Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02238479 1998-0~-2
C3693PCl
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DETER~ T COMPOSITIQNS CONTAIMING SOIB RELEASE POLYMERS
TECHNICAL AR~.~
The present invention relates to laundry detergent
compositions containing sodium tripolyphosphate builder and
also containing certain water-soluble or water-dispersible
polyesters exhibiting improved soil release properties.
BACKGROUN~ AND PRIOR ART
Polyesters of terephthalic and other aromatic
dicarboxylic acids having soil release properties are
widely disclosed in the art, in particular, the so-called
PET/POET (polyethylene terephthalate/polyoxyethylene
terephthalate) and PET/PEG (polyethylene
terephthalate/polyethylene glycol) polyesters which are
disclosed, for example, in US 3 557 039 (ICI), GB 1 467 098
and EP 1305A (Procter & Gamble). Polymers of this type are
available commercially, for example, as Permalose,
Aquaperle and Milease (Trade Marks) (ICI) and Repel-O-Tex
(Trade Mark) SRP3 (Rhone-Poulenc). Other patent
publications disclosing soil release polymers which are
condensation products of aromatic dicarboxylic acids and
dihydric alcohols include EP 185 427A, EP 241 984A,
EP 241 985A and EP 272 033A (Procter & Gamble).
EP 357 280A (Procter & Gamble) discloses sulphonated
end-capped linear terephthalate oligomers which are
condensation products of a low molecular weight diol,
preferably propylene glycol or ethylene glycol, with
terephthalic acid.
AMENDED SHEET
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C3 693PCl
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The present invention is based on the use, in
detergent compositions built with sodium tripolyphosphate/
of a class of non-end-capped sulphonated polyesters based
on dicarboxylic acids and polyols which provide especially
effective soil release, especially from polyester fabrics,
and which are also effective in reducing soil redeposition
in the wash.
DEFINITION OF THE INVENTION
The present invention accordingly provides a detergent
composition for washing fabrics, comprising:
(a) from 2 to 50 wt% of an organic surfactant system
comprising one or more anionic, nonionic, cationic,
amphoteric or zwitterionic surfactants,
(b) from 10 to 80 wt~ of a builder component comprising
one or more inorganic or organic detergency builders, and
comprising at least 5 wt% (based on the detergent
composition) of sodium tripolyphosphate,
(C) a soil release effective amount of a water-soluble or
water-dispersible non-end-capped sulphonated polyester
comprising monomer units of
(i) an unsulphonated aromatic diacidic monomer (A),
(ii) a sulphonated aromatic diacidic monomer (SA)
(iii) optionally a hydroxylated aromatic or aliphatic
diacidic monomer (HA), in an amount replacing up to
50 mole~ of (A) and/or (SA),
AMzN~E~SHt~
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(iv) a polyol (P) selected from ethylene glycol,
propylene glycol, isopropylene glycol, glycerol,
1,2,4-butanetriol and 1,2,3-butanetriol, and oligomers
of these having from 1 to 8 monomer units,
the polyester having a sulphur content within the
range of from 0.5 to 10 wt%;
(d) optionally other detergent ingredients to 100 wt%.
DETAILED DESCRIPTION OF THE INV~NTION
The ~olvesters
The polyesters with which the invention is concerned
are defined above. The polyesters and their preparation
are disclosed and claimed in WO 95 32997A (Rhône-Poulenc).
Preferred polyesters have the following features:
- the unsulphonated diacidic monomer (A) is an aromatic
dicarboxylic acid or an anhydride of a lower (Cl-~4) alkyl
diester thereo~, selected from terephthalic acid,
isophthalic acid, 2,6-naphthalene dicarboxylic acid,
anhydrides and lower (Cl-C4) alkyl diesters thereof;
- the sulphonated diacidic monomer (SA) is a sulphonated
aromatic dicarboxylic acid, anhydride, or lower (Cl-C4)
alkyl diester thereof;
- the mole ratio (A):[(A) + (SA)] is within the range of
from 60:100 to 95:100, preferably from 65:100 to 93:100;
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- the mole ratio (SA):~(A) + (SA)] is within the range
of from 5:100 to 40:100, preferably from 7:100 to 35:100;
- the hydroxylated monomer (HA), if present, is a
hydroxylated aromatic dicarboxylic acid, or anhydride or
lower (C1-C4) dialkyl ester thereof;
- the hydroxylated monomer ~HA), if present, does not
replace more than 30 mole% of (A) andtor (SA)
- the quantity of (P) is such that the ratio of OH
functional groups of (P) to COOH functional groups (or
equivalents) of (A) + (SA) + any (HA) is within the range
of from 1.05:1 to 4:1, preferably from 1.1:1 to 3.5:1, and
more preferably from 1.8:1 to 3:1;
- the polyester has a number average molecular weight of
less than 20 000,
- the sulphur content is within the range of from 1.2 to
8 wt%;
- the hydroxyl group content is at least 0.2 OH
equivalent per kg of polyester.
The unsulphonated diacidic monomer (A)
As previously indicated, the monomer (A) preferably
consists of at least one dicarboxylic acid or anhydride
chosen from terephthalic, isophthalic and 2,6
naphthalenedicarboxylic acids or anhydrides or their
diesters.
