[0001] The present invention refers to a liquid rinse aid composition comprising a biosurfactant
selected from the group of mannosylerythritol lipids, the use of such compositions
in an automatic dish washer and methods for cleaning kitchenware and/or tableware
in an automatic dishwasher comprising bringing such a composition into contact with
said kitchenware and/or tableware during the rinse step.
[0002] Rinse aids are added during the rinsing step of automatic dishwashing programs to
prevent droplet formation, so that water drains from the surfaces in thin sheets,
rather than forming droplets, which prevents "spotting".
[0003] "Spotting" on washed items is caused by droplets of water drying and leaving behind
dissolved limescale minerals, thereby rendering the washed table- or kitchenware less
attractive to the consumer. Rinse aids can also improve drying performance as there
is less water remaining to be evaporated off the washed items. A thinner sheet of
water also has a larger surface-area than a droplet of the same volume, which increases
the likelihood of water molecules evaporating. This results in less energy consumption
in order to dry the washed items.
[0004] The above-mentioned effects are generally achieved by rinse aids comprising nonionic
surfactants. However, conventional rinse aids entirely rely on nonionic surfactants
derived from ethoxylated fatty alcohols. Such surfactants are synthesized from petroleum
fractions and therefore require high amounts of energy and non-renewable resources
during production. Consequently, there is a need for rinse aid compositions being
more environmentally friendly and saving recources. It was therefore an object of
the present invention to provide a rinse aid composition yielding excellent spotting
results, in which at least a part of conventional nonionic surfactants is saved. This
object is met by the use of particular, selected surfactants known in the art as biosurfactants.
[0005] Biosurfactants are surfactants which can be produced by biotechnological processes,
i.e. using fungi or bacteria, from renewable resources, like sugars and/or oils derived
from plants. A further advantage of biosurfactants is that these compounds are readily
biodegradable.
[0006] A drawback of the replacement of conventional nonionic surfactants by biosurfactants
is a decrease in drying and spotting performance of the resulting rinse aids. However,
the present inventors have surprisingly found that drying and spotting performance
of rinse aid compositions comprising biosurfactants can be improved by incorporating
mannosylerythritol lipids into such rinse aid compositions.
[0007] Mannosylerythritol lipids are molecules having the general formula (I) below.

[0008] Depending on the degree of acetylation, mannosylerythritol lipids are divided into
subtypes called MEL-A (R
1 = R
2 = Ac), MEL-B (R
1 = Ac, R
2 = H), MEL-C (R
1 = H, R
2 = Ac) and MEL-D (R
1 = R
2 = H), wherein Ac is the abbreviation for an acetyl residue.
[0009] Within the context of the present invention, for all subtypes n may be an integer
having a value between 1 and 24, preferably between 2 and 18, more preferred between
4 and 12 and between 14 and 18, most preferred 3, 4, 5, 9, 10, 11, 15, 16 or 17.
[0010] Such biosurfactants are typically produced using bacteria of the species Pseudozyma
or Ustilago.
[0013] However, none of the above-mentioned prior art documents teaches beneficial properties
of mannosylerythritol lipids when incorporated into a rinse aid composition.
[0014] In case within this disclosure the rinse aid composition according to the present
invention is defined as being free of a specific component, "free" in this context
means that, despite efforts taken to avoid the presence of said component in the rinse
aid composition, a total amount of not more than 10 ppm, preferably not more than
5 ppm, more preferred not more than 2 ppm of said component may be present in the
rinse aid composition according to the present invention. Most preferred the inventive
rinse aid composition contains less than 1 ppm, or 0 ppm of any undesired components.
[0015] Amounts given within here are presented in wt.-% based on the total weight of the
inventive rinse aid composition, unless otherwise stated.
