7'?~
FOAMI~G SURFACTANT COMPOSITIONS
Technical Field
This invention relates to surfactant combinations which
provide controllable aqueous foams. Such compositions can
be used in any situation where foams are desirable, includ-
ing the laundry, personal cleaning produets, dishwashing,
fire fighting, oil well drilling, ore beneficiation, solu-
tion mining, washing hair, preparation of foamed solid
structures, etc.
Description of the Prior Art
Alkylpolyglycosides which are surfactants have been
disclosed in U.S. Patents 3,598,B65; 3,721,633; and
3,772,269. These patents also disclose processes for
making alkylpolyglycoside surfactants and built liquid
detergent compositions containing these sur~actants.
U.S. Patent 3,219,656 discloses alkylmonoglucosides and
suggests their utility as foam stabilizers for other
surfactants. Various polyglycoside surfactant structures
and processes for making them are disclosed in U.S~
Patents 2,974,134; 3~640,998; 3,839,318; 3,314,936;
3,346,558; 4,011,389; 4,223,129.
All percentages, parts and ratios used herein are by
weight unless otherwise speeified.
Summary of the Invention
This invention relates to the discov2ry of certain
combinations of surfactants whieh provide unusual foams.
Specifically this invention relates to foaming
compositions comprising
(1) an alkylpolysaccharide surfactant having the
formula RO(RlO)tZX wherein Z is a moiety
derived from a reducing saccharide containing
from 5 to 6 carbon atoms, preferably a glucose,
galactose, glucosyl, or galactosyl residue or
mixtures thereof; R is a hydropnobic group
selected from the group consisting of alkyl,
alkyl phenyl, hydroxyalkyl phenyl or hydroxy-
,
-- 2 --
alkyl ~roups or mixtures thereof in which sa;d allcyl;
~roups contain from about 8 to about 20 carbon atoms
preferably from about 10 to about 16 carbon atoms,
most preferably from about 12 to about 14 carbon
` atoms; R1 contains from 2 to 4 carbon atoms, preferably
ethylene, propylene and/or glyceryl, t is from 0 to
about 30, preferably 0 to about 10, most preferably 0;
wherein x is a number from ;-bout 1 . 5 to to about l O,
preferably 1.5 to 4, most preferably 1.6 to 2.7; and
(2) an anionic cosurfactant which is a sulfate, sulfonate
and/or carboxylate or mixtures thereof neutralizecl with
one or more cationic moieties (M) to complete the
- formula,- preferably the - anionic cosurfactant has the
formula
R (SO3)y(COO)z~ q;
,vherein F< is an alkyl, alkylphenyl, hydroxyalkyl-
phenyl or hydroxyalkyl, or mixtures thereof, said alkyl
groups containing from about 6 to about 30 carbon
atoms, preferably about 10 to about 18 carbon atoms; y
is a number from 0 to about 4, z is a number from 0 to
about 4, y + z is at least 1, and 1~1 is a cationic moiety
with q bein~ selected to complete the formula,
wherein the ratio of (2) to (I) is from about l:lû to about
25 I0:1 (i.e., 0.1` to 10.0) e-xcept that when the cosurfactant is
an alkylbenzene sulfonate, the ratio of (2) to (ll is at least
about 1:2 ~i.e., at least about 0.5) and when y is 0 and z is
one, the ratio of (2) to (I) is at least about 1:2 (i.e., at
least about O.S), and
when the anionic cosurfactant does not contain
sulfonate or carboxylate ~roup x must be from 1.5 to 3 and
the alliylpoh~saccharide surfactant must have a free fatty
alcohol content of less than about 2~ by ~vei3ht.
7'~
.~ ..
-- 3 --
It has surprisingly been found tl1at the cosurfactan-ts inter
act with the allcylpolysaccharide surfactant of this invention to
provide a relatively stable foam which is readily rinsed.
The invention also relates to the process oF producing foams
utilizing aqueous solutions containing from about 0.01~ to abou-t
95% of the mixed surfactants.
Description of the Preferred Embodiments
The Alkylpolysaccharide Surfactant
The alkylpolysaccharides are those having a hydrophobic group
containing from about 8 to about 20 carbon atoms, preferably from
about 10 to about 16 carbon atoms, most preferably from 12 to
14 carbon atoms, and a polysaccharide hydrophilic group
containing from about 1.5 to about 10, preferably from 1,5 to 4,
most preferably from 1.6 to 2.7 saccharide units (e.g., galacto-
side, glucoside, fructoside, glucosyl, fructosyl and/or galactosyl
units). Mixtures of saccharicle moieties may be used in the alkyl
polysaccharide surfactants. The number x indicates the number
of saccharide units in a particular alkylpolysaccharide surfactant.
For a particular all;ylpolysaccharide molecule x can only assume
integral values. In any physical sample of alkylpolysaccharicle
surfactants there ~vill in general be molecules having different x
values. Ti1e physical sample can be characterized by the average
value of x and this average value can assume non-integral values.
I n this specification the values of x are to be understood to be
average values~ The hydrophobic group (R) can be attached at
the 2-, 3-, or 4-positions rather than at the 1-position, (thus
giving e.g. a glucosyl or galactosyl as opposed to a glucoside or
galactoside), However, attachment throucJh the 1-posieion, i.e.,
glucosides, galactosides, fructosicles, etc., is preferred. In the
preferred product the additional saccharide units are predomin-
ately attached to the previous saccharide unit's 2-position.
Attachment through the 3-, 4-, and 6-positions can also occur.
Optionally and less desirably there can be a polyalkoxide
chain joining the hydrophobic moiety ( F<) and the polysaccharide-
chain. The preferred alkoxide moiety is ethoxide.
Typical hydrophobic ~roups inclucl alkyl groups, either;
satura-ted or unsaturatecl, branched or unbranchecl containin~3
from about 8 to about 20, preferably from about 10 to about 16
carbori atoms. Preferably, the alkyl group is a straight chain
sa-turated alkyl group~ The alkyl ~roup can contain up to 3
hydroxy groups and/or thè polyalkoxide cilain can con~ain up -to
about 30, prcferably less tilan 10, most preferably 0, alkoxide
moieties .
