Note: Descriptions are shown in the official language in which they were submitted.
CA 02305193 2008-04-17
- 1 -
ALKOXYLATED AMINES AND THEIR USE IN CLEANING COMPOSITIONS
Technical Field
The present invention relates to acidic cleaning
compositions, and in particular to acidic antimicrobial
cleaning composition suitable for use on hard surfaces.
Backaround to the Invention
Many formulations have been proposed in the literature for
so-called 'descaler' compositions. These generally
comprise sufficient acid to give a low pH and may comprise
a thickening agent to as to cause the composition to be
retained on sloping surfaces, such as the inside of toilet
bowls. As described in more detail below, known thickeners
include both ethoxylated and unethoxylated tertiary amines,
either alone or in combination with a hydrotrope. Known
acids for use in such compositions include sulphamic and
phosphoric acids.
GB 1443244 relates to acid cleaners and descalers which
comprise as a thickening agent an ethoxylated tertiary
amine of which ETHOMEEN S12" (N, N-dihydroxyethyl-oleylamine)
is given aS, an example. The composition also comprises
acids which are selected from mineral acids and acid salts
of strong inorganic acids such as suiphamic acid.
Bacteriocides are an additional, optional component.
CA 02305193 2000-03-29
WO 99/19431 PCT/EP98/06633
- 2 -
FR 2459830 discloses compositions which comprise non-
ethoxylated and ethoxylated amines together with sulphamic
acid. The composition may also comprise disinfectants.
AU-A-57022/86 relates to cleaning systems which comprise a
mixture of sulphamic and phosphoric acids and an acid
stable surfactant. Bacteriocides are optional and formalin
is disclosed as a bacteriocide which improves the
antibacterial effect of the acids.
EP-B-0276501 discloses thickened aqueous cleaning
compositions which comprise 0.1-50%wt of a weak acid having
a pK >2 (of which sulphamic acid is given as an example),
0.1-20%wt of an amine which can include 2% of oleyl-bis(2-
hydroxyethyl)amine and 0.01%-5%wt hydrotrope (sodium
xylene-sulphonate is given as an example). Disinfecting
agents are optional.
EP-A-0314232 relates to compositions which undergo a
viscosity increase on dilution and discloses that thickened
liquid detergent compositions can be prepared with an amine
oxide, amine (such as ETHOMEEN S12), betaine or quaternary
ammonium compound and hydrotrope (sodium xylene-
sulphonate). It is stated in the specification that amine
oxides and quaternary ammonium compounds are known to have
biocidal properties and that further microbiocides
including organic peracids are optional. These compositions
can be of acidic, neutral or alkaline pH.
CA 02305193 2000-03-29
WO 99/19431 PCT/EP98/06633
- 3 -
One problem with the known compositions is that the
viscosity of the compositions drifts with time, and, in
particular falls when the product is stored.
Brief Description of the Invention
We have determined that compositions which comprise a
specific mixture of both saturated and unsaturated
alkoxylated aliphatic amines in the presence of an anionic
surfactant show an improved stability of viscosity on
storage. Surprisingly, we have found that the addition of a
anionic sulphonate surfactant hydrotrope to these
formulations has the additional benefit that the surface
energy of surfaces treated with the composition is reduced
and the subsequent deposition of limescale is retarded.
Detailed Description of the Invention
According to a first aspect of the present invention there
is provided an alkoxylated aliphatic amine with 8-18 carbon
atoms and 1-8 moles ethoxylation wherein the mole ratio of
saturated to unsaturated aliphatic residues falls in the
range 40:60 to 80:20.
According to a second aspect of the present invention there
is provided a cleaning composition which comprises
CA 02305193 2000-03-29
WO 99/19431 PCT/EP98/06633
- 4 -
a) 0.01-15%wt an alkoxylated aliphatic amine with 8-18
carbon atoms and 1-8 moles ethoxylation wherein the
mole ratio of saturated to unsaturated aliphatic
residues falls in the range 40:60 to 80:20, and
b) 0.01-15%wt of an anionic surfactant.
