Note: Descriptions are shown in the official language in which they were submitted.
WO 01/19507 CA 02397811 2002-03-15 pCT~S00/23719
Title: Ternary Surfactant Blends Comprising Cationic, Anionic, and Bridging
Surfactants and Methods of Preparing Same
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Specification
This application claims benefit of U.S. Provisional Application No.
60/154,750, filed September 17, 1999.
(Case No. T00,015-C)
TO ALL WHOM IT MAY CONCERN:
Be it know that we, Daniela T. Bratescu, a citizen of Romania and a resident
of 1927 West Central
Road, Town of Glenview, County of Cook, State of Illinois, 60025; and Randal
J. Bernhard, a citizen of the
United States and a resident of 39771 North Wittenburg Drive, Town of
Lindenhurst, County of Lake,
State of Illinois, 60002, have invented certain new and useful improvements in
Ternary Surfactant Blends Comprising Cationic, Anionic, and Bridging
Surfactants and Methods
of Preparing Same
of which the following is a specification.
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Ternary Surfactant Blends Comprising Cationic, Anionic, and Bridging
Surfactants and Methods
of Preparing Same
This application claims benefit of U.S. Provisional Application No.
60/154,750, filed September 17, 1999.
Field of the Invention
The present invention relates to surfactant blends comprising a mixture of at
least one cationic
surfactant, at least one anionic surfactant and optionally at least one
"bridging surfactant" selected from
semi-polar nonionic, ethoxylated alkanolamide, and amphoteric/zwitterionic
surfactants, and mixtures
thereof. More specifically, the invention relates to stable, synergistic
mixtures of cationic, anionic, and
bridging surfactants that are useful as bulk surfactant blends.
Background of the Invention
Anionic-cationic surfactant mixtures are well known to the art. See generally,
U.S. Pat. Nos.
5,441,541, 5,472,455, 5,204,010, 4,790,856, 4,298,480, 3,730,912 (all to The
Colgate-Palmolive
Company), 5,622,925, 5,607,980, 5,565,145, 4,913,828, 4,659,802, 4,436,653,
4,338,204, 4,333,862,
4,132,680 (all to The Procter & Gamble Co.); also see WO 97/03164, WO 97/12022
and WO 96/37591
(all to The Procter & Gamble Co.), and WO 97/28238 and WO 97/15647 (both to
Reckit & Colman, Inc.).
See also, U.S. Pat. Nos. 5,610,187 and 4,247,538 (both to Witco Corp.),
5,344,949 (to Th. Goldschmidt
AG), 5,332,854 and 5,324,862 (both to Dai-/chi Kogoyo Seiyaku Co., Ltd.),
4,273,760 (to National Starch
and Chemical), and 4,264,457 (to DeSoto, Inc.). Mixed surfactant systems have
also been disclosed in
"Mixed Surfactant Systems", ACS Symposium Series 501, P.M. Holland and D.N.
Rubingh (June 17-19,
1991 ).
Additionally, there have been many studies and symposia on mixed surfactant
systems. See, for
example, Scamehorn, J. F., ed., "Phenomena in Mixed Surfactant Systems", ACS
Symposium Series 311,
Washington, D.C. (1986). The effects of alkyl groups and oxyethylene groups in
nonionic surfactants on
the surface tension of anionic-nonionic systems have been described. See Abe
et al., J. Colloid Interface
Sci., 107, p. 503 (1985); Ogino et al., J. Colloid Interface Sci., 107, p. 509
(1985); and Rosen et al., J.
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Colloid Interface Sci., 95, 443 (1983). Interaction between betaines and
cationic surfactants has also
been studied. See Zhu et al., J. Colloid Interface Sci., 108, 423 (1985).
Mixed surfactant systems have shown synergistic improvements in surfactant
properties compared
to the properties of their individual surfactant components. Synergism
increases with the degree of
charge difference. Thus, the greatest synergistic surfactant property
improvements are realized when
mixing anionic and cationic surfactants. See Rosen et al. in "Phenomena in
Mixed Surfactant Systems"
(Scamehorn, J. F., ed.), ACS Symposium Series 311, Washington, D.C. (1986),
pp. 144-162; Zhao et al.
in "Phenomena in Mixed Surfactant Systems" (Scamehorn, J. F., ed.) ACS
Symposium Series 311,
Washington, D.C. (1986) pp. 184-198.
In detergent applications, although in principle any surfactant is suitable,
in practice only anionic
and nonionic surfactants typically are used. Cationic surfactants, especially
quaternary ammonium salts,
can decrease detergency and enhance soil redeposition when used in heavy-duty
liquid detergents.
Consequently, there is a general notion that anionic and cationic surfactants
cannot be used in the same
formula without loss of efficacy. Similar worries regarding potential loss of
efficacy exist when
contemplating use of cationic surfactants in hair and skin conditioning
applications. Thus, anionic-cationic
surfactant mixtures have been used only sparingly in the production of
consumer cleaning products and
personal care products.
Studies on anionic-cationic systems are recent and few compared to studies on
other mixed
surfactant systems. However, strong synergism has been exhibited by these
systems. Surface activity
properties, particularly the critical micelle concentration (cmc), surface
tension, and microemulsion
behavior (Bourrel et al., Tenside Detergents, 21, 311 (1984)), were the most
studied properties. For
example, the surface activities of mixed aqueous solutions of sodium
dihexylsulfosuccinate with
dioctyl(hydroxyethyl)methylammonium chloride and sodium dihexylsulfosuccinate
with
octyl(hydroxyethyl)dimethylammonium chloride were much higher than those of
the single surfactants.
See Zao, G., Huoxue Xuebo, 43, 705 (1985) (Ch. Chem. Abstracts 103:184033n).
The strong synergistic
effect on surface pressure for mixed solutions of cationic and anionic
surfactants has been studied
quantitatively. When dilute solutions of sodium dodecylsulfate and
dodecyltrimethylammonium bromide
were mixed, tile surface pressure increased by more than 40 mN/m. Also, the
cmc and the minimum
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surface tension were lower for the mixture than for either the anionic or
cationic surfactants alone
(Lucassen-Reynders et al., J. Colloid Interface Sci., 81, p. 150 (1981 )).
However, mixed anionic-cationic mixtures also have shown antagonistic effects
relative to the
properties of the individual surfactant components. See Chobanu et al., Izv.
Akad. Nauk. Mold. SSR, Ser.
Biol. Khim. Nauk., 5, p. 66 (1982). Unlike other mixed surfactant systems,
most anionic-cationic
surfactant mixtures studied are insoluble or only slightly soluble in water.
Hence, practical use of anionic-
cationic surfactant mixtures has been very limited in areas where a relatively
high concentration of
surfactants is needed (see U.S. Pat. No. 5,472,455, to Mehreteab, issued Dec.
5, 1995). Thus, there is a
need for soluble anionic-cationic surfactant mixtures.
At present, very few anionic-cationic surfactant mixtures have been found
which produce clear
solution phases over a wide concentration range at equimolar composition. See
generally, Khan, A.;
Marques, E.; Spec. Surfactants 1997, 37-80, edited by Robb, I. D. Blackie.
Typically, anionic-cationic
surfactant mixtures are present as microemulsions, rather than as clear,
homogeneous solutions.
Usually, the anionic and/or cationic surfactant must be alkoxylated to even
maintain such a
microemulsion.
Because the probability of synergism between surfactants increases with the
strength of
interaction, the greatest probability of synergism with anionic surfactants
exists in anionic-cationic or
anionic-zwiterionic mixtures. See generally, Surfactant and Interfacial
Phenomena; Rosen, M.; John Wiley
& Sons, Inc. 1989 p. 402. Surfactant performance is gauged by the so-called ~i
value, which is a negative
number indicating how much less a system's actual surface tension is compared
to its calculated surface
tension. Surfactant mixtures exhibiting larger deviations between calculated
and actual surface tension
perform better; thus, surfactant performance increases with progressively more
negative p values.
However, with respect to anionic-cationic mixtures, the variations in
surfactant type and size that produce
progressively more negative (3 values unfortunately are accompanied by
decreasing solubility. Hence
anionic-cationic synergism is limited by the formation of an insoluble salt,
which typically occurs when the
combined number of carbon atoms in the chains of both surfactants totals more
than about twenty. See
generally, Lomax, E; Specialty Chemicals 1993, v 13 n 4 p 223-227). A method
for enhancing the
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solubility of anionic-cationic surfactant mixtures is therefore needed to
allow achieving maximum negative
~3 values.
Without being bound by any particular theory, the benefits associated with
solubilized
anionic/cationic systems are best explained by the theory that surfactant
molecules of opposite charge
pack more closely to each other in micelles due to the absence of any
electrostatic repulsion. This close
packing in turn leads to more efficient soil removal. See generally, Lomax,
E., supra. Prior art attempts to
solubilize anionic-cationic surfactant systems include the use of organic
solvents, such as butanol or
ethanol. Also, reported is the use of nonionic surfactants as solubilizing
agents or incorporation of alkoxy
groups into the anionic and/or cationic surfactants. Unfortunately, addition
of organic solvents presents a
fire hazard. Additionally, addition of nonionic components tends to keep the
anionic and cationic
surfactant molecules further apart, decreasing the overall efficacy of the
system. Once again without
being bound by any particular theory, the oppositely charged surfactant
molecules are kept further apart
due to stearic hindrance and because of the osmotic effects which force water
molecules between the two
surfactant molecules, diminishing the beneficial effect of closer packing.
Thus, there is a need for anionic-cationic surfactant blends that are
efficacious, readily soluble in
water at a variety of concentrations, easy to handle, and safe to handle.
Accordingly, it has been
surprisingly discovered that soluble and substantially soluble mixtures of
anionic and cationic surfactants
can be prepared without the use of flammable organic solvents. The anionic-
cationic blends of the
present invention generally form clear solutions at a variety of
concentrations in water.