Suitable allcyl polysaccharides are decyl, dodecyl, tetradecyl,
hexadecyi, and octadecyl, di-, tri-, tetra-, penta-, and hexaglu-
cosides, galactosides, lactosides, fructosides, fructosyls, lac-
tosyls, glucosyls and/or galactosyls and mixtures thereof.
-- - The alkylmonosaccharides are relatively less soluble in water
- than the higher alkylpolysaccharides. When used in admixture
with alkylpolysaccharides, the alkylmonosaccharides are solubili~ed
to some extent. The use o~ allcylmonosaccharicles in aclrnixture
with allcylpolysaccharides is a preferred mode of carrying out the
invention. Suitable mixtures include coconut alkyl, di-, tri-,
tetra-, and pentaglucosides ancl tallow alkyl tetra-, penta-, and
2 0 hexag 1 u cos ides .
The preferred alkyl polysaccharides are alkyi poly~lucosides
having the formula
R O(Cll~l2nO)t~z2)x
wherein Z is derived from glucose, R is a hydrophobic group
selected from the group consisting of allcyl, allcylphenyl, hydroxy-
alkyl, hydroxyalkylphenyl, and mixtures tilereof in which said
alkyl groups contain from abou-t 10 to about 18, preferably from
12 to 1 ~ carbon atoms; n is 2 or 3, preferably 2, t is from 0 to
about 10, preferably 0; and x is from 1.5 to about 8, preferably
from 1.5 to ~, most preferably from 1.6 to 2.7. To prepare these
compounds a long chain alcohol ( R20H) can be reacted ~,vith
glucose, in the presence of an acid catalyst to for-m the desired
glllcoside. Alternatively the alkylpolyglucosides can be prepared
by a two step proc~dure in which a short chain alcohol ( C1 6) is
~5 reacted with glucose or a polyglucoside (x=2 to L~) to yield a
~8~)~7~
short chain alliyl ~lucoside (x=1 to ~1) which can in turn b~
reacted with a longer chain alcohol ~R OH) to displace the short
cl-ain alcohol and obtain the desired allcylpolyglucoside. If this
two step proce~ure is used, the short chain allcylglucoside con-
tent of the final alkylpolyglucosid~ material should be less than
509~, preferably less than 10~, more preferably less than 5%, most
preferably U~ of the alkylpoly~lucosid~.
The ar~ount ~f unreacted alcohol ~the free fatty alcohol
content) in the desired alkylpolysaccharide surfactant is pre-
LO ferably less than a~out 2~, more pre~er~bly less than about 0 . 5by wei~ht of ~he total of the alkyl polysaccharide plus unreacted
alcohol. The amount of alkylmonosaccharide is about 20~6 to about
70~, preferably 30% to 60~, most preferably 30% to 50~ by weight
of the total of the alkylpolysaccharide. For some uses it is
ii desirable to l-lave ~he alkylmonosaccharide content less than about
0%.
As used herein, "alkylpolysaccharide surfactant" is
intended to represent both the preferred glucose and
galactose derived surfactants and the less preferred
,~C alkylpolysaccharide surfactants. Throughout this
specification "alkylpolyglucoside" is used to include
alkylpolyglucosidas because the stero chemistry o~ the
saccharide moiety is changed during the preparation
reaction.
THE ANIONIC COSURFACTANTS
Anionic cosurfactants can be selected from the group
consisting of sulfates, sulfonates, carboxylates and mixtures
thereof. The cosurfactants are neutrali~ed with a cationic
moiety or moieties selected from the group consisting of
alkali metal, e.g. sodium or potassium, alkaline earth metal,
e.g. calcium or magnesium, ammonium, substituted ammonium,
including mono-, di-, or tri-, ethanolammonium cations.
Mixutres of cations can be desirable. The anionic
cosurfactants useful in the present invention all have
3~ detergent properties and are all water soluble or dispersible
in water.
,. .
- 5a -
Alkylbenzene Sulfonates
One of the preferred cosurfactants for use in this
invention is an alkylbenzene sulfonate. The alkyl group
can be either saturated or unsaturated, branched or
straight chain and is optionally substituted with a
hydroxy group. Middle phenyl positions are generally
preferred for volume of foaming in light soil conditions.
9~
However in heavLer soil conditions, phenyl attachment
at the 1- or 2-position is preferred.
` The preferred alkylbenzene sulfonates contain a straight
alkyl chain containing from about 9 to about 25 carbon atoms,
preferably from about 10 to about 13 carbon atoms, and the cation
is sodium, potassium, ammonium, mono-, di-, or triethanolammon-
ium, calcium or magnesium and mixtures thereof. Magnesium is the
- 10 preferred cationic moiety. These same cations are preferred for
other anionic surfactants and ingredients. The magnesium aikyl-
benzene sulfonates where the phenyl group is attached near the
middle of the alkyl chain are surprisingly better than the ones
with the phenyl near the end of the chain when the polysaccharide
chain averages greater than about 3 saccharide units. Suitable
alkylbenzene sulfonates include Cll alkylbenzene sulfonates ~vith
low 2-phenyl content.
The alkylbenzene sulfonate cosurfactant is desirable in the
foaming compositions of the invent!on since the foams produced
therewith are exceptionally stable, have a large volume, rinse
quickly, and do not have a "slippery" feel. These co~positions
are particularly desirable for industrial and comrlercial processes
as discussed hereinafter. The volume of foam produced using the
alkylbenzene sulfonate cosurfactant is larger than for any other
2~ cosurfactant.
Soap
Other preferrecl cosurfactants for use in this invention are
carboxylates, e.g. fatty acid soaps and si~ilar surfactants. The
soaps can be saturated or unsaturated and can contain various
'Q substituen~s such as hydroxy groups and alpha-sulfonate groups.
Preferably, the hydrophobic portion of the soap is a straight
chain saturated or unsaturatecl hyclrocarbon. The hydrophobic
portion of the soap usually contains from about 6 to about 30
carbon atoms, preferably from about 10 ~o about 18 carbon atoms.
The use of carboxylate cosurfactants is especially valuable since
the alkylpolysaccharide surfactants are exceptional lime
soap dispersers.
