Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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DETERGENT COMPOSITIONS
TECHNICAL FIELD
The present invention relates to detergent
compositions, especially particulate detergent compositions,
suitable for the laundering of fabrics in domestic or
commercial washing machines, containing a detergency builder
system which is a combination of a specific aluminosilicate
and a polycarboxylate polymer.
BACKGROUND AND PRIOR ART
Detergent compositions for heavy-duty fabric washing
conventionally contain materials - detergency builders
- to lower the concentration of calcium water hardness
ions in the wash liquor and thus to give good detergency
in hard water as well as in soft water.
Alkali metal aluminosilicate ion-exchangers,
especially the crystalline sodium aluminosilicate zeolite
4A, are now well-known replacements for the inorganic
phosphates traditionally used as detergency builders in
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fabric washing detergent~. It is also well known that
zeolites show certain deficiencies in detergency
building, as compared with phosphates, and that
supplementary building power is generally desirable. In
many zero-phosphate premium detergent powders now on the
European market, homo- or copolymers of acrylic acid are
included for this purpose.
Detergent compositions built with crystalline
aluminosilicate (zeolite) and also containing
polyacrylate or acrylic/maleic copolymer are disclosed, for
example, in EP 221 777A, EP 240 356A, EP 270 240A,
EP 340 013A, EP 358 473A, EP 367 339A, EP 390 251A and
EP 352 135A (Unilever); EP 215A, EP 63 399A, EP 66 915A,
EP 130 640A and EP 137 669A (Procter & Gamble);
EP 228 OllA and EP 291 869A (Henkel); and
EP 229 671A (Kao).
Water-softening or detergency building granules based
on zeolites and polycarboxylate polymers are disclosed in
EP 184 794A, EP 243 908A and EP 344 629A (Henkel),
EP 289 767A and EP 289 768A (Degussa), GB 1 568 420 and
GB 2 210 055A (Colgate), DE 3 316 513A (Benckiser), and
DE 3 707 806A (Dispo-Kommerz AG).
EP 384 070A (Unilever) describes and claims a novel
zeolite P (maximum aluminium zeolite P, or zeolite MAP)
having an especially low silicon to aluminium ratio, not
greater than 1.33 and preferably not greater than 1.15.
This material is demonstrated to be a more efficient
detergency builder than conventional zeolite 4A.
The present invention is based on the discovery that
the novel combination of zeolite MAP and polycarboxylate
polymer provides an especially effective detergency builder
system.
~3405CA1 2062332
DEFINITION OF THE INVENTION
The present invention provides a detergent composition
suitable for fabric washing, comprising:
(i) from 5 to 40 wt% of one or more detergent-active
compounds selected from anionic, nonionic, cationic,
amphoteric and zwitterionic detergent-active compounds and
combinations thereof,
(ii) a detergency builder composition comprising:
(a) zeolite P having a silicon to aluminium ratio not
exceeding 1.33 (hereinafter zeolite MAP), in an amount
of from 10 to 45 wt% (anhydrous basis) based on the
whole composition,
(b) a polycarboxylate polymer in acid and/or a salt
form, in an amount of from 2 to 6 wt% based on the
whole composition.
the weight ratio of (a) to (b) being within the range of
from 4.5:1 to 9.5:1.
,. . ,~, ~
..
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DETAILED DESCRIPTION OF TRE INVENTION
The deter~ent composition
The detergent composition of the invention contains, as
essential components, a detergent-active compound, and a
detergency builder system.
The deter~ent-active compound
The detergent compositions of the in~ention will
contain, as essential ingredients, one or more
detergent-active compounds (surfactants) which may be chosen
from soap and non-soap anionic, cationic, nonionic,
amphoteric and zwitterionic detergent-active compounds, and
mixtures thereof. Many suitable detergent-active compounds
are available and are fully described in the literature, for
example, in "Surface-Ac'ive 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 and nonionic
compounds.
Anionic surfactants are well-known to those skilled in
the art. Examples include alkylbenzene sulphonates,
particularly linear alkylbenzene sulphonates having an alkyl
chain length of C8-C15; primary and secondary alkyl
sulphates, particularly C12-C15 primary alkyl sulphates;
alkyl ether sulphates; olefin sulphonates; alkyl xylene
sulphonates; dialkyl sulphosuccinates; and fatty acid
ester sulphonates. Sodium salts are generally preferred.
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Nonionic surfactants that may be used include the
primary and secondary alcohol ethoxylates, especially the
aliphatic C12-C15 primary and secondary alcohols ethoxylated
- with an average of from 3 to 20 moles of ethylene oxide per
mole of alcohol; and alkylpolyglycosides.
