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EP 2 794 833 B1 |
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EUROPEAN PATENT SPECIFICATION |
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Mention of the grant of the patent: |
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03.02.2016 Bulletin 2016/05 |
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Date of filing: 19.11.2012 |
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International Patent Classification (IPC):
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International application number: |
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PCT/EP2012/072971 |
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International publication number: |
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WO 2013/092049 (27.06.2013 Gazette 2013/26) |
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ISOTROPIC AQUEOUS LIQUID LAUNDRY DETERGENT COMPRISING SEQUESTRANT
ISOTROPES WÄSSRIGES FLÜSSIGWASCHMITTEL MIT KOMPLEXBILDNER
DÉTERGENT LIQUIDE AQUEUX ISOTROPIQUE POUR LA LESSIVE COMPRENANT UN SÉQUESTRANT
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Designated Contracting States: |
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AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL
NO PL PT RO RS SE SI SK SM TR |
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Priority: |
20.12.2011 EP 11194458
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Date of publication of application: |
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29.10.2014 Bulletin 2014/44 |
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Proprietors: |
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- Unilever PLC
London, Greater London EC4Y 0DY (GB) Designated Contracting States: CY GB IE MT
- Unilever N.V.
3013 AL Rotterdam (NL) Designated Contracting States: AL AT BE BG CH CZ DE DK EE ES FI FR GR HR HU IS IT LI LT LU LV MC MK NL NO PL PT RO RS SE SI SK SM TR
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Inventors: |
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- GREEN, Andrew, David
Bebington
Wirral
Merseyside CH63 3JW (GB)
- PARRY, Alyn, James
Bebington
Wirral
Merseyside CH63 3JW (GB)
- WELLS, John, Francis
Bebington
Wirral
Merseyside CH63 3JW (GB)
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References cited: :
WO-A1-02/34872 US-A1- 2006 275 566
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FR-A1- 2 677 370
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Note: Within nine months from the publication of the mention of the grant of the European
patent, any person may give notice to the European Patent Office of opposition to
the European patent
granted. Notice of opposition shall be filed in a written reasoned statement. It shall
not be deemed to
have been filed until the opposition fee has been paid. (Art. 99(1) European Patent
Convention).
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TECHNICAL FIELD
[0001] This invention relates to isotropic aqueous liquid laundry detergents that deliver
lower than normal levels of surfactants to the wash and have correspondingly higher
than normal levels of performance enhancers comprising polymers, enzymes and sequestrants
to compensate for the reduced cleaning due to the reduction in surfactant. These performance
enhancers are more weight efficient than the surfactant they replace and thus facilitate
compositions that require very low dosage.
BACKGROUND
[0002] WO09153184 (Unilever) suggests that a laundry detergent liquid concentrate may be designed by
replacing surfactant with a mixture of more weight efficient ingredients selected
from polymers and enzymes. A preferred composition uses a combination of EPEI and
a polyester soil release polymer (SRP) to achieve excellent oily soil and particulate
detergency at significantly lower in-wash surfactant levels than would normally be
delivered from a high performance liquid. The exemplified compositions comprise anionic
surfactant comprising linear alkyl benzene sulphonate neutralised with sodium hydroxide
and further comprise soap formed by neutralisation of fatty acid by sodium hydroxide.
The compositions are alkaline. It has been found that the SRP used for the examples
has a higher level of stability if the concentrated liquid compositions including
it are formulated at about pH6.5. There is insufficient space for a conventional bleaching
system in such concentrated liquids. However, it is known that bleachable stains may
also be removed if relatively high levels of sequestrants are included in the liquid.
In the examples of
WO09153184 the sequestrant used was Dequest 2066, a polyphosphonate. Other sequestrants disclosed
in
WO09153184 are: alkali metal, citrates, succinates, malonates, carboxymethyl succinates, carboxylates,
polycarboxylates and polyacetyl carboxylates. Specific examples include sodium, potassium
and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids,
C
10-C
22 fatty acids and citric acid. Other examples are DEQUEST™, organic phosphonate type
sequestering agents and alkanehydroxy phosphonates.
