerical iterative techniques to an error in x of less than 0.001;
(b) find the range of Y from the equation
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0089)
using 100 ppm and 10,000 ppm as the boundary values for W, for each end of the CR range;
(c) the nonionic/cationic ratio (NCR) range for optimum performance is then within
the range obtained by substituting the boundary values for Y into the formula
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0090)
[0047] Put another way, steps (b) and (c) may be combined into a single equation which may
be solved directly for the NCR.
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0091)
[0048] 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 concentration, C
R is essentially independent of concentration. This means that for conventional laundry
usage concentrations (e.g., 100 ppm to 10,000 ppm, and especially from about 250 ppm
to about 3,000 ppm), the C
R of most commercial cationic/ nonionic surfactant mixtures (wherein the cationic component
has a CMC of less than about 100 ppm, measured at 105°F water containing 7 grain/gallon
of mixed calcium and magnesium hardness) will be independent of the actual usage concentration,
so that using a concen- cration of about 1,000 ppm in the above calculation will be
a satisfactory approximation for the entire rance. As used herein, if a concentration
range is not specified, the 1,000 ppm C
R is meant.
[0049] By way of example, the optimum ratio for grease/oil removal for Composition A of
Example I, herein, given
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0092)
calculated below. For this system, the following
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0093)
cither known or selected as indicated:
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0094)
1,000 ppm (selected as representative of usage conditions)
c1 = 1.957 x10-5 ppm
c2 = 2.1875 x 10-5 ppm
B = -2.3
M1 = 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)
[0050] Substituting the values for and C
R into equation (a):
(1-x)e
-2.8x2 = 0.0073.
[0051] Solving iteratively for x, it is found that x'= 0.922.
[0052] Using this value for x, it is found that
f1 = 0.983
f2 = 0.0925
Δ = (0.0925) (2.1875 x 10-5) - (0.983) (1.967 x 10-5) = -1.73 x 10-5
[0053] Substituting these values into equation (b), it is found that:
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0095)
Y = 0.938
[0054] Substituting this value for Y into equation (c), the nonionic/cationic ratio is determined.
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0096)
[0055] It will be noted that this ratio corresponds to the ratio actually found in Example
I, Composition A.
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0097)
[0056] nonionic/cationic mixture (and in preferred embodiments the nonionic/cationic mixture
plus any electrolytes present in the composition) falls between about 0 and about
95°C, preferably between about 10 and about
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0098)
more preferably between about 20 and about 65°C, especially between about 30 and about
50°C. For cold Warer detergency, the surfactant mixture should have a
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0099)
point between about 0 and about 25°C. The fact Than a composition has a cloud point
within these temperature ranges assures that the composition can be utilized under
laundry temperature conditions to achieve nupstanding removal of greasy/oily soils.
If a compo-
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0100)
does not have a cloud point within the temperature
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0101)
specified, it will not yield the outstanding
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0102)
the present invention inside that temperature range. The compositions
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0103)
exhibit their best grease/oil removal performance
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0104)
the temperature of the wash solution in which they are
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0105)
within about 20°C, preferably within about
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0106)
most preferably within about 10°C, of the
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0107)
the nonionic/cationic surfactant mixture.
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0108)
another way, the laundry solution temperature range
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0109)
preferred compositions deliver optimum
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0110)
removal lies between the cloud point temper-
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0111)
the system in the absence of the cationic
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0112)
and about 30°C, preferably about 25°C, most preferably about 20°C, above that cloud
point temperature. As used herein, the term "cloud point" means the
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0113)
which a graph which plots the light
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0114)
intensity of the composition versus wash solution temperature begins to sharply increase
to its maximum value, under the following experimental conditions:
[0057] The light scattering intensity is measured using a Model VM-12397 Photogoniodiffusometer,
manufactured by Societo Francaise d'instruments de controle ct- d'analyses, France
(the instrument being hereinafter referred to as (SOFICA). The SOFICA-sample cell
and its lid are washed with hot acetone and allowed to dry. The surfactant mixture
is made and put into solution with distilled water at a concentration of 1000 ppm.
Approximately a 15 ml. sample of the solution is placed into the sample cell, using
a syringe with a 0.2p nucleopore filter. The syringe needle passes through the sample
cell lid, so that the cell interior is not exposed to atomospheric 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 rateX 1°C/minute); the temperature of the sample
is determined by the temperature of the bath. The light scattering (90° angle) intensity
of the sample is then determined at various temperatures, using a green filter and
no polarizer in the SOFICA.
[0058] The preferred nonionic and cationic components used in the present compositions are
chosen, combined, and used based on three basic criteria : (1) the final composition
must satisfy the cloud point criteria, given above, and should be such that the surfactant
mixture cloud point temperature is within about 20°C of normal wash solution temperatures,
(2) the reduced cationic monomer concentration of the surfactant mixture preferably
falls within the range defined above ; and (3) the concentration of the detergent
composition in the wash solution should be sufficient to give the desired cleaning
performance under normal laundering temperatures.
[0059] ![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0115)
in the present inven
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0116)
surfactants which have relative. low CMCs and low cloud points (i.e., the temperature
at which an aqueous solution of the surfactant exhibits turbidity). These surfactants
can be used to prepare detergent compositions, laundry solutions of which, at lower
temperatures, will form the desired nonionic/cationic mixture cloud point without
requiring the addition of other ingredients, such as electrolytes or anionic surfactants.