Preferred detergent-active systems, suitable for
compositions intended for use in automatic fabric washing
machines, comprises anionic non-soap surfactant, or
nonionic surfactant, or combinations of the two in any
ratio, optionally together with soap.
The total amount of detergent-active compounds present
may suitably lie in the range of from 5 to 40 wt%.
The deterqency builder system
The detergency builder system of the invention contains
two essential components: zeolite MAP and a polycarboxylate
polymer.
Zeolite MAP is defined as an alkali metal
aluminosilicate of the zeolite P type having a silicon to
2s aluminium ratio not greater than 1.33, preferably not
greater than 1.20, more preferably not greater than 1.15 and
most desirably not greater than 1.10.
Zeolite MAP and its use in detergent compositions are
described and claimed in EP 384 070A (Unilever).
The silicone to aluminium ratio is preferably within
the range of from 0.9 to 1.33, and more preferably within
the range of from o.9 to 1.2.
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I
Especially preferred is zeolite MAP having a silicon to
aluminium ratio not greater than 1.07.
- Zeolite MAP generally has a calcium binding capacity of
at least 150 mg CaO per g of anhydrous aluminosilicate.
Although zeolite MAP like other zeolites contains water
of hydration, for the purposes of the present invention
amounts and percentages of zeolite are expressed in terms of
the anhydrous material.
The second essential component of the detergency
builder system of the invention is a polycarboxylate
polymer. This term is used to mean a water-soluble
polymeric polycarboxylic acid, a water-soluble salt of a
polymeric polycarboxyllc acid, or a mixture of these.
Preferred polycarboxylate polymers are homo- and
copolymers of acrylic acid and/or maleic acid, in acid
and/or salt form. Especially preferred polymers are acrylic
acid homopolymers, and acrylic/maleic copolymers. The
acrylic/maleic copolymers disclosed in EP 25 S51B (BASF) are
of particular interest.
Polymeric polycarboxylates which may suitably be used,
alone or in comblnation, in the compositions of the present
invention include the following:
Polymer type Trade name Supplier Averaqe
m wt
Polyacrylate Versicol* Allied 3500
E5 Colloids
35 Polyacrylate Versicol* Allied 27 oo0
E7 Colloids
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Polymer type Trade name SuPplierAveraqe
m wt
- Polyacrylate Versicol* Allied70 000
E9 ............. Colloids
. .
Polyacrylate Narlex* National5000
LD 30 Adhesives
Polyacrylate Narlex* National25 000
LD 34 Adhesives
Polyacrylate Acrysol* R~hm & 1000
LMW-10 Haas
Polyacrylate Acrysol* R~hm & 2000
LMW-20 Haas
Polyacrylate Acrysol* R~hm & 4500
LMW-45 Haas
Polyacrylate Acrysol* R~hm &60 000
Al-N Haas
25 Polyacrylate Sokalan* BASF 2500
PA-20
Polyacrylate Sokalan* BASF 15 000
PA-40
Polyacrylate Sokalan* BASF 70 000
PA-70
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Polymer type Trade name Supplier Average
m wt
- Polyacrylate Sokalan* BASF 250 000
PA-llO
Ethylene/ EMA* Monsanto
maleic acid
10 Methyl vinyl Gantrez* GAF
ether/maleic acid AN 119 Corporation
Acrylate/ Sokaian* BASF
maleate CP5, CP7
Acrylic DKW* National
phosphinate Adhesives
Acrylic Belsperse* Ciba-Geigy
20 phosphinate
*denotes Trade Mark
The weight ratio of aluminosilicate to polYmer is
preferably within the range of from 2:1 to 10:1, more
preferably from 4.5:1 to 9.5:1.
Preferred builder systems
Detergent compositions of the invention comprise from 10 to 45 wt%, more
preferably from 12 to 30 wt%, of zeolite MAP; and from 2 to 6 wt% of the polymer.
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Bleach system
Detergent compositions according to the invention
may also suitably contain a bleach system. This preferably
comprises one or more peroxy bleach compounds, for example,
inorganic persalts or organic peroxyacids, which may be
employed in conjunction with bleach precursors to improve
bleaching action at low temperatures.
The bleach system preferably comprises a peroxy bleach
compound, preferably an inorganic persalt, optionally in
conjunction with a precursor.
Preferred inorganic persalts are sodium perborate
monohydrate and tetrahydrate, and sodium percarbonate.