[0003] FR2677370 (NLN SA) teaches to use a sequestering agent for liquid detergent compositions for
linen (washing) containing at least 20 percent by weight of water. It consists of
a mixed alkaline-earth metal and alkali metal ammonium C2-C8 alkanolamine or C2-C8
alkaneamine salt of 1-hydroxyethane-11-diphosphonic acid (HEDP) or of a mixture of
the said mixed salts. Another subject of the invention is the stable liquid detergent
compositions containing the said sequestering agent. The HEDP is added to liquid detergents
that don't have bleach. Alkanolamine neutralised surfactants may pose a problem for
alkali metal salts of HEDP. This precipitation problem is made worse by protease in
the liquid. The invention uses either sodium or potassium salts of HEDP premixed with
magnesium chloride. TEA / HEDP compositions at pH 7.7 are stable when magnesium chloride
is added.
[0004] We have confirmed this common general knowledge that the sequestrant 1-Hydroxyethylidene-1,
1-Diphosphonic Acid, abbreviated as HEDP and available from Thermphos as Dequest 2010,
gives excellent performance on bleachable stains, even when delivered from the mildly
acidic concentrated liquid chosen for soil release polymer stability. However, HEDP
has been found to be much harder to incorporate into isotropic liquids with acceptable
physical stability compared with the prior art Dequest 2066, this is especially a
problem at the incorporation levels needed for a 20ml dose to European front loading
automatic washing machines. In particular the high temperature stability of acid HEDP
containing versions of the liquids found in
WO09153184 has been found to be poor.
[0005] WO 99/49009 (P&G) - suggests that the presence of certain EPEI polymers may stabilise HEDP in
liquid detergent compositions. We have found that the presence of high levels EPEI
does not provide sufficient stability to compositions of the type disclosed in
WO09153184 if they are formulated with HEDP in place of Dequest 2066, at least this is true
for the EPEI we have tested: Sokalan HP20 which is a nonionic polyethylene imine with
a backbone molecular weight of about 600, ethoxylated with an average of 20 moles
of ethylene oxide per nitrogen.
[0006] US2008015135 (P&G) discloses compact fluid laundry detergent compositions having good economics
good cleaning and positive consumer value impression. Amine oxide or betaine may be
used. HEDP is one of many possible chelants in the general disclosure.
[0007] JP2007077362A (Lion) discloses a liquid detergent composition for clothing which is effective for
mud stain and has excellent storage stability. The composition comprises (A) a polyoxyethylene
alkyl ether containing a 10-20C alkyl group and having the average addition mol number
of ethylene oxide of 3-26 (B) 1-hydroxyethane-11-diphosphonic acid and/or its salt
(C) monoethanolamine (D) one or more compounds selected from a semi-polar surfactant
an amphoteric surfactant a polyoxyethylene addition type ammonium salt and a polyoxyethylene
addition type amine. Paragraph 0032 makes clear that the pH should not be acidic.
Amine oxides and Betaines are both preferred surfactants in these MEA containing liquids
with HEDP. It seems that the LAS does not have to be neutralised with MEA. Besides
being alkaline these compositions contain no EPEI or polyester soil release polymer.
Examples use as "B-1": 1-hydroxyethane-1,1-diphosphonic acid. The maximum level of
HEDP incorporated in the examples is 1%. This is insufficient to obtain the required
level of cleaning for low surfactant dose compositions of the type disclosed in
WO09153184.
[0008] It is desired to include at least 1.5 wt%, preferably at least 2 wt% of HEDP into
low in wash surfactant high polymer, high enzyme compositions of the type disclosed
in
WO09153184.
SUMMARY OF THE INVENTION
[0009] According to the present invention there is provided an isotropic liquid laundry
detergent comprising:
- a) at least 10 wt% of a surfactant system, the surfactant system comprising:
a(i) at least 5 wt% ethoxylated alcohol nonionic surfactant,
a(ii) optionally, amine oxide amphoteric surfactant,
a(iii) at least 5 wt% linear alkyl benzene sulphonate formed from neutralisation of
LAS acid by an amine that buffers at the pH of the composition and a second amine
that does not buffer because its pKa is at least 2 units higher than the in-bottle
pH of the composition,
a(iv) soap formed from the neutralisation of fatty acid by the first and second amine,
and
a(v) optionally, Alkyl ether sulphate;
- b) at least 1.5 wt% HEDP,
- c) at least 5 wt% of a polymer system comprising nonionic EPEI and nonionic PET POET
polyester soil release polymer, and
- d) at least 2 enzymes.
the in-bottle pH of the composition being in the range 6.0 to less than 7, preferably
6.3 to 6.7.
