Note: Descriptions are shown in the official language in which they were submitted.
W094/03~70 ' PCT/US93/06836
2141~
U8E OF MODIFIED ~OLYE8TER8 FOR T~E RBMOVAL
OF GRBA8E OF FABRIC8
Technical Field
The present invention relates to the use of modified
polymers known for their soil-release prope-rties, as
cleaning agents for grease stain removal of fabrics in
combination with a non-ionic surfactant.
Background of the invention
Products used in laundering operation contain a number of
ingredients which provide certain basic benefits. For
example, laundry cleaning products are formulated with
detergent surfactant systems to remove a variety of soils
from clothes during washing. These laundry products can
also include ingredients which provide through-the-wash
fabric conditioning benefits such as softening and anti-
static performance.
.
In addition to standard cleaning, softening and anti-static
benefits, laundry detergent can also impart other desirable
W094/03~70 ~ PCT/US93/06836
properties. One is the ability to confer soil release
properties to fabrics woven from polyester fibers. The
hydrophobic character of polyester fabrics makes their
laundering difficult, particularly as regards oily soil and
oily stains. The oily soil or stain preferentially "wets"
the fabric. As a result, th.,e oily soil or stain is
difficult to remove in an aqueous"iaundering process.
Certain polyesters have been found to be particularly
useful as soil release compounds in laundry detergent
composition. During the laundering operation, these soil
release polyesters adsorb onto the surface of fabrics
immersed in the wash solution. The adsorbed polyesters then
form a hydrophilic film which remains on the fabric after it
is removed from the wash solution and dried. This film can
be renewed by subsequent w~ch;ng of the fabric with a
detergent composition containing the soil release
polyesters.
Such polyesters are disclosed in e.g. US Patent 4 116 885
and 4 711 730.
Continuous effort has been put against improving soil
release polyesters; in e.g. EPA 272 033 have been described
such improved polyesters. More recently, EPA 311 372 has
described further improved soil release agents consisting of
sulfoaroyl end-capped polyesters.
It has been found that certain modified polyesters
described in EPA 311 342 not only act as a soil release
agents on polyester fabrics, but are also able to remove
soils from cotton-containing fabrics and to disperse such
soils, during the main laundering cycle of a laundry process
as described in our co-pending application EP92.202.383.3.
W094/03570 2 ~ PCT/US93/06836
A long-standing problem is the grease stain removal. With
present detergent compositions it is difficult to remove
efficiently said grease from fabrics especially from
polyester fabrics.
It has now been surprisingly found that the modified
polyesters as described in EPA 311.342 in combination with
selected nonionic surfactants with a low ethoxylation
degree, shows an unexpected greasy stain removal of the
fabrics.
The detergent composition according to the invention
comprises a modified polyester being a random copolymer of
dimethyl terephtalate, dimethyl sulfoisophtalate ethylene
glycol and 1-2 propane diol, the end groups consisting
primarily of sulfobenzate and secondarily of mono esters of
ethylene glycol and/or propane-diol and a non-ionic
surfactant C8_18 primary alcohol ethoxylate containing from
2 to 5 moles of ethylene oxide per mole of alcohol. Most
preferred is a detergent composition wherein the non-ionic
surfactant is C12_15 primary alcohol ethoxylate cont~i n ing 3
moles of ethylene oxide per mole of alcohol. Present in the
detergent composition in a ratio 1 : 0.3 to 1 : 2.0 provides
a surprising thickening effect. This provides the formulator
with a potentially effective method by which said selected
non-ionic surfactant can be processed into granular
dertergents.
It has further been found that the claimed modified
polyester can have a thickening effect on said selected non-
ionic surfactant.
W094/0~7~1 4 1 6 - PCT/US93/068
DETAILS DESCRIPTION OF THE INVENTION
The modified Polyesters
The modified polyesters herein are random copolymers of
dimethyl terephtalate, dîmethyl sulfoisophtalate, ethylene
glycol and 1-2 propane diol, the end groups consisting
primarily of sulphobenzoate and secondarily of mono esters
of ethylene glycol and/or propane-diol. The target being to
obtain is a polymer capped at both end by sulphobenzoate
groups, "primarily", in the present context most of said
copolymers herein will be end-capped by sulphobenzoate
groups. However, some copolymers will be less than fully
capped, and therefore their end groups may consist of
monoester of ethylene glycol and/or propane 1-2 diol,
thereof consist "secondarily" of such species.
The selected polyesters herein contain about 46% by weight
of dimethyl terephtalic acid, about 16% by weight of propane
-1.2 diol, about 10% by weight ethylene glycol about 13% by
weight of dimethyl sulfobenzoid acid and about 15% by weight
of sulfoisophtalic acid, and have a molecular weight of
about 3.000. The polyesters and their method of preparation
are described in detail in EPA 311 342.
Furthermore, it has been found that the combined use of
the present modified polyesters with a cellulase enzyme
and/or certain co-dispersing agents and/or certain nonionic
surfactants provides superior cleaning benefits.
The non-ionic surfactants
The non-ionic surfactants according to the present
invention are C8_18 primary alcohol ethoxylates containing
from 2 to 5 mole of ethylene oxide per mole of alcohol.
W094/03~70 2 1 ~ PCT/US93/06836
Preferred are : a C12_15 primary alcohol ethoxylates
containing about 3 moles of ethylene oxide per mole of
alcohol
The modified polyesters herein are present in the
detergent composition at a ratio to the non-ionic
surfactants of, from 1 : 0.3 to 1 : 20, preferred is 1 : 6
to 1 : 20.
DETERGENT COMPOSITION
The detergent compositions herein can be in a liquid or
granular form and are preferably delivered directly to the
drum and not indirectly and via the outer casing of the
machine. This can most easily be achieved by incorporation
of the composition in a bag or container from which it can
be released at the start of the wash cycle in response to
agitation, a rise in temperature or immersion in the wash
water in the drum. Such a container will be p~aced in the
drum, together with the fabrics to be washed. Alternatively
the washing machine itself may be adapted to permit direct
addition of the composition to the drum e.g. by a dispensing
arrangement in the access door.
