Note: Descriptions are shown in the official language in which they were submitted.
~o~s~
FOAMING SURFA(::TANT COMPOSITIONS
TechnicaL Field
This invention relates to sur~actant combinations which
provide controllable aqueous foams. ,Such compositions can
be used in any situation where foams are desirable, includ-
ing the laundry, personal cleaning products, dishwashing,
fire fightingt 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 3,598,86S; 3,721,633; ancl
3~772/269O These patents also disclose processes for
making alkylpolyglycoside surfactants and built liquid
detergent composi~ions containing these surfactants.
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;
3,34~,558; 4,011,389; 4,2~3,129.
~11 percentages, parts and ratios used herein are by
weight unless otherwise specified.
Summary of the Invention
This invention relates to the discovery of certain
combinations of surfactants which provide urlusual foams.
Specifically this invention relates to foam~ng
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, glucosyll or galactosyl residue or
mixtures thereof; R is a hydrophobic group
selected from the group consisting of alkyl,
alkyl phenyl, hydroxyalkyl phenyl or hydroxy
~2;,' ' "' !
~`
-- 2 --
all<yl groups or mixtures thereof in which said all<yl~
yroups contain from about ~ to abou-t 20 carbon atoms
preferably from about 10 to aboLIt 16 carbon atoms,
most preferably from about 12 to about 14 carbon
` ator7s; F~ contains from 2 to ~I carbon atoms, preferably
ethylene, propylene ancl/or glyceryl, t is from 0 to
about 30, preferably 0 to about 10, most preferably 0;
wl-erein x is a number from about 1 5 to to about 10,
preferably 1 5 to 4, most preferably 1 6 to 2 7; and
(2) an anionic cosurfactant which is a sulFate, sulfonate
andlor carboxylate or mixtures thereof neutralized with
one or more cationic moieties (M) to complete the
formula, preferably the anionic cosurfactant has the
forrnula
R (5O3)y(COO)zl~Jlq;
wherein R is an alkyl, allcylphenyl, 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 Ll, z is a number from 0 to
about 4, y + z is at least I, ancl ~1 is a ca tionic moiety
with q bein~ selected to complete the formula,
wherein the ratio of (2, to (I) is from about l lO to about
25 I0 1 (i e, 0.1 to 10.0) ~xcept that when the cosurfactant is
an all~ylbenzene sulfonate, the ratio of (2) to (I) 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 0 5), and
when the anionic cosurfactant does not contain
sulfonate or carboxylate ~3roup x must be from I 5 to 3 and
the all<ylpoh~saccharide surfactant must have a free fatty
alcohol content of less than about 2% by wei~ht
5~
-- 3 --
It llas surprisingly been found that the cosur-factants inter-
~act with the alkylpolysaccharide surfactant of this inven-tion to
provide a relatively stable foam which is readily rinsecl.
The invention also relates to the process of producing foams
utili7illg aqueous solutions containing from about 0.019~ to about
95~ of the mixed surfactants.
Description of the Preferred Embodiments
The Alkylpolysaccharide Surfactant
The all<ylpolysaccharides are those having a hydrophobic group
IO 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., gaiacto-
IS side, glucoside, ~ructoside, glucosyl, fructosyl and/or galactosyl
units). Mixtures of saccharide moie-ties may be used in the alkyl
polysaccharide surfactants. The number x indicates the number
of saccharide units in a particular alkylpolysaccharide surfac-tant.
For a particular allcylpolysaccharide molecule x can only assume
a~ integral values. In any physical sample of alkylpolysaccharide
surfactants -there will in general be molecules haviny dif-Ferent x
values. The physical sample can be characteri~ed by the average
value of x and this average value can assume non-integral values.
In 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 ~-positions rather than at the 1-position, (thus
giving e.g. a glucosyl or galactosyl as opposed to a glucoside or
~alactoside). However, attachment through the 1-position, i.e.,
glucosides, galactosides, fructosides, etc., is preferred. In the
~o preferred product the additional saccharide units are predomin-
ately attached to the previous saccharide unit's 2-position.
Attachment through the 3~ -, and 6-positions can also occur.
Optionally and less desirably there can be a polyalkoxide
chain joining the hydrophobic rnoiety ( R) and the polysaccharide-
chain. The preferred alkoxide moiety is ethoxide.
Typical hydrophobic groups inclucie allcyl groups, either,~
saturated or unsaturated, branched or unbranched containing
from about 8 to about 20, preferably from about 10 to about 16
carbon atoms. Preferably, the all<yl cJroup is a straiqht chain
5 ~ saturated allcyl ~roup. The alkyl group can contain up to 3
hydroxy groups ancl/or the polyaikoxide chain can contain up -to
about 30, preferably less than 10, most preferably 0, allcoxide
moieties .
Suitable all<yl polysaccharides are decyl, dodecyl, tetradecyl,
hexadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexa~lu-
cosides, galactosicies, lactosides, fructosides, fructosyls, !ac-
tosyls, glucosyls and/or galactosyls and mixtures thereof.