[0010] HEDP is 1-hydroxyethane 1,1-diphosphonic acid (HEDP). Preferably the composition
comprises at least 2 wt%, more preferably at least 2.5 wt%, HEDP
[0011] Preferably the composition contains triethanolamine (TEA) as the buffer amine and
monoethanolamine (MEA) as the non buffering amine with pKa at least 2 units higher
than the in-bottle pH of the composition. Preferably, the surfactant system containing
an amine oxide together with a linear alkylbenzene sulfonate (LAS), a neutralised
fatty acid and an ethoxylated alcohol. Advantageously, the composition comprises at
least 0.75 wt%, preferably at least 1.0 wt% amine oxide (a(ii)).
[0012] The composition also contains two or more enzymes and a polymer system containing
ethoxylated polyethyleneimine (EPEI) and a polyethylene terephthalate (PET) polyoxyethylene
terephthalate (POET) polyester. Preferred compositions comprise at least 4 wt% EPEI.
More preferred compositions comprise at least 3 wt% polyester based soil release polymer.
[0013] The in-bottle pH of the composition lies in the range 6.0 to less than 7, preferably
6.3 to 6.7. By in-bottle we mean in whatever container or pack the liquid is stored.
It could be a plastic pack in the form of a bottle, squeezable or rigid, stored upright
or inverted, or a unit dose format such as a soluble pouch, or a sachet.
[0014] Preferably the composition comprises at least 1.5 wt% triethanolamine.
[0015] The composition may comprise at least 10 wt% nonionic surfactant. The composition
may comprise as an additional anionic surfactant at least 2 wt% alkyl ether sulphate.
[0016] When the composition comprises MEA and TEA, the weight ratio of TEA to MEA is preferably
from 1:1 to at most 20:1. The weight ratio of LAS acid to the total of MEA and TEA
lies in the range 1.1:1 to 2.5:1.
[0017] According to a second aspect of the invention there is provided a washing process
comprising the steps of adding to a front loading automatic washing machine 25 ml
or less, preferably 20 ml, of a composition according to the first aspect, diluting
it with at least 800 times as much tap water, washing clothes with the wash liquor
formed by the dilution step and then rinsing the clothes.
DETAILED DESCRIPTION OF THE INVENTION
[0018] HEDP is not stable in concentrated isotropic aqueous laundry liquids as crystallization
occurs on storage at low temperature. This instability is due to poor solubility of
Na-HEDP. This salt of HEDP is formed when a composition comprising the acid form of
HEDP is neutralised using sodium hydroxide. Sodium hydroxide is the normal neutralising
system employed with linear alky benzene sulphonate surfactant in liquid detergent
compositions. In more dilute liquids the amount of excess water is sufficient to keep
even the sodium salt of the HEDP in solution. This becomes more difficult as the amount
of water is reduced for a concentrated composition. The stability problem gets even
worse when water hungry polymers are included into the composition at high levels
as is the case with the liquids proposed in
WO09153184.
[0019] With Empigen BB the level of HEDP that could be incorporated and retain stability
was less than 0.4 wt%.
[0020] The necessary physical stability of HEDP in aqueous detergent liquids was obtained
by replacing TEA/NaOH with TEA/MEA for buffering and pH adjustment (while still maintaining
pSRP hydrolytic stability). The Empigen BB carbobetaine was also removed. Empigen
BB and Dequest 2010 appear to be incompatible. In preferred embodiments to optimise
the sequestrant cleaning benefit, Empigen OB amine oxide was added into the composition.
[0021] The MEA may be defined as a non buffering material because the pKa of its conjugate
acid lies more than 2 units higher than the final, in-bottle pH of the composition
provided the composition is formulated as an acidic in bottle composition. TEA must
therefore also be used to provide some buffering capacity to the concentrated composition.
This ensures that the polyester soil release polymer and other ingredients are maintained
at the correct pH for their optimum storage stability.
[0022] Thus although the invention has been described with reference to use of TEA and MEA
in practice the MEA could in principle be fully or partially replaced with other weak
or strong bases which lie outside the buffering region of interest (pH 6 to 7). Examples
of such materials include diethanolamine.