Such detergent compositions make it easier to fulfill the cloud point requirements
set forth herein, and yield outstanding removal of greasy and oily soils from fabrics.
[0060] In formulating and utilizing the compositions of the present invention, it is preferred,
for typical American automatic washing conditions, that the nonionic surfactant, the
cationic surfactant, and any additional components be chosen and used in amounts such
that the temperature at which the detergent composition in the aqueous laundry solution
has a cloud point, as'defined above, will be between about 30°C and 50°C, preferably
at about 45°C. Where the compositions are used under different washing conditions,
the compositions are formulated such that, at the desired use concentration, they
exhibit their cloud point at a temperature which is within about 20°C of the desired
washing temperature. Thus, for example, in Japan (where washing temperatures are generally
lower than those used in the United States), the compositions are desirably formulated
so as to have their cloud point close to about 15°C.
[0061] The cloud point temperature for a given composition in the wash solution depends
upon the physical and
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0117)
properties (such as CMC and solubility) of the
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0118)
nonionic and additional components included
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0119)
composition, and may no lowernd by inerensing the alkyl chain langths of the nonionic
or cationic
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0120)
by doereasing the
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0121)
of ethoxylation of the nonionic component,
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0122)
as phosphates, polyposphonates,
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0123)
or sulfates, particularly ir rolatively low amounts (such as from about 1 to about
15% of a given
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0124)
More specifically, it is preferred that the detergent compositions of the present
invention, when used in the aqueous laundry solution, have cloud points which fall
within about 15°C, preferably within about 10°C, and most preferably within about
5°C, of the temperature of the laundry solution. It has been found that when these
laundry solution temperature/cloud point relationships are met, the greasy and oily
soil removal capacity of the laundry solution increases dramatically.
[0062] Although not intending to be bound by theory, it is believed that when a detergent
composition of the present invention is in a laundry solution with oily- soiled fabrics,
the cationic component is adsorbed onto the fabric, thereby neutralizing the negative
charge on the fabric. This charge neutralization enhances the adsorption of the nonionic
surfactant onto the fabric, thereby causing the roll up of the oily soil. The soil
is then easily removed by agitation. It is by formulating cationic/nonionic surfactant
mixtures which satisfy the cloud point and the preferred reduced cationic monomer
concentration requirements that this mechanism, and hence, greasy/oily soil removal,
is optimized.
Fatty Amide Component
[0063] In a particular embodiment of the present invention the nonionic surfactant/cotionic
surfactant mixture 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
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0125)
defined above, in order to maximise the cleaning benetits obtained.
[0064] In ronionic/cationic systems,
the ratio of the total cationic and nonionic components to the amide component included,
is in the range of from about 5:1 to about 50:1, preferably from about 8:1 to about
25:1. These compositions result in excellent particulate soil removal performance,
as well as improved soil antiredeposition characteristics
[0065] Amides useful in these preferred compositions include, but are not limited to, carboxylic
acid amides, sulfonic acid amides, phosphonic acid amides, and boronic acid amides
Preferred amides include those having the formulae:
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0126)
wherein.R
1 is C
8 to C
20 alkyl, alkenyl, alkyl phenyl or alkyl benzyl, preferably C
10 to C
18 alkyl, and most preferably C
11 alkyl; and each R
2 is hydrogen, or C
1 to C
8 alkyl or hydroxyalkyl, preferably hydrogen. Specific examples of these compositions
include a mixture of stearoyl choline bromide (present in the washing solution at
120 ppm), coconu alcohol polyethoxylate containing an average of 5 moles of ethylene
oxide (present in the wash solution at about 357 ppm), and a midcut coconutalkyl ammonium
amide (present in the wash solution at about 50 ppm); and a mixture of stearoy choline
bromide (100 ppm), coconut alcohol polyethoxylate containing an average of 5 moles
of ethylene oxide (357 ppm), and lauramide (R
1 equals C
11 and R
2 is hydrogen; at 45 Ppm).
Additional Components
[0066] The compositions of the present invention may also contain additional ingredients
generally found in laundry detergent compositions, at their conventional art-established
levels. These additional components are preferably selected such that the composition
as a whole satisfies the cloud point criteria described above..
[0067] The compositions of the present invention may contain up to about 15%, preferably
up to about 5%, and most preferably from about 0.1% 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, to St. John, and combinations of
certain nonionics therewith, as disclosed in U.S. Patent 2,954,348, issued September
27, 1960, to Schwoeppe, both disclosures being incorporated herein by reference. Other
suds suppressor components useful in the compositions of the present invention include,
but are not limited to, those described below.
[0068] Preferred silicone suds suppressing additives are described in U.S. Patent 3,933,672,
issued January 20, 1976, Bartolotta et al, incorporated herein by reference. 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:
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0127)
wherein x is from about 20 to about 2,000, and R and R'
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0128)
suds regulating component for use in the
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0129)
tions, and are described in detail in U.S. Patent 4,056,481, Tate, issued November
1, 1977, incerperatea herein by reference. The microcrystalline waxes are substantially
water-insoluble, but are water-dispersible in the presence of organic surfactants.
Preferred microcrystalline waxes have a melting point from about 65°C to 100°C, a
molecular weight in the range from 400-1,000, and a penetration value of at least
6, measured at 77°F by ASTM-D1321. Suitable examples of the above waxes include: microcrystalline
and oxidized microcrystalline petrolatum waxes; Fischer-Tropsch and oxidized Fischer-Tropsch
waxes; ozokerite; ceresin; montan wax; beeswax; candelilla; and carnauba wax.