Summary of the Invention
Surfactant blends of the present invention are useful for preparing a variety
of finished consumer
cleaning products, including for example, liquid dish detergents, laundry
detergents, automatic dishwasher
detergents, hand soaps, laundry bars, personal cleansing bars, multi-purpose
cleaners, multi-functional
shampoos, body washes, and textile treatment compositions. Surfactant blends
of the present invention
also may be employed as surfactants in agricultural and pesticide
applications. Additionally, the surfactant
blends may be utilized in antimicrobial detergent formulations (e.g.,
antimicrobial hard surface cleaners,
hand soaps, shampoos, and dish detergents), soft-terg delivery systems and pre-
spotter compositions.
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Surfactant blends of the present invention may be prepared in various
concentrations and exhibit a wide
range of rheological behavior. The surfactant blends display excellent
detergent and conditioning
properties.
One aspect of the present invention relates to surfactant complexes comprising
at least one
cationic surfactant, at least one anionic surfactant, and at least one
"bridging surfactant" selected from
nonionic, semi-polar nonionic, and amphoteric/zwitterionic surfactants, and
mixtures thereof. These
complexes are useful as rheology modifiers in a wide variety of surfactant
compositions.
The present invention furnishes substantially water-soluble ternary surfactant
blends which
provide improved performance, such as for example, increased surface tension
reduction, improved
wetting times, and increased foam volume and stability, to detergent and
personal care surfactant
formulations. Additionally, ternary blends of the present invention provide
for improved greasy, oily soil
removal from surfaces and textiles. The blends are also capable of providing
conditioning properties to
skin, hair and textiles.
Surprisingly, it has been discovered that complexes of anionic and cationic
surfactants can be
utilized in combination with a bridging surfactant to produce ternary
surfactant blends which allow the
anionic-cationic complex to remain relatively soluble in aqueous solutions,
and at a variety of
concentrations, without the use of solubilizing organic solvents or insertion
of alkoxy chains into the
anionic or cationic surfactants. Surprisingly, blends of the present invention
generally are flowable at
concentrations as high as about 80 percent by weight. Additionally, the
surfactant blends when diluted to
a concentration of about 0.1 percent by weight in water generally form a clear
aqueous solution
substantially free of precipitates. As used herein, the term "flowable" means
fluid under gravity at ambient
conditions (about 1 atmosphere of pressure at about 25°C) without
application of mechanical energy. As
used herein, the term "clear" means allowing at least 50% transmittance
measured spectrophotometrically
at 700 nanometers using water as the standard for 100% transmittance.
Typically, the ternary surfactant
blend comprises (a) at least one cationic surfactant, (b) at least one anionic
surfactant, and (c) at least
one bridging surfactant, wherein the molar ratio of (a):(b):(c) is generally
about 1:1:1. However, to
optimize performance, the molar ratio of the components can vary as conditions
may dictate.
In one aspect, the invention provides a surfactant blend comprising:
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(a) a cationic surfactant which is a quaternary ammonium compound of the
formula:
Rt +
R2- N- R3 X
R4
where
R~, Rz, and R3 are independently ethyl or methyl;
R4 is an alkyl group having an average of from about 8 to about 16 carbon
atoms;
and
X is halogen, sulfate, methosulfate, ethosulfate, tosylate, acetate,
phosphate, nitrate,
sulfonate, or carboxylate;
(b) an anionic surfactant which is
(i) an alkyl sulfate having an average of from about 8 to about 16 carbon
atoms;
(ii) an alkyl sulfonate having an average of from about 8 to about 18 carbon
atoms;
(iii) an alkyl ether sulfate having an average of from about 8 to about 16
carbon atoms in the
alkyl portion and from about 1 to about 30 moles of ethylene oxide;
(iv) an a-olefin sulfonate having an average of from about 12 to about 18
carbon
atoms;
(v) an a-sulfonated C,-C6 alkyl ester of a fatty acid having an average of
from about 11 to
about 16 carbon atoms;
(vi) a sulfosuccinate having an average of from about 10 to about 16 carbon
atoms;
(vii) a sarcosinate having an average of from about 10 to about 16 carbon
atoms; or
(viii) a sulfoacetate having an average of from about 12 to about 20 carbon
atoms;
or mixtures thereof; and
(c) a bridging surfactant selected from the group consisting of amine oxides,
ethoxamides, and
betaines;
wherein the total concentration of combined cationic, anionic, and bridging
surfactants is from
about 30 to about 80 percent by weight, and wherein the surfactant blend is
flowable.
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In another aspect, the invention provides a method of preparing a ternary
surfactant composition
comprising combining:
(a) a cationic surfactant which is a quaternary ammonium compound of the
formula:
R1 +
I
R2- N- R3 X
R4
where
R,, R2, and R3 are independently ethyl or methyl;
R4 is an alkyl group having an average of from about 8 to about 16 carbon
atoms;
and
X is halogen, sulfate, methosulfate, ethosulfate, tosylate, acetate,
phosphate, nitrate,
sulfonate, or carboxylate; and
(b) an anionic surfactant which is
(i) an alkyl sulfate having an average of from about 8 to about 16 carbon
atoms;
(ii) an alkyl sulfonate having an average of from about 8 to about 18 carbon
atoms;
(iii) an alkyl ether sulfate having an average of from about 8 to about 16
carbon atoms in the
alkyl portion and from about 1 to about 30 moles of ethylene oxide;
(iv) an a-olefin sulfonate having an average of from about 12 to about 18
carbon
atoms;
(v) an a-sulfonated C,-C6 alkyl ester of a fatty acid having an average of
from about 11 to
about 16 carbon atoms;
(vi) a sulfosuccinate having an average of from about
10 to about 16 carbon atoms;
(vii) a sarcosinate having an average of from about
10 to about 16 carbon atoms; or
(viii) a sulfoacetate having an average of from about
12 to about 20 carbon atoms;
or mixtures thereof; and
(c) a bridging surfactant selected from the group consisting of amine oxides,
ethoxamides, and
betaines;
wherein the bridging surfactant is added first or second, and wherein the
total concentration of
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combined cationic, anionic, and bridging surfactants is from about 30 to about
80 percent by weight, and
wherein the surfactant blend is flowable.
In still another aspect, the invention provides a method for enhancing the
solubility of an anionic-
cationic surfactant complex comprising combining:
(a) an anionic-cationic complex formed by combining in any order:
(i) a cationic surfactant which is a quaternary ammonium compound of the
formula:
R1 +
R2- N- R3 X
R4
where
R~, R2, and R3 are independently ethyl or methyl;
R4 is an alkyl group having an average of from about 8 to about 16 carbon
atoms; and
X is halogen, sulfate, methosulfate, ethosulfate, tosylate, acetate,
phosphate, nitrate,
sulfonate, or carboxylate; and
(ii) an anionic surfactant which is
(1 ) an alkyl sulfate having an average of from about 8 to about 16 carbon
atoms;
(2) an alkyl sulfonate having an average of from about 8 to about 18 carbon
atoms;
(3) an alkyl ether sulfate having an average of from about 8 to about 16
carbon atoms in the alkyl portion and from about 1 to about 30 moles of
ethylene oxide;
(4) an a-olefin sulfonate having an average of from about 12 to about 18
carbon atoms;
(5) an a-sulfonated C,-C6 alkyl ester of a fatty acid having an average of
from about
11 to about 16 carbon atoms;
(6) a sulfosuccinate having an average of from about 10 to about 16 carbon
atoms;
(7) a sarcosinate having an average of from about 10 to about 16 carbon atoms;
or
(8) a sulfoacetate having an average of from about 12 to about 20 carbon
atoms;
or mixtures thereof; and
(b) a bridging surfactant selected from the group consisting of amine oxides,
ethoxamides, and
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betaines.
Thus, the invention provides surfactant blends comprising a synergistic
mixture of anionic and
cationic surfactants that are generally water soluble without the use of
organic solvents or insertion of
alkoxy chains into either the anionic or cationic surfactant.
The invention further provides surfactant blends exhibiting excellent
detergent properties
comprising a synergistic mixture of anionic and cationic surfactants that are
generally flowable at
concentrations as high as about 80 percent by weight, and, when diluted to a
concentration of about 0.1
percent by weight in water, generally form clear aqueous solutions
substantially free of precipitates.
These and other aspects and advantages, as well as the scope, nature, and
utilization of the
claimed invention will become apparent to those skilled in the art from the
following detailed description
and claims.
Detailed Description of a Preferred Embodiment
Cationic and anionic surfactants form complexes that are generally insoluble
because the charged
heads (anionic or cationic) responsible for water solubility are neutralized
during complexation.
Surprisingly, it has been found that if the cationic surfactant and anionic
surfactant are combined with a
bridging surfactant to form a ternary blend, a substantially water-soluble
system is produced. In ternary
surfactant blends of the invention, the use of additional hydrophilic groups
(such as ethylene oxide groups
or additional charge that remains un-neutralized during complexation) on the
anionic or cationic surfactant
is not necessary to produce a water-soluble complex. Water solubility is
assured if an appropriate
bridging surfactant is utilized in combination with the anionic and cationic
surfactant.
The present invention provides ternary blends of cationic, anionic and
bridging surfactants
wherein anionic/cationic complexes are formed. While not intending to be
limited by a particular theory, it
is believed that the quaternary ammonium agent (a cationic surfactant) and
anionic surfactants typically
form ion pair complexes in aqueous solutions. The ion pairs formed between tri-
short chain, mono-long
chain quaternary ammonium halides and many anionic surfactants have low
solubility and precipitate as a
solid salt at typical use concentrations. This not only has a negative effect
on cleaning performance, but
also prevents use of such anionic-cationic ion pair complexes in isotropic
liquid detergents. On the other
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hand, ion pairs formed by such cationic surfactants and many anionic
surfactants in the presence of a
bridging surfactant are much more soluble in bulk surfactant compositions, as
detailed herein. This
increased solubility allows for greater flexibility in formulating with the
bulk surfactant compositions (i.e. the
surfactant blends), such as for example, the formulation of isotropic liquid
detergents. Ternary surfactant
blends of the invention are generally flowable at concentrations as high as
about 80 percent by weight.