When the compositions are in liquid form, a rigid
container such as disclosed in EPA 151 549 can be used the
detergent composition herein are preferably in granular
form, and the container will be flexible, such as a bag or
pouch. The bag may be of fibrous construction coated with a
water impermeable protective material so as to retain the
contents, such as is disclosed in EPA no. 0 018 678.
Alternatively it may be formed of a water insoluble
synthetic polymeric material provided with an edge seal or
closure designed to rupture in aqueous media as disclosed in
EPAs nos. 0 011 500, 0 011 501, 0 011 502, and 0 011 968. A
convenient form of water frangible closure comprises a water
soluble adhesive disposed along and sealing one edge of a
W094/03570 ~ PCT/US93/06836
2 ~ 4~ ~'L6 6
pouch formed of a water impermeable polymeric film such as
polyethylene or polypropylene.
In a variant of the bag or container product form,
laminated sheet products can ~e employed in which a central
flexible layer is impr,,egnated and/or coated with a
composition and then one or more outer layers are applied to
produce a fabric-like aesthetic effect. The layers may be
sealed together so as to remain attached during use or may
separate on contact with water to facilitate the release of
the coated or impregnated material.
An alternative laminate form comprises one layer embossed
or deformed to provide a series of pouch-like containers
into each of which the detergent components are deposited in
measured amounts, with a second layer overlying the first
layer and sealted thereto in those areas between the pouch-
like containers where the two layers are in contact. The
components may be deposited in particulate, paste or molten
form and the laminate layers should prevent egress of the
contents of the pouch-like containers prior to their
addition to water. The layers may separate or may remain
attached together on contact with water, the only
requirement being that the structure should permit rapid
release of the contents of the pouch-like containers into
solution. The number of pouch-like containers per unit area
of substrata is a matter of choice but will normally vary
between 500 and 25,000 per square meter.
Suitable materials which can be used for the flexible
laminate layers in this aspect of the invention include,
among others, sponges, paper and woven and non-woven
fabrics.
However the preferred means of carrying out the washing
process according to the present invention includes the use
of a reusable dispensing device having walls that are
W094/03570 7 2~ 6 PCT/US93/06836
permeable to liquid but impermeable to the solid
compositlon.
Devices of this kind are disclosed in EPAs Nos. 0 343 069
and 0 344 070. The latter Application discloses a device
comprising a flexible sheet in t~e form of a bag extending
from a support ring defining an orifice, the orifice being
adapted to admit to the bag sufficient product for one
washing cycle in a washing cycle. A portion of the washing
medium flows through the orifice into the bag, dissolves the
product, and the solution then passes outwardly through the
orifice into the washing medium. The support ring is
provided with a masking arrangement to prevent regress of
wetted, undissolved, product, this arrangement typically
comprising radially extending walls extending from a central
boss in a spooked wheel configuration, or a similar
structure in which the walls have a helical form.
The detergent compositions herein contain a surfactant.
A wide range of surfactants can be used in the detergent
compositions. A typical listing of anionic, nonionic,
ampholytic and zwitterionic classes, and species of these
surfactants, is given in US Patent 3 664 961 issued to
Norris on May 23, 1972.
Mixtures of anionic surfactants are particularly suitable
herein, especially mixtures of sulphonate and sulphate
surfactants in a weight ratio of from 5:1 to 1:2, preferably
from 3:1 to 2:3, more preferably from 3:1 to 1:1. Preferred
sulphonates include alkyl benzene sulphonates having from 9
to 15, especially 11 to 13 carbon atoms in the alkyl
radical, and alpha-sulphonated methyl fatty acid esters in
which the fatty acid is derived from a C12-C18 fatty source
preferably from a C16-Clg fatty source. In each instance
the cation is an alkali metal, preferably sodium. Preferred
sulphate surfactants are alkyl sulphates having from 12 to
W O 94/03570 PC~r/US93/06836
2~ 8
18 carbon atoms in the alkyl radical, optionally in
admixture with ethoxy sulphates having from 10 to 20,
preferably 10 to 16 carbon atoms in the alkyl radical and an
average degree of ethoxylation of 1 to 6. Examples of
preferred alkyl sulphates he,rë~i~ are tallow alkyl sulphate,
coconut alkyl sulphate, an,~d- C14_15 alkyl sulphates. An
exemple of a preferred'~ethoxy sulphate is the so-called
AE3S(C12_1s alkyl 3 times ethoxylated sulphate). The cation
in each instance is again an alkali metal cation, preferably
sodium.
One class of nonionic surfactants particularly useful in
the present invention are condensates of ethylene oxide with
a hydrophobic moiety to provide a surfactant having an
average hydrophilic-lipophilic balance (HLB) in the range
from 5 to 17, preferably from 6 to 14, more preferably from
7 to 12. The hydrophobic (lipophilic) moiety may be
aliphatic or aromatic in nature and the length of the
polyoxyethylene group which is condensed with any particular
hydrophobic group can be readily adjusted to yield a water-
soluble compound having the desired degree of balance
between hydrophilic and hydrophobic elements.
In addition to the selected non-ionic surfactants herein
the present compositions can also contain additional non-
ionic surfactants such as the C9-C15 primary alcohol
ethoxylates containing 6-8 moles of ethylene oxide per mole
of alcohol, particularly the C14-C15 primary alcohols
containing 6-8 moles of ethylene oxide per mole of alcohol.
Another suitable class of additional nonionic surfactants
comprises alkyl polyglucoside compounds of general formula
RO (cnH2no)tzx
wherein Z is a moiety derived from glucose; R is a saturated
hydrophobic alkyl group that contains from 12 to 18 carbon
W094/03~70 21 ~ PCT/US93/06836
,~ ,
atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to
4, the compounds including less than 10~ unreacted fatty
alcohol and less than 50% short chain alkyl polyglucosides.
Compounds of this type and their use in detergent are
disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.
Also suitable as additional nonionic surfactants are poly
hydroxy fatty acid amide surfactants of the formula
R2 - C - N - Z, wherein Rl is H,
Il I .