According to a third aspect of the present invention there
is provided a process for retarding the deposition of
limescale on a surface which comprises the step of treating
said surface with a cleaning composition having a pH of
less than 1 which comprises:
a) 0.01-15%wt an alkoxylated aliphatic amine with 8-18
carbon atoms and 1-8 moles ethoxylation wherein the
mole ratio of saturated to unsaturated aliphatic
residues falls in the range 40:60 to 80:20, and,
b) 0.01-15%wt of an anionic surfactant.
Amines
Typically, the alkoxylated aliphatic amine is an
ethoxylated tertiary amine of the general formula:
H(A)X-N(R)-(A)YH
CA 02305193 2000-03-29
WO 99/19431 PCT/EP98/06633
- 5 -
wherein R is an alkyl or alkenyl group comprising 8-18
carbon atoms, A is an ethoxy or propoxy group and x and y
may be the same or.different and are integers from 1-3.
The preferred materials are ethoxylated amines wherein A is
-OCH2CH2- .
Preferably x and y are both 1. In preferred embodiments of
the invention R is mixed saturated and unsaturated C14-C18
alkyl and is most preferably derived from fatty acids
residues of which the majority correspond to oleic and/or
stearic acids.
Preferably the mole ratio of saturated to unsaturated fatty
acids falls into the range 50:50 to 66:33.
A particularly suitable alkoxylated aliphatic amine is a
material known as ETHOMEEN BTB/12T"`, available from AKZO.
BTB/12 is believed to be a mixture of material derived from
fully hardened tallow and the oleyl derivative in a 65/35
ratio. Such a mixed material can be prepared by synethesis
using an appropriate ratio of mixed starting materials or
obtained by mixing an alkoxylated aliphatic amine such as
ETHOMEEN HT12"M (ex AKZO) with an unsaturated material such
as ETHOMEEN S12. ETHOMEEN S12Tm (ex AKZO) is N,N-
(dihydroxyethyl)-oleylamine.
In embodiments of the invention as cleaning products, the
preferred levels of the alkoxylated aliphatic amine are
CA 02305193 2000-03-29
WO 99/19431 PCT/EP98/06633
- 6 -
1-10%wt on product with levels of 2-6%wt on product being
particularly preferred.
Anionic Surfactants
In particularly preferred embodiments of the invention the
alkoxylated aliphatic amine is present together with an
anionic surfactant. Preferably, the levels of these
materials are such that they interact so as to thicken the
composition
Suitable anionic surfactants include the sulphonate
hydrotropes. Preferred surfactants are alkylarylsulphonates
such as salts, particularly alkali metal salts, of toluene,
cumene or xylene sulphonate. The preferred anionic
surfactant is sodium cumenesulphonate. A suitable material
is ELTESOL SC 40Tm (ex. Albright and Wilson). Typical
levels of anionic surfactant range from 0.05-2%wt on
product.
Preferably, formulations comprising the alkylaryl
sulphonates are formulated at a pH below 1. Without wishing
to limit the invention by reference to any theory of
operation, it is believed that at a pH below 1, the
ethoxylated amine behaves as a cationic surfactant and
interacts with the alkylaryl sulphonate to form a water-
insoluble gel which deposits as a monolayer on surfaces.
It is believed that this monolayer lowers the surface
CA 02305193 2000-03-29
WO 99/19431 PCT/EP98/06633
- 7 -
energy of the surface and retards or prevents the
deposition of further limescale.
The preferred mole ratio of the ethoxylated amine and the
anionic surfactant is 3-3.5, more preferably 3.25-3.5.
The preferred viscosity of the cleaning compositions
according to the present invention is between 50 mPas and
1000 mPas when measured at 11.7 sec-1 shear and at 25 C
using Haake RV2 rotoviscometer (RTM) and an MV1 bob
Acids
Typically, cleaning compositions which embody the present
invention comprise 0.01-15%wt of a limescale removing acid,
preferably an organic acid and more preferably sulphamic
acid. In such embodiments, typical levels of the acid (for
instance the amino sulphonic acid) range from 1-l0%wt on
product with levels of 2-6% on product being particularly
preferred.
It is preferred that the pH of the compositions according
to the invention should have a pH of <2.0, more preferably
a pH <1Ø
CA 02305193 2000-03-29
WO 99/19431 PCT/EP98/06633
- 8 -
PeroxStgea Sources
Preferred embodiments of the invention are cleariing and"/or
hygiene compositions which comprises a peroxygen compound.