Additionally, the surfactant blends when diluted to a concentration of about
0.1 percent by weight in water
generally form a clear aqueous solution substantially free of precipitates.
One indication that an anionic-cationic complex is solubilized within the
ternary surfactant blends
of the invention is the unique surface tension properties exhibited by the
ternary surfactant blends. The
interfacial surface tension and detergency behavior of an anionic-cationic
complex is very different
compared to either of the individual anionic and cationic surfactant
components. In particular, an anionic-
cationic complex exhibits significantly lower interfacial surface tension and
significantly higher foaming
than either an anionic or cationic surfactant alone. In similar fashion, the
interfacial tension between
certain oils and an aqueous solution of a ternary surfactant blend of the
invention was found to be lower
than the interfacial tension between the same oils and an aqueous solution of
the individual anionic,
cationic, or bridging surfactants, or combinations of two of these
surfactants. This indicates that an
anionic-cationic complex, once formed, remains solubilized in aqueous
solutions of ternary surfactant
blends of the invention. Surprisingly, anionic-cationic complexes remain
solubilized within aqueous
solutions of ternary surfactant blends even when one or both of the cationic
and anionic surfactants
contain substantially no alkylene oxide groups or additional charges that
remain unneutralized during
complexation.
Long-term storage stability is often lacking in mixtures employing anionic-
cationic complex
mixtures due to the tendency of anionic and cationic surfactants in
combination to produce precipitates in
water. Typically, such compositions are not stable and separate into two
phases on storage, rendering
them aesthetically and functionally unacceptable. Surprisingly, ternary
surfactant blends of this invention
are generally provided in the form of a flowable composition that can be
expected to be stored for long
periods of time prior to sale or use. The formation of an anionic-cationic
precipitate is avoided herein, and
a lack of such a precipitate in the compositions of this invention is one of
this invention's advantages.
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In another embodiment, the invention provides methods for preparing ternary
surfactant blends.
The ternary blends of the invention are readily obtained by merely pre-mixing
either the anionic or the
cationic surfactant with the bridging surfactant, followed by mixing with the
surfactant not pre-mixed.
In other embodiments, the present invention provides complexes useful as
rheology modifiers.
The present invention further encompasses consumer detergent, laundry and
personal care products
prepared using the surfactant blends and/or complexes detailed herein. The
essential, as well as the
optional, components of the present invention are described below.
Cationic Surfactants
Generally, the cationic surfactant is a surfactant selected from the group
comprising fatty amine
salts, fatty diamine salts, polyamine salts, quaternary ammonium salts,
polyoxyethyleneated fatty amine
salts, quaternized polyoxyethyleneated fatty amines, and mixtures thereof. A
variety of cationic
surfactants useful in the present invention are well known in the art.
Cationic surfactants useful herein
include those disclosed in the following documents, all of which are
incorporated by reference herein: M.
C. Publishing Co., McCutcheon's Detergents & Emulsifiers, (North American Ed.,
1993); Schwartz et al.,
Surface Active Agents, Their Chemistry and Technology, New York; Interscience
Publisher, 1949; U.S.
Pat. No. 3,155,591, Hilfer, issued Nov. 3, 1964; U.S. Pat. No. 3,929,678,
Laughlin et al., issued Dec. 30,
1975; U.S. Pat. No. 3,959,461, Bailey et al., issued May 25, 1976; and U.S.
Pat. No. 4,387,090, Bolich, Jr.,
issued June 7, 1983. Suitable anions include but are not limited to halogen,
sulfate, methosulfate,
ethosulfate, tosylate, acetate, phosphate, nitrate, sulfonate, and
carboxylate.
Cationic surfactants in the form of quaternary ammonium salts include mono-
long chain alkyl-tri-
short chain alkyl ammonium halides, wherein the long chain alkyl group has
from about 8 to about 22
carbon atoms and is derived from long-chain fatty acids, and wherein the short
chain alkyl groups can be
the same or different but preferably are independently methyl or ethyl.
Examples of quaternary ammonium salts useful herein include but are not
limited to cetyl trimethyl
ammonium chloride and lauryl trimethyl ammonium chloride. A particularly
preferred quaternary
ammonium salt is cetyl trimethyl ammonium chloride.
Salts of primary, secondary and tertiary fatty amines are also suitable
cationic surfactant
materials. The alkyl groups of such amine salts preferably have from about 12
to about 22 carbon atoms,
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and may be substituted or unsubstituted. Secondary and tertiary amine salts
are preferred, tertiary amine
salts are particularly preferred. Suitable amine salts include the halogen
(i.e fluoride, chloride, bromide),
acetate, phosphate, nitrate, citrate, lactate and alkyl sulfate salts. Amine
salts derived from amine, such
as for example, stearamido propyl dimethyl amine, diethyl amino ethyl
stearamide, dimethyl stearamine,
dimethyl soyamine, soyamine, myristyl amine, tridecyl amine, ethyl
stearylamine, N-tallowpropane
diamine, ethoxylated (5 moles E.O.) stearylamine, dihydroxy ethyl
stearylamine, and
arachidylbehenylamine, are useful herein. Such salts also include stearylamine
hydrogen chloride,
soyamine chloride, stearylamine formate, N-tallowpropane diamine dichloride
and stearamidopropyl
dimethylamine citrate. Additionally cationic surfactants included among those
useful in the present
invention are disclosed in U.S. Pat. No. 4,275,055, Nachtigal, et al., issued
June 23, 1981, incorporated
herein by reference.
In addition to the above, cationic surfactants particularly useful herein are
those of the general
formula:
R1 +
RZ-N-R3 X
R4
where R,, R2, and R3 are independently ethyl or methyl; RQ is an alkyl group
having an average of from
about 8 to about 16 carbon atoms; and X is an a suitable ion including but not
limited to halogen, sulfate,
methosulfate, ethosulfate, tosylate, acetate, phosphate, nitrate, sulfonate,
or carboxylate.
Other quaternary ammonium compounds and amine salt compounds include those of
the above
general formula in the form of ring structures formed by covalently linking
two of the radicals. Examples
include imidazolines, imidazoliniums, and pyridiniums, etc., wherein said
compound has at least one
nonionic hydrophile-containing radical as set forth above. Specific examples
include 2-heptadecyl-4,5
dihydro-1H-imidazol-1-ethanol, 4,5-dihydro-1-(2-hydroxyethyl)-2-isoheptadecyl-
1-phenylmethylimidazolium
chloride, and 1-[2-oxo-2-[[2-[(1-oxoctadecyl)oxy]ethyl]amino]ethyl] pyridinium
chloride. Additionally, useful
polymerizable surface active agents include those of the above general formula
in the form of ring
structures formed by covalently linking two of the R,-R4 groups.
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The quaternary ammonium salts of the present invention may be prepared by a
variety of
methods known to the art, including for example, halide exchange, wherein a
halide based quaternary
ammonium compound is ion exchanged with X, where X is defined above.
The most preferred cationic surfactants for use in the present invention
include octyltrimethyl
ammonium chloride, decyltrimethyl ammonium chloride, dodecyltrimethyl ammonium
bromide,
dodecyltrimethyl ammonium chloride, Cetac~-30, BTC°-65NF, BTC~-835 and
BTC°-885, all commercially
available from Stepan Company.
Anionic Surfactants
The anionic surfactants that may be utilized according to the present
invention are well known to
the art and are described below in a representative manner. Generally
speaking, a variety of anionic
surfactants useful in the present invention are well known in the art. Anionic
surfactants useful herein
include those disclosed in the following documents, all of which are
incorporated by reference herein: M.
C. Publishing Co., McCutcheon's Detergents & Emulsifiers, (North American Ed.,
1993); Schwartz et al.,
Surface Active Agents, Their Chemistry and Technology, New York; Interscience
Publisher, 1949; U.S.
Pat. No. 4,285,841, Barrat et al, issued Aug. 25, 1981; and U.S. Pat. No.
3,919,678, Laughlin et al, issued
Dec. 30, 1975.
The anionic surfactants of the present invention generally include salts
(including, for example,
sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di-
, and triethanolamine
salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate
surfactants. Other suitable anionic
surfactants include the isethionates such as the acyl isethionates, N-acyl
taurates, fatty acid amides of
methyl tauride, alkyl succinates and sulfosuccinates, monoesters of
sulfosuccinate (especially saturated
and unsaturated C,2-C,8 monoesters), diesters of sulfosuccinate (especially
saturated and unsaturated
C6-C,4 diesters), and N-acyl sarcosinates. Resin acids and hydrogenated resin
acids are also suitable,
such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin
acids present in or derived
from tallow oil.
Anionic sulfate surfactant
Anionic sulfate surfactants suitable for use in the compositions of the
invention include the linear
and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty
oleyl glycerol sulfates, alkyl
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phenol ethoxylate sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-
C,~ acyl-N-(C,-C4 alkyl) and -
N-(C,-CZ hydroxyalkyl) glucamine sulfates, and sulfates of
alkylpolysaccharides such as the sulfates of
alkylpolyglucoside.
Alkyl sulfate surfactants are preferably selected from the group consisting of
the C8-C22 alkyl
sulfates. Most preferably, the alkyl sulfate surfactant is a C8-C,6 alkyl
sulfate. Alkyl ethoxysulfate
surfactants are preferably selected from the group consisting of the C8-CZZ
alkyl sulfates that have been
ethoxylated with from about 0.5 to about 30 moles of ethylene oxide per
molecule. Most preferably, the
alkyl ethoxysulfate surfactant is a C8-C,6 alkyl sulfate which has been
ethoxylated with from about 1 to
about 30 moles of ethylene oxide.