O Rl
or R1 is C1_4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl
or a mixture thereof, R2 is C5_31 hydrocarbyl, and Z is a
polyhydroxyhydrocarbyl having a linear hydrocarbyl chain
with at least 3 hydroxyls directly connected to the chain,
or an alkoxylated derivative thereof. Preferably, R1 is
methyl, R2 is a straight C11_15 alkyl or alkenyl chain such
as coconut alkyl or mixtures thereof, and Z is derived from
a reducing sugar such as glucose, fructose, maltose,
lactose, in a reductive amination reaction.
A further class of surfactants are the semi-polar
surfactants such as amine oxides. Suitable amine oxides are
selected from mono Cg-C20, preferably C10-Cl4 N-alkyl or
alkenyl amine oxides and propylene-1,3-diamine dioxides
wherein the remaining N positions are substituted by methyl,
hydroxyethyl or hydroxypropyl groups.
Another class of surfactants are amphoteric surfactants,
such as polyamine-based species.
Cationic surfactants can also be used in the detergent
compositions herein and suitable quaternary ammonium
surfactants are selected from mono C8-C16, preferably C10-
C14 N-alkyl or alkenyl ammonium surfactants wherein
W O 94/03570 ~` ; PC~r/US93/06836
6 ~o ~,
remaining N positions are substituted by methyl,
hydroxyethyl or hydroxypropyl groups.
Mixtures of surfactant types are preferred, more
especially anionic-nonionic and also anionic-nonionic-
cationic mixtures. Partic~larly preferred mixtures are
described in British Pate~ No. 2 040 987 and European
Published Application No. o 087 914. The detergent
compositions can comprise from 1%-70% by weight of
surfactant, but usually the surfactant is present in the
compositions herein an amount of from 1% to 30%, more
preferably from 10-25% by weight.
The detergent compositions herein also contain a builder
Builder materials will typically be present at from 5% to
80% of the detergent compositions herein. The compositions
herein should preferably be free or substantially free of
phosphate-containing builders (substantially free being
herein defined to constitute less than 1% of the total
detergent builder system), and the builder system herein
consists of water-soluble builders, water-insoluble
builders, or mixtures thereof.
Water insoluble builders can be an inorganic ion eYchAnge
material,commonly an inorganic hydrated aluminosilicate
material, more particularly a hydrated synthetic zeolite
such as hydrated Zeolite A, X, B or HS.
Preferred aluminosilicate ion-exchange materials have the
unit cell formula
Mz [(A102)Z (sio2)y] xH20
wherein M is a calcium-exchange cation, z and y are at least
6; the molar ratio of z to y is from 1.0 to 0.5 and x is at
least 5, preferably from 7.5 to 276, more preferably from 10
to 264. The aluminosilicate materials are in hydrated form
W094/03S70 2 1 4 1 ~ ~ 5 PCT/US93/06836
11 ' '
and are preferably crystalline containing from 10% to 28%,
more preferably from 18% to 22% water.
The above aluminosilicate ion exchange materials are
further characterized by a particle size diameter of from
e ~1 to 10 micrometers, preferably from 0.2 to 4 micrometers.
The term "particle size diameter" herein represents the
average particle size diameter of a given ion exchange
material as determined by conventional analytical techniques
such as, for example, microscopic determination utilizing a
scanning electron microscope. The aluminosilicate ion
exchange materials are further characterized by their
calcium ion exchange capacity, which is at least 200 mg
equivalent of CaCO3 water hardness/g of aluminosilicate,
calculated on an anhydrous basis, and which generally is in
the range of from 300 mg eq./g to 352 mg eq./g. The
aluminosilicate ion exchange materials herein are still
further characterized by their calcium ion exchange rate
which is described in detail in GB-1 429 143.
Aluminosilicate ion exchange materials useful in the
practice of this invention are commercially available and
can be naturally occurring materials, but are preferably
synthetically derived. A method for producing
aluminosilicate ion exchange materials is discussed in US
Patent No. 3 985 669. Preferred synthetic crystalline
aluminosilicate ion exchange materials useful herein are
available under the designation Zeolite A, Zeolite B,
Zeolite X, Zeolite HS and mixtures thereof. In an
especially preferred embodiment, the crystalline
aluminosilicate ion exchange material is Zeolite A and has
the formula
l2[(A12)12 (sio2)12] xH20
wherein x is from 20 to 30, especially 27. Zeolite X of
formula Na86 [(Alo2)86(sio2)lo6] - 10
W094/03570 i ~` PCT/US93/06836
~ 12
.276H20 is also suitable, as well as Zeolite HS of formula
Na6 t(Alo2)6(sio2)6] 7-5 H2O)-
Another suitable water-insoluble, inorganic builder
material is layered silicate, e.g. SKS-6 (Hoechst). SKS-6
is a crystalline layered ~siiicate consisting of sodium
silicate (Na2Si2O5). The high Ca++/Mg++ binding capacity is
mainly a cation exchange mechanism. In hot water, the
material becomes more soluble.
The water-soluble builder can be a monomeric or oligomeric
carboxylate chelating agent.
Suitable carboxylates containing one carboxy group include
lactic acid, glycollic acid and ether derivatives thereof as
disclosed in Belgian Patent Nos. 831 368, 821 369 and 821
370. Polycarboxylates containing two carboxy groups include
the water-soluble salts of succinic acid, malonic acid,
(ethylenedioxy) diacetic acid, maleic acid, diglycollic
acid, tartaric acid, tartronic acid and fumaric acid, as
well as the ether carboxylates described in German
Offenlegenschrift 2 446 686, and 2 446 687 and U.S. Patent
No. 3 935 257 and the sulfinyl carboxylates described in
Belgian Patent No. 840623. Polycarboxylates containing
three carboxy groups include, in particular, water-soluble
citrates, aconitrates and citraconates as well as succinate
derivatives such as the carbo-xymethyloxysuccinates
described in British Patent 1 379 241, lactoxysuccinates
described in Netherlands Application 7205873, and the
oxypolycarboxylate materials such as 2-oxa-1,1,3-propane
tricarboxylates described in British Patent No. 1 387 447.