BIOSURFACTANTS
[0016] The rinse aid composition according to the present invention comprises at least one
biosurfactant selected from the group of mannosylerythritol lipids. Said biosurfactant(s)
may be of any of the subtypes MEL-A to MEL-D as defined in Formula (I) above or a
mixture of mannosylerythritol lipids of said subtypes. This means that of the two
hydroxy groups present in the at least one biosurfactant, 0 to 2 may be acetylated
and n may be an integer having value between 1 and 24, preferably between 2 and 18,
more preferred between 4 and 12 and between 14 and 18, most preferred 3, 4, 5, 9,
10, 11, 15, 16 or 17.
[0017] The above-defined biosurfactant(s) may be present in the rinse aid composition in
a total amount of from 1 to 15 wt.-%, preferably from 3 to 12 wt.-%, more preferred
from 5 to 10 wt.-%, based on the total weight of the rinse aid composition.
ADDITIONAL NONIONIC SURFACTANTS
[0018] The rinse aid composition may preferably additionally comprise at least one further
nonionic surfactant different from mannosylerythritol lipids.
[0019] Preferred nonionic surfactants different from mannosylerythritol lipids are alkoxylated
fatty alcohols, alkoxylated fatty acids or combinations thereof. The relative hydrophilic
alkoxy-chain may comprise or essentially consist of ethylene oxide, propylene oxide
or butylene oxide or combinations thereof.
[0020] The length of this alkoxy-chain can vary between averagely 1 and averagely 200 (total)
ethylene oxide-, propylene oxide- or butylene oxide-groups or combinations thereof,
including 4, 6, 8, 10, 13, 15, 20, 25, 30, 40, 50, 80, 100 and the ranges between
the particularly mentioned. The relative hydrophobic hydrocarbon-chain from the fatty
alcohol or fatty acid can be saturated, monounsaturated or poly-unsaturated and linear
or branched. The length of this hydrocarbon-chain may vary between 4 and 30 carbon
molecules, including 6, 8, 10, 11, 12, 14, 16, 18, 20, 5 22, 24, 26 or 28.
[0021] Preferred surfactants of this type may be represented by the formula R
1O(CH
2CH
2O)
x(CH(CH
3)CH
zO)
yH, wherein R
1 is a linear or branched, saturated or unsaturated hydrocarbon residue having 4 to
30 C atoms, preferably 6 to 26, even more preferred 10 to 24 carbon atoms, x preferably
is an integer of from 8 to 200, preferably from 20 or from 25 to 200, y preferably
is an integer of at most 100 and x+y is preferably below 200.
[0022] Particularly preferred are alcohol ethoxylates that can be prepared by ethoxylation
of a fatty chain alcohol. The preferred alcohol ethoxylates have a hydrocarbon-chain
that ranges from 4 up to 26 carbon atoms, including 4, 6, 8, 10, 12, 14, 16, 18, 20,
22 and between averagely 1 and averagely 200 ethylene oxide-groups, including averagely
4, 6, 20 8, 10, 13, 15, 20, 25, 30, 40, 50, 80, 100 ethylene oxide-groups. Also preferred
are fatty acid ethoxylates that can be prepared by a reaction of fatty acid with ethylene
oxide or a polyglycol with the general formula RCOO-(CH
2CH
2O)
nH. When a polyglycol is used a mixture of mono- and di-esters (RCOO-(CH
2CH
2O)
n-OCOR) is produced. The preferred fatty acid has a hydrocarbon-chain R that varies
from 4 up to 26 carbon molecules, including 4, 6, 8, 10, 12, 14, 16, 18, 20, 22. The
number of ethylene oxide-groups in the fatty acid ethoxylate is between averagely
1 and averagely 200 ethylene oxide-groups, including averagely 4, 6, 8, 10, 13, 15,
20, 25, 30, 40, 50, 80, 100 ethylene oxide-groups.
[0023] Such additional nonionic surfactants may be any nonionic surfactant known in the
art with the exception sorbitan esters, i.e. mono-, di- or triesters of sorbitol and
fatty acids, which the composition is free of. If present, additional nonionic surfactants
are most preferably selected from ethoxylated alcohols.