[0023] A proviso on the selection of the neutralising system is that the amount of alkali
metal salts should not exceed 0.2 wt% in the liquid composition and they are preferably
substantially absent to avoid the alkali metal, particularly sodium, forming HEDP
salts that come out of solution and render the liquid non isotropic with poor cleaning
due to the HEDP being absent from the upper parts of the liquid after storage in-bottle.
[0024] The TEA buffer could be partial or fully replaced with another material whose conjugate
acid has a pKa of about 6.5.
[0025] The amphoteric surfactant could also be replaced with another that has a capacity
to buffer to an acidic pH.
[0026] The invention will now be further described with reference to the following non-limiting
examples.
EXAMPLES
[0027] In the following examples the key to the material abbreviations is as follows:
- MPG
- is mono propylene glycol.
- MEA
- is monoethanolamine
- TEA
- is triethanolamine.
- 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.
- Empigen® OB
- is amine oxide ex Huntsman
- SLES 3EO
- is sodium lauryl ether sulphate with 3 moles EO.
- Dequest® 2010
- is HEDP (1-Hydroxyethylidene -1,1,-diphosphonic acid).
- EPEI
- is Sokalan HP20 - ethoxylated polyethylene imine cleaning polymer: PEI(600) 20EO ex
BASF.
- SRP
- is Texcare SRN170 polyester soil release polymer ex Clariant.
- Mannanase
- is Mannaway® 4.0L, a mannanase enzyme ex Novozymes.
- Pectate Lyase
- is Xpect® 1000L, a Pectate lyase enzyme ex Novozymes
- Cellulase
- is Endolase® 5000L, a cellulase ex Novozymes.
- Amylase
- is Stainzyme 12L, an amylase ex Novozymes.
- Protease
- is Relase® Ultra 16XL ex Novozymes.
- Preservative
- is Proxel GXL
- Colorant
- is a mixture of Patent Blue and Yellow dyes.
- Perfume
- is free oil perfume
- Empigen® BB
- is an alkyl betaine ex Huntsman (Coco dimethyl carbobetaine).
- NaOH
- is 47% sodium hydroxide solution.
[0028] For stability testing "Pass" means a stable and isotropic liquid was maintained for
at least 12 weeks storage. "Fail" means that material had precipitated or the liquid
had split into distinct phases. The target level of inclusion of HEDP for stain removal
and cleaning is over 2.5 wt% in these liquids.
Comparative Example A - using NaOH to adjust pH to 6.5
[0029] HEDP was added at gradually increasing amounts to the liquid composition given in
table 1 and the pH adjusted to 6.5 with sodium hydroxide. The stability is shown in
table 2.
Table 1 - Benchmark compositions: NaOH and Empigen BB
COMPOSITION |
A |
RAW MATERIAL |
% as 100% |
Demin water |
to 100% |
MPG |
17.00 |
NaOH |
to pH 6.5 |
TEA |
3.50 |
NI 7EO |
12.74 |
LAS acid |
8.49 |
SLES 3EO |
4.24 |
Empigen BB |
1.50 |
Prifac 5908 |
1.50 |
EPEI |
5.50 |
SRP |
3.75 |
Perfume |
2.43 |
Dequest 2010 |
0 - 0.9 |
Table 2 - Stability of NaOH and Empigen BB compositions with HEDP
12 weeks stability at given temperature |
% Dequest 2010 |
RT |
5 °C |
% NaOH |
0 |
Pass |
Pass |
0.18 |
0.4 |
Fail |
Fail |
0.39 |
0.5 |
Fail |
Fail |
0.40 |
0.6 |
Fail |
Fail |
0.45 |
0.8 |
Fail |
Fail |
0.56 |
0.9 |
Fail |
Fail |
0.56 |
[0030] HEDP crystallizes out of the liquid at levels of NaOH greater than 0.3 when the carbobetaine
Empigen BB used. Insufficient HEDP can be included in this acidic modification of
the liquids disclosed in
WO09153184.