[0069] Alkyl phosphate esters represent an additional preferred suds suppressant for use
herein. These preferred phosphate esters are predominantly monostearyl phosphate which,
in addition thereto, can contain di- and tristearyl phosphates; and monooleyl phosphates,
which can contain di- and trioleyl phosphates.
[0070] 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, u
p to 50 mole percent of dialkyl phosphate and up to about 5 mole percent of trialkyl
phosphate.
[0071] The detergent compositions of the present invention may, subject to the limitations.on
phosphate, discussed above, also include from about 1 to about 60%, preferably low
levels of from about 1 to about 15%, of electrolyte components, such as conventional
detergency builders, especially alkaline, polyvalent anionid builder salts. ' The
alkaline salts primarily serve to maintain pH of the cleaning solution in the range
of from about 7 to about 12, preferably from about 6 to about 11, to modify the cloud
point of the detergent composition, and to provide a source of ionic strength. However,
it is important to emphasize that the compositions of the present invention are capable
of previding excellent cleaning even in the complete absence of such builder materials.
[0072] Suitable detergent builder salts useful herein can be of the polyvalent inorganic
or polyvalent organic type, or mixtures of these varieties. Nonlimiting examples of
suitable water-soluble, inorganic alkaline detergent builder salts include: alkali
metal carbonates, borates, phosphates, polyphosphates, bicarbonates, silicates, and
sulfates. Specific examples of such salts include sodium and potassium tetraborates,
perborates, bicarbonates,, carbonates, tripolyphosphates, orthophosphates, pyrophosphates
and hexametaphosphates.
[0073] Examples of suitable organic alkaline detergency builder salts include: (1) water-soluble
aminopolyacetates, for example, sodium and potassium ethylenediamine tetraacetate,
nitrilotriacetate, and N-(2-hydroxyethyl)nitrilotriacetates;
(2) water-soluble salts of phytic acid, for example, sodium and potassium phytates;
and
(3) water-soluble polyphosphonates, including sodium, potassium, and lithium salts
of ethane-1-hydroxy-1,1- diphosphonic acid; sodium, potassium, and lithium salts of
ethylene diphosphonic acid; and the like.
[0074] Additional organic builder salts useful herein include the polycarboxylate materials
described in U.S. Patent 3,364,103, incorporated herein by reference, including the
water-soluble alkali salts of mellitic acid. The water-soluble salts of polycarboxylate
polymers and copolymers, such as those described in U.S. Patent 3,368,067, incorporated
herein by reference, are also suitable as builders herein.
[0075] A further class of detergency builder materials useful in the present invention are
insoluble sodium aluminosill- cates, particularly those described in Belgium Patent
814,874, issued November 12, 1974, incorporated herein by reference. This patent discloses
and claims detergent compositions containing sodium aluminosilicates having the formula
Na
z(AlO
2)
z(SiO
2)
y-XH
2O, wherein z and y are integers equal to at least 6, the molar ratio of z to y is
in the range of from 1.0:1 to about 0.5:1, and X is an integer from about 15 to about
264, said aluminosilicates having a calcium ion exchange capacity of at least 200
milligrams equivalent/gram and a calcium ion exchange rate of at least about 2 grains/gallon/minute/
gram. A preferred material is Na
12(SiO
2-AlO
2)
12-27H
2O.
[0076] Mixtures of organic and/or inorganic builders may be used herein. One such mixture
of builders is disclosed in Canadian Patent 755,038 and consists of a ternary mixture
of sodium tripolyphosphate, trisodium nitrilotriacetate, and trisodium ethane-1-hydroxy-1,1-diphosphonate.
[0077] Other preferred builder materials which may be used in the compositions of the present
invention include alkali metal carboxymethyl tartronates, commercially available at
about 76% active together with about 7% ditartronate, about 3% diglycolate, about
6% sodium carbonate, and about 8% water; and anhydrous sodium carboxymethyl succinate,
commercially available at about 76% active together with about 22.6% water, and a
mixture of other organic materials, such as carbonates.
[0078] In addition to the cationic and nonionic surfactants discussed above, the detergent
compositions of the present invention may additionally contain up to about 50%, preferably
from about 5 to about 30%, of anionic surfactants, zwitterionic surfactants, or mixtures
of such- surfactants. Surfactants of these types useful in the compositions of the
present invention are listed in U.S. Patent 3,717,630, Booth, issued February 20,
1973, and U.S. Patent 3,332,880, Kessler et al, issued July 27, 1967, both of which
are incorporated herein by reference. Specific nonlimiting examples of surfactants
suitable for use in the instant compositions arc as follows: These surfactants arc
selected such that the composition as
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0130)
monomer toncentration criterla deseribed above.
[0079] Water-soluble salts of the higher fatty acids, i.e., "soaps", are useful as an anionic
surfactant herein.
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0131)
metal
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0132)
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0133)
armonium and alkanol-
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0134)
fatty acids containing from about 8 to about 24 carbon atoms and preferably from about
10 tc about 20 carbon atoms. Soaps can be made by direct saponification of fats and
oils or by the neutralization of free fatty acids. Particularly useful are the sodium
and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow,
i.e., sodium or potassium tallow and coconut soaps.