[0024] Ethoxylated alcohols may be selected from the group of C
8-C
20 ethoxylated alcohols, preferably from the group of C
8-C
10 and C
16-C
18 ethoxylated alcohols.
[0025] Commercially available mixtures of ethoxylated alcohols comprise for example those
sold under the trade names of Plurafac
® and Emulan
® by BASF.
[0026] If such additional nonionic surfactants are present, such nonionic surfactants may
be present in the rinse aid composition in a total amount of from 0.1 to 10 wt.-%,
preferably from 0.3 to 6 wt.-%, more preferred from 0.5 to 4 wt.-%, most preferred
from 0.7 to 2 wt.-% based on the total weight of the rinse aid composition.
[0027] Consequently, if applicable, the ratio of the total amount of biosurfactant(s) to
the total amount of other nonionic surfactant(s) may be between 20:1 and 1:1, preferably
between 10:1 and 3:1, more preferred between 8:1 and 5:1.
ACIDIC COMPONENT
[0028] The rinse aid composition according to the present invention highly preferred comprises
an acidic component and preferably has an acidic pH value, i.e. the pH of the rinse
aid composition is preferably below 7. An acidic pH value is beneficial in order to
avoid precipitation of magnesium and/or calcium hydroxides from the rinsing liquor.
If precipitated, these salts would then become deposited in form of a cloudy or milky
film on the washed dishware, which is considered as an improper cleaning result by
the consumer.
[0029] Such an acidic component may be an organic or inorganic, mono- or polyprotic acid,
and/or an anionic surfactant containing phosphoric acid mono- and/or diester groups.
[0030] Organic or inorganic acids may be selected from any water-soluble organic or inorganic
acids, preferably selected from the group consisting of phosphoric acid, sulfuric
acid, hydrochloric acid, boric acid, lactic acid, citric acid, formic acid, acetic
acid, glycolic acid, succinic acid, adipic acid, malic acid, maleic acid, gluconic
acid and tartaric acid.
[0031] Anionic surfactants containing phosphoric acid mono- and/or diester groups are preferably
selected from ethoxylated alkyl phosphates and/or ethoxylated alkyl aryl phosphates.
[0032] Preferred alkyl phosphates and alkyl ether phosphates can be prepared by treating
fatty alcohols or (fatty) alcohol ethoxylates with a phosphorylating agent which yields
in a mixture of mono- and di-esters of phosphoric acid.
[0033] Preferably, the acidic component is selected from phosphoric acid and/or ethoxylated
alkyl phosphates and such phosphates are preferably selected from C
8-C
20 ethoxylated alkyl phosphates, more preferred C
8-C
16 ethoxylated alkyl phosphates, even more preferred C
8-C
14 ethoxylated alkyl phosphates, most preferred C
8-C
10 ethoxylated alkyl phosphates, wherein preferably ethoxylated alkyl phosphates contain
3 to 10 ethylene oxide repeating units (EO), more preferred 4 to 8 EO, even more preferred
4 to 6 EO and most preferred 5 EO.
[0034] Such anionic surfactants are commercially available, for example under the trade
name of Servoxyl
® by KLK OLEO.
[0035] Acidic components as defined above may be present in the rinse aid composition in
a total amount of from 0.1 to 10 wt.-%, preferably from 0.5 to 5 wt.-%, more preferred
from 1 to 3 wt.-%, based on the total weight of the rinse aid composition.
SOLVENTS
[0036] The rinse aid composition according to the present invention is a liquid rinse aid
composition. It may therefore comprise 50 to 98 wt.-%, preferably 75 to 95 wt.-%,
more preferred 80 to 90 wt.-%, based on the total weight of the rinse aid composition,
of a solvent or a mixture of solvents.
[0037] This enables the rinse aid composition to become readily dissolved in the rinsing
liquor, thereby avoiding redeposition of any undissolved components from the rinse
aid composition on washed items.
[0038] The solvent or mixture of solvents may comprise one or more solvents selected from
water, ethanol, 2-propanol and/or glycerol and preferably comprises water.
