Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
1314t.~
- l - C.3267
DETERGENT COMPOSITIONS
T~CHNICAL FIELD
The present invention relates to fabric washing
detergent compositions built with zeolite and having
improved antiredeposition properties.
BACKGROUN~ AND PRIOR ART
Redeposition of soil removed from washed articles
back onto the articles themselves is a well-known problem
which is of particular significance with textile fabrics,
and many solutions to this problem have been suggested.
Classically, sodium carboxymethyl cellulose was
incorporated into fabric washing compositions, and that
compound is still used today. More recently, copolymers
of ethylene or vinyl methyl ether and maleic anhydride,
copolymers of acrylic acid and maleic anhydride, and
homopolymers of acrylic acid have been suggested in the
patent literature; see, for example, GB l 269 848
(Procter & Gamble) and GB 1 460 893 (Unilever).
1 ~ 1 4 ~ 2 - C.3267
- EP 219 048A (BASF) discloses the use of graft
copolymers of polyalkylene oxide with vinyl acetate as
greying inhibitors in the washing and post-wash treatment
of synthetic textile fabrics.
We have now discovered that detergent compositions
built predominantly or wholly with zeolite and containing
a graft copolymer of this type in conjunction with an
acrylic and/or maleic polymer exhibit surprisingly
enhanced soil suspension (antiredeposition) properties on
polyester and polyester/cotton fabrics. A corresponding
improvement is not observed with phosphate-built
compositions.
~FINITION OF THE INVENTION
The present invention provides a detergent
composition comprising:
(a) from 2 to 50% by weight of a detergent active
system comprising one or more anionic, nonionic,
cationic, zwitterionic or amphoteric surfactants;
(b) from 10 to 60% by weight of crystalline or
amorphous alkali metal aluminosilicate;
(c) from 0.5 to 5~ by weight of a polycarboxylate
polymer comprising (meth)acrylate units and/or maleate
units; and
~d) from 0.1 to 3% by weight of a graft copolymer
of (i) polyethylene, polypropylene or polybutylene oxide
with (ii) vinyl acetate (optionally partially saponified)
in a weight ratio of (i) to (ii) of from 1:0.2 to 1:10.
- 3 - C.3267
1314~
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to detergent
compositions containing four specified ingredients - a
surfactant system, an aluminosilicate builder, a
polycarboxylate polymer, and a graft copolymer - which
may additionallv contain any other conventional detergent
ingredients, for example, other builders, bleach systems,
antifoam systems, fluorescers, inorganic salts, and other
materials well known to those skilled in formulating
detergents. The compositions of the invention may take
any suitable form, for example, powders, liquids or bars.
The surfactant system
The total amount of detergent-active material
(surfactant) in the compositions of the invention is from
2 to 50~ by weight, and is preferably from 5 to 40% by
weight.
The compositions of the invention may contain one or
more soap or non-soap anionic, nonionic, cationic,
amphoteric or zwitterionic surfactants, or combinations
of these. Many suitable detergent-active compounds are
available and are fully described in the literature, for
example, in "Surface-Active Agents and Detergents",
Volumes I and II, by Schwartz, Perry and Berch.
The preferred detergent-active compounds that can be
used are soaps and synthetic non-soap anionic
surfactants and nonionic surfactants.
~ 3 - 4 ~ C.3267
Synthetic anionic surfactants are well known to
those skilled in the art. Examples include alkylbenzene
sulphonates, particularly sodium linear alkvlbenzene
sulphonates having an alkyl chain length of C8-C15;
primary and secondary alkyl sulphates, partic~larly
sodium C12-C15 primary alcohol sulphates; olefin
sulphonates; alkane sulphonates; dialkyl
sulphosuccinates; and fatty acid ester sulphonates.
Suitable nonionic detergent compounds which may be
used include in particular the reaction products of
compounds having a hydrophobic group and a reactive
hydrogen atom, for example, aliphatic alcohols, acids,
amides or alkyl phenols with alkylene oxides, especially
lS ethylene oxide either alone or with propylene oxide.