The alkylrnonosaccharides are relatively less soluble in water
than the higher aikylpolysaccharides. When used in aclmixture
with alkylpolysaccharides, the all<ylmonosaccharides are solubilized
to some exten-t. The use of alkylmonosaccharides in admixture
with alkylpolysaccharides is a preferrecl mocie of carrying out the
inven-tion. Suitable mixtures include coconut alkyl, di-, tri-,
tetra-, and pentaylucosides ancl tallo~,v alkyl -tetra-, penta-, and
hexaglucosides.
The preferred alkyl polysaccharides are alkyl polyglucosides
havin~ the formula
R O(Cn~l2nO)t(z2)x
wherein Z is derived from glucose, R is a hydrophobic group
2~ selected from the group consisting of alkyl, alkylphenyl, hydroxy-
alkyl, hydroxyalkylphenyl, and mixtures thereof in which said
aikyl ~r oups contain from about 10 to about 18, preferably from
12 to 14 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
frorn 1.5 to 4, most preferably from 1.6 to 2.7. To prepare these
compounds a long chain alcohol (R2O~i) can be reacted with
glucose, in tile presence of an acid catalyst to form the desired
ylucoside. Alternativeh/ the alkylpolyglucosicies can be prepared
by a two step procedure in which a short chain alcohol (C1 6) is
~5 reacted with ~lucose or a poly~lucoside (x=2 to 4) to yield a
s~
-- 5 --
short chain allcyl ylucoside ~x=1 to l~) which can in turn b~
reacted with a longer chain alcohol (R O~l) to displace the short
chain alcohol and obtain the desired alkylpolyglucosicle. If this
two step procedure is ~Ised, the short chain alkyl~lucoside con-
r tent of the final alkylpolyglucoside material should be less than
50~, preferably less than 10%, more preferably less than 5%, most
preferably 0% of the alkylpolyglucoside.
The al~ount of unreacted alcohol (the fr~e fatty alcohol
conten~) in the desired alkylpolysaccharide surfactant is pre-
l(; ferably less than about 2~6, more preferably less than about 0.5
by weight of ~he total of the alkyl polysaccharide plus unreac-ted
alcohol. The amount of alkylmonosaccharide is about 20~ to about
709~, preferably 30% to 60~6, most preferably 309s -to 50% by weight
of the total of the alkylpolysaccharide. For some uses it is
l i desirable to have the alkylmonosaccharide content less than about
10%.
As used herein, "alkylpolysaccharide surfactant" is
intended to represent both the preEerred glucose and
g~lactose derived surfactants and the less preEerred
~C alkylpolysaccharide surfactants. Throughout this
specification "alkylpolyglucoside" is used to include
alkylpolyglucosides because the stero chemistry of the
saccharide moiet.y 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 neutralized with a cationic
moiety or moieties selected Erom the group consis-ting oE
alkali metal, eOg. sodium or potassium, a~kaline earth metal,
e.g. calcium or magnesium, ammonium, substituted ammonium,
including mono~, di-, or tri~, ethanolamrnonium cations.
Mixutres oE cations can be desirable. The anionic
cosurEactants useful in the present inven-tion all have
3~ detergent properties and are all wa-ter 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 unsa-turated, 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.
-- 6 --
However in heavier soil conditions, phenyl attachment
at the 1- or 2 position is preferred.
` The preferred alkylt>enzene sulfollates 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 sodiur~, potassium, ammonium, mono~, di-, or triethanolammon-
ium, calcium or magnesium and mi,ctures thereof. Ma~nesium is the
preferred cationic moiety. These same cations are preferred for
other anionic surfactants and ingredients. The maynesium alkyl-
benzene sulfonates ~,vhere 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 ~reater than about 3 saccharide units. Suitable
alkylbenzene sulfonates include C~ll alkylbenzene sul fonates ~vith
low 2-phenyl content.
The alkylbenzene sulfonate cosurfactant is desirable in the
foaming compositions of -the inven~!on since the foams producecl
2() therewith are exceptionally stable, have a large volume, rinse
quickly, and do not have a "slippery" feel. These corrlpositions
are particularly desirable for industrial and commercial processes
as discussecl llereinafter. The volume of foam produced using the
alicylbenzene sulfonate cosurfactant is lar~er than for any other
2 ~ cosurfactant.
Soap
-
Other preferred cosurfactants for use in this invention are
carbo~ylates, e.g. fatty acid soaps and sir,lilar surfactants. The
soaps can be saturated or unsaturated and can contain various
'~ substituents such as hydroxy groups and alpha-sulfonate groups.
Preferably, the hydrophobic portion of the soap is a straignt
chain saturated or unsaturatecJ hydrocarbon. The hydrophobic
portion of the soap usually contains from about 6 to about 30
carbon ator.1s, preferably from about 10 to about 13 carbon atoms.