Polycarboxylates containing four carboxy groups include
oxydisuccinates disclosed in British Patent No. 1 261 829,
1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane
tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
Polycarboxylates containing sulfo substituents include the
W094/03~70 2~ 6 PCT/US93/06836
13
sulfosuccinate derivatives disclosed in British Patent Nos.
1 398 421 and 1 398 422 and in U.S. Patent No. 3 936 448,
and the sulfonated pyrolysed citrates described in British
Patent No. 1 082 179, while polycarboxylates containing
phosphone substituents are disclosed in British Patent No. 1
439 000.
Alicyclic and heterocyclic polycarboxylates include cyclo-
pentane-cis, ciC, cis-tetracarboxylates, cyclopentadienide
pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-
tetracarboxylates, 2,5-tetrahydrofuran - cis
dicarboxylates, 2,2,5,5-tetrahydrofuran-tetracarboxylates,
1,2,3,4,5,6-hexane -hexacarboxylates and and carboxymethyl
derivatives of polyhydric alcohols such as sorbitol,
mannitol and xylitol. Aromatic polycarboxylates include
mellitic acid, pyromellitic acid and the phtalic acid
derivatives disclosed in British Patent No. 1 425 343.
Of the above, the preferred polycarboxylates are
hydroxycarboxylates containing up to three carboxy groups
per molecule, more particularly citrates.
Preferred builder systems for use in the present
compositions include a mixture of a water-insoluble
aluminosilicate builder such as zeolite A, or of a layered
silicate (SKS/6) and a water-solubie carboxylate chelating
agent such as citric acid.
other builder materials that can form part of the builder
system for the purposes of the invention include inorganic
materials such as alkali metal carbonates, bicarbonates,
silicates.
Other suitable water-soluble organic salts are the homo-
or co-polymeric acids or their salts, in which the
polycarboxylic acid comprises at least two carboxyl radicals
separated from each other by not more than two.carbon atoms.
W094/03~70 ~ PCT/US93/06836
~ 14 O
Polymers of this type are disclosed in GB-A-l,5s6,756.
Examples of such salts are polyacrylates of MW 2000-5000 and
their copolymers with maleic anhydride, such copolymers
having a molecular weight of ; from 20,000 to 70,000,
especially about 40,000.
In a preferred embodiment of the present invention, the
detergent compositions herein will contain a cellulase
enzyme such as described above, at levels of from 0.025% to
10% of the composition.
In another preferred enbodiment of the present invention,
the detergent compositions or detergent additives herein
will contain a soil anti redeposition or soil suspension
agent, in combination with the modified polyesters herein.
Antiredeposition and soil suspension agents suitable
herein include cellulose derivatives such as
methylcellulose, carboxymethylcellulose and
hydroxyethylcellulose, homo- or co-polymeric polycarboxylic
acids or their salts and polyaminoacid compounds. Polymers
of this type include the polyacrylates and maleic anhydride-
acrylic acid copolymers previously mentioned as builders, as
well as copolymers of maleic anydride with ethylene,
methylvinyl ether or methacrylic acid, the maleic anhydride
constituting at least 20 mole percent of the copolymer.
Polyaminoaccid compounds such as those derived from aspartic
acid are for instance disclosed in British patent
application n 9226942.2.
These materials are normally used at levels of from 0.5%
to 10% by weight, more preferably from 0.75% to 8%, most
preferably from 1% to 6% by weight of the composition.
The present detergent compositions are preferably in
granular form and more preferably in a "compact" form, i.e.
W094/03570 21 ~ PCT/US93/06836
1~
having a density, which is higher than the density of
conventional detergent compositions. The preferred density
of the compositions herein ranges from 550 to 950g/liter,
preferably 650 to 850g/liter of composition, measured at
20C.
The present "compact" form of the most preferred
compositions herein is best reflected, in terms of
composition, by the amount of inorganic filler salt;
inorganic filler salts are conventional ingredients of
detergent compositions in powder for, in conventional
detergent compositions, the filler salts are present in
substantial amounts, typically 17-35% by weight of the total
composition.
In the most preferred compositions herein, the filler salt
is present in amounts not exceeding 15% of the total
composition, preferably not exceeding 10%, most preferably
not exceeding 5% by weight of the composition.
Inorganic filler salts, such as meant in the present
compositions are selected from the alkali and alkaline-
earth-metal salts of sulfates and chlorides.
A preferred filler salt is sodium sulphate.
The present compositions will typically include optional
ingredients that normally form part of detergent
compositions. Enzymes, optical brighteners, bleaches,
bleach activators, suds suppressors, anticacking agents,
dyes and pigments are examples of such optional ingredients
and can be added in varying amounts as desired.
Enzymes such as proteases, cellulase, lipases, or amylases
are particularly desirable ingredients of the compositions
herein, in particular cellulase.
-
2i~4 16 PCT/US93/06836
The cellulase usable in the combination with the modifiedpolyesters herein may be any bacterial or fungal cellulase,
having a pH optimum of between 5 and 9.5.
Suitable cellulases are disclosed in GB-A-2 075 028; GB-A-
2 095 275 and DE-OS-24 47 83~.
Examples of such cellulases are cellulase produced by a
strain of Humicola insolens (Humicola grisea var.
thermoidea), particularly by the Humicola strain DSM 1800,
and cellulase 212-producing fungus belonging to the genus
Aeromonas, and cellulase extracted from the hepatopancreas
of a marine mullosc (Dolabella Auricula Solander).
The cellulase added to the composition of the invention
may be in the form of a non-dusting granulate, e.g.
"marumes" or "prills", or in the form of a liquid in which
the cellulase is provided as a cellulase concentrate
suspended in e.g. a nonionic surfactant or dissolved in an
aqueous medium.
Preferred cellulases for use herein are characterized in
that said cellulase they provide at least 10% removal of
immobilized radioactive labelled carboxymethyl-cellulose
according to the C14CMC-method described in EPA 350 098 at
25x10-6% by weight of cellulase protein in the laundry test
solution.
Most preferred cellulases are those as described in
International Patent Application WO 91/17243. For example,
a cellulase preparation useful in the compositions of the
invention can consist essentially of a homogeneous
endoglucanase component, which is immunoreactive with an
antibody raised against a highly purified 43kD cellulase
derived from Humicola insolens, DSM 1800, or which is
homologous to said 43kD endoglucanase.