The cationic moiety tM) for carboxylate cosurfactants
is selected from the group consisting of alkali metal, for
exa;nple, sodium or potassium, alkaline earth metal, for
example, calcium or magnesium, ammoniumJ or substituted
ammonium, including mono-, di-, or triethanolammonium
cations. Mixtures of cations can be desirable.
In addition to the preferred alkylbenzene sulfonate and
soap cosurfactants many other surfactants which contain
sulfonate or carboxylate groups can be used in the foaming
compositions of the invention. Generally the use of these
latter cosurfactants produces less foam volume than does
the use of the preferred cosurfactants. However, the
alkylpolysaccharide surfactant stabilizes the foams which
are produced and allows the foams to be rinsed more
quickly.
One group of cosurfactants that are of interest because
of their superior detergency are the zwitterionic deter
gents which contain both a cationic group, either ammonium,
phosphonium, sulfoni~m or mixtures thereof and a sulfonate
or carboxylate group. Preferably there are at least about
four atoms separating the cationic and anionic groups.
Suitable zwitterionic surfactants are disclosed in U~S.
Patents 4,159,277; 3,928,251; 3,925,262; 3,929,678;
3,227,749; 3,539,521; 3,383,321; 3,390,034; and 3J239~560.
Such cosurfactants are especially desirable for shampoos~
Another group of cosurfactants are the amphoteric
detergents which have the same general structure as the
zwitterionic surfactants but with an amine group instead
of the quaternary ammonium group.
Yet other cosurfactants are the alkyl (paraffin or
olefin) sulfonates, preferably with a more central hydro-
philic group, containing from about 6 to about 30 carbon
atoms. Compositions containing these cosur~actants produce
the least volume of foam, if that is desired. The hydro-
phobic group can contain up to
C)974
about 10 hydroxy groups and/or ether linka~3es. Examples include;
C1LI 15 paraffin sulFonates and C1l~ 16 olefin sulfona-tes.
Still another cosurfactant is a soap structure containing up
-to about 10 ether linkages in the chain and from about I to about
1~ carbon atoms between ether linkages with from about 6 to about
30 carbon atoms in a terminal portion containing no ether link-
ages .
The preferred all<ylpolyglucosides that contain an average
of from 1.5 to 4 ~lucoside units, preferably from 1.6 to 2.7
glucoside units; less than about 50% short chain alkylpolyglu-
cosides; less than about 10%, preferably less than about 2%, most
preferably less than about 0.5% unreacted fatty alcohol, increase
the sudsing ability of conventional sulfate deter~3ent cosurfact-
ants, especially alkyl sulfate and alkyl polyether sulfate cosur-
factants having the formula:
R O(CnH2nO)t 53 M
wherein R is an allcyl or hydroxyalkyl group containing from
about 8 to about 18 carbon atoms, n is 2 or 3, t can vary from 0
to about 30, and M is a cationic moiety as definecl above, the
cosurfactant being water soluble or dispersible.
A preferred foaming composition of the invention herein
comprises
(1 ) an alkylpolysaccharide surfactant having the formula
RO(R1O)t(Z)X wherein Z is a moiety derived from a
reducing saccharide containing from 5 to 6 carbon atoms
and wherein R is a hydrophobic group selected from the
group consisting of alkyl, alkylphenyl, hydroxyalkyl-
phenyl or hydroxyalkyl groups or mi,ctures thereof in
which said alkyl groups contain from about 8 to about
18 carbon atoms; Rl contains from 2 to about 4 carbon
atoms; t is from 0 to about 30; and x is a number from
about 1 . 5 to about 10, preferably 1 . 5 to 4, most pre-
ferably 1 . 6 to 2 . 7 and
(2) a mixture of cosurfactants neutrali~ed with one ~r more
cationic moieties consisting essentially of:
(a) from about 1~ to about 95~ pre-ferably about 10~6 to
~vg~
about 50~ of a water soluble allcylbenzene sulfonate~
cosurfactant in which the alkyl group contains
from about 10 to about 13 carbon atoms, and
(b) from about 5% to about 99%, preferably 50-90~ of a
cosurfactant. selected from the group consisting of
an allcyl glyceryl ether sulfollate in which -the alkyl
group con-tains from about 8 to about 18 carbon
atoms, an alpha-olefin sulfona-te in which the olefin
group contains from about 10 to about 18 carbon
atoms, an alkyl polyethoxylate carboxylate in which
the alkyl group contains from about 10 to about 18
carbon atoms, and the polyethoxylate chain contains
from about 2 to about 6 ethoxylate ~3roups, and
mixtures thereof.
Such compositions have improved suds mileage as compared
to compositions containing only the alkyl benzene sulfonate cosur-
factant and the alkylpolysaccharide surfactant.
Another preferred embodiment of a foaming composition of
the invention herein comprises
20 ~1 ) an all;ylpolysaccharide surfactant having the formula
RO~R10)t~Z)X wherein Z is a moiety derivecl from a
reducing saccharide containing from 5 to 6 carbon
atoms and wherein R is a hydrophobic group selected
from the group consisting of allcyl, alkylphenyl, hy-
droxyalkylphenyl or hydroxyalkyl groups or rnixtures
thereof in which said alkyl groups contain from about 8
to about 18 carbon atoms; R contains from 2 to about L~
carbon atoms; t is from 0 to about 30 and x is a
number from about 1.5 to about 10;
30 ~2) an anionic cosurfactant selected from the group con-
sisting of sulfates, sulfonates, carboxylates and mix-
tures thereof neutralized with one or more cationic
moieties ~1 to complete the formula, the ratio of (2) to
(1) being from about 1:10 to about 10:1; and
74
-- 10 --
3) from about 2% to about 106 of an auxiliary foam booster
selected from the group consisting of:
(a) amides having the formula
R7 -C-N- ~ R ) 2
wherein ~7 is an alkyl ~roup containing fron~ about
8 to about 18 carbon atoms, preferably about 12 to
about 14 carbon atoms and each ~8 jS the same or
different and is selected from -the group consisting
of hydrogen, C1 3 allcyl, C1_3 alkanol, and
-(C2H4O-)1_4H groups and mixtures thereof;
(b) amine oxides having the formula:
o
R4(oR5)bN(R6)2
wherein R is an allcyl group containing from about
8 to about 18 carbon atoms, prefera~ly from 12 to
14 carbon atorns, each 1~ contains t-vo or three
carbon atoms, b is from 0 to about 30, each R is
- the same or different ancl is selected from the
group consisting of Cl_3 allcyl, C1_3
-(C2H4O)1_6H groups and mixtures thereof and
(c) mixtures thereof.