3 . Tbe use of carboxylate cosurfactants is especially valuable since
the alkylpolysaccharide surfactants are exceptional lime
soap dispersers.
The cationic moiety (M) ~or carboxylate cosurfactants
is selected from the group consisting of alkali metal, for
example, sodium or potassium, alkaline earth metal, for
example, calcium or magnesium, ammonium, 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 u5e 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, sulfonium 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; 3~390/094; and 3,239,560.
Such cosurfactants are especially desirable for shampoos~
Another group of cosurfac~ants are the ampho~erio
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) sul~onates, pre~erably with a more central hydro-
philic group, containing from about 6 to about 30 carbon
atoms. Compositions containing these cosur~actants pro-
duce the least volume of foam, if that is desired. The
hydrophobic group can contain up to
-- 8 --
about 10 hydroxy groups and/or e-ther linkages. Examples includè~
C1l1 15 paraffin sulfonates and Clll 16 olefin sulfonates.
Still another cosurfactant is a soap structure containin~3 up
to about 10 ~ther linka~es in the chain and from about I to about
4 carbon atoms between ether linka~es wi-th from about 6 to about
30 carbon atoms in a terminal portion containing no ether link-
ages .
The preFerred alkylpolyglucosides that contain an average
of from 1.5 to 4 glucoside units, preferably from 1.6 to 2.7
10 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~ent cosurfact-
ants, especially alkyl sulfate and alkyl polye-ther sulfate cosur-
15 factants having the formula:
3 R O(cnH2nO)t 53 M
wherein R is an alkyl 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 defined above, the
20 cosurfactant being water soluble or dispersible.
A preferred foaming composition of the inven-tion herein
comprises
(1 ) an alkylpolysaccharide surfactant having the formula
RO(R1O)t(Z)X whe~ein Z is a moiety derived from a
reducing saccharide containing from S to 6 carbon atoms
ancl wherein R is a hydrophobic group selected from t~e
group consis-ting of alkyl, alkylphenyl, hydroxyalkyl-
phenyl or hydroxyalkyl groups or mixtures thereof in
which said alkyl groups contain from about 8 to about
1~ carbon atoms; K1 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-
f~rably 1.6 to 2.7; ancl
(2) a mixture of cosurfactants neutralized with one or more
cationic moielies consisting essentially of:
(a) frorn about 1~ to about 95% preferably about 10% to
5~
about 50% of a water soluble alkylbenzene sulfonate~
cosurfactant in which the alkyl group contains
from about 10 to about 13 carbon atoms, and
(b) from about 596 to about 999~, preferably 50-90~ of a
cosurfactant selected from the group consisting of
an allcyl glyceryl ether sulfonate in which the alkyl
group contains from about ~3 to about 18 carbon
atoms, an alpha-oleFin sul-fonate 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 groups, and
mixtures thereof.
Such compositions have improved suds mileage as compared
to compositions containing only -the alkyl benzene sulfonate cosur-
factant and the alkylpolysaccharide surfactan-t.
Another preferred embodimen-t of a foaming composition of
-the invention herein comprises
20 ( 1 ) an alkylpolysaccharide sur-factant havin~ the forrnula
RO(R1O)t(Z3X wherein Z is a moie-ty 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, hy-
droxyalkylphenyl or hydroxyalkyl groups or mixtures
thereof in which said alkyl groups contain from about 8
to about 18 carbon atoms; R contains from 2 to about 4
carbon atoms; t is from 0 to about 30; and x is a
number from abou t 1 . 5 to about 10;
30 (2) an anionic cosurfactant selected from the group con-
sisting of sulfates, sul~onates, carboxylates and mix-
tures thereof neutrali~ed with one or more cationic
moieties M -to comple~e the formula, the ratio oF (2) to
( 1 ) beir7g from about 1 :10 to about 10 :1; and
s~
- 10 -
(3) from about 2% -to about 10% of an auxiliary foam booster"
selected from the group consisting oF:
~a) amides having the formula
R7-C-N- ( RS ) 2
wherein R7 is an alkyl ~roup containin~3 from about
~ to about 1~ carbon atoms, preferably about 12 to
about 14 carbon atoms and each R8 is the same or
different and is selected from the group consisting
of hydrogen, C1 3 alkyl, C1 3 alkanol, and
(C2H4O-~1_4H groups and mixtures thereof;
(b) amine oxides having -the formula:
R4~oR )bN(R )2
wherein R ~ is an alkyl group containin~ from abou-t
to about 1~ carbon atoms, preferably from 12 to
14 carbon atoms, each R5 con-tains two or three
carbon atoms, b is from 0 to about 30, each R is
the same or different and is selected from the
group consisting of C1_3 al~yl, C1_3
-(C2H40)1_6H groups and mixtures thereof; and
(c) mixtures thereof.
Such compositions provide superior grease/oil removal and
suds mileage.