A particularly preferred aspect of the invention employs mixtures of CS alkyl
sulfate (Polystep° B-
29, commercially available from Stepan Company, Northfield, Illinois) and
alkyl ethoxysulfate surfactants.
Such mixtures have been disclosed in WO 93/18124, incorporated by reference
herein.
Anionic sulfonate surfactant
Anionic sulfonate surfactants suitable for use herein include the salts of C5-
C2o linear alkylbenzene
sulfonates, alkyl ester sulfonates, C6-C2z primary or secondary alkane
sulfonates, C6-C24 olefin sulfonates,
alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl
glycerol sulfonates, and any mixtures
thereof.
Anionic sulfonate surfactants are preferably selected from the group
consisting of the C8-
C22 alkyl sulfonates and C8-C22 a-olefin sulfonates. Most preferably, the
anionic sulfonate surfactant is an
C8-C,8 alkyl sulfonate, such as Bioterge° PAS-8S (commercially
available from Stepan Company,
Northfield, Illinois), or a C,z-C,$ a-olefin sulfonate, such as
Bioterge° AS-40 (commercially available from
Stepan Company, Northfield, Illinois).
Anionic carboxylate surfactant
Suitable anionic carboxylate surfactants include the alkyl ethoxy
carboxylates, the alkyl polyethoxy
polycarboxylate surfactants and the soaps ("alkyl carboxyls"), especially
certain secondary soaps as
described herein.
Suitable alkyl ethoxy carboxylates include those with the formula
RO(CHzCH20)xCH2C00-M'
wherein R is a Cs to C,8 alkyl group, x ranges from 0 to 10, and the
ethoxylate distribution is such that, on
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a weight basis, the amount of material where x is 0 is less than about 20
percent and M is a cation.
Suitable alkyl polyethoxy polycarboxylate surfactants include those having the
formula
RO(CHR,CHR20)R3 wherein R is a Cs to Cps alkyl group, x ranges from 1 to 25,
R, and Rz are selected
from the group consisting of hydrogen, methyl acid radical, succinic acid
radical, hydroxysuccinic acid
radical, and mixtures thereof, and R3 is selected from the group consisting of
hydrogen, substituted or
unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures
thereof.
Suitable soap surfactants include the secondary soap surfactants which contain
a carboxyl unit
connected to a secondary carbon. Preferred secondary soap surfactants for use
herein are water-soluble
members selected from the group consisting of the water-soluble salts of 2-
methyl-1-undecanoic acid, 2-
ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-
pentyl-1-heptanoic acid.
Anionic sulfosuccinate surfactant
Suitable anionic sulfosuccinates include those having the formula
O O O O
XO-IICH CHII-O-M+ or XO-IICH CHII-OY
21 + 21 +
S03- M S03- M
where
X and Y are the same or different and are selected from the group consisting
of
R and R(CHzCH20)X, where x has an average value from about 1 to about 30;
R is C8-C22 alkyl;
and M is an alkali metal counterion.
Anionic sulfosuccinate surfactants are preferably selected from the group
consisting of
the Cs-C22 sulfosuccinates. Most preferably, the anionic sulfosuccinate
surfactants is a mono-
C,o-Cps alkyl sulfosuccinate such as disodium laureth sulfosuccinate (Stepan-
Mild~ SL3, commercially
available from Stepan Company, Northfield, Illinois)
Anionic a-sulfonated methyl ester surfactant
Suitable a-sulfonated methyl esters include those having the formula
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WO 01/19507 PCT/US00/23719
O O
XO-CHII O-M+ or XO-CHII-OY
O _ M+ S03- M+
3
where
X and Y are the same or different and are selected from the group consisting
of
C8-CZZ alkyl;
and M is an alkali metal counterion.
Anionic a-sulfonated methyl ester surfactants are preferably selected from the
group
consisting of the a-sulfonated C~-Cs alkyl esters of fatty acids having an
average of from about 8 to about
22 carbon atoms. Most preferably, the anionic a-sulfonated methyl ester
surfactants is selected from the
group consisting of the a-sulfonated C,-Cs alkyl esters of fatty acids having
an average of from about 11
to about 16 carbon atoms. Most preferably, the anionic a-sulfonated methyl
ester surfactants is Alpha
Step° MC-48 or Alpha Step° ML-40 (both commercially available
from Stepan Company, Norfhfield,
Illinois).
Alkali metal sarcosinate surfactant
Other suitable anionic surfactants are the alkali metal sarcosinates of the
formula
RCON(R,)CHZCOOM, wherein R is a C5-CzZ linear or branched alkyl or alkenyl
group, R, is a C,-C4 alkyl
group and M is an alkali metal ion. Preferred alkali metal sarcosinate
surfactants include but are not
limited to the myristyl and oleoyl methyl sarcosinates in the form of their
sodium salts. Most preferably,
the alkali metal sarcosinate surfactant is a C,o-C,6 sarcosinate such as
Maprosyl° 30 (commercially
available from Stepan Company, Northfield, Illinois).
Alkyl sulfoacetates
Other suitable anionic surfactants are the alkyl sulfoacetates of the formula
RO(CO)CHZS03M,
wherein R is a C,2-C2o alkyl group and M is an alkali metal ion. Preferred
alkyl sulfoacetates include but
are not limited to the lauryl and myristyl sulfoacetates in the form of their
sodium salts. Most preferably,
the alkyl sulfoacetate is Lathanol° LAL (commercially available from
Stepan Company, Northfield, Illinois).
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Bridging Surfactants
The bridging surfactants of the present invention are selected from the group
consisting of semi-
polar nonionic, ethoxamide, and amphoteric surfactants and mixtures thereof.
Especially preferred
bridging surfactants include amine oxides, ethoxylated alkanolamides, and
betaines.
Semi-Polar Nonionic Surfactants
Semi-polar nonionic surfactants include water-soluble amine oxides having an
alkyl
moiety containing from about 10 to about 18 carbon atoms and 2 moieties
selected from the group
consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to
about 3 carbon atoms.
Semi-polar nonionic surfactants also include water-soluble sulfoxides having
alkyl moieties containing
from about 10 to about 18 carbon atoms and a moiety selected from the group
comprising alkyl groups
and hydroxyalkyl groups of from about 1 to about 3 carbon atoms.
The present invention encompasses semi-polar nonionic surfactants that are
amine
oxides formed as shown in Scheme I, wherein R~, R2, R3 independently are
substituted or unsubstituted
hydrocarbyl groups of from about 1 to about 30 carbon atoms, or hydrocarbyl
groups having from about 1
to about 30 carbon atoms and containing one or more aromatic, ether, ester,
amido, or amino moieties
present as substituents or as linkages in the radical chain; and wherein X- is
an anion group selected from
the group consisting of halogen, sulfonate, sulfate, sulfinate, sulfenate,
phosphate, carboxylate, nitrate,
and acetate. Additionally, useful semi-polar nonionic surfactants include
those of the below general
formula in the form of ring structures formed by covalently linking two of the
R,-RQ groups. Examples
include unsaturated imidazolines, imidazoliniums, and pyridiniums, and the
like. Particularly preferred
semi-polar nonionic surfactants include alkylamine and amidoamine oxides.
Scheme I: Amine Oxide-Derived Surface Active Agents
R1 R
/N\ H2~-~ 1~1~0
R2 R3 / \
R2 R3
Particularly preferred amine oxides include but are not limited to
Ammonyx° C8 (octylamine
oxide), Ammonyx° C10 (decylamine oxide), Ammonyx° LO
(laurylamine oxide), Ammonyx° MO
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(myristylamine oxide), Ammonyx° MCO (myristyl/cetylamine oxide), and
Ammonyx° CDO
(cocamidoproylamine oxide), all commercially available from Stepan Company,
Northfield, Illinois.
Ethoxamides
Ethoxamides (also termed ethoxylated alkanolamides or polyethylene glycol
amides) suitable for
use in the present invention include those having the formula
O
CH3(CHZ),r,C-N(CH2CH20)nH or RI ~ -N(CH CH O) H
2 2 n
Y
where
RCO- represents the fatty acids derived from coconut oil;
m is an integer from about 8 to about 16;
n has an average value of about 3;
Y is hydrogen or (CHZCHzO)PH; and
p is 0, 1 or more.
Preferred ethoxamides include but are not limited to Amidox° C-2 (PEG-3
cocamide), Amidox° C-5 (PEG-
6 cocamide), and Amidox° L-5 (PEG-6 lauramide), all commercially
available from Stepan Company,
Northfield, Illinois.
Amphoteric Surfactants
Suitable amphoteric surfactants are selected from the group consisting of
alkyl glycinates,
propionates, imidazolines, amphoalkylsulfonates (sold under the tradename
Miranol~ by Rhone Poulenc),
N-alkylaminopropionic acids, N-alkyliminodipropionic acids, imidazoline
carboxy-lates, N-alkylbetaines,
amido propyl betaines, sarcosinates, cocoamphocarboxyglycinates, amine oxides,
sulfobetaines, sultaines
and mixtures thereof. Additional suitable amphoteric surfactants include
cocoamphoglycinate,
cocoamphocarboxyglycinate, lauramphocarboxyglycinate, coco-amphopropionate,
lauramphopropionate,
stearamphoglycinate, cocoamphocarboxypropionate, tallowamphopropionate,
tallowamphoglycinate,
oleoamphoglycinate, caproamphoglycinate, caprylamphopropionate,
caprylamphocarboxyglycinate, cocoyl
imidazoline, lauryl imidazoline, stearyl imidazoline, behenyl imidazoline,
behenylhydroxyethyl imidazoline,
WO 01/19507 CA 02397811 2002-03-15 pCT/US00/23719
capryl-amphopropylsulfonate, cocamphopropylsulfonate,
stearamphopropylsolfonate, oleoampho-
propylsulfonate and the like.