Preferred bleach precursors are peracetic acid
precursors, especially tetraacetylethylene diamine (TAED);
peroxybenzoic acid precursors; and the novel quaternary
ammonium and phosphonium bleach activators disclosed in
US 4 751 015 and US 4 818 426 (Lever Brothers Company), more
especially cholyl p-sulphophenyl carbonate (CSPC).
If desired, the bleach system may also include a bleach
stabiliser (heavy metal sequestrant).
Other ingredients
The compositions of the invention may if desired
containg water-soluble silicates such as sodium silicate.
The amount of soluble silicates in the compositions of the
invention is preferably kept to a relatively low level:
preferably below 5 wt%, and more preferably below 1 wt%.
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The compositions of the invention may advantageously
contain alkali metal carbonate, to provide alkalinity
rather than for detergency building. The amount of
- alkali metal, preferably sodium, carbonate may suitably
5 range from 2 to 20 wt~, pre~erably from 5 to 15 wt%.
Other materials that may be present in detergent
compositions of the invention include fluorescers,
antiredeposition agents, inorganic salts such as sodium
sulphate, enzymes, lather control agents, fabric
softening agents, ~igments, coloured speckles, and
perfumes. This list is not intended to be exhaustive.
Preparation of the detergent comPositions
Detergent compositions of the invention may be prepared
by any suitable method. The particulate detergent
compositions which are the preferred embodiment of the
invention are suitably prepared by spray-drying a slurry
of compatible heat-insensitive ingredients, and then
spraying on or postdosing those ingredients unsuitable
for processing via the slurry.
The skilled detergent formulator will have no
difficulty in deciding which ingredients should be included
in the slurry and which should not.
Both the zeolite MAP and the polymeric builder
component are suitable for inclusion in the slurry, although
it may be advantageous for processing reasons for part of
the zeolite MAP to be incorporated post-tower.
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The particulate detergent compositions of the
invention may be prepared to any suitable bulk density.
Compositions having bulk densities of at least 400 g/l, more
preferably at least 500 g/l, are of especial interest.
The deter~ency builder composition
The detergency builder system of the invention may be
exist as a composition in its own right that may be used for
water softening or added to the wash liquor to enhance the
performance of an unbuilt or underbuilt detergent
composition In hard water.
Such a composition may, for example, form the building
or water-softening component of a Baukasten (building block)
detergent composition as described and claimed in
EP 419 036A (Unilever), published on 27 March 1991, in which
a main wash powder is supplied together with separately
packaged additives (builder, bleach) that need only be used
when the wash conditions demand them.
A typical composition of this type might contain from
50 to 80 wt% zeolite MAP (anhydrous basis), and from 2 to
10 wt% polycarboxylate polymer.
A composition of this type may in principle contain no
components other than the two essential components (zeolite
MAP and polymer), although in practice it may be desirable
to include other ingredients, for example, sodium carbonate, -
and binders such as nonionic surfactants or cellulose
derivatives.
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A builder composition of the type under discussion may
also be used as a raw material or premix in the manufacture
of more fully formulated detergent compositions. However,
the invention also includes within its scope detergent
compositions prepared by ad~ixing the two builder materials
(zeolite MAP and polymer) separately and independently with
other detergent ingredients.
The invention is further illustrated by the following
non-limiting Examples, in which parts and percentages are by
weight unless otherwise stated.
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EXAMPLES
Examples l to 3, Comparative ExamPle A
Four detergent compositions containing zeolite and
polycarboxylate polymer were prepared to the following
formulations (in parts by weight):
parts
Linear alkylbenzene sulphonate 6.80
Nonionic surfactant (7EO) 3.10
Nonionic surfactant (3EO) ~.90
Soap 1.73
Builder system:
Zeolite MAP or 4A(anhydrous basis) ) see below
Acrylic/maleic copolymer
20 Antifoam granules 1.20
Sodium carbonate 9.60
Sodium silicate 0.55
TAED granules 6.60
Sodium perborate monohydrate 16.25
Dequest 2047 0.75
Enzyme (Savinase 6.OT) l.lO
Fluorescer 0.21
Sodium carboxymethyl cellulose 0.83
55.62
The polymer was an acrylic/maleic copolymer in sodium
salt form, Sokalan (Trade Mark) CP5 ex BASF, Ludwigshafen,
Germany.
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The zeolite MAP was prepared on a pilot scale by a
method similar to that described in Examples 1 to 3 of
EP 384 070A (Unilever). Its silicon to aluminium ratio was
-- 1.10.
The zeolite 4A was Wessalith (Trade Mark) P powder ex
Degussa.