Such compositions provide superior grease/oil removal and
suds mileage. i-
Preferred anionic cosurfactants are alkylben2ene sulfonate,
alpha-olefin sulfonate, alkylsulfates, alkylpolyethoxylate sulfates
and paraffin sulfonates and mixtures thereof. The cationic
moieties are selected from the group consisting of sodium,
potassium, ammonium, monoethanolammonium, diethanolammonium,
30 triethanolammonium, calcium, magnesium and mixtures thereof.
Preferred compositions of this embodiment of the invention
comprise from 1% to about 956, preferably 56 to about 506 of an
- al'cylpolysaccharide surfactant in which the alkyl group contains
from 12 to 14 carbon atoms, x is from 1 . 5 to 4, more preferably
35 1.6 to 2.7; from 16 to about 956, preferably from about 106 to
~:~L8(~7~
about 50% of an anionic cosurfactant neutralized with one or more~
cationic moieties and which is a mixture of
~1 ) from 1% to about 95~6, preferably from about 5% to about
50~ of an alkyl benzene sulfonate in which the alkyl
group contains from about 8 to about 13 carbon atoms
or an alpha-olefin sulfonate in which the olefin group
contains from about 10 to about 18 carbon atoms, or
mixtures thereof; and
(2) from 1% to about ~5~g, preferably from about 5~ to about
50% of an alkyl polyethoxylate sulfate in which the alkyl
group contains from about 8 to about 18 carbon atoms,
preferably from 12 to 14 carbon atoms and from about
one to about six ethoxylate moieties and wherein from
about 1~ -to about 100%, preferably from about 10% to
about 80% of the cationic moieties are magnesium and
wherein the auxiliary foam booster is an amide.
Another preferreci foaming composition oF the invention
herein is an agglomerated light duty detergent granule composi-
tion comprising
~1 ) from about 5% to about 60%, preferably from 1 0~s to
about 20% of an alkylpolysaccharide surfactant having
ti-e formula RO(R )t(~)x wilerein Z is a moiety
derived from a reducing saccharide moiety containing
from 5 to 6 carbon atoms and wherein R is a
hydrophobic group selected from the group consisting
of alkyl, alkylphenyl, hydroxyalkylphenyl or
hydroxyalkyl grups or mixtures -thereof in which said
alkyl groups contain from about 8 to about 18 carbon
atoms, preferably from 12 to 14 carbon atoms; R
contains from 2 to about 4 carbon atoms; t is from 0 to
about 30; and x is a number from about 1 5 to about
10, preferably 1 5 to 4, most preFerably 1 6 to 2 7;
(23 from about 5~ to about 60~ of an alkyl benzene sul-
fonate cosurfactant in which the alkyl group contains
frorn about 10 -to about 13 carbon atoms, said alkyl
397~
- 12 -
benzene sulfonate neutralized with one or more
cationic moieties ~M) to balance the formula;
t3~ from about 5~ to about 60~, preferably from about
10~ to about 20~ of an alkylpolyethoxylate sulfate
cosurfactant in which the alkyl group contains
from about 10 to about 16 carbon atoms and in
which there are from 1 to about 6 ethoxylate
groups, said alkylpolyethoxylate sulfate neutra-
lized with one or more cationic moieties M to
complete the formula.
(4) from about 5~ to about 30~ o~ a water soluble
inorganic salt selected from the group consisting
of sodium and potassium sulfates, chlorides,
carbonates, phosphates, and mixtures thereof.
The Processes
Mixtures of alkylbenzene sulfonate and/or the soap
cosurfactant and the alkylpolysaccharide surfactant can be
used at levels of from about 0.01~ to about 95%, in ratios
of cosurfactant to alkylpolysaccharide of from about 10:1
to about 1:10, in water with agitation to provide foams.
These foams are relatively stable and, if not disturbed,
can exist for several days, Furthermore, the foam has
structural integrity and does not spread out. The foams
prepared using mixtures of alkylbenzene sulfonate and the
alkylpolysaccharide are unique in that they do not have a
"slippery" feel. All of the foams rinse quickly.
- The unusual properties of the foams of this invention
make them valuable for use not only in soap bars, bubble
baths, shaving creams, laundry, dishwashing, and washing
hair, where a good volume of stable suds and quick rins-
ability are desirable, but also in a large number of fieldsunrelated to detergency.
The compositions and processes of this invention are
particularly valuable for use in the "foam" or "mist" well
drilling processes in which the foam is used to carry water
and/or soil particles to the surface of the bore hole. A
description of such a drilling method can be found in U.S.
- 13 -
Patents 3,303,896; 3,111,178; 3,130,798; and 3,215,~00. In
such a process, the surfactants are present at a level of
from about 0.01% to about 5%, preferably from about 0.01~
to about 2~, most preferably ~rom about 0.05~ to about 0.5%.
The preferred cosurfactant is an alkylbenzene sulfonate.
The compositions and processes of this invention are also
of considerable value in fire ighting or fire prevention
processes where a stable foam is used to extinguish a flame
or sparks by cutting off the oxygen supply. This includes
Eire fighting and foa~ing runways for crash-landings as
disclosed in U~S. Patents 27514,310; 3,186,943; 3,422,011;
3,457,172; 3,479,285; and 3,541,010. Concentrations of from
about 0.1~ to about 5% are useful.
The compositions and processes of this invention are also
especially valuable in the field of preparing gypsum board,
plastic, and resin foams. The foams of this invention pro-
vide a stable relatively thick structure permitting solid-
ification of the resins, plastics, cellulosic particles,
etc., into stable foam structures having light densities,
thick cell walls and good structural integrity. Examples of
forming processes which utilize foaming agents are described
in U.S. Patents 3,669,898; 4,907,982; and 4,423,720.