Examples of betaines and sultaines which are suitable for use as bridging
surfactants are alkyl
betaines and sultaines sold under the tradename Mirataine° by Rhone
Poulenc, and Lonzaine~ by Lonza,
S Inc., Fairlawn, N.J. Additional examples of betaines and sultaines include
cocobetaine, cocoamidoethyl
betaine, cocoamidopropyl betaine, lauryl betaine, lauramidopropyl betaine,
palmamidopropyl betaine,
stearamidopropyl betaine, stearyl betaine, cocosultaine, lauryl sultaine,
tallowamidopropyl hydroxysultaine
and the like. Particularly preferred amphoteric surfactants include Amphosol~
CA (cocamidopropyl
betaine) and Amphosol~ DM (lauryl betaine), both commercially available from
Stepan Company,
Northfield, Illinois.
Optional Ingredients
The following optional ingredients can be present in various quantities. The
ternary surfactant
blends may be formulated with optional components, such as fragrances,
emollient, solvents, humectants,
optical brightners, thickeners, powders, viscosity modifiers, hydrotropes,
preservatives, bluing agents, and
dyes, to produce a wide variety of end use products.
Although the use of such optional components is not essential to the present
invention, and may
in fact be somewhat less preferred depending on the desired final formulation
and end use application,
suitable optional emollients useful in formulating with blends of the present
invention include, for example,
stearyl alcohol, glyceryl ricinoleate, glyceryl stearate, propane-1,2-diol,
butane-1,3-diol, mink oil, cetyl
alcohol, stearamidopropyl dimethylamine, isopropyl isostearate, stearic acid,
isobutyl palmitate, isocetyl
stearate, oleyl alcohol, isopropyl laurate, hexyl laurate, decyl oleate,
octadecan-2-ol, isocetyl alcohol,
eicosanyl alcohol, behenyl alcohol, cetyl palmitate, silicone oils such as
dimethylpolysiloxane, dimethicone
copolyols, di-n-butyl sebacate, isopropyl myristate, isopropyl palmitate,
isopropyl stearate, butyl stearate,
polyethylene glycol, triethylene glycol, lanolin, cocoa butter, corn oil,
cotton seed oil, tallow, lard, olive oil,
palm kernel oil, rapeseed oil, safflower seed oil, soybean oil, sunflower seed
oil, olive oil, sesame seed oil,
coconut oil, arachis oil, castor oil, acetylated lanolin alcohols, petrolatum,
mineral oil, butyl myristate,
isostearic acid, palmitic acid, isopropyl linoleate, lauryl lactate, myristyl
lactate, decyl oleate, and myristyl
myristate, and mixtures thereof.
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Optional solvents useful in formulating with blends of the present invention
include, for example,
ethyl alcohol, propylene glycol, water, isopropanol, castor oil, ethylene
glycol monoethyl ether, diethylene
glycol monobutyl ether, diethylene glycol monoethyl ether, dimethyl
sulphoxide, dimethyl formamide, and
tetrahydrofuran, and mixtures thereof.
Optional humectants useful in formulating with blends of the present invention
include, for
example, glycerin, sorbitol, sodium 2-pyrrolidone-5-carboxylate, soluble
collagen, dibutyl phthalate,
propylene glycol, and gelatin, and mixtures thereof.
Optional powders useful in formulating with blends of the present invention
include, for example,
chalk, talc, fullers earth, kaolin, starch, gums, colloidal silicon dioxide,
sodium polyacrylate, tetra alkyl
and/or trialkyl aryl ammonium smectites, chemically modified magnesium
aluminum silicate, organically
modified montmorillonite clay, hydrated aluminum silicate, fumed silica,
carboxyvinyl polymer, cellulosics
such as hydroxyethyl cellulose and sodium carboxymethyl cellulose, ethylene
glycol monostearate, zinc or
magnesium stearate, zinc oxide and magnesium oxide, and mixtures thereof.
These components may
also be used as thickeners in fluid or semi-fluid compositions.
Examples of other optional ingredients useful in formulating with blends of
the present invention
include, for example, volatile and non-volatile silicones; silicone polymers;
preservatives, such as para-
hydroxy benzoate esters; humectants, such as butane-1,3-diol, glycerol,
sorbitol, polyethylene glycol;
stabilizers, such as sodium chloride or ammonium chloride; buffer systems,
such as lactic acid together
with a base such as sodium hydroxide; oils and waxes, such as avocado oil,
Evening Primrose oil, mineral
oil, petrolatum, sunflower oil, beeswax, ozokerite wax, paraffin wax, lanolin,
lanolin alcohol; emollients;
thickeners; activity enhancers; colorants; whiteners; fragrances; and
bactericides, and mixtures thereof.
The blends of the present invention may also be formulated with optional
detergent builder
materials. Nearly any detergent builders known in the art can be formulated
with the present blends.
Examples of useful detergent builders are described in U.S. Pat. Nos.
4,321,165, (to Smith et al, issued
Mar. 23, 1982) and 5,565,145 (to Watson et al., issued Oct. 15, 1996), both
incorporated herein by
reference. Detergent builders can optionally be included in the compositions
herein to assist in controlling
mineral hardness. Inorganic as well as organic builders can be used. Builders
are typically used in fabric
laundering compositions to assist in the removal of particulate soils. The
level of builder can vary widely
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depending upon the end use of the composition and its desired physical form.
When present in a final
formulation, the compositions will typically comprise at least about 1 %
builder. Liquid formulations typically
comprise from about 5% to about 50%, more typically about 5% to about 30%, by
weight, of detergent
builder. Granular finished formulations typically comprise from about 10% to
about 80%, more typically
from about 15% to about 50% by weight, of the detergent builder. Lower or
higher levels of builder,
however, also can be acceptable.
Enzymes and enzyme stabilizers can be formulated with blends of the instant
invention for a wide
variety of fabric laundering purposes, including removal of protein-based,
carbohydrate-based, or
triglyceride-based stains, for example, and for fabric restoration. Examples
of useful enzymes and
enzyme stabilizers are described in U.S. Pat. No. 5,565,145 (to Watson et al.,
issued Oct. 15, 1996),
incorporated herein by reference. Useful enzymes include, for example,
proteases, amylases, lipases,
and cellulases, as well as mixtures thereof. Other types of enzymes may also
be included. They may be
of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast
origin. However, a particular
enzyme choice is governed by several factors such as pH-activity and/or
stability optima, thermostability,
stability versus active detergents, builders and so on. In this respect
bacterial or fungal enzymes are
preferred, such as bacterial amylases and proteases, and fungal cellulases.
Suitable examples of proteases are the subtilisins which are obtained from
particular strains of B.
subtilis and B. licheniforms. Another suitable protease is obtained from a
strain of Bacillus, having
maximum activity throughout the pH range of 8-12, developed and sold by Novo
Industries A/S under the
registered trade name ESPERASE. The preparation of this enzyme and analogous
enzymes is described
in British Pat. Specification No. 1,243,784 of Novo. Proteolytic enzymes
suitable for removing protein-
based stains that are commercially available include those sold under the
tradenames ALCALASE and
SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-
Synthetics, Inc. (The
Netherlands). Other proteases include Protease A (see European Patent
Application 130,756, published
Jan. 9, 1985) and Protease B (see European Patent Application Ser. No.
87303761.8, filed Apr. 28, 1987,
and European Patent Application 130,756, Bott et al, published Jan. 9, 1985).
Amylases include, for example, -amylases described in British Patent
Specification No.
1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL,
Novo Industries.
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Cellulases suitable for use with ternary surfactant blends of the present
invention include both
bacterial or fungal cellulase. Preferably, they will have a pH optimum of
between 5 and 9.5. Suitable
cellulases are disclosed in U.S. Pat. 4,435,307, Barbesgoard et al, issued
Mar. 6, 1984, which discloses
fungal cellulase produced from Humicola insolens and Humicola strain DSM1800
or a cellulase 212-
producing fungus belonging to the genus Aeromonas, and cellulase extracted
from the hepatopancreas of
a marine mollusk (Dolabella Auricula Solander). Suitable cellulases are also
disclosed in GB-A-2.075.028;
GB-A-2.095.275 and DE-OS.247.832CAREZYME (Novo) is especially useful.
Suitable lipase enzymes include those produced by microorganisms of the
Pseudomonas group,
such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent.
1,372,034. See also lipases
in Japanese Patent Application 53,20487, laid open to public inspection on
Feb. 24, 1978. This lipase is
available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade
name Lipase P Amano,
hereinafter referred to as Amano-P. Other commercial lipases include Amano-
CES, lipases ex
Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673,
commercially
available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum
lipases from U.S.
Biochemical Corp., U.S.A. and Diosynth Co., The Netherlands, and lipases ex
Pseudomonas gladioli. The
LIPOLASE enzyme derived from Humicola lanuginosa and commercially available
from Novo (see also
EPO 341,947) is a preferred lipase for use herein.
A wide range of enzyme materials and means for their incorporation into
synthetic detergent
compositions are also disclosed in U.S. Pat. No. 3,553,139, issued Jan. 5,
1971 to McCarty et al.
Enzymes are further disclosed in U.S. Pat. No. 4,101,457, Place et al, issued
Jul. 18, 1978, and in U.S.
Pat. No. 4,507,219, Hughes, issued Mar. 26, 1985, both. Enzyme materials
useful for liquid detergent
formulations, and their incorporation into such formulations, are disclosed in
U.S. Pat. No. 4,261,868,
Hora et al, issued Apr. 14, 1981. Enzymes for use in detergents can be
stabilized by various techniques.
Enzyme stabilization techniques are disclosed and exemplified in U.S. Pat. No.
3,600,319, issued Aug. 17,
1971 to Gedge, et al, and European Patent Application Publication No. 0 199
405, Application No.