Where present, typical sources of peroxygen species include
one or more of hydrogen peroxide, peracetic acid and/or
other organic or inorganic peroxygen sources. Hydrogen
peroxide is a preferred source of peroxygen species.
Typical levels of hydrogen peroxide range from 1-10$wt on
product with levels of 3-8% being particularly preferred.
Nonionic Surfactants
Preferred compositions according to the invention
additionally comprise nonionic surfactant.
Suitable nonionic surfactants include alkoxylated alcohols,
preferably ethoxylated alcohols. Suitable nonionic
detergent active compounds can be broadly described as
compounds produced by the condensation of alkylene oxide
groups, which are hydrophilic in nature, with an organic
hydrophobic compound which may be aliphatic or alkyl
aromatic in nature.
The length of the hydrophilic or polyoxyalkylene radical
which is condensed with any particular hydrophobic group
can be readily adjusted to yield a water-soluble compound
CA 02305193 2000-03-29
WO 99/19431 PCT/EP98/06633
- 9 -
having the desired degree of balance between hydrophilic
and hydrophobic elements.
The preferred alkoxylated alcohols are selected from the
group comprising ethoxylated alcohols of the general
formula:
Rl - ( OCHZCH2 ) m-OH
wherein Rl is straight or branched, C8 to C18 alkyl or
hydroxyalkyl and m is, on average, 1-14. Ethoxylated
alcohols suitable for use in the present invention include
LIAL 111.10EO [TM] available in the marketplace from DAC.
Typical levels of nonionic surfactant in products according
to the present invention range from 0-5%.
Particularly preferred compositions according to the
present invention comprise:
a) 1-10%wt, preferably 3-5%wt sulphamic acid,
b) 1-10%wt, preferably 2-5%wt ethoxylated amine,
c) 0-5%wt, preferably 0.05-1%wt, nonionic surfactant,
d) 0.05-2%wt, preferably 0.4-1.1%wt, anionic surfactant
hydrotrope,
e) 1-10%wt, preferably 4-6%wt, hydrogen peroxide
Minors
While the combination of the surfactants in the
compositions of the invention provide a thickening effect
CA 02305193 2008-04-17
- 10 -
it is possible to add other thickeners. Gums, particularly
xanthan gums are suitable thickeners. Preferred xanthan
gums are the Kelzan?' series (available from Kelco Corp).
Typical levels of xanthan gum range from 0.05-1wt%. The
resulting viscosity of the composition, as measured on a
Haake RV2 rotoviscometer) is preferably in the range 10-200
mPas at 20 sec-1 shear and 25 C, using an MV1 bob. More
preferably the viscosity is 10-100 mPas under the
conditions mentioned above.
Metal ion sequestrants such as ethylene diamine
tetraacetates, amino-poly phosphonates (such as those in
the DEQUEST' range ex. Monsanto) and phosphates and a wide
variety of other poly-functional organic acids and salts,
can also optionally be employed. Preferred metal ion
complexing agents are selected from dipicolinic acid,
ethylene diamine tetra acetic acid (EDTA) and its salts,
hydroxy-ethylidene diphosphonic acid (Dequest" 2010),
ethylenediamine-tetra(methylene phosphonic acid) (Dequests"
2040), diethylene-triamine-penta(methylene phosphonic acid)
(Dequestlm 2060).
Optional, minor components also include those typically
found in cleaning compositions and are selected from
opacifiers, colours perfumes and fluorescers.
Preferred levels of perfume range from 0.05-2%wt. Acid
stable perfumes are available from a variety of sources.
A particularly preferred composition according to the
present invention comprises:
CA 02305193 2008-04-17
- 11 -
ETHOMEEN BTB/12 ex AKZO 2-5% Ethoxylated amine
SULPHAMIC ACID 4%
HYDROGEN PEROXIDE 5%
LIAL" 111.10EO ex DAC 0.1% Nonionic surfactant
ELTESOL" SC40 ex Albright 0.4-1.1$* Sodium Cumene
Sulphonate
BRILLIANT BLUE 9 ex WJE 0.0021% CI 307047/colour
PERFUME ex IFF 0.12% Othello 39
DEQUEST- 2066 ex Monsanto 0-0.3%
WATER to 100%
*variable to adjust viscosity
Typical products having the above formulation made with
3.0%wt of the amine and around 0.56%wt of the SCS are
preferably clear, have a specific gravity of 1.040 g/ml, an
initial viscosity at 106 sec-1 (at 25 C) of 120mPas, an
initial viscosity at 11.7 sec-l (at 25 C) of 300-600 mPas
and pH 0.9 (at 25 C).