Preferred anionic cosurfactants are alkylbenzene sulfonate,
alpha-olefin sulfonate, alkylsulfates, alkylpolyethoxylate sul-fates
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
cornprise from 1~ to abou-t 95%, preferably 5P~ to about 50% of an
-alkylpolysaccharicie 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 1O to about 95~O, preferably from about 10% to
about 50% of an anionic cosurfac-tant neutralized with one or more~
cationic moieties and which is a mixture of
~1) from 16 to about 95~, preferably from about 5% to about
50~6 of an alkyl benzene sulfonate in which the allcyl
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 a~oms, or
mixtures thereof; and
(2) frorr 1% to about 95%, 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 1 L~ 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 rnoieties are magnesium: and
wherein the auxiliary foam booster is an amide.
Another pre-ferred foaming composition of the invention
herein is an ayglomerated light duty detergen-t granule composi-
tion cornprising
( 1 ) from about 56 to about 60%, preferably from 1 OP6 to
about 20-6 of an alkylpolysaccharide surfactant having
the formula RO(R )t(Z)x wherein Z is a moiety
derived from a reducing saccharide moiety containing
from 5 to 6 car;bon 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 ~3 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 frorn about 1.5 to about
10, preferably 1.5 to 4, most preferably 1 6 to 2.7;
(2) frorn about 5% to abou~ 60P6 of an alkyl ben~ene sul-
fonate cosurfactant in which the alkyl group contains
from about 10 to about 13 carbon atoms, said alkyl
~ 12 ~
benzene sulfonate neutralized with one or more
cationic moieties (M) to balance the formula;
(3) from about 5~ to about ~0%, 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 neu~ra-
lized with one or more catlonic moieties M to
complete the formula.
(4) from about 5% to about 80% of a water soluble
inorganic salt selected from the group consisting
of sodi~l 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 foamsO
These foams are relatively stable and, iE not disturbed,
can exist for several days~ Furthermore, the foam has
structural integrity and do~s not spread out. The foams
prepared using mixtures of alkylbenzene sulfonate and ~he
alkylpolysaccharide are unique in that they do not have a
"slippery" feel. All of the foams rinse ~u.ickly~
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 fields
unrelated 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.
, ~,,,;~
Patents 3,303,896; 3,111,178; 3,130,798; and 3,215,200. 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 from 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 fighting or fire prevention
processes where a stable foam is used to extinguish a flame
or sparks by cutting o~f the oxygen supply. This includes
fire fighting and foaming runways for crash~landings as
disclosed in U.SO Patents 2,514,310; 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 use~ul.
The compositions and processes of this invention are also
especially valuable in the field oE preparing gypsum board,
plastic, and resin foams. The foams of this invention pro-
vide a stable rela~ively thick structure permitting solid-
ification of the resins, plastics, cellulosic particles,
etc., into stable oam structures having light densities,
thick cell walls and good structural lntegrity. Examples of
forming processes which utilize foaming agents are described
in U.S. Patents 3,669 J 898; 4,907,982; and 4,423,720.
The flotation of minerals so as to concen~rate the
mineral valuesr e.g., in the Eoam (beneficiation), can
be carried out advantageously using the compositions and
processes of this invention. Such processes are described
in U.5. 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 invention involves makin~ use of their exceptional
stablility to provide temporary insulation for plants when
freezing conditions are expected. An alkylbenzene sulfonate
is the preferred cosurfactant and the foam can be applied ~o
the foliage etc., of the plan~s. Such a process is disclosed
in U.S. Patent 3,669 t 898.
: i
-
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 detergent
5 ~ compositions in washing dishes comprise from about 5% to about
50%, preferably -from about 10~ to about l~0~ 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,
C~ 3 alkanolamines, C2 4 polyols, mixtures thereof, and the
balallce water. It is a special advanta~3e of the compositions of
this invention that they can be made in concentrated form ~up to
about 50~ by wt. of the mixture of surfactants) Yvith only very
Iow levels of organic solvents and without the addi-tion of expen-
sive hydrotropic materials. Additional suds boosters or builders
such as trialkyl 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 1% to about 95%,
preferably from about 5% to about 20% of the mixture of surfac-
tan ts mentioned hereinbefore, from about 1~ to abou t 5~ of an
alkanol amide, from about 0 . 5% to about 3~ of a polymeric thick-
ener, and the balance water. I t is a special advantage of the
shampoos that they rinse quickly and readily.