86200586.5, published Oct. 29, 1986, Venegas. Enzyme stabilization systems are
also described, for
example, in U.S. Pat. No. 3,519,570.
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The optional enzymes useful herein may be stabilized by the presence of water-
soluble sources of
calcium and/or magnesium ions in the finished compositions which provide such
ions to the enzymes.
Calcium ions are generally somewhat more effective than magnesium ions and are
preferred herein if only
one type of cation is being used. Additional stability can be provided by the
presence of various other
disclosed stabilizers, especially borate species. See Severson, U.S. Pat. No.
4,537,706. Typical
detergents, especially liquids, will comprise from about 1 to about 30,
preferably from about 2 to about 20,
more preferably from about 5 to about 15, and most preferably from about 8 to
about 12, millimoles of
calcium ion per liter of finished composition. This concentration can vary
somewhat, depending on the
amount of enzyme present and its response to the calcium or magnesium ions.
The level of calcium or
magnesium ions should be selected so that there is always some minimum level
available for the enzyme,
after allowing for complexation with builders, fatty acids, etc., in the final
composition. Any water-soluble
calcium or magnesium salt can be used as the source of calcium or magnesium
ions, including, but not
limited to, calcium chloride, calcium sulfate, calcium malate, calcium
maleate, calcium hydroxide, calcium
formate, and calcium acetate, and the corresponding magnesium salts. A small
amount of calcium ion,
generally from about 0.05 to about 0.4 millimoles per liter, is often also
present in the final composition
due to calcium in the enzyme slurry and formula water. In solid detergent
compositions the final
formulation may include a sufficient quantity of a water-soluble calcium ion
source to provide such
amounts in the laundry liquor. In the alternative, natural water hardness may
suffice.
Generally, the aforementioned levels of calcium and/or magnesium ions are
sufficient to provide
enzyme stability to a finished formulation. More calcium and/or magnesium ions
can be added to the
compositions to provide an additional measure of grease removal performance.
Accordingly, final
formulations prepared from the blends disclosed herein typically will comprise
from about 0.05% to about
2% by weight of a water-soluble source of calcium or magnesium ions, or both.
The amount of water-
soluble ion can vary with the amount and type of enzyme employed in the final
composition.
Final compositions based on the blends detailed herein may also optionally
contain various
additional stabilizers, especially borate-type stabilizers. Boric acid is
preferred, although other compounds
such as boric oxide, borax and other alkali metal borates (e.g., sodium ortho-
, meta- and pyroborate, and
W~ 01/19507 CA 02397811 2002-03-15 pCT/US00/23719
sodium pentaborate) are suitable. Substituted boric acids (e.g., phenylboronic
acid, butane boronic acid,
and p-bromo phenylboronic acid) can also be used in place of boric acid.
Bleaching agents, bleach activators, chelating agents, anti-redeposition
agents, polymeric
dispersing agents, optical brighteners, suds suppressors, dye transfer
inhibition agents, optical
brighteners, and soil release agents can be formulated with blends of the
instant invention. Examples of
such materials are generally described in U.S. Pat. No. 5,565,145 (to Watson
et al., issued Oct. 15, 1996),
incorporated herein by reference.
Various other detergent additives or adjuvants may be present in the detergent
product to give it
additional desired properties, either of functional or aesthetic nature. Thus,
there may be included in the
formulation minor amounts of soil suspending or anti-redeposition agents, e.g.
polyvinyl alcohol, fatty
amides, sodium carboxymethyl cellulose, hydroxy-propyl methyl cellulose;
optical brighteners, e.g. cotton,
amine and polyester brighteners, for example, stilbene, triazole and benzidine
sulfone compositions,
especially, sulfonated substituted triazinyl stilbene, sulfonated
naphthotriazole stilbene, benzidine sulfone,
etc., most preferred are stilbene and triazole combinations.
Bluing agents such as ultramarine blue; enzymes, preferably proteolytic
enzymes, such as
subtilisin, bromelin, papain, trypsin and pepsin, as well as amylase type
enzymes; bactericides, e.g.
tetrachlorosalicylanilide, hexachlorophene; fungicides; dyes; pigments (water
dispersible); preservatives;
ultraviolet absorbers; anti-yellowing agents, such as sodium carboxymethyl
cellulose, complex of C12 to
C22 alkyl alcohol with C12 to C1g alkylsulfate; pH modifiers and pH buffers;
color safe bleaches, perfume,
and anti-foam agents or suds suppressors, e.g. silicon compounds, can also be
used.
In the case of final formulations, other optional ingredients include
neutralizing agents, buffering
agents, phase regulants, hydrotropes, polyacids, suds regulants, opacifiers,
antioxidants, preservatives,
bactericides, dyes, perfumes, and brighteners described in the U.S. Pat. No.
4,285,841, Barrat et al,
issued Aug. 25, 1981, incorporated herein by reference. Other ingredients
useful in final detergent
compositions can be formulated with blends of the instant invention, including
carders, processing aids,
pigments, solvents for liquid formulations, solid fillers for bar
compositions, sodium sulfate, sodium
chloride, protein hydrolysates, cholesterol derivatives, UV absorbers,
chelating agents, etc. If high
sudsing is desired, suds boosters such as the C1p-C1g alkanolamides can be
incorporated into the final
26
WO 01/19507 CA 02397811 2002-03-15 pCT~S00/23719
compositions, typically at 1%-10% levels. The C10-C14 monoethanol and
diethanol amides illustrate a
typical class of such suds boosters. If desired, soluble magnesium salts such
as MgCl2, MgS04, and the
like, can be added at levels of, typically, 0.1 %-2%, to provide additional
suds and to enhance grease
removal performance to a final formulation.
S Additionally, the blends may contain non-conventional surfactants, such as
fluorosurfactants,
gemini surfactants and polymeric cationic and anionic surfactants. Blends of
the present invention are
prepared from readily available, economical raw materials, and generally their
preparation does not
require any special handling or equipment. The blends may be prepared in a
batch mode or a continuous
mode.
The ternary surfactant blends of the present invention typically contain water
as the se!vent;
however, other solvents may optionally be employed, either alone or in
combination with water. Low
molecular weight primary or secondary alcohols, exemplified by methanol,
ethanol, propanol, and
isopropanol, are suitable optional solvents. Monohydric alcohols are preferred
optional solvents, but
polyols such as those containing from 2 to about 6 carbon atoms and from 2 to
about 6 hydroxy groups
I S (e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1,2-propanediol)
can also be used. The
compositions may contain from about 5 to about 90 percent, typically from
about 10 to about 50 percent by
weight of water and/or optional solvent.
While pH is of secondary significance herein, the ternary surfactant blends of
the present invention
typically are prepared having a pH of between about 2 and about 10, preferably
between about 5 and
about 8. Techniques for controlling pH at recommended usage levels include the
use of buffers, alkalis,
acids, etc., and are well known to those skilled in the art. Suitable
materials for adjusting the pH of these
compositions include triethanolamine, diethanolamine, sodium carbonate, sodium
bicarbonate, and the
like.
Ternary surfactant blends of this invention may be formulated into
commercially useful products
having an active level of cationic, anionic and bridging surfactants combined
of from about 0.1 to about 98
percent by weight solids. More typically, ternary surfactant blends of the
present invention are flowable
and have a total surfactant concentration of from about 5 to about 80 percent
by weight of the
composition. Ternary surfactant blends of the invention are preferably clear
and exhibit no precipitate
27
WO 01/19507 CA 02397811 2002-03-15 pCT~S00/23719
formation upon aging. Additionally, the ternary surfactant blends may be
processed into a variety of
forms such as, for example, liquids, solutions, solids, powders, flakes, semi-
solids, gels, "ringing" gels, G-
phase liquids/pastes, hexagonal liquid crystal phases, or thick non-flowable
pastes. The ternary
surfactant blends may be spray dried, flaked, or extruded. Although not
critical to the present invention,
the blends may be prepared "neat" or in a conventional solvent such as water,
low molecular weight
alcohol or hydrocarbon, or a mixture thereof, to produce a solution of the
ternary surfactant blend. The
present invention encompasses ternary surfactant systems in dry form and as
aqueous solutions. Ternary
surfactant blends in concentrations up to 100 percent by weight may be
isolated by drying a solution of the
blend. Conversely, ternary surfactant blend solutions may be prepared by
dissolving a solid form of the
blend in water, low molecular weight alcohol, low molecular weight glycol, or
mixtures thereof.
One skilled in the art will recognize that modifications may be made in the
present invention
without deviating from the spirit or scope of the invention. The invention is
illustrated further by the
following examples, which are not to be construed as limiting the invention or
scope of the specific
procedures or compositions described herein. All documents, e.g., patents and
journal articles, cited
above or below are hereby incorporated by reference in their entirety.