[0080] Another class of anionic surfactant includes water-soluble salts, particularly the
alkali metal, ammonium and alkanolammonium salts, of organic sulfuric reaction products
having in their molecular structure an alkyl group containing from about 8 to about
22 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the
term "alkvl" is the alkyl portion of acyl groups.) Examples of this group of synthetic
surfactants which can be used in the present detergent compositions are the sodium
and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols
(C
8-C
18 carbon atoms) produced by reducing the glycerides of tallow or coconut oil; and sodium
and potassium alkyl- brenzene sulfonates, in which the alkyl group contains
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0135)
9 to about 15 carbon atoms in straight chain or branched chain configurations, e.g.,
those of the type described in U.S. Patents 2,220,099 and 2,477,383, incor-
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0136)
herein by reference.
[0081] ![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0137)
anionic surfactant compounds useful herein
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0138)
the sodium alkyl glyceryl ether sulfonates,
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0139)
those ethers or higher alcohols derived from
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0140)
and coconut oil; sodium coconut oil fatty acid
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0141)
sulfonates and sulfates; and sodium or
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0142)
salts of alkyl phenol polyethylene oxide ether
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0143)
1 to about 10 units of ethylene
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0144)
molecule and wherein the alkyl groups contain
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0145)
8 to about 12 carbon atoms.
[0082] The alkaline earth metal salts of synthetic anionic surfactants are useful in the
present invention. In particular, the magnesium salts of linear alkylbenzene sulfonates,
in which the alkyl group contains from 9 to about 15, especially 11 to 13, carbon
atoms, are useful.
[0083] Other useful anionic surfactants herein include the water-soluble salts of esters
of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the
ester group; water-soluble salts of 2-acyloxy-alkane-l-sulfonic acids containing from
about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon -
atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon
atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; water-soluble
salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy
alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and
from about 8 to 20 carbon atoms in the alkane moiety.
[0084] Preferred water-soluble anionic organic surfactants for use herein include linear
chain alkylbenzene sulfonates containing from about 10 to 16 carbon atoms in the alkyl
group; alkyl sulfates containing from about 10 to 20 carbon atcms; the coconut range
alkyl glyceryl sulfonates; and alkyl ether sulfates wherein the alkyl moiety contains
from about 10 to 20 carbon atoms and wherein the average degree of ethoxylation varies
between about 1 and 6.
[0085] Specific preferred anionic surfactants which may be used herein include: sodium-linear
C
10-C
12 alkylbenzene sulfonate; triethanolamine C
10-C
12 alkylbenzene sulfonate; sodium tallow alkyl sulfate; sodium coconut alkyl glyceryl
ether sulfonate; and the sodium salt of a sulfated condensation product of C
14-C
18 alcohol with from about 1 to about 10 moles of ethylene oxide.
[0086] It is to be recognized that any of the foregoing anionic surfactants can either be
used separately or in mixtures.
[0087] Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium,
and sulfonium compounds in which the aliphatic moieties can be straight or branch
chain, wherein one of the aliphatic substituents contains from about 8 to 18 carbon
atoms and one contains anionic water-solubilizing group. Particularly-preferred zwitterionic
materials are the ethoxylated ammonium sulfonates and sulfates disclosed in U.S. Patent
3,925,262 and U.S. Patent 3,929,678. The inclusion of these surfactants in the compositions
supplement the excellent greasy and oily soil removal performance with outstanding
clay soil removal performance.
[0088] Particularly preferred ethoxylated zwitterionic surfactants have the formulae:
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0146)
and
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0147)
[0089] The above compounds which contain 8 moles of ethylene oxide are also preferred. Additional
preferred zwitterionic surfactants include those having the formula
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0148)
wherein the sum of x +
y is equal to about 15.
[0090] While the compositions may advantagecusly contain electrolytes, anionic surfactants
and zwitterionic surfactants, as described above, selected so as to satisfy the cloud
point requirement, a preferred class of compositions is substantially free of interfering
anions, which may interact with the cationic component and thereby hinder cleaning
and fabric conditioning performance. What constitutes an "interfering anion" depends
upon the nonionic and cationic components contained in a detergent composition, as
well as properties of the particular anion, such as structure, bulk and dissociation
constant. In these compositions - the anionic materials should 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. For example, in preferred compositions,
when an anionic material has a dissociation constant of at least about 1 x 10
-3 (such as sodium toluene sulfonate) it may be contained in an amount up to about 40%,
by weight, of the cationic surfactant; where the anionic material has a dissociation
constant of at least about 1 x 10 , but less than about 1 x 10 , 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 1 x 10
-5 (such as sodium C
11.8 linear alkylbenzene sulfonate), it may be contained only in amounts up to about 10%
by weight, of the cationic surfactant. Particularly preferred compositions of this
type are those substantially free of phosphate, poly- phosphate, silicate, and polycarboxylate
builder anions, carboxymethylcellulose, and anionic surfactants.
[0091] Other compatible adjunct components which may be included in the compositions of
the present invention, in their conventional 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.. Buffers may also be added to control the pH of the compositions, with
low molecular weight amino acids, particularly glycine, being preferred where the
composition is in the form of a clear-liquid. However, because of the numerous and
diverse performance advantages of the compositions of the present invention, many
components, such as builders, static control agents, fabric softening agents and germicides,
generally will not be necessary. The compositions of the present invention may additionally
contain monoethanolamine, diethanolamine, or triethanolamine components in amounts
up to about 30%, preferably from about 5 to about 20%. These components are useful
as alkalinity sources and in formulating clear homogeneous liquid products which satisfy
the cloud point requirements when placed in an aqueous laundry solution.