Specific nonionic detergent compounds are alkyl ~C6 22)
phenol-ethvlene oxide condensates, the condensation
products of linear or branched aliphatic C8 20 primary or
secondary alcohols with ethylene oxide, and products made
by condensation of ethylene oxide with the reaction
products of propylene oxide and ethylenediamine. Other
so-called nonionic detergent compounds include long-chain
tertiary amine oxides, tertiary phosphine oxides, and
dialkyl sulphoxides.
Especially preferred are the primary and secondary
alcohol ethoxylates, especially the C12 15 primary and
secondary alcohols ethoxylated with an average of from 5
to 20 moles of ethylene oxide per mole of alcohol.
It may also be desirable to include one or more
soaps of fatty acids. These are preferably sodium soaps
derived from naturally occurring fatty acids, for
- example, the fatty acids from coconut oil, beef tallow,
sunflower or hardened rape seed oil.
1 3 i '~ C.3267
A preferred type of detergent composition suitable
for use in most automatic fabric washing machines
contains anionic and nonionic surfactant together in a
weight ratio of at least 0.67:1, preferably at least 1:1,
and more preferably within the range of from 1:1 to 10:1.
Soap may also be present if desired.
The aluminosilicate builder
The detergent compositions of the invention contain
from 10 to 60% by weight, preferably from 15 to 50% by
weight, of crystalline or amorphous alkali metal
aluminosilicate builder.
The alkali metal (preferably sodium)
aluminosilicates used in the compositions of the
invention may be either crystalline or amorphous or
mixtures thereof, and they have the general formula:
0.8-1.5 Na2O. Al2O3. 0.8-6 SiO2.
These materials contain some bound water and are
required to have a calcium ion exchange capacity of at
least about 50 mg CaO/g. The preferred sodium
aluminosilicates contain 1.5-3.5 SiO2 units (in the
formula above). Both the amorphous and the crystalline
materials can be prepared readily by reaction between
sodium silicate and sodium aluminate, as amply described
in the literature.
1 31 41 ~ - 6 - C.3267
Suitable crystalline sodium aluminosilicate
ion-exchange detergency builders are described, for
example, in GB 1 473 201 (Henkel) and GB 1 429 143
(Procter & Gamble). The preferred sodium
aluminosilicates of this type are the well-known
commercially available zeolites A and X, and mixtures
thereof. Especially preferred is zeolite 4A.
Other builders may also be included in the
compositions of the invention if necessary or desired:
suitable organic or inorganic water-soluble or
water-insoluble builders will readily suggest themselves
to the skilled detergent formulator. Inorganic builders
that may be present include alkali metal (generally
sodium) ortho-, pyro- and tripolyphosphate, and
carbonate; while organic builders include
nitrilotriacetates, citrates and
carboxymethyloxysuccinates. This list is not intended
to be exhaustive. The total level of detergency builder
is generally within the range of from 20 to 80% by
weight.
According to a preferred embodiment of the
invention, the compositions contain less than 10% by
weight of inorganic phosphate builders, and are more
preferably substantially free of inorganic phosphate.
1 31 4 1 ~
- 7 - C.3267
The polvcarboxvlate polymer
The compositions of the invention also contain from
0.5 to 5~ by weight, preferably from 1 to 3~ by weiqht,
of a polycarboxylate polymer containing (meth)acrylate
and/or maleate units. These anionic polymers may be in
acid form or in wholly or partially neutralised salt
form. Preferred polymers are homopol$~mers and copolymers
of acrylic acid. Of especial interest are
polyacrylates, acrylic/maleic acid copolymers, and
acrylic phosphinates.
Suitable polymers, which may he used alone or in
combination, include the following:
Polymer type Trade name Su~plierAverage
m.wt.