Example 1 - using MEA to adjust pH to 6.5
[0031]
Table 3 - Modified compositions: MEA and no amphoteric
COMPOSITION |
1 |
RAW MATERIAL |
% as 100% |
Demin water |
to 100% |
MPG |
15.00 |
MEA |
to pH 6.5 |
TEA |
3.50 |
NI 7EO |
12.74 |
LAS acid |
8.49 |
SLES 3EO |
4.24 |
Prifac 5908 |
0.75 |
EPEI |
5.50 |
SRP |
3.75 |
Perfume |
1.39 |
Dequest 2010 |
0 - 3 |
Table 4 - Stability of MEA neutralized compositions
12 week stability at given temperature |
% Dequest 2010 |
RT |
5 °C |
% MEA |
0.0 |
Pass |
Pass |
0.19 |
2.0 |
Pass |
Pass |
1.61 |
2.5 |
Pass |
Pass |
1.94 |
3.0 |
Fail |
Fail |
2.31 |
[0032] With the carbobetaine removed and use of MEA to neutralise the LAS acid, high enough
levels of HEDP may be successfully incorporated in this isotropic liquid with 0.75%
fatty acid at pH 6.5.
Example 2 - using MEA with amine oxide
[0033]
Table 5 - Modified compositions: MEA and Empigen AO
COMPOSITION |
2 |
RAW MATERIAL |
% as 100% |
Demin water |
to 100% |
MPG |
15.00 |
MEA |
to pH 6.5 |
TEA |
3.50 |
Fluorescer |
0.10 |
NI 7EO |
12.74 |
LAS Acid |
8.49 |
Prifac 5908 |
0.75 - 3.00 |
Empigen OB |
1.50 |
SLES 3EO |
4.24 |
Dequest 2010 |
2.62 |
EPEI |
5.50 |
SRP |
3.75 |
Mannanase |
0.70 |
Pectate Lyase |
0.60 |
Cellulase |
0.25 |
Amylase |
0.70 |
Protease |
1.75 |
Preservative |
0.016 |
Colorants |
0.78 |
Perfume |
1.87 |
Table 6 - Stability of MEA neutralized Empigen OB compositions with HEDP
stability at given temperature |
% Fatty Acid |
RT |
5 °C |
37 °C |
45 °C |
FT |
0.75 |
Pass |
Pass |
Pass |
>8-weeks |
>1-week |
1 |
Pass |
Pass |
Pass |
>8-weeks |
>1-week |
1.25 |
Pass |
Pass |
Pass |
>8-weeks |
>1-week |
1.5 |
Pass |
Pass |
Pass |
>8-weeks |
>1-week |
[0034] Conclusion: even increasing the fatty acid up to 1.5 (and thus the amount of MEA
needed for neutralization - 1 wt% fatty acid requires 1.91 wt% MEA) still gives a
stable isotropic liquid with the required level of HEDP for effective cleaning.
1. An isotropic liquid laundry detergent comprising:
a) at least 10 wt% of a surfactant system, the surfactant system comprising:
a(i) at least 5 wt% ethoxylated alcohol nonionic surfactant,
a(ii) optionally, amine oxide amphoteric surfactant,
a(iii) at least 5 wt% linear alkyl benzene sulphonate formed from neutralisation of
LAS acid by an amine that buffers at the pH of the composition and a second non-buffering
amine that does not buffer because its pKa is at least 2 units higher than the in-bottle
pH of the composition,
a(iv) soap formed from the neutralisation of fatty acid by the first and second amine,
and
a(v) optionally, Alkyl ether sulphate;
b) at least 1.5 wt% HEDP (hydroxyethylidene-1,1,Diphosphonic acid)
c) at least 5 wt% of a polymer system comprising nonionic EPEI (ethoxylated polyethylene
imine) and nonionic PET POET (Polyethylene terephthalate polyoxyethylene terephthalate)
polyester soil release polymer, and
d) at least 2 enzymes.
the in-bottle pH of the composition being in the range 6.0 to less than 7, preferably
6.3 to 6.7.
2. A composition according to claim 1 comprising at least 0.75 wt%, preferably at least
1.0 wt% amine oxide (a(ii)).
3. A composition according to any preceding claim in which the buffer amine is triethanolamine
(TEA).
4. A composition according to any preceding claim in which the non-buffering amine with
pKa at least 2 units higher than the in-bottle pH of the composition is monoethanolamine
(MEA).
5. A composition according to any preceding claim comprising at least 1.5 wt% triethanolamine.
6. A composition according to any preceding claim comprising at least 4 wt% EPEI.
7. A composition according to any preceding claim comprising at least 3 wt% polyester
based soil release polymer.
8. A composition according to any preceding claim comprising at least 2 wt%, preferably
at least 2.5 wt%, HEDP.
9. A composition according to any preceding claim comprising at least 10 wt% nonionic
surfactant.