Additional Ingredien-ts
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 . I n de
tergent compositions -the compositions can contain any of the well
known ingredients including minor amounts of other surfactants,
c3etergency builders, soil suspending agents, brighteners, abras-
ives, dyes, fabric conditioning agents, hair conditioning agen-ts,
hydro-tropes, solvents, fillers, clays, perfumes, etc. Suil:able
ingredients are disclosed in U.S. ~atents 4,166,039--~Vise;
4,157,978-'Llenaclo; 4,056,481--Tate; 4,049,586--Collier;
3S
~L9~
- 15 -
4,035,257--Cherney; 4,019,~98--Benson et al; 4,000,080--
Bartolotta et al; and 3,983,078--Collins. The shampoo
compositions oE this invention can contain any of the
additional ingredients known to the art to be suitable for
use in shampoos. Listings of suitable additional ingred-
ients, including low levels of other surfactants can be
found in U.S~ Patents 4,089,945; 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. ~or example, raising the pH to above about
8.5 by alkaline materials or incorporating the ter~iary alco-
hols of the Jones et al, Canadian Patent 1,160,131 issued
January 10~ 1984 Such ingredients are desirable for some
consumers since the solutions do not have the normal "soapy"
feel associated with surfactant 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 ~remium Product
Commercial Commercial of the
Product Product Invention
U.S. Crystal U.S.
Whi~ ~Palmoliv ~
FORMULA Weight %Weight ~Weight %
Sodi~n Cll 8 alkyl
benzene sulfonate 10.5 13.0 18.0
C12_13 alkylpoly-
~lucoside~ 3(>2%
free fatty alcohol) - - 12.0
-- 16 --
Sodium 14-15 Y
polyethoxylate3 sul fate5.5 12.0
Balance of forrnula inc. water 84.0 70,0 70.0
SUDSI NG
Rela-tive Volume of Suds(m!) 110 125 220
0.2% solutions
CONSUMER TEST
Overall preference, % 10 18 23
Favorable sudsing
10 comments, % 711 85 90
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 consumers wore
rubber gloves during -the test. The differences are significant at
20 the 95% confidence level for the invention over the generic
product .
The relative volume of suds in ml. is determined by the
following test prccedure:
100 ml of the test solution at 115F is placed in a 500 ml
25 graduated cyliner: the solution is agitated by repea-ted inversion
of the graduated cylinder until the amount of suds in the cylinder
does not increase with further agitation. Suds hei~ht is
measured directly on the cylinder scale making allowance for the
height o-f liquid remaining in the cylinder. The test solution is
30 made by adding the test product to water having a hardn~ss oF 7
gr. per U.S. gallon (Ca/l~/lg = 3/1) .
- 17 -
EXAMPLE l l -~
LAS Suds Boosting
lVt, % of: A B C D E F G
_
5Sodium C11 8 all~yl-
benzene sulfonate 0 20 40 50 60 80 100
C12-l 5 alkYlPoly2-3
ylucoside 100 80 60 50 40 20 0
Relative Volume
of suds ~ml) 140 220 280 300 310300 240
The suds (foam) were genera-ted as clescribed in Ex. I using
300 ppm of the surfactant mixtures in ci-ty water (~9 grains per
gallon). The results clearly show the sudsing syner~ism For
lS ratios greater than about 1 :2, i.e. for -the foaming composition of
the invention herein.
EXAMPLE l l l
Soap Sucls Boosting
~Vt. ~ of: A B C D E F
20 Sodium oleate 0 20 40 60 80 100
Cl 2-l 5 al kYIPI`/2-3
glucoside l O0 80 60 40 20 0
Relative Volurne
of suds (ml.) ~ 160 270 280 300 310260
The suds were genera~ed as in Ex. I using 50û ppm. of the
surfactant mixtures. This clata clearly indicates the sudsing
synergism for the foaming composition of the invention herein,
s~
EXAMPLE I V
FoamincJ wi-th Soap
Effect of ~lardness on Relative Volume of Suds
grains harclness
0 2 ~I 6
Sodium oleate 225 lO O O
Sodium oleate plus Cl 2-15
all<ylpoly2_3 glucoside
(3:2 ratio) 360 100 55 10
The suds were generated as in Ex. I using 500 ppm. of the
surfactant mixtures.
EXAMPLE V
Allcyl Polyglucosidy (Cl2 15 alkYIPIY 2 3 g
Suds E3Oosting for the Following Representative CosurFactants
(3:2 ratio; 500 ppm)
% increase in Foaming
Sodium C11 8 all<ylbenzene sulfonate 100-150
Socliurn oleate 50-75
2 0 3-lN -coconuta I kyl-N,N-di methy I ] -
2-hydroxy-1-sulfonate 40-60
Soclium C1L~ 15 olefin sulfonate 20-40
Sodium coconut alkyl sulfate 10-30
Sodium coconut aiky! polyethoxylate3 sulfate 0-20
The above data clearly dernonstrate the criticality of utilizing
a carboxylate or sulfonate anionic detergent cosurfactant for
sudsing synergism with the alkyl polyglucoside surfactant.
EXAMPLE Vl
Glucoside Chain Length Criticality
40:60 wt. ratio of C12_15 alkyl polyglucoside to sodium C12
alkylbenzene sulfonate (500 ppm. concentration) where the gluco~
sicle portion is:
S~
_ 19 _
Relative Vol-ime
of Suds (ml)
Monoglucoside 180
Diglucoside 240
S Pentaglucoside 260
Decag lucoside 170
Sodium C11 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, significant synergism is obtained only with 1.5 or more
glucoside units and preferably less than abou-t 10, more preFer-
ably less than about 8 glucoside units.
