Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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SANITARY CLEANER
Field Of The Invention
The present invention relates to an aqueous sanitary cleaning composition
having biocidal activity and to the use of said cleaning composition for
cleaning of,
disinfecting of, and/or lime removal from surfaces, especially from surfaces
in
bathrooms, kitchens and the like.
Background
Aqueous cleaning compositions for the removal of dirt and lime in sanitary
or kitchen areas are well-known. These compositions normally are based on
inorganic and/or organic acids as well as surfactants. As additional agents
these
compositions often further comprise colouring agents, perfumes, viscosity
control
agents, disinfecting and bleaching agents, preservatives, and further
auxiliary
substances.
For the removal of persistent lime scale it is required that the cleaning
compositions have a high acidity. Since strong inorganic acids such as
hydrochloric
acid and sulphuric acid lead to corrosion of metallic surfaces, material
incompatibility and cause environmental pollution, cleaning compositions are
widely used which are based on sulfamic acid. Sulfamic-acid-based cleaning
compositions have a high scale-removing capability. Additional advantages of
these
zo cleaning compositions are that they can be used safely and that they are
eco-friendly.
Cleaning compositions merely based on sulfamic acid have some
disadvantages with respect to biocide regulations, material compatibility,
perfume
stability, and oxidation problems.
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Sulfamic acid has some drawbacks with respect to its oxidative properties.
Sulfamic acid causes corrosion when it comes into contact with metal surfaces.
In
contact with plastic surfaces it causes an accelerated aging of the plastic
materials
that may lead to, for example, stress corrosion cracking. Another problem that
is
sometimes observed with cleaning compositions according to the state of the
art is
that the plastic bottles in which the compositions are filled begin to shrink
after a
certain storage time. This is not acceptable for safety and aesthetics
reasons.
Therefore, it is also desirable to provide a sanitary cleaning composition
being less
corrosive to metal surfaces and more compatible to various other materials
such as
plastics.
Another problem which can be observed when formulating cleaning
compositions with sulfamic acid as the sole acid component is that the
stability of
perfumes also contained in the cleaning composition may be reduced. It is
assumed
that due to the oxidative properties of the sulfamic acid the perfumes
decompose
within a few weeks or months when storing the aqueous composition.
It is also desirable that these cleaning compositions have biocidal activity.
By the term "biocidal" it is meant that proliferation of microorganisms can be
controlled by employing the cleaning composition. Microorganisms for which
sanitary compositions are useful to limit proliferation include, but are not
limited to,
Gram positive bacteria, Gram negative bacteria, yeasts, fungi, and algae.
Certain of
these microorganisms, when uncontrolled, can grow to dangerous levels
resulting in
food contamination or may directly infect humans. According to European
biocide
directives and European standards for proofed chemical disinfectants and
antiseptics
used in food, industrial, domestic, and institutional areas, disinfectant
products sold
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in Europe must pass the following standards. The standards are found in the
document entitled, "Chemical Disinfectants and Antiseptics ¨ Application of
European Standards for Chemical Disinfectants and Antiseptics prEN 14885."
In particular, that document includes standards for testing the efficacy
of disinfectants and antiseptics. These standards arc referred to as,
"Chemical
disinfectants and antiseptics ¨ Quantitative suspension test for the
evaluation of
bactericidal activity of chemical disinfectants and antiseptics used in food,
industrial, domestic, and institutional areas NF EN 1276 and NF EN 1650 and NF
to EN 13697." The tests run and standards required are dependent upon the
use of the
product and the class of microbes the product is attempting to reduce. That
is, a
different standard is followed for bacteria as compared to yeast.
Therefore, it is the aim of the present invention to provide an aqueous
sanitary cleaning composition having biocidal activity which has an increased
material compatibility, enables higher perfume stability, and is less
corrosive to
metal surfaces such as steel and aluminium, but nevertheless has good lime-
removing capacity and good cleaning properties.
Summary Of The Invention
It has surprisingly been found that the above-defined object can be achieved
?o by providing an aqueous sanitary cleaning composition comprising
benzalkonium
chloride in an amount of up to about 5 wt.%, a hydroxycarboxylic acid in an
amount
up to about 10 wt.% and water, wherein the weight ratio of the benzalkonium
chloride to the hydroxycarboxylic acid is about 1:5 up to about 1:1.