ENZYMES
[0039] A skilled person will acknowledge that biosurfactants are more prone to enzymatic
degradation than conventional surfactants. Therefore, in order to avoid such degradation
of biosurfactants by cleavage of ester or ether bonds, it is therefore particularly
preferred that the rinse aid composition according to the present invention is free
of enzymes cleaving such bonds.
[0040] Free in this context means that, despite efforts taken to avoid the presence of enzymes
in the rinse aid composition, a total amount of not more than 1 ppm of ester or ether
cleaving enzymes may be present in the rinse aid composition according to the present
invention.
MISCELLANEOUS INGEDIENTS
[0041] The rinse aid composition according to the present invention may additionally to
the above-mentioned components comprise any ingredients known by a skilled person
useful in a rinse aid composition. Such components may for example be complexing or
sequestering agents, salts or corrosion inhibitors.
[0042] Preferred salts are water-soluble salts of magnesium, zinc and/or bismuth, as these
ions are able to suppress glass corrosion occurring from excess chelating agents,
which may present in the rinsing liquor for example due to low water hardness of the
used rinsing water.
[0043] In a preferred embodiment, the rinse aid composition contains a mixture of: biosurfactants
selected from mannosylerythritol lipids, ethoxylated fatty alcohols, in particular
those selected from C
8-C
10 and C
16-C
18 ethoxylated fatty alcohols, acidic components, in particular those selected from
C
8-C
10 ethoxylated alkyl phosphates and phosphoric acid and water. In a particularly preferred
embodiment, the rinse aid composition consists of these components.
PROPERTIES
[0044] The inventive rinse aid composition may have a pH value of from 1.5 to 4, preferably
from 2 to 3. It may have a density from 1.00 to 1.30, preferably 1.00 to 1.15, more
preferably 1.00 to 1.05.
EXAMPLE
[0045] All tested rinse aid compositions contained 7.5 wt-% of the respective biosurfactant,
1 wt.-% of nonionic surfactant C
16-C
18 alcohols, ethoxylated, 1.9 wt.-% of acidic components (C
8-C
10 ethoxylated fatty alcohol phosphates) and ad 100 wt.-% water and had an acidic pH
value.
[0046] Biosurfactants tested were two rhamnolipid-based biosurfactants, namely Raphynal
V1 200 (abbreviated as RL 1), and a mixture of approx. 65 to70 % diramnolipids and
approx. 15 to 20 % mono-ramnolipids (abbreviated as RL 2), one sophorolipid-based
biosurfactant, namely Rewoferm
® SL One (ex Evonik) (abbreviated as RL 3) and mannosylerythritol lipids as described
herein (a mixture of lipids having in formula (I) values for n of 4, 10 and 16; inventive
example, abbreviated as MEL).
[0047] Dishes were washed in a Miele GSL-2 dishwasher over 6 cycles in the standard program
at 50 °C (rinsing time 8 minutes). The water hardness was 9 °GH.
[0048] Dishes used were eight glasses (goblet-formed, cola and longdrink glasses), six plastic
dishes of different materials (melamine-based, polypropylene-based and styrene-acrylonitrile-based),
four steel knives and six black ceramic dishes.
[0049] Dishes were checked for droplets and spotting after 4, 5 and 6 cycles, respectively.
The number of droplets were determined 30 minutes after finishing the respective number
of cycles, while spotting was determined 3 hours after finishing the respective number
of cycles, both by visual inspection of an experienced person.
[0050] Drying performance was rated on a scale of 0 to 10, wherein 0 stands for no droplets
remaining on the respective dishes and wherein 10 stands for a high number of droplets.
[0051] Spotting performance was rated on a scale ranging from 1 to 7, wherein 1 stands for
a high number of spots on the respective dishes and 7 stands for no spots.
[0052] Results are shown in Figures 1 and 2. The values are given as average values over
4, 5 and 6 cycles for all dishes of the same respective material and as average values
for all dishes over 4, 5 and 6 cycles (right column).