As used in the Examples appearing below, the following designations, symbols,
terms and
abbreviations have the indicated meanings:
Material Definition
Alpha Step~MC-48 Sodium alphasulfo methyl C,z-,8 ester (and) disodium
alphasulfo C,2_,8
fatty acid salt (commercially available from Stepan Company, Northfield
Illinois)
Alpha Step~ML-40 Sodium alphasulfo methyl ester (and) disodium alphasulfo
lauric acid salt
(commercially available from Stepan Company, Northfield Illinois)
Polystep" B-29 Sodium octyl sulfate (commercially available from Stepan
Company,
Northfield Illinois)
Polystep° B-25 Sodium decyl sulfate (commercially available from Stepan
Company,
Northfield Illinois)
Polystep~ B-22 Ammonium lauryl ether sulfate (3E0) (commercially available
from
Stepan Company, Northfield Illinois)
Polystep° B-20 Ammonium lauryl ether sulfate (12E0) (commercially
available from
Stepan Company, Northfield Illinois)
28
W~ 01/19507 CA 02397811 2002-03-15 PCT/US00/23719
Bioterge~ PAS-8S Sodium octyl sulfonate (commercially available from Stepan
Company,
Northfield Illinois)
Maprosyl°30 Sodium lauroyl sarcosinate (commercially available from
Stepan
Company, Northfield Illinois)
Stepan-Mild~ SL3 Disodium laureth sulfosuccinate (commercially available from
Stepan
Company, Northfield Illinois)
Steol~ CS-370 Sodium laureth sulfate (3E0) (commercially available from Stepan
Company, Northfield Illinois)
Steol° CS-460 Ammonium laureth sulfate (3E0) (commercially available
from Stepan
Company, Northfield Illinois)
Stepanol° WA-Extra Sodium lauryl sulfate (commercially available from
Stepan Company,
Northfield Illinois)
20Bioterge AS-40 Sodium C14-16 olefin sulfonate (commercially available
from Stepan
Company, Northfield Illinois)
QC8 Octyltrimethylammonium chloride
25QC10 Decyltrimethylammonium chloride
QC12 or DTMAB Dodecyltrimethylammonium bromide
Cetac~30 Cetyltrimethylammonium chloride (commercially
available from Stepan
30 Company, Northfield Illinois)
BTC~ 65NF Dimethylbenzylammonium chloride (commercially
available from Stepan
Company, Northfield Illinois)
35BTC~ 885 Quaternium 24 (and) dimethylbenzylammonium chloride
(commercially
available from Stepan Company, Northfield Illinois)
Ammonyx LO Lauramine oxide (commercially available from Stepan
Company,
Northfield Illinois)
40
Ammonyx MCO Myristyl/cetyl amine oxide (commercially available
from Stepan Company,
Northfield Illinois)
Ammonyx C8 Octylamine oxide (commercially available from
Stepan Company,
Northfield Illinois)
45
Ammonyx~ C10 Decylamine oxide (commercially available from
Stepan Company,
Northfield Illinois)
Amphosol° CA Cocamidopropyl betaine (commercially available from Stepan
Company,
50 Northfield Illinois)
Amphosol~ DM Lauryl betaine (commercially available from Stepan Company,
Northfield
Illinois)
29
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Amidox~ C-2 PEG-3 Cocamide (commercially available from Stepan Company,
Northfield Illinois)
Amidox~ C-5 PEG-6 Cocamide (commercially available from Stepan Company,
Northfield Illinois)
Amidox~ L-5 PEG-6 Lauramide (commercially available from Stepan Company,
Northfield Illinois)
15
One skilled in the art will recognize that modifications may be made in the
present invention
without deviating from the spirit or scope of the invention. The invention is
illustrated further by the
following examples, which are not to be construed as limiting the invention or
scope of the specific
procedures or compositions described herein.
WO 01/19507 CA 02397811 2002-03-15
PCT/US00/23719
In the following examples, all amounts are stated in percent by weight of
active material
unless indicated otherwise. Surface tension measurements, Draves wetting
measurements, and Ross
Miles foaming initial and final measurements all were taken at 0.1 %
concentration of the surfactant blend
in water.
Example 1
Various surfactant blends were prepared as shown in Table I. The appearance of
each blend as
a concentrated (30-40%) and dilute (0.1-1.0%) composition was noted.
None of the prepared blends comprising only anionic and cationic surfactants
were single-phase
at both concentrations. This observation confirms the limited solubility
nature of anionic-cationic
complexes.
Surprisingly, however, the addition of an amine oxide, ethoxamide, and/or
betaine
bridging surfactant to the anionic-cationic blends eliminated precipitation
and produced clarity
improvements in all cases, in most cases producing solutions that were clear
at both concentrations. This
observation demonstrates that the bridging surfactant promotes solubility of
the anionic-cationic complex.
31
WO 01/19507 CA 02397811 2002-03-15 PCT/US00/23719
Table I
Surfactant System Appearance Appearance
(concentrated diluted
Stepanol~ WA-Extra ppt ppt
/QC8
Stepanol WA-Extra /QC8/Clear Clear
Am hosol CA
Stepanol~ WA-Extra Clear Clear
/QC8/
Ammonyx C10
Polystep B-25/QC10 ppt ppt
Polystep B-25/QC10/ No ppt - opaque Clear
Am hosol CA
Polystep B-25/QC10/ No ppt - opaque s1. hazy
Ammon MCO
Polystep B-29/QC10 ppt ppt
Polystep B-29/QC10/ Clear Clear
Am hosol CA
Polystep B-29/QC10/ Clear Clear
Ammon LO
Polystep B-29/OC10/ Clear Clear
Amidox C-5
Steol~' CS-460/OC12 ppt ppt
Steol" CS-460/QC12/ Clear Clear
Ammonyx LO
Steol" CS-460/Cetac ppt ppt
30
Steol" CS-460/Cetac Clear Clear
30/
Ammonyx LO/
AI ha Ste ~ MC-48
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WO 01/19507 CA 02397811 2002-03-15 PCT/US00/23719
Example 2
A ternary surfactant blend of an anionic surfactant, a cationic surfactant,
and a bridging surfactant
was prepared by mixing at room temperature equal moles of Alpha Step~ ML-40,
QC10, and Amphosol~
CA. A 33.03% clear liquid phase free of precipitate was obtained. This
surfactant blend displayed
remarkable synergism, as shown in Table II, which shows that the ternary
surfactant blend possesses
surface tension, wetting, and foaming properties all dramatically better than
the properties of any single
surfactant or combination of two surfactants.
Table II
~0
Surfactant Surface Tension Wetting Foaming
S stem - mN/m (s) InitiaI/Final
cm
Alpha Step~ ML-4026.92 81 12/11.8
QC10 39.28 100 0/0
Amphosol CA 36.75 100 13/12.9
QC 10/ 34.67 100 15/14.5
Amphosol CA
Alpha Step ML-40/30.33 17 14.5/14.3
Am hosol~' CA
Alpha Step' ML-40/ppt ppt ppt
QC10
Alpha Step" ML-40/26.11 4 15.7/15.7
QC10/Am hosol~
CA
33
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Example 3
Several ternary surfactant blends as shown in Table III were prepared by
mixing at room
temperature equal moles of an anionic surfactant, a cationic surfactant, and a
bridging surfactant.
Appearance, surface tension, wetting, and foaming properties were evaluated
for each blend over a range
of pH. For the systems tested, when a betaine is used as the bridging
surfactant, clarity can be
maintained over a wide pH range. When an amine oxide is used as the bridging
surfactant, clarity can be
maintained when pH is above about 7.
Table III
Surfactant pH AppearanceAppearanceSurface WettingFoaming
System (33-34% (0.1 % Tension (s) Initial/Final(c
active active) mN/m m
Alpha StepMC-48/10.7 clear clear 29.42 13 15.5/15.4
QC8/Amphosol~ 7.9 clear clear 29.21 12 15.3/15.2
CA
5.5 clear clear 29.62 15 15.1/15
3.7 clear clear 27.95 10 15.4/15.3
2 clear clear 26.94 14 15.3/15.2
Alpha StepMC-48/11.2 clear clear 27.31 6 14.8/14.7
QC8/Ammonyx LO 7.6 clear clear 26.65 6 14.4/14.2
6 clear haz 25.69 19 10.7/10.5
4 clear ve haz 25.6 44 2.2/2
2 clear reci itate---- ---- ----
PolystepB-25/ 10.8 clear clear 27.26 5 16.9/16.8
QC8/Amphosol~ 7.7 clear clear 27.73 5 17/16.9
CA
5.8 clear clear 26.92 5 17.9/17.8
4 clear clear 26.87 6 17/16.9
2 clear s1. haz 25.74 12 4/3.8
Polystep~B-25/ 10.4 clear clear 24.59 8 16/16
QC8/Ammonyx LO 8.8 clear clear 24.35 3 15.5/15.5
8 clear clear 24.76 5 15.8/15.7
6 fl-white s1. haz 24.98 33 9/8.8
4 2 la ers ____ ____ ____ ____ I
2 fl-white reci itate---- ---- ----
34
WO 01/19507 CA 02397811 2002-03-15 pCT/US00/23719
Example 4
Several ternary surfactant blends as shown in Table IV were prepared by mixing
at room
temperature equal moles of an anionic surfactant, a cationic surfactant, and a
bridging surfactant.
Appearance, surface tension, wetting, and foaming properties were evaluated
for each blend. The results
indicate that when magnesium ions are added to the ternary surfactant blends,
the clarity and surfactant
properties of the mixture are maintained.
Table IV
Surfactant AppearanceAppearance Surface Wetting Foaming
System (34-35% (0.1 % active)Tension (s) Initial/Final(c
active mNlm m
AlphaStep MC-48/clear clear 29.62 15 ~ 15.1/15
QC8/Amphosol~
~A
Alpha~Step MC-48/clear clear 28.73 15 15.1/15
QC8/Amphosol~
CA
+ 1:1 mole ratio
of
Alpha~Step MC-48:
M CI
AlphaStep MC-48/clear clear 28.51 12 15.1/15
QC8/Amphosol~
CA
+ 1:0.5 mole
ratio of
Alpha~Step MC-48:
M CIZ
AlphaStep MC-48/clear clear 26.65 6 14.4/14.2
QC8/Ammonyx~
LO
AlphaStep MC-48/clear clear 26.65 6 15.5/15.4
QC8/Ammonyx~
LO
+ 1:1 mole ratio
of
Alpha~Step MC-48:
M CIZ
Alpha~Step MC-48/clear clear 26.94 6 15..5/15.4
QC8/Ammonyx LO
+ 1:0.5 mole
ratio of
Alpha~Step MC-48:
M CI2:
35
WO 01/19507 CA 02397811 2002-03-15 pCT/US00/23719
Example 5
Several ternary surfactant blends as shown in Table V were prepared by mixing
at room
temperature equal moles of an anionic surfactant, a cationic surfactant, and a
bridging surfactant.
