FIELD OF INVENTION
[0001] The present invention belongs to the area of detergents and refers to a new blend
of surfactants, rinse aid compositions comprising them and their use as rinse aid
surfactants.
STATE OF THE ART
[0002] Nowadays, higher demands are placed on machine-washed dishes than on manually washed
dishes. For example, even dishes completely cleaned of food residues are not assessed
as perfect if, after machine dishwashing, they still have whitish spots based on water
hardness or other mineral salts which, due to a lack of wetting agent, originate from
dried water drops. In order to obtain brilliantly clear and spot-free dishes, rinse
aids are therefore used. The addition of liquid or solid rinse aid ensures that the
water runs off from the ware as completely as possible, meaning that the wide variety
of surfaces are residue-free and shiny at the end of the wash programme. Standard
commercial rinse aids are mixtures of non-ionic surfactants, solubility promoters,
organic acids solvents, polymers and dyes, water and optionally preservatives and
fragrances. The aim of the surfactants in these compositions consists in influencing
the interfacial tension of the water in such a way that it can run off from the ware
in the thinnest possible, coherent film so that no water drops, streaks or films are
left behind during the subsequent drying process (so-called wetting effect). A distinction
is generally made here between two types of deposits: firstly, the so-called "spotting"
is investigated, which arises as a result of drying water drops, and secondly "filming"
is evaluated, i.e. layers which are formed by the drying of thin water films containing
food rests or increased salt concentration in rest water. For the evaluation, test
persons are currently used who visually evaluate the parameters of "spotting" and
"filming" on cleaned objects, e.g. plates, glasses, knives etc. Modern dishwashing
detergents therefore comprise rinse aids in order to improve the run-off of water
from the surfaces of the ware. However, there are rinse aids which do not dry equally
as well on all substrates, such as e.g. plastic and metal. In order to get round this
effect, complex rinse aids are formulated which have e.g. silicone compounds and/or
fluorinated compounds, as are described in
US 5,880,089 or
US 2005/0143280 A1. However, these compounds are biodegradable with difficulty, if at all, and some are
even hazardous to the environment.
[0003] More recently, moreover, combination products have increasingly been used; these
combine the different functions, such as cleaning, clear rinsing, water softening
and optionally metal protection, in particular silver protection, or a glass protection
function in one, preferably solid, supply form. Such compositions are referred to
as multifunctional compositions. Thus, for example so-called three-in-one products
which combine cleaner, rinse aid and water softener in the form of a solid compact
("tab") are found on the market. As a result of the increased use of such multifunctional
compositions, however, the drying performance has become worse compared to using a
classic rinse aid. Drying performance is to be understood here as meaning to what
extent the cleaned ware still has water, preferably water drops, on the surface after
passing through the dishwashing process. The water remaining on the surface then has
to either be removed mechanically (e.g. by wiping dry) or the ware has to be left
to dry in the air. The user thus has to wait until the water has evaporated. In this
connection, however, residues (e.g. lime and/or surfactant residues or other residues
which were dissolved or dispersed in the water) remain on the surface and lead to
unaesthetic spots or streaks. This is true to a particular extent on shiny or transparent
surface, such as e.g. glass or metal. For improved drying in a dishwasher, an extension
or intensification of the drying phase would also in principle be conceivable, e.g.
as a result of increasing the temperature in the drying step. However, not all ware
withstands higher temperatures, and plastic articles in particular may be sensitive.
An extension of the drying phase is in most cases perceived as a disadvantage by users.
[0004] The state of the art proposes quite a number of non-ionic surfactants as suitable
additives for rinse aids in order to improve performance and reduce cycle time. For
example:
[0005] However, none of these examples fulfil the needs as explained above.
[0006] As a matter of fact, the measures as described above lead to an increased energy
consumption of the machine. However, it is desired to avoid the latter since energy
consumption is becoming an ever more important selling criterion for dishwashing detergents.
For some time, consumers have already been paying more and more attention to the energy
consumption of domestic appliances. There are even already standards, inter alia for
energy consumption and drying performance, thus e.g. the standard
OEVN/OENORM EN 50242 edition 2003-11-01, valid for Austria, or the contextually similar standard for Germany,
DIN EN 50242. Here in particular the edition 2005-06 "Electric dishwashers for household use-measurement
methods for use properties" (IEC 60436:2004, modified); German version EN 50242:2004).