In order that the present invention may be further
understood it will be illustrated hereafter with reference
to the following non-limiting examples and with reference
to the accompanying figures wherein:
Figure 1 shows the viscosity of materials according to the
present invention and comparative examples in mPas at 11.7
CA 02305193 2000-03-29
WO 99/19431 PCT/EP98/06633
- 12 -
sec-las measured using on a Haake RV2 rotoviscometer and an
MV1 bob after storage at room temperature.
Figure 2 shows the viscosity of materials according to the
present invention and comparative examples in mPas at 106
s-1, as measured using on a Haake RV2 rotoviscometer (RTM)
and an MV1 bob after storage at room temperature.
Figure 3 shows the viscosity of materials according to the
present invention and comparative examples in mPas at 106
s-1, as measured using on a Haake RV2 rotoviscometer and an
MV1 bob after storage at 37 C.
Figure 4 shows the viscosity of materials according to the
present invention and comparative examples in mPas at 11.7
sec-l measured on a Haake RV2 rotoviscometer and an MV1 bob
after storage at 37 C.
CA 02305193 2000-03-29
WO 99/19431 PCT/EP98/06633
- 13 -
EXAMPLES:
Example 1: Viscositv Stabilitv
A composition was prepared as follows:
ETHOMEEN BTB/12 ex AKZO 3% Ethoxylated amine
SULPHAMIC ACID 4%
HYDROGEN 5%
PEROXIDE
LIAL 111.10EO ex DAC 0.1% Nonionic surfactant
ELTESOL SC 40 ex Albright 0.4-1.1$* Sodium Cumene
Sulphonate
BRILLIANT BLUE ex WJE 0.0021% CI 307047/colour
PERFUME ex IFF 0.12% Othello 39
DEQUEST 2066 ex Monsanto 0.15%
WATER to 100%
In order to demonstrate the interaction of the ethoxylated
amine and the anionic surfactant, the other components were
each under and over dosed at +/- 10%. Results are shown in
Table 1 below, for an initial viscosity of 500 m.Pas at
11.7 sec-1 shear.
CA 02305193 2000-03-29
WO 99/19431 PCT/EP98/06633
- 14 -
TABLE 1
VISCOSITY
Component -10% +10%
ETHOMEEN BTB/12 950 190
SULPHAMIC ACID 530 600
HYDROGEN PEROXIDE 550 620
LIAL 111.10EO 560 460
ELTESOL SC 40 145 1330
PERFUME 510 600
DEQUEST 2066 470 560
From the above it can be seen that the greatest
modification of viscosity occurs when the relative levels
of the anionic surfactant and the ethoxylated amine are
varied, and that variation in the levels of the other
components has little effect.
As shown by the figures in Table 2 below, the molar ratio
of the ethoxylated amine / anionic surfactant can be
modified to give thickening at a range of viscosities.
Again, a finished product similar to that described above
was used.
CA 02305193 2000-03-29
WO 99/19431 PCTIEP98/06633
- 15 -
Table 2(all with 3.0% Ethomeen BTB12)
% Sodium Cumene Molar Ratio Viscosity mMas
(11.7 sec-1 shear, 25 C)
0.69% 2.89 1500(non-flowing gel)
0.63% 3.03 1000
0.60% 3.18 700
0.59% 3.24 400
0.57% 3.35 300
0.56% 3.42 200
0.54% 3.51 75
0.50% 3.83 -10(water thin)
Compositions having a viscosity between 50 mPas and 1000
mPas (a molar ratio of from 3-3.5) were flowable
compositions which were suitable for use as toilet
cleaners. Compositions with a lower viscosity were too
thin to stay on sloping surfaces, while those with a higher
viscosity could not be dispensed with ease. Compositions
with a viscosity of from 200-700 mPas were particularly
suited to this purpose.