W O 94/03~70 ~ P(~r/US93/06836
~7
The modified polyesters herein typically achieve their
cleaning benefits on cotton-containing fabrics by being
incorporated into a detergent composition including other
detersive ingredients, at a level of from 0.025% to 10% by
weight of the composition.
Alternatively, the modified polyester herein can be added
separately, to the laundry cycle, in the form of a detergent
additive; said additive posssibly containing other selected
detergent active materials, such as soil anti-redeposition
agents and co-dispersing agents, and/or cellulase enzyme; in
particular, the modified polyesters herein can be used to
pre-treat cotton-containing fabrics, before the main wash
cycle of a laundering process.
Preferred optical brighteners are anionic in character,
examples of which are disodium 4,41-bis-(2-diethanolamino-4-
anilino -s- triazin-6-ylamino)stilbene-2:21 di~ulphonate,
disodium 4, - 41-bis-(2-morpholino-4-anilino-s-triazin-6-
ylaminostilbene-2:21 - disulphonate, disodium 4,41
- bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:21 -
disulphonate, monosodium 41,411 -bis-(2,4-dianilino-s-
triazin-6 ylamino)stilbene-2-sulphonate, disodium 4,41 -bis-
~2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-
ylamino)stilbene-2,21 - disulphonate, disodium 4,41 -bis-(4-
phenyl-2,1,3-triazol-2-yl)-stilbene-2,21 disulphonate,
disodium 4,41bis(2-anilino-4-(1-methyl-2-hydroxyethylamino)-
s-triazin-6-ylamino)stilbene-2,21disulphonate and sodium
2(stilbyl-411-(naphtho-11,21:4,5)-1,2,3 - triazole-211-
sulphonate.
-
Any particulate inorganic perhydrate bleach can be used,in an amount of from 3% to 40% by weight, more preferably
from 8% to 25% by weight and most preferably from 12% to 20%
by weight of the compositions. Preferred examples of such
W O 94/03~70 PC~r/US93/06836
2 ~ 6 18
bleaches are sodium perborate monohydrate and tetrahydrate,
percarbonate, and mixtures thereof.
Another preferred separately mixed ingredient is a peroxy
carboxylic acid bleach precursor, commonly referred to as a
bleach activator, which is preferably added in a prilled or
agglomerated form in granular detergents. Peroxygen
bleaching agents are preferably combined with bleach
activators, which lead to the in situ production in aqueous
solution (i.e. during the washing process of the peroxy acid
corresponding to the bleach activator). Examples of suitable
compounds of this type are disclosed in British Patent Nos.
1586769 and 2143231 and a method for their formation into a
prilled form is described in European Published Patent
Application No. 0 062 523. Preferred examples of such
compounds are tetracetyl ethylene diamine and sodium 3, 5, 5
trimethyl hexanoyloxybenzene sulphonate, diperoxy dodecanoic
acid as described for instance in US 4 818 425 and
nonylamide of peroxyadipic acid as described for instance
in US 4 259 201 and n-nonanoyloxybenzenesulphonate (NOBS),
and acetyl triethyl citrate (ATC) such as described in
European patent application 91.870207.7.
Bleach activators are for instance normally employed at
levels of from 0.5% to 10% by weight, more frequently from
1% to 8% and preferably from 2% to 6% by weight of the
composition.
Optionally metallo-catalysts/MnPC can be used at a
preferred about 0.2 part to the total detergent composition
according to the invention.
Another optional ingredient is a suds suppressor,
exemplified by silicones, and silica-silicone mixtures.
Silicones can be generally represented by alkylated
polysiloxane materials while silica is normally used in
finely divided forms exemplified by silica~aerogels and
W094/03570 2 1 ~ . i PCT/US93/06836
~ 19 '
xerogels and hydrophobic silicas of various types. These
materials can be incorporated as particuiates in which the
suds suppressor is advantageously releasably incorporated in
a water-soluble or water-dispersible, substantially non-
~ .
surface-active detergent impermeable carrier. Alternatively
the suds suppressor can be dissolved or dispersed in a
liquid carrier and applied by spraying on to one or more of
the other components.
As mentioned above, useful silicone suds controlling
agents can comprise a mixture of an alkylated siloxane, of
the type referred to hereinbefore, and solid silica. Such
mixtures are prepared by affixing the silicone to the
surface of the solid silica. A preferred silicone suds
controlling agent is represented by a hydrophobic silanated
(most preferably trimethyl-silanated) silica having a
particle size in the range from 10 millimicrons to 20
millimicrons and a specific surface area above 50 m2/g
intimately admixed with dimethyl silicone fluid having a
molecular weight in the range from about 500 to about 200
000 at a weight ratio of silicone to silanated silica of
from about 1:1 to about 1:2.
A preferred silicone suds controlling agent is disclosed
in Bartollota et al. U.S. Patent 3 933 672. Other
particularly useful suds suppressors are the self-
emulsifying silicone suds suppressors, described in German
Patent Application DTOS 2 646 126 published April 28, 1977.
An example of such a compound is DC-544, commercially
availably from Dow Corning, which is a siloxane/glycol
copolymer.
The suds suppressors described above are normally employed
at levels of from 0.001% to 2% by weight of the composition,
preferably from 0.01% to 1% by weight. The incorporation of
the suds mofidiers is preferably made as separate
particulates, and this permits the inclusion therein of
W094/03570 PCT/US93/06836
2 ~ 6 '`' 20
other suds controlling materials such as C20-C24 fatty
acids, microcrystalline waxes and high MW copolymers of
ethylene oxide and propylene oxide which would otherwise
adversely affect the dispersibility of the matrix.
Techniques for forming such suds modifying particulates are
disclosed in the previously,~mentioned Bartolotta et al U.S.
Patent No. 3 933 672.
Fabric softening agents can also be incorporated into
detergent compositions in accordance with the present
invention. These agents may be inorganic or organic in
,type. Inorganic softening agents are exemplified by the
smectite clays disclosed in GB-A-1 400 898.