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The combination of benzalkonium chloride with the presence of the
hydroxycarboxylic acid gives the cleaning composition of the invention good
biocidal activity along with good lime-removal properties as well as a good
material
compatibility with respect to plastic and metallic materials. Furthermore, the
perfume stability of such a composition is better when compared with cleaning
compositions of the state of the art based solely on sulfamic acid.
Optionally, an additional acid may be added to the invention. In order to
further improve the material compatibility, the perfume stability and to
further
reduce the skin-irritant properties either sulfonic acid or sulfamic acid is
included in
an alternative embodiment of the present invention. Sulfonic or sulfamic acid
is
present in an amount of only up to about 6 wt.%, preferably in an amount of up
to
about 5 wt.% or below. In order to ensure sufficient lime-removing properties
of the
cleaning composition according to the invention, sulfamic acid is preferably
present
in a minimum amount of up to about 1 wt.% and more preferably in a minimum
amount of up to about 2 wt.%. The sulfamic acid to be used is favourably
sulfamic
acid itself but is not limited to this acid. Also, for example, N-alkyl, N-
aryl, or N-
ally1 derivatives thereof, if highly soluble in water, can be used.
Detailed Description of the Invention
For the following defined terms, these definitions shall be applied, unless a
different definition is given in the claims or elsewhere in this
specification.
All numeric values are herein assumed to be modified by the term "about,"
whether or not explicitly indicated. The term "about" generally refers to a
range of
numbers that one of skill in the art would consider equivalent to the recited
value
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(i.e., having the same function or result). In many instances, the terms
"about" may
include numbers that are rounded to the nearest significant figure.
Weight percent, percent by weight, % by weight, wt.%, and the like are
synonyms that refer to the concentration of a substance as the weight of that
substance divided by the weight of the composition and multiplied by 100.
The recitation of numerical ranges by endpoints includes all numbers
subsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4,
and 5).
As used in this specification and the appended claims, the singular forms "a",
"an", and "the" include plural referents unless the content clearly dictates
otherwise.
Thus, for example, reference to a composition containing "a compound" includes
a
mixture of two or more compounds. As used in this specification and the
appended
claims, the term "or" is generally employed in its sense including "and/or"
unless the
content clearly dictates otherwise.
The term "surfactant" or "surface active agent" refers to an organic chemical
that when added to a liquid changes the properties of that liquid at a
surface.
Hydrocarboxylic acids are defined as organic acids having at least one
hydroxyl group and at least one carboxyl group in the molecule. A wide range
of
hydrocarboxylic acids can be used in the cleaning compositions according to
the
invention. These acids include for example lactic acid, maleic acid, citric
acid,
zo glycolic acid, tartaric acid, hydracylic acid, a-hydroxybutyric acid,
glyceric acid,
tartronic acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid,
gallic
acid, mandelic acid, and tropic acid or mixtures thereof
In a preferred embodiment the selected hydrocarboxylic acid is lactic acid.
Lactic acid provides the advantage that it is slightly antimicrobial. That is
why lactic
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acid is notified as having disinfecting properties whereas, for example,
sulfamic acid
is not notified accordingly. Notification procedures follow European biocide
regulations. In Germany they are integrated in the chemical regulations
started in the
year 2002. The advantage of using lactic acid as a component in a sanitary
cleaning
composition therefore is that such a composition additionally has disinfecting
properties and may be labelled accordingly.
The hydroxycarboxylic acid of the sanitary cleaning composition according
to the invention is present in an amount of up to about 12 wt.%. An amount of
up to
wt.% or even above about 0.5 wt.% is also sufficient with respect to the aimed
10 properties of the cleaning composition according to the invention. In
order to ensure
a sufficient perfume-stability of the cleaning composition according to the
invention
the hydroxycarboxylic acid is preferably present in a minimum amount of about
1
wt.% and more preferably in a minimum amount of 2 wt.%. One skilled in the art
will recognize that in order to achieve desirable biocidal activity, the
amount of
hydroxycarboxylic acid will vary according to the other components of the
composition. For example, if the amount of benzalkonium chloride is raised,
the
amount of lactic acid may be lowered while still having effective biocidal
activity
and limescale removal properties.
Benzalkonium chloride (alkyl dimethyl benzyl ammonium chloride) is a
mixture of alkylbenzyl dimethylammonium chlorides of various alkyl chain
lengths.