Polyacrylate Versicol* Allied 3500
E5 Colloids
Polyacrylate Versicol* Allied27 000
E7 Colloids
Polyacrylate Versicol* Allied70 000
E9 Colloids
Polyacrylate Narlex* National5000
LD 30 Adhesives
Polyacrylate Narlex* National25 000
LD 34 Adhesives
131413~
- ~ - C.3267
Polymer type Trade name SupPlier Average
m.wt.
Polyacrylate Acrysol* Rohm & 1000
LMW-10 Haas
Polyacrylate Acrysol* Rohm & 2000
LMW-20 Haas
Polyacrylate Acrysol* Rohm & 4500
LMW-45 Haas
Polyacrylate Acrysol* Rohm & 60 000
Al-~ Haas
Polyacrylate Sokalan* BASF 2500
PA-20
Polyacrylate Sokalan* BASF 15 000
PA-40
Polyacrylate Sokalan* BASF 70 000
PA-70
Polyacrylate Sokalan* BASF 250 000
PA-110
1~141~
- 9 - C.3267
PolYmer type Trade name SupPlier
Ethylene/ EMA* Monsanto
5 maleic acid
Methyl vinyl Gantrez* GAF
ether/maleic acid AN 119 Corporation
10 Acrylate/ Sokalan* BASF
maleate CP5, CP7
Acrylic DKW* National
phosphinate Adhesives
Acrylic Belsperse* Ciba-Geigy
phosphinate
*denotes Trade Mark
The qraft copolymer
The graft copolymers used in the compositions of the
present invention are described and claimed in EP 219 048A
(BASF). They are obtainable by grafting a polyalkylene
oxide of molecular weiqht (number average) 2000 - 100 000
with vinyl acetate, which may be partially saponified, in a
weight ratio of polyalkylene oxide to vinyl acetate of 1:0.2
to 1:10. The vinyl acetate may, for example, be saponified
to an extent of up to 15%. The polyalkylene oxide may
contain units of ethylene oxide, propylene oxide and/or
butylene oxide; polyethylene oxide is preferred.
1 s 1 '~ 1 ~3")
- 10 - C.3267
Preferably the polyalkylene oxide has a
number-average molecular weight of from 4000 to 50 000,
and the weight ratio of polyalkylene oxide to vinyl
acetate is from 1:0.5 to 1:6. Especially preferred are
polymers derived from polyethylene oxide of molecular
weight 2000-50 000 and having a weight ratio of
polyethylene oxide to vinyl acetate of from 1:0.5 to 1:6.
A material within this definition, based on
polyethvlene oxide of molecular weight 6000 (equivalent
to 136 ethylene oxide units), containing approximately
3 parts by weight of vinyl acetate units per 1 part by
weiqht of polyethylene oxide, and having itself a
molecular weight of 24 000, is commercially available
from BASF as Sokalan (Trade Mark) HP22.
The polymers are present in the compositions of the
invention in amounts of from 0.1 to 3% by weight,
preferably from 0.3 to 1% by weight.
Optional ingredients
As well as the four ingredients - surfactant
system, detergency builder, polycarboxylate polymer and
graft copolymer - already specified, the compositions
of the invention may contain any other non-interfering
ingredients known to be suitable for incorporation into
detergent compositions.
For example, the detergent compositions according to
the invention may suitably contain a bleach system.
Preferred are peroxy bleach compounds, for example,
inorganic persalts or organic peroxyacids, which may be
employed in conjunction with activators to improve
t3141~
~ C.3267
bleaching action at low wash temperatures. The skilled
detergent worker will have no difficulty in applying the
normal principles to choose a suitable bleach system.
Other materials that may be present in the detergent
compositions of the invention include sodium silicate,
fluorescers, inorganic salts such as sodium sulphate,
enzymes, lather control agents or lather boosters as
appropriate, pigments, and perfumes. Again, this list
is not intended to be exhaustive.
Preparation of detergent compositions
Detergent compositions of the invention may be
prepared by any suitable method. Deterqent powders are
suitably prepared by spray-drying a slurry of compatible
heat-insensitive components, and then spraying on or
postdosing those ingredients unsuitable for processing
via the slurry. ~he skilled detergent formulator will
generally have no difficulty in deciding which components
should be included in the slurry and which should be
postdosed or sprayed on.
The graft copolymer is available as a solution
having a solids content of 20% which is stable at slurry
processing temperatures and can be incorporated in the
slurry without problems, provided that the pH is
maintained below 12.
Similarly, the polycarboxylate polymer can nor~.ally
be included in the slurry.
The invention is further illustrated by the
following non-limiting Examples, in which parts and
percentages are by weight unless otherwise stated.
1 3 1 4 1 ~8
- 12 ~ C.3267
EXAMPLES
Examples 1 to 3
Detergent compositions were prepared to the
following formulation by conventional slurry-making,
spray-drying and postdosing techniques:
%
Sodium linear alkylbenzene sulphonate 9.0
Nonionic surfactant 7EO 4.0
Zeolite 4A (hydrated basis) 24.0
15 Sodium alkaline silicate 5.0
Sodium sulphate 19.3
Sodium carbonate 7.0
Sodium carboxymethvlcellulose 0.5
Fluorescer 0.7
20 Sodium perborate monohydrate 8.0
Tetraacetylethylenediamine (76% granules) 3.0
F.nzyme granules 0.5
Sodium polyacrylate (see below) 0 or 2.0
Graft copolymer (Sokalan HP22) 0 or 0.5
25 Water and minor ingredients to 100.0
The sodium polyacrylate polymers used were Sokalan
PA 20, PA 40 and PA 110 (see previously). The polymers
present in the various compositions prepared are shown in
Table 1 below.
.:. , . :
- 13 - C.3267
The soil suspension (antiredeposition) properties of
the compositions were compared by means of the following
procedure. Two new, clean, unwashed polyester test
cloths were washed together with five soiled cloths in a
tergotometer at 60C in 50 (French) hard water ~Ca:Mg
ratio 4:1) at a liquor to cloth ratio of about 50:1, the
wash liquor containing 4 g/l of the detergent composition
under test. The soiled cloths carried a range of
different soils such as clay, oil, fat, proteinaceous,
and ink. The wash cycle was repeated a further nine
times, the soiled cloths being replaced by new soiled
cloths (with the same range of soils) for each wash
cycle.
The reflectance of the two new cloths was measured
before washing, and after the tenth wash cycle. The
reduction in reflectance of the washed fabrics after ten
washes is shown in Table 1; the lower the reduction in
reflectance, the less redeposition had occurred.
It will be seen that Compositions 1 to 3 illustrates
the invention while Compositions A to E are comparative.
The graft copolymer Sokalan HP22 had little effect on its
own on redeposition. The polyacrylates became
increasingly effective with increasing molecular weight
at reducing redeposition, but for each of them the effect
was considerably enhanced by the presence of the graft
copolymer.
; . . .:.: -
1 31 ~
- 14 - C.3267
Table 1
Example Polymers Reflectance
chanqe
(delta R460*)
A no polymers -6.0
B 0.5% Sokalan HP22 -7.1
C 2.0% Sokalan PA 20 -6.0
10.5% Sokalan HP22 + 2.0% Sokalan PA 20 -4.0
D2.0% Sokalan PA 40 -4.3
20.5% Sokalan HP22 + 2.0% Sokalan PA 40 -2.3
E2.0% Sokalan PA 110 -2.3
30.5% Sokalan HP22 + 2.0% Sokalan PA 110 -1.6
Examples 4 and 5
The procedure of Examples 1 to 3 was repeated using
acrylic/maleic copolymers instead of the sodium
polyacrylates. These were Sokalan CP5 and Sokalan CP7,
which differ in the proportions of acrylic units and
maleic units they contain: Sokalan CP5 contains about
70% by weight of acrylic units and 30% by weight of
maleic units, while Sokalan CP7 contains about 50% by
weight of each.
1 3 ~ $
- 15 - C.3267
The compositions prepared, and the results obtained,
are shown in Table 2 below, the controls A and B being
shown again for comparison. Ag2in, numbered
compositions illustrate the invention while those
represented bv letters are comparative. The two
acrylate/maleate copolymers were both quite effective at
reducinq redeposition, but for each of them the effect
was considerably enhanced by the presence of the graft
copolymer.
Table 2
15 Example Polymers Reflectance
change
(delta R
4~0
20 A no polymers -6.0
B 0.5% Sokalan HP22 -7.1
F 2.0% Sokalan CP 5 -3.4
40.5% Sokalan HP22 + 2.0% Sokalan CP 5 -2.6
G2.0% Sokalan CP 7 -4.0
50.5% Sokalan HP22 ~ 2.0% Sokalan CP 7 -3.2
.
-
1 3 1 ~ 1 ~ 8
- 16 - C.3267
Comparative Examples H to V
The procedure of Examples 1 to 5 was repeated using
a phosphate-built detergent composition having the
following formulation:
Parts
Sodium linear alkylbenzene sulphonate9.0
10 Nonionic surfactant 7EO 4.0
Soap 1.1
Sodium tripolyphosphate 30.0
Sodium alkaline silicate 6.0
Sodium sulphate 12.9
15 Sodium carbonate S.0
Sodium carboxymethylcellulose 0.6
Fluorescer 0.3
Sodium perborate tetrahydrate 18.0
Enzyme granules 0.5
20 Lather contxol granules 1.3
Polycarboxylate polymer (see below)0 or 2.0
Graft copolymer (Sokalan HP22) 0 or 0.5
Water and minor ingredients to 100.0
The compositions prepared, and the reflectance
reduction results obtained, are shown in Table 3 below.
- 17 - C.3267
Table 3
Example PolYmers Reflectance
change
(delta R460*)
H no polymers -2.6
J 0.5% Sokalan HP22 -1.5
L 2.0% Sokalan PA 40 -2.0
M0.5% Sokalan HP22 + 2.0% Sokalan PA 40 -2.0
N2.0~ Sokalan PA 70 -2.8
P0.5% Sokalan HP22 + 2.0% Sokalan PA 70 -1.8
Q2.0% Sokalan PA 110 -2.7
P0.5% Sokalan HP22 + 2.0% Sokalan PA 110 -1.8
S2.0% Sokalan CP 5 -2.2
T0.5% Sokalan HP22 + 2.0% Sokalan CP 5 -1.8
U2.0% Sokalan CP 7 -3.0
V0.5% Sokalan HP22 + 2.0% Sokalan CP 7 -2.0
In all cases, the combination of polymers was
inferior to the graft copolymer alone, showing that the
benefit that characterises the present invention is not
observed in detergent compositions built with sodium
tripolyphosphate.
1 ~1 4 I ~
- 18 - C.3~7
Examples 6 and 7
The procedure of ~,xamples 1 and 5, with the same
zeolite-built detergent composition and the same
polymers, was repeated using polyester/cotton test
cloths. The results were as shown in Table 4 below.
Table 4
Example Polymers Reflectance
change
~delta R460*)
W no polymers -5.6
X 0.5% Sokalan HP22 7.5
Y 2.0% Sokalan PA 20-5.1
60.5% Sokalan HP22 + 2.0% Sokalan PA 20-2.4
z2.0% Sokalan CP 7 -4.5
70.5% Sokalan HP22 + 2.0% Sokalan CP 7-3.9
It will be seen that combinations of these two
representative polycarboxylate polymers with the graft
copolymer gave antiredeposition benefits on
polyester/cotton fabric.