The flotation of minerals so as to concentrate the
mineral valuest e.g., in the foam (beneficiation), can
be carried out advantageously using the compositions and
processes of this invention. Such processes are described
in U.S. Patents 4,147,644; 4,139,482; 4,139,481; 4,138,350;
4,090,972 and 3,640,862.
A special advantage of the compositions and processes
of this inventi~n involves making use of their exceptional
stablility to provide temporary insulation for plants when
freezing conditions are expected. An alkylbenzene sulfonate
is the preEerred cosurfactant and the foam can be applied to
the foliage etc., of the plants. Such a process is disclosed
in U~S. Patent 3,669,898.
79~
The range of utilities which are possible with the composi-`
tions and processes of this invention include all of the above and
many more.
Typical compositions for use as light duty liquid cletergent
5 compositions in washing dishes comprise from about 5% to about
50~, preferably from about 10~ to about 40~ of the mixture of
surfactants disclosed hereinbefore. From about 1% to about 50~ of
a solvent selected from the group consisting of Cl_3 alkanols,
Cl_3 allcanolamines, C2_4 polyols, mixtures thereof, and the
10 balance water. It is a special advantage of the compositions of
this invention that they can be made in concentrated form ~up to
about 5096 by ~IYt. of the mixture of surfactants~ with only very
low levels of organic solvents and without the addition of expen-
sive hydrotropic materials. Additional suds boosters or builders
15 such as triall<yl amine oxides and fatty acid amides can also be
used in amounts up to about 20~6. Fatty alcohols should not be
used .
Shampoo compositions comprise from about 190 to about 95g~,
preferably from about 5% to about 20% of the mixture of surfac-
20 tants mentioned hereinbefore, from about 1% to about 5% of anall<anol amide, from about 0.5~ to about 3?6 of a polymeric thiclc-
ener, and tlle balance water. It is a special advantaJe of the
sharnpoos that they rinse quickly and readily.
Additional Ingredients -`
.. . . . .. .
The compositions and processes of this invention can utili~e
other compatible ingredients, including other surfactants, in
addition to the mixture of surfactants herein disclosed. In de-
tergen-t compositions the compositions can contain any of the well
known ingreclients including minor amounts of other surfactants,
30 detergency builders, soil suspending a~ents, brighteners, abras-
ives, dyes, fabric conditioniny agents, hair conditioning agents,
hydrotropes, solvents, fillers, clays, perfumes, etc. Suitable
ingredients are disclosed in U.S. Patents 4,166,039--Wise;
4,157,978--Llenado; 4~056,481--Tate; 4,049,586--Collier;
- 15 -
4,035,257--Cherney; 4,019,g98--Benson et al; 4,000,080--
Bartolotta et al; and 89983,078--Collins. The shampoo
compositions of this invention can contain any of the
additional ingredients known to the art to be suitable for
use in shampoos. Bistings of suitable additional ingred-
ients, including low levels of other surfactants can be
found in U.S. Patents ~,089,945, 3,987,161; and 3,962,418.
Of special interest are ingredients which modify the feel
of aqueous solutions containing the foaming compositions of
this invention. For example, raising the pH to above about
8.5 by alkaline materials or incorporating the tertiary alco~
hols of the Jones et al, Canadian Patent 1,160,131 issued
January 10, 1984. Such ingredients are desira~le for some
consumers since the solutions do not have the normal "soapy"
feel associated with surractant solutions.
The following nonlimiting examples illustrate the foaming
compositions of the present invention.
EXAMPLE 1
Relative Volume of Suds Comparison and Consumer Preferance
A B C
Generic Premium Product
Commercial Commercial of the
Product Product Invention
U.S. Crystal U.S.
White~ Palmolive~
F _~LA Weight % Weigh~ % Wei~
Sodium Cll 8 alkyl
benzene sulfonate 10.5 18.0 18.0
C12-13 alk
glucoside2_3 (~
free fatty alcohol) ~ .0
., ,.~,
~`-'
7'~
-- 1 6
m 14-15 all<yl
polyethoxylate3 sulfate 5 . 5 12 . 0
Balance of formula inc. water 84. 0 70. 0 70 . 0
SUDSI NG
5 ~ Relative Volume of Sucls (ml) 110 125 220
0 . 2% solutions
CONSUMER TEST
Overall preference, % lQ 18 23
Favorable sudsing
10 comments, % 7~1 85 ~0
Favorable rinsing
comments, % 3 6 10
The foaming composition of the invention is superior to a
15 representative generic product and at least equivalent to a
representative premium commercial product and is preferred by
consumers for rinsing reasons. The test involved 50 consumers
washing soiled dishes in the test solutions. The consurners wore
rubber ~31Oves during the -test. The differences are siynificant at
20 the 95~ conficlence level for the invention over the generic
product .
The relative volume of suds in ml. is determined by the
following test procedure:
100 ml of the test solution at 11 5F is placed in a 500 ml
25 graduated cyliner: the solution is agitated by repeated inversion
of the graduated cylinder until the amount of suds in the cylinder
does not increase with further agitation. Suds heic3ht is
measured directly on the cylinder scale making allowance for the
height of liquid remaining in the cyiinder. The test solution is
30 made by addin~ the test product to water having a hardness of 7
gr. per U.S. gallon (Ca/Mg = 3/1).
EXAI\/IPLE 11 -~
LAS Suds Boostin~
i~`lt. % of: A B C D E F G
SSodium C1 1 ~ alkyl-
benzene sulfonate 0 20 40 50 60 80 100
Cl 2 15 alkylPIY2 3
glucoside 100 80 60 50 40 20 0
Relative Volume
10 of suds (ml) 140 220 280 300310 300 240
The suds (foam) were generated as described in Ex. I using
300 ppm of the surfactant mixtures in city water (~9 grains per
gallon). The results clearly show the sudsing synergism for
15 ratios greater than about 1:2, i.e. for the foaminy composition of
the invention herein.
EXAMPLE 11 i
Soap Suds Boosting
Wt. % of: A B C D E F
20 Sodium oleate 0 20 40 60 80 100
Cl 2-15 alkYIPIY2-3
glucoside 100 80 60 40 20 0
Relative Volume
of suds (ml.) 160 270 280 300310 260
The suds werè generated as in Ex. I using 500 ppm. of the
surfactant mixtures. This data clearly indicates the sudsing
synergism for the foaming composition of the invention herein.