In a further aspect of the invention the sanitary cleaning composition
optionally comprises urea. The cleaning composition according to the invention
comprises urea especially in the case that perfumes are also contained in the
composition. Urea increases the solubility and stability of the perfumes in
the
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aqueous cleaning composition. If urea is used it is present in an amount of
about
0.25 to about 10 wt.%, preferably about 0.5 to about 8 wt.%, and more
preferably in
an amount of about 1 to about 6 wt.%.
The composition according to the invention may comprise one or more
surfactants in addition to the benzalkonium chloride that is a cationic
surfactant,
preferably selected from the group consisting of cationic, non-ionic, and/or
amphoteric surfactants, or mixtures thereof The preferred surfactants are non-
ionic
surfactants. If additional surfactants are used they are usually present in
the
composition in an amount of about 0.1 to about 10 wt.%, preferably about 0.5
to
about 5 wt.%, and more preferably in an amount of about 1 to about 4 wt.%.
Non-ionic, cationic, and amphoteric surfactants useful in the context of
aqueous cleaning compositions are well-known to the skilled artisan. All
members
of these known surfactants can be used in the cleaning compositions according
to the
present invention as long as they are compatible with the other compounds used
in
these compositions. Furthermore, it is within the routine work of a person
skilled in
the art to choose an appropriate surfactant from the groups of cationic, non-
ionic, or
amphoteric surfactants or a mixture of more than one such surfactants.
However, in
the cleaning composition according to the present invention the surfactant or
the
mixture of surfactants is preferably selected from the group of non-ionic
and/or
cationic surfactants that comprises, for example, ethoxylates of alcohols,
amines,
amides and acids. Preferred surfactants are non-ionic surfactants such as
alcohol
ethoxylates.
Other compounds that can be used as auxiliary or optional compounds in the
sanitary cleaning composition are perfumes and dyes. If one or more perfumes
are
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used in the cleaning composition of the invention they are usually present in
an
amount of about 0.01 to about 2 wt.%, preferably in an amount of about 0.05 to
about 0.8 wt.%, and most preferably in an amount of about 0.1 to about 0.6
wt.%. If
one or more dyes are used they are usually present in an amount of about
0.0001 to
about 0.1 wt.%, preferably in an amount of about 0.0005 to about 0.01 wt.%,
and
most preferably in an amount of about 0.001 to about 0.005 wt.%.
An auxiliary or optional compound that may also be included in the cleaning
composition according to the invention is one or more alcohol. The alcohol can
be
used to solve the perfume and/or other auxiliary compounds in a premix
solution
that is then used to formulate the cleaning composition. A preferred alcohol
is
ethanol. If one or more alcohols are used they are usually present in an
amount of
about 0.05 to about 10 wt.%, preferably in an amount of about 0.1 to about 5
wt.%,
and most preferably in an amount of about 0.5 to about 2 wt.%.
In further embodiments the sanitary cleaning composition of the invention
may optionally comprise additional agents like disinfecting agents,
preservatives,
corrosion inhibitors, complex builders, enzymes and bleaching agents.
In order to provide a sanitary cleaning composition being less irritant to the
human skin the pH value of the freshly formulated cleaning composition
according
to the invention is adjusted to be equal or above about 0.8, preferably equal
or above
zo about 0.9, and most preferably equal or above about 1.05. However, it is
generally
observed that after a storage time of a few weeks or month the pH value of
such
cleaning compositions increases due to decomposing reactions. Therefore, a
cleaning composition according to the invention that had a pH value of, for
example,
1.05 freshly after formulation may have a pH value of up to about 1.4 after 4
months
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storage at 40 C. Preferably, the pH of the invention formulation remains
below
about 2 even after extended storage of up to about 6 months.
In one embodiment of the present invention the cleaning composition
comprises hydroxycarboxylic acid in an amount of up to about 12 wt.%,
benzalkonium chloride in an amount of up to about 6 wt.%, one or more
surfactants
in an amount of about 0.5 to about 5 wt.%, urea in an amount of about 1 to
about 8
wt.%, one or more alcohols in an amount of about 0.1 to about 5 wt.%, wherein
the
weight ratio of the hydroxycarboxylic acid to the benzalkonium chloride is
between
about 5:1 and about 1:1. Optional additional ingredients include but are not
limited
to one or more perfumes in an amount of about 0.05 to about 0.8 wt.%, one or
more
dyes in an amount of about 0.0005 to about 0.01 wt.% and water.