Organic fabric softening agents include the water-soluble
tertiary amines as disclosed in GB-A-l 400 898. Organic
fabric softening agents include the water-insoluble tertiary
amines as disclosed in GB-A-1514276 and EP-B-O 011 340 and
their combination with mono C12-C14 quaternary ammonium
salts are disclosed in EP-B-0 026 527 and EP-B-O 026 528 and
di-long-chain amides as disclosed in EP-B-O 242 919. Other
useful organic ingredients of fabric soft~nin~ systems
include high molecular weight polyethylene oxide materials
as disclosed in EP-A-O 299 575 and 0 313 146.
In the preferred granular detergent compositions herein,
levels of smectite clay are normally in the range from 5% to
20%, more preferably from 8% to 15% by weight with the
material being added as a dry mixed component to the
remainder of the formulation. Organic fabric softening
agents such as the water-insoluble tertiary amines or di-
long-chain amide materials are incorporated at levels of
from 0.5% to 5~ by weight, normally from 1% to 3% by weight
whilst the high molecular weight polyethylene oxide
materials and the water-soluble cationic materials are added
at levels of from 0.1% to 2%, normally from 0.15% to 1.5% by
weight. These materials are normally added to the spray
dried portion of the composition, although in some instances
W094/03570 2 1 ~ PCT/US93/06836
21
it may be more convenient to add them as a dry mixed
particulate, or spray them as a molten liquid on to other
solid components of the composition.
The compositions herein may also contain dye-transfer
inhibiting agents such as polyvinylpyrrolidones having a
molecular weight from 5 000 to 2 200, typically present in
the preferred granular detergent compositions herein, at
level such as to deliver from 5 to 500 mg/l of said
polyvinyl pyrrolidones in the wash solution. Also PVPVI
could be used as dye-transfer inhibiting agent in detergent
compositions.
The compositions of the invention may fully contain from
0.05% to 5% by weight of the composition, prefereably from
0.05% to 1% by weight, most preferably from 0.1% tot 0.5% by
weight of a chelant (heavy metal sequestrant).
A suitable chelant for inclusion in th~ detergent
compositions in accordance with the invention is
ethylenediamine-N, N'-disuccinic acid (EDDS) or the alkali
metal, alkaline earth metal, ammonium, or substituted
ammonium salts thereof, or mixtures thereof. Preferred EDDS
compounds are the free acid form and the sodium or magnesium
salt thereof. Examples of such preferred sodium salts of
EDDS include Na2EDDS and Na4EDDS. Examples of such preferred
magnesium salts of EDDS include MgEDDS and Mg2EDDS. The
magnesium salts are the most preferred for inclusion in
compositions in accordance with the invention.
Other chelants include the organic phosphonates, including
amino alkylene poly (alkylene phosphonate), alkali metal
ethane l-hydroxy diphosphonates, nitrilo trimethylene
phosphonates, ethylene diamine tetra methylene phosphonates
and diethylene triamine penta methylene phosphonates. The
phosphonate compounds may be present either in their acid
form or as a complex of either an alkali or alkaline metal
W094/03570 PCT/US93/06836
~h~ ~ 4~ 22
ion, molar ratio of said metal ion to said phosphonate
compound being at least 1:1. Such complexes are described in
US-A-4,259,200. Preferably, the organic phosphonate
compounds where present are in the form of their magnesium
salt. The level of phosphorus containing chelants in the
compositions of the invention is preferably minimised, with
their complete exclusion from the compositions being most
preferred. Other chelants suitable for inclusion herein
include amino polycarboxylate chelants such as EDTA and
HEDTA.
Makinq Process
Compositions according to the present invention can be
made via a variety of methods including dry mixing, spray
drying, agglomeration and granulation and combinations of
any of these techniques. The compositions according to the
present invention can be prepared with different bulk
densities, from conventional granular products to so-called
"concentrated" products (i.e. with a bulk density above
600g/1).
EXAMPLES
The following examples illustrate the invention and
facilitate its understanding.
The abbreviations for the individual ingredients have the
following meaning:
LAS: sodium salt of linear dodecyl benzene sulfonate
AS: sodium salt or C14-15 alkyl sulfate
TAS: sodium salt of tallow alcohol sulfate
FA45E7: fatty alcohol (C14-C15) ethoxylated with about 7
moles of ethylene oxide
-
W094/03~70 2 I ~ B PCT/US93/06836
23
FA25E3: fatty alcohol (C12-15) ethoxylated with about 3
moles of ethylene oxide
CAT: C12 alkyl trimethyl ammonium chloride
Clay: smectite clay
Zeolite A4:sodium salt of zeolite 4A with average
particle size between 1 - 10 micrometer
SRS-6: crystalline layered silicate (Hoechst)
Copolymer AA/MA: copolymer of acrylic acid and maleic acid
PAA: Polyacrylate polymer
CMC: carboxymethylcellulose
Phosphonate:sodium salt of ethylenediamine tetramethylene
phosphonic acid
EDTA: sodium salt of ethylenediamine tetra acetate
PB1: NaB02.H202
TAED: tetra acetyl ethylene diamine
PVP: Polyvinylpyrrolidone
Silicate (R=n): SiO2/Na20=n
Cellulase:43kD species according to the description
herein above
Amylase: Termamyl 60T (Novo-Nordisk)
Lipase: Lipolase lOOT (Novo-Nordisk)
Protease: Savinase 4T (Novo-Nordisk)
SSS: Suds Suppressing System (silica/silicone mixture)
The modified polyester used throughout the following
examples correspond to the species described in claim 2
herein.
The method of preparation was as follow:
The process of preparation of the selected polyester herein
includes mixing all the monomers in a round bottomed flask,
stirring at 180C, until a clear solution results, and
continue stirring for 24 hours. Then transferring the
contents of the round bottomed flask to a further single
necked round bottomed flask (typically 1 litre), heating
under vacuum for 45 minutes at 200C, removing from flask
and cooling. A clear glass solid is obtained, which is then
crushed gently to be used.
W094/03570 r PCT/US93/06836
2 ~ ,6 24
Example 1:
The following detergent composition was prepared.