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Preferahly, monomer ~A) is present in a quantity
corresponding to a molar ratio (A)/[(A) + (SA)] within the
range of from 95:100 to 60:100, preferably from 93:100 to
65:100.
The unsulphonated diacidic monomer (A) preferably
consists of 50 to 100 mole%, more preferably 70 to
90 mole%, of terephthalic acid or anhydride or lower alkyl
(methyl, ethyl, propyl, isopropyl, butyl) diester, and of 0
to 50 mole%, more preferably from 10 to 30 mole%, of
isophthalic acid or anhydride and/or of 2,6-
naphthalenedicarboxylic acid or anhydride or lower alkyl
(methyl, ethyl, propyl, isopropyl, butyl) diester; the
preferred diesters are methyl diesters.
1~
In the unsulphonated diacidic monomer (A) there may
additionally be present minor quantities of aromatic
diacids other than those mentioned above, such as ortho-
phthalic acid, anthracene, l,8-naphthalene, 1,4-naphthalene
and biphenyl dicarboxylic acids or aliphatic diacids such
as adipic, glutaric, succinic, trimethyladipic, pimelic,
azelaic, sebacic, suberic, itaconic and maleic acids, etc.
in the form of acid, anhydride or lower (methyl, ethyl,
propyl, isopropyl, butyl) diesters.
.
The sul~honated diacidic monomer (SA)
~referably, the sulphonated dlacid~c r~or~or~er (SA)
consists of at least one sulphonated aromatic or
sulphonated aliphatic dicarboxylic acid or anhydride or
lower (Cl-C4) alkyl diester. Aromatic dicarboxylic acids
and their derivatives are preferred.
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Preferably, monomer (SA) is present in a quantity
corresponding to a molar ratio (SA)/[(A) + (SA)] within the
range of from 5:100 to 40:100, more preferably from 7:100
to 35:100.
The sulphonated diacidic monomer (SA) has at least one
sulphonic acid group, preferably in the form of an alkali
metal (preferably sodium) sulphonate, and two acidic
functional groups or acidic functional group equivalents
(that is to say an anhydride functional group or two ester
functional groups) attached to one or a number of aromatic
rings, when aromatic dicarboxylic acids or anhydrides or
their diesters are involved, or to the aliphatic chain when
aliphatic dicarboxylic acids or anhydrides or their
diesters are involved.
Suitable aromatic sulphonated diacidic monomers
include sulphoisophthalic, sulphoterephthalic, sulpho-
ortho-phthalic acids or anhydrides, 4-sulpho-2,7-
naphthalenedicarboxylic acids or anhydrides, sulpho 4,4'-
bis (hydroxycarbonyl) diphenyl sulphones,
sulphodiphenyldicarboxylic acids or anhydrides, sulpho
4,4'-bis(hydroxycarbonyl) diphenylmethanes, sulpho-5-
phenoxyisophthalic acids or anhydrides or their lower
(methyl, ethyl, propyl, isopropyl, butyl) diesters.
Suitable aliphatic sulphonated diacidic monomers (SA)
include sulphosuccinic acids or anhydrides or their lower
alkyl (methyl, ethyl, propyl, isopropyl, butyl) diesters.
The most preferred sulphonated diacidic monomer (SA)
is sulphoisophthalic acid in acid, anhydride or diester
(preferably dimethyl ester) form, very particularly
dimethyl 5-sodiooxysulphonylisophthalate.
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The h~droxvlated diacidic monomer (HA)
~ The hydroxylated diacidic monomer (HA), which is
optionally present and can replace up to 50 mole%,
preferably up to 30 mole%, of (A) and/or (SA),
consists of least one hydroxylated aromatic or aliphatic
dicarboxylic acid or anhydride or a lower (Cl-C4) al~yl
diester thereof.
The hydroxylated diacidic monomer (HA) has at least
one hydroxyl group attached to one or a number of aromatic
rings when it is an aromatic monomer or to the aliphatic
chain when it is an aliphatic monomer. Aromatic monomers
are preferred.
Suitable hydroxylated diacidic monomers (HA) include
5-hydroxyisophthalic, 4-hydroxyisophthalic,
4-hydroxyphthalic, 2-hydroxymethylsuccinic,
hydroxymethylglutaric and hydroxyglutaric acids, in acid,
anhydride or lower alkyl diester form.
The ~olyol (P)
The polyol (P) may be a oligomer comprising up to 8
monomer units, preferably up to 6 and more preferably up to
4 monomer units, but is most preferably a monomer. The
polyol is selected from ethylene glycol, propylene glycol,
glycerol, 1,2,4-butanetriol, 1,2,3-butanetriol and
3~ combinations of these, and their lower (2 to 8, preferably
2 to 6, more preferably 2 to 4) oligomers.
Preferably, the polyol (P) is present in a quantity
corresponding to a ratio of the number of OH functional
groups of the polyol (P) to the number of COO~ functional
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groups or functional group equivalents of the total
diacidic monomer (A) + (SA) + (HA) within the range of from
1.05:1 to 4:1, preferably from 1.1:1 to 3.5:1 and more
preferably from 1. 8: 1 to 3:1.
The preferred polyols (P) are ethylene glycol and
glycerol, ethylene glycol being especially preferred.
Preferably, the sulphonated diacidic monomer (SA)
consists of at least one sulphonated aromatic dicarboxylic
acid or anhydride or of a mixture of sulphonated aromatic
acids or anhydrides and of sulphonated aliphatic acids or
anhydrides or their diesters when the polyol (P) does not
contain any polyol other than a glycol or when the
hydroxylated diacidic monomer (~A) is absent.
Molecular weiaht
Preferably, the polyester used in accordance with the
invention has a number average molecular weiaht not
exceeding 20 000, and preferably not exceeding 15 000.
The molecular weight may be much lower than these
limits. Polyesters having molecular weights below 1000,
for example, 500-1000, have proved highly effective.
Number average molecular weight may be measured by gel
permeation chromatography, for example, in
dimethylacetamide cont~;n;ng 10-2 N of LiBr, at 25~C, or in
tetrahydrofuran. The results are expressed as polystyrene
e~uivalents.
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H~droxyl functional qroup content
Preferably, the hydroxyl functional group content of
the polyester, expressed as OH equivalent/kg of polyester,
is at least 0.2. The hydroxyl functional group content
may be estimated from proton NMR, the measurement being
carried out in dimethyl sulphoxide.
The elementary unit considered in the definition of
the mole of monomer (A), (SA) or (HA) is the COOH
functional group in the case of the diacids or the COOH
functional group equivalent in the case of the anhydrides
or of the diesters.
Es~eciallv ~referred ~olvestexs
An especially preferred polyester is obt~;n~hle from
the following monomers:
- terephthalic acid (Al) in lower alkyl (preferably
methyl) diester foxmi
- optionally isophthalic acid (A21 in acid or anhydride
form;
- optionally a hydroxylated terephthalic or isophthalic
acid (HA) in acid or anhydride form;
the mole ratio (Al):[(Al) + (A2)] or
(Al):~Al + HA)] or (Al):[(Al) + (A2) + (HA)] being within
the range of from 50:100 to 100:100, preferably from 70:100
to 90:100;
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- sulphoisophthalic acid (SA), preferably in lower
alkyl, preferably methyl, diester form; and
- monoethylene glycol and/or glycerol (P).
Preferred polyesters in accordance with the invention,
based on terephthalic acid, isophthalic acid,
sulphoisophthalic acid and monoethylene glycol, may be
described as having backbone units of the following
~ormula:
O O
- C - Ar - C - O - (CH2 - CH2 - ~) n -
where Ar = terephthalic, isophthalic or sulphoisophthalic,
and n represents 1, 2, 3 or 4. Typical mole percentages
for the different values of n are as follows:
n = 1 58.7
n - 2 30.5
n = 3 8.8
n = 4 1.9,
only trace quantities, if any, of polyethylene oxide units
in which n is greater than four being present.
The majority of endgroups are of the formula
- Ar - COO - (CH2 - CH2 - ~ - )~
=
wherein n is 1, 2, 3 or 4,
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a minority being of the formulae
- Ar - COOH or - Ar - COOR
wherein R is a lower alkyl group, preferably methyl.
These polyesters, unlike many disclosed in the prior
art, are not end-capped with hydrocarbon or sulphonated
capping groups.
Pre~aration of the polvesters
The polyesters may be prepared by the usual
esterification and/or transesterification and
polycondensation processes, for example, by esterification
and/or transesterification in the presence of a catalyst of
the polyol P with the various diacidic monomers (in acid,
anhydride or diester form), and polycondensation of the
polyol esters at reduced pressure in the presence of a
polycondensation catalyst.
A preferred process for the preparation of the
polyesters is disclosed and claimed in WO 95 32997A
(Rhône-Poulenc).
~eter~ent compositiQn~
The polyesters are suitably incorporated into
detergent compositions in amounts of from 0.01 to 10 wt%,
preferably from 0.1 to 5 wt% and more preferably from 0.25
to 3 wt%.
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The detergent compositions of the invention also
contain, as essential ingredients, one or more detergent-
active compounds (surfactants), and a detergency builder
system including sodium tripolyphosphate; they may also
5 ~ optionally contain bleaching components and other active
ingredients to ~nh~nce performance and properties.
The surfactant system
The detergent-active compounds (surfactants) 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-Active Agents and
Detergents", Volumes ~ 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.
The total amount of surfactant present ranges from 2
to 50 wt%, preferably from 5 to 40 wt%.
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-Cl5; primary and secondary
alkylsulphates, particularly C8-Cl5 primary alkyl sulphates;
alkyl ether sulphates; olefin sulphonates; alkyl xylene
sulphonates; dialkyl sulphosuccinates; and fatty acid
ester sulphonates. Sodium salts are generally preferred.
The polyesters of the present invention are especially
suitable for use in compositions cont~in;ng anionic
sulphonate and sulphate type surfactants, for example,
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primary alkyl sulphates, alkyl ether sulphates,
alkylbenzene sulphonates, and mixtures of these.
According to one preferred embodiment of the
invention, the compositions of the invention contain a
surfactant system which consists of anionic surfactant
only, or of anionic and nonionic surfactants in a weight
ratio of at least 0.9:1, preferably at least 1:1. The
anionic surfactant is preferably ]?resent in an amount of
from 5 to 45 wt%, more preferably from 10 to 40 wt%.
Nonionic surfactants that may be used include the
primary and secondary alcohol ethoxylates, especially the
C8-C20 aliphatic alcohols ethoxylated with an average of
from 1 to 20 moles of ethylene oxide per mole of alcohol,
and more especially the C10-Cl5 primary and secondary
aliphatic alcohols ethoxylated with an average of from 1 to
10 moles of ethylene oxide per mole of alcohol.
Non-ethoxylated nonionic surfactants include
alkylpolyglycosides, glycerol monoethers, and
polyhydroxyamides (glucamide~.
Especially preferred are ethoxylated nonionic
surfactants, alkylpolyglycosides, and mixtures of these.
As well as the non-soap surfactants listed above,
detergent compositions of the invention may also
advantageously contain fatty acid soap.
The deteraency builder svstem
The detergent compositions of the invention also
contain a detergency builder system. The total amount of
detergency builder in the compositions will suitably range
from 5 to 80 wt%, preferably from 10 to 60 wt%.
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The builder system contains, as an essential
ingredient, sodium tripolyphosphate (STP) in an amount of
at least 5 wt%, preferably at least 10 wt%, based on the
whole composition.
The STP may be the sole builder present, in which case
it is preferably present in an amount of at least 15 wt96,
and p~eferably at least 20 wt%, suitably from 20 to 50 wt96.
Alternatively the STP may be used in combination with
one or more other builders, which may be inorganic or
organic.
Other inorganic builders that may be present include
other phosphate builders, for example, sodium
orthophosphate and/or sodium pyrophosphate; sodium
carbonate, if desired in corr~ination with a crystallisation
seed for calcium carbonate, as disclosed in GB 1 437 950
(Unilever); crystalline and amorphous aluminosilicates,
for example, zeolites as disclosed in GB 1 473 201
(Henkel), amorphous aluminosilicates as disclosed in
GB 1 473 202 (Henkel) and mixed crystalline/amorphous
aluminosilicates as disclosed in GB 1 470 250 (Procter &
Gamble); and layered silicates as disclosed in EP 164 514B
(Hoechst).
Especially preferred are combinations of STP with
other phosphates, with sodium carbonate, and with sodium
aluminosilicate (zeolite). An especially preferred
builder system comprises at least 5 wt% of STP in
cornbination with at least 10 wt% of zeolite A.
The zeolite may be the commercially available zeolite
4A now widely used in laundry detergent powders. Other
zeolites that may be used include zeolites X and Y.
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Alternatively, it may be maximum aluminium zeolite P
(zeolite MAP) as described and claimed in EP 384 070B
- (Unilever).
Zeolite MAP is defined as an alkali metal
aluminosilicate of the zeolite P type having a silicon to
aluminium ratio not exceeding 1.33. Especially preferred
is zeolite MAP having a silicon to aluminium ratio not
exceeding 1.07, more preferably about 1.00.
Supplementary organic builders that may be present
include polycarboxylate polymers such as polyacrylates,
acrylic/maleic copolymers, and acrylic phosphinates;
monomeric polycarboxylates such as citrates, gluconates,
oxydisuccinates, glycerol mono-, di- and trisuccinates,
carboxymethyloxysuccinates, carboxymethyloxymalonates,
dipicolinates, hydroxyethyliminodiacetates, alkyl- and
alkenylmalonates and succinates; and sulphonated fatty
acid salts. This list is not intended to be exhaustive.
Detergent compositions according to the invention may
also suitably contain a bleach system, which may contain
peroxy bleach compounds, for example, inorganic persalts or
organic peroxyacids, capable of yielding hydrogen peroxide
in aqueous solution. Suitable peroxy bleach compounds
include organic peroxides such as urea peroxide, and
inorganic persalts such as the alkali metal perborates,
percarbonates, perphosphates, persilicates and
persulphates. Preferred inorganic persalts are sodium
perborate monohydrate and tetrahydrate, and sodium
percarbonate. The peroxy bleach compound is suitably
present in an amount of from 5 to 35 wt%, preferably from
10 to 25 wt%.
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The peroxy bleach compound may be used in conjunction
with a bleach activator (bleach precursor~ to improve
bleaching action at low wash temperatures. The bleach
precursor is suitably present in an amount of from 1 to
8 wt%, preferably from 2 to 5 wt%.
A bleach stabiliser (heavy metal sequestrant) may also
be present. Suitable bleach stabilisers include
ethylenediamine tetraacetate (EDTA) and the
polyphosphonates such as ethylenediamine tetramethylene
phosphonate ( EDTMP) and its salts, and diethylenetriamine
pentamethylene phosphonate (DETPMP) and its salts.
The present invention is also of especial
applicability to non-bleaching compositions suitable for
washing delicate fabrics. Such compositions may, for
example, have one or more of the following characteristics:
- a 1 wt% aqueous solution pH, in demineralised water,
not exceeding 10.5, and preferably not exceeding 10;
- absence, or an extremely low level, of fluorescer;
- presence of a polycarboxylate polymer, for example, an
acrylic/maleic copolymer such as Sokalan (Trade Mark) CP5
ex BASF;
- presence of a polymer effective to inhibit dye
transfer, for example, polyvinyl pyrrolidone;
- presence of a heavy metal sequestrant, for example,
the aminomethylenephosphonic acids and salts such as EDTMP
and DETPMP mentioned above in the context of bleach
stabilisation.
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The compositions of the invention may also contain one
or more enzymes. Suitable enzymes include the proteases,
amylases, cellulases and lipases usable for incorporation
in detergent compositions.
Preferred proteolytic enzymes (proteases) are normally
solid, catalytically active protein materials which degrade
or alter protein types of stains when present as in fabric
stains in a hydrolysis reaction. They may be of any
suitable origin, such as vegetable, ~n;~l, bacterial or
yeast origln.
Proteolytic enzymes or proteases of various ~ualities
and origins and having activity in various pH ranges of
from 4-12 are available and can be used in the instant
invention. Examples of suitable proteolytic enzymes are
the subtilisins, which are obtained from particular strains
of B. subtilis and B. licheniformis, such as the
commercially available subtilisins Maxatase ~Trade Mark),
as supplied by Gist-Brocades N.V., Delft, Holland, and
Alcalase (Trade Mark), as supplied by Novo Industri A/S,
Copenhagen, Denmark.
Also suitable is a protease obtained from a strain of
Bacillus having maximum activity throughout the pH range of
8-12, being commercially available, e.g. from Novo Industri
A/S under the registered trade-names ~sperase (Trade Mark)
and Savinase (Trade Mark). The preparation of these and
analogous enzymes is described in GB 1 243 785. Other
commercial proteases are Kazusase (Trade Mark) (obt~;n~hle
from Showa-Denko of Japan), Optimase (Trade Mark) (from
Miles Kali-Chemie, Hannover, West Germany), and Superase
(Trade Mark) (obtainable from Pfizer of U.S.A.).
Proteases having isoelectric points below 10 include
Alcalase, Maxatase, Optimase and Primase (all Trade Marks).
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Proteases having isoelectric points of lQ or above include
Savinase, Maxacal, Purafect, Opticlean and Esperase (all
Trade Marks~.
Detergency enzymes are commonly employed in granular
form in amounts of from 0.01 to 5.0 wt%.
Other materials that may be present in detergent
compositions of the invention include inorganic salts such
as sodium carbonate, sodium sulphate or sodium silicate;
antiredeposition agents such as cellulosic polymers;
fluorescers; inorganic salts such as sodium sulphate;
lather control agents or lather boosters as appropriate;
dyes; coloured speckles; perfumes; foam controllers;
and fabric softening compounds. This list is not intended
to be exhaustive.
Detergent compositions of the invention may be of any
suitable physical form, for example, powders or granules,
liquids, gels and solid bars.
Detergent compositions of the invention may be
prepared by any suitable method. Particulate detergent
compositions 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.
Particulate detergent compositions of the invention
preferably have a bulk density of at least 400 g/l, more
preferably at least 5Q0 g/l. Especially preferred
compositions have bulk densities of at least 650 g/litre,
more preferably at least 700 g/litre.
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Such powders may be prepared either by post-tower
densification of spray-dried powder, or by wholly non-tower
methods such as dry mixing and granulation; in both cases
a high-speed mixer/granulator may advantageously be used.
Processes using high-speed mixer/granulators are disclosed,
for example, in EP 340 013A, EP 357 339A, EP 390 251A and
EP 420 317A (Unilever).
E~AMPT.~.. S
The invention is further illustrated by the following
non-limiting Examples, in which parts and percentages are
by weight unless otherwise stated. Throughout the
Examples * denotes a Trade Mark.
Polvmers
The polymer in accordance with the invention used
(Polymer 1) was a water-soluble sulphonated polyester of
terephthalic acid, isophthalic acid, sulphoisophthalic acid
and ethylene glycol having the following approximate
composition :
- diacidic monomer comprising approximately 77 mole%
terephthalate, 3.7 mole% isophthalate, 18.2 mole~
sulphoisophthalate;
- ratio of OH groups ex ethylene glycol to COOH groups
ex diacid monomers approximately 1.22;
- number average molecular weight, by GPC in
tetrahydrofuran at 25~C with calibration against
polystyrene st~n~rdst 534; weight average molecular
weight 1667;
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- sulphur content 2.4 wt%;
- hydroxyl group content approximately 1.4-1.5 per kg
polyester.
For comparative purposes, the following commercially
available polymers were used:
Polymer A: Sokalan (Trade Mark) HP22 ex BASF, a graft
copolymer of polyethylene glycol and polyvinyl acetate.
Polymer B: Repel-O-Tex (Trade Mark) ex Rhône-Poulenc, a
PET/POET polymer, used in the form of a granule (50% wt%
polymer, 50 wt% sodium sulphate).
Polymer C: Aquaperle (Trade Mark) 3991 ex ICI, a
PET/POET polymer.
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EXAMPLE 1
Phosphate-built particulate detergent compositions
were prepared to the following general formulation, using
spray-drying and postdosing techniques:
Na linear alkylbenzene sulphonate5.60
Nonionic surfactant 7EO 4.20
Nonionic surfactant 3EO 3.30
Soap 0.25
Pristerine* 4916 (fatty acld) 0.28
Sodium alkaline silicate 5.60
Sodium tripolyphosphate 22.00
Sodium car3~onate 9.00
Sodium carboxymethylcellulose 0.30
Acrylic/maleic copolymer (Sokalan* CP5) 0.97
EDTA (4Na salt) 0.12
Fluorescer 0.16
Sodium sulphate 27.00
Sodium perborate 13.00
TAED
Soil release polymer (see below) 0 or 0.40
Antifoam granule, enzymes,
sodium carbonate, perfume, water to 100.00
Soil release and detergency were measured using
radio(3H)-labelled triolein as a soil. The wash regime
was as follows: polyester cloths were washed for 20
minutes in Tergotometers in the test formulations (with or
without soil release polymer at 0.4 wt%), at the product
dosages stated, at 40~C in 24~FH (calcium only) water.
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Single wash: soiled cloths were washed as described above.
Prewash: as single wash but no soil present; after
prewash the fabrics were rinsed in a beaker with 1 litre of
water at 20~C and dried overnight.
Main wash: as for single wash but using pretreated
fabrics.
Deteraency results
Product dosage: 7.8 g/litre
Polymer % Deterqencv
tO.4 wt~
Single wash Prewash + main wash
None 79.1 53.6
Polymer 1100.0100.0
Polymer A86.3 87.1
Polymer B92.6100.0
Polymer C79.1 53.6
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F'.~MPLE 2
Phosphate-built particulate detergent compositions
were prepared to the following general formulation, using
spray-drying and postdosing techni~ues:
Na linear alkylbenzene sulphonate 25 . 00
Zeolite 1.17
Sodium tripolyphosphate21. 68
Sodium silicate 5.00
Calcium carbonate 10.00
~odium sulphate 2 1 . 2 4
~odium carboxymethylcellulose 0.70
Fluorescer 0.01
Acrylic/maleic copolymer (Sokalan* CP5) 1.80
Perfume 0. 25
Protease (Savinase* 6T)0 . 20
Lipase (Lipolase* 100T) 0. 05
Amylase (Termamyl* 60T)O . 08
Antifoam (silicone oil/silica) 0.01
Soil release polymersee below
Moisture and impuritiesto 100.00
The formulations had a bulk density of 420-440 g/litre
and a 1 wt% a~ueous solution pH in demineralised water at
25~C of 9.7-9.8.
Soil release and detergency on knitted polyester test
cloths stained with Oilsol Blue dye/olive oil, were
assessed in the tergotometer at two different product
dosages, using the following wash regimes:
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3. 8 g/l 1. 3 g/l
Water hardness 25:3 Ca:Mg 15:3 Ca:Mg
pH 8.45 8.22
Temperature 2 8~C
Soak/wash time 30 min soak/10 min wash
Prewashes 5
Replicates 2
Detergency was assessed by measuring reflectance
before and after washing using Micromatch (Trade Mark)
apparatus. The differences (~R 5 80 * ~ are shown in the
following Table:
Polvmer % 3.8 g/ 1 1.3 g/1
None 0 32.68 22.94
Polymer 1 0.5 57.2g 63. 02
Polymer A 1.0 50. 63 27. 96
Polymer B 0.5 52.05 50. 41
Stain removal was also assessed visually by an
experienced panel of five people. The results, expressed
on a scale of 1 (heavy st~;n;ng, initial stain) to 10
(complete removal), were as follows:
Polymer % 3.8 g/l 1.3 g/l
Initial
None 0 3 3
Polymer 1 0. 5 10 10
Polymer A 1.0 6 4
Polymer B 0.5 8 8
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EXAMPLE 3
Further phosphate-built particulate detergent
compositions were prepared to the following general
formulation, using spray-drying and postdosing techni~ues:
Na linear alkylbenzene sulphonate 25.00
Sodium tripolyphosphate 22.50
Sodium silicate 5,00
Sodium sulphate 28.90
Sodium carbox~methylcellulose 0. 70
Acrylic/maleic copolymer (Sokalan* CP5) 2.00
Sodium carbonate 2.00
Fluorescer speckles l.Q0
Citric acid (anhydrous) 3.00
Protease (Opticlean* M375)0.784
Lipase (Lipolase* 100T)0. 253
Antifoam (silicone oil/silica) 0. 04
Perfume 0. 33
Soil release polymersee below
Moisture and impuritiesto 100.00
The formulations had a bulk density of 370-430 g/litre
and a 1 wt% aqueous solution pH in demineralised water at
25~C of g.7-9.8.
Detergency was assessed, as in Example 2, by measuring
reflectance before and after washing using Micromatch
(Trade Mark) apparatus. The differences (AR 580*) are
shown in the following Table:
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Polvmer % 3.8 g/ 1 1.3 g/l
None 0 30.34 38.56
Polymer 1 0. 25 57.84 60.67
Polymer A 1.0 53.23 59.48
Polymer B 0. 25 53.71 61.77
Polymer B 0. 35 54.50 58.53
Soil release properties were also assessed at a
product dosage of 1.3 g/l, by measuring relectance after a
first wash and again after a second wash. The wash regime
in the tergotometer was as follows:
Test cloth Knitted polyester
Stain Oilsol Violet/olive oil
Water hardness 21: 6 Ca:Mg
Temperature 2 8~C
Prewashes none
Soak/wash time 30 min soak/10 min wash
Rinse time 2 x 2 min
Results
Polymer % R 580*
Wash 1 Wash 2 Di fference
None 0 42.30 44.49 2.19 )2.70
43.34 46.55 3.2
.0 46.75 58.31 11.56 ) 12.99
56.05 70.47 14.42
B 1.0 50.45 60.52 10.07 )10.12
45.58 55.75 10.17
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EXAMPLE 4, COMPARATIVE EXAMPLES D and F.
In these Examples, the effects of Polymers 1 and B in
formulations built with STP and with zeolite were compared.
The zeolites used were zeolite 4A (Wessalith* P de Degussa)
and zeolite P having a Si:A1 ratio less than 1.33 (zeolite
MAP)(Doucil* A24 ex Crosfield Chemicals).
Ingredients were dosed separately into tergotometers
to give the following formulations:
Parts by weight
~ E 4
Sodium linear alkylbenzene
sulphonate 20.00 20.00 20.00
Sodium carbonate 25.00 25.00 25.00
~ Sodium chloride 20.00 20.00 20.00
Zeolite MAP 22.00 - -
Zeolite A - 22.00
Sodium tripolyphosphate - - 22.00
Soil release polymer ~ -----0 or 1.00-------
Soil release and detergency on polyester cloths soiled
with radio(3H)labelled triolein were measured, as in
Example 1, using the single-wash regime described in
Example 1 (20 minutes, 25~C, 24~FH (calcium only) water).
The "product" dosage was 1.5 g/l. The results were as
shown overleaf.
In all three compositions Polymer 1 caused a
significant detergency increase. Polymer B caused smaller
detergency increases in the two zeolite formulations, but
in the STP formulation the presence of Polymer B actually
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brought about a substantial fall in detergency, while the
presence of Polymer 1 caused a comparable rise in
detergency.
The difference between the effects of the two polymers
was most marked in the STP formulation.
Com~arative Example D: zeolite M~P
DetergencyPolymer benefit
No polymer 29.6
Polymer 1 56.7 27.1
Polymer B 37.2 7.6
Benefit of Polymer 1 over Polymer B = 19.5
Co~arative Example E: zeolite 4A
DetergencyPolymer Benefit
No polymer 50.0
Polymer 1 73.8 23.8
Polymer B 62.0 12.0
Bene~it of Polymer 1 over Polymer B = 11.8
~xam~le 4: Sodium tri~olyPhosphate
DetergencyPolymer Benefit
No polymer 63.1
Polymer 1 75.3 12.2
Polymer B 50.8 -12.3
Benefit of Polymer 1 over Polymer B = 24.5
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EXAMPLES 5 to 7
Examples of phosphate-built non-bleaching high
bulk density particulate detergent compositions cont~ning
soil release polymers of the invention are as follows:
6 7
Na LASl 28. 66 24.7015.00
Na PAS2 2.88 4.19
Nonionic 9EO - - 2 . 51
Zeolite 18.84 21.316 . 24
Ma tripolyphosphate 29. 69 6.78 39.25
Na carbonate - 16.4323.52
Na bicarbonate 6 . 26 - 2.97
Na silicate - - 2.37
SCMC 0.78 0.78 0.57
Fluorescer 0.01 0.5 60 . 30
Copolymer (Sokalan* CP5)1.93 1.99 1.18
Protease (Savinase* 6T)0.32 0.40 0.70
Lipase (Lipolase* lOOT)0.08 0.10 0.26
Amylase (Termamyl* 6 0T ) 0 .14
Soil release polymer 0.50 0.50 0.50
Perfume 0.40 0.40 0.60
Moisture and impurities ----- to 100.00 ----
Bulk density (g/litre) 780-820 ca. 800 ca. 800
lSodium linear alkylbenzene sulphonate
2Sodium primary alcohol sulphate
The composition of Example 5 is of low solution pH
(9.7-9.8) and is especially suitable for washing delicate
fabrics.
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EXAMPLE 8
A further example of a high bulk density non-
bleaching phosphate-built powder of low solution pH in
accordance with the invention, suitable for washing
delicate fabrics, is as follows:
Na LAS 6.50
Nonionic 6/7EO 4.00
Soap 4.30
Na tripolyphosphate 29.17
Na silicate 10.00
SCMC 0.43
Polyvinyl pyrrolidone 0.95
Na sulphate 17.00
Na carbonate (heavy) 6.00
Ammonium sulphate 2.00
Citric acid 2.25
Na metasilicate 2.00
Amorphous aluminosilicate 1.12
Protease (Savinase* 6T) 0.20
Lipase (Lipolase* lOOT) 0.05
Amylase (Termamyl* 60T) 0.25
Cellulase (Celluzyme* 0.7T) 0.40
Soil release polymer 0.55
Perfume 0.40
Moisture and impurities to 100.00
The bulk density of this formulation is 700 g/litre
and the 1 wt% aqueous solution pH in demineralised water is
9.7-9.8.
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EXAMPLES 9 ~nd 10
Examples of high bulk density phosphate-built
- 5 bleaching particulate detergent compositions in accordance
with the invention are as follows:
2 10
lQ
Na LAS 6.50 9.0o
Nonionic 6/7E0 4.00 4.00
Soap 4.30
Na tripolyphosphate 28.40 30 00
Na silicate 10.00 10.00
SCMC 0.36 0.36
Fluorescer 0.20 0.20
EDTA 0.06 0.06
Na carbonate (heavy)18.50 18.72
Citric acid 2.25 2.25
Na perborate 4H20 8.55 8.55
TAED 2.08 2.08
Amorph. aluminosilicate0.86 0.97
Protease (Savinase* 4.8T)) 0.65 1.00
Lipase (Lipolase* lOOT)
Soil release polymer O.55 0.55
Perfume 0.40 0 40
Moisture and impurities ---- to 100.00 -----
Bulk density (g/litre)700 700
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E~AMprl~s 11 and 12
Examples of phosphate-built spray-dried non-bleaching
particulate detergent compositions in accordance with the
invention cont~;n;ng high levels of anionic surfactant are
as follows:
11 12
Na LAS 26.00 26.00
Na tripolyphosphate 26.00 26.00
Na alkaline silicate 9.00 9.16
Sodium sulphate ~in base) 14.57 9.71
SCMC 1.00 1.00
Fluorescer 0. 25 0.25
Sodium carbonate 10.00 10.00
Sodium sulphate (postdosed) - 6.41
Enzyme (Maxacal* 600000)0.14 0.20
Soil release polymer 0. 50 0.50
EDTA, colour, nonionic
surfactant, water, perfume ----- to 100.00 -----
Bulk density (g/litre) 365-435 365-435
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E~MPLES 13 and 14
Examples of phosphate-built high bulk density non-
bleaching particulate detergent compositions in accordance
with the invention containing high levels of anionic
surfactant are as follows:
13 14
Na LAS 26.00 26.00
Na tripolyphosphate26.00 26.00
Na alkaline silicate9. 53 9.53
Sodium sulphate (in base) 12. 52 12.52
SCMC 1.04 1.04
Fluorescer 0.2 6 0. 2 6
Sodium carbonate 8. 47 8.53
Zeolite A (as hydrated)3.00 3.00
Enzymes: Savinase*/Lipolase* 0.50 0.50
Soil release polymer0.50 0.50
Perfume 0.25 0.30
EDTA, colour, water etc ----- to 100.00 ----
Bulk density (g/litre)720-800 720-800
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EX~MPT ~ 15
An example of a high bulk density phosphate-built
bleaching particulate detergent composition in accordance
with the invention containing a high level of anionic
surfactant is as follows:
Na LAS 26.355
Na tripolyphosphate 24. 478
Na alkaline.silicate 8. 931
Sodium sulphate (in base)8.215
SCMC 0.938
Fluorescer 0.149
Sodium carbonate 5.365
Zeolite A (as hydrated) 3. 576
Sodium perborate (monohydrate) 7.294
TAED green granules 2.824
EDTMP (Dequest* 2047) 0.471
Enzymes: Savinase*/Lipolase*0. 224
Kazusase* 0.224
Soil release polymer 0.500
Perfume ~ 300
EDTA, colour, water etcto 100.00
Bulk density 720-800 g/litre
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EXAMPT.~.~ 16 and 17
Further examples of phosphate-built non-bleaching
particulate detergent compositions in accordance with the
invention, one spray-dried and the other of high bulk
density, are as follows:
16 17
Na LAS 6.50 11.25
Na tripolyphosphate 28.00 39.25
Na alkaline silicate 9.00 4.13
Sodium sulphate (in base) 24.30 5.42
EDTA 0.01 0.004
SCMC 1.00 1.00
Fluorescer 0. 3 8 0.38
Nonionic surfactant 7EO3.00 5.00
Soap 5.00
Antifoam granule - 2.00
Sodium carbonate 12.00 22. 68
Enzymes: Savinase*/Lipolase* 0.22 0.70
Soil release polymer0 .50 0,50
Perfume 0.15 0.30
EDTA, colour, water etc----- to 100.00 ----
Bulk density (g/litre)375-425 760-840
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MPLE 1 8
An example of a phosphate- and carbonate-built spray-
dried particulate detergent composition in accordance with .
the invention containing a high level of anionic
surfactant, a bleach system and a photobleach, is as
follows:
Na LAS 22.00
Na carbonate (heavy) 15.00
Na tripolyphosphate 13 . 3 0
Na alkaline silicate 7.30
Na sulphate 22.30
Na perborate 8.00
TAED 2.40
SCMC 0. 3 5
EDTMP 0.40
Protease (Savinase* 6T) 0.65
Lipase (Lipolase* lOOT) 0.13
Fluorescer 0.20
Cu phthalocyanine 0.011
Soil release polymer 0.50
Perfume 0.25
Moisture and impurities to 100.00
Bulk density 460 g/litre
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EXAMPT F ~ 1 9 and 20
Examples of high bulk density non-bleaching
particulate detergent compositions in accordance with the
invention containing mixed zeolite, phosphate and carbonate
builders are as follows:
21
Na LAS 18.00 22.00
Nonionic 7E0 1.60 2.00
Na soap (stearate) - 2.00
Na tripolyphosphate 22.50 28.00
Zeolite A (anhydrous basis) 8.00 12.00
Na carbonate 25.00 27.00
Fluorescer 0.12 0.12
SCMC 0.55 0.55
Na sulphate 19.50 0.49
Savinase* 6.OT/Lipolase* lOOT 0.75 0.75
Soil release polymer 0.50 0.50
Perfume 0.35 0.35
Moisture and minor ingredients ----- to 100.00 -----
Bulk density (g/litre) 850 840
* * *
.... ~ ~.
