Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02195511 2004-08-25
AN ISOTROPIC LIQUID DETERGENT CONTAINING HYDROPHOB1CALLY
MODIFIED POLYMERS AND HYDROTROPES
-Field of the invention
The present invention relates to so-called "isotropic° (i.e., non-
structiued) detergent
compositions comprising certain hydrophobically modified polar polymers (i.e.,
soil arrti-
redeposition polymers) which have not previously been used in such isotropic
formulations.
The hydrophobic modification allows formation of far more stable solutions
(clear versus
hazy) than otherwise possible. Variables which make the compositions more
hydrophobic
(i.e., use of appropriate hydrotrope; greater amounts of
saltlelectrolytdbuilder; less anionic
relative to nonionic) are especially preferred.
Bat .around & Prior Art
The liquid detergent art may be broken down into those detergents in which all
components
of the liquid system are dissolved into one single liquid phase (e.g., the
isotropic liquids); aad
those which contain sufficient surfactant andlor electrolyte to form a
lamellar droplet
comprising "onion" type layers dispersed in an electrolyte medium which is
capable ~f
suspending undissolved particles in the liquid. These latter liquids are also
known as so-called
duotropic or structured liquids.
One problem in the swctured liquid art has been to find a balance betwccn the
stability oftbe
composition and the desirable viscosity of the composition. The viscosity is
dependent on
volume fraction of liquid occupied by the lamellar droplets: While increasing
volume fraction
is bcnef3cial from a stability point of view, it also creates higher viscosity
which may be
undesirable from the point of view of dispensing as well as dispersion in the
washing
machine.
US 5,147,576 to Montague et al., where the inten;elativn between surfactants,
electrolytes.
volume'fra~tion etc. is discussed .
CA 02195511 2004-08-25
2
relates to novel deflacculating polymers which allow incorporation of
more surfactants andlor electrolytes while still maintaining a stable, low
viscosity product.
The polymers of the Montague et al. reference comprise a hydrophilic backbone
which is
generally a linear, branched or highly crass-linked molecular composition
containing one or
mare types of hydrophilic manamer units; and hydrophobic side chains, for
example, selected
from the group consisting of siloxanes, saturated or unsaturated alkyl and
hydrophobic alkoxy
groups, aryl and aryl-alkyl groups, and mixtures thereof.
These polymers were not however, taught for use in isotropic aqueous liquids.
While the Montague e~t al. reference discloses at column 8, lines 26-29 that
some polymers
having hydrophilic backbanes and hydrophobic side chains are known (e.g. US
4,759,868 to
Clarke), there is no teaching there that decreasing the molar ratio of
hydrophilic monomers to
hydrophobic side chains (e.g., to under about 20) will result in increased
solubility of the
polymer, thereby leading to enhanced stability and clear appearance of the
isotropic liquid.
)(n fact, US 4,759,868 to Clarke suggests the effect to be opposite to that
observed in the
subject invention, i.e., the reference suggests that a lower molar ratio of
hydrophilic to
hydrophobic monomer (such that the polymer has more pendant side groups and is
more
hydrophobic) should result in denreased solubilization. The subject invention,
by contrast,
teaches greater hydrophobicity (i.e., more pendant groups) leads to enhanced
solubilization.
Furthermore, the use of a hydrotrope is not taught in either US 5,147,576 to
Montague et al.
or US 4,759,868 to Clarke. Indeed, the use of hydrotrope is counterproductive
in structured,
lamellar liquids to the extent that it inhibits formation of the lamellar
phase critical in such
structured liquids (see column 19, line 17-24 of Montague et al.)
By contrast, the use of a hydrotrope is essential in the isotropic liquid
detergent formulations
of the subject invention because those formulations not containing the
hydrotrope have a
much narrower formulation flexibility in terms of the surfactant composition
and level as well
Z~ 9551 ~
as the electrolyte level. Tn fact, the type and level of hydrotrope used may
critically govern
the solubility of the hydrophobically modified polymers of the type used in
the subject
invention. That is, while not wishing to be bound by theory, those hydrotropes
which mast
enhance hydrophobicity of the composition are superior in terms of aiding
solubilization of
the polymer. The criticality of the hydrotrope type used on the polymer
solubility is shown in
the examples.
In addition, US 4,759,868 to Clarke is limited to high nonionic surfactant
compositions
whereas the system disclosed in the present application are not so limited
(mixtures of anionic
and nonionic surfactants are preferred). As will also be shown in the
examples, the ratio of
anionic to nonionic surfactants can play a critical role in determining the
solubility of the
hydrophobically modified polymers of the type disclosed in the present
invention (i.e.,
compositions more nonionic in character being preferred).
US :5,308,530 to Aronson et al, also discloses certain hydrophobically
modified hydrophilic
polymers. Specifically, the reference teaches a builder which is an
interpolymer [A-B]m [C~,
where A and B are hydrophilic groups modified by hydrophobic monomer C. lin
this
reference, A cannot equal B. In the polymer of the invention, by contrast, the
hydrophilic
chain is comprised of acrylate monomer only (i.e, is a homopolymer). 'These
nnolecules are
more soluble than those with mixtures of A and B.
Although US 5,308,530 does teach the use of hydrotropes and surfactant blends,
the
criticality in terms of (1) hydrotrope type; (2) surfactants type (anionic vs.
nonionic); and (3)
salt concentration in enhancing the compatibility between the polymer and the
detergent
fornmlation is clearly not recognized. That is the reference does not
recognize different types
and levels of hydrotrope can be used to significantly enhance or reduce the
solubility of these
polymers in solution. Stated differently, there is no comparison of the
different solubilities of
the polymer based on type and levels of hydrotrope {indeed only one
formulation, number 2
of example 3 ( see column 16, line 51 ) is ever tested- So many variables are
tested there is
cleanly np recognition of the effect of any one variable (i.e., hydrotrope).
21 ~!~51 1
4
Further, no trend with regard to actives used in the composition or salt
concentrations used
was observed in the Aronson et al. reference. Again, this contrast with the
subject invention
where effect of types of surfactant on solubility of polymer or effect of
electn~lyte
concentrations on solubility of polymer (i.e., electrolyte was required) was
clearly observed.
Finally, liquids of the Aronson et al. reference are not pH jump liquids and
do not contain
sorbitol, such as the preferred liquids of the subject invention. The p)~i of
the Aronson et al.
liquids is about 10 while the pH of the liquids of the invention is about 6,0
to about 8Ø
In short, Montague et al. and Clarke are structured liquid references versus
isotropic liquid
references wherein the use of hydrotropes is not prescribed; and Aronson et
al.. contains
polymers which are structurally different (A cannot equal B); and wherein
compositional
variables for enhancing solubility are not recognized in any event. Further,
the liquids of
Aronson et al. are not pH jump liquids.
A brochure from National Starch & Chemicals Company discloses use of a
acrylatelstyrene
copolymer (FIf1200) in various powder or liquid cleaners. The specific
isotropic liquids of the
invention and ability to improve anti-redeposition properties are not
disclosed Applicants
further note a paper by R. Hodgetts et al. at the Seise Partum and
Woschrnitite:l Conference
(SEPAWA), of Bacl_ Durchheim (Germany) on October 18,20th, 1995. This
reference does
not appear to disclose use of the H1200 polymers in isotropic liquids, let
alonE; the specific
isotropic compositions of the invention.
As will be explained in more detail hereinbelow, a preferred sub-class of
composition
according to the present invention contains a hydrophobic oil.
The use of hydrocarbon oils and polymers in surfactant systems can be found,
for example, in
U.S. Patent No. 4,353,806 to Canto et a1_ and U.S. Patent No. 4,561,991 to
Herbots et al,
However, the polymers disclosed in the above-mentioned art are not the
hydrophobically
modified polymers of the type discussed in the present application.
Furthermore, the use of
hydnotropes is not discussed in U.S. Patent No. 4,353,806 to Canter et al. The
importance of
CA 02195511 2004-08-25
the use of the hydrotrope and its criticality in polymer solubilizationrhas
already been
discussed above_ Also, the oil type discussed in U.S. Patent 4,561,991 to
Herbots et al. are
limited to terpenes and benzyl alcohol. The suitable oils in the present
disclosure are of a
different type and will be discmsed in the specification and examples below.
WO 95/I4,762 to Colgate Palmolive teaches microemulsion composition
comprising 0.1-20% by wt. anionic; 0.1-50% by wt. cosurfactant; 0.1-10% by wt.
"grease
release agent" which may be a type of hydrophobically modified copolymer
having structure
derned by I; and 0.1-10% by wt. water insoluble hydrocarbon.
The copolymer defined by formula 1 is hydrophobically modified on e-very
repeating
monomeric unit, i.e., molar ratio of hydrophile to hydrophobe can be 1:1 and
even less. By
contrast; the ratio of the copolymers of the invention ranges from about 10 to
about 40, i.e,
there are far fewer pendant hydrophobic groups. While not wishing to be bound
by theory,
applicants believe the oil of the Colgate reference must have a different
function to that of the
subject invention where oil is needed to enhance hydrophobicity and thereby
helps in the
dissolution of polymers. The molecules of Colgate, which are already highly
hydrophobic,
,,;
do not need addition of oil to further aid in dissolution.
Finally, an article by Bigger-Jorgensen et al. in I,angmuir 11: 1934-1941
(1995) teaches a
microemulsion cvrnprising a nonionic surfactant, water and oil system
comprising
hydrophobically modif ed polyacrylate (Hr~IPA).
While the TiMPA of the reference dissolves in their system, it would not
dissolve in a fully
formulated detergent composition (i.e., which must contain at least one
anionic). That is, the
reference is not concerned with and, therefore, fails to teach or suggest that
modifications
must be made to solubilize polymers in detergent compositions. Specifically,
the invention
teaches that there not only must be a defined ratio of hydrophobic to
hydrophilic groups, but
that there is a MW ceiling (i.e., 20,000); that hydrotropes must be present;
and that oil must
be present.
2195511
In addition, purely nonionic active systems do not dissolve in liquids
containing builder salts
such as citrate. Also, pure nonionic systems perform poorly on particulate
soils.
In short, not all systems are the same, and there is a great deal of skill in
defining exactly
which polymers and under what conditions ingredients must be used to ensure
solubility.
Brief summary of the invention
Unexpectedly, the applicants have found that in isotropic liquid compositions
comprising (1)
a surfactant or mixture of surfactants {e_g., mixture of anionic and nonionic
surfactants); (2) a
hydrotrope and (3) electrolyte, the use of polymer having a hydrophilic
backbone
{hydrophilic backbone made of one monomer only, e.g., acrylate) wherein there
is a critical
molar ratio of hydrophilic groups (e.g., the backbone) to hydrophobic
"anchors" ("tail")
attached to the backbone (or in other words, molar ratio of hydrophilic to
hydrophobic
monomers), yields solutions which are more stable (e.g., clearer) and have
better anti-
redeposition properties than they otherwise would be if
(1) the specific polymer with these ratios were not used; and
(2) hydrotrope, and electrolyte variables (and preferred surfactant variables)
were not met.
For purposes of this invention, it has been found that "hazy" formulations are
unstable and
tend to phase separate (i_e., within 7 days of preparation). Such phase
separation are generally
not acceptable in product formulation.
The applicants have also found that in isotropic liquid compositions
comprising (1) a
surfactant or a mixture of surfactants (e.g., mixture of anionic and nonionic
surfactants
wherein at least one anionic is required); (2) a hydrotrope; and (3) an
aliphatic (saturated or
unsaturated, straight or branched chained) hydrocarbon oil having specified
molecular weight
and/or carbon chain length, the use of polymer having a hydrophilic bac><:bone
wherein there
is a critical molar ratio (i.e., below 40, preferably below 30, more
preferably below 20) of
hydrophilic group (of the backbone) to hydrophobic "anchors" attached to the
backbone (or in
CA 02195511 2004-08-25
7
other words, molar ratio of hydrophilic to hydrophobic monomers), yields
solutions which
are clearer than they otherwise would be if the critical molar ratio and the
oil criticalities were
not met.
The present invention relates to specific class of isotropic liquids (i.e.
having specific
amounts and types of hydrotrope; preferred surfactants; and minimum
electrolyte) containing
specific polymers which polymers have a critical molar ratio of number of
hydrophilic
"backbone" groups (single monomer hydrophilic backbone) to number of
hydrophobic
"anchor" or tail groups.
When polymers having this criticality of hydrophilic to hydrophobic groups are
added to the
specific isotropic compositions, unexpectedly it has been found that the
compositions are
much more stable (i.e. clearer) compared to if the polymers not having this
critical molar
ratio (as well as addition of hydrotrope and electrolyte) had been added.
While not wishing to
be bound by theory, it is believed that the lower ratio of hydrophilic groups
to hydrophobic
.,
backbone groups makes the overall polymer more hydrophobic, thereby allowing
the
polymers to more easily solubilize because of the hydrophobic interaction with
the core of the
surfactant micelles (which are hydrophobic), thereby in turn making a stable
(i.e. clear) rather
than hazy solution.
Use of a single monomer hydrophilic backbone group (i.e., acrylate) makes the
molecule
more soluble than a mixed monomer hydrophilic backbone.
Additionally, the amount and type of hydrotrope, the ratio of anionic to
nonionic surfactants
and salt concentration may govern the solubility of the polymer. Again, while
not wishing to
be bound by theory, nonionic hydrotropes, lower ratio of anionic to nonionic
surfactants and
higher electrolyte (encompassing both salts and builders) concentration tend
to increase the
solubility of the polymers by increasing the hydrophobicity of the micellar
core and are
therefore preferred. In fact, use of some hydrotropes and some electrolyte is
required.
CA 02195511 2004-08-25
Futtherlnorc, within the aforementioned class of liquids according to the
present inventia~n is
a sub-class of liquids containing specibc polymers having a critical molar
ratio of number of
hydrophilic "backbone" groups to number of hydrophobic "anchor" groups. Molar
ratio '
criticality below about 40, preferably below 30, preferably below 20 (i.e., 0
to 2Q, preferably
at or greater than about 1 to 20).
Vllhen polymers having the ratio of hydrophilic to hydrophobic groups as
defined for the sub-
class are added to the specific isotropic compositions, unexpectedly it has
been found that the
compositions are much more stable (i.e., clearer) compared bo if the polymers
not having this
critical molar ratio had been added. While not wishing to be bound by theory,
it is belicv~
that the relatively low ratio makes the overall polymer more hydrophobic,
thereby allowing
the polymers to more easily solubilize because of the hydrophobic itrimaction
with the core
of the surfactant micelles (which are hydrophobic) and thereby make a stable
(i.e., clear)
rather than hazy solution. On the other hand, if the ratio is lower; there is
no need for an oil
because the pendant hydrophobic groups would allow the molecule to solubilize
anyway.
Without wishing to be bound by theory, such compositions of the subject
invention are
believed to insult in clarity at ratios which need not be as low (i.e., the
compound aeod not
be as hydrophobic) as those of the companion case without oil because the oil
makes the
compositions even more hydrophobic.
Thus, the present invention provides an isotropic liquid detergent composition
comprising:
(1)from 1% to 85% by weight of surfactant;
(2)from 0.1% to 25% by weight of hydrotrope selected
from propylene glycol, ethylene glycol, glycerol,
sorbitol, mannitol, glucose and mixtures thereof;
;)from 0.1'~ to 20% by weight of electrolyte; anc
(4)from 0.1% to 10% by weight of polymer having
CA 02195511 2004-08-25
9 ,
(a)hydrophilic backbone comprising monomer units
selected from:
(i) one or more ethylenically unsaturated
hydrophilic monomers selected from the group
consisting of unsaturated C1-6 acids, ethers,
alcohols, aldehydes, ketones and esters;
and/or
(ii) one or more polymerizable hydrophilic cyclic
monomer units; and/or
(iii) one or more non-ethylenically unsaturated
polymerizable hydrophilic monomers selected
from the group consisting of glycerol and
other polyhydric alcohols;
wherein one or more of said monomers is optionally
substituted with one or more amino, amine, amide,
sulphonate, sulphate, phosphonate, hydroxy,
carboxyl or oxide groups;
(b)at least one monomer containing a pendant
hydrophobic group;
said polymer having a MW of from 1,000 to 20,000;
wherein the molar ratio of the hydrophilic monomers to
t~~e pendant hydrophobic groups) is less than 10.
!.
CA 02195511 2004-08-25
l~
Detergent Active
The compositions of the invention contain one or more surface active agents
selected from,
the group consisting of anionic, nonionic, cationic, ampholytic and
zwitterionic surfactants or
mixtures thereof, The preferred surfactant detergents for use in the present
invention arc
mixtures of anionic and nonionic surfactants although it is to be understood
that any
surfactant may be used alone or in combination with any other surfactant or
surfactants.
Anionic Surfactant Detergents
Anionic surface active agents which may be used in the present invention are
those surface
active compounds which contain a long chain hydrocarbon hydrophobic group in
their
molecular structure and a hydrophile group, i.e. water solubilizing group such
as carboxylate,
sulfonate or sulfate group or their corresponding acid form. The anionic
surface active agents
include the alkali metal (e:g. sodium and potassium) water soluble higher
alkyl aryl
sulfonates, alkyl sulfonates, alkyl sulfates and the alkyl poly ether
sulfates. They may also
include fatty acid or fatty acid soaps. One of the preferred groups of anionic
surface active
agc~r~ts are the alkali metal, ammonium or alkanolamine salts of higher alkyl
aryl sulfonat~
and alkali metal, ammonium or alkanolamine salts of higher alkyl sulfates.
Preferred hip~er
alkyl sulfates are those in which the alkyl groups contain 8 to Z6 carbon
atoms, preferably lZ
to 22 carbon atoms and more preferably ) 4 to 18 carbon atoms. The alkyl group
in the alkyl
aryl sulfonate preferably contains 8 to 16 carbon atoms and more preferably 10
to 15 carbon
atoms. A particularly preferred alkyl aryl sulfonate is the sodium potassium
or ethanolamine
Clo to Ct6 benzene sulfonate, e.g. sodium linear dodecyl benzene sulfonate.
The primary and
secondary alkyl sulfates can be made by reading long chain alpha-olefins with
sulfites or
bisulfites, e.g. sodium hisulfite. The alkyl sulfonates can also be made by
reacting long chain
normal paraffin hydrocarbons with sulfur dioxide and oxygen as describe in
U.S. Patent ~Tos.
2,503,280, 2,507,088, 3,372,188 and 3,260,741 to obtain normal or secondary
higher alkyl
sulfates suitable for use as surfactant detergents.
CA 02195511 2004-08-25
I1
The alkyl substituent is preferably linear, i.e. normal alkyl, however,
branched chain alkyl
sulfonates can be employed, although they are not as good with respect to
biodegradability.
The alkane, i.e. alkyl, substituent may be terminally sulfonated or may be
joined, for
example, to the 2-carbon atom of the chain, i.e. may be a secondary sulfonate.
It is
understood in the art that the substituent may be joined to any carbon on the
alkyl chain. The
higher alkyl sulfonates can be used as the alkali metal salts, such as sodium
and potassium.
The preferred salts are the sodium salts. The preferred alkyl sulfonates are
the C,o to ClR
primary normal alkyl sodium and potassium sulfonates, with the Clo to C15
primary normal
alkyl sulfonate salt being more preferred.
Mixtures of higher alkyl benzene sulfonates and higher alkyl sulfates can be
used as well as
mixtures of higher alkyl benzene sulfonates and higher alkyl polyether
sulfates.
The alkali metal or ethanolamine alkyl aryl sulfonate can be used in an amount
of 0 to 70%,
preferably S to SO% and more preferably S to 1 S% by weight.
The alkali metal or ethanolamine sulfate can be used in admixture with the
alkylbenzene
sulfonate in an amount of 0 to 70%, preferably S to SO% by weight.
Also normal alkyl and branched chain alkyl sulfates (e.g., primary alkyl
sulfates) may be used
as the anionic component.
The higher alkyl polyethoxy sulfates used in accordance with the present
invention can be
normal or branched chain alkyl and contain lower alkoxy groups which can
contain two or
three carbon atoms. The normal higher alkyl polyether sulfates are preferred
in that they have
a higher degree of biodegradability than the branched chain alkyl and the
lower poly alkoxy
groups are preferably ethoxy groups.
The preferred higher alkyl polyethoxy sulfates used in accordance with the
present invention
are represented by the formula:
R'-O(CH2CH20)p-S03M,
CA 02195511 2004-08-25
12
where R' is CR to Czo alkyl, preferably C1o to C~g and more preferably C12 to
Cps; p is 2 to 8,
preferably 2 to 6, and more preferably 2 to 4; and M is an alkali metal. such
as sodium and
potassium, or an ammonium cation. The sodium and potassium salts are
preferred.
A preferred higher alkyl poly ethoxylated sulfate is the sodium salt of a
triethoxy C~z to Cls
alcohol sulfate having the formula:
G12.1s-Q-~CHz~l~~3-S~~la
Examples of suitable alkyl ethoxy sulfates that can be used in accordance with
the present
invention are Clz.~s normal or primary alkyl triethoxy sulfatc, sodium salt; n-
decyl diethoxy
sulfate, sodium salt; C~Z primary alkyl diethoxy sulfate, ammonium salt; Cps
primary alkyl
triethoxy sulfate, sodium salt; C13 primary alkyl tetraethoxy sulfate, sodium
salt; mixed C».is
normal primary alkyl mixed tri- and tetraethoxy sulfate, sodium salt; stearyl
pentaethoxy
sulfate, sodium salt; and mixed Clalg normal primary alkyl triethoxy sulfate,
potassium salt.
The normal alkyl ethoxy sulfates are readily biodegradable and are'preferred.
The alkyl
poly-lower alkoxy sulfates can be used in mixtures with each other and/or in
mixtures with
the above discussed higher alkyl benzene, sulfonates, or alkyl sulfates.
The alkali metal higher alkyl poly ethoxy sulfate can be u.~ed with the
8lkylbenzene sulfonate
andlor with an alkyl sulfate, in as amount of 0 to 70'/0, preferably 5 to 50%
and more
preferably 5 to 20% by weight of entire composition.
Nonionic Surfactant
Nonionic surfactants which can be used with the invention, alone or in
combination with
other surfactants are described below.
As is well known, the nonionic surfactants are characterized by the presence
of a hydrophobic
group and an organic hydrophilic group and are typically produced by the
condensation of an
CA 02195511 2004-08-25
13
organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide
(hydrophilic
in nature). Typical suitable nonionic surfactants are those disclosed in U.S.
Patent Nos.
4,316,812 and 3,630,929.
Usually, the nonionic surfactants are polyalkoxylated lipophiles wherein the
desired
hydrophile-lipophile balance is obtained from addition of a hydrophilic poly-
lower alkoxy
group to a lipophilic moiety. A preferred class of nonionic detergent is the
alkoxylated
alkanols wherein the alkanol is of 9 to 18 carbon atoms and wherein the number
of moles of
aIkylene oxide (of 2 or 3 carbon atoms) is from 3 to 12. Of such materials it
is preferred to
employ those wherein the alkanol is a fatty alcohol of 9 to 11 or 12 to I S
carbon atoms and
which contain from 5 to 8 or 5 to 9 alkoxy groups per mole.
Exemplary of such compounds are those wherein the alkanol is of 10 to I S
carbon atoms and
which contain about 5 to 9 ethylene oxide groups per mole, e.g. Neodol 25-9
and Neodol
23-6.5, which products are made by Shell Chemical Company, Inc. The former is
a
condensation product of a mixture of higher fatty alcohols averaging about 12
to 15 carbon
atoms, with about 9 moles of ethylene oxide and the latter is a corresponding
mixture wherein
the carbon atoms content of the higher fatty alcohol is 12 to 13 and the
number of ethylene
oxide groups present averages about 6.5. The higher alcohols are primary
alkanols.
Another subclass of alkoxylated surfactants which can be used contain a
precise alkyl chain
length rather than an alkyl chain distribution of the alkoxylated surfactants
described above.
Typically, these are referred to as narrow range alkoxylates. Examples of
these include the
Neodol-1 ~R~ series of surfactants manufactured by Shell Chemical Company.
Other useful nonionics are represented by the commercially well known class of
nonionics
sold under the trademark Plurafac by BASF. The Plurafacs are the reaction
products of a
higher linear alcohol and a mixture of ethylene and propylene oxides,
containing a mixed
chain of ethylene oxide and propylene oxide, terminated by a hydroxyl group.
Examples
include C13-C~5 fatty alcohol condensed with 6 moles ethylene oxide and 3
moles propylene
oxide, C13-Cts fatty alcohol condensed with 7 moles propylene oxide and 4
moles ethylene
CA 02195511 2004-08-25
14
oxide, C13-C~5 fatty alcohol condensed with 5 moles propylene oxide and 10
moles ethylene
oxide or mixtures of any of the above.
Another group of liquid nonionics are commercially available from Shell
Chemical
Company, Inc_ under the bobanol or Neodol trademark: Dobanol 91-5 is an
ethoxylated
Cy-C> > fatty alcohol wish an average of 5 moles ethylene oxide and Dabanol 25-
7 is an
ethoxylated C,s-Cls fatty alcohol with an average of 7 moles ethylene oxide
per mole of fatty
alcohol.
In the compositions of this invention, preferred nonionic surfactants include
the C12-Cl5
primary fatty alcohols with relatively narmw contents of ethylene oxide in the
range of from
about 6 to 9 moles, and the C.s to C, ~ fatty alcohols ethoxylated with about
5-6 moles ethylene
oxide.
Another class of nonionic surfactants which can be used in accordance with
this invention are
glycoside surfactants. Glycoside surfactants suitable for use in accordance
with the present
invention include those of the formula:
RO-RIO-~,(Z)x
wherein R is a monovalent organic radical containing from about 6 to about 30
(prefeaably
from about 8 td about 18) carbon atoms; R' is a divalent hydrocarbon radical
containing from
about 2 to 4 carbons atoms; O is an oxygen atom; y is a number which can have
an average
value of from 0 to about 12 but which is most preferably zero; Z is a moiety
derived from a
reducing saccharide containing 5 or b carbon atoms; and x is a number having
an average
value of from 1 to about 7 0 (preferably from about I 1l2 to about 10).
A particularly preferred group of glycoside surfactants for use in the
practice of this invention
includes those of the formula above in which R is a monovalent organic radical
(linear or
branched) containing from about 6 to about 18 (especially from about 8 to
about 18) carbon
CA 02195511 2004-08-25
atoms; y is zero; z is glucose or a moiety derived therefrom; x is a number
having art average
value of from 1 to about 4 (preferably from about 1 1l2 to 4).
Nonionic surfactants which may be used include polyhydroxy amides as discussed
in U.S.
Patent No. 5,312,954 to Letton et al. and aldobionamides such as disclosed in
11.5. Patens No.
5,3 89,279 to Au et al.
Generally, nonionics ~rould comprise 0-50'/° by wt., preferably 5 to
50'0, more preferably 5
to 25% by wt. of the cornposition_
Mixtures of two or more of the nonionic surfactants can be used.
Cationic Surfactants
Many cationic surfactants are known in the art, and almost any cationic
surfactant having at
least one long chain alkyl group of about y 0 to 24 carbon atoms is suitable
in the present
invention. Such compounds are described in "Cationic Surfactants", fungermann,
1970,
Specif c cationic surfactants which can be used as surfactants in the subject
invention are
described in detail in U.S. Patent No. 4,497,718,
As with the nonionic and anionic surface, the compositions of the imrention
may use
cationic surfactants alone or in combination with any of the other surfactants
known in the
art. Of course, the compositions may contain no cationic surfactants at all.
Amphoteric Surfactants
Ampholytic synthetic surfactants can be broadly described as derivatives of
aliphatic or
aliphatic derivatives of heterocyclic secondary and tertiary amines in which
the aliphatic
radical may be straight chain or branched and wherein one ofthe aliphatic
substituents
contains from about 8 to 18 carbon atoms and at least one contains an anionic
water-soluble
CA 02195511 2004-08-25
16
goup, e.g. carboxylate, sulfonate, sulfate. Examples of compounds falling
within this
definition are sodium 3-(dodecylamino)propionate, sodium
3-(dodccylamino)propane-1-sulfonate, sodium 2-{dodecylamino)ethyl sulfate,
sodium
2-(diatethylamino)octadecanosle, disodium 3-(N
carboxymethyldodecylamino)propane
1-sulfonate, disodium octadecyl-imrninodiacetate, sodium
1-carboxymethyl-2-undecylimidazole, and sodium
N,N-bis(2-hydroxyethyl~2-sulfato-3-dodecoxypropylamine. Sodium
3..(dodecylamino)propane-1-sulfonate is preferred. ,
Zwitterionic surfactants can be broadly descn'bed as derivatives of secondary
and tertiary
amines, derivatives of heterocyclic secondary and tertiary amines, or
derivatives of
quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds.
The
cationic atom in the quaternary compound can be part of a heten'cyclic rind_
In all of these
compounds there is at least one aliphatic group, straight chain or branched,
containing from
about 3 to 18 carbon atoms and at least one aliphatic substituent containing
an anionic
water-solubilizing goup, e.g_, carboxy, sulfonate, sulfate, phosphate, or
phosphonate.
Specific examples of zwitterionic surfactants which may be used are set forth
in U.S. Patent
No. 4,062,647:
l~gent Alive level
The amount of active used may vary from 1 to 85% by weight, preferably l0 to
50% by
weight.
As noted the preferred surfactant systems of the invention are mixtures of
anionic and
nonionic surfactants.
Particularly preferred systems iaciude, for example, mixtures of linear alkyl
aryl sulfonates
(LAS) and linear alkoxylated (e.g., ethoxylated) sulfates (AES) with
alkoxylated nonionics
for example in the ratio of 1.2.1 {i.e., 3:1 anionic to nonionic).
CA 02195511 2004-08-25
17 '
In one embodiment of the invention, applicants have increased ,the ratio of
anionic (such as
LAS or AES) relative to nonionic. While not wishing to be bound by theory,
this appears to
make the compositions less hydrophobic and, therefore, makes the compositions
less stable
(e.g., polymer won't dissolve as readily into micelles, perhaps because the
micelles are less
hydrophobic).
Preferably, the nonionic should comprise, as a percentage of an
anionic/nonionic system, at
least 20%, more preferably at least 25%, up to about 75% of the total
surfactant system. A
particularly preferred surfactant system comprises anionic:nonionic in a ratio
of 3:1
The compositions of the invention are all unstructured, isotropic
compositions:
The detergent compositions of the invention are also preferably pH jump
compositions. A pH
jump heavy duty liquid (HDL) is a liquid detergent composition containing a
system of
components designed to adjust the pH of the wash liquor. To achieve the
required pH
regimes, a pH jump system can be employed in this invention to keep the pH of
the product
low for enzyme stability in multiple enzyme systems (e.g., protease and lipase
systems) yet
allow it to become moderately high in the wash for detergency efficacy. One
such system is
borax 1 OH2O/ polyol. Borate ion and certain cis 1,2 polyols complex when
concentrated to
cause a reduction in pH. Upon dilution, the complex dissociates, liberating
free borate to raise
the pH. Examples of polyols which exhibit this complexing mechanism with borax
include
catechol, galacitol, fructose, sorbitol and pinacol. For economic reasons,
sorbitol is the
preferred polyol.
Sorbitol or equivalent component (i.e., 1,2 polyols noted above) is used in
the pH jump _
formulation in an amount from about 1 to 25% by wt., preferably 3 to 15% by
wt. of the
composition.
Borate or boron compound is used in the pH jump composition in an amount from
about 0.5
to 10.0% by weight of the composition, preferably 1 to 5% by weight.
CA 02195511 2004-08-25
Ig
Hvdrotroves
Another ingredient required by the subject invention is hydrotropes. In
general, addition of
hydrotropes helps to incorporate higher levels of surfactants into isotropic
liquid detergents
than would otherwise be possible due to phase separation of surfactants from
the aqueous
phase: Iiydrotropes also allow a change in the proportions of different types
of surfactants,
namely anionic, nonionic, cationic and zwitterionic, without encountering the
problem of
phase separation. Thus, they increase the formulation flex~'bility.
Hydrotropes function
through either of the following mechanisms: t) they increase the solubility of
the surfactant in
the aqueous phase by changing the solvent power of the aqueous phase; shoe
chain alcohols
such as ethanol,isopropanol and also glycerol and propylene glycol are
examples in this class
and ii) they prevent formation of liquid crystalline phases of surfactants by
disrupting the
packing of the hydrocarbon chains of the surfactants in the micelles; alkali
metal salts of alkyl
aryl sulfonates such as xylene sulfonate, cumene sulfonate and alkyl aryl
disulfonates such as
'DOWFAX~1 family of hydrvtropes marketed by Dow Chemicals are examples in this
cla,RS.
Although normally hydrotropes of the second goup mentioned {Group II) would be
expected
to increase solubility of polymer, it was unexpectedly found that addition of
alkyl aryl
sulfotiate_s at concentrations usually used in liquid detergents (-- 1 to 15
weight percent)
caused a decrease in the solubility of the hydrophobically modified polymers
of the present
invention. While not wishing to be bound by theory, applicarns believe that
these Group II
hydrotropes actually tend to decrease the hydrophobicity of the core of the
surfactant
micelles, thereby decreasing the interaction between the hydrophobic groups of
the
hydrophobically modified polymer and the micelle. Thus, the more weight
efficient the
hydrotrope (i.e., this second class of hydrotropes) the larger is the decrease
in the
hydrophobicity of the micelles and, as a consequence, the lower the solubility
of the
hydrophobically modified polymer. Thus, a more weight efficient hydrot~npe
(e.g., a
hydrotTOpe such as cumene sulfonate which, for a given surfactant system, is a
better
hydrotrope) decreases the solubility of the polymer while a less weight ~cient
hydrotrope
(e.g., xylene sulfonate) increases the solubility.
CA 02195511 2004-08-25
19
In other words, while intuitively one of ordinary skill in the an would prefer
the weight
efficient hydrotropes of Class n above, the preferred hydrotropes of this
invemion are the less
weight efficient, but solubility enhancing, hydrotropes of Class I.
Preferred hydrotropes in the compositions of the present invention are
polyols, which may
also act as enzyme stabilizers, such as propylene glycol, ethylene glycol,
glycerol, sort~itol,
mannitol and glucose.
These would not traditionally be considered good hydrotropes but, a's noted
above, these
compounds do not decrease the hydrophobicity of the micelles as much thereby
allowing
hydrophobically modified polymers to solubilize better.
In general. hydrotrope_s should be present in an amount of about 1 % to 25% by
wt.,
preferably 1 % to IO'/o by wt. of the composition.
Certain compositions of the invention further contain an aliphatic hydrocarbon
oil which is
believed to make the compvsiiivns more hydrophobic and so help the l;tability
(i.e., clarity) of
the solution even when the polymer has higher ration of number of hydrophilic
group {i.e.,
i0 m 40, prafcrably IS to 40) to number of hydrophobic group (i.e., rendering
it not quite as
bydmphobic).
The aliphatic group is a saturated or unsaturated, straight or branch chained
hydrocarbon
having 5 to 19, preferably 8 to 18 carbons. The molecular weight of these oils
will generally
be about 50 to about 300 .
Examples of such oil include, but are not limited to heptanes, octaves,
nonanes, dccanes, etc.,
through C,R; olefines such as octenes, nonenes, through Clg; and all isomeric
variations (e_g.,
isooctane) thereof.
CA 02195511 2004-08-25
The oil can be used at levels varying from about 0.1 to 20% by weight,
preferably 0.5 tro
10%, more preferably 0.5% to S% by weight of the composition.
Builders/Electroh tr,~,-se
Builders which can be used according to this invention include conventional
alkaline
detergency builders, inorganic or organic, which should be used at levels from
about 0.1% too
about 20.0'/° by weight of the composition, preferably from 1.0% to
about 10.0°Y° by weight,
more preferably 2% to 5% by weight.
As electrolyte may be used any water-soluble salt. Electrolyte may also be a
detergency
builder, such as the inorganic builder sodium tripolyphosphate, or it may be a
non-functional
electrolyte such as sodium sulphate or chloride. Preferably the inorganic
builder comprises all
or part of the electrolyte. That is the term electrolyte encompasses both
builders and salts.
Examples of suitable inorganic alkaline detergency builders which may be used
are
water-soluble alkalimetal phosphates, polyphosphates, borates, silicates and
also carbonates.
Specific examples of such salts are sodium and potassium triphosphates,
pyrophosphates,
orthophosphates, hexametaphosphates, tetraborates, silicates and carbonates.
Examples of suitable organic alkaline detergency builder salts are: (1) water-
soluble amino
polycarboxylates, e.g.,sodium and potassium ethylenediaminetetraacetates,
nittiloiriacetates
and N-(2 hydroxyethyl)-nitrilodiacetates; (2) water-soluble salts of physic
acid, e_g., sodium
and potassium phytates (see U.S. Patent No. 2,379,942); (3) water-soluble
pvlyphosphonates,
including specifically, sodium, potassium and lithium salts of
ethane-1-hydroxy-1,1-diphosphonic acid; sodium, potassium and lithium salts
ofmethylene
diphosphonic acid; sodium, potassium and Lithium salts of ethylene
diphosphonic acid; and
sodium, potassium and lithium salts of ethane-1,1,2-triphosphonic acid. Other
examples
include the alkali metal salts of ethane-2-carboxy-1,1-diphosphonie acid
hydroxymethanediph~sphunic acid, carboxyldiphosphonic acid,
ethane-1-hydroxy-1,1,2-triphosphonic acid, ethane-2-hydroxy-1,1,2-
triphosphonic acid,
propane-1,1,3,3-tetraphosphonie acid, propane-1,1,2,3-tetraphosphonic acid,
and
CA 02195511 2004-08-25
21
propane-1,2,2,3-tetraphosphonic acid; (4) water-soluble salts of
polycarboxylate polymers
and copolymers as described in U.S. Patent No 3,308,067.
In addition, polycarboxylate builders can be used satisfactorily, including
water-soluble salts
of mellitic acid, citric acid, and carboxymethyloxysuccinic acid, salts of
polymers of itachnic
acid and malefic acid, tarnate monosuccinate, tartrate disuccinate and
mixtures thereof
(TMS/'fDS).
Certain zeolites or aluminosilicates can be used. One such aluminosilicate
which is useful in
the compositions of the invention is an amorphous water-insoluble hydrated
compound of the
formula Nax(yAIOZ.SiOz), wherein x is a number from 1.0 to 1.2 and y is 1,
said amorphous
material being further characterized by a Mg++ exchange capacity of from about
50 mg eq,
CaC03lg. and a particle diameter of from about 0.01 micron to about 5 microns.
7"his ion
exchange builder is more fully described in British Pat No. 1,470,250.
A second water-insoluble synthetic aluminosilicate ion exchange material
useful herein is
crystalline in nature and has the formula Na,[(AIO~y.(SIOs)]xHZO, wherein z
and y are
.,
integers of at least b; the molar ratio of a to y is in the range from 1.0 to
about 0.5, and x is an
integer from about 15 to about 264; said aluminosilicate ion exchange material
having a
particle size diameter from about 0.1 micron to about 100 microns; a calcium
ion exchange
capacity on an anhydrous basis of at least about 200 milligrams equivalent of
CaC03 hardness
per gram; and a calcium exchange rate on an anhydrous basis of at least about
2
grains/gallon/minuteJgtam. These synthetic aluminosilicatcs are more fully
described in
)3ritish Patent No. 1,429,143.
In general, the more electrolyte that is used, the more hydrophobic are the
micelles and,
according to what applicants believe to be the theoretical mechanism of the
invention, the
better for the hydrophobically modified polymer to dissolve.
CA 02195511 2004-08-25
22
Enzymes
s .
One or more enzymes as described in detail below, may be used in the
compositions of the
invention.
If a lipase is used, the lipolytic enzyme may be either a fungal lipase
producibie by Humi cola
lanug_inosa and Thermomvces Ianuginosus, or a bacterial lipase which show a
positive
immunological cross-reaction with the antibody of the lipase produced by the
microorganism
Chromobacter viscosum var. I~olvticum NRRL B-3673. This microorganism has been
described in Dutch patent specification 154,269 of Toyo Jozo Kabushiki Kaisha
and has been
deposited with the Fermentation Research Institute, Agency of Industrial
Science and
Technology, Ministry of International Trade and Industry, Tokyo, Japan, and
added to the
permanent collection under nr. KO Hatsu Ken Kin Ki 137 and is available to the
public at the
United States Department of Agriculture, Agricultural Research Service,
Northern Utilization
and Development Division at Peoria, Illinois, USA, under the nr. NRRL B-3673.
The lipase
produced by this microorganism is commercially available from Toyo Jozo Co.,
Tagata,
Japan, hereafter referred to as "TJ lipase". These bacterial lipases should
show a positive
immunological cross-reaction with the TJ lipase antibody, using the standard
and well-known
immunodiffusion procedure according to Ouchterlony (Acts. Med. Scan., 133,
pages 76-79
( 1950).
The preparation of the antiserum is carried out as follows:
Equal volumes of 0.1 mg/ml antigen and of Freund's adjuvant (complete or
incomplete) are
mixed until an emulsion is obtained. Two female rabbits are injected with 2 ml
samples of the
emulsion according to the following scheme:
day 0 : antigen in complete Freund's adjuvant
day 4 : antigen in complete Freund's adjuvant
day 32: antigen in incomplete Freund's adjuvant
day 60: booster of antigen in incomplete Freund's adjuvant
CA 02195511 2004-08-25
z3
The serum containing the required antibody is prepared by centrifugation of
clotted blood,
taker on day 67.
The titre of the anti-TJ-lipase antiserum is determined by the inspection of
precipitation of ,
serial dilutions of antigen and antiserum according to fhe Ouchterlony
procedure. A 25
dilution of antiserum was the dilution that still gave a visible precipitation
with as antigen
concentration of 0.1 mg/ml.
All bacterial lipases showing a positive immunological cross-reaction with the
Tl-lipase
antibody as hereabove described are lipases suitable in this embodiment of the
invention,
Typical examples thereof are the lipase ex Pseudomonas fluorescens IAM 1057
available
from Amano Pharmaceutical Co., Nagoya, Japan, under the trade-name Amano-P
lipase, the
lipase ex Pseudomonas fraei FERM P 1339 (available under the trade-name Amano-
B), the
lipase ex Pseudomonas nitroreducens var. lipolyticum FERM P1338, the lipase
eac
Pseudomonas sv, available under the trade-name Amano CES, the lipase ex
Pseudomonas
cevacia. lipases ex Chromobacter viscosum, e.g. Chromobacter viseosum var.
lipolyrticum
NRRL B-3673, commercially available from Toyo Joto Co., Tagata,~~apan; and
further
Chromobacter viscasum lipases from U,S. Biochemical Corp. USA and Diosynth
Go_, The
Netherlands, and lipases ex Pseudomonas ladioli.
An example of a fungal lipase as defined above is the lipase ex 1-hunicoia
lanu~inosa,
available from Amano under the tradename Amano CE; the lipase ex liumicola
lanuainosa as
described in the aforesaid European Patent Application 0;258,068 (NOVO), as
well as the
lipase obtained by cloning the gene from Humicola larntginosa and expressing
this gene in
Aspergillus or,raae, commercially available from NOVO induslri A/S under the
tradename
"Lipalase". This lipolase is a preferred lipase for use in the present
invention.
While various specific lipase enzymes have been described above, it is to be
understood that
any lipase which can confer the desired lipolytic activity to the compositian
may be used and
the invention is not intended to be limited in any way by specific choice of
lipase enzyme.
CA 02195511 2004-08-25
24
The lipases of this embodiment of the invention are included in the liquid
detergent
composition in such an amount that the final composition has a Iipolytic
enzyme activity of
from 100 to 0.005 LU/ml in the wash cycle, preferably 25 to 0.05 LU/ml when
the
formulation is dosed at a level of about .l-10, more preferably .5-7, most
preferably 1-2
g/liter.
A Lipase Unit (LU) is that amount of lipase which produces 1/pmol of
titratable fatty acid per
minute in a pH stat under the following conditions: temperature 30°C;
pH = 9.0; substrate is
an emulsion of 3.3 wt.% of olive oil and 3.3% gum arabic, in the presence of
13 mmol/1 Ca2+
and 20 mmol/1 NaC1 in 5 mmol/1 Tris-buffer.
_.... _ ._.._... _ ....._.._._Natur_a~ly~_mixtures _of the above_lipases can
be used. The lipases can be used in their
non-purified form or in a purified form, e.g. purified with the aid of well-
known absorption
methods, such as phenyl sepharose absorption techniques.
If a protease is used, the proteolytic enzyme can be of vegetable, animal or
microorganism
origin. Preferably, it is of the latter origin, which includes yeasts, fungi,
molds and bacteria.
Particularly preferred are bacterial subtilisin type proteases, obtained 'from
e.g. particular
strains of B. subtilis and B licheniformis. Examples of suitable commercially
available
proteases are Alcalase, Savinase, Esperase, all of NOVO Industri a/S; Maxatase
and Maxacal
of Gist-Brocades; Kazusase of Showa Denko; BPN and BPN' proteases; Optimase
from
Solvay and so on. The amount of proteolytic enzyme, included in the
composition, ranges
from 0.05-50;000 GU/mg. preferably 0.1 to 50 GU/mg, based on the final
composition.
Naturally, mixtures of different proteolytic enzymes may be used.
While various specific enzymes have been described above, it is to be
understood that any
protease which can confer the desired proteolytic activity to the composition
may be used and
this embodiment of the invention is not limited in any way be specific choice
of proteolytic
enzyme.
CA 02195511 2004-08-25
In addition to Iipases or proteases, it is to be understood that other enzymes
such as cellu Iases,
oxidases, amylases, peroxidases and the like which are well known in the art
may also be
used with the composition of the invention. The enzymes may be used together
with co-
factors required to promote enzyme activity, i.e., they may be used in enzyme
systems, if
required. It should also be understood that enzymes having mutations at
various positiows
(e.g., enzymes engineered.for performance and/or stability enhancement) are
also
contemplated by the invention. One example of an engineered commercially
available
enzyme is Durazym~R~ from Novo.
The enzyme stabilization system may comprise calcium ion; boric acid,
propylene glycol
and/or short chain carboxylic acids. The composition preferably contains from
about 0.01 to
about 50, preferably from about 0.1 to about 30, more preferably from about I
to about 20
millimoles of calcium ion per liter.
When calcium ion is used, the level of calcium ion should be selected sos that
there is always
some minimum level available for the enzyme after allowi~ig for complexation
with builders,
etc., in the composition. Any water-soluble calcium salt can be used as the
source of calcium
ion, including calcium chloride, calcium formate, calcium acetate and calcium
propionate. A
small amount of calcium ion, generally from about 0.05 to about 2.5 millimoles
per liter, is
often also present in the composition due to calcium in the enzyme slurry and
formula water.
Another enzyme stabilizer which may be used in propionic acid or a propionic
acid salt
capable of forming propionic acid. When used, this stabilizer may be used in
an amount from
about 0.1% to about 15% by weight of the composition.
Another preferred enzyme stabilizer is polyols containing only carbon,
hydrogen and oxygen
atoms. They preferably contain from 2 to 6 carbon atoms and from 2 to 6
hydroxy groups.
Examples include propylene glycol (especially 1,2 propane diol which is
preferred), ethylene
glycol; glycerol, sorbitol, mannitol and glucose. The polyol generally
represents from about
0.1 to 25% by weight, preferably about 1.0% to about 15%, more preferably from
about 2%
to about 8% by weight of the composition.
CA 02195511 2004-08-25
26
The composition herein may also optionally contain from about 0.25% to about
5%, most
preferably from about 0.5% to about 3% by weight of boric acid. The boric acid
may be, but
is preferably not, formed by a compound capable of forming boric acid in the
composition.
Boric acid is preferred, although other compounds such as boric oxide, borax
and other alkali
metal borates (e.g., sodium ortho-, mete- and pyroborate and sodium
pentaborate) are
suitable. Substituted boric acids (e.g., phenylboronic acid, butane boronic
acid and a p-bromo
phenylboronic acid) can also be used in place of boric acid.
One preferred stabilization system is a polyol in combination with boric acid.
Preferably, the
weight ratio of polyol to boric acid added is at least 1, more preferably at
least about 1.3.
Another preferred stabilization system is the pH jump system such as is taught
in ~J.S. Patent
No. 5,089,163 to Aronson et al.
Optional Ingedients
In addition to the enzymes mentioned above, a number of other optional
ingredients may be
used.
Alkalinity bufl<'ers which may be added to the compositions of the invention
include
monoethanolzunine, triethanolamine, borax and the like.
Other materials such as clays, particularly of the water-insoluble types, may
be useful
adjuncts in compositions of this invention. Particularly useful is bentonite.
This material is
primarily montmorillonite which is a hydrated aluminum silicate in which about
116th of the
aluminum atoms may be replaced by magnesium atoms and with which varying
amounts of
hydrogen, sodium, potassium, calcium, etc. may be loosely combined. The
bentonite in its
more purified form (i.e. free from any grit, sand, etc.) suitable for
detergents contains at least
50% monimorillonite and thus its ration exchange capacity is at least about SO
to 75 meq per
100$ of bentonite. Particularly preferred bentonites are the Wyoming or
Western U.S.
CA 02195511 2004-08-25
27
bentonites which have been sold as Thixo-jets 1, ?, 3 and 4 by Georgia Kaolin
Co. These
bentonites are known to soften textiles as described in British Patent No.
401, 413 to Marriott
and British Patent No. 461,221 to Marriott and Guam.
In addition, 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
Improvements in the physical stability and anti-settling properties of the
composition may be
achieved by the addition of a small effective amount of an aluminum salt of a
higher fatty
acid, e.g., aluminum stearate, to the composition. The aluminum stearate
stabilizing agent can
be added in an amount of 0 to 3%, preferably 0.1 to 2.0% and more preferably
0.5 to 1.5%.
There also 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: A preferred anti-redeposition
agent is sodium
carboxylmethyl cellulose having a 2:1 ratio of CM/MC which is sold under the
tradename
Relatin DM 4050.
Optical brighteners for cotton, polyamide and polyester fabrics can be used.
Suitable optical
brighteners include Tinopal LMS-X, stilbene, triazole and benzidine sulfone
compositions,
especially sulfonated substituted triazinyl stilbene, sulfonated
naphthotriazole stilbene,
benzidene sulfone, etc., most preferred are stilbene and triazole
combinations. A preferred
brightener is Stilbene Brightener N4 which is a dimorpholine dianilino
stilbene sulfonate.
Anti-foam agents, e.g. silicon compounds, such as Silicane L 7604, can also be
added in
small effective amounts.
Bactericides, e.g. tetrachlorosalicylanilide and hexachlorophene, fungicides,
dyes, pigments
(water dispersible), preservatives, e.g. formalin, ultraviolet absorbers, anti-
yellowing agents,
such as sodium carboxymethyl cellulose, pH modifiers and pH buffers, color
safe bleaches,
CA 02195511 2004-08-25
28
perfume and dyes and bluing agents such as lragon $lue L2D, Detergent Blue
4721572 and
ultramarine blue can be used.
Also, soil release polymers and cationic softening agents may be used.
Polvtner
The polymer of the invention is one which, as noted above, has previously been
used in
structured (i.e., lamellar) compositions such as those described in U.S.
Patent No. 5,147,576
to Montague et al. This is
because the polymer allows the incorporation of greater amounts of surfactants
andlor
electrolytes than would otherwise be compatible with the need for a stable,
low-viscosity
product as well as the incorporation, if desired, of greater amounts of other
ingredients to
which lamellar dispersions are highly stability-sensitive.
In general, the polymer comprises a "backbone" component which is a monomer
(single
monomer) as discussed below and a "tail" portion which is a second monomer
which is
hydrophobic in nature (e.g., lauryl methacrylate or styrene).
The hydrophilic backbone generally is a linear, branched or highly cro.RS-
linked molecular
composition containing one type of relatively hydrophobic monomer unit wherein
the
monomer is preferably sufficiently soluble to form at least a 1°~ by
weight solution when
dissolved in water. The only limitation to the structure of the hydrophilic
backbone is that a
polymer corresponding to the hydrophilic backbone made from the backbone
monomeric
constituents is relatively water soluble (solubility in water at ambient
temperature and at pH
of 3.0 to 12.5 is preferably more than 1 gll). The hydrophilic backbone is
also preferably
predominantly linear, e.g., the main chain of backbone constitutes at least
50% by weight,
preferably more than 75%, most preferably more than 90'~'o by weight.
The hydrophilic backbone is composed of one monomer unit selected from a
variety of units
available for polymer preparation and linked by stay chemical links including
CA 02195511 2004-08-25
29
O O O
-O-, C-O, - C-C -, - C-O -, - C-N, - C-N, and - P. -
OH
s.
Preferably the hydrophobic side chains are part of a monomer unit which is
incorporated in
the polymer by copolymerizing hydrophobic monomers arid the hydrophilic
monomer
making up the backbone. A "tail" group preferably comprises a monomer unit
comprising the
hydrophobic side chains which are incorporated in the "tail" monomer. The
polymer is made
by copolymerizing hydrophobic monomers (tail group comprising hydrophobic
groups) and
the hydrophilic monomer making up the backbone. The hydrophobic side chains
preferably
include those which when isolated from their linkage are relatively water
insoluble, i.e.,
preferably less than 1 g/1, more preferred less than 0.5 g/1, most preferred
less than 0. ~ g/1 of
the hydrophobic monomers, will dissolve in water at ambient temperature at pH
of 3.0 to
12.5. '
Preferably, the hydrophobic moieties are selected from siloxanes, saturated
and unsaturated
alkyl chains, e.g., having from 5 to 24 carbons, preferably 6 to 18, most
preferred 8 to 16
carbons, and are optionally bonded to hydrophilic backbone via an alkoxylene
or
polyalkoxylene linkage, for example a polyethoxy, polypropoxy, or butyloxy (or
mixtures of
the same) linkage having from 1 to 50 alkoxylene groups. Alternatively, the
hydrophobic side
chain can be composed of relatively hydrophobic alkoxy groups, for example,
butylene oxide
and/or propylene oxide, in the absence of alkyl or alkenyl groups. Another
preferred
hydrophobic group include styrene.
Monomer units which make up the hydrophilic backbone include:
( 1 ) unsaturated, preferably mono-unsaturated, C~.~ acids, ethers, alcohols,
aldehydes, ketones
or esters such as monomers of acrylic acid, methacrylic acid, malefic acid,
vinyl-methyl ether,
vinyl sulphonate or vinylalcohol obtained by hydrolysis of vinyl acetate,
acrolein;
CA 02195511 2004-08-25
(2) cyclic units, unsaturated or comprising other groups capable of forming
inter-monomer
linkages, such as saccharides and glucosides, alkoxy units and malefic
anhydride;
(3) glycerol yr other saturated polyalcohols.
Monomeric units comprising both the hydrophilic backbone and hydrophobic side
chain may
~be substituted with goups such as amino, amine, amide, sulphonate, sulphate,
phosphonate,
phosphate, hydroxy, carboxyl and oxide goups.
The hydrophilic backbone is composed of one unit. 'rhe backbone may also
contain small
amounts of relatively hydrophilic units such as those derived from polymers
having a
solubility of less than 1 g/1 in water provided the overall solubility of the
polymer meets the
requirements discussed above. Examples include polyvinyl acetate or polymethyl
methacrylate.
(CH~ H
RZ
Ra
~a
-z
-n
wherein: z is l; x:z (i.e., hydrophilic backbone to hydrophobic tail) is less
than 20, preferably
less than 17, more preferably less than 10; in which the monomer units may be
in random
order; and n is at least 1: R~ represents -CO-O-, -O-, -O-CO-, -CHZ-, -CO-1VH-
or is absent;
Rz represents from 1 to 50 independently selected alkyleneoxy groups
preferably ethylene
oxide or propylene oxide groups, or is absent, provided that when R3 is absent
and Rd
CA 02195511 2004-08-25
31
represents hydrogen or contains no more than 4 carbon atoms, then RZ must
contain an
alkyleneoxy group with at least 3 carbon atoms;
R3 represents a phenylene linkage, or is absent;
R4 represents hydrogen or a C~.24 alkyl or CZ_24 alkenyl group, with the
provisos
a) when Rl represents -O-CO-, RZ and R3 must be absent and R4 must contain at
least ~
carbon atoms;
b) when R2 is absent, R4 is not hydrogen and when R3 is absent, then R4 must
contain at least
carbon atoms;
RS represents hydrogen or a group of formula -COOA;
R.~ represents hydrogen or Cl-4 alkyl; and A is independently selected from
hydrogen, alkali
metals, alkaline earth metals, ammonium and amine bases and C~~.
Alternatively, the
Rs
H-C) H
5 Rt
R2
R3
R4
-z
-n
group (defined by z) can be substituted benzene
group such as, for example styrene. The present invention is directed to the
observation that,
when polymers such as those described above (known as deflocculating or
decoupling
polymers in the "structured liquid" art) are used in isotropic liquids and
further when there is
a criticality of hydrophilic groups to hydrophobic groups, (as well as
required hydrotrope and
CA 02195511 2004-08-25
32
electrolyte levels; and preferred hydrotropes and surfactants used) the
liquids are far more
stable (i.e., they do not phase separate and-become hazy, but rather stay
clear) than if these
required or preferred variables had not been met:
More particularly, when the molar ratio of hydrophilic to hydrophobic monomer
is less than
about 20 (i.e., 0 to 20), preferably less than about 10 (i.e., 0.5 to 10),
mast preferably, less
than about 7 to about 1 (i.e., preferably greater than or equal to 1), an
isotropic liquid which
would otherwise be unstable (less clear) hazy becomes clear.Minimal amounts of
hydrotrope
and electrolytes are required.Although applicants have not achieved optimal
clarity except
wherein the molar ratio was below about 10, it is possible to achieve such
clarity when
conditions are appropriately manipulated.
While not wishing to be bound by theory, it is believed that there is a
dependence on the
hydrophobicity (which is related to the charge density) of the micelles which
is governed by
the type of surfactant and hydrotrope system used, as well as the electrolyte
Ievel.Higher
anionic to nonionic ratios of surfactants (higher LAS or AES vs. alcohol
ethoxylate) as wet)
as hydrotropes (higher cumene sttlfonate versus propylene glycol) tend to make
the micelle
less hydrophobic (more charged) thereby reducing the solubility of the
hydrophobically
modified polymer.Furthermore, decreasing the salt level increases the charge
on the micelle
(by providing less counter ions to neutralize the charge on the micelles)
thereby making it
more hydrophilic and in turn reducing the solubility of the polymer.
The second aspect of the present invention is based on the observation that,
when such
polymers (known as deflocculating or decoupling polymers in the "structured
liquid" art) are
used in isotropic liquids and further when there is a criticality of
hydrophilic group to .
hydrophobic groups and oil is added, the liquids are for more stable (i.e.,
they do not phase
separate and become hazy, but rather stay clear) than if this criticality had
not been met.
More particularly, When the molar ratio is in the range of below about 40,
preferably below
about 30, more preferably below about 20, an isotropic liquid which would
otherwise be
unstable (less clear) becomes clear.
CA 02195511 2004-08-25
33
The polymer should be used in an amount comprising 0.1 to 10'/o by wt.,
preferably 0.25% to
5% by wt- of the composition.
The following examples are intended to clarify the invention further and are
not intended to
limit the invention in any way.
All percentages are intended to be percentages by weight, unless stated
otherwise.
I cola
Surfactants:Linear allrylbenzene sulfonic acid (LAS acid) was purchased from
Vista
Chemicals; alcohol ethoxy sulfate (AES Neodol 2S-3S) and ethoxyIated alcohols
(Neodol 25-
9) were purchased from Shell Chemicals.
Polymers:Hydrophobically modified acrylate and acrylatellauryl methacrylate
based polymers
(decoupling polymers) of different molecular weights and wntaining different
ratios of
hydrophobic groups with tails per molecule were synthesized and 'characterized
at National
Starch and Chemicals; and hydrophobieally modified acrylate styrene based
polymers such as
i~i100 and H1200 from National Starch and Chemicals.
Hydrotropes:Sodium Cumene sulfonate (SCS) and sodium xylene sulfonate (SXS)
were
supplied by Stepan Chemicals and propylene glycol was purchased from Fisher
Scientific.
0i s: Hydrocarbon oils are supplied by Fisher Scientific and Aldrich; and
Shetl Sol 7I is Clz-
C,4 saturated hydrocarbon oil from Shell.
Ocher Reagenis:Sorbitol was supplied as a 70 wt.% aqueous solution by 1CI
Americas,
sodium borate 10 aq., sodium citrate 2 aq. and glycerol were purchased from
Fisher
Scientific.
CA 02195511 2004-08-25
34 . .
Methods: The formulations were prepared by adding to water, sodium citrate,
sorbitol, borate,
hydrotrope and sodium hydroxide in a beakcr and stirred at 35 - 50°C
until the solution
bccame clear. This was followed by the addition of LAS acid and Neodo125-9.Thc
mixtwe
was then cooled to 25°C and the desired amount of Neodol 25-3S (59%
AES) was
added.Required amount of polymer was then added to the base formulation at
room
tcmperature ( 18 - 23°C).
the following base formulation was used in the examples 1-10 of the invention.
Base Formulation
C~mnonent Wt.% Remarks
Sodium alkyl benzene 2.6 - 23.0 Anionic surfactant
sulfonate
(LAS)
Alcohol ethoxy sulfate 2.6 - 23.0 Anionic surfactant
C12-Cis,
3E0 (AES)
Alcohol ethoxylate C12-Cis,2.6 - 23.0 Nonionic surfactant
9E0
Sodium citrate 2 aq. 0 - 5.0 Builder
Sodium borate 10 aq. 4_0 Enzyme stabilizer
Sorbitol (70% active) 6.4 Fxizyme stabilizer
Glycxrol 2,7 Enzyme stabilizer
Propylene glycollcumene1.0 - 4.0 Hydrotrope
sulfonatelxylene sulfonate
Polymer {hydrophobically0.0 - 2,0 Anti-redeposition
modified)* ~~t
Deionized water Balance
CA 02195511 2004-08-25
Notes: i) ?otal surfactants concentration = 28 to 30 wt.°~~
(ii) See US 5,089,163 to Aronson et al., for example with regard to enzyme
stabilization,
* acrylate/lauryl methacrylate polymer having varying molecular weights.
Example 1
Solubility of Hydrophobically Modified Polymers in Base,Formulation Containing
2.5 wt.%
Citrate; Propylene Glycol; and LAS, LES and Neodol 25-9 in the Ratio of 1:2: I
.
Polymer HydrophobicMW Molar ratio Concn. Appearance
of
Anchors/ Daltons backbone groupWt.%
Molecule (e.g., acrylate)
to monomer
with tail
group
(e.g., lauryl
. ,
methacrylate)
Decoupling 0.9 9150 105.4 0.78 Haze
Polymer* 1.30 Hazy
Decoupling 2.0 7500 37.2 1.0 Hazy
Polymer
Decoupling 1.3 3800 28.4 1.00 Hazy
Polymer
Decoupling 1.8 3560 18.3 0.9 Hazy
Polymer 1.5 Hazy
Decoupling 3.4 6100 16.4 0.83 Hazy
Polymer 1.38 Hazy
Decoupling 2.8 2370 6.3 0.99 Clear
Polymer 1.65 Clear
CA 02195511 2004-08-25
36
This example shows that the clarity of the liquid depends on the molar ratio
between the
number of hydrophilic backbone monomers and hydrophobic tail groups (also
attached to
monomers). Polymer having a ratio below 10, preferably below 7, produce clear
liquid while
those having a ratio above 20 produce a hazy liquid.The lower the value of the
above defined
molar ratio, more hydrophobic is the polymer.While not wishing to be bound by
theory, it is
believed that polymers that are more hydrophobic produce clear liquids because
they are
more easily solubilized due to hydrophobic interaction with the ore of the
surfactant micelles,
which are also hydrophobic.
* Acrylate/lauryl methacrylate
CA 02195511 2004-08-25
37
Exam~,le 2
Solubility of Hydrophobically Modified Polymers in Base Formulation Same as
~Exampl a l ,
but Coniaining3.75 wt. % Citrate
Polymer HydrophobicMW Molar ratioConcn. Appearance
of
Anchors/ Daltons backbone Wt.% i
' I
Molecule group (e.g.,
acrv_ late)
to
monomer
with
tail group
(e.g.,lauryl
' methacrylate)
Decoupling0.9 9150 105.4 0.78 Hazy
Polymer 1.30 Hazy
Decoupling2.0 7500 37.2 0.75 Hazy
..
Polymer 1:25 Hazy
Decoupling1.3 3800 28.4 1.00 Hazy
Polymer 1.67 Hazy
Decoupling1.8 3560 18.3 0.9 Hazy
Polymer 1.5 Hazy
Decoupling3.4 6100 16.4 0.83 Hazy
Polymer ~ 1.38 Hazy
Decoupling2.8 23?0 6.3 0.99 Clear
Polymer 1.65 Clear
As in Example 1, the clarity of the liquid depends on the ratio between the
number of
hydrophilic backbone monomers and hydrophobic tail groups.As in formulations
containing
only 2.5 weight sodium citrate 2 aq., in formulations containing 3.75 wt.%
sodium citrate
polymer having hydrophilic to tail ratio below 10, preferably below 7 are
clear, and, those
above 10 are unclear.
CA 02195511 2004-08-25
Exam a 3
Solubility of Hydrophobically Modified Polymers in Base Formulation Containing
2.5 vvt.%
Citrate and Cumene Sulfonate ("classic" hydrtrtrope); and LAS, LES and Neodol
in ratio of
1:2:1
Polymer HydrophobicMW Molar Coven Appearance
ratio
or
AnehorSJ Daltonsbackbone wt.Xo
Molecule group
(e.g.>
aaylate)
to
monomer
whir tail
(e.g_,lauryl
methacrylate)
a wt.~2.s%s msc
C5 S
becouplirlg0.9 915p 105.4 0.78 ~Iazy
Polymer J .30 Nary
Decoupling1.3 3800 28.4 1.00 Hazy
polyrarr 1.G7 Hazy
Decoupling1.8 35Gp 18.3 0.9 Nary
Polymer 1.5 Hazy
becoupling3.4 6IU0 llS.4 0.83 Nary
Polymer 1.3 Nary
R
Decoupling2_8 2370 6.3 0.99 Hazy Hazy (,yes
Polynux 1.63 Hary Hazy Clear
a. I l 1 I t I I II
In formulations containing cumene sulfonaie rather than. propylene glycol
(compare to
Example 1 ) polymers having a molar ratio between number of hydrophilic
backbone
monomec~ and number of hydrophobic tail groups per molecule of less than 20,
preferably
less than 17) produce an unstablelhazy liquid above a cumene suifonate
concentration of 1.0
CA 02195511 2004-08-25
39
wt.%.It should be noted that in formulation containing 2.5 wt.% sodium
citrate, 2 aq, and
propylene glycol (instead of cumene sulfonate, see Example 1), polymer having
the above
defined ratio value of below 10, preferably below 7 produced a clear liquid-
This is believed
to be true because the core of the micelles formed in the presence of cumene
sulfonate are
less hydrophobic than those fornted in presence of propylene glycol.Thus
propylene glycol is
preferred.
Exam,~le 4
Solubility of Hydrophobically Modified Polymers in Hase Formulation Containing
2.5 wt:%
Citrate, Xylene Sulfonate (SXS); and LAS, LES and Neodol in ratio of 1:x:1
Polymer HydrophobicMW Molar ratioConca Appearance
of
Anchors/ Daltonsbackbone Wt.%
group
Molecule (e.g.,
acrylate)
to monomer
with tail
group
(e.g.,
lauryl
mcthacrylate)
4wt.% 2.5wt%lwt./,
SXS S7~c5 SXS
Dccoupling0.9 9150 IOS.a 0.78 Hazy
Polymer 1.30 Nary
Decoapling1.3 , 3800 28.4 1.00 Hazy
PoIyurcr 1.67 Nazy
Decoupling1.R 3560 18.3 0.9 Hary
Polymer 1.5 Hazy
Decouplirtg3.4 6100 1C.4 0.83 Hazy
Polymer 1.38 Hazy
Decoupling2.R ?370 6.3 0.99 Hazy Clear Clear
Polymer 1.b5 1-lazyHazy Clear
1 I n t I J I I a
CA 02195511 2004-08-25
40 ,
In the case of xylene sulfonate instead of cumene sulfonate (compare fixample
3), the '
composition began to clarify even at Z.5 wt.% xylene sulfonate. .
VNhile not wishing to be bound by theory, this is believed to be because
cumene sulfonate
being a mote "weight ef~'icient" hydrotrope {i.e., better hydrotrope),
actually acts to make the
solution less hydrophobic.This in turn results in poorer solubility because
the hydrophobieally
modified polymer prefers greater hydrophobicity. The xylene sulfonate, being
less ei~icient,
keeps the solution more hydrophobic and, therefore, makes polymer more
soluble.
x Ie 5
Solubility of Hydrophobically Modified Polymers in Base Formulation Containing
Propylene
glycol and LAS,LES and Neodol 25 in the ratio of 1:2:1:
Polymer: lJecoupling type of MW = 2370 l~altons; Hydrophobic Anchors/Molecule
= 2.8;
Hydrophilic Backbone: tail = 6.3
Citrate ConcentrationAppearance
Wt. %
0.0 Hary
2.5 Clear
3.7.5 Clear
This example is to show that, if no electrolyte (citrate) had been used in
Examples 1. and 2
{Z.5% & 3.75% by wt. used respectively in these examples), then the
composition would have
been hazy (i.e., polymers not dissolve therein).
Thus, the example shows that some electrolyte is required.
CA 02195511 2004-08-25
41
Example 6
Solubility of Hydrophobically Modified Polymers in Base formulation Containing
Propylene
Glycol, 0.0 wt.% Citrate and LAS, AES and Neodol 25-9 in the Ratio of 1:1:8
Polymer HydrophobicMW Daltons Concn. Appearance
Anchors/ Wt.%
Molecule
Decoupling 0.9 9150 0.78 Hazy
Polymer 1.30 Hazy
Decoupling 2.0 7500 0.75 Hazy
Polymer . 1.25 Hazy
Decoupling 1.3 3800 1.00 Hazy
Polymer 1.67 Hazy
Decoupling 1.8 3560 0.9 '~ Hazy
Polymer 1.5 Hazy
Decoupling 3.4 6100 0.83 Hazy
Polymer 1.38 Hazy
Decoupling 2.8 2370 0.99 Clear
Polymer 1.65 Hazy
I 1 I I
This example shows that when ratio of nonionic is increased, then clarity can
be obtained
even where it would not otherwise be possible.
While not wishing to be bound by theory, this is believed to be because
compositions with
high levels of nonionic are more hydrophobic than compositions with high
levels of
anionic.This in turn makes hydrophobically modified polymer more soluble.
CA 02195511 2004-08-25
42
ExamQle 7
Solubility of Hydrophobically Modified Polymers in Base Formulation Containing
Propylene
Glycol, 0.0 wt.% Citrate and LAS,LES and Neodol 25-9 in the Ratio 8:1:1
Polymer HydrophobicMW Molar ratio Concn.Appearance
of
Anchors/ Daltonsbackbone Wt.%
group
Molecule (e.g., acrylate)
to
monomer with
tail group
(e.g.,lauryl
methacrylate)
Decoupling0.9 . 9150 105.4 0.78 Hazy
Polymer 130 Hazy
Decoupling2.0 7500 37.2 0.75 Hazy
Polymer 1.25 Hazy
Decoupling1.3 3800 28.4 1.6'x,Hazy
Polymer
Decoupling1.8 3560 18.3 0.9. Hazy
Polymer I.5 Hazy
Decoupling3.4 6100 16.4 0.83 Hazy
Polymer 1.38 Hazy
Decoupling2.8 2370 6.3 0.99 Hazy
Polymer ~ 1.65 Hazy
~I I t 1 I I B
While not wishing to be bound by theory, applicants believe that, in contrast
to Example 6,
high levels of anionic do not increase hydrophobicity of composition and,
therefore,
compositions remain hazy.
CA 02195511 2004-08-25
43
Example 8
Solubility of Hydrophobically Modified Polymers in Base Formulation Containing
0.0 Wt.
Citrate and LAS, LES and Neodol 25-9 in 'the Ratio of 1:8:1
Polymer HydrophobicMW Molar ratio Concn. Appearance
of
Anchors/ Daltonsbackbone Wt.% .
group
Molecule (e.g., acrylate)
to monomer
with tail
group
(e.g..lauryl
methacrylate)
Decoupling0.9 9150 105.4 0.78 Hazv
Polymer 1.30 Hazy
Decoupling2.0 7500 37.2 0.75 Haze
Polymer 1.25 Hazy
.',
Decoupling1.3 3800 28.4 1.00 Hazy
Polymer 1.67 Hazv
Decoupling1.8 3560 18.3 0.9 Hazy
Polymer 1.5 Hazv
Decoupling3.4 6100 16.4 0.83 Hazy
Polymer I.38 Haze
Decoupling2.8 2370 6.3 0.99 Hazy
Polymer 1.65 Hazy
As in Example 7, solutions with higher levels of anionic are not believed to
be as
hydrophobic and, accordingly, polymers do not readily dissolve.
CA 02195511 2004-08-25
44
Example 9
Formulations with and without acrylate/lauryl methacrylate copolymer (MW 4500,
acrylate/lauryl methacrylate ratio = 18.3) were evaluated for performance on
dirty motor oil
stains for stain removal.
Formulations used in the evaluation are listed in table below:
Ingredient Formulation Formulation
1 2
Alcohol ethoxy sulfate, C~Z-C15,14.0 14.0
3E0
Sodium alkyl benzene sulfonate,8.0 8.0
C~~-C~5
Alcohol ethoxylate, Clz-CAS, 8.0 8.0
9E0
Sodium citrate dihydrate 5.0 5.0
Propylene glycol 4.0 4.0
Sodium borate pentahydrate 3.1 3.1
Sorbitol 4.5 4.5
Ethanol 2.3 2.3
Glycerol 2.7 2.7
Enzymes 1. l 1.1
Acrylate/lauryl methacrylate 0.0 2.0
copolymer
Minors (fluoresces, perfume, >0.5 >0.5
colorant,
preservative)
Water to 100% to l00%
Swatches were prewashed in a dye free commercial liquid laundry detergent five
times to age
the material, remove spinning oils, and increase absorbency of the
cloth.Cotton swatches
were type TIC429 (Textile Innovators, Inc.); SO/50 polyester/cotton blend
swatches were type
CA 02195511 2004-08-25
TIC7403 (Textile Innovators,lnc.); polyester swatches were type TF730 (Textile
Fabrics,
Inc.)
Four replicate swatches were stained per fabric, per formulation, making a
total of eight
swatches per fabric.A measured quantity of dirty motor oil ( 10 drops per
cotton swatch, 11
per polyester/cotton blend swatch and 25 per polyester swatch) was applied to
the swatches in
a 2" diameter circle at the center of the swatch.Care was taken to ensure that
the oil uniformly
coated the entire circle area.The stains were then allowed to age for one
hour.
6.5 g of each formulation was applied per stained swatch and allowed to stand
for 30 minutes.
The test formulations were then added (0.4 cup) to a filled (95°F, 120
ppm, 2:1 Ca:Mg)
standard top-loading washing machine (Lady KenmoreT"' model 80 heavy duty
washer by
Sears, Roebuck, and Co.) and allowed it to mix for one minute.The machine was
then stopped
and soiled test cloths treated with test formulation were added (4 each of
cotton, 50/50
cotton/polyester blend, and polyester).The cloths then conti~riued washing on
the cotton/sturdy
cycle of the washing machine, then were dried in a static dryer.
The stain removal was evaluated by comparing the L,a,b readings before
staining and after
washing:Readings were taken on a Gardner reflectometer with no ultraviolet
light.The results
are expressed as stain removal indices, where the stain removal index (SR1) is
calculated as:
SRI = 100 - ~(L~ ~) z+ tai ~) Z+ (b~ bW) Z) 1~
where the subscripts c and w represent clean swatches (before staining) and
washed stained
swatches, respectively.
L = Lightness index difference
a, b = Chromaticity index difference
(ColorguardTM System 2000 Colorimeter Ciperators Manual - BYK Gardner lnc..
Siive~~
Springs, Man~land, U.S. 209I0)
CA 02195511 2004-08-25
46
Results for the two formulations are as follows:
Formulation # Stain Removal
Index
Cotton Cot./poly. blendPolyester
1 67.77 57.65 37.91
2 69. 3 0 60. 00 3 7. 99
Least sig. diff. (95%)0.38 0.89 1.87
confidence interval)
Stain removal benefit2.53 2.35 0.08
of
polymer
Thus, formulation 2, which contains acrylate/lauryl methacrylate copolymer,
clearly removes
the stain better than does the formulation without polymer on cotton and on
the poly/corion
blend.
CA 02195511 2004-08-25
47
Examyle 10
The following formulae were tested for antiredeposition.performance.The
polymer tested was
an acrylate/styrene copolymer with MW 3500 and an acrylate/styrene ratio of
1.5.
Ingedient Formulation Formulation
1 2
Alcohol ethoxy sulfate, C~Z-C15,14.0 14.0
3E0
Sodium alkyl benzene sulfonate,8.0 8.0
Gtl-C,s
Alcohol ethoxylate, G12-C,S,8.0 8.0
9E0
Sodium citrate dihydrate 5.0 5.0
Propylene glycol 6.7 6.7
Sadium borate pentahydrate 3.1 3.1
Sorbitol 4.5 4.5
Ethanol 1.5 1.5
Enzymes 1.1 1 _ 1
Acrylate/styrene copolymer 0.0 2.0
Minors (fluorescer, perfume,>0.5 =0.5
colorant,
preservative)
Water to 100% to 100%
Both formulations were clear and stable.
Soiled swatches were made as described above.Unsoiled swatches were of the
same materials
described for soiled swatches and were prewashed before usage by the same
method used far
soiled swatches.
CA 02195511 2004-08-25
48
The test formulations were added (0.4 cup) to a filled (95°F, 120 ppm
hardness, 2:1 Ca:Mg)
standard top-loading washing machine (Lady Kenmore model 80 heavy duty washer
by
Sears, Roebuck, and Co.) and allowing it to mix for one minute.The machine was
then
stopped and test cloths (soiled by the procedure described in the previous
example) were
added (4 each of cotton, 50/50 cotton/polyester blend, and polyester).The
washer was
restarted and allowed to agitate for 90 seconds; then the unsoiled cloths were
added (3 each of
cotton, blend, and polyester; cotton first, then blend, then polyester)
without stopping the
machine.The cloths then continued to wash on the cotton/sturdy cycle of the
washing
machine, then were dried in a static dryer.
Because deposition of the oil onto clean fabric was uneven, it could not be
quantified by the
reflectance procedure described in the previous example.Instead, the
deposition of oil onto
the cloths was judged visually and a "score" assigned to swatches washed in
each product.The
"score" was a number between 0 (no deposition) to 5 (extensive deposition).The
"scores"
reported are averages of all the cloths of the fabric per test
formulation.Little deposition was
found on cotton or poly/cotton blend swatches for either foimulation.For the
polyester
swatches, the scores were:
Formulation # Deposition score on polyester
2
The results indicate that Formulation 2, with the acrylate/styrene
copolymer,has improved
anti-redeposition properties over the formulation without the polymer
(Formulation 1).Both
formulations are clear and stable; thus the polymer, which has an
acrylate/styrene ratio of 1.5,
can be stabilized in this formulation.
CA 02195511 2004-08-25
49
The following base formulation was used in the examples 11 - I7 of the
invention.
Base Formulation
Component Wt. % Remarks
LAS acid 2.6 - 21.0 Anionic surfactant
Neodol ZS-3S (59% active4.7 - 38.0 Anionic surfactant
AES)
Neodol 25-9 2.fi - 23_0 Nonionic surfactant
Sodium hydroxide (50% 0.65 - 5.3 Alkali
aq.)
Sodium citrate 2 aq. 0 - 5.0 Builder
Sodium borate 10 aq. 4.0 Enzyme stabilizer
Sorbitol (70% active) 6.4 Enzyme stabilizer
Glycerol 2.7 Enzyme stabilize
Propylene glycol/cumene4.0 ~ydiotrope
sutfonate
Polymer (hydrophobically0.0 - 2.0 Anti-redeposition
modified) agent
Oil 0.1 - 3.0 Solubilizing agent
Deionized water ~ Balance
Notes: i) Total surfactants concentration = 28 wt.%
ii) Alkali is added to neutralize LAS acid; alkali (50% aq. solution) to LAS
acid ratio is
maintained constant at 0.25
CA 02195511 2004-08-25
(iii) See U.S. Patent No. 5,089,163 to Aronson et al., for example, hereby
incorporated by
reference into the subject application, with regard to enzyme stabilizers.
(iv) Control had no oil
Example 11
Solubility of Hydrophobically Modified Polymers in Base Formulation Containing
2.5 wt.%
Citrate and Propylene Glycol and LAS, AES and Neodol 25-9 in the Ratio of
1:2:1.
Appearance
Polymer HydrophobicMW Molar ratioPolymerNo n- ' Shell
of
Anchors/ Daltonsbackbone Concn. Oil heptaneSo171
Molecule group (e.g.,Wt.%
acrylate)
to
monomer ' -
with
tail group
(e.g., lauryl
methacrylate)
Decoupling0.9 9150 105.4 0.78 Hazy Hazy Hazy
* Polymer 1.30 Hazy - Hazy
Decoupling2.0 7500 37.2 1.0 Hary Hazy Hazy
Polymer ~ .
Decoupling1.3 3800 28.4 1.00 Hazy Hazy Hary
Polymer
Decoupling1.8 3560 18.3 0.9 Hazy Clear Hazy
Polymer 1.5 Hazy Hazy Hazy
Decoupling3.4 6100 16.4 0.83 Hazy Clear Hazy
Polymer 1.38 Hazy Hary Hazy
Decoupling2.8 2370 6.3 0.99 ClearClear Clear
Polymer 1.65 ClearClear Clear
t t t t I I I
CA 02195511 2004-08-25
51
~' Acrylate/lauryl methacrylate polymer of varying molecular weights.
This example shows that the clarity of the liquid (i.e., stability) depends on
the molar ratio
between the number of hydrophilic monomers and hydrophobic anchors/monomers.
Polymer
having a ratio below 10 produce clear liquid (whether oil added or not) while
those having a
ratio above 20 produce a hazy liquid. The lower the value of the above defined
ratio, more
hydrophobic is the polymer. While not wishing to be bound by theory, it is
believed that
polymers that are more hydrophobic produce clear liquids because they are more
easily
solubilized due to hydrophobic interaction with the core of the surfactant
micelles which are
also hydrophobic.
This example shows that oil improved the clarity where, at relatively low
ratios, the
composition was hazy. Thus, even at ratio of 10 to 20, for example, addition
of the oil began
to start clarification, while this clearly did not begin when no oil was used
until ratio of below
10.
CA 02195511 2004-08-25
52
Example 12
Solubility of Hydrophobically Modified Polymers in Base Formulation, Same as
Example 11,
but Containing 3.75 wt. % Citrate and Propylene Glycol
Appcarana
Polymer HydrophobicM Molar ratioPolymer No n heptaneShell
W of oil
Anchors/ Daltonsbackbone Concn. So171
Molecule group (e.g.,Wt%
acrylatc)
to
monomer
with tail
~uP (e.g.,
lauryl
methacrylatc)
Decoupling0.9 9150 105.4 0.78 Hazy Hazy Hazy
Polymer 1.30 Hazy - Hazy
Decoupling2.0 7500 37.2 0.75 Ha-ry Hazy Hary
Polymer 1.25 Hazy Hazy Hazy
Decoupling1.3 3R()U28.4 I.00 Hazy Hury Hey
Polymer 1.67 Hary Hazy Hazy
Decoupling1,8 3560 18.3 0.9 Hary Glear Clear
Polymer 1_5 Hazy -
Decoupling3.4 6100 16.4 0.83 Haiy Hazy Clear
Polymer 1.38 Hazy Hazy Clear
Decoupling2.R 2370 G.3 0.99 ClcxirHazy Clear
Polymer 1.65 Clear Clear Clear
A.s in Example i 1, the clarity of the liquid depends on the molar ratio
between the number of
hydrophilic monomers and the number of hydrophobic anchors per molecule. As in
formulations containing 2.5 weight percent sodium citrate 2 aq., formulations
containing
CA 02195511 2004-08-25
53
polymer having the above defined ratio of lower than about 10 are clear and
those containing
polymers having ratio above about 20 are unclear.
Also, this example again shows that addition of oil began clarification at
much lower ratio
than would otherwise be needed if there were no oil. In this case, the Shell
Sol 71 was clearly
superior to n-heptane since haziness reappeared with the n-heptane at 16:4
ratio.
Example 13
Solubility of Hydrophobically Modified Polymers in Base Formulation Containing
3.75 wt.%
Citrate (like Example 12), but Cumene Sulfonate Instead of Propylene Glycol
Appearance
Polymer HydrophobicMW Molar ratioConcn.No n- Shell
of
Anchors/ Daltonsbackbone Wt.% oil heptaneSol7I
Molecule group (e.g.,
acrylate)
to
monomer
with tail
~uP (e~g~~
Iauryl
methacrylate)
Decoupling0.9 9150 105.4 ~ 0.78 Hazy Hary Hazy
Polymer 1.30 Hazy Hazy Hazy
Decoupling1.3 3800 28.4 1.00 Hazy Hazy Hazy
Polymer 1.67 Hazy Hazy Hazy
Decoupling1.8 3560 18.3 0.9 Hazy Clear Hazy
Polymer 1.5 Hazy Hazy Hazy
Decoupling3.4 6100 16.4 0.83 Hazy Hazy Clear
Polymer 1.38 Hazy Hazy Clear
Decoupling2.8 2370 6.3 0.99 Hazy Clear Clear
Polymer 1.65 Hazy Clear Clear
CA 02195511 2004-08-25
54
Tn formulations containing cumene sulfonate instead of propylene glycol (PPG),
even
polymers having a molar ratio between number of hydrophilic monomers and
number of
hydrophobic anchors per molecule of less than 10 produce a hazy (unstable)
liquid. In
formulation containing x.75 wt.% sodium citrate 2 aq. and propylene glycol
(instead of
cumene sulfonate), polymer having the above defined ratio value of below 10
produced a
clear liquid. This is believed to be true because the core of the micelles
formed in the
presence of cumene sulfonate are less hydrophobic than those containing
propylene glycol.
However, again, when oils were added, clarity was obtained at ratios below 10,
even using
the less hydrophobic cumene sulfonate instead of propylene glycol (for both n-
heptane aad
Shell Sol 71). Further use Shell Sol 71 brought clarity even at ratios at
levels of 15.4. Again,
the general superiority of oil addition is clearly shown.
CA 02195511 2004-08-25
$5
Example 14
Solubility of Hydrophobically Modified Polymers in Base Formulation Containing
Propylene
Glycol, 0.0 wt.% Citrate and LAS, AES and Neodol 25-9 in the Ratio 8:1.1
APPS
Polymer HydrophobicMW Motar PolymeNo n- Shell
ratio
Anchorsi Daitonof r oil heptaneSo171
Molecule s t~acld~onCConcat.
group Wt.%
(e.g.~
acrylate)
In
monomer
with
tail
~nP (e-&.
lauryl
methaaylat
e)
Decoupling0.9 9150 105.4 0.78 Hazy Hazy Hazy
Polymer 1.30 Hazy Hazy Hazy
DecouplingZ.0 7400 37.2 0.75 Hary Hazy Hazy
Polymer 1.25 Hazy Hazy Hazy
Decoupling1.3 3800 28.4 1.UU Hary Hazy Hey
Polymer 1.67 Hazy Racy Hazy
Decoupling1.8 3560 18.3 0.9 Hazy Hazy Clear
Polyrncr 1_5 Hazy Hazy Clear
Decoupling3.4 6100 1G.4 0.83 Hazy Hazy Qca~r
Polymer 1.38 Hazy Hazy Ct~
Decoupling2.8 23?0 6.3 0.99 Hazy Hary CJsar
Polymer 1.65 Hazy Hazy Nary
rt n 1 . 1 1 I i I 1
CA 02195511 2004-08-25
56
In this example, the polymer having a molar ratio between the number of
hydrophilic
monomers and the number of hydrophobic anchors per molecule below 10 produced
hazy
liquid although the liquid containing propylene glycol and LAS; AES and Neodol
25-9 in the
ratio of 1:2.1 produced a clear liquid when polymers having the above defined
ratio of below
was added (see Example 11). Analogous to the example of the composition
containing
cumene sulfonate (Example 13), the micelles containing high LAS concentration
are less
hydrophobic (and, therefore, presumably do not interact well with hydrophobic
polymer).
As for oil addition, while n-heptane did not improve clarity, addition of
Shell-Sol clearly
enhanced clarity, even at ratios as high as 18.3.
CA 02195511 2004-08-25
S7
Example 15
Solubility of I3ydrophobieally Modified Polymers in ease Formulation
Containing 0.0 wt.%
Citrate and LAS, AES and Neodol 25-9 in the Ratio of 1:8:1
Appearance
Polymer HydmphobiCMW Molar P0lyrnCrI~fo n- Shell
ratio
of
Anchors) Daltonsbackbone Coach.oil heptanSo171
Molecule group Wt.% a
(e_g.,
acrylate)
to
monomer
with fail
group
(e.g.,
lanryl
methacrylatc)
Decoupling0.9 ylSU 105.4 0.78 Hazy Hey ~y
Polymer 1.3(I HatfyHazy Ha2y
Decoupling2.U 75UU 37.2 0.75 Hazy Hazy Hazy
~ly~ 1.25 Hazy Hazy Hacy
Decoupling1 _3 38UU 28.4 l _0U Hazy Hary Hazy
Polyrncx 1.67 Hazy Hazy Hazy
Uccoupling1.8 3560 18.3 0.9 Hazy Hazy Hacy
Polymer 1.5 Hazy Hazy H;szy
Decoupling3.4 61UU 16.4 0,83 ~y Hey Hey
~13'rn~ 1.38 Hazy Nary Hazy
Decoupling2_8 2370 6.3 0,99
Hazy Clcar Hazy
Polyrncr 1.65
Hacy Clear Hazy
In this example, the polymer having a molar ratio between the number of
hydrophilic
monomers and the number of hydrophobic anchors per molecule below 10 produced
hazy
liquid although the liquid containing propylene glycol and LAS, ABS and Neodol
25-9 in the
CA102195511 2004-08-25
58
ratio of 1:2:1 produced a clear liquid when polymers having the above defined
ratio of below
was added (same as Example 14). This is again believed to be because the
micelles
containing high AES concentration are less hydrophobic.
Regarding oil addition, in this example, addition of heptane improved clarity
(i.e., at ratio of
below about 10.
Example 16
Solubility of Hydrophobically Modified Polymers in Base Formulation Containing
Propylene
Glycol, 0.0 wt.% Citrate and LAS, AES and Neodol 25-9 in the Ratio of 1:1:8
Appearance
Polymer HydrophobicMW Molar ratioPolyme No n-heptaneShell
of oil
Anchors/ Daltonsbackbone r So171
Molecule group (e.g.,Concn.
acrylate) Wt.%
to
monomer
with
tail group
(e.g.,
lauryl
methacrylate)
Decoupling0.9 9150 105.4 0.78 Hazy Hazy Hazy
Polymer 1.30 Hazy Hazy Hazy
Decoupling2.0 7500 37.2 0.75 Hary Hazy Hazy
Polymer ~ 1.25 Hazy Hazy Hary
Decoupling1.3 3800 28.4 1.00 Hazy Hazy Hazy
Polymer ~ 1.67 Hazy Hazy Hary
Decoupling1.8 3560 18.3 0.9 Hary Hazy Hazy
Polymer 1.5 Hazy Hazy Hary
Decoupling3.4 6100 16.4 0.83 Hazy Hary Hazy
Polymer 1.38 Hary Hazy Hazy
Decoupling2.8 2370 6.3 0.99 Clear Clear Clear
Polymer 1.65 Hazy Clear Clear
.. ,
CA 02195511 2004-08-25
59
This formulation is similar to that of the formulation containing LAS, AES and
Neodol 25-9
in the ratio of 1:2:1 (Example 11) in that it even produced a clear liquid
upon addition of
polymers having a molar ratio between the number of the hydrophilic monomers
and the
number of hydrophobic anchors per molecule of below 10. This is again due to
the fact that
micelles containing high levels of nonionic surfactants (Neodol 25-9) are more
hydrophobic
than those containing high levels of anionic surfactants. The more hydrophobic
the micelles
are, the higher will be the interaction between the micelle and the
hydrophobically modified
polymer and the better is the chance of producing a clear liquid.
The addition of oil here helped only at ratio of 6.3 and concentration level
of 1.65.
CA 02195511 2004-08-25
Exam 1u a l7
Base Formulation
Component Wt. 10
LAS acid 2.6 - 21.0 Anionic Surfactant
Neodol 25-3 (AES) 4.7 - 38.0 Anionic Surfactaat
Neodol 25-9 2.6 - 23_0 Nonionic Surfactant
Sodium Hydroxide (50'/o 0.65 - 5.3 Alkali
activt)
Sodium Citrate 2 aq. 0 - 7 Builders
Sodium Borate 10 aq. 4.0 Enzyme Stabilizer
Sorbitol (70% active) (i.4 Enzyme Stabilizer
Glycerol 2.7 Enzyme Stabilizer
Propylene GlycoUCumene 4.0 Hydrotrope
Sulfonate
Polymer (IFlydrophobically0.0 - 2.0 Anti-Redeposition
Modified) Agent
Oil 0.0 - 3.0 Polymer Solubilizing
Deionized Water Balance Agent
J
Notes: i) Total surfactants concentration - 28 wt.%
ii) Alkali is added to neutralize LAS acid; alkali (50% aq. solutions) to LAS
acid ratio is
maintained at 0.25.
CA 02195511 2004-08-25
61
SPECIFIC FORMULATiQN
Component Wt.
LAS Acid
Neodol 25-3 (AES 25-3 S) 23.7
Neodol 25-9 8.0
Sodium Hydroxide (5O% aq.)1.9
/
Sodium Citrate 2 sq. 5.0
Sodium Borate 10 aq. 4.0
Sorbitol (70% aq.) 6.4
Glycerol 2.7
Propylene ('rlycol 4.0
Oil 0.0 - 3.0
Deionized Water Balance,
Applicants then tested various oils in the specific formulations as shown
below.
CA 02195511 2004-08-25
62
Name Oil Chain Type Amount,
Ixngth Wt.~
I.0
Z.0
3.0
n-HeptaneC~ Aliphatic ~ saturatedSol_ Sol. Insol.
Toluene C~ Aromatic Sol. Insol. Insol.
1-Octene C8 Aliphatic - unsaturatedSol. Sol_ Sol.
.
Octane C8 Aliphatic - saturatedSol. Sol_ Sol.
Dodecane C,z Aliphatic - saturatedSol. Sol_ Sol.
Shellsol C,z_,4 Aliphatic - saturatedSol. Sol. Sol_
71
TetradecaneC14 Aliphatic - saturatedSol. Sol. Sol.
HexadecaneC,~ Aliphatic - saturatedSol_ Sol. Sol.
OctadecaneC,s Aliphatic - saturatedSol. Sol. Sol.
Eicusane CzQ Aliphatic - saturatedInsol. Insol Insol.
.
Docosane Cz2 Aliphatic - saturatedInsol. Insol Insol.
.
Soybeaa C12-Clg Fatty acid lnsol. Insol Insol.
oil Fatty acids .
This Example shows that only aliphatic hydrocarbons in the range of CT-Cl8 are
soluble.