EXAMPLE Vl l
Alkylbenzene sulfonates (LAS)
Homologs/phenyl-position (3:2 ratio; 500 ppm)
Relative Volume
of Suds ( ml )
20 Ex . I l 's alkylpoly~lucoside plus:
Sodium C11 LAS, high 2-phenyl210
Sodium C11 LA5, low 2-phenyl 250
Sodium C12 LAS, high 2-phenyl225
Sodium C12 LAS, iow 2-phenyl 225
25 Sodium C14 LAS, high 2-phenyl210
Sodium C1LI LAS, low 2-phenyl215
As can be seen from the above, in ~3eneral C11, low 2-phenyl
LAS is preferred for sudsing.
~9~5~
- 20 -
EXAMPLE Vl l l ;
Suds Boosting of Alkyl
Poiyglucosides and Effect of Soil
Relative Volume of Suds (ml)
~lithou t
5Oil Witl~ Soil
0.5% 1.0
0.2% aqueous solution of a
detergent composition
lO formulated with:
15% sodium C11 8 allcyl-
benzene su I fonate
11.8 L ) 120 50 25
9~ C11.8 LAS %
Ex. I l 's alkyl poly~lucoside 310 130 70
30% C11.8 LAS 190 140 100
20~ C11 8 LAS -~ 12%
Ex. I's all<ylpolyglucoside 380 170 100
*
Test method of Ex. I modified by adding to the test solu-
tion the indicated amount of soil. % is w-t. % of test solution.
The soil is a 44~/56% by weicJht mixture of Fluffo~) and
PRE~) both of which products are available in the United States
from The Procter ~ Camble Company.
As can be seen from the above, the benefit for the invention
is even more remarkable when soil is present.
EXAMPLE I X
Relative Volume of Suds (ml)
No Soil 1% Soil Present
Ceneric commercial product
(Crystal ~Yhite~)** 110 30
Premiurn commerical product B
(Palrnolive Liquic)~) 120 100
f'rcmilJM commercial product C
1 2 5 12 0
3L~g~;34~
12~ C11 8 LAS/8~ Ex. Il's -~
alkyl poly~lucoside 180 120
18% C11 8 LAS/12% Ex. Il's
allcyl polyglucoside 240 150
5~ 24% C11 g LAS/16% Ex. Il's
alkyl polyglucoside 300 180
Soil is added as described in Ex. Vl 1.
Crystal V~hite(~3 is available from Colgate-Palmolive Co.
Palmolive Liquid~3 is available from Colgate-Palmolive Co.
10 Joy~ is available from The Procter Gamble Company.
Suds ~enerated as in Ex. I usin~3 a test solution containing
0.2% by wt. of the indicated commercial product or 0.2% of a
product formulated with the surractant 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 liquids.
EXAMPLE X
Wt. ~ of: A B C D E F
20 C1 1 8 LAS (Sodium) 20 40 6080 100
Sucrose monolaurate 100 80 60 4020 0
Relative Volume
of suds [ml.) 30 100 150 190210220
300 ppm of surfactant mixture used in test solution of Ex. I.
The above demonstrates that structures which are sirnilar to
the alkyl polyglucosides do not provide the benefi~s of this in-
vention .
EXAl\iIPLE Xl
Shampoo
Cocamido propyl betaine (30% aqueous solution) 50.00%
Ex. I's alkyl polyglucoside 5-00~
Polyethylene ~Iycol clistearate 1 . 00%
35 Preservative ~ 03%
Distille~ water q.s. 100.00%
S~
- 22 -
EXAMPLE Xl l
Shampoo
Alpha-olefin sulfonate (40% aqueous solu-tion) 30.00%
Ex. I's alkyl polyglucoside 3.00%
Hydroxyethyl cellulose 0.80%
Perfume ' 1 . 00%
Preservative 0.04~
~istilled water q.s. 100.00%
EXAMPLE X l l l
Paraffin Sulfonate Suds Boosting
Wt. % of: P~ B C D E F
Mixture of sodium C14_15
15 paraffin sul-fonate 0 20 40 60 80 100
C12-15 G4_5 100 80 60 40 20 0
Relative Vol. of Suds (ml) 185 250 275 275 235 210
Test Conditions:
Total concentration o-F 300 ppm; water having 8 grains of
20 mixed hardness.
C12 15G4_5 is a notation for an alkyl polysaccharide
surfactant in ~/hich there are 4-5 glucoside uni-ts and in which
the alkyl group has 12-15 carbons.
EXAMPLE XIV
Sodium vs. I~lagnes~um Alkylbenzene Sulfonate
Relative Volume of Suds (ml.)