[0092] Compositions of the present invention may be manufactured 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.
[0093] These articles consist of a
water-insoluble substrate which releaseably incorporates an effective amount, preferably
from about 20 to 80 grams of the detergent composition of the present invention. A
particular preferred substrate article incorporates a bleaching component and a fieacn
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0149)
the substrate, together with the nonionic/cationic surfactant mixture.
[0094] A particularly preferred composition of the present invention is an aqueous heavy-duty
liquid laundry composition containing from about 10 to about 50%, preferably about
15 to 40%, of the nonionic surfactant, from about 1 to about 10%, preferably about
1 to 6%, of the cationic surfactant; and which additionally contains from about 5
to about 30%, preferably about 10% of monoethanolamine, diethanolamine, triethanolamine,
or mixtures thereof. These compositions may also contain from about 3 to about 20%
of an anionic surfactant, particularly one of the ethoxylated or nonethoxylated alkyl
sulfate variety. One embodiment of buch a composition contains monoethanolamine, coconut
trimethylammonium chloride as at least a portion of the cationic component, and a
mixture of the condensation product of secondary C
12 alcohol with an average of 7 moles of ethylene oxide together with the condensation
product of secondary C
12 alcohol with an average of 5 moles of ethylene oxide, in a ratio of higher ethoxylated
nonionic to lower ethoxylated nonionic of about 3:1, as the nonionic surfactant. In
these compositions, the amounts and ratios of the component may be varied so as to
produce a clear, homogeneous product which exhibits the required cloud point characteristics
in the aqueous laundry solution.
Laundry Processes
[0095] In its broadest aspect, this invention envisions a process for cleaning solid surfaces
soiled with greasy and/or oily materials utilizing an aqueous laundry soiution comprising
from about 0.01% to about 0.3% by weight or a
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0150)
within about 20°C, preferably within about 15°C. more preferably within about 10°C
cf the cloud point of the nonionic/ cationic surfactant mixture. It is, generally,
at the point where the laundry solution temperature is equal to the cloud point that
a given system will give its best greasy/oily soil removal performance. Particularly
preferred laundry solutions are those in which the ratio of the nonionic surfactant
to cationic surfactant is from 5.1:1 to about 100:1, particularly from 5.1:1 to about
50:1, more particularly from about 6:1 to about 40:1, especially from about 6:1 to
about 20:1.
[0096] Prior to this invention, it was totally unexpected that combinations of nonionic
and cationic surfactants, even with a builder present, could provide cleaning of either
greasy and oily soils or particulate soils which was competitive with commercial fully-built
anionic detergents. Further, there was no indication that reduced cationic monomer
concentration and cloud point were critical elements to obtaining removal of greasy
and oily soils. It was therefore totally unexpected that such combinations could be
used to provide superior performance even in low or non-phosphate systems, as well
as in systems containing no builder or relatively non-effective builders.
[0097] Such performance is obtained where the newly-discovered cloud point and reduced cationic
monomer concentration criteria, set forth herein, are met in the washing process.
The process requires that the laundry solution be near the cloud point temperature
of the detergent composition, which in general is well above the nonionic's CMC. The
cationic surfactant concentration should not be too low or too high above the cationic's
CMC for optimal greasy/oily soil removal performance. These criteria and the numerous
other constraints set by considerations, such as ecological desirability and safety,
help define the preferred compositions set forth herein.
[0098] With the process of this invention, it is also possible to achieve superior particulate
soil removal if sufficient cationic surfactant is present in the laundry solution.
[0099] It may be necessary to balance the need for a relatively high concentration of cationic
surfactant (e.g., at least about 50 ppm) with other factors and it will be recognized
that for very high nonionic:cationic ratios it may not be possible, at present usage
concentrarions, to achieve the best particulate soil removal. However, the particulate
soil removal and greasy/oily soil removal achieved by these processes are superior
to that provided by any known commercial-detergent while permitting the detergent
formulator to meet the ecological and safety concerns of the present day.
[0100] In addition to the benefits found in cleaning, the present invention provides an
impressive array of secondary, but extremely desirable, benefits which are almost
anknown in the conventional anionic detergent compositions and processes of the prior
art. For example, depending upon the identity and concentrati.on of the cationic component,
it is possible to provide the benefits known in the prior art for such cationics,
e.g., antibacterial action, antistatic effects, softening effects for textiles, and
an effect not heretofore noted, the prevention or minimization of the transfer of
certain.dyes from one fabric-to another in the cleaning process.
[0101] In general, the compositions of the present invention are used in the laundering
process by forming an aqueous solution containing from about 0.01 (100 ppm) to 0.3%
(3000 ppm), preferably from about 0.02 to 0.2%, most preferably from about 0.03 to
about 0.15%, of the nonionic/cationic detergent mixture, within the cloud point and
reduced monomer concentration limitations defined above, and agitating the soiled
fabrics in that solution. The faprics are chen rinsed and dried. When used in this
manner, the compositions. of the present invention yield exceptionally good greasy
and oily soil removal, as well as particulte sell removal and fabric conditioning
berformance
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0151)
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0152)
laundry, industrial laundry or hard surface cleaning operations, concentrations
as high as about 2% may be used.