In an alternate embodiment of the present invention the cleaning composition
comprises an additional acid, either sulfonic or sulfamic acid in an amount of
about
1 to 10 wt.%, hydroxycarboxylic acid in an amount of about 1 up to about 12
wt.%,
one or more non-ionic surfactants in an amount of about 1 to about 4 wt.%,
urea in
an amount of about 1 to about 3 wt.%, one or more alcohols in an amount of
about
0.5 to about 2 wt.%. Optionally, the following ingredients may also be added.
These include but are not limited to one or more perfumes in an amount of
about 0.1
to about 0.6 wt.%, one or more dyes in an amount of about 0.001 to about 0.005
wt.% and water, wherein the weight ratio of the hydroxycarboxylic acid to the
benzalkonium chloride is between about 1:5 and about 1:1.
In a further preferred aspect of the invention the sanitary cleaning
composition does not comprise any thickening agents, for example does not
comprise polysaccharide thickener. However, in other aspects of the invention
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thickening agents may also be present in the sanitary cleaning composition
according to the invention.
Furthermore, the cleaning composition according to the invention preferably
does not comprise ammonium sulfate as an auxiliary compound. However, in a
special aspect of the invention also ammonium sulfate may be comprised in the
composition.
In a preferred embodiment of the present invention the cleaning composition
comprises lactic acid in an amount of about 2 up to about 12 wt.%,
benzalkonium
chloride in an amount of about 2 up to about 4 wt.%, one or more non-ionic
lo surfactants in an amount of about 1 to about 3 wt.%, urea in an amount
of about 1 to
about 3 wt.%, ethanol in an amount of about 0.5 to about 2 wt.%, one or more
perfumes in an amount of about 0.1 to about 0.6 wt. %, one or more dyes in an
amount of about 0.001 to about 0.005 wt.% and water, wherein the weight ratio
of
the lactic acid to the benzalkonium chloride is between about 1:5 and 1:1. In
yet
another embodiment, the composition does not include a thickening agent or
sulfamic acid.
The invention may be provided in the form of a concentrate. The concentrate
may be formulated without any water or can be provided with a relatively small
amount of water in order to reduce the expense of transporting the
concentrate.
Then the concentrate is provided as a liquid, it may be desirable to provide
it in a
flowable form so that it can be pumped or aspirated. It has been found that it
is
generally difficult to accurately pump a small amount of a liquid. It is
generally
more effective to pump a larger amount of a liquid. Accordingly, although it
is
desirable to provide the concentrate with as little water as possible in order
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transportation costs, it is also desirable to provide a concentrate that can
be
dispensed accurately. As a result, a concentrate according to the invention,
when it
includes water, it can include water in an amount of between about 0.1 wt. %
and
about 99 wt %, between about 30 wt % and about 90 wt. %, and between about 60
wt. % and about 89 wt. %.
The water that is provided as part of the concentrate may be relatively free
of
hardness such as deionized water. Alternatively, the water that is part of the
concentrate may have some hardness. The concentrate may then be diluted with
either deionized water, or more likely, it will be diluted with local water
containing
varying amounts of hardness. That is, the concentrate may be formulated with
water
that includes dissolved solids, and can be formulated with water that can be
characterized as hard water. In a preferred embodiment, water substantially
free of
dissolved solids is used in both the concentrate, if one is provided, and as
the water
of dilution to prepare a use composition.
The sanitary cleaning composition according to the invention can be used for
cleaning of, disinfecting of, and/or lime removal from various surfaces.
Examples
for such surfaces which can be found in sanitary or kitchen areas are brass,
copper,
aluminium, stainless steel, zinc, polyvinylchloride (PVC), polypropylene,
acrylonitrile butadiene styrene (ABS), polyacetate, polystyrene, polyethylene
(PE),
zo polymethyl methacrylate (PMMA, plexiglas), polycarbonate, ceramic,
tiles,
porcelain, painted and plastic coated surfaces and enamel or any other
surfaces in
sanitary or kitchen areas. The sanitary cleaning composition of the invention
has
limited corrosivity on various surfaces. It was surprisingly found that the
composition of the invention exhibited the desirable properties of (1)
biocidal
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activity, (2) removes lime scale, (3) has better material compatibility, and
(4) is
substantially biodegradable. It is remarkable that a cleaning composition
meets all
of these desirable criteria.