A range of compositions of the type described above were
prepared with differing degrees of saturation in the
ethoxylated amine. The materials used were:
`S12' an N,N-dihydroxyethyl-oleylamine (ETHOMEEN S12),
`HT12' a fully hardened N,N-dihydroxyethyl-tallowylamine
(ETHOMEEN HT12 ) ,
CA 02305193 2000-03-29
WO 99/19431 PCT/EP98/06633
- 16 -
150/50' an equal weight mixture of `S12' and `HT12', and
166/33' a mixture of `HT12' and `S12' in a 66:33 weight
ratio (similar to BTB12)
The effect of storage on viscosity is shown in figures 1-4.
Figure 1 shows the viscosity of materials according to the
present invention and comparative examples in mPas at 11.7
sec-', as measured using on a Haake RV2 rotoviscometer and
an MV1 bob after storage at room temperature. It can be
seen that the viscosity of the `HT12' sample rose with time
until the product became a non-flowing gel. The viscosity
of the `S12' sample fell, such that the product eventually
became too thin to be retained on sloping surfaces. The
viscosities of the products containing a mixture of
hardened and unhardened tallow remained in the acceptable
range on storage.
Figure 2 shows the viscosity of materials according to the
present invention and comparative examples in mPas at 106
sec-1, as measured using on a Haake RV2 rotoviscometer and
an MV1 bob after storage at room temperature. It can be
seen that the viscosity of the `HT12' sample first fell and
then rose. The viscosity of the `S12' sample fell, such
that the product eventually became too thin to be retained
on sloping surfaces. The viscosities of the products
containing a mixture of hardened and unhardened materials
remained in the acceptable range on storage.
CA 02305193 2000-03-29
WO 99/19431 PCT/EP98/06633
- 17 -
Figure 3 shows the viscosity of materials according to the
present invention and comparative examples in mPas at 106
secas measured using on a Haake RV2 rotoviscometer and
an MV1 bob after storage at 37 C. It can be seen that the
viscosity of the `HT12' sample again first fell and then
rose. The viscosity of the 'S12' sample fell, such that
the product eventually became too thin to be retained on
sloping surfaces. The viscosities of the products
containing a mixture of hardened and unhardened materials
remained in the acceptable range on storage.
Figure 4 shows the viscosity of materials according to the
present invention and comparative examples in mPas at 11.7
sec-1, as measured using on a Haake RV2 rotoviscometer and
an MV1 bob after storage at 37 C. It can be seen that the
viscosity of the `HT12' sample again rose. The viscosity of
the `S12' sample fell, such that the product eventually
became too thin to be retained on sloping surfaces. The
viscosities of the products containing a mixture of
hardened and unhardened materials remained in the
acceptable range on storage.
Exa=le 2: Liznescale Prevention
Hard water of -60 degrees French was prepared by flushing
carbon dioxide through tap-water containing both calcite
and dolomite overnight. Pairs of tiles were cleaned with a
detergent composition and ethanol and rinsed with tap
water. One of the tile was treated with a composition
CA 02305193 2000-03-29
WO 99/19431 PCT/EP98/06633
- 18 -
according to the present invention (that of Example 1),
with a contact time of 20 minutes: the tile was then rinsed
with water. The hard water was then dripped onto the tiles
for 24 hours, allowing one drop to fall onto each tile
every five minutes. Results for treated and untreated
tiles were compared visually using a panel of ten people,
scoring on a scale of 0=limescale absent and 5= more
encrusted tile: results being presented in Table 3 below.
In addition the limescale was titrated after dissolution
with dilute HC1. The results of titration are expressed in
mg of calcium carbonate per tile in Table 3 below.
Examples were performed in replicates A, B and C.
CA 02305193 2000-03-29
WO 99/19431 PCT/EP98/06633
19 -
Table 3
Treated Untreated
Tile Tile
Replicate Visual mg CaCo3 visual nig CaCo3
A 3.3 0.91 5.0 2.1
B 3.4 1.2 5.0 1.5
C 3.3 1.4 5.0 2.1
It can be seen from these results that the treatment of the
tile had a measurable effect on the degree of limescale
deposited on the tile in the test both as measured
chemically and as seen on the surface.