[0053] It becomes clear from these figures that an inventive rinse aid composition comprising
mannosylerythritol lipids as biosurfactants shows better average drying and spotting
performance over all tested dishes than rinse aids containing other biosurfactants.
1. A rinse aid composition comprising:
at least one biosurfactant selected from the group of mannosylerythritol lipids; and
at least one acidic component;
wherein the rinse aid composition is free of ingredients selected from enzymes and/or
sorbitan esters.
2. The rinse aid composition according to claim 1, wherein the mannosylerythritol lipid(s)
is/are present in a total amount from 1 to 15 wt.-%, preferably from 3 to 12 wt.-%,
more preferred from 5 to 10 wt.-%, based on the total weight of the rinse aid composition.
3. The rinse aid composition according to any preceding claim further comprising at least
one further nonionic surfactant different from mannosylerythritol lipids.
4. The rinse aid composition according to claim 3, wherein the further nonionic surfactant(s)
is/are selected from ethoxylated alcohols.
5. The rinse aid composition according to claims 3-4, wherein the further nonionic surfactant(s)
is/are selected from the group of C8-C20 ethoxylated alcohols, preferably selected from the group of C8-C10 and C16-C18 ethoxylated alcohols.
6. The rinse aid composition according to claims 3-5, wherein the further nonionic surfactant(s)
is/are present in a total amount of from 0.1 to 10 wt.-%, preferably between 0.3 to
6 wt.-%, more preferred from 0.5 to 4 wt.-%, most preferred from 0.7 to 2 wt.-% based
on the total weight of the rinse aid composition.
7. The rinse aid composition according to claims 3-6, wherein the ratio of the total
amount of biosurfactant(s) to the total amount of further nonionic surfactant(s) is
of from 20:1 to 1:1, preferably from 10:1 to 3:1, more preferred from 8:1 to 5:1.
8. The rinse aid composition according to any preceding claim,
wherein the acidic component(s) is/are selected from
(I) the group containing phosphoric acid, sulfuric acid, hydrochloric acid, boric
acid, lactic acid, citric acid, formic acid, acetic acid, glycolic acid, succinic
acid, adipic acid, malic acid, maleic acid, gluconic acid and tartaric acid; and/or
(II) anionic surfactants containing phosphoric acid mono- and/or diester groups.
9. The rinse aid composition according to claim 8, wherein anionic surfactants are selected
from ethoxylated alkyl phosphates and/or ethoxylated alkyl aryl phosphates.
10. The rinse aid composition according to claims 8-9, wherein the acidic component(s)
is/are selected from phosphoric acid and/or ethoxylated alkyl phosphates, wherein
ethoxylated alkyl phosphates are selected from C8-C20 ethoxylated alkyl phosphates, preferably C8-C16 ethoxylated alkyl phosphates, more preferred C8-C14 ethoxylated alkyl phosphates, most preferred C8-C10 ethoxylated alkyl phosphates.
11. The rinse aid composition according to any preceding claim,
wherein the acidic component(s) is/are present in a total amount of from 0.1 to 10
wt.-%, preferably from 0.5 to 5 wt.-%, more preferred from 1 to 3 wt.-%, based on
the total weight of the rinse aid composition.
12. The rinse aid composition according to any preceding claim being a liquid rinse aid
composition comprising 50 to 98 wt.-%, preferably 75 to 95 wt.-%, more preferred 80
to 90 wt.-%, based on the total weight of the rinse aid composition, of a solvent
or a mixture of solvents.
13. The rinse aid composition according to claim 12, wherein the solvent or mixture of
solvents comprises one or more solvents selected from water, ethanol, 2-propanol and/or
glycerol, preferably water.
14. Use of the composition according to any preceding claim as a rinse aid in an automatic
dishwasher.
15. A method of cleaning kitchenware and/or tableware in an automatic dishwasher comprising
adding a composition according to claims 1-13 in the rinsing step.