The sanitary cleaning composition according to the invention can be used as
a concentrated composition. However, typically it is used as a ready-to-use
solution
in any desired dilution in the range of 10:1 to 1:400 of the composition in
water. A
preferred dilution is 1:10 in water. The ready-to-use solution can be applied
by
spraying or as a foam cleaner.
The sanitary cleaning composition according to the invention is useful for
lo biocidal purposes. That is, to reduce the proliferation of microbes. For
the purposes
of this application, "microbes" or "microorganisms" as used herein includes
but is
not limited to Gram positive and Gram negative bacteria, algae, fungi, and
yeasts.
Any microbe or microorganism that can cause pathology in humans is desirable
to
eliminate or reduce the colony forming units thereof In a preferred
embodiment, a
composition of the invention is effective in reducing the colony forming units
of a
Gram positive bacteria, such as Staphylococcus aureus, by a logarithm of 3,
preferably 4, and most preferably 5 when contacting a sample for about 5
minutes at
degrees C.
The aqueous sanitary cleaning composition according to the invention can be
zo formed by mixing together all compounds comprised in the composition,
preferably
beginning with water. Then the other compounds are added to the water. If
desired, a
ready-to-use composition can then be prepared as mentioned above. An
additional
pre-mix step is normally not required especially not for the perfume added to
the
aqueous mixture. In cleaning compositions which are only sulfamic-acid-based
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according to the state of the art it is normally necessary to dissolve the
perfume
compound in, for example, ethanol and then to add this pre-mix to the aqueous
mixture prepared before. Therefore, it is a further advantage of the sanitary
cleaning
composition of the present invention that this pre-mix step can be avoided.
Examples
In the following tests aqueous sanitary cleaning compositions according to
the invention and according to the state of the art were prepared and compared
with
respect to their lime-removal capacity, their cleaning capacity, their
biocidal activity,
and their material compatibility and corrosiveness.
Cleaning compositions were prepared according to amounts listed in Table 1.
Examples C1-C4 are comparative examples lacking the benzalkonium chloride
component. Example 1 is illustrative of the invention.
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Table 1
Component Exp. Cl Exp. C2 Exp. C3 Exp. C4 Exp. 1
Water Deionized 76.3085 76.3085 81.5285 76.3085 80.5485
Fatty alcohol C10-
1.2
14; 6 EO
Isotridecanol
1.20 1.20 1.20 1.20
Ethoxylate (8 EO)
Secondary Alkane
1.29 1.29 1.29 1.29
Sulfonate (SAS)
Sodium alkane
0.60 0.60 0.60 0.60
sulphonate
Alkyl Dimethyl
Benzyl Ammonium 4.9
Chloride 50%
Urea technical 5.00 5.00 5.00 5.00 2.00
Sulfamic Acid 10.00
Lactic Acid 80% 10.00 4.78 5.00 10.00
Citric Acid 5.00
Ethanol 5.00 5.00 5.00 5.00 1.00
DET Perfume 0.60 0.60 0.60 0.60
Tropeach perfume 0.35
Basic Violet 10 0.00025 0.00025 0.00025 0.00025 0.00025
Acid Yellow 3 0.00125 0.00125 0.00125 0.00125 0.00125
LIME-REMOVAL CAPACITY
The lime-removal capacity was tested using the marble-block method
according to which marble blocks of 30x30x20 mm dimension were brushed under
water and dried for 24 hours in a drying chamber at 50 C. For the examination
of
the lime-removing capacity the marble-block is placed in 200 ml of the aqueous
sanitary cleaning composition for 1 hour at room temperature. The lime-
removing
capacity is the amount of marble in milligrams that dissolves within 1 hour.
The
difference in weight of the marble block at the beginning and in the end of
the
dissolving procedure is equal to the lime-removing capacity.
The formulation from Example 1 shown above in Table 1 was tested for
lime-removal capacity. Table 2 shows the lime-removing capacity at room
temperature of the cleaning compositions according to the Example 1. Room
temperature, as used herein refers to temperatures in the range of 68 to 74
degrees
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Fahrenheit. The lime-removing capacity was tested with the composition
concentrate (Example 1 formulation) as shown in column 1 and with 5 wt %
concentrate diluted in water and 2 wt % concentrate diluted in water (columns
2 &
3). The samples were run in duplicate.