-- 18 --
EXA~lPLE IV
Foamin~ with Soa,o
Effect of ~lardness on Relative Volume of Suds
~rains hardness
0 2 4 6
Sodium oleate 225 10 0 0
So~lium oleate plus C12_15
alkylpoly2_3 ~31ucoside
~3: 2 ratio) 360 100 55 10
10
The suds were generated as in Ex. I using 500 ppm. of the
surfactant mixtures.
EXAMPLE V
Alkyl Poly~ucosid~ (C1~ 15 alkylpoly 3 ~lucoside)
15 Suds Boosting for the Following Representative Cosurfactants
(3: 2 ratio; 500 ppm)
% increase in foaming
Sodium C11 8 allcylbenzene sulfonate - 100-150
Sodium oleate 50-75
20 3-1 N -coconuta Ikyl-N, N -dimethy I ~ -
2-hydroxy-1-sulfonate 40-60
Sodium C14 15 olefin sulfonate 20-40
Sodium coconut alkyl sulfate 10-30
Sodium coconut alkyl polyethoxylate3 sulfate 0-20
The above data clearly demonstrate the criticality of utilizing
a carboxylate or sul-Fonate anionic detergent cosurfactant for
sudsing synergism with the allcyl polyglucoside surfactant.
EXAl\lPLE Vl
Glucoside Chain Length Criticality
40: 60 wt- ratio of C12-15 all~yl polygl~Jcoside to sodium C12
allcylbenzene sulfonate (500 ppm. concentration) where the gluco-
side portion is:
9~'~
- 19 -
Relative Volume
of Suds ~ mi )
Monoglucoside 1 80
Diglucoside 240
Pentaglucoside 260
Decaglucoside 1 70
Sodium C1 1. 8 alkylbenzene
sulfonate alone 160
10 "Diglucoside" etc. indicates the average glucoside chain
length in the sample is two, etc. As can be seen from the
above, signiflcant synergism is obtained only with 1 . 5 or more
glucoside units and preferably less than about 10, more prefer-
- ably less than about 8 glucoside units.
EXAI~/lPLE Vl I
Allcylbenzene sulfonates ( LAS)
~lomologs/phenvl-position (3:2 ratio; 500 ppm)
Relative Volume
of Suds ( ml )
20 Ex. I I's alkylpolygl-Jcoside plus:
Sodium C1 1 LAS, high 2-phenyl 210
Sodium C1 1 LAS, low 2-phenyl250
Sodium C12 LAS, high 2-phenyl225
Sodium C1 2 LAS, low 2-phenyl225
25 Sodium Cl L~ LAS, ~iigh 2-pheriyl 210
Sodium C1 4 LAS, low 2-phenyl215
As can be seen from the above, in general C~ QW 2-phenyl
LAS is preferred for sudsing.
- 20 -
EXAMPLE Vl l l -~.
Suds Boos-ting of Alkyl
Polyglucosides and Effect of Soil
Rela-tive Volume of Suds ~ml)
~'~ithout
Soii With Soil
0.5% 1.0
0.2% aqueous solution of a
detergent composition
10 formulated with:
15% sodium C1 1 ~ alkyl-
benzene sulfonate
(C11 8 LAS~ - - 120 50 - - 25
11 . 8 LAS 12%
15Ex. Il's alkyl poly~lucoside 310, 130 70
~6 C11.8 LAS 190 140 100
20% C1 1 8 LAS ~ 12%
Ex l's alkylpolyglucoside 380 170 100
20Test method of Ex. I rnodified by adding to the -test solu-
tion the indicated amount of soil. % is wt. 96 of test solution.
The soil is a 44%/5G~ by weight mix-ture of Fluffo(~? and
PREP~) both of which products are available in the United States
from The Procter ~ Gamble Company.
25As can be seeh from the'~above, the benefit for the invention
is even more remarkable when soil is present.
EXAl\lPLE IX
Relative \/olume of Suds lm!)
No Soil 1% Soil Present
30 Generic commercial product
(Crystal ~ ite(~))** 110 30
Premium commerical product E3
~ Palmolive Liquic~) 120 100
Premium commercial product C
35 ( (~)) 125 120
8~7~
~ 21 --
.
12~ Cll 8 LAS/8% Ex. Il's
alkyl polyglucoside1~0 120
1&% C11 8 LAS/12% Ex. Il's
alkyl polyglucoside240 150
24% Cll ~ LAS/16~ Ex. Il's
allcyl polyglucoside300 180
Soil is added as described in Ex. Vl 1.
** ~
Crystal White~ is available from Colgate-Palmolive Co.
Palmolive Liquid~ is available from Colyate-Palmolive Co.
10 Joy~) is available from The Procter ~ Gamble Company.
Suds generated as in Ex. I usinq a test solution containing
0.2~ by wt. of the indicated commercial product or 0.2% of a
product formulated with the surfactant mixtures shown.
15 As can be seen, the simple mixtures of surfactants represen-
tative of this invention can be formulated to be superior, or at
least equal, to even the best light-duty dishwashing licluids.
EXAMPLE X
Wt. % of: A ~ C D E F
20 C11 8 LAS (Sodium) 20 40 6080 100
Sucrose monolaurate 100 80 6040 20 0
Relative Volume
of suds (ml.) 30 100 150 190210 220
~ !-
300 ppm of surfactant mixture used in test solu-tion of Ex. I.
The above demonstrates that structures which are similar to
the alkyl polyglucosides do not provide the benefits of this in-
vention .
EXAMPLE Xl
Shampoo
Cocamido propyl betaine (30% aqueous ~olution) 50.00%
Ex. I's alkyl polyglucoside 5.006
Polyethylene glycol distearate 1. 00%
35 Preserva tive 03%
Distilled water q.s. lOO.OOQo
-- 22 --
EXAMPLE X l l
Shampoo
Alpha-olefin sulfonate ~40% aqueous solution~ 30.00
Ex. I's alkyl polyglucoside 3.00
Hydroxyethyl cellulose 0.80~
Perfume 1. 006
Preservative 0. 04~
Dis-tilled water - q.s. 100.006
EXAMPLE X l l l
Paraffin Sulfonate Suds Boosting
Wt. ~ of: A B C D E F_
Mixture of sodium C1 ~5
15 paraffin sulfonate 0 20 40 60 80 100
~12-15 G"_5 100 80 60 40 20 0
Relative Vol. of Suds(ml) 185 250 275 275 235 210
Test Conditions:
l otal concentration of 300 ppm; water having 8 grains of
20 mixed hardness.