Without Soil ~Vith Soil
0.6% 1.0%
0.2% aqueous solution of a
30 detergent compos;tion with:
15Q~ Ex. Il's alkyl poly-
glucoside; 22% C11 ~
alkylbenzene sulfonate with
the benzene group attached
- 23 -
primarily to the center ~;~
of the alkyl chain, sodium
neutralized 450 150 75
15~ Ex. Il's alkyl polyglucoside;
22~ C~ 8 alkylbenzene
sulfonate with the ben~ene
group attached primarily to
the center of the alkyl chain,
magnesium neutralized 450 200 110
10 Premium product ~Joy(~)) 350 120 75
*
Soil added to the test solution as in Ex. Vl l l .
EXAMPLE XV
The optimum alkylpolysaccharides, especially alkylpolygluco-
sides have an HLB of from about 6 to about 27 and a critical
**
micelie concentration ~CMC) of less than about 1000ppm, prefer-
ably less than about 50Q. Short chain alkylpolysaccharides in
which ti1e alkyl group contains less than about 8 carbon atoms
have unacceptably high CMC's and those alkylpolysaccharides
haviny more than about 4 saccharide units have unaccep-tably high
20 HLB's as is shown in the following table in which the alkyl group
and the glucoside chain length were varied.
X of GL~ G1 G2 G3 GL~ G5
Glucosides
X of
25Carbons ` ~--
C4 HLE 5.1 12.4 17.9 23.3 28.834.2
C6 HLB 4.2 11.4 17.0 22.4 27.833.2
C8 HLB 3.2 10.5 16.0 21.4 26.932.3
30CI~IC ~7000
C10 HLB 2.2 9.6 15.0 20.4 26.031.4
CMC ~700 2000E
C12 ~ILB 1.3 8.6 lL~.1 19.5 25.030.'~
CMC ~6 . 0 ~70 ~200 225E ~250
-- 2~ -
C~ lLB 0.4 7.6 13.2 18.6 24.0 29.4
ChlC ~6 ~20 25-60E
C16HLB 0.0 6.7 12.2 17.6 23.1 28.5
CMC ~0.3 ~0.6 ~4
5~ C HLi3 0 0 5.8 11.2 16.6 22.2 27,6
CMC
E=Estimated
HLB determined according -to Davies: Proc. ~ International
Congress, SurFace Activity 1,426, But-terwor-ths, London, 1957.
10 pprn
As can be seen above, (1) longer pure glucoside chain
lengths raise the HLi, and lower the molecule's surface activity
(high CMC) and ~2) the shorter alkyl chain lengths have extremely
high CMC's even as the monoglucoside.
EXAMPLE XVI
The following formulas were prepared:
A i3 C
Magnesium linear Cl 1 2
alkylbenzene sulfonate 22.4 22.4 22,4
20 C12 13 all<ylpolyyluco-
side (Gl 7~ (<2g6 free
fatty alcohol) 14.9 14.9 14.9
Cg_l l alkoxypropyldi-
hydroxyethyl amine oxide - 4
25 C12 alkyldihydrOXY !-
ethyl amine oxide - - 4
Ethanol 5 5 5
~`~ater balance balance balance
Formulas A, B 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 prol:ein, carb~)hydrate
and edible acid). Dinner plates are washed with 4 rnl. of soil on
35 each plate and the suds height is measured after each five plates.
5~
-- 25 --
30 plates in t~tal are washed and the integral of the suds height
talcen over the nurnber of plates washed is reported as the SDW
grade ~SD~Y = Suds During Washing).
A B C
SDW g rade 2I~ 28 . ~ 28 . 4
This shows -that the addition of a small amo~lnt of -these
amine oxides dramatically increases the amount of dishes that can
be washed. Similar results are obtained when a fa-tty 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 alkylpolyglucosicle
(G2 2) (<2~6 free fatty alcohol) are then mixed in. The mixture is
transferred into a fluid bed dryer operated at room temperature
(e.g., Aeromatic Inc., IModel STREA-1 ), then 100 grams of a 50%
solution of said allcylpolyglucosicle is sprayed onto the powder.
20 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 a-t 30 in. of Hg
vacuum at 50"C for ten hours to remove excess waterO
In a similar manner 60 grams of a 50% solution of said alkyi-
25 polyglucoside is sprayed ont~ 100 gram of Berkite and 50 grams
of sodium dodecylbenzene sul-fonate flakes are admixed with the
product to give a light duty granule.
EXAMPLE XVI l l
Ammonium C1 1 2 linear alkyl benzene sulfonate was admixed
30 with C12 alkylpolyglucoside G3 5 in a ratio of about ~:1. The
mixture was used a-t a level of 400 ppm in ci ty 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. Substitution of a sodium
35 C12 16 alkyl glyceryl ether sulfonate for 25g~ and 40% of the
-- 26 --
mixture extended tlle point at which there was no suds to 1.5 and~
1.75 grams of soil per 200 ml. of wash solution respectively.