As can be seen from Table 2, the best lime-removing capacity is observed
with the concentrated composition, however, the diluted Example 1 compositions
also demonstrate lime-removing capacity.
Table 2
1
Mass (mg)...ittititAttitate
Ifjaa.li 47.9265 46.2734 45.7025
fitigiommil 45.0036 46.2133 45.6841
IVOighting
õ\ 4 2.9229 0.0601 0.0184
"\\ pi#011111 46.9602 46.0626
48.2787
ifitiAtiaNd 44.0681 45.9994 48.2614
Weight
" 2.8921 0.0632 0.0173
Inti t,ote,Atei:i 2.9075 0.0617 0.0178
1287 0 1335 00380
COMPARATIVE LIME REMOVAL CAPABILITY
Formulations according to Examples C2, C3, and C4 provided in Table 1
above were prepared and lime removal capabilities of each were compared
against
Example 1. As described above, the lime-removal capacity was tested using the
marble-block method according to which marble blocks of 30x30x20 mm dimension
were brushed under water and dried for 24 hours in a drying chamber at 50 C.
For
the examination of the lime-removing capacity the marble-block is put in 200
ml of
the aqueous sanitary cleaning composition to be tested for 1 hour at room
temperature. The lime-removing capacity is the amount of marble in that
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within the 1 hour the block was in the 200 ml aqueous cleaning solution. The
difference in weight as measured in milligrams of the marble block at the
beginning
and in the end of the dissolving procedure is equal to the lime-removing
capacity.
Results are shown in Table 3 below. The formulation of Example 1 prepared
according to the present invention performed well against the comparative
examples.
Only Example C2 performed better in the lime removal test as compared to the
invention.
Table 3
Formulation Exp. C2 Exp. C3 Exp. C4 Exp. 1
% scale 25.73 17.93 8.78 21.49
removal after
24 hours
WETTING POWER
Samples were prepared having different surfactant compositions. Table 4
shows the compositions of each Example. Microfiber cloths were soaked in 100m1
of each of the Examples provided below. The cloths were wrung for 3 seconds
and
the saturated cloths were then applied to a previously washed and dried black
PVC
slab. The formulation of Example 1 from Table 1 is repeated below for
convenience.
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Table 4
Example 1 2 3 4 5 6 7 8 9
Component
Water (DI) 80.9 80.2 81.4 77.8 81 80 78.2
80.6 82.1
Lactic Acid 80% 10 10 10 10 10 10 10 10 10
Alkyl Dimethyl Benzyl 4.9 4 4 4 4 4.9 4.9 4.9 4.9
Ammonium Chloride
50%
Ethanol 1 1 1 1 1 1 1 1 1
Urea 2 2 2 2 2 2 2 2 2
Isotridecanol 2.8 2.1
Ethoxylate; 8 EO
Fatty alcohol C10-14 1.2 1.6
6E0
Cocodimethylaminoxide 5.2 3.9
30%
Long chain alcohol 2 1.5
alkoxylated
Upon wiping the surface with the prepared microfiber cloths, each of the
Examples had excellent wetting power meaning that the surface had a uniform
moistened film.
CLEANING CAPACITY
The cleaning capacity is measured. Test soil is prepared with the
formulation according to Table 5 below.
Table 5 ¨ Soil Solution
Component Mass (% by weight)
Degussa Special Black 4 (pigments) 7.0
Henkel KgaA Myritol 318 (oil) 17.0
Esso Telura 310 ¨ (oil) 40.0
White Spirit 80/110 ¨ (fuel) 36.0
The oil (Esso Telura 310 and the Henkel KgaA Myritol) and white spirit
were combined. To this combination the pigments (Degussa Special Black) were
added and mixed. The combination was mixed 8 hours. The combination was then
allowed to sit for 3 days and the combination was mixed again 5 hours or until
combined. The combination then sat for an additional 11 days for a total of 14
days.