C12 1 5G4 5 is a notation for an allcyl polysaccharide
surfactant in which there are 4-5 glucoside units and in which
the alkyl group has 12-15 carbons.
EXAMPLE X IV
Sodium vs. Magnes~um Alkylbenzene Sulfonate
-
Relative Volume of Suds ~ml. )
*
Without Soil ~Vith Soil
0 . 6% 1 . 06
0.26 aqueous solution of a
30 cletergent composition with:
156 Ex. Il's alkyl poly-
glucoside; 22~ Cl l 8
alkylbenzene sulfonate with
the benzene group attached
- 23 -
primarily to the center ,~
of the alkyl chain, sodium
neutrali~ed 450 15075
15% Ex. Il's all<yl polyglucoside;
2 0 C11.8 alkylben~ene
sulfonate with the benzene
group attached primarily to
the center of the alkyl chain,
mac3nesium neutralized 450 200110
10 Premium product tJoy~)) 350 12075
Soil added to the -test solution as in E~. Vl l l .
EXAMPLE XV
The optimum alkylpolysaccharides, especially all<ylpolygluco-
- sides have an HLB of from about 6 to about 27 and a critical
15 micelle concentration (CMC) of less than about 10UOppm, prefer-
ably less than about 500. Short chain alkylpolysaccharides in
which the alkyl group contains less than about 8 carbon atoms
have unacceptably high CMC's and those all<ylpolysaccharides
having more than about 4 saccharide units have unacceptably high
20 HLB's as is shown in the followincJ table in which the alkyl group
and the glucoside chain length were varied.
it of Go Gl G2 G3 G~l G5
Glucosides
o f
25 Carbons ` !-
--
C4 HLB 5.1 12.4 17.9 23.3 28.8 34.2
C6 HLB 4.2 11.4 17,0 22.4 27.8 33.2
C8 HLB 3.2 10.5 16.0 21.4 26.9 32.3
Ci~llC ~7000
C1O HLB 2,2 9.6 15.0 20.4 26.0 31.4
CMC ~700 2000E
C12 HLB 1.3 8.6 14.1 19.5 25.0 30.4
CMC ~6.0 ~70 ~200 225E ~250
:~8~
-- 2~ --
C14 ~ILE~ O.Ll 7.6 13.2 18.6 24.0 29.~i
CMC ~6 ~2025-60E
C16 HLE30.0 6.7 12.2 17.6 23.1 28.5
CMC~0.3 ~0.6 ~4
C18 ~IL13 0.0 5.8 11.~ 16.6 22.2 27.6
CMC ~1
E=Estimated
HLB determined accordirig to Davies: Proc. ~ International
Congress, Surface Activity 1,426, Butterworths, London, 1957.
10 ppm
As can be seen above, (1) longer pure glucoside chain
lengtl s raise the HLE~ and lower the molecule's surface activity
(high CMCj and- ~2) the shorter alkyl chain lengths ha~e extremely
high CMC's even as the monoglucoside.
EXAMPLE XVI
The following formulas were prepared:
A B C
Magnesium linear C11 2
alkylbenzene sulfonate 22.4 22.4 22.4
20 C12 13 all~ylpolygluco-
side (G1 7) (<2% free
fatty a Icohol ) 14.9 14.9 14.9
C9 11 allcoxypropyldi-
hydroxyethyl amine oxide - 4
25 C12 alkylclihYdrXY
ethyl amine oxide - - 4
Ethanol 5 5 5
Water balance balance balance
Formulas A, 3 and C were compared by generating suds
with a constant source of agitation under standard conditions ~ 1
gal. water, 115F. (46.1C) 7 gr. hardness in a 3 gal. dishpan
using a standardized mixture of fat plus protein, carbohydrate
and edible acid). Dinner plates are wasi1ed with ~ ml. of soil on
35 each plate and the suds height is measured after each five plates.
~< ~ )g7~
, .
-- 25 --
30 plates in total are washed and the integral of the suds height~
taken over the number of plates washed is reported as the SD~V
grade ~SD~ = Suds During ~'~ashing).
,'\ B C
S SDW grade 24 28.S 28.4
This shows that the addition of a small amount of these
amine oxides dramatically increases the amount of dishes that can
be washed. Similar results are obtained when a fatty acid amide,
e.g., a coconut fatty acid amide, diethanol amide, and/or isopro-
panol amide is substituted, at least in part for the specific amine
oxides .
EXAMPLE XVI I
105 grams of sodium dodecylbenzene sulfonate are mixed with
350 grams of anhydrous sodium sulfate. After the mixture is
ground into a fine powder, 70 g of C12_13 alkylpolyglucoside
IG2 2) (<2~ free fatty alcohol) are then mixed in. The mixture is
transferred into a fluid bed dryer operated at room temperature
(e.g., Aeromatic Inc., Model STREA-1 ), then 100 grams of a 50%
solution of said allcylpolycJlucoside is sprayed onto the powder.
7.5 milliliters of a 1% polar blue solution are sprayed onto the
powder and a small portion of perfume is then added. The
resulting granule is dried in a vacuum oven at 30 in. of Hg
vacuum at 50C for -ten hours to remove excess water.
In a similar manner 60 grams of a 50?6 solution of said alkyl-
polyglucoside is sprayed onto 100 gram of Berkite and S0 grams
of sodium dodecylbenzene sulfonate flakes are admixed with the
product to give a light duty granule.