[0007] There is therefore an increased need for technical solutions for making dishwashing
processes more effective and in particular more energy-saving. Such solutions may
also be the use of dishwashing detergents, or additives in such compositions, which
shorten the high energy-expenditure drying step, or make it possible to dry at a lower
temperature, while providing the same or even better results in shorter times.
[0008] Ways are therefore sought to improve the drying performance of cleaners for hard
surfaces, particular with regard to plastic and metal ware, and more particular of
dishwashing detergents for automatic dishwashing, where, here, in particular those
solutions are sought in which the performance in the clear-rinse cycle is increased
in order to shorten time and to save energy.
DESCRIPTION OF THE INVENTION
[0009] Object of the present invention is a liquid rinse aid composition, comprising a surfactant
blend comprising or consisting of
- (a) a first non-ionic surfactant of formula (I)
R1O(EO)n1(PO)p(EO)n2 (I)
in which
R1 stands for a linear alkyl radical having 9 or 11 carbon atoms;
n1 stands for 0 or an integer of from 6 to 10;
n2 stands for 0 or an integer of from 6 to 10;
p stands for an integer of from 4 to 6;
and
- (b) a second non-ionic surfactant of formula (II)
R2O(EO)m1(PO)q(EO)m2 (II)
in which
R2 stands for a linear alkyl radical having 10 carbon atoms;
m1 stands for 0 or an integer of from 6 to 10;
m2 stands for 0 or an integer of from 6 to 10;
q stands for 0 or an integer of from 4 to 6;
on condition that both sums (n1+p+n2) and (m1+q+m2) is different from 0.
[0010] Surprisingly, it has been observed that surfactants blends comprising the non-ionic
surfactants of formula (I) and (II), preferably in a ratio by weight of from about
1:5 to about 5:1 provides superior results with regard to drying cycle and cleaning
performance of rinse aids, preferably with regard to plastic and metal, which are
the most difficult materials to rinse. The effect is demonstrated for various substrates
in comparison with other non-ionic surfactants known from the state of the art for
the same purpose.
SURFACTANT BLENDS
[0011] The surfactant blends as proposed by the invention represent a binary mixture of
an oxoalcohol and a fatty alcohol alkoxylated, more particularly component (a) represents
an alkoxylated C
9/11 oxoalcohol of formula (I), wherein n1 stands for 8 to 9, p stands for 5 to 6 and
n2 stands for 0. On the other hand, component (b) represents a fatty alcohol having
10 carbon atoms (or a pure synthetic decanol) of formula (II), wherein m1 stands for
8 to 9, q stands for 5 to 6 and m2 stands for 0.
[0012] The preparation takes place in the manner known to the person skilled in the art
by reacting fatty alcohols or oxoalcohols with the alkoxides in the presence of acidic
or basic catalysts. The components may show a broad or narrow homologue distribution.
[0013] The rinse aid compositions according to the present invention may contain the components
(a) and (b) are in a ratio by weight of 5:1 to 1:5 and more particular in a ratio
by weight of 2:1 to 3:1.
CO-SURFACTANTS
[0014] The compositions of the present invention may encompass co-surfactants (component
c) different from components (a) and (b). Preferably, these co-surfactants -or emulsifiers
- are of non-ionic nature, however also anionic or amphoteric surfactants are suitable.
[0015] Non-ionic surfactants. Other surfactants may also be added to the preparations as
emulsifiers, including for example:
- products of the addition of 2 to 30 mol ethylene oxide and/or 0 to 5 mol propylene
oxide onto linear C8-22 fatty alcohols, onto C12-22 fatty acids and onto alkyl phenols containing 8 to 15 carbon atoms in the alkyl group;
- C12/18 fatty acid monoesters and diesters of addition products of 1 to 30 mol ethylene oxide
onto glycerol;
- glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated
fatty acids containing 6 to 22 carbon atoms and ethylene oxide addition products thereof;
- addition products of 15 to 60 mol ethylene oxide onto castor oil and/or hydrogenated
castor oil;
- polyol esters and, in particular, polyglycerol esters such as, for example, polyglycerol
polyricinoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate isostearate.
Mixtures of compounds from several of these classes are also suitable;
- addition products of 2 to 15 mol ethylene oxide onto castor oil and/or hydrogenated
castor oil;
- partial esters based on linear, branched, unsaturated or saturated C6/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol,
pentaerythritol, - dipentaerythritol, sugar alcohols (for example sorbitol), alkyl
glucosides (for example methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides
(for example cellulose);
- mono-, di and trialkyl phosphates and mono-, di- and/or tri-PEG-alkyl phosphates and
salts thereof;
- wool wax alcohols;
- polysiloxane/polyalkyl polyether copolymers and corresponding derivatives;
- mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol and/or
mixed esters of C6-22 fatty acids, methyl glucose and polyols, preferably glycerol or polyglycerol,
- polyalkylene glycols and
- glycerol carbonate.
[0016] Polyglycol ethers. The addition products of ethylene oxide and/or propylene oxide onto fatty alcohols,
fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters
of fatty acids or onto castor oil are known commercially available products. They
are homologue mixtures of which the average degree of alkoxylation corresponds to
the ratio between the quantities of ethylene oxide and/or propylene oxide and substrate
with which the addition reaction is carried out. C
12/18 fatty acid monoesters and diesters of addition products of ethylene oxide onto glycerol
are known as lipid layer enhancers for cosmetic formulations.
[0017] Alkoxylated alcohols. Particular suitable are the alkoxylated alcohols. As a consequence of the preparation,
alcohol alkoxylates are referred to as fatty alcohol or oxo alcohol alkoxylates and
preferably conform to the formula (III),
R3O(CH2CHR4O)zH (III)
in which R
3 is a linear or branched alkyl and/or alkenyl radical having 6 to 22 carbon atoms,
R
4 is hydrogen or an alkyl radical having 1 to 3 carbon atoms and z is numbers from
1 to 50.
The fatty alcohol alkoxylates according to the formula (III) can preferably contain
ethylene oxide groups, propylene oxide groups or both alkoxides, where these may be
present blockwise (first one block of ethylene oxide, then one block of propylene
oxide, or vice versa; or the molecule contains several blocks of different alkoxylates
in succession, where a block is to be understood as meaning at least two identical
alkoxide group) or in random distribution.
[0018] Partial glycerides. Typical examples of suitable partial glycerides are hydroxystearic acid monoglyceride,
hydroxystearic acid diglyceride, isostearic acid monoglyceride, isostearic acid diglyceride,
oleic acid monoglyceride, oleic acid diglyceride, ricinoleic acid monoglyceride, ricinoleic
acid diglyceride, linoleic acid monoglyceride, linoleic acid diglyceride, linolenic
acid monoglyceride, linolenic acid diglyceride, erucic acid monoglyceride, erucic
acid diglyceride, tartaric acid monoglyceride, tartaric acid diglyceride, citric acid
monoglyceride, citric acid diglyceride, malic acid monoglyceride, malic acid diglyceride
and technical mixtures thereof which may still contain small quantities of triglyceride
from the production process. Addition products of 1 to 30 and preferably 5 to 10 mol
ethylene oxide onto the partial glycerides mentioned are also suitable.
[0019] Sorbitan esters. Suitable sorbitan esters are sorbitan monoisostearate, sorbitan sesquiisostearate,
sorbitan diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate,
sorbitan dioleate, sorbitan trioleate, sorbitan monoerucate, sorbitan sesquierucate,
sorbitan dierucate, sorbitan trierucate, sorbitan monoricinoleate, sorbitan sesquiricinoleate,
sorbitan diricinoleate, sorbitan triricinoleate, sorbitan monohydroxystearate, sorbitan
sesquihydroxystearate, sorbitan dihydroxystearate, sorbitan trihydroxystearate, sorbitan
monotartrate, sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate,
sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate, sorbitan tricitrate,
sorbitan monomaleate, sorbitan sesquimaleate, sorbitan dimaleate, sorbitan trimaleate
and technical mixtures thereof. Addition products of 1 to 30 and preferably 5 to 10
mol ethylene oxide onto the sorbitan esters mentioned are also suitable.
[0020] Polyglycerol esters. Typical examples of suitable polyglycerol esters are Polyglyceryl-2 Dipolyhydroxystearate
(Dehymuls® PGPH), Polyglycerin-3-Diisostearate (Lameform® TGI), Polyglyceryl-4 Isostearate
(Isolan® GI 34), Polyglyceryl-3 Oleate, Diisostearoyl Polyglyceryl-3 Diisostearate
(Isolan® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450), Polyglyceryl-3
Beeswax (Cera Bellina®), Polyglyceryl-4 Caprate (Polyglycerol Caprate T2010/90), Polyglyceryl-3
Cetyl Ether (Chimexane® NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and Polyglyceryl
Polyricinoleate (Admul® WOL 1403), Polyglyceryl Dimerate Isostearate and mixtures
thereof. Examples of other suitable polyolesters are the mono-, di- and triesters
of trimethylol propane or pentaerythritol with lauric acid, cocofatty acid, tallow
fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like optionally
reacted with 1 to 30 mol ethylene oxide.