10. A composition according to any preceding claim comprising as an additional anionic
surfactant at least 2 wt% alkyl ether sulphate.
11. A composition according to any preceding claim comprising MEA and TEA wherein the
ratio of TEA to MEA is at least 1:1 and preferably at most 20:1.
12. A composition according to claim 11 wherein the ratio of LAS acid to MEA and TEA lies
in the range 1.1:1 to 2.5:1.
13. A washing process comprising the steps of adding to a front loading automatic washing
machine 25 ml or less, preferably 20 ml, of a composition according to any preceding
claim, diluting it with at least 800 times as much tap water, washing clothes with
the wash liquor formed by the dilution step and then rinsing the clothes.
1. Isotropes Flüssigwaschmittel, umfassend:
a) mindestens 10 Gew.-% eines Tensidsystems, wobei das Tensidsystem Folgendes umfasst:
a(i) mindestens 5 Gew.-% nicht-ionisches Tensid auf der Basis von ethoxyliertem Alkohol,
a(ii) gegebenenfalls ein amphoteres Tensid auf der Basis von Aminoxid,
a(iii) mindestens 5 Gew.-% lineares Alkylbenzolsulfonat, das durch Neutralisation
von LAS-Säure mit einem Amin, das den pH-Wert der Zusammensetzung puffert, und einem
zweiten Amin, das keine Pufferwirkung ausübt, da sein pKa-Wert mindestens 2 Einheiten
höher als der in der Flasche vorliegende pH-Wert der Zusammensetzung liegt, gebildet
worden ist,
a(iv) Seife, die durch Neutralisation der Fettsäure mit dem ersten und zweiten Amin
gebildet worden ist, und
a(v) gegebenenfalls Alkylethersulfat;
b) mindestens 1,5 Gew.-% HEDP (Hydroxyethyliden-1,1-diphosphonsäure),
c) mindestens 5 Gew.-% eines Polymersystems, das nicht-ionisches EPEI (ethoxyliertes
Polyethylenimin) und nicht-ionisches PET-POET (Polyethylenterephthalat-polyoxylethylenterephthalat)-Polyester-Schmutzlösungspolymer
umfasst, und
d) mindestens 2 Enzyme;
wobei der in der Flasche vorliegende pH-Wert der Zusammensetzung im Bereich von 6,0
bis weniger als 7 und vorzugsweise im Bereich 6,3 bis 6,7 liegt.
2. Zusammensetzung nach Anspruch 1, umfassend mindestens 0,75 Gew.-% und vorzugsweise
mindestens 1,0 Gew.-% Aminoxid (a(ii)).
3. Zusammensetzung nach einem der vorstehenden Ansprüche, wobei es sich beim puffernden
Amin um Triethanolamin (TEA) handelt.
4. Zusammensetzung nach einem der vorstehenden Ansprüche, wobei es sich beim nichtpuffernden
Amin mit einem pKa-Wert von mindestens 2 Einheiten über dem in der Zusammensetzung
in der Flasche vorherrschenden pH-Wert um Monoethanolamin (MEA) handelt.
5. Zusammensetzung nach einem der vorstehenden Ansprüche, umfassend mindestens 1,5 Gew.-%
Triethanolamin.
6. Zusammensetzung nach einem der vorstehenden Ansprüche, umfassend mindestens 4 Gew.-%
EPEI.
7. Zusammensetzung nach einem der vorstehenden Ansprüche, umfassend mindestens 3 Gew.-%
Schmutzlösungspolymer auf Polyesterbasis.
8. Zusammensetzung nach einem der vorstehenden Ansprüche, umfassend mindestens 2 Gew.-%
und vorzugsweise mindestens 2,5 Gew.-% HEDP.
9. Zusammensetzung nach einem der vorstehenden Ansprüche, umfassend mindestens 10 Gew.-%
nicht-ionisches Tensid.
10. Zusammensetzung nach einem der vorstehenden Ansprüche, umfassend als zusätzliches
anionisches Tensid mindestens 2 Gew.-% Alkylethersulfat.
11. Zusammensetzung nach einem der vorstehenden Ansprüche, umfassend MEA und TEA, wobei
das Verhältnis von TEA zu MEA mindestens 1:1 und vorzugsweise mindestens 20:1 beträgt.
12. Zusammensetzung nach Anspruch 11, wobei das Verhältnis von LAS-Säure zu MEA und TEA
im Bereich von 1,1:1 bis 2,5:1 liegt.