EXAMPLE XVI l l
Ammonium C1t 2 linear alkyl benzene sulfonate was admixed
with C12 alliylpolyglucoside G3 5 in a ratio of about 2:1. The
mixture was used at a level of 400 ppm in city water. The initial
suds volume was more than 300 ml., but after the addition of
about 1.25 grams of a standard grease soil per 200 ml. of wash
solution, the suds had disappeared. Substieution of a sodium
C12 16 alkyl glyceryl ether sulfonate for 25% and 40~ of the
g7'~
- 26 -
mixture extencled the point at which there was no suds to 1 . 5 and
1.75 cgrams of soil per 200 ml. of wash? solution respectively~
Similar r esults are obtained when a sodium, potassium,
ammonium, or monoethanolammonium C1 2-16 allcylpolyethoxy3
5~ acetate, or C1l~_16 olefin sulFonate or mixtures thereof is
substituted for at least part of the alkyl glyceryl ether sulfonate.
EXAMPLE X I X
The following formula was prepared with alkylpolyglucosides
having 0.3~ and 1% free fatty alcohol respectively.
Wt. %
Ammonium Cl l 2 linear alkyl
benzene sulfonate 17 . 5
Magnesium Cl l 2 linear - alkyl
benzene sulfonate 6.4
15 Amrnonium C1 2-13 allcyl poly-
ethoxylate (0.8) sulfate6.1
C12_13 alkYIPIY~IUCside G1.7
Minors and water balance
The SDI?`~ values for the low and high alcohol samples were
20 12 . 9 and 12 . 2 respecively with an LSDo 05 at 0 . 6 . See Ex . XVI
for test method.
E~AMPLE XX
The following formulas were prepared:
% by weight
? ~A B C D
Ammonium/magnesium C11 2
linear alkyl benzene
sulfonate 2~??.2 21.8 - -
Ammoniumlmac?nesium Cl 2-15
30 olefin sulfonate - - 12.8 10.6
AmmoniUm/ma9nesium C1 2-13
alkyl sulfonate - - 19.2 15.9
Arnmonium Cl 2-13 alky
polyethoxylate (0.8)
35 sulfate 6.5 5.8
C12 fatty acid diethanoi-
amide - 3.8 - S .5
C12-13 alkylpoly5lucoside
G 1 7 ~ f ree fa tty
5 ~alcohol <0.5%) 5.3 4.8 4 3,3
Minors and l,Yater balance
A B C D
The SDW I ndex 79 89 97 107
The SDW index is -the SDW grade for each product as a
10 percentage of the SDIIV value of a standard commercial product.
The following are examples of particularly pre-ferred compo-
sitions. The broad and preferred ranges of ingredients which
can be used are given in the second and third columns, respec-
- tively, in each example.
EXAI\/IPLE XX I
% by Weight
Amrnonium C~ alkyl
benzene sulfonate 17.5 10-35 12-25
Ma~nesium C11 4 alkyl
20benzene sul-fonate 6.4 0-11 3-9
Ammonium C12-13 alkyl poly-
ethoxylate ~0.8) sulfates 6.1 2-11 3-9
C12-13 alkyl polyglucoside
(1.7) derived from glucose
( <0.5% free fatty ~alcohol ) ~ .0 2-11 2-7
Ethanol 3.7 0-10 0-5
Ammonium xylene sulfonate 3.0 0-10 0-5
H2O ~ minor components,
e. g ., perfume Balance
EXA~IPLE XXI!
% by ~Yeisht
AMmonium C12_13 alkyl
sulfate 15.7 7-23 10-20
14-16 olefi
sulfonate 10.4 4-19 6-13
7'~
-- 28 --
MgC12 6~12 5.6 0-11 2-10
Coconut monoethanol amide 5 . 5 2-8 3-7
Cl2-13 alkyl polyglycoside
(1.7) derived from glucose
(<0.5% frce fatty alcohol) 5.9 2-t2 3-9
Ethanol 11. 0 0-10 0-10
H2O and minor components,
e.g., perfume Balance
The alkyl groups in the surfactants of Examples XXI and
10 XX l l can vary from about 10 to about 16 carbon atoms and the
cations can be ammonium, sodium, potassium, monoethanolammonium,
diethanolammonium, triethanolammonium, magnesium, or preferably,
mixtures therof. Any of the preferred alkyl polyglycosides can
be used and other known amine oxide and amide suds boosters
l S disclosed herein can be used.
EXAMPLE XX l l l
When a 2:1 mixture of an ammonium C11 2 alkylbenzene
sulfonate and the C12 13 alkylpoly~3lucoside (2-4) (>2% free fatty
alcohol) are tested under the conditions of Example l l the ini~ial
20 suds volur,le is good, but the SDW grade is not as good as some
premium commercial products. Substitution of between 25~ and
S0~ of the mixture with a sodium C12 16 alkyl glyceryl ether
sulfonate, or sodium C1 4 16 olefin sulfonate, or sodium C1 2 13
alkyl polyethoxylate~3~ acetate increases the SD~V grade without
25 loweriny the initial 'sudsing e~cessively.
Known analytical techniques can be used to determine the
structures of the alkylpolysaccharide surfactants herein; f~r
example, to determine the qlycosidic chain length, the amount of
butyl glucoside, the free fatty alcohol content~ and the level of
30 unreacted polysaccharide. ~lore specifically, gas or liquid
chromatography can be used to determine the unreacted alcohol
content and the unreacted polysaccharide content respectively.
Proton nmr can be used to determine the average glycosidic chain
length. The point of attachment of the hydrophilic portion of the
35 molecule to the hydrophobic portion of the molecule can be
determined by 1 3C nmr.
97~
-- 29 --
The alkylpolysaccharide surfactants are complex mixturesn~
Their components vary depending upon the nature of the starting
ma-terials and the reaction by which they are prepared. Analyti-
cal standards which are useful in calibrating instruments for
5 analyzing the components of a particular alkylpolysaccharide
surfactant can be obtained from Calbiochem Behring Co. LaJolla,
California. These standards include those for octylglucoside
(Calbiochem #494559), decylglucoside ~Calbiochem #252715),
dodecylmaltoside (Calbiochem ~32~i3555).
The HLBs of al~ylpolysaccharide surfactants useful in the
foaming compositions of this invention have the values given in
EXAMPLE XV; the CMCs will approximate those values given in
the same example. Alkylpolysaccharide surfactants having the
structures specified in -the claims and characterized by one or
15 more of the standard analytical techniques will give the results
indicated in the examples.
WHAT lS CLAIMED IS:
