Note: Descriptions are shown in the official language in which they were submitted.
CA 02195510 2004-08-16
G 6327 (~
no~."",~ x: ~oasss
STICK PRETREATMENT COMPOSITIONS
Field of the Invention
This invention relates to a laundry pretreatment composition in stick form
which contains
a hydrophobically modified polar polymer and nonionic surfactants. These can
be used ,
to effect or enhance stain removal in lieu of or in advance of, the main wash.
Background of the Invention .
Prewash stain remover compositions for the laundry havc been in use for many
years.
Recently developed preueater compositions available in liquid, spray and gel
forms are
usually based on nonionic surfactants. The consumer applies the stain remover
to the soiled
portions of the garments before washing with a laundry detergent. The
ingredients in the
prewash stain remover or in-wash whitener/stain remover work to remove stains,
but either
high levels of costly ingedients are required or a plateau in stain removal is
observed with
increasing concentration of the ingredient. A convenient application method
for a .
pretreatment composition is by the stick form. So-called stick forms
essentially comprise the
composition in the form of a block (often bar-or-stick shaped or cylindrical
in shape), which
block is solid or else has the consistency of soap or hard wax. As used
herein, the terms
"stick", "stick form", stick composition" etc. are to be construed as
referring to pretreatment
compositions having such a physical consistency. Stick compositions are
convenientiy sold
often in a dispensing holder. It is difficult to produce stick forms which
have optimal
hardness to effectively deliver the pretreater compositions.
Stick form versions of such pretreaters are generally aqueous based rather
than solvent based
and contain both nonionic surfactants and anionic soaps such aqueous based
systems, while
exhibiting proper hardness characteristics, often compromise cleaning
performance (see U.S.
No. 5,147,576 owned by S.C. Johnson.)
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C 6327 (V) 2
It has aow been found that inclusion of hydrophobically modifiied polar
polymers helps to
signiftcantly enhance the stain removal performance of the prewash stain
remover. Similar
compositions rnay also be used as in wash laundry additives to boost whitening
effects and
improve stain removal. Zt has also now been found that such formulations
containing
hydrophobically modified polar polymers when used in conjunction with a
detergent
significantly boosts whitening and improve stain removal.
Deflocculating polymers which allow incorporation of more surfactants andlor
electrolytes in
a detergent composition are described in U.S. Patent No. 5,147,576 issued to
Montague
The polymers of the Montague reference comprise a hydrophilic backbone which
is generally
a linear branched or highly cross-linked molecular composition containing one
or more types
of hydrophilic monomer units; and hydrophobic side chains, for example,
selected from the
group consisting of siloxanes, saturated or unsaturated alkyl and hydrophobic
alkoxy groups;
aryl and alkylarlyl groups, and mixtures thereof.
These polymers were not, however, taught for use in pretrcater or in-wash
laundry boosting
compositions which are designed far direct application to stains or for
boosting the
performance of detergents, respectively, and reduire compositions which are
significantly
different from detergcnts_ These compositions are preferably based on nonionic
aqueous
solutions.
Although U.S. Patent No. 5,308,530 does teach the use of these polymers in
detergent
formulas there is no suggestion or discussion that such combinations would
provide improved
pretreater yr laundry additive compositions.
Thus, there still exists a need in the art for a stable pretreater
compositions based on non-ionic
surfactants for improved cleaning performance on stains. This improvement is
effected by
the present invention incorporating hydrophobically modified polar polymers
which enable
CA 02195510 2004-08-16
C 6327 (V) 3
the composition to penetrate both oil and water based stains for improved
cleaning
performance.
It is therefore an object of the present invention to provide an aqueous
laundry stain prttl-eater
composition which provides outstanding cleaning performance on a variety of
stains for a
variety of fabrics.
Another object of the invention is to provide an aqueous nonionic based
composition which
boosts the fluorescer whitening of detergents without added fluoreacer and
improves stain
removal.
Another object of the invention is to provide a stick prctreater composition
which has an
effective hardness profile, is shelf stable and which is free of chelating
agents yet does not
compromise cleaning performance_
Summary of th~Invention
According to the invention there is provided a stick pretreatment composition
comprising
(a) from 30 to 80% by weight of nonionic surfactant;
(b) from 1 to 20% by weight of an anionic soap having an unsaturation range of
from 0 to 5% based on the total fatty acid in the composition; and
(c) from 0.1 % to 10% by weight of a polymer having:
1 ) a hydrophilic backbone comprising one or more monomer units selected
from:
i) one or more ethylenically unsaturated hydrophilic monomers selected
from the group consisting of unsaturated C» acids, ethers, alcohols,
aldehydes, ketones and esters; and/or
ii) one or more polymerizable hydrophilic cyclic monomer units; and/or
' CA 02195510 2004-08-16
C 6327 (V) 4
iii) one or more non-ethylenically unsaturated polymerizable hydrophilic
monomers selected from the group consisting of glycerol and other
polyhydric alcohols; wherein said monomer units are independently
optionally substituted with one or more amino, amine, amide,
sulphonate, sulphate, phosphonate, hydroxy, carboxyl or oxide groups;
and
2) at least one monomer containing a pendant hydrophobic group and
optionally also, a pendant hydrophilic group;
said polymer having a MW of 1,000 to 20,000;
wherein the molar ratio of backbone hydrophilic group to pendant
hydrophobic group is less than 20.
Enzymes and an enzyme stabilizing system are optionally incorporated into the
composition for improved cleaning.
The compositions of the invention provide improved stain removal by the
pretreater
composition prior to the laundry wash. When used as an in wash additive, they
also
provide enhanced fluorescer effectiveness and stain removal.
Detailed Description of Preferred Embodiments
The present invention relates to compositions which may be used as pretreaters
in stick
form.
The compositions are based on nonionic surfactants and are preferably
substantially free
of synthetic (non-soap) anionic surfactants. They also contain specific
polymers which
have a critical molar ratio of a number of hydrophilic "backbone" groups
(single
monomer hydrophilic backbone) to a number of hydrophobic "anchor" or tail
group.
When the polymers of the invention are added to the specific compositions, it
has been
unexpectedly found that the compositions have better stain removal efficacy
compared to
compositions which do not contain the polymers.
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C 6327 (~
Hvdrophobicallv Modif ed Polar Poll
The polymer useful in 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.
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 cross-
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 g/1). 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'/° by weight.
The hydrophilic backbone is composed of one monomer unit selected from a
variety of units
available for polymer preparation and linked by any chemical links including:
0 o a
-D., Cue, -GG, ~.0, ~-N, ~N, and P- (n
OH
The "tail" group comprises a monomer unit comprising hydrophobic side chains
which are
incorporated in the "tail" monomer. The polymer is made by copolymerizing
hydrophobic
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C 6327 (~ 6
monomers (tail group comprising hydrophobic groups) and the hydrophilic
motrotiier maldno
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/l, more
preferred Iess than 0.5 g/1, most preferred less than 0.1 glt 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.
Monomer units which make up the hydrophilic backbone include:
(1) unsaturated, preferably mono-unsaturated, C1.6 acids, ethers, alcohols,
aldehydes, ketoses
or esters such as monomers of acrylic acid, methacrylic acid, malefic acid,
vinyl-methyl ether,
vinyl sulphonate or vinyl alcohol obtained by hydrolysis of vinyl acetate,
acrvlein;
(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 or other saturated polyalcohols.
Monomeric units comprising both the hydrophilic backbone and hydrophobic side
chain may
be substituted with gnaups such as amino, amine, amide, sulphonate, sulphate,
phosphonate,
phosphate, hydroxy, carboxyl and oxide groups.
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C 6327 (~ . 7
The hydrophilic backbone is composed of one unit: The backbone may also
contain small
amounts of relatively hydrophilic units such as those derived from polymers
having a
solubility of less than 1 gll in water provided the overall solubility of the
polymer meets the
requirements discussed above. F~camples include polyvinyl acetate or
polymethyl
methacrylate. ~ .
(CH C) '
Rs Ri
-x R
I2
R3
--- z
n
wherein
z is l;
x:z {i.e., hydrophilic backbone to hydrophobic tail) is less than 20,
prcfcrably less than 17,
more preferably less than 10;
in which the monomer units may be in random order, and
n is at least 1:
Ri represents -CO-O-, -O-, -O-CO-, -CHZ-, -CO-NH- or is absent;
RZ represents from 1 to 50 independently sclccted alkyleneoxy groups
preferably ethylene
oxide or propylene oxide groups, or is absent, provided that when R3 is absent
and R4
represents hydrogen or contains no more than 4 carbon atoms, then Rz must
contain an
alkyleneoxy group with at least 3 carbon atoms;
Rs represents a phenylene linkage, or is absent;
CA 02195510 2004-08-16
C 637 {~ 8
R~ represents hydrogen or a Ci.~, alkyl or Ci.=,, alkenyl group, with the
proviso's. '
a) when R, represents -O-CO-, Rz and R3 must be absent and R, must contain at
least 5
carbon atoms;
b) when R2 is absent, R4 is not hydrogen and when R3 is absent, then R,~ must
contain at least .
S carbon atoms;
Rs represents hydrogen or a group of formula -CODA; .
R6 represents hydrogen or C1-4 alkyl; and A is independently selected from
hydrogen, alkali
metals, alkaline earth metals, ammonium and amine bases and C1.~ alkyl groups.
Alternatively, the group such as,
( ~t3-')
Rs ~,
Rz
1
I
group (defined by z) can be substituted with benzeae, for example styrene.
'The present invention is direct 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 pretreatcr or laundry additive booster formulations they provide
enhanced stain
removal and, when used in the wash with a detergent containing fluorcscer,
they enhance the
fluorescxr whitening_
The polymer should be used in an amount comprising 0.01 to 10'/o by wt.,
preferably 0.1% to
5% by wt. of the composition.
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Nonionic Surfactants
The nonionic surfactants useful in the present invention arse those compounds
produced by the
condensation of alkylene oxide groups with an organic hydrophobic material
which may be-
aliphatic or alkyl or aromatic in nature. The link of the hydrophilic or
polyoxyalkylene
radical which is condensed with any particular hydrophobic group can be
readily adjusted to
yield a water soluble compound having the desired degree of balance betweea
hydrophilic
and hydrophdtic elements. lllustrative, but not limiting examples, of various
suitable non-
ionic surfactant types are:
(a) polyoxyethylene or polyoxypropylene condensates of aliphatic alcohols,
whether linear-
or branched-chain and unsaturated or saturated, containing from about 6 to
about 24 carbon
atoms and incorporating from about 2 to about 50 ethylene oxide andlor
propylene oxide
units. Suitable alcohols include "coconut" fatty alcohol, "tallow" fatty
alcohol, tauryl alcohol,
myristyl alcohol and oleyl alcohol. Particularly preferred nonionic surfactant
compounds in
this category are the "Neodol" type products, a registered trademark of the
Shell Chemical
Company. .
Also included within this category are nonionic surfactants having a formula:
R-(CHa,CHO~CH=CI~iZ~(CH~CHO)ZH L LIi
Rt Rz
wherein R is a linear alkyl hydrocarbon radical having an average of 6 to 1$
carbon atoms, R1
and Rz are each linear alkyl hydrocarbons of about 1 to about 4 carbon atoms,
x is an 'integer
of from t to 6, y is an integer of from 4 to ZO and z is an integer from 4 to
25.
A preferred nonionic surfactant included within this category are compounds of
formula:
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C 6327 (V) . 10
Rs--(CHzCti~~yeH ( z V 1
wherein R3 is a C6-CZ~ linear or branched alkyl hydrocarbon radical and a is a
numbcr from 2
to 50; more preferably R3 is a Ce-C~$ linear alkyl mixture snd a is a number
from 2 to 15.
(b) polyoxyethylene or polyoxypropylene oondensates of aliphatic carboxylic
acids, whether
linear- or branched-chain and unsaturated or saturated, containing from about
8 to about Z8
carbon atoms in the aliphatic chain and incorporating from about 2 to about 50
ethylene oxide
andlor propylene oxide units. Suitable carboxylic acids include "coconut"
fatty acids (derived
from coconut oil) which contain an average of about 12 carbon atoms, ~tallow'
fatty acids
(derived firm tallow-class fats) which contain an average of about 18 carbon
atoms, palmitic
acid, myristic acid, stearic acid and lauric acid.
(c) polyoxyethylene or polyoxypropylene condensatss of alkyl phenols, whether
linear- or
branched-chain and unsaturated or saturated, ~ntaining from about 6 to 12
carbon atoms and
incorporating from about 2 to about 25 moles of ethylene oxide andlor
propylene oxide
(d) polyoxyethyiene derivativcs of sorbitan mono-, di-, and tri-fatty acid
esters wherein the
fatty acid component has between 12 and 24 carbon atoms. The preferred
polyoxyethylene
derivatives are of sorbitan monolaurate, sorbitan trilaurate, sorbitan
monopalmitate, sorbitan
tripalmitate, sorbitan monastearate, sorbitan monoisostearate, sorbitan
tripalmitate, $orbitan
monostearate, sorbitan monoisostearate, sorbital tristearate, sorbitan
manooleatc, and sorbitan
trialeate. The polyoxyethylene chains may contain between about 4 and 30
ethylene oxide
units, preferably about 20. The sorbitan ester derivatives contain 1, 2 or 3
polyoxyethylenc
chains dependent upon whether they are mono-, di- or tri-acid esters.
(e) polyoxycthylene-polyoxypropylene block copolymers having formula:
CA 02195510 2004-08-16
c s3z~ (~ 11
HO(CHzCHZO)a(CH(CH3)CH2O)b(CH~CH2~)~H M
Or
HO(CH(CH3)CHZO)d(CHICH=O)~(CHCH3CHzO~H (Vi)
wherein a, b, c, d, a and f are iategers from 1 to 350 reflecting the
respective polyethylene
oxide and polypropylene oxide blocks of said polymer. The polyoxyethylene
component of
the block polymer constitutes at least about 10% of the block polymer. The
material
preferably has a molecular weight of between about 1,000 and 15,000, more
preferably from
about 1,500 to about 6,000. These materials are well-known in the art. They
are available
under the trademark "Pluronic" and "Pluronic R"~ a product of BASF
Corporation.
(f) Alkyl glycosides having formula:
R''~s0)n(Z'~
whereto R4 is a monvvalecrt organic radical (e.g., a monovalent saturated
aliphatic,
unsaturated aliphatic or aromatic radical such as alkyl, hydroxyulkyl,
alkcnyl,
hydroxyalkenyl, aryl, alkylaryl, hydroxyalkylaryl, arylalkyl, alkenylaryl,
arylalkenyl,. etc.)
containing from about 6 to about 30 (preferably from about 8 to 18 aad more
preferably from
about 9 to about 13 ) carbon atoms; RS is a divalent hydrocarbon radical
cont$ining from 2 to
about 4 carbon atoms such as ethylene, propylene or butylene (most preferably
the unit
(R50~ represents repeating units of ethylene oxide, propylene oxide and/or
random or block
combinations thereof); n is a number having an average value of from 0 to
about 12; Zl
represents a moiety derived from a reducing saccharide containing S err 6
carbon atoms (mast
preferably a glucose unit); and p is a number having an average value of from
0.5 to about 10
preferably from about 0.5 to about 5.
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C 6327 (1~ 12
Fxampics of commercially available materials from Henkel Kommanditgesellschaft
Aktien of
Dusseldorf, Germany include APG~ 300, 325 and 350 with R° being C9-Cli,
n is 0 and p is
1.3, 1.6 and 1.8-2.2 respectively; APG°° 500 and 550 with R4 is
C,Z--C,3, n is 0 and p is 1.3
and 1_8-2.2, respectively; and APG°~ 600 with R4 being Clz-C,4, n is 0
and p is 13_
Particularly preferred is APGe 600.
The nonionic surfactant which are most preferred are the polyoxyalkylone
condensates of
paragraphs "(a)" and "(b)" and the alkyl glycosides. Most preferred are the
polyoxyalkylene
condensates.
The nonionic is used iri an amount of about 0.1 to about 20 wt_ % in liquid,
paste or gel
products and from about 30 to about 80 wt%, preferably up to 60, more
preferably up to
40wt.% in stick products..
Op~jonal Pol
Conventional Polymers also referned to as antiredeposition polymers may also
be
incorporated in the formulations of the invention. Such polymers include
polycacboxylates
(e.g. copolymers of acrylatdmaleate commercially available as Sokolan~
copolymers
supplied by BASF; polyoxyalkylene copolymers (e.g. Pluronic Series supplied by
BASF);
carboxymethylcelluloses (e.g. CMC Series supplied by Union Carbide);
methylcellulose (e.g.
Methocel from Dow Chemical) and ethoxyiated polyamines (e.g. ethoxylated tetra
ethylene
pentamine from Shell Chemical Co).
Especially preferred arc the polycarboxylate polymers. The polymers should be
incorporated
in the formulations of the inventian in an amount of up to about 5 wt. %,
preferably 0. I wt %
to 3 wt. %, most pr~eferdbly 0.5 wt. % to 1 wt_ %.
Anionic Soaps
The pretreater formulations of the invention are preferably substantially free
of synthetic
(non-soap) anionic surfactants. It is possible, however. to add less from
about 5 wt. %,
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C 6327 (~ 13
preferably less than 3 wt. % of an anionic soap to liquid, paste or gel
compositions according
to the inv~tion, particularly for some in-wash formulations intended to boost
whitening of
fabrics. Compositions according to the present invention which are in stick
form contain
from about lwt.% to about 20wt.% of anionic soap.
The term "soap" is used herein in its popular sense, i.e., the alkali metal or
alkanol ammonium
salts of aliphatic alkane- or alkene monocarboxylic acads_ Sodium, potassium,
mono-, dipand
tri-ethanol ammonium rations, or combinations thereof; are suitable for
purposes of this
invention. In general, sodium soaps are used in the compositions of this
invention, but from
about 1°~ to about 250 of the soap may be potassium soaps. The soaps
useful herein are the
well known alkali metal salts of natural or synthetic aliphatic {alkanoic or
alkanoic) acids
having about 8 to 22 carbons, preferably about 1Z to about 18 carbon atoms.
'They may be
described as alkali metal carboxylates of acrylic hydrocarbons having about l2
to about 22
carbon atoms. They also include soaps derived from natural carboxylic acids
such as
"coconut" fatty acids (derived from coconut oil) which contain an average of
about 12 carbon
atoms, "tallow" fatty acids {derived from tallow-cuss fats) which contain an
average of about
18 carbon atoms, palmitic acid, myristic acid, stearic acid and lauric acid.
The soaps preferably
contain saturated or partially saturated fatty acids. Excessive unsaturation
should be avoided.
Typical stick form stain remover compositions according bo the present
invention will
comprise about I-20 wt %, preferably 5-15 wt. % of normally distributed
stearic soap
(nominally X95% CteHs6Uz) as the gelling agent. The current invention
preferably uses blends
of saturated soaps (carbon chain lengths of Ca-C~~ as the coagel structurant
which solidifies
the stain tresunent sticks. The coagel structuring is usod in the margarine
industry to solidify
oil and water mixtures. A coagel solid relies on the stn~cturing of
alternating water and oil bi-
layer Iamellar sheets to form a macroscopically solid phase. Without being
limited to a theory,
it is believed that the blend of saturated soaps modifies the surfactant and
oil interface in order
to form the hi-layer lamellar sheets necessary for the coagel structuring.
CA 02195510 2004-08-16
C 6327 (~ 14
For stick formulations according to the present invention it is preferred to
use blends of soaps
neutralized (in-situ) from the following table:
;L~ !'i C~prylicCupric Lurk Mya~ioP.ImlticStaticL~nsalurafed.
of Total
Fatty Gftm4:Ci~Ifm~Culi~,oGuHv,O~c~.n~..dsy.H~
Acid
in
Fonrwlation' .
p~(c~d 06.0 0-5.0 3.0-40.00-18.010.0-60.05.00.00-5.0
R~
Most 3.5-5.53.04.8 14.3-37.310.B-15.2t7.5-29.513.I-26.00-2.8
Yrcfemed .
Example'0 0 0 0 0-5 93-I000-20
The novel benefits of the current invention which uses a blend of saturated
soaps and coagel
structuring are as follows:
1) When the coagel stick is applied to a stain on cloth and then washed, the
mixed
saturated soaps helps to avoid a cubic surfactant phase between the stick and
the stain in the
aqueous phase. A cubic phase is very impermeable which inhibits the transfer
of cleaning
ingredients and the release of the stain fmm the cloth. Avoiding this cubic
phase by using the
blended saturated soaps improves the stain performance an oil stains compared
to conventional
stain sticks.
2) due to the bi-layer structuring of a coagel stick the dissolution rate in
an aqueous
solution (i.e., wash liquor) is much greater then with conventional stain
sticks. This improves
performance and ensures that no treatment stick remains on the cloth after
washing.
3) The eoagel structurant breaks down under the friction of contact with the
cloth.
Thus, under the friction of application to a dry stain, the localized region
of contact for the
las described in U.S_ Patent No. 5,147,576.
CA 02195510 2004-08-16
c s~z~ ~ is
coagel stick liquefies. This ensures that the treatment stick is easy to
apply, the stick has a
user friendly glide texture, and on application the liquef ed stick formula
cea penetrate deeper
into the stain, removing the stain mare completely than with convemional stick
formulations.
Formulations containing the preferred blend of saturated soaps also contain
the ,.
hydrophobically modified polar polymer of the invention.
Anionic Surfactants
Synthetic anionic surfactants are preferably substantially or completely
excluded from
compositions according to the present invention. If present at'all, then they
are only included
in minor amounts such as less than 10%, preferably less than S%, more
preferably less than
2%, still more preferably less than 1%, especially less than
0.5°Y°, e.g_ less than 0.1% by
weight of the total composition. If present, such anionic surfactants may be
chosen from any
of those known in the art of formulating detergent compositions, such as the
usual linear alkyl
benzene sulphonates, primary alkyl sulphates, alkyl ether sulphates etc.
Though, most
preferred of all is total exclusion of synthetic anionic surfactants.
Enzymes
Enzymes may optionally be included in the pretrcater or in wash formulations
to enhance the
removal of soils from fabrics, if present, the enzymes are in an amount of
from about 0 to 10
weight %, preferably 1 to about 5 wt. %. Such enzymes include proteases (e.g.
Alculase ,
Savinase'° and Esperase'm from Novo Industries A/S), amylases {e.g.
Tetmamyi~ from Novo
Industries A/5), Iipolases (e.g, Lipolasem from Novo Industries AIS) and.
cellulases, (e.g.
cehuiyrne from Nova Industries A/S).
Enzyme Stabilising System
Stabilizers or Stabilizer systems may be used in conjunction with enzymes and
generahy
comprise from about 1 to 15% by weight of the composition.
CA 02195510 2004-08-16
C 6327 (~ 16
The enzyme stabilization system may comprise calcium ion; boric acid, propyl~e
glycol
andlor 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 1
to about 20
millimoles of calcium ion per litre.
When calcium ion is used, the level of calcium ion should be selected so that
there is always
some minimum level available for the enzyme after allowing 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
miUimoles per litre, is
often also present in the composition due to calcium in the enzyme slurry and
formula water.
Another enzyme stabilizer which may be used is 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 1 S% 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 propanediol which is
preferred), ethylene
glycol, glycerol, sorbitol, marinitol and glucose. The polyol generally
represents from about
0.5% to about 1 S%, preferably from about 1 _0% to about 8% by weight of the
composition.
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 berates (e.g: sodium ortho-, mete- and pyroborate and sodium
pentabarate) are suitable.
Substituted boric acids {e.g., phenylboronic acid, butane boronic acid and a p-
bromo
pheaylboronic acid) can also be used in
CA 02195510 2004-08-16
C 6327 (~ 17
place of boric acid.
One especially preferred stabilization system is a polyol in combination with
boric acid:
Prcterably, the weight ratio of polyol to boric acid added is at Least 1, more
preferably at least
about 1.3.
Preparation of Formulations
The formulations of the invention may be prepared in any form known in the art
such as
liquid, (including in spray form), paste or gel. Those compositions should be
prepared by
conventional formulation methods such as those described in U.S. 5,186,856,
particularly
directed to an aqueous form.
In general, aqueous liquid, paste yr gel formulations arc prepared by mixing
the nonionic and
selected polymers together and heating the mixture to a temperature of up to
160°F. The
mixture is then cooled and the enzymes and eruyme stabilising system may be
added.
Optional ingredients, such as preservatives, dyes and perfumes arc added to
the cooled
mixtures. The compositions are the packaged and stared.
Those formulations of the invention which are in stick forms are prepared as
follows, but may
be prepared in any form known in the art for stick forms.
The fatty acids) used are typically neutralized to soap in-situ. The nonionic
surfactant, the
blend of fatty acids) and the polyols such as sorbital, glycerol, propylene
glycol arc heated to
about 70°C to form a homogeneous melt mixture. Water and neutralizing
base (typically
caustic) are then added to neutralize the fatty acid(s). The polymer is then
added and mixed
until the mixture is homogeneous. The homogenous mixture is than cooled to
just above the
mixtures dropping point. Any heat labile additional ingredients (i.e.,
enzymes, fragrance,
preservatives) are then added. The composition is then packaged, cooled aad
stored.
CA 02195510 2004-08-16
C 6327 (~ 18
Alternatively, the initial melt mixture can be added to a premixed mixtZUe of
water, caustic
and polymer to perform the in-situ neutralization.
Thickeners ..:
Thickeners may be incorporated into the formulations of the invention
particularly to import '
viscosity to liquid yr to produce gel or paste consistency. Such thickeners
include, but are not
limited to natural thickeners such as xanthan gums and other conventional
polymeric
thickeners as known in the art. The thickeners may comprise up to 5% of the
formulation.
Preferably, 0.1 wt. % to 3 wt. %, most preferably 0.3 wt % to 1 wt. %. .
Optionally, an antifoam agent may be incorporated into formulations according
to the
invention in an amount of up to 2 wt. %, preferably 0.05 to 1 wt. %, to reduce
the level of air
entrapped in the solidified sticks. Suitable antifoams include mono- and
distearyl acid
phosphate, silicone oil, silicon emulsion, silicon Compounds snd mineral oil.
Preferably,
silicon emulsions are used.
O ionallng~.~ients
One or more optional additives may be included in the formulations including
perfumes,
dyes, pigment, opacifiers, germicides, optical brightenecs, anticorinsional
agents and
preservatives. Each additive incorporated in the composition should be present
in an amount
of up to about 0.5% by wt.
The following examples will serve to distinguish this invention from the prior
art and
illustrate its embodiments more fully. Unless otherwise indicated, alI parts,
percentages and
proportions referred to are by weights.
i
CA 02195510 2004-08-16
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ExamQles
Example 1
A aqueous ~pretreater formulation according to the invention was prepared as
Sample A
below. As a comparison, an aqueous pretreater formulation without the selected
,
hydrophobically modified polymer was prepared as Sample B.
Ta I 1
Samples
Ingredient ~ A B
boric acid 1.4 l.4
P~PYlene glycol 3.0 3.0
alcohol ethoxylate~ 4.7 4.7
Narlex~ I)C-1j 0.5 0
enzyme 0.7 0.7
xanthan gum 0.3 0.3
preservative .003 .003.
deionized water to
100% 1
The liquid composition of the invention was made by charging a vessel with
water and
heating to 160 F, adding the boric acid and stirring the liquid until a clear
solution was
obtained. The surfactant was then added, and the heater turned off. The
polymer of Sample A
was then added when the solution temperature was between 120-150°F. The
enzymes were
is nonionic surfactam having 12-15 carbon atoms in the hydrophobic group and 9
EOs and supplied
as Neodol 25-9 by Shell Chemical Co_
'a copolymer of acrylic acid and lauryl methacrylic acid supplied by National
Starch and Chemical
Co.
CA 02195510 2004-08-16
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added when the solution temperature was below 120°1r, then preservative
was added. The pH
of the formulation was then adjusted to 7.0 (f 0.5).
Example 2
The stain removal performance of the inventive composition (Sample A) versus
Sample B
without the selected polymer was evaluated on four (4) different stains and on
three types of
fabric as follows.
The three types of fabrics used to evaluate the compositions were: ,
I)100% couon
2) 50%/50"/s polyesterlcoteon blend
3) double knit 100% polyester
Cloths 1 and 2 were obtained from Textile Innovators (Windsor, North
Carolina), and the
polyester cloth 3 was obtained from Test Fabrics (h~ddlesex, New Jersey).
Prior to staining
the cloths were prewashed five times with a fluorescer free detergent at 130"F
(and dried) to
remove spinning oils and increase the absorbency of the cloth. Swatches were
cut to 4-3l4" x
8-3/4", and a 2" diameter circle inscribed in the middle.
Four different stains were used as follows:
l ) Grass (1:2 gram of water by wt blended and ftltcred).
2) Liquid foundation make=up
3) Cows blood
4) Mud (strained dirt mixed 1; I with water and blended)
The stains were applied over the 2" circle an each swatch as outlined in Table
2:
i
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Table 2 '
Stain Dosage Treatmedt
r
,
Cotton Blend Polyester
grass 8 drops~(2x)8 drops (2x)114 tsp. overnight
blood 7 drops 7 drops 18 drops overnight
make-up 7 drops 6 drops 38 drops overnight
mud 1/8 tsp 118 tsp I/4 tsp overnight
Stained clothes were treated with the liquid pretreater and washed in 17
gallons of 95"F tap
water with a commercial laundry detergent followed by a cold rinse. The
cloths' were then
placed in a static dryer until dry. flight replicates of each stain with each
cloth were
performed.
Stain removal was measured by reflectometry and colour change using a Pacific
Scieatitnc
Colorgard System model 5 colorimeter. The stain removal index (SRI) gives a
numerical
value for stain removal and is defined as;
SRI = 100 - ~~-r - L")= ~' (ac - aw)a 'f' ~c - b"")~]ln
Where. ,
L = measured lightness (reflectance) value
a = measured greennesslredness value
b = measured blueness/yellowness value
a = clean cloth
w = stained and washed cloth
Results were reported as SRI index values.
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Stain removal data for Samples A and H for the four stains on the three types
of cloth were
observed and are reported in Table 3 below;
le 3 ..
STAIN '
REMOVAL
INDEX
VALI1E
Sample 100/ 50/50 100/
Cotton PolyesterlCotton Polyester
Stain A B LSD4 A B LSD' A B LSD'
Grass 94.89 89.340.52 80.97 7ti_Z9O.Z7 96.7992.91 0.50
Mud 78.32 77.990.94 83.18 79.702.08 88.8785.94 1.74
Make-up 77.65 75_361,03 8437 79.332.11 99.2899.29 0.05
Blood 91.01 90.420.23 94.31 93.960.15 99.0098,?6 0.16
I I I I I 1 I i I I 1
It was thus observed that the inventive Sample A was significarnly more
effective at stain
removal than observed with Sample B ,which did not contain the selected
polymer.
Example 3
The following gel compositions were prepared as described in Example I.
~I,SD = Least Significant Difference at 95% confidence Ievel.
CA 02195510 2004-08-16
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Table 4
~ngedient Sample C Sample D
boric acid 1.4 1.4
propylene glycol 3.0 3.0
alcohol ethoxylate 14 14
enzyme 1 _S 1.5
xanthan gum 0.7 0.7
Narlex~ DC-1 0 0.5
water to 100%
Sample C did not contain the hydrophobically modified polymer while Sample D
contained
Narlex~ DC-1, a copolymer of acrylic acid and lauryl methaaylic acid supplied
by National
Starch and Chemical Co. The cleaning performance of Sample C versus Sample D
was
evaluated as described in Example 2 on 2 different stains and three types of
fabrics with the
results presented in Table 5:
i
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Ta_ ble 5
STAIN
REMOVAL
1NI?EX
VALUES
Stain 100% 50/50 100%
Cotton Polyester/cotton Polyester
C D LSDS C D LSDI C D LSD'
,grass 92.16 94.030.29 94.4b 94.91 0.23 95.94 96.7 0.29
8 ,
mud 76.71 78.890.91 79.$5 79.94 1.63 90.09 92.5 0.85
i s i i i i i i i r
From the results described in Table 5, it was observed that the inventive
formulation was
significantly better in stain removal than the sample without the polymer of
the invention.
Example 4
A gel form of the inventive formulation incorporating a styrene containing
acrylic acid
copolymer was prepared as described in Example 1 and presented in Table 6
below:
sLSD = Least Significant Difference at 95% confidence level.
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Table 6
Ingredient % Active
boric acid 1.4
propylene glycol 3.0
alcohol ethoxylate 14
enzyme 1.5
xanthan gum 0.7
ALCO EXP 24996 0. S
Deionized water to 100%
Example 5
An aqueous composition incorporating a styrene containing acrylic acid
copolymer was
prepared as described in Example 1 having the formula described in Table 7:
6a styrene containing acrylic acid copolymer supplied by Alco under the Series
HI00.
i
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Table 7
,..
Ingredient % Active
boric acid 1.4
propylene glycol 3,0
alcohol ethoxylate 4.7
enzyme 0_7
xanthan gum 0.3
ALCO 1;XP 2499e 0.5
~Deioniud water ~ to 100'/0
Example 6
The following laundry additive compositions were prepared as described in
Example 1:
~'a nonionic surfactant supplied by Shell as Neodol 25-9.
8a styrene containing acrylic acid copolymer supplied by Alco under the Series
H100.
i
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T le 8
E F
4
boric acid 1.4 1.4 ,
propylene glycol 4.0 4.0
alcohol ethoxylate9 2.0 2.0
enzyme 0.7 0.7
xanthan gum 0.3 0.3
Narlex DG 1' I .0 1.0
monoethanolamine - 0.4
coconut fatty acid - 2.0
deionized water to I00%
Samples of composition E were prepared as described in Example 1. Samples of
composition
F were prepared by adding the monoethanolamine and coconut fatty acid to the
alcohol
ethoxylate (as described in Example 1), adding the monoethanolamine first
followcd by the
fatty acid.
fixample 7
The fluorescent whitening of the inventive compositions used as laundry
additives with a
commercial detergent containing fluorescer whitening agents versus the
detergent alone was
evaluated on soiled cloths. Soil cloths were obtained from ENlPA, St. Gallen,
Switzerland.
EMPA 112 is composed of cocoa, milk and sugar on cotton. EMPA 116 is composed
of
9a nonionic surfactant supplied by Shell as Neodol 25-9.
'°a styrene containing asxylic acid copolymer supplied by Alto under
the Series H100.
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blood, milk, and Indian ink on cotton. EMPA 117 has the same soil as EMPA 116
but it is~on
pvlyesterlcotton. VC'D is composed of vacuum cleaner dust on polyester/cotton.
AS-10 is
composed of milk powder, ground nut oil, carboxymethylcarubin,and small levels
of dyes on
cotton.
The inventive products were used at a conventional booster level together with
the
commercial detergent. The composition of the detergent is shown in Table 9.
Four of each
soil cloth type were washed at the same time and the evaluation was done
twice. The results
are shown in Table 9. Fluorescer values are calculated using the following
equation form
reflectance data taken on a Gardner reflectometer with and without an
ultraviolet filter. ''
F= 0.08 + 2.61 (Z",~-Zw,)
where:
F = fluaresoor value .
0.08 and x_61 are instnrmental parameters
wo = without ultraviolet f Iter
w = with ultraviolet filter -
Z = (0.7a - b~I59.27
L = reflectance
b = yellow-blue value
a = green-red value
Fluorescent whitening of inventive formulations:
CA 02195510 2004-08-16
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T le 9
F'~.UORESCEN?
WHT~NirlG
Product VCD A~-10 EMPA 112 EMPA 116 EMPA
117
detergent alone5.39 3.94 1.13 0.43 - 0.04
+ formula G 6.01 5.41 1.77 1.55 0.33
+ formula Fi 5.97 5.34 1.87 1.61 0.43
least sig. 0,26 0.26 0.16 0.16 0.16
diff
The inventive formulations increase the fluorescent whitening of the detergent
significantly.
The boost in fluorescent whitening due to the iwentive formulations is
unexpected because
these do not contain fluorescer.
CA 02195510 2004-08-16
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Example 8
A stick formulation according to the invention was prepared as Sample G below.
As a
comparison, an aqueous pretreater formulation without the sclcctcd
hydrophobically modified
polymer was prepared as Sample H.
Table 10
Samples
Ingredient G H '
propylene glycol 11 _0 11.0 ,
alcohol ethoxylate''57.9 57.9
Narlex~ 13C-1'z 0.3 0
stearic acid'3 4.4 4.4
coconut fatty acid'47.9 7.9
sodium hydroxide 2.1 2.1
deionized water to
100%
"a nonionic surfactant having 12-15 carbon atoms in the hydrophobic Sroup and
9 EOs and
supplied as Neodol 25-9 by Sheli Chemical Co.
'Za copolymer of acrylic acid and tauryl methatxylic acid supplicd by National
Starch and
Cheraical Ca.
'3stearic acid containing a mixture of C,z.l8 saturated fatty acids suppliod
as Emersol 132 by
Henkle_
'partially hydrogenated coconut fatty acid C$-C~ saturated fatty acids
supplied by Heakle.
CA 02195510 2004-08-16
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The nonionic surfactant, the anionic surfactant, the polymer and the propylene
glycol werc
added together in a mixture with lorry to medium agitation. The batch was
heated up 40°C.
The fatty acid was then added and heating was continued until the batch
reached 55°C. Once
the fatty acid was completely melted, the water was added with heating to
maintain the batch
at 50-55°C. Once the batch was homogeneous, the sodium hydroxide was
added_ The batch
was then mixed for 45 minutes to ensure full neutralization of the fatty acid.
The batch was
then cooled to 50°C. The batch was then placed in a package and allowed
to air cool with
chilling.
Example 9
The stain removal performance of the imrentive composition (Sample F) versus
Sample G
without the selected polymer was evaluated on three (3) different stains and
on three types of
fabric as follows.
The three types of test cloths used to evaluate the compositions were:
1 ) I 00% cotton
2) 50°/./50'/o polyester/cotton blend
3) double knit 1009~o polyester
Cloths 1 and 2 were obtained from Textile Innovators (Windsor, Norrh
Carolina), and the
polyester cloth 3 was obtained from Test Fabrics (Middlesex, New Jersey).
Prior to staining,
the cloths were prewashed S times in Dye Free Liquid "all" at 130°F
(and dried) to remove
spinning oils and increase the absorbency of the cloth. Swatches were cut to 4-
3/4" x 8-3/4",
and a 2" diameter circle inscribed in the middle.
Three different stains were used as follows:
I) Grass (1008 grass clippings added to 200g water, blended, filtered through
cotton ballast,
100g more clippings and ZOOg more water added to filtrate, and new mixture
filtered).
CA 02195510 2004-08-16
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2) Cooking OiUFood CotoraM (17 gms. of annato seed colorant are dissolved in
400 fans. of
cooking oil and the mixture is passed tEu~ough a cheex cloth filtex)_
3) Mud (strained dirt mixed 1:1 with water and blended).
The slams were applied over the 2" circle on each swatch as outlined in Table
11: .
Table l i
Dosage Treatment ~ ,
Stun Cotton Blend polyester . , ,
mud 1/8 tsp 1B tsp 1/4 tsp overnight
grass 8 drops (2x)8 drops 114 tsp. overnight
(2x)
cooking oiUfood12 drops 12 drops - ovenright
colorant
The stain cloth were pretreated (by nrbbingJ with the stick Application of the
stick is dose
using minimal force, allowing the natural gliding tendency of the stick to
drive the movement.
The stained and treated clothes were allowed to sit for 5 minutes before
washing. 'The washes
were done using the recommended dosages of a laundry liquid deterg~t in warm,
95°F water
and rinsed in cold water. The cloths were then placed in a static dryer until
dry. Four
replicates of each stain with each cloth Were performed.
Stain removal was measurod by reflectometry and color change using a Pacific
Scientific
Colorgard System model 5 colorimeter. The stain removal index (SRn gives a
numerical
value for stain removal and is defmod as:
SRI = 100 - ~(Le - ~-w)2 + (~ - ~.)2 + (be - bw)=1 ~a
Where.
i
CA 02195510 2004-08-16
C 6327 (~ ~ 33
L = measured lightness (reflectance) value
a = measured gree~nesslredness value ,
b = measured biueness/yellowness value , .
c = clean cloth
w = stained and washed cloth ,
Stain removal data for Samples G and H for the three stains on the three types
of cloth were
observed and are reported in Table 12 below:
Table 12 '
Stain
Removal
Index
Values
Stain 100% 50150 100'/o
Cotton Polyester
Polyester/Cotton
Stain G H LSD G H LSD G H LSD
Mud 74.4972.63 1.08 78.52 ~ 77.381.53 94.91 94.50 0.39
Grass 88.8288.7 1.66 93.56 93.45 0.34 96.21 96.94 0.71
Cooking 90.5990.41 1.12 92.05 91.29 0.27 NIA NIA NIA
~il/Food 9 1 5 9
Colorant
LSD = Least Significant Dii1'erence at 95% ~nf dance level.
it was thus observed that the inventive Sample G consistently gave
directionally better stain
removal than observed with Sample H which did not contain the selected
polymer.
i
' CA 02195510 2004-08-16
C 6327 (~ 34
Exam le 0
Stick forces of the inventive formulation incorporating a styrene containing
acrylic acid
copolymer were prepared as described in Example 8 and presented in Table 13
below:
Table 13
Ingredient % Active
propylene glycol 11.0 '
alcohol ethoxylatels57.9
Ar,CO ~7CP 2499' 0.5
stearic acids' 4.4
coconut fatty acidl87.9
~
sodium hydroxide 2.1
deionized water
to 100% .
'-a nonionic surfactant supplied by Shell as Neodol 25-9.
' 6a styrene containing acrylic acid copolymer supplied by Alco under the
Series H100.
"stearic acid containing a mixture of C~Z.~x saturated fatty acids supplied as
Emersol 13? by
Henkle.
'Bpartially hydrogenated coconut fatty acid CB-C~ saturated fatty acids
supplied by Henkle.