Surface tension, wetting, and foaming properties were evaluated for each
blend. The results indicate that
surfactant properties of the ternary blends can be tailored by altering the
identity of the bridging surfactant,
or the chain length of the anionic and/or cationic surfactant. For example,
increasing the chain length of
the cationic surfactant decreases wetting time (12 seconds, compared to 5
seconds). Furthermore,
increasing the chain length of the anionic surfactant also decreases wetting
time (7 seconds, as compared
to 3 seconds). Finally, changing the bridging surfactant from an amine oxide
to a betaine increases
foaming (14.7 cm., compared to 17.3 cm.).
Table V
Surfactant Surface TensionWetting Foaming
S stem mN/m s Initial/Final
cm
Bioterge~ PAS-8S/ 25.72 12 14.7/14.6
QC8/Ammon LO
Bioterge PAS-8S/ 26.58 5 15.7/15.5
DTMAB/Ammon LO
Polystep B-29/ 24.88 7 14.7/14.6
QC8/Ammon LO
Polystepc B-25/ 24.35 3 15.5/15.5
OC8/Ammon LO
Polystep~ B-25/ 27.73 5 17.0/16.9
QC8/Am hosol CA
36
WO 01/19507 CA 02397811 2002-03-15 pCT/US00/23719
Example 6
Several ternary surfactant blends as shown in Table VI were prepared by mixing
at room
temperature equal moles of an anionic surfactant, a cationic surfactant, and a
bridging surfactant.
Appearance, surface tension, wetting, and foaming properties were evaluated
for each blend. The results
indicate that clarity and surfactant properties of the ternary blends of the
invention can be maintained for a
range of anionic, cationic, and bridging surfactants.
Table VI
Surfactant AppearanceAppearanceSurface Wetting Foaming
System (% active)(0.1 % Tension (s) Initial/Final(c
active)
mN/m m
BiotergePAS-8S/ clear (34.42)clear 24.37 14 13.0/12.6
t
DTMAB/Ammon ~ C8
Maprosyl30/ clear (31.79)clear 27.56 4 13.7/13.5
DTMAB/Ammon ~ C8
Stepan-MildSL3/ clear (31.93)clear 29.10 11 13.2/13.1
DTMAB/Ammon x~ C8
BiotergePAS-8S/ clear (32.28)clear 27.41 ---- ----
Cetac 30/Ammon
C8
Stepan-MildSL3/ clear (30.62)clear 26.97 ---- ----
Cetac 30/Ammon x
C8
Bioterge~PAS-8S/ clear (33.77)clear 25.72 12 14.7/14.6
QC8/Ammon ~ LO
Alpha Step MC48/ clear (34.44)clear 26.65 6 14.4/14.2
QC8/Ammon x LO
Maprosyl30/ clear (31.21clear 28.66 5 15.5/15.4
)
QC8/Ammon x~ LO
BiotergeAS-40/ clear (34.52)clear 27.88 9 14.2/14.0
QC8/Ammon x~ LO
Stepan-Mild"SL3/ clear (31.48)clear 27.88 12 14.5/14.3
QC8/Ammon x~ LO
Alpha StepML-40/ clear (33.25)clear 25.69 4 15.1/15.0
QC8/Ammon LO
PolystepB-29/ clear (32.16)clear 24.88 7 14.7/14.6
QC8/Ammon x~ LO
PolystepGB-25/ clear (34.05)clear 24.35 3 15.5/15.5
QC8/Ammon x LO
37
WO 01/19507 CA 02397811 2002-03-15 pCT~S00/23719
Table VI (cont'd)
Surfactant AppearanceAppearanceSurface WettingFoaming
System (% active)(0.1 % Tension (s) Initial/Final(c
active)
mN/m m
Bioterge~PAS-8S/ clear (33.39)clear 30.99 46 14.5/14.5
QC8/Am hosol~ CA
Alpha StepMC-48/ clear (34)clear 29.62 15 15.1/15.0
QC8/Am hosol~ CA
Maprosyl30/ clear (31.2)clear 30.89 15 14.8/14.7
QC8/Am hosol CA
BiotergeAS-40/ clear (34.06)clear 29.96 15 14.1/14.0
QC8/Am hosol CA
Stepan-Mild~SL3/ clear (31.45)clear 30.84 29 13.8/13.8
QC8/Am hosol CA
Alpha StepML-40/ clear (32.97)clear 28.73 8 15.9/15.8
QC8/Am hosol~ CA
StepanolWA-Extra/ clear (30.76)clear 27.21 15 3.0/2.9
QC8/Am hosol~ CA
PolystepB-29/ clear (32.02)clear 30.67 29 15.6/15.5
QC8/Am hosol CA
PolystepB-25/ clear (33.64)clear 27.73 5 17.0/6.9
QC8/Am hosol~ CA
Steol~CS-370/ clear (42.3)clear 26.55 19 10.3/10.0
DTMAB/Ammon ~ LO
Steol~CS-460/ clear (45.01clear 26.28 22 7.4/7.3
)
DTMAB/Ammon x''
LO
BiotergeGPAS-8S/ clear (31.89)clear 28.12 10 14.5/14.4
Cetac30/Ammon x~
LO
PolystepB-20/ clear (29.95)clear 37.44 ---- ----
Cetac30/Ammon x
LO
Polystep~B-22/ clear (29.84)clear 30.16 ---- ----
Cetac30/Ammon x~
LO
38
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Example 7
Various surfactant blends were prepared as shown in Table VII. The appearance
of each blend
as a concentrated (33-38%) and dilute (0.1-1.0%) composition was noted. These
blends comprised
multiple anionic surfactants and were clear upon the addition of an amine
oxide, demonstrating that the
bridging surfactant promotes solubility of anionic-cationic complexes even in
mixed anionic systems.
Table VII
Surfactant System Appearance Appearance
concentrated diluted
Steol CS-460 / clear clear
Alpha Step~ MC-48/
DTMAB/Ammon ~ LO
Maprosyl30/ clear clear
Alpha Step ~~IC-4~3/
DTMAB/Ammon ~ LO
Polystep~ B-20/ clear clear
Alpha Step MC-48/
DTMAB/Ammon x LO
Polystep~ B-22/ clear clear
Alpha Step MC-48/
DTMAB/Ammon ~ LO
15
39
WO 01/19507 CA 02397811 2002-03-15 pCT~S00/23719
Example 8
Various concentrated (30-40%) surfactant blends were prepared as shown in
Table VIII. The
appearance of each blend was noted. None of the concentrated blends in Table
VIII that comprised only
anionic and cationic surfactants were flowable. Surprisingly, however, the
addition of an amine oxide,
ethoxamide, and/or betaine bridging surfactant to the anionic-cationic blends
rendered a final composition
that was flowable. This observation demonstrates that the present invention
allows for production of
flowable concentrated surfactant blends comprising anionic, cationic, and
bridging surfactants
Table VIII
Surfactant System Appearance
concentrated
Stepanol WA-F_xtra /QC10paste
Stepanol~ WA-Extra /QC10/flowable
Ammon C8
Stepanol~ WA-Extra /QC10/flowable
Ammonyx~ C8/Amphosol~
CA
Stepanol WA-Extra /QC10/flowable
Ammon ~ MCO
Stepanol WA-Extra /QC10/flowable
Ammon LO
Stepanol WA-Extra /QC10/flowable
Ammon C10
Stepan-Mild SL3~/Cetac paste
30
Stepan-Mild SL3~/Cetac flowable
30/
Amidox~ C-5
Stepan-Mild SL3'~/Cetac flowable
30/
Ammon '' C8
40
WO 01/19507 CA 02397811 2002-03-15 pCT/US00/23719
Example 9
Various concentrated (30-40%) surfactant blends were prepared as shown in
Table IX and Table
X. The appearance of each blend was noted. The concentrated blends in Table
IX, which comprised
anionic, cationic, and bridging surfactants, were flowable. The concentrated
blends in Table X, presented
for comparison purposes, were not flowable even though these blends comprised
anionic, cationic, and
bridging surfactants and were prepared according to the same procedure used in
preparing the blends in
Table IX. This observation demonstrates that not every combination of anionic,
cationic, and bridging
surfactant is flowable. However, routine screening of combinations of anionic,
cationic, and bridging
surfactants allows determining which ternary surfactant blends are flowable.
Table IX
Surfactant System Appearance
concentrated
Maprosyl 30/DTMAB~ flowable
Ammon C8
Stepan-Mild SL3/QC10/ flowable
Amidox C-5
Bioterge~ PAS-8S/DTMAB/ flowable
Ammonyx~ C8
Alpha Step MC-48/DTMAB/ flowable
Ammonyx" C8
Steol CS-370/Cetac 30/ flowable
Ammonyx~ C8
41
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Table X
Surfactant System Appearance
concentrated
Maprosyl 30/Cetac 30/ paste
Ammon ~ LO
Maprosyl 30/Cetac 30/ paste
Ammon x MCO
Stepan-Mild SL3/Cetac paste
30/
Ammon LO
Stepan-Mild~ SL3/Cetac paste
30/
Ammon MCO
Bioterge~ PAS-8S/Cetac paste
30/
Ammon MCO
Bioterge~ PAS-8S/DTMAB/ paste
Ammonyx~ MCO
Bioterge PAS-8S/Cetac paste
30/
Amphosol CA
Alpha Steps MC-48/Cetac paste
30/
Ammonyx~ MCO
Alpha Step~ MC-48/DTMAB/paste
Ammonyx MCO
Steol'' CS-370/OC10/ paste
Ammonyx LO
The invention and the manner and process of making and using it, are now
described in such full,
clear, concise and exact terms as to enable any person skilled in the art to
which it pertains, to make and
use the same. Although the foregoing describes preferred embodiments of the
present invention,
modifications may be made therein without departing from the spirit or scope
of the present invention as
set forth in the claims. To particularly point out and distinctly claim the
subject matter regarded as
invention, the following claims conclude this specification.
42