[0021] Anionic surfactants. Typical anionic emulsifiers are aliphatic C
12-22 fatty acids, such as palmitic acid, stearic acid or behenic acid for example, and
C
12-22 dicarboxylic acids, such as azelaic acid or sebacic acid for example. Further suitable
anionic surfactants are also the salts of alkyl esters of phosphoric acid, preferably
the mono- or dialkyl esters, where the alkyl radicals preferably have 6 to 12 and
in particular 8 to 12 carbon atoms.
[0022] Amphoteric surfactants. Other suitable emulsifiers are amphoteric or zwitterionic surfactants. Zwitterionic
surfactants are surface-active compounds which contain at least one quaternary ammonium
group and at least one carboxylate and one sulfonate group in the molecule. Particularly
suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N,N-dimethyl
ammonium glycinates, for example cocoalkyl dimethyl ammonium glycinate, N-acylaminopropyl-N,N-dimethyl
ammonium glycinates, for example coco-acylaminopropyl dimethyl ammonium glycinate,
and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18 carbon
atoms in the alkyl or acyl group and cocoacylaminoethyl hydroxyethyl carboxymethyl
glycinate. The fatty acid amide derivative known under the CTFA name of
Cocamidopropyl Betaine is particularly preferred. Ampholytic surfactants are also suitable emulsifiers.
Ampholytic surfactants are surface-active compounds which, in addition to a C
8/18 alkyl or acyl group, contain at least one free amino group and at least one -COOH-
or -SO
3H- group in the molecule and which are capable of forming inner salts. Examples of
suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkylaminobutyric
acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropyl glycines,
N-alkyl taurines, N-alkyl sarcosines, 2-alkylaminopropionic acids and alkylaminoacetic
acids containing around 8 to 18 carbon atoms in the alkyl group. Particularly preferred
ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate
and C
12/18 acyl sarcosine.
HYDROTROPES
[0023] As a further component, the rinse-aid compositions comprise a hydrotrope (component
d). Hydrotropes are agents which act as solubility promoter for a second, more sparingly
soluble substance.
[0024] The preferred hydrotropes are selected from the group of cumene sulfonates, xylene
sulfonates, propylene glycols and their mixtures, and here preferably 1,2-monopropylene
glycol, preference being given to cumene- and xylene sulfonates.
[0025] Cumene- and xylene sulfonates are to be regarded as particularly preferred component
(d), here in particular the sodium salts of cumene- or xylene sulfonate. Particular
preference is given to cumene sulfonate, sodium salt.
ORGANIC ACIDS
[0026] As another optional component (e), the rinse aids according to the invention may
comprise an organic acid and here usually organic hydroxycarboxylic acids which are
preferably selected from the group mandelic acid, lactic acid, hydroxysuccinic acid,
citric acid, tartaric acid and their mixtures, with particular preference being given
to citric acid.
RINSE AID COMPOSITIONS
[0027] The rinse aid compositions of the present invention may further comprise non-ionic
surfactants different from components (a) and (b), cumene sulfonate and/or citric
acid.
[0028] In particular such composition may encompass
- (a) 5 to 15 % b.w. surfactant of formula (I);
- (b) 1 to 5 % b.w. surfactant of formula (II);
- (c) 0 or 1 to 5 % b.w. co-surfactants;
- (d) 0 or 1 to 15 % b.w. hydrotropes;
- (e) 0 or 1 to 5 % b.w. organic acids,
on condition that the amounts add with water and optionally usual auxiliary agents
to 100 % b.w.
[0029] The compositions of the present invention can also comprise polymers, although it
may be preferred for the compositions to be free from polymers, in particular free
from polymers which comprise poly(meth)acrylic acid monomers.
[0030] The compositions are prepared by mixing the different components, optionally with
the input of energy by stirring and/or heating of the mixtures. Preferably, after
introducing the water as initial charge, the remaining components are added in any
order with stirring and then the mixture is further stirred until clear.
[0031] Besides the essential components a) to c) and water, further ingredients that are
customary per se may also be present in the rinse aids according to the invention.
These are preferably selected from the group of alcohols and here preferably the short-chain
alcohols ethanol, propanol, isopropanol, butanol, isobutanol. Moreover, the compositions
can also comprise further additives, such as e.g. alkylpyrrolidones, polymers, e.g.
polycarboxylates or preservatives, e.g. isothiazolinones.