13. Waschverfahren, umfassend die folgenden Stufen:
Zugeben von 25 ml oder weniger und vorzugsweise von 20 ml einer Zusammensetzung gemäß
einem der vorstehenden Ansprüche in eine Frontlader-Waschmaschine, Verdünnen mit mindestens
dem 800-fachen an Leitungswasser, Waschen der Textilien mit der durch die Verdünnungsstufe
gebildeten Waschflüssigkeit und anschließend Spülen der Textilien.
1. Détergent pour le linge liquide isotrope comprenant :
a) au moins 10 % en masse d'un système de tensioactif, le système de tensioactif comprenant
:
a(i) au moins 5 % en masse de tensioactif non ionique d'alcool éthoxylé,
a(ii) éventuellement, un tensioactif amphotère d'oxyde d'amine,
a(iii) au moins 5 % en masse de benzènesulfonate d'alkyle linéaire formé à partir
de la neutralisation d'acide LAS par une amine qui tamponne au pH de la composition
et d'une seconde amine de non-tampon qui ne tamponne pas puisque son pKa est au moins
2 unités supérieures au pH dans la bouteille de la composition,
a(iv) un savon formé à partir de la neutralisation d'acide gras par les première et
seconde amines, et
a(v) éventuellement, un sulfate d'alkyléther ;
b) au moins 1,5 % en masse de HEDP (acide hydroxyéthylidène-1,1,diphosphonique)
c) au moins 5 % en masse d'un système polymère comprenant un polymère libérant la
saleté de polyester d'EPEI non ionique (polyéthylèneimine éthoxylée) et de PET POET
non ionique (polyéthylène téréphtalate polyoxyéthylène téréphtalate), et
d) au moins 2 enzymes,
le pH dans la bouteille de la composition se trouvant dans l'intervalle de 6,0 à moins
de 7, de préférence de 6,3 à 6,7.
2. Composition selon la revendication 1 comprenant au moins 0,75 % en masse, de préférence
au moins 1,0 % en masse d'oxyde d'amine (a(ii)).
3. Composition selon l'une quelconque des revendications précédentes, dans laquelle l'amine
de tampon est la triéthanolamine (TEA).
4. Composition selon l'une quelconque des revendications précédentes, dans laquelle l'amine
de non-tampon avec un pKa d'au moins 2 unités supérieures au pH dans la bouteille
de la composition est la monoéthanolamine (MEA).
5. Composition selon l'une quelconque des revendications précédentes comprenant au moins
1,5 % en masse de triéthanolamine.
6. Composition selon l'une quelconque des revendications précédentes comprenant au moins
4 % en masse d'EPEI.
7. Composition selon l'une quelconque des revendications précédentes comprenant au moins
3 % en masse de polymère libérant la saleté à base de polyester.
8. Composition selon l'une quelconque des revendications précédentes comprenant au moins
2 % en masse, de préférence au moins 2,5 % en masse, d'HEDP.
9. Composition selon l'une quelconque des revendications précédentes comprenant au moins
10 % en masse de tensioactif non ionique.
10. Composition selon l'une quelconque des revendications précédentes comprenant comme
un tensioactif anionique supplémentaire au moins 2 % en masse de sulfate d'alkyléther.
11. Composition selon l'une quelconque des revendications précédentes comprenant MEA et
TEA dans laquelle le rapport de TEA à MEA est d'au moins 1:1 et de préférence d'au
plus 20:1.
12. Composition selon la revendication 11, dans laquelle le rapport d'acide LAS à MEA
et TEA se trouve dans l'intervalle de 1,1:1 à 2,5:1.
13. Procédé de lavage comprenant les étapes d'addition dans une machine de lavage automatique
à chargement frontal de 25 ml ou moins, de préférence de 20 ml, d'une composition
selon l'une quelconque des revendications précédentes, de dilution de ceux-ci avec
au moins 800 fois d'eau courante, de lavage de vêtements avec le liquide de lavage
formé par l'étape de dilution et de rinçage subséquent des vêtements.
REFERENCES CITED IN THE DESCRIPTION
This list of references cited by the applicant is for the reader's convenience only.
It does not form part of the European patent document. Even though great care has
been taken in compiling the references, errors or omissions cannot be excluded and
the EPO disclaims all liability in this regard.
Patent documents cited in the description