.% by weight
LAS 9
TAS 3
FA45E7 2.5
ZEOLITE 33
SODIUM CITRATE 21
SODIUM CARBONATE 3
SODIUM SULPHATE 5
PAA 3.5
PROTEASE 1.6
CELLULASE o.5
MODIFIED POLYESTER 0.5
Testinq ~rocedure:
A bundle of soiled fabrics containing fabrics which were
stained with a range of stains such as particulate soils,
greasy soils, enzymatic soils and bleachable soils on cotton
and polycotton fabrics were washed in a compact detergent
with the formulation as shown. One half of each bundle was
washed with detergent composition as shown and the other
half was washed with the same composition without the
cellulase. The testing was carried out at 40C in water of
25H (German hardness). All testing was repeated 4 times.
Stain removal was evaluated relative to a reference stain of
each type previously washed under identical conditions. The
formulation used for the washing of the reference fabrics
contained no modified polyester or cellulase.
Stain removal was evaluated using the well known schefe
scale of panel score units determined by two judges as
follows:
W O 94/03570 ~ P(~r/US93/06836
1 = I think there is a difference between the two stains.
2 = There is certainly a difference between the two stains.
3 = There is a big difference between the two stains.
4 = There is a black and white difference between the two
stains.
The average data compared to the reference fabric was
calculated. The results on the greasy stains on polycotton
material were as follows.
8tain Preference for exam~le 1
compositio~
versus refere~oe
Dirty motor oil +1.1*
Make up +0.5*
* Statistically significant
BX~nP1e 2:
A detergent of formulation similar to that described in
example 1 was used to wash a bundle of soiled fabrics which
were stained with a range of soils of particulate, greasy,
enzymatic and bleachable types. One half of each bundle was
washed in the formulation described in example 1, the other
half of the bundle was washed in the identical formula
without modified polyester. The conditions used for washing
these bundles were 40C and 25H water. 4 replicates of
each test were carried out and the samples were graded
accordingly to the % stain removal. This was calculated
using the McBeth (colour spectrometer) using the
conventional 1 a b system. The tests were repeated using
W094/03~70 '~ PCT/US93/06836
~ 26
different levels of modified polyesters between 0.025% and
10% by weight of the detergent composition.
The results are detailed below:
~QVel o. 025%~` 0.1% 0.5% 10%
8tain reDIov
aver~g~
greasy o~ 52~ 64% 69% 73%
polycotton
Typical greasy stains considered include dirty motor oil,
shoe polish and make up.
Figures quoted are average %stain removal enhancement above
the reference product.
Ex~mDle 3:
Enhanced greasy stain removal by the combination of modified
polyester and carboxy methyl cellulose.
Polycotton swatches were pretreated a number of times with a
detersive formulation containing the carboxy methyl
cellulose (CMC). The purpose of this was to give the fabric
a history of CMC deposition onto the cotton of the
polycotton. The polycotton was then dryed and stained with
dirty motor oil (DMO). One half of the stains was washed in
a detersive formulation similar to that described in example
one to act as a reference whilst the other half was washed
in the same formulation only containing the modified
polyester herein.
The swatches were graded ~y calculating the % stain removal
from each tracer using the hunter colour lab system. All
data was also compared to swatches which had been treated in
W094/03570 ~ f~ PCT/US93/06836
27
exactly the same way as described above only with a
detersive formulation containing soil release polymer and no
CMC. The results are described below.
Reference ModifiedCMC/modified
(CMC onlY) polyester~olvester
only
Average %
stain removal 21% 43% 79%
Test conditions 40~C/25H water - 4 replicates
ExamPle 4:
Pretreatment solution compositions containing the modified
polyester herein were prepared as shown below
Formulation: 1 2 3 4 5 6
Modified polyester 0.5 1.0 3.0 5.0 6.0 6.0
LAS 40 50 75 75
FA45E7 13 17 17 - 30 22
~aleic/acrylic 46.5 32 5.0 20 64 72
copolymer
All the solutions were used to pretreat polycotton fabrics
prior to washing which had previously been stained with a
range of greasy type stains such as dirty motor oil, sun tan
lotion make up and lipstick.
All fabrics which had previously been treated with any of
the compositions described showed marked improvement in the
stain removal from the polycotton when compared to an
unpretreated stain.
The following compact detergent compositions were also
prepared:
W094/03~70 PCT/US93/06836
28
COMPACT DETERGENT COMPOSITIONS
(all levels in % by wei~ht)
Examples: V VI VII VIII IX X XI XII
LAS 11.00 -- 6.50 -- 6.50 -- -- --
TAS -- -- 3.25 3.90 2.25 -- -- --
AS 5.00 ~12.00 -- -- -- 6.00 6.50 6.50
FA45E7 4.00 1.00 2.20 6.00 2.20 3.00 -- --
FA25E3 -- -- -- -- -- 6.00 7.00 7.00
CAT -- -- -- 2.45 -- -- -- --
Tallow glucose amide -- 10.00 -- -- -- -- -- --
Na citrate/citric 18.00 5.00 12.00 15.00 12.00 4.00 4.00 4.00
Zeolite 4A 32.00 15.00 16.00 20.00 14.00 13.00 13.00 12.50
SKS-6 -- 12.00 -- -- -- 12.00 12.00 12.00
Copolymer AA/MA 4.10 5.00 3.50 3.50 -- 5.00 3.00 3.00
Polypeptide 4.00 -- 2.00 2.00
Phosphonate 0.19 1.00 -- -- 1.00 -- -- --
EDTA -- -- 0.32 0.32 -- -- -- --
Na carbonate/ 3.00 2.50 10.00 10.00 10.00 9.00 10.00 10.00
bicarbonate
Silicate (R2) 3.00 2.00 2.50 2.50 2.50 3.50 3.50 3.50
CMC ~~ 0-50 ~~ ~ 0-50 0-30
Clay -- -- 8.60 8.60 -- --- -- --
PB1 -- -- 11.50 -- 12.00 -- 12.00 12.00
Percarbonate -- -- -- 12.00 -- 23.00 -- --
TAED -- -- 3.20 -- 4.00 6.00 4.00 4.00
Protease 1.20 1.60 1.40 1.40 1.40 1.40 1.40 1.40
Cellulase 0.50 -- 0.30 0.10 0.10 0.10 0.10 0.10
Lipase 0.40 0.30 0.30 0.30 0.30 0.30 0.30 0.30
Amylase 0.20 0.30 -- -- -- -- -- --
Na Sulfate 2.00 2.50 3.50 3.50 4.00 3.50 4.00 4.00
PVP -- 0.50 1.00 -- -- -- -- --
PVNO ---- ---- ---- ---- ---- ---- ---- 50
SSS 0.40 0.40 0.50 0.50 0.50 0.50 0.50 0.50
Modified polyester 0.30 0.40 0.30 0.50 0.50 0.50 0.50 0.50
Minors + water Balance to 100%
W094/03570 PCT/US93/06836
29 ~ 6
j
Example 5
Enhanced grease stain removal by the combination of
r modified SRP and C25E3 (=AE3 in this example).
The combination of SRP and C25E3 has been tested vs
products available such as Skip Micro System (SMS) and Skip
Regular.
The following remarkable results are obtained concerning
greasy stains removal :
a) SMS
Gre~sy St~ln- Remo~l CottonPolyco~ton Polyes~er
Referenc- S~S - equ~l do--ge 140g
ArleL Ultr--D t 0.325RP - 40 C -0.40 -0.34 -1.02s
Arl-l Ultr--D + 0.32SRP + 4.72AE3-40 C -0.16 0.21 0.06
Arlel Ultr--D + 52 AE7 - 60 C -1.13s -1.66s n/e
Arl-l Ultr--D + 0.32 SRP - 60 C -1.15s -1. 708 -1.60s
Arlel Ultr--D + 82 A~3 nll A~7 - 60 C -0.41 0.01 n/-
Arlel Ultrn-D + 0.325RP + 4.72AE3-60 C -0.10 -0.49s -0.44s
b) Skip Regular
Gre~y St ln- Remo~l CottonPolycotton PoLyester
Reference Sklp Regulnr - 215g ~s 140g
Arlel Ultr~-D + 4.72 AE3 - 40 C -0.57 -0.71s -1.86s
Arlel Ultre-D + 0.32 SRP + 4.72 AE3-40 C-0.26 0.23 0.83s
W094/03~70 , ~ , PCT/US93/06836
4~G 30
The comparison with Skip Regular clearly shows that SRP +
AE3 gives better performance than AE3 alone. This is not the
case with SMS.
The addition of AE3 a,ls,,o, improves the performance on
grease. AE3 and SRP added ~ogether to Ariel Ultra-D either :
I) boost AE3 performance (vs Skip Regular) or,
II) show no benefi~ vs AE3 alone (vs SMS).
Exam~le 6
SRP Synergy with nonionic C25E3 (=AE3).
Backqround
The polypropylene material of the granulette is a very
hydrophobic surface to which oily soils such as DMO are
attracted and stuck fast.
Conclusions
1) The effect of SRP on the cleaning of the granulette is
dependent on the ratio of SRP to Surfactant. A low ratio of
SRP to surfactant results in an improved cleaning. High
SRP:surfactant gives worse cleaning.
0.025g SRP/Sg Ariel Ult. 0.05g SRP/3g Ariel Ult.
SRP:NI surfactant ratio (1:6 0:6) (1:2 0:2)
Grade of polyprop Clean Dirty Very Dirty Dirty
2) The critical factor in this phenomenon is the presence
and type of Nonionic. Surfactant and water alone gives a
dirty granulette, as does SRP and water alone.
SRP level ppm 0 50 100 0 0
Product level ppm 0 0 0 6000 10000
Fabric grade Very Dirty Dirty Very Dirty Dirty Dirty
W094/03~70 21 ~i ~1 B PCT/US93/06836
3) Significantly, SRP and a nil nonionic Ariel also give a
dirty fabric.
SRP level ppm 0 50 0 50
Nonionic level ppm . O 0 500 500
Product level ppm 10000 10000 10000 10000
Fabric grade Dirty Dirty Dirty Clean
4) Use of C25AE3 nonionic results in better cleaning and a
further boost to the SRP effect.
SRP level ppm 0 50
Nonionic level ppm 500 AE3 500 AE3
Product level ppm 10000 10000
Fabric grade Clean Very Clean
5) The synergy with nonionic extends to an improved
cleaning of Shoe Polish when both SRP and C25E3 are used in
the pretreatment and washing of polyester fabric.
Ariel Ultra Ariel 45E7 Ariel Ariel + 0.5%
3.26% 45E7 +0.5% SRP +3.26% C25E3 SRP + 3.26% C25E3
% Removal of
Shoe Polish 29 28 35 44 (si~nificant)
In result there is a synergistic cleaning benefit when SRP
and nonionic (AE3) are used together wherein the benefit is
dependant upon the ratio SRP over nonionic (AE3) as outlined
below.
SRP:nonionic ratioBenefit
1:2 No
1:6 Yes
1:10 Yes
1:20Yes (but slightly reduced)
W094/03~70 PCT/US93/06836
2~ 32
Example 7
Numerous attemps have been made to thicken C25E3 with
various different detergent ingredients with limited
success. The use of modified soil release polymers according
to this invention provides~a method of thickening C25E3.
By mixing C25E3 with soil release polymer solution in the
ratio of one part C25E3 to 0.3 parts soil release polymer at
room temperature with mild stirring one forms a thick white
viscous paste which does not separate upon standing.
- Different soil release polymers may provide the same
thickening effect.
- Higher levels of soil release polymers produce a thicker
paste.
Ratio
C25E3Soil release Thickening effect
polymer
3 0.3 None
2 0.3 Slightly thicker but separates
on se~n~ing
1 0.3 Thick stable white paste
1 2.0 Thick stable white paste
Conditions
Room tempature, mild stirring
This above shows the thickening of nonionic surfactant
C25E3 by the addition of a soil release polymer solution as
described in this application. This provides the formulator
with a potentially effective method by which C25E3 can be
processed into granular detergents.