[0032] The compositions can, however, also comprise perfumes, dyes, UV protection, e.g.
benzophenones, pH regulators and further customary additives, e.g. those for preventing
glass or metal corrosion and for protecting metals against tarnishing. The pH of the
compositions can be in the range from pH 3 to 10, preferably from pH 3.5 to 8 and
particularly preferably from 4 to 7 or 4 to 6. It is generally the case that acidic
compositions (pH<7) may be preferred.
[0033] However, preference is given to those aqueous compositions which comprise only the
components (a) to (e). Furthermore, it may be advantageous to dispense with the presence
of hydrocarbons and in particular terpenes. In one preferred embodiment of the invention,
the compositions are therefore free from terpenes and/or hydrocarbons.
[0034] The present application further provides the use of compounds of the general formula
(I) according to claim for producing aqueous rinse aids, or for producing dishwashing
detergents. Particular preference is moreover given to the use of compounds of the
general formula (I) according to the above description for improving the drying performance
of rinse aids for dishwashing, or of dishwashing detergents.
SURFACTANT BLENDS
[0035] Another object of the present invention relates to a surfactant blend consisting
of
- (a) a first non-ionic surfactant of formula (I)
R1O(EO)n1(PO)p(EO)n2 (I)
in which
R1 stands for a linear alkyl radical having 9 or 11 carbon atoms;
n1 stands for 0 or an integer of from 6 to 10;
n2 stands for 0 or an integer of from 6 to 10;
p stands for 0 or an integer of from 4 to 6;
and
- (b) a second non-ionic surfactant of formula (II)
R2O(EO)m1(PO)q(EO)m2 (II)
in which
R2 stands for a linear alkyl radical having 10 carbon atoms;
m1 stands for 0 or an integer of from 6 to 10;
m2 stands for 0 or an integer of from 6 to 10;
q stands for 0 or an integer of from 4 to 6;
on condition that both sums (n1+p+n2) and (m1+q+m2) is different from 0.
[0036] Preferably the components (a) and (b) are present in said blend in a ratio by weight
of from 1:5 to 5:1, and preferably 2:1 to 3:1.
[0037] The surfactant blends according to formulae (I) and (II) can be incorporated into
customary rinse aids and in particular dishwashing detergents on their own or in combination
with the components (c) to (e). The dishwashing detergents may be solid, or in pressed
form, e.g. as a tablet, or be liquid or gel-like. The compounds of the formula (I)
are present in ready-formulated dishwashing detergents preferably in amounts of from
1 to 45 percent by weight, in particular in amounts of from 4 to 30 percent by weight
and particularly preferably in amounts of from 15 to 30 percent by weight.
[0038] Such ready-formulated, thus standard commercial dishwashing detergents comprise e.g.
builder materials, surfactants, bleaches, bleach activators, enzymes, enzyme stabilizers,
corrosion inhibitors, film inhibitors, complexing agents, inorganic salts, graying
inhibitors, foam inhibitors, silicone oils, soil release compounds, colour transfer
inhibitors, salts of polyphosphonic acids, optical brighteners, fluorescent agents,
disinfectants, fragrances, dyes, antistatics, ironing auxiliaries, phobicization and
impregnation agents, swelling and nonslip agents, UV absorbers, pH regulators, or
a mixture thereof.
[0039] Typical formulations of such compositions for machine dishwashing comprise pentasodium
triphosphate (s. sodium phosphates) in amounts of 0, or 1 to 50 percent by weight.
Sodium citrate in amounts of from 30 to 45 percent by weight, sodium polycarboxylate
in amounts of from 5 to 8 percent by weight, sodium metasilicate in amounts of from
10 to 60 percent by weight, 0 sodium hydrogen carbonate in amounts of from 10 to 25
percent by weight, sodium disilicate in amounts of from 10 to 30 percent by weight,
sodium perborate in amounts of from 5 to 10 percent by weight, bleach activators in
amounts of from 2 to 4 percent by weight, enzymes, preferably protease and amylase,
in amounts of from 1 to 6 percent by weight, low-foam non-ionic surfactants in amounts
of from 1 to 20 percent by weight, silver/glass protection and fragrances in amounts
up to 5 percent by weight. Suitable surfactants are anionic, non-ionic, cationic and/or
amphoteric surfactants, where non-ionic surfactants and here low-foam non-ionic surfactants
may be particularly preferred. The latter are preferably selected from the class of
fatty alcohol alkoxylate, preferably the fatty alcohol ethoxylates, where end-group-capped
derivatives may also be suitable.
INDUSTRIAL APