TECHNICAL FIELD
[0001] This invention relates to concentrated aqueous alkaline liquid detergent compositions
with low intrinsic foaming and in particular to liquids comprising soil release polymer
(SRP) substantive to polyester fabrics. In this specification, unless indicated to
the contrary, no distinction is made between polymer and oligomer. Both are termed
polymers.
BACKGROUND
[0002] It has been proposed to use polyester based SRPs in detergent compositions, especially
in laundry detergent compositions to promote improved soil removal from polyester
fabrics. Such polymers may have a polyester midblock with one or two end blocks of
capped polyethylene glycol attached to the midblock via ester linkages, see e.g.
WO 2012/104159,
EP 0523956 and
GB 1 466 639.
[0003] US 4759876 (Colgate) proposes an aqueous liquid concentrate comprising such a SRP. The preferred
liquids have around 80 wt% of the surfactant system as nonionic which gives these
compositions low in wash foaming and furthermore is expected to provide the concentrated
compositions with low intrinsic foaming. The compositions are formulated to be acidic
and triethanolamine free to protect the SRP.
[0004] The SRP used is a copolymer of polyethylene terephthalate and polyoxyethylene terephthalate
of molecular weight 22 000 wherein the polyoxyethylene is of molecular weight 3 400,
the molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate units
is about 3:1 and the proportion of ethylene oxide to phthalic moiety in the polymer
is about 22:1.
[0005] WO2009/153184 (Unilever) proposes to dose a main wash surfactant at low levels so that the in wash
surfactant level is lower than normal. What would be the consequential unsatisfactory
wash performance, resulting from the low in-wash surfactant levels, is boosted by
inclusion of unusually high levels of specific polymers and enzymes in the liquid.
A key polymer, preferably included at high levels in the composition, is SRP substantive
to polyester. The one used in the examples of
WO2009/153184 is of polyester chemistry (terephthalic acid/propandiol condensation polymer with
methoxy PEG 750 end cap). It is sold under the trade name TexCare® SRN170 by Clariant.
The examples of this document suggest using a higher ratio of non-soap anionic surfactant
to nonionic than is found in the examples of
US 4759876.
[0006] Concentrated detergent liquids following the principles set out in
WO2009/153184 may suffer from high levels of intrinsic foaming. By intrinsic foaming is meant that
the concentrated composition itself forms a foam layer when subjected to aeration.
This is a problem for handling of the compositions in the factory, particularly the
bottle filling operation. It is, however, a considerable problem when the consumer
will dose the composition using a volume measure, as is frequently the case for detergent
compositions used for laundry. If the composition foams as it is dispensed through
a nozzle or some similar dispensing device the mass dose will be too low for the measured
volume dose and the consumer will not obtain the expected performance from her product.
Compositions with increased levels of solvent hungry ingredients, in particular sequestrants,
may exhibit even higher intrinsic foaming. High levels of perfume, the incorporation
of ethoxylated polyethyleneimine and the use of amino based counter ions also tend
to make intrinsic foaming more significant.
[0007] Use of an additional antifoam system is possible. The introduction of silicone antifoam
could be considered, but it cannot be stably incorporated into the low viscosity compositions
that suffer most from intrinsic foaming. Furthermore, if an external structuring system
was to be used to suspend the silicone it would add cost and use up valuable formulation
space. Thus a more efficient solution is desired.
[0008] EP 1 661 933 (Sasol) describes amphiphilic non-ionic oligoesters that have soil release properties
after storage in alkaline detergent liquid. In the exemplary formulae a PO block of
up to 10, but preferably 2 to 4 may be added between the midblock esters and the PEG
endblock. The tested material has 4 such PO repeat units added. The mid block is essentially
1,4 - phenylene and 1,2 propylidene. Neither TEA nor alkoxylated polyethyleneimine
is used with these polymers. The examples show that the soil release performance of
this polymer after storage is superior to a polymer not having a PO block.
SUMMARY OF THE INVENTION
[0009] According to the present invention there is provided a concentrated alkaline liquid
detergent composition comprising:
- a) 5 to 60 wt% surfactant comprising anionic surfactant and optionally nonionic surfactant
and optionally amphoteric surfactant and optionally soap of which at least 35% of
the total surfactant is anionic non-soap surfactant,
- b) at least 30 wt% water,
- c) at least 0.25 wt% soil release polymer
characterised in that:
- (i) the soil release polymer has the formula (I), and
X-[(OCH2CH2)q-]-block-[(OCH2CH(CH3))p]-[OC(O)-G1-C(O)O-G2)n]-OC(O)-G1-C(O)O-[((CH3)CHCH2O)p-]-block-[(CH2CH2O)q]-X (I)
wherein the G
1 moieties are all 1,4-phenylene moieties; the G
2 moieties are all C
1-4 alkyl substituted ethylene moieties, each X is C
1-4 alkyl, preferably methyl or n-butyl; each q is from 12 to 120; each p is from 1 to
10, preferably 2 to 5; and n is from 2 to 10. The notation "block" is used here as
is known to the polymer chemist to mean that the parts of the backbone either side
of this notional division - e.g. [(OCH
2CH
2)
q] and [(OCH
2CH(CH
3))
p] are not randomly polymerised, rather they are formed as homogeneous blocks.
[0010] The compositions are especially useful as laundry detergent compositions.
[0011] Preferably the compositions comprise at least 0.5 wt% of the soil release polymer.
[0012] Preferably the compositions comprise at least 0.5 wt% triethanolamine, more preferably
they comprise at least 1 wt% triethanolamine.
[0013] More preferably the compositions comprise at least 0.5 wt% of the soil release polymer
and at least 1 wt% triethanolamine.
[0014] Because the non-soap anionic surfactant is believed to be the main source of the
intrinsic foaming the ratio of non-soap anionic surfactant to soil release polymer
should preferably be at most 25:1, more preferably 15:1 and most preferably at most
9:1.
[0015] The polyesters soil release polymers of formula (I) have surprisingly been found
to confer significant intrinsic antifoaming benefits to the concentrated detergent
liquids.
Preferably the composition further includes at least 2 wt% nonionic alkoxylated polyethyleneimine
with at least 3 moles of alkoxylation per nitrogen.
[0016] The block polyesters of formula (I) are linear block polyesters. n preferably ranges
from 3 to 9, especially for polymers made from dimethyl terephthalate, and 1,2-propylene
glycol.
[0017] The most preferred linear block polyesters are those where n is from 6 to 8.
[0018] Most preferably, in the formula (I), p is 2 and q is from 18 to 60.
[0019] In one embodiment at least 10% of the groups G
2 are dimethylene substituted. This optional modification helps to keeps the esters
in the midblock intact as fabric substantivity and thus soil release properties are
otherwise lost and the improved resistance to hydrolysis is of no practical significance.
This midblock modification appears to make no difference to the anti foam properties
of the polymer.
[0020] The end blocks - [((CH
3)CHCH
2O)
p-]-block-[(CH
2CH
2O)
q]-X may both be present, alternatively only one of the two possible end blocks needs
to be present, throughout this specification and claims references to end blocks include
the situation where one or other end block is missing unless the context requires
otherwise. Preferably the polymer has two end blocks. If one of the end blocks is
missing then capping group X will similarly be missing from that end.
[0021] The alkaline liquid detergent compositions may comprise the polymer (d) in amounts
of up to 15 wt%, preferably from 1 to 10 wt%, most preferably from 1.5 to 7 wt%.
Preferably the alkaline concentrated detergent liquid composition is isotropic. The
composition may comprise at least 5 wt% non-soap anionic surfactant. Suitably the
liquid may comprise linear alkyl benzene sulphonate (LAS), Alkyl ether sulphate (AES),
Nonionic and optionally an amine oxide or betaine, the LAS being formed from LAS acid,
neutralized at least in part, with TEA. Amines may also be used as the counter ion
for the AES. It is preferred for stability reasons to keep the total level of alkali
metal ions less than 1 wt% of the composition.
[0022] To maximise the benefit of the other cleaning technologies that are essentially or
optionally included in the liquid, especially anionic surfactant, the liquid is alkaline.
It is preferred that the maximum concentrated composition pH is 8.4, more preferably
at most 8.2.
DETAILED DESCRIPTION OF THE INVENTION
[0023] The invention is a combination of a selected group of polyester soil release polymers
with surprising antifoaming properties and a liquid detergent base that has high intrinsic
foaming.
[0024] All percentages are weight percent except where indicated otherwise or where the
context makes it obvious that something else is intended.
The polyester soil release polymer (with antifoam properties)
[0025] The invention requires the selection of a soil release polymer with a polyester mid
block and its incorporation into an alkaline concentrated detergent liquid, comprising
surfactant and triethanolamine.
[0026] The SRPs with suitable antifoam effect have the formula (I):
X-[(OCH
2CH
2)
q-]-block-[(OCH
2CH(CH
3))
p]-[(OC(O)-G
1-C(O)O-G
2)
n]-OC(O)-G
1-C(O)O-[((CH
3)CHCH
2O)
p-]-block-[(CH
2CH
2O)
q]-X (I)
X-[(OCH
2CH
2)
q]-block-[(OCH
2CH(CH
3))
p]- and - [((CH
3)CHCH
2O)
p-]-block-[(CH
2CH
2O)
q]-X are generally connected at the ends of the polymer backbone or mid block. The
mid block is responsible for making the polymer fabric substantive, particularly towards
polyester fabrics. The endcaps of large blocks of EO groups are highly hydrophilic
and can be considered to swing away from the fabric to provide the surface modification
that promotes soil release. Thus it is an essential feature of the polymers of the
present invention to have capped EO end block(s).
[0027] The polymer will be nonionic. Ionic polymers are generally not phase stable in concentrated
alkaline detergent liquids.
Mid block or backbone
[0028] The mid block ]-[(OC(O)-G
1-C(O)O-G
2)
n]-OC(O)-G
1-C(O)O- is responsible for making the polymer fabric substantive, particularly towards
polyester fabrics. It has little effect on the antifoam properties of the polymer.
[0029] The esters in the midblock may in practice be formed either way around.
[0030] The G
1 moieties comprise 1,4-phenylene moieties.
[0031] The G
2 moieties are substituted ethylene moieties having C
1-4 alkyl substituents. A preferred mono substituted ethylene moiety is 1,2 propylene
which is derived from the condensation of 1,2 propane diol.
[0032] For the G
2 moieties, most preferred substituted ethylene moieties are the monomethyl substituted
G
2 formed from 1,2-propylene diol, and the dimethyl substituted G
2 formed from 2,3 butylene diol. The use of 1,2 di methyl substituted ethylene shows
superior protection of adjacent ester bonds due to that fact that it is always going
to be the case that there is a methyl group on the carbon atom adjacent to the ester.
The contrasts with the situation for the monomethyl material formed from 1,2 propane
diol. In that case the methyl group may arrange itself adjacent to the ester or it
may alternatively arrange itself to be on the carbon of the ethylene that is more
remote from the ester.
[0033] 2,3 butylene is a meso stereo isomeric compound. It is thought that once reacted
into the polymer chain the different forms behave in similar ways as far as the hindering
of hydrolysis is concerned. The optically active RR or SS diastereoisomers are preferred
over the RS (meso) diastereoisomer. Thus, the preferred form of the 2,3 butylene glycol
used is the RR or SS optically active forms either isolated, or as a racemic mixture.
In practice a mixture of the meso and racemic forms has been found to give satisfactory
results.
[0034] A preferred diol to form the desired group G
2 may be selected from the group of diols of formula (II):
syn n+1,n+2 alkylene diol (II)
n being an integer from 1 to c-3, where c is the number of carbons in the alkylene
chain.
[0035] The most preferred diols are syn 2,3 butane diol and 1,2 propane diol.
[0036] G
2 may comprise up to 20 mol% moieties derived from 2,3 butane diol derivatives, i.e.
an ethylene moiety with a methyl group substituted on each carbon in the backbone.
[0037] It has been found that the value of n needs to be at least 2 in order for the antifoam
polymers used in the invention to have sufficient polyester substantivity. The maximum
value for n can range up to 26. By comparison, polyesters used in fibre making typically
have a much higher molecular weight with n from 50 to 250. Typically, n ranges from
2 to 16, preferably 4 to 9 most preferably 6 to 8. Generally, the larger the n value,
the less soluble is the polymer. Because it is an average, n is not necessarily a
whole number for the polymer in bulk.
End block
[0038] The following examples suggest that it is the propoxylation of the end blocks that
gives the antifoam benefit. The degree of propoxylation should be from 1 to 10 propylene
oxide units on average per end block. It is in a block. 2 to 5 PO is preferred due
to having the right balance of antifoam properties. The antifoam benefit does not
seem to increase linearly with the amount of propoxylation.
[0039] The polymers have an EO block that has more alkoxy units than the PO block, preferably
the EO block has at least 1.5 times the number of moles or units (q) as the PO block
(p), more preferably at least 5 times as many, even 10 times as many, or more. q is
at least 6, and is preferably at least 10. The value for q usually ranges from 18
to 80. Typically, the value for q is in the range of from 30 to 70, preferably 40
to 70.
[0040] The terminal end cap X on the EO blocks is preferably as small as possible. X is
preferably methyl, ethyl, or n-butyl and most preferably methyl or n-butyl.
[0041] As the value for q increases, the value for n in the midblock should be increased
so that the polymer will deposit well on the fabric during laundering.
[0042] Since p and q are made by anionic polymerisation routes this results in blocks with
discrete block lengths in contrast to the midblock made by polycondensation routes.
Molecular weight
[0043] Preferred polymers for use in liquid detergent compositions have molecular weights
Mw within the range of from 1000 to 20 000, preferably from 1500 to 10 000. Preferably
the molecular weight is greater than 4 000. The polydispersity of the polymers is
preferred to be less than 3.
Preparation of the polymer
[0044] The soil release polymers of the present invention can be prepared by methods known
to the person skilled in the art.
US 4,702, 857 and
US 4,711,730 describe a method of synthesis that may be adapted to produce the block polyesters
of the present invention. In one process the end blocks are made in a separate process
and then added to the mid block. A suitable process to manufacture the block copolymers
used for the end blocks is described below.
End block manufacture
[0046] The reaction scheme is set forth below:
Reaction A: Sodium hydride reacts with PEG to yield activated chain ends.
Reaction B: The addition of PO proceeds at the ends of the PEG chains to form a block
of PO.
[0047] An alternative process forms the mid block and reacts it with PO and mPEG.
Mid block manufacture
[0048] The mid block may be formed by condensation of methyl esters of terephthalic acid
with the appropriate aliphatic diol, preferably using an excess of one of them as
set forth in more detail in the following examples. If the dicarboxylic acid is used
in alkyl ester form, the reaction is suitably carried out in the presence of a base
catalyst, at an elevated temperature, for example, 120 to 180 °C, and, if desired,
under reduced pressure. The lower alcohol, normally methanol, generated during the
reaction is distilled off.
[0049] Suitable catalysts include alkyl and alkaline earth metals, for example lithium,
sodium, calcium and magnesium, as well as transition and Group IIB metals, for example,
antimony, manganese, cobalt and zinc. The catalysts are usually used as oxides, carbonates
or acetates. A preferred catalyst comprises antimony trioxide and calcium acetate.
[0050] The esters and oligomers produced in the condensation (ester interchange) reaction
may then be polymerised to the desired molecular weight, by raising the temperature
further, typically to 180 to 250 °C.
[0051] The degree of polymerisation may be monitored by gel permeation chromatography, NMR,
and end-group titrations.
The detergent liquids
[0052] Following the approach proposed in
WO2009/153184 the preferred liquids have high amounts of soil release polymer, EPEI, enzymes, and
sequestrant relative to the total detersive surfactants level. By careful selection
of these performance ingredients to be ones that perform better when in wash surfactant
levels are lower, the overall detergency of the wash liquor can be adjusted to match
that of a wash liquor delivered from a conventional liquid which has broadly similar
levels of performance additives and higher levels of surfactants in the wash liquor.
The issues with such an approach to concentration are twofold. First the additives
that exhibit this high performance property in combination must be found and then
they must be stably incorporated into the concentrated liquid which has surfactants
in the normal range or slightly lower than normal for a concentrated liquid but performance
additives included at much higher levels than normal in the concentrated liquid. Because
of the degree of difficulty in putting the full formulation together with so many
constraints the selection of a multifunctional soil release polymer so that it not
only provides effective soil release performance but also solves the intrinsic foaming
problem is highly advantageous and unexpected for the person skilled in formulating
liquid detergents.
[0053] The amount of surfactant makes up at least 5 wt% of the total liquid composition,
preferably it makes up from 12 to 60 wt%. The compositions according to the invention
most preferably have total active detersive surfactant levels of at least 15 wt%.
[0054] The compositions may be concentrated laundry detergent compositions designed to be
added to a 10 litre wash in small doses that require them to be diluted in at least
500 times their own volume of water to form a main wash liquor comprising at most
0.5 g/l surfactant. They may also be concentrated compositions designed for hand wash
or top loading automatic washing machines. In hand wash less water may be used and
in top loading automatic washing machines a higher amount of water would normally
be used.
[0055] The dose of detergent liquid is adjusted accordingly to give similar wash liquor
concentrations.
Surfactants
[0056] Surfactants assist in removing soil from the textile materials and also assist in
maintaining removed soil in solution or suspension in the wash liquor. Anionic or
blends of anionic and nonionic surfactants are a preferred feature of the present
invention. The amount of anionic surfactant is preferably at least 5 wt%.
[0057] To obtain the full benefit of the invention it is preferred that the ratio of nonionic
surfactant to total surfactant is at most 3:2. Compositions with higher levels of
nonionic do not suffer from intrinsic foaming to such an extent.
Anionic
[0058] Preferred alkyl sulphonates are alkylbenzene sulphonates, particularly linear alkylbenzene
sulphonates having an alkyl chain length of C
8-C
15. The preferred counter ion for concentrated alkaline liquids is one or more ethanolamines,
for example monoethanolamine (MEA) and triethanolamine (TEA). This introduces TEA
into the composition.
[0059] The linear alkyl benzene sulphonate surfactants may be Detal LAS with an alkyl chain
length of from 8 to 15, more preferably 12 to 14.
[0060] It is further desirable that the composition comprises an alkyl polyethoxylate sulphate
anionic surfactant of the formula (II):
RO(C
2H
4O)
xSO
3-M
+ (II)
where R is an alkyl chain having from 10 to 22 carbon atoms, saturated or unsaturated,
M is a cation which makes the compound water-soluble, especially an ammonium or substituted
ammonium cation, or less preferably an alkali metal, and x averages from 1 to 15.
[0061] Preferably R is an alkyl chain having from 12 to 16 carbon atoms, x averages from
1 to 3, preferably x is 3; M may be an ethanolamine, or other material chosen from
the list of buffers, to avoid ion exchange of sodium with the counter ion of the LAS.
However, since some sodium can be tolerated the counter ion can be sodium if low levels
of this surfactant are used. The anionic surfactant sodium lauryl ether sulphate (SLES)
may be used provided total alkali metal salts in the composition remain low. An average
of 3 moles of ethylene oxide per mole is preferred.
Nonionic
[0062] Nonionic surfactants include primary and secondary alcohol ethoxylates, especially
C
8-C
20 aliphatic alcohol ethoxylated with an average of from 1 to 20 moles of ethylene oxide
per mole of alcohol, and more especially the C
10-C
15 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 alkyl polyglycosides, glycerol monoethers and polyhydroxy amides (glucamide).
Mixtures of nonionic surfactant may be used. When included therein the composition
contains from 0.2 wt% to 40 wt%, preferably 1 wt% to 20 wt%, more preferably 5 to
15 wt% of a non-ionic surfactant, such as alcohol ethoxylate, nonylphenol ethoxylate,
alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acid monoethanolamide,
fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl
derivatives of glucosamine ("glucamides").
[0063] Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates,
especially the C
8-C
20 aliphatic alcohols ethoxylated with an average of from 1 to 35 moles of ethylene
oxide per mole of alcohol, and more especially the C
10-C
15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to
10 moles of ethylene oxide per mole of alcohol.
Amine Oxide
[0064] The composition may comprise up to 10 wt% of an amine oxide of the formula (III):
R
1N(O)(CH
2 R
2)
2 (III)
[0065] In which R
1 is a long chain moiety each CH
2R
2 are short chain moieties. R
2 is preferably selected from hydrogen, methyl and -CH
2OH In general R
1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated,
preferably, R
1 is a primary alkyl moiety. R
1 is a hydrocarbyl moiety having chain length of from about 8 to about 18. Preferred
amine oxides have R
1 is C
8-C
18 alkyl, and R
2 is H. These amine oxides are illustrated by C
12-
14 alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide.
[0066] A preferred amine oxide material is Lauryl dimethylamine oxide, also known as dodecyldimethylamine
oxide or DDAO. Such an amine oxide material is commercially available from Huntsman
under the trade name Empigen® OB.
[0067] Amine oxides suitable for use herein are also available from Akzo Chemie and Ethyl
Corp. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine
oxide manufacturers.
[0068] Whereas in certain of the preferred embodiments R
2 is H, it is possible to have R
2 slightly larger than H. Specifically, R
2 may be CH
2OH, such as: hexadecylbis(2-hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine
oxide, stearylbis(2-hydroxyethyl)amine oxide and oleylbis(2- hydroxyethyl)amine oxide.
[0069] Preferred amine oxides have the formula:
O
- - N
+(Me)
2R
1 (IV)
where R
1 is C
12-16 alkyl, preferably C
12-14 alkyl; Me is a methyl group.
Zwitterionic
[0070] Nonionic-free systems with up to 95 %wt LAS can be used provided that some zwitterionic
surfactant, such as carbobetaine, is present. A preferred zwitterionic material is
a betaine available from Huntsman under the name Empigen® BB. Betaine improves particulate
soil detergency in the compositions of the invention.
Additional surfactants
[0071] Other surfactants than the preferred LAS, AES, and nonionic may be added to the mixture
of detersive surfactants. However, cationic surfactants are preferably substantially
absent.
[0072] Although less preferred, some alkyl sulphate surfactant (PAS) may be used, especially
the non-ethoxylated C
12-15 primary and secondary alkyl sulphates.
Soap may be used. Levels of soap are preferably lower than 5 wt%; more preferably
lower than 3 wt% most preferably lower than 1 wt%.
EPEI
[0073] For detergency boosting it is advantageous to use a second polymer with the soil
release polymers of the present invention this is a polyalkoxylated polyethyleneimine.
[0074] Polyethylene imines are materials composed of ethylene imine units -CH2CH2NH- and,
where branched, the hydrogen on the nitrogen is replaced by another chain of ethylene
imine units. These polyethyleneimines can be prepared, for example, by polymerizing
ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulphite,
sulphuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, and the like. Specific
methods for preparing these polyamine backbones are disclosed in
U.S. Pat. No. 2,182,306, Ulrich et al., issued Dec. 5,1939;
U.S. Pat. No. 3,033,746, Mayle et al., issued May 8,1962;
U.S. Pat. No. 2,208,095, Esselmann et al., issued Jul. 16, 1940;
U.S. Pat. No. 2,806,839, Crowther, issued Sep. 17, 1957; and
U.S. Pat. No. 2,553,696, Wilson, issued May 21, 1951.
[0075] Preferably, the EPEI comprises a polyethyleneimine backbone of about 300 to about
10000 weight average molecular weight; and the polyalkoxylation comprises polyethoxylation.
The polymer is nonionic and has no permanent quaternisation of the polyamine nitrogens;
although they may be protonated depending on the pH. A preferred nonionic EPEI may
be represented as PEI(X)YEO where X represents the molecular weight of the unmodified
PEI and Y represents the average moles of ethoxylation per nitrogen atom in the polyethyleneimine
backbone. The ethoxylation may range from 3 to 40 ethoxy moieties per polyalkoxyl
chain, preferably it is in the range of 16 to 26, most preferably 18 to 22. A minority
of the ethoxy units may be replaced by propoxy units.
[0076] When present the alkoxylated polyethyleneimine polymer is present in the composition
at a level of between 0.01 and 25 wt%, and preferably at a level of at least 2 wt%
and/or less than 9.5 wt%, most preferably from 3 to 9 wt% and with a ratio of non-soap
surfactant to EPEI of from 2:1 to 7:1, preferably from 3:1 to 6:1, or even to 5:1.
Other polymers
[0077] In addition to the polyester soil release polymer with antifoam properties and the
optional EPEI the composition may comprise other polymeric materials, for example:
dye transfer inhibition polymers, anti redeposition polymers and cotton soil release
polymers, especially those based on modified cellulosic materials. Especially when
EPEI is not present the composition may further comprise a polymer of polyethylene
glycol and vinyl acetate, for example the lightly grafted copolymers described in
WO2007/138054. Such amphiphilic graft polymers based on water soluble polyalkylene oxides as graft
base and side chains formed by polymerisation of a vinyl ester component have the
ability to enable reduction of surfactant levels whilst maintaining high levels of
oily soil removal.
Hydrotrope
[0078] In the context of this invention a hydrotrope is a solvent that is neither water
nor conventional surfactant that aids the solubilisation of the surfactants and other
components, especially polymer and sequestrant, in the liquid to render it isotropic.
Among suitable hydrotropes there may be mentioned as preferred: MPG (monopropylene
glycol), glycerol, sodium cumene sulphonate, ethanol, other glycols, e.g. di propylene
glycol, diethers and urea. MPG and glycerol are preferred hydrotropes.
Enzymes
[0079] It is preferable that at least one or more enzymes selected from protease, mannanase,
pectate lyase, cutinase, esterase, lipase, amylase, and cellulase may be present in
the compositions. Less preferred additional enzymes may be selected from peroxidase
and oxidase. The enzymes are preferably present with corresponding enzyme stabilizers.
The total enzyme content is preferably at least 2 wt%, even as high as at least 4
wt%.
Sequestrants
[0080] There is not room to include high levels of builders in the concentrated compositions.
Thus, sequestrants are preferably included. Such materials tend to have low solubility
in the concentrated liquids so the multifunctionality of the antifoam soil release
polymer assists in stably incorporating these materials into the compositions.
[0081] Preferred sequestrants include organic phosphonates, alkanehydroxy phosphonates and
carboxylates available under the DEQUEST trade mark from Thermphos.
[0082] The preferred sequestrant level is less than 10 wt% and preferably less than 5 wt%
of the composition. A particularly preferred sequestrant is HEDP (1-Hydroxyethylidene
-1,1,-diphosphonic acid), for example sold as Dequest 2010. Also suitable but less
preferred as it gives inferior cleaning results is Dequest® 2066 (Diethylenetriamine
penta(methylene phosphonic acid or Heptasodium DTPMP).
Buffers
[0083] In addition to the 1% TEA the presence of buffer is preferred for pH control; preferred
buffers are MEA, and TEA. They are preferably used in the composition at levels of
from 5 to 15 wt%, including the 1% TEA. Other suitable buffer materials may be selected
from the group consisting of amino alcohol compounds having a molecular weight above
61 g/mol, which includes MEA. Suitable materials also include, in addition to the
already mentioned materials: monoisopropanolamine, diisopropanolamine, triisopropanolamine,
monoamino hexanol, 2-[(2-methoxyethyl) methylamino]-ethanol, propanolamine, N-methylethanolamine,
diethanolamine, monobutanolamine, isobutanolamine, monopentanolamine, 1-amino-3-(2-methoxyethoxy)-
2-propanol, 2-methyl-4-(methylamino)-2-butanol and mixtures thereof.
Further Optional Ingredients:
[0084] It may be advantageous to include fluorescer and /or bleach catalyst in the compositions
as further high efficiency performance additives. Their inclusion is also made easier
by the soap reduction made possible by inclusion of the propoxylated polyester soil
release polymers. Perfume and colorants will desirably be included in the compositions.
The compositions may contain viscosity modifiers, foam boosting agents, preservatives
(e.g. bactericides), pH buffering agents, polyelectrolytes, anti-shrinking agents,
anti-wrinkle agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting
agents, antistatic agents and ironing aids. The compositions may further comprise,
pearlisers and/or opacifiers or other visual cues and shading dye.
Packaging and dosing
[0085] The liquids may be packaged as unit doses in polymeric film soluble in the wash water.
Alternatively the liquids may be supplied in multidose plastics packs with a top or
bottom closure. A dosing measure may be supplied with the pack either as a part of
the cap or as an integrated system.
[0086] The invention will now be further described with reference to the following non-limiting
examples.
EXAMPLES
Key to ingredients used:
[0087]
- MPG
- is mono propylene glycol.
- TEA
- is triethanolamine.
- MEA
- is Monoethanolamine.
- NI 7EO
- is C12-15 alcohol ethoxylate 7EO nonionic Neodol® 25-7 (ex Shell Chemicals).
- LAS acid
- is C12-14 linear alkylbenzene sulphonic acid.
- Prifac® 5908
- is saturated lauric fatty acid ex Croda.
- SLES 3EO
- is sodium lauryl ether sulphate with 3 moles EO.
- EPEI
- is Sokalan HP20 - ethoxylated polyethylene imine cleaning polymer: PEI(600) 20EO ex
BASF.
- Perfume
- is free oil perfume.
- Dequest® 2010
- is HEDP (1-Hydroxyethylidene -1,1,-diphosphonic acid).
- Empigen® OB
- is Amine oxide ex Huntsman.
- TexCare SRN-170
- is soil release polymer ex Clariant.
- SRP 1
- is an antifoam soil release polymer with propoxylation and having: G2 = 80 mol% monomethyl ethylene 20 mol% 1,2 dimethyl ethylene, p=3 q=45, X=Methyl,
n=6-7.
- SRP 2
- is an antifoam soil release polymer with propoxylation and having G2 100 mol% monomethyl ethylene, p=5 q=45, X=Methyl, n=6-7.
- SRP 3
- is an antifoam soil release polymer with propoxylation and having G2 100 mol% monomethyl ethylene, p=2 q=45, X=Methyl, n=6-7.
- Preservative
- is Proxel GLX antimicrobial preservative, a 20% solution of 1,2 benzisothiazolin-3-one
in dipropylene glycol and water ex Arch Biocides.
- Colorant
- is a mixture of equal part patent blue and acid yellow
Example 1 - concentrated liquid compositions with SRP
[0088] A series of compositions designed to be dosed at 35 ml per wash was formulated with
no SRP, with prior art SRPs and with propoxylated SRPs. The compositions used are
given in Table 1. They were subjected to a foam evaluation using the following protocol:
A 30 ml sample of the concentrated detergent composition was added to a 100 ml measuring
cylinder. The cylinder was sealed and shaken 20 times to generate foam. The cylinder
was left to stand for 1 minute and the foam height measured. The protocol was repeated
up to 6 times for each sample and the average taken. The results are given in Table
2.
[0089] It can be seen from Table 2 that TexCare® SRN240, a polymer of similar molecular
weight and construction to that of the propoxylated SRPs (but without any propoxylation),
causes the composition to foam and is very similar to that of the base alone and TexCare®
SRN170. All three propoxylated SRPs cause a significant reduction in foaming.
Table 1 - Liquid detergent compositions
|
|
Compositions Wt % as 100% |
Ingredient |
%AD |
1 |
2 |
3 |
4 |
5 |
6 |
Demin water and MEA to adjust pH |
100 |
balance |
balance |
balance |
balance |
balance |
balance |
MPG |
100 |
20.00 |
20.00 |
20.00 |
20.00 |
20.00 |
20.00 |
TEA |
100 |
2.00 |
2.00 |
2.00 |
2.00 |
2.00 |
2.00 |
NI 7EO |
100 |
7.28 |
7.28 |
7.28 |
7.28 |
7.28 |
7.28 |
LAS Acid |
97.1 |
4.85 |
4.85 |
4.85 |
4.85 |
4.85 |
4.85 |
Prifac 5908 |
100 |
0.69 |
0.69 |
0.69 |
0.69 |
0.69 |
0.69 |
SLES 3EO |
70 |
2.42 |
2.42 |
2.42 |
2.42 |
2.42 |
2.42 |
Empigen OB |
30 |
0.86 |
0.86 |
0.86 |
0.86 |
0.86 |
0.86 |
EPEI |
80 |
3.14 |
3.14 |
3.14 |
3.14 |
3.14 |
3.14 |
Dequest 2010 |
60 |
1.50 |
1.50 |
1.50 |
1.50 |
1.50 |
1.50 |
TexCare SRN-170 |
70 |
0.00 |
2.14 |
0.00 |
0.00 |
0.00 |
0.00 |
SRP 1 |
100 |
0.00 |
0.00 |
2.14 |
0.00 |
0.00 |
0.00 |
SRP 2 |
100 |
0.00 |
0.00 |
0.00 |
2.14 |
0.00 |
0.00 |
SRP 3 |
100 |
0.00 |
0.00 |
0.00 |
0.00 |
2.14 |
0.00 |
TexCare SRN-240 |
40 |
0.00 |
0.00 |
0.00 |
0.00 |
0.00 |
2.14 |
Preservative |
20 |
0.01 |
0.01 |
0.01 |
0.01 |
0.01 |
0.01 |
Colorant & Fluorescer |
0.1 |
0.06078 |
0.06078 |
0.06078 |
0.06078 |
0.06078 |
0.06078 |
Perfume |
100 |
1.43 |
1.43 |
1.43 |
1.43 |
1.43 |
1.43 |
Total |
100 |
100.00 |
100.00 |
100.00 |
100.00 |
100.00 |
100.00 |
Viscosity @25°C and 23 s-1 (Pas) |
|
0.0633 |
0.0527 |
0.0660 |
0.0659 |
0.0656 |
- |
Table 2
|
Foam volume (ml) |
Composition |
Rep 1 |
Rep 2 |
Rep 3 |
Rep 4 |
Rep 5 |
Rep 6 |
Ave |
StDev |
1 |
30 |
42 |
35 |
- |
- |
- |
35.67 |
6.03 |
2 |
22 |
30 |
25 |
34 |
26 |
27 |
27.33 |
4.17 |
3 |
1 |
1 |
1 |
- |
- |
- |
1 |
0 |
4 |
3 |
3 |
3 |
- |
- |
- |
3 |
0 |
5 |
2 |
2 |
2 |
2 |
2 |
2 |
2 |
0 |
6 |
- |
- |
- |
35 |
25 |
33 |
31 |
5.29 |
1. A concentrated alkaline liquid detergent composition comprising:
a) 5 to 60 wt% surfactant comprising anionic surfactant and optionally nonionic surfactant
and optionally amphoteric surfactant and optionally soap of which at least 35% of
the total surfactant is anionic non-soap surfactant,
b) at least 30 wt% water
c) at least 0.25 wt% soil release polymer
characterised in that:
(i) the soil release polymer has the formula (I), and
X-[(OCH2CH2)q-]-block-[(OCH2CH(CH3))p]-[(OC(O)-G1-C(O)O-G2)n]-OC(O)-G1C(O)O-[((CH3)CHCH2O)p-]-block-[(CH2CH2O)q]-X (I)
wherein the G1 moieties are all 1,4-phenylene moieties; the G2 moieties are all C1-4 alkyl substituted ethylene moieties, each X is C1-4alkyl, preferably methyl or n-butyl; each q is from 12 to 120; each p is from 1 to
10, preferably 2 to 5; and n is from 2 to 10.
2. A composition according to claim 1 further comprising at least 0.5 wt% triethanolamine
(TEA).
3. A composition according to claim 2 comprising at least 1 wt% triethanolamine.
4. A composition according to any preceding claim comprising at least 0.5 wt% of the
soil release polymer (c).
5. A composition according to any preceding claim in which the ratio of non-soap anionic
surfactant to soil release polymer is at most 9:1.
6. A composition according to any preceding claim wherein each G2 has one or two C1-4 alkyl substituents with at most one on each carbon.
7. A composition according to any preceding claim wherein the C1-4 alkyl moieties are methyl moieties.
8. A composition according to any preceding claim comprising at least 2 wt% alkoxylated
polyethylene imine.
9. A composition according to any preceding claim comprising at least 5 wt% anionic surfactant.
10. A composition according to any preceding claim comprising Alkyl ether sulphate anionic
surfactant.
11. A composition according to any preceding claim comprising linear alkyl benzene sulphonate
(LAS), the LAS being neutralised from LAS acid, at least in part, with triethanolamine
(TEA).
12. A composition according to any preceding claim comprising at least 2 wt% of the soil
release polymer (c).
13. A composition according to any preceding claim comprising at least three enzymes.
14. A composition according to any preceding claim comprising at least 1 wt% sequestrants.
15. A composition according to any preceding claim comprising at least 0.5 wt% amine oxide.
16. A composition according to any preceding claim comprising up to 25 wt% hydrotrope.
17. A composition according to any preceding claim comprising at most 1 wt% alkali metal
ions.
18. A composition according to any preceding claim with a viscosity measured at 23 s-1 at 25°C of less than 0.1 Pa.s.
19. A composition according to any preceding claim comprising less than 5 wt%, soap, preferably
less than 3 wt%, most preferably less than 1 wt%.
1. Konzentrierte alkalische flüssige Reinigungsmittelzusammensetzung, umfassend:
a) 5 bis 60 Gew.-% Tensid, umfassend anionisches Tensid und gegebenenfalls nichtionisches
Tensid und gegebenenfalls amphoteres Tensid und gegebenenfalls Seife, wovon mindestens
35% des gesamten Tensids ein anionisches Nicht-Seifentensid darstellt,
b) mindestens 30 Gew.-% Wasser,
c) mindestens 0,25 Gew.-% Soil-Release-Polymer,
dadurch gekennzeichnet, dass
(i) das Soil-Release-Polymer die Formel (I) und
X-[(OCH2CH2)q-]-block-[(OCH2CH(CH3))p]-[(OC(O)-G1-C(O)O-G2)n]-OC(O)-G1-C(O)O-[((CH3)CHCH2O)p-]-block-[(CH2CH2O)q]-X (I)
hat,
worin die G1-Anteile sämtlich 1,4-Phenylen-Anteile sind,
die G2-Anteile sämtlich C1-4-Alkyl-substituierte Ethylenanteile sind,
jedes X ist C1-4-Alkyl, vorzugsweise Methyl oder n-Butyl,
jedes q von 12 bis 120 ist, jedes p von 1 bis 10 ist, vorzugsweise 2 bis 5, und n
von 2 bis 10 ist.
2. Zusammensetzung gemäß Anspruch 1, des Weiteren umfassend mindestens 0,5 Gew.-% Triethanolamin
(TEA).
3. Zusammensetzung gemäß Anspruch 2, umfassend mindestens 1 Gew.-% Triethanolamin.
4. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, umfassend mindestens 0,5
Gew.-% des Soil-Release-Polymers (c).
5. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, worin das Verhältnis des
anionischen Nicht-Seifen-Tensids zu dem Soil-Release-Polymer höchstens 9:1 ist.
6. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, wobei jedes G2 einen oder zwei C1-C4-Alkyl-Substituenten mit höchstens einem an jedem Kohlenstoff aufweist.
7. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, worin die C1-C4-Alkyl-Anteile Methyl-Anteile darstellen.
8. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, umfassend mindestens 2
Gew.-% alkoxylierte Polyethylenimine.
9. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, umfassend mindestens 5
Gew.-% anionisches Tensid.
10. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, umfassend als anionisches
Tensid Alkylethersulfat.
11. Zusammensetzung nach irgendeinem vorhergehenden Anspruch, umfassend lineares Alkylbenzolsulfonat
(LAS), wobei das LAS von LAS-Säure, zumindest zum Teil, mit Triethanolamin (TEA) neutralisiert
ist.
12. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, umfassend mindestens 2
Gew.-% des Soil-Release-Polymers (c).
13. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, umfassend mindestens drei
Enzyme.
14. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, umfassend mindestens 1
Gew.-% Komplexbildner.
15. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, umfassend mindestens 0,5
Gew.-% Aminoxid.
16. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, umfassend bis zu 25 Gew.-%
hydrotropes Mittel.
17. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, umfassend höchstens 1 Gew.-%
Alkalimetallionen.
18. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch mit einer Viskosität, gemessen
bei 23 s-1 bei 25°C, von weniger als 0,1 Pa.s.
19. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, umfassend weniger als 5
Gew.-% Seife, vorzugsweise weniger als 3 Gew.-% und höchst bevorzugt weniger als 1
Gew.-%.
1. Composition de détergent liquide alcaline concentrée comprenant :
a) de 5 à 60 % en poids de tensioactif comprenant un tensioactif anionique et éventuellement
un tensioactif non ionique et éventuellement un tensioactif amphotère et éventuellement
du savon dont au moins 35 % du tensioactif total sont un tensioactif de non-savon
anionique,
b) au moins 30 % en poids d'eau
c) au moins 0,25 % en poids de polymère libérant la saleté
caractérisée en ce que :
(i) le polymère libérant la saleté présente la formule (I), et
X-[(OCH2CH2)q-]-séquence-[(OCH2CH(CH3))p]-[(OC(O)-G1-C(O)O-G2)n]-OC(O)O-G1-C(O)O-[((CH3)CHCH2O)p-]-séquence-[(CH2CH2O)q]-X (I)
où les moitiés G1 sont toutes des moitiés 1,4-phénylène ; les moitiés G2 sont toutes des moitiés éthylène substituées par un groupe alkyle en C1-4, chaque X est un groupe alkyle en C1-4, de préférence méthyle ou n-butyle ; chaque q est de 12 à 120 ; chaque p est de 1
à 10, de préférence de 2 à 5 ; et n est de 2 à 10.
2. Composition selon la revendication 1 comprenant de plus au moins 0,5 % en poids de
triéthanolamine (TEA).
3. Composition selon la revendication 2 comprenant au moins 1 % en poids de triéthanolamine.
4. Composition selon l'une quelconque des revendications précédentes comprenant au moins
0,5 % en poids du polymère libérant la saleté (c).
5. Composition selon l'une quelconque des revendications précédentes dans laquelle le
rapport de tensioactif anionique de non-savon au polymère libérant la saleté est d'au
plus 9:1.
6. Composition selon l'une quelconque des revendications précédentes, dans laquelle chaque
G2 présente un ou deux substituants alkyle en C1-4 avec au plus un sur chaque carbone.
7. Composition selon l'une quelconque des revendications précédentes, dans laquelle les
moitiés alkyle en C1-4 sont des moitiés méthyle.
8. Composition selon l'une quelconque des revendications précédentes comprenant au moins
2 % en poids de polyéthylène imine alcoxylée.
9. Composition selon l'une quelconque des revendications précédentes comprenant au moins
5 % en poids de tensioactif anionique.
10. Composition selon l'une quelconque des revendications précédentes comprenant un tensioactif
anionique de sulfate d'alkyléther.
11. Composition selon l'une quelconque des revendications précédentes comprenant un benzènesulfonate
d'alkyle linéaire (LAS), le LAS étant neutralisé à partir d'acide de LAS, au moins
en partie, avec de la triéthanolamine (TEA).
12. Composition selon l'une quelconque des revendications précédentes comprenant au moins
2 % en poids du polymère libérant la saleté (c).
13. Composition selon l'une quelconque des revendications précédentes comprenant au moins
trois enzymes.
14. Composition selon l'une quelconque des revendications précédentes comprenant au moins
1 % en poids de séquestrant.
15. Composition selon l'une quelconque des revendications précédentes comprenant au moins
0,5 % en poids d'oxyde d'amine.
16. Composition selon l'une quelconque des revendications précédentes comprenant jusqu'à
25 % en poids d'hydrotrope.
17. Composition selon l'une quelconque des revendications précédentes comprenant au plus
1 % en poids d'ions de métaux alcalins.
18. Composition selon l'une quelconque des revendications précédentes avec une viscosité
mesurée à 23 s-1 à 25°C inférieure à 0,1 Pa.s.
19. Composition selon l'une quelconque des revendications précédentes comprenant moins
de 5 % en poids de savon, de préférence moins de 3 % en poids, encore mieux moins
de 1 % en poids.