Similar results are obtained when a sodium, potassium,
ammonium, or monoetllanolammonium C1 2-1 6 alkylpolyethoxy3
acetate, or C1LI_16 olefin sulfonate or mixtures thereof is
substitutecl for at least part of the alkyl glyceryl ether sulfonate.
EXAMPLE X I X
The following formula was prepared with alkylpolyglucosides
having 0 . 3% ancl 1% free fatty alcohol respectively .
~,Vt. %
Ammonium C1 1 2 linear alkyl
benzene sulfonate 17 . 5
Magnesium Cl 1 2 linear alkyl
benzene sulfonate 6 . 4
15 Ammonium C12 13 alkyl poly-
ethoxy I ate ( 0 . 8 ) su I fate 6 . 1
C12 13 alkYIPIY~IUCside G1.7
Minors and water balance
The SDW 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.
EXAMPLE XX
The following formulas were prepared:
% by weight
` f-A B C D
_
Ammonium/magnesium C11 2
linear alkyl benzene
sulfonate 24. 221 . 8
Ammonium/magnesium C12-15
30 olefin sulfonate - - 12 . 8 10 . 6
Ammonium/magnesiUm C12_13
alkyl sulfonate - - 19 . 2 15 ~ 9
Ammonium C1 2-13 alkyl
polyethoxylate ~0.8)
35 sulfate 6 . 55 . 8
~9C~ 450
- 27 -
C12 fatty acid diethanol- ,~
amide - 3.8 - 5.5
C12_l 3 al~;ylpolyglucoside
Gl 7 ~free fatty
5~ alcohol <O.S~) 5.34.8 4 3.3
~llinors and water balance
A B C D
The SD~ I ndex 79 89 97 107
The SD~V index is the SDW grade for each product as a
l O percentage of the SDW value of a standard commercial product.
The following are examples of particularly preferred compo-
sitions . The broad and preferred ranges of ing redients which
can be used are given in the second and third columns, respec-
tively, in each example.
EXAMPLE XX I
% by Weight
Ammonium C11 L~ alkyl
benzene sulfonate 17.5 10-3512-25
Magnesium C11 4 alkyl
benzene sulfonate 6.4 0-11 3-9
Ammonium C12 13 alkyl poly-
ethoxylate (0.8) sul fates 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
EXAMPLE XX I i
~ by l,Yeight
Ammoniurn C1 2 13 alkyl
suifate 15.7 7-23 10-20
Sociiurn C14 16 olefin
sulfonate 10.4 4-19 6-13
~c~
-- 2~3 --
MgC12 6H2 5. 6 0-11 2-10
Coconut monoethanol amide 5 . 5 2-8 3-7
C12_13 alkyl polyglycoside
(1.7) derived from glucose
5 ` ( ~0 . 5% free fatty alcohol ) 5 . 9 2~12 3-9
Ethanol 4. 0 0-l O 0-l O
~12O and rninor components,
e.g., perfume Baiance
The allcyl groups in the surfactants of Examples XXI and
10 XXII can vary from about 10 to about 16 carbon atoms and the
cations can be ammcnium, sodium, potassium, monoethanolammonium,
diethanolammonium, triethanolammonium, magnesium, or preferably,
mixtures therof. ~ny of the preferred alkyl polyglycosides can
be used and other known amine oxide and amide suds boosters
15 disclosed herein can be used.
EXAM PLE X X 111
~Vhen a 2:1 mixture of an ammonium C11 2 alkylbenzene
C12-13 a~l<YIPOIy~l~lcoside ~2-4) (>2~6 f f
alcohol) are tested under the conditions of Example l l the ini-tial
20 suds volur,~e is good, but -the SDW grade is not as good as some
premium commercial products. Substi-tution of between 25~6 and
50% of the mixture with a sodium C12-16 alkyl glyceryl eth
sulfonate, or sodiurn C14 16 olefin sulfonate, or sodium C12 13
alkyl polyethoxylate(3) acetate increases the SD~,V grade without
~5 lo~,vering the initial sudsing excessively.
I'nown analytical techniques can be used to determine the
structures of the alkylpolysaccharide surfactants herein; for
example, to determine the glycosidîc chain length, the amount of
butyl glucoside, the free fatty alcohol con-tent, and the level of
30 unreacted polysaccharide. More 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 t~le hydrophobic portion of the molecule can be
determined by 3C nmr.
5~
- 29 -
The aikylpolysaccharide surfactants are complex mixtures`
Their components vary dependin~ upon the nature of the startiny
materials and the reaction by which they are prepared. Analyti-
c21 standards which are useful in calibrating instruments for
5 ~ analyzin~ the components. of a particular alkylpolysaccharide
surfactant can be obtained from Calbiochem Behring Co. L aJolla,
California. These standards include those for octyl~lucoside
(Calbiocherm ~494559), decylglucoside [Calbiochem ~252715),
dodecylmaltoside (Calbiochem #32~13555).
The HLBs of alkylpolysaccharide 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 resul-ts
indicated in the examples.
, . . .