[0102] All percentaqes, parts, and ratios used herein are by weight unless otherwise specified.
[0103] The follcwing nonlimithing examples illustrate the compositions and method of the
present invention.
EXAMPLE I
[0104] Two compositions of the present invention were formulated by mixing together the
components given below in the amounts specified. The cationic surfactants were chosen
so as to be at least water-dispersible when the compositions were used in the laundry
solution.
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0154)
[0105]
Composition B is about 35 °C.
[0106] The cleaning performance of these compositions was tested against that of a standard
granular detergent composition having the following formulation:
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0156)
[0107] For each of the above detergent compositions a set of three 11" x 11" swatches (one
made of double knit polyester, one a 65/35 polyester/cotton blend, and one cotton)
were each stained with four separate stains (dirty motor oil, lipstick, triolein,
and a clay-in- water suspension). The three swatches were then added to an average
six pound load of clean mixed fabrics, containing cotton, polyester, and cotton/polyester
fabrics, and the load was washed in a full scale henmore washer using one of the compositions
described above. Each of the compositions was added to the washing solution at a usage
concentration of about 0.1%. Composition A had a pH of 8 in the washing solution,
and Composition B had a pH of about 9.7. The wash water was at a temperature of 105°F
(40°C) and contained 9 grains per gallon of natural hardness. After the laundering
was complete, each of the swatches was graded for the removal of each stain on 1 to
10 scale, with 0 signifying complete removal and 10 signifying no removal at all.
For each treatment, the total of the clay removal grades were added up and the total
of the grease/oil removal grades were added up. Thus, for each treatment the clay
removal score could range from 0, for complete removal, up to 30, for no removal;
and for the grease and oil stains, the scores could range from 0, for complete removal,
up to 90, for no removal. The results obtained are summarized in the table below.
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0157)
[0108] These data demonstrate the excellent grease and oil soil removal performance, as
well as the excellent particulate soil removal performance, obtained by the use of
the compositions of the present invention, even in the absence of any builder components.
[0109] Substantially similar results are obtained where the nonionic components in Compositions
A and B, above, are replaced by a C
14-15 alcohol polyethoxylate containing an average of 4 moles of ethylene oxide (HLB =
8.9), a C
12-13 alcohol polyethoxylate containing an average of 6.5 moles of ethylene oxide, a C
14-15 alcohol polyethoxylate containing an average of·7 moles of ethylene oxide (HLB =
11.5) a C
12-13 alcohol polyethcxylate containing an average of 3 moles of ethylene oxide (HL3 =
7.9), and the same product which is stripped so as to remove substantially all lower
ethoxylate and unethoxylated fractions, a secondary C
15 alcohol polyethoxylate containing an average of 9 moles of ethylene oxide (HL3 =
12.7), a coconut alcohol pclyethoxy- late containing an average of 5 moles of ethylene
oxide, a C
10 alcohol polyethoxylate containing an average of moles of ethylene oxide, a C
14 alcohol polycthoxylate containing an average of 6 moles of ethylene oxide, a C
12 alcohol polyethoxylate containing an average of 4 moles of ethylene oxide, a C
12-13 alcohol polyethoxylate containing an average of 9 moles of ethylene oxide (HLB =
13.3), a C
14-15 alcohol polyethoxylate containing an average of 3 moles of ethylene-oxide (HLB =
8.9), a C
14-15 alcohol polyethoxylate containing an average of 9 moles of ethylene oxide (HLB =
12.8), and mixtures of those surfactants.
[0110] Excellent cleaning results are also obtained where the ratio of nonionic surfactant
to cationic surfactant in Compositions A and B, above, are 6:1, 7:1, 9:1, 10:1, 12:1,
17:1, 20:1, or 25:1.
[0111] Similar results are also obtained where the sodium carbonate and sodium silicate
components of Composition B, above, are replaced in whole or in part by other alkali
metal tetraborates, perborates, bicarbonates, or carbonates in comparable amounts.
[0112] Substantially similar results are also obtained where the cationic surfactants of
Compositions A and B are replaced in whole or in part with decylalkyl trimethylammonium
chloride, decylalkyl trimethylammonium hydroxide, C
14 alkyl trimethylammonium chloride,
tridecylalkyl methylammonium chloride, a mixture of methyl (1) tallowalkyl amido ethyl
(2) tallowalkyl imidazolinium methyl sulfate (VARISOFT 475) together with coconutalkyl
trimethylammonium chloride (ADOGEN 461) in a ratio of VARISOFT to ADOGEN of about
1:1, 3:3, 3:1, 2:3, or 1:3; or a mixture of palmitylalkyl trimethylammonium chloride
with coconutalkyl trimethylammonium chloride in a ratio of palmityl to coconut compound
of about 3:1, 2:1, 3:2, 1:1, 1:2, or 1:3, cr surfactants having the following formulae:
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0163)
EXAMPLE II
[0113] The following two detergent compositions of the present invention were formulated
by combining the components described below in the specified amounts. The cationic
surfactants were chosen so as to be at least water-dispersible when the compositions
were used in the laundry solution.
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0164)
[0114] Composition C had a reduced cationic monomer ccncen- tration of about 0.005, and
a cloud point of about
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0165)
while Composition D had a reduced cationic monomer concentration about 0.0135, and
a cloud point of about
[0115] ![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0166)
The grease/oil and particulate soil removal performance of each composition was then
tested using the method described in Example I, above. Both compositions were used
at a product concentration of about · 0.1% in the washing solution, in water having
a temperature of 105°F (40°C). Composition C had a pH of 8 and Composition D had a
pH of 7.9 in the washing solution. Composition C was used in water containing 7 grains
per gallon of natural hardness, while Composition D was used in water containing 7,
14,
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0167)
grains per gallon of natural hardness.
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0168)
performance of these compositions is
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0169)
below.
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0170)
[0116] The above compositions yielded excellent grease and oil soil removal, was well as
particulate soil removal and fabric conditioning benefits, even in the presence of
increased concentrations of hardness in the washing solution, without requiring the
presence of builder components.
[0117] Excellent cleaning results are also obtained where the ratio of nonionic surfactant
to cationic surfactant in Compesitions C and D, above, are about 10:1, 15:1, 20:1,
25:1, 30:1, 40:1, or 50:1.
EXAXPLE III
[0118] Two compositions of the present invention were formulated by combining the components
described below in the given amounts and proportions. Each of these detergent compositions,
when added to a 105°F laundry solution appeare turbid, indicating the presence of
separated phases in the laundry solution.
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0172)
[0119] The grease/oil and particulate soil removal perfermance of Compositions E and F were
then tested against the control composition of Example I using the test method described
in Example I, above. All washes were done using water at 105°F (40°C), containing
7 grains per gailon, of natural hardness. Compositions E and G were used at the usage
concentration of about 0.1% in the laundry solution, while the control composition
was used at a usage concentration of 0.14%. Composition E had a pH of 10.2 in the
laundry solution. The soil removal results obtained are summarized in the table below:
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0173)
[0120] These data demonstrate the outstanding
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0174)
soil removal performance and particulate
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0175)
EXAMPLE IV
[0121] A composition of the present invention was formulated by combining the components
given below in the stated proportions.
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0177)
[0123] These data indicate the outstanding greasy/oily soil removal and particulate soil
removal performance which are obtained by using the compositions of the present invention.
EXAMPLE V
[0124] The relationship between greasy/oily soil removal performance and cloud point/laundry
solution temperature was demonstrated in the following manner. The detergent composition
tested was a mixture of the condensation product of C
12 alcohol with 5 moles of ethylene oxide and C
16 alkyl.trimethylammonium chloride, in a nonionic:cationic ratio of 19:1. The composition
was used at a concentration of 1000 ppm'in distilled water.
[0125] The greasy/oily soil removal performance of this composition was tested, as a function
of wash water temperature, using a Tergotometer having one 10 minute wash cycle and
two 2 minute rinse cycles. For each test, two 7.5 cm square desized polyester knit
swatches were weighed. The swatches were then stained with 200 mg. technical grade
triolein (containg 0.0083% Oil Red-0, for visualization), and weighed again. The swatches
were allowed to age for about 2 hours, and were washed in the Tergotometer (1000 ml
water; 1000 ppm of the detergent composition)', air dried, and reweighed. The percent
triolein removal was calculated using the formula: 100 x [wt (soiled) - wt (washed)]/[wt
(soiled) - wt (clean)]. This procedure was repeated at a series of wash water temperatures.
[0126] The light scattering intensity of the detergent composition, as a function of solution
temperature, was determined as follows
[0127] The light scattering intensity was measured using a Model MV-12397 Phctogoniodiffusometer,
manufactured by Societe Francaise d'instruments de controls et d'analyses, France
(the instrument being hereinafter referred to as SOFICA). The SOFICA sample cell and
its lid were washed with hot acetone and allowed to dry. The surfactant mixture was
made and put into solution with distilled water, at a concentration of 1000 ppm. Approximately
a 15 ml. sample of the solution was placed into the sample cell, using a syringe with
a 0.2µ nucleopore filter. The syringe needle passed through the sample cell lid, so
that the cell interior was not exposed to atomospheric dust. The sample was kept in
a variable temperature bath, and both the bath and the sample were subject to constant
stirring. The bath temperature was heated using the SOFICA's heater and cooled by
the addition of ice (heating rate χ1°C/minute); the temperature of the sample was
determined by the temperature of the bath. The light scattering intensity of the sample
was then determined at various temperatures, using a green filter and no polarizer
in the SOFICA.
[0128] The results of these tests are summarized in the following table.
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0183)
[0129] These data show that the optimum triolein removal for this detergent composition
occurs in a wash solution having a temperature of about 50°C; this is approximately
the same temperature at which the light scattering of the solution begins to sharply
increase in moving toward its maximum value (i.e., the cloud point of the nonionic/cationic
surfactant mixture). It is therefore seen that by using this detergent composition
in a wash solution having a temperature close (i.e., within about 20°C) to the composition's
cloud point, the maximum triolein removal for that composition is achieved.
EXAMPLE VI
[0130] A heavy duty liquid laundry detergent composition, having the formula given below,
is formulated by mixing together the following components in the stated proportions.
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0184)
[0131] This product has a cloud point which falls between 30°C and 50°C and when used in
an automatic laundering operation at a concentration of about has a pH of about 7.5,
and provides excellent removal of both particulate and greasy/oily soils.
FXAXPLE VII
[0132] A substrate article, for use in the automatic laundering operation, is made by inprecnating
an 8" x 11" sheet of a Scott
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0185)
having an air permeability of about
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0186)
a basis weight of about 77.5 grams per eq. yd., and a thickness of 44 mils, with about
50 grams of the composition described in Example VI, above. The sheet is then dried
to remove excess moisture. This article provides a convenient method for introducing
the compositions of the present invention into the laundering solution, as well as
providing excellent cleaning, statis control, fabric softening and dye transfer inhibition
performance.
[0133] A substrate article may also be made by coating one side of an
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0187)
sheet of melt-blown polypropylene, having a thickness of about 29 mils, a basis weight
of about 58.5
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0188)
and an air permeability of about 66
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0189)
with about 60 grams of the detergent composition described in Example VI, placing
an identical
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0190)
over the coated sheet, and heat-sealing together the
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0191)
two substrates, enclosing the
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0192)
the article.
EXAMPLE VIII
[0134] A solid particulate detergent composition of the present invention, having the formulation
given below, is made in the following manner.
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0193)
[0135] The nunionic and cationic components are mixed together, and are then mixed with
the solid urea, while concurrently being warmed. The resultant product is then mixed
with the carbonate, silicate and minor components. This product, when used in an automatic
laundering operation at conventional usage concentrations, has a pH of about 9, and
provides excellent particulate and greasy/oily soil removal.
EXAMPLE IX
[0136] A solid particulate detergent composition of the present invention, having the formulation
given below, is made in the manner described in Example VIII, above.
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0194)
[0137] This product, when used in an automatic washing machine at conventional usage concentrations,
has a pH of about 9, and provides excellent particulate and greasy/oily soil removal
performance.
EXAMPLE X
[0138] A heavy duty liguid laundry detergent composition, having the formula given below.
is formulated by mixing together the following components in the stated proportions.
The composition, when formulated, has a turbid appearance.
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0195)
[0139] This product, when used in an automatic laundering operation at a concentration of
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0196)
has a pH of about 9.5, and provides excellent removal of both particulate and greasy/oily
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0197)
The product may also be used as. a pretreatment
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0198)
onto greasy/oily soils prior to the laundering operation.
[0140] A heavy duty liquid laundry detergent composition of the present invention, having
the formula given below, is formulated by mixing tegether the following components
in the stated proportions.
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0200)
[0141] This product, when used in an automatic laundering operation at a concentration of
about 0.05%, has a pH of about and provides excellent removal of greasy/ oily, body,
and particulate soils, as well as providing static control and dye transfer inhibition
benefits to the fabrics laundered therewith.
[0142] Substantially similar results are obtained where the cationic component is replaced,
in whole or part, with palmitylalkyl trimethylammonium chloride, or hydrogenated tallowalkyl
trimethylammonium chloride; and the nonionic component is replaced, in whole or part,
with the condensa- tion product of C
12 alcohol with 5 moles of ethylene oxide, the condensation product of C
14-15 alcohol with 7 moles of ethylene oxide, or mixtures thereof.
EXAMPLE XII
[0143] A heavy duty liquid laundry detergent composition, having the formula given below,
is formulated by mixing- together the following components in the stated proportions.
The composition, when formulated, has a clear, homogeneous appearance.
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0202)
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0203)
temperatures than do American washing conditions.
EXAMPLE XIII
[0144] ![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0204)
[0145]
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0205)
[0146] This product provides excellent removal of particulate, greasy/oily
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0206)
when used under conventional Japanese leundry concitions, which gonerally utilize
lower water temperatures than do American washing conditions.
EXAMPLE XIV
[0147] A heavy duty liquid laundry detergent composition, having the formula given below,
is formulated by mixing together the following components in the stated proportions.
The composition, when formulated, has a clear, homogeneous appearance.
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0207)
[0148] This product has desirable sudsing characteristics and provides excellent removal
of particulate, greasy/ oily and body soils when used under conventional Japanese
laundry conditions, which generally utilize lower water temperatures than do American
laundering conditions.
EXAMPLE XV
[0149] A heavy duty liquid laundry detergent composition, having the formula given below,
is formulated by mixing together the following compenents in the stated proportions.
The composition, when formulated, has a clear, homogeneous appearance.
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0208)
[0150] This product has desirable sudsing characteristics and provides excellent removal
of particulate, greasy/ oily, and body soils when used under conventional Japanese
laundry conditions, which generally utilize lower water temperatures than do American
laundering conditions.
EXAMPLE XVI
[0151] A heavy duty liquid detergent composition, having the formula given hereinaftor,
was prepared by mixing together the listed components in the stated proportions.
![](https://data.epo.org/publication-server/image?imagePath=1979/02/DOC/EPNWA1/EP78200065NWA1/imgb0209)
[0152] - The above composition was homogeneous and storage- stable over prolonged periods
of time. In addition, it provided, by reference to prior art compositions, unexpectedly
superior greasy stain removal performance.
[0153] Substantially similar results are obtained where the cationic component is replaced,
in whole or in part, by a comparable level of a quaternized nitrogen-containing ingredient
selected from the group consisting of: coconut- alkyl trimethylammonium chloride,
coconutalkyl trimethyl- ammonium bromide, benzyl dihydroxyethylmethylammonium chloride,
ethoxylated coconutalkyl quaternary ammonium compounds wherein from 2 to 8 moles of
ethylone oxide are condensed onto the nitrogen, and mixtures thereof.