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The combination was then mixed for 1 hour before use. White PVC strips (White
PVC-film Benova 4812080, 1.3 m/ 50 m/ 0.12mm as purchased from Benecke-
Kaliko AG) were coated with the soil solution using a flat paintbrush with
flat
bristles, about 55 mm wide. The prepared strip was either (a) wiped 10 times
with
soil solution and allowed to dry for at least 30 minutes, or (b) wiped twice
with soil
solution and allowed to dry for 2-3 hours.
Two grams test soil was applied with the flat brush on the white PVC foil.
Horizontal strokes were alternated with vertical strokes 7 times in each
direction.
The final coat was at right angles to the scouring movement. The soil was
allowed
to dry for one hour.
For the evaluation of the cleaning capacity the following test was undertaken
for the compositions provided in Table 4 above diluted at 1 wt% in hard water
to
prepare use compositions. The test results are shown in Table 6 below.
A polyester sponge submerged in water was removed from the water and
allowed to drain. The sponge was compressed for 10 seconds in a sponge press
and
placed in a Gardner apparatus with a weight of 400 g. Twelve ml use
composition
was poured on top of the soiled strip and the sponge. The cycle counter on the
Gardner apparatus Gardner wet abrasion scrub tester apparatus model 494 (DIN-
ASTM-515); supplied by Erichsen GmbH & Co. KG. was set to 10. Upon
zo completion of the wipe cycle, the sponge was discarded. The test strip
was rinsed
under running deionized water. The test strips were hung for drying. Each use
composition was tested on 6 strips.
The test strip's whiteness was analyzed by a Minolta Chroma Meter CR-200
chromatometer. The instrument was calibrated with the provided white tile. The
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reflection was taken at 7 different spots per strip. The average of the result
gives the
percentage of the cleanability. Single large deviating results were rejected
from the
calculation.
Valuation of the results:
For the use composition and a possible comparative dilution, the average is
calculated for all measurements:
¨ E
N = number of measurements (6 x 7 = 42)
x = degree of whiteness per measure spot
Xarithm = Average cleaning performance
Standard deviation:
2
Sx 1 ------- t)2
.
Control:
The measurements are influenced by the quality of water and the environmental
conditions in the lab (temperature and humidity). Therefore, only the results
achieved at once and on the same day are comparable.
Table 6: Cleaning capacity
Example # diluted at 1 wt% in hard water Total avg. L % Stain Removal
1 66.48
2 62.97
3 64.52
4 62.99
5 65.60
6 58.62
7 61.17
8 66.01
9 57.91
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As can be seen from the results in Table 6, the cleaning capacity of the
aqueous sanitary cleaning composition prepared according to the invention
including
surfactants (Examples 1-8) performed better than Example 9 that did not
contain
additional surfactants.
CORROSIVENESS
The corrosiveness of Example 1 (shown in Table 1 above) was tested on
samples of brass, copper, chromed brass, aluminium, and stainless steel
(50x20x2
mm). The test samples were entirely submerged in the aqueous sanitary cleaning
composition. The loss of mass of the test samples was evaluated after their
exposure
to the cleaning composition for three weeks at room temperature. The results
are
listed in Table 7 below.
Table 7: Corrosiveness Week 1
Sample Example 1 - Material Initial Mass Mass
% Mass
Mass (g) after 1 Difference
Difference
week (g) (g)
A Brass 43.7458 43.6948 -0.0510
0.1166
Copper 44.870 44.7074 -0.1646 -
0.3668
Chromed 45.6103 45.6005 -0.0098 -0.0215
Brass
Aluminum 19.9675 19.9515 -0.0160 -0.0801
Stainless 38.6937 38.6942 0.0005
0.0013
Steel
Zinc 37.7150 36.9467 -0.7683 -
2.0371
Table 8: Corrosiveness Week 2
Sample Example Material Initial Mass Mass % Mass
1 Mass (g) after 2
Difference Difference
weeks (g) (g)
A Brass 43.7458 43.6447 -0.1011 -
.2311
Copper 44.870 44.5310 -0.3410 -0.7599
Chromed 45.6103 45.5770 -0.0333 -
0.0730
Brass
Aluminum 19.9675 19.9300 -0.0375 -
0.1878
Stainless 38.6937 38.6934 -0.0003 -
0.0008
Steel
Zinc 37.7150 36.7716 -0.9434 -
2.5014
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Table 9: Corrosiveness Week 3
Sample Example Material Initial Mass Mass % Mass
1 ¨ 5 wt% Mass (g) after 3 Difference Difference
in water weeks (g)
(g)
A Brass 43.7458 43.5893 -0.1565 -0.3577
Copper 44.870 44.1371 -0.7349 -1.6378
Chromed 45.6103 45.5502 -0.0601 -0.1318
Brass
Aluminum 19.9675 19.9128 -0.0547 -0.2739
Stainless 38.6937 38.6941 0.0004 0.0010
Steel
Zinc 37.7150 36.6194 -1.0956 -2.9049
As can be seen from Tables 7-9, the loss of mass is well within acceptable
ranges, that being very low, when the metal sheets were exposed to the
sanitary
cleaning composition according to the invention (Example 1).
The results demonstrate that the sanitary cleaning composition according to
the invention is minimally corrosive to metal surfaces.
MATERIAL COMPATIBILITY
Another example for good material compatibility or even, depending on the
point of view, less corrosiveness can be observed when plates of copper or
brass are
exposed for 3 weeks to diluted cleaning compositions according to Example 1 as
provided in Tables 7-9 above. There was little change in the appearance of the
copper and the brass plates that were put into a composition according to
Example 1.
In summary, the above evaluations show that the cleaning compositions
according to the invention have good material compatibility, are minimally
corrosive
to metal surfaces such as steel and aluminium, but nevertheless have good lime-
removing capacity and good cleaning properties.
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BIOCIDAL ACTIVITY
Example 1 was used to test the biocidal activity of the invention. Example 1
was
diluted on a percent by volume basis with hard water (300 mg/Kg CaCO3) to
prepare
0.5%, 1%, and 2% use compositions. Bacterial suspensions were prepared using
the
listed bacterial genus species and having the listed colony forming units as
shown in
Table 10 below. One ml of each bacterial suspension was added to an 8 ml
sample
of each of the prepared use compositions. The mixtures were maintained at 20
degrees C +/- 1 degree C for 5 minutes +/- 10 seconds by placing the sample in
a
bath. At the end of the contact time, one ml of each test sample was placed in
8 ml
lo of a neutralizing agent (composition provided below) to stop the
activity of the
disinfectant and to remove the residual inhibitory effect of the product.
A one ml aliquot of each neutralized sample was than plated in duplicate via
the
pour method on Petri dishes containing Tryptone Soy Agar (see composition
below).
Neutralizing Agent:
Component Amount
Lecithin 3 grams
Polysorbate 80 30 grams
Disodium phosphate (12H20) 9 grams
Monopotassium phosphate 1.5 grams
Distilled water 1000 ml
Tryptone Soy Agar
Tryptone, pancreatic digest of casein 15.0g
Soya peptone, papaic digest of soybean meal 5.0g
Sodium chloride 5.0g
Agar 15.0g
Water 1,000m1
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Results are shown in Table 10 below. According to the European Standards,
concentrations are considered bactericidal when the number of viable cells is
reduced by at least 5 log (105).
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Table 10
: Viable count
N : Number of cfulml of the bacterial test suspensiai
: Number of cfulml in the test mixture
R: Reduction in v
Bacterial
Test Test Test
procedure at concentration (4400
Organisms Suspension
0.5(4 24
V. > 300 ; > 300 29 ; 28 3 ; 2
Pseudomonas N: 1.9 x 108 Na > 3 x 103 2.85 x 102 <1.50 x
aeruginosa 102
ATCC 15442 R <6.33 x 103 6.67 x 104
4it
Ve 41 ; 47 0 ; 0 0 ; 0
Escherichia coli N : 3.0 x 108 Na 4.40 x 102 <1.50 x 102 <1.50 x
ATCC 10536 102
6.82 x 104 410.0i46.1"
.7% 3'4
Ve > 300 ; > 300 16 ; 12 1 ; 0
Staphylococcus N : 3.2 x 108 Na > 3 x 103 < 1.50 x 102 <
1.50 x
aureus 102
ATCC 6538 R < 1.07 x 104t1x 1O
>213
0.05(4 0.1(4 0.5(4
Ve > 300 ; > 300 > 300 ; > 300 0 ;
0
Enterococcus N : 1.8 x 108 Na > 3 x 103 > 3 x 103 < 1.50 x
hirae 102
ATCC 10541 R <6.00 x 103 <6.00 x 103
24