The builder systems of the four compositions were as
follows:
A 1 2 3
Zeolite 4A (anhydr) 27.30
Moisture 7.50
Zeolite MAP (anhydr) - 27.30 25.00 22.00
Moisture 7.20 6.60 5.80
Polymer 4.504.50 4.50 4.50
Ratio (a):(b) (6.07) 6.07 5.56 4.89
Total (a)+(b):
parts31.80 31.80 29.50 26.50
%33.5033.6032.16 30.14
Detergency was measured in a Candy (Trade Mark) washing
machine using the 40~C main wash only cycle. Test cloths
as specified below were washed together with a 3 kg soiled
load, using two different product dosages and two different
water hardnesses.
The results, expressed as reflectance differences at
460 nm (delta R460), were as follows:
3S
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Test cloths
(1) oil/silica/ink soil on cotton;
(2) Indian ink/olive oil soil on polyester/cotton;
(3) Indian ink/olive oil/silica/casein soil on cotton;
(4) Indian ink/olive oil/silica/casein soil on
polyester/cotton.
(i) Water hardness 15~ (French), Product dosaqe 4.8 q,/l
Test cloth A 1 2 3
(1) 20.4 23.0 23.6 22.2
(2) 12.5 14.7 13.6 10.7
(3) 27.4 28.1 27.9 26.8
(4) 24.1 24.8 25. 2 24. 5
(ii) Water hardness 25~ rFrench), product dosaqe 6.4 q/l
Test cloth A 1 2 3
(1) 22.9 24.3 24.3 21.6
(2) 11.8 14.5 15.3 1~.8
(3) 27.7 28.5 28.4 27.9
(4) 25.3 26.0 25.8 24.7
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ExamPle 4, ComParative Example B
Two detergent compositions containing zeolite and
polycarboxylate polymer were prepared to the following
formulations:
B 4
Linear alkylbenzene sulphonate6.70 6.70
Nonionic surfactant (7EO) 3.07 3.07
Nonionic surfactant (3EO) 6.23 6.23
Soap 1.83 1.83
Builder system:
Zeolite MAP - 28.00
Zeolite 4A 28.00
Acrylic/maleic copolymer 3.00 3.00
Sodium carbonate 15.08 15.08
Sodium silicate 0.46 0.46
Sodium carboxymethyl cellulose0.56 0.56
Fluorescer 0.22 0.22
Antifoam granules 1.20 1.20
TAED granules 7.35 7.35
Sodium perborate monohydrate14.00 14.00
Enzyme (Savinase 6.OT) 1.10 1.10
Moisture 11.00 11.00
100. 00 100 . 00
The zeolite MAP, zeolite 4A and copolymer were as used
3~ in Examples 1 to 3.
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The ratio of zeolite (anhydrous basis) to polymer in
each case was 9.33, and the total amount of zeolite plus
polymer in each case was 31Ø
Detergency was measured in a Miele (Trade Mark) 756
washing machine using the 40~C main wash cycle. Test
cloths as specified below were washed together with a 4 kg
soiled load, using two different product dosages and two
different water hardnesses.
The results, expressed as reflectance differences at
460 nm (delta R460), were as follows:
Test cloths
(l), (3) as in Examples l to 3
(5) Indian ink/olive oil/silica plus a small amount of
casein, on cotton.
(i) Water hardness 20~(French), Ca:Mq 2.0,
product dosaqe 3.4 q/l
Test cloth B 4
(l) 18.11 24.48
(3) 31.95 36.05
(5) 21.96 26.38
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(ii) Water hardness 40~(French), Ca:Mq 2:1,
Product dosaqe 5.6 ~
5 Test cloth B 4
(1) 14.32 21.07
(3) 27.45 31.01
(5) 18.77 21.29
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Example 5
A composition containing lower percentages of zeolite
MAP and acrylic/maleic copolymer was prepared as follows:
.
Linear alkylbenzene sulphonate6.00
Nonionic surfactant (7EO) 2.75
Nonionic surfactant (3EO) 4.25
Soap 1.75
Zeolite MAP (anhydrous basis) (a) 12.00
Acrylic/maleic copolymer (b) 2.00
15 Antifoam granules 1.20
Sodium carbonate 14.00
Sodium silicate 0.55
TAED granules 3.00
Sodium perborate tetrahydrate20.00
Dequest 2047 0.75
Enzyme (Savinase 6.OT) O.40
Fluorescer 0.21
Sodium carboxymethyl celluloseO.83
Moisture and salts 10.00
The zeolite MAP and copolymer were the same as those
used in Examples 1 to 4.
30The ratio of zeolite MAP to copolymer was 6.00 and the
total amount of zeolite MAP and copolymer was 14.00.
The composition exhibited excellent cleaning and
detergency performance.
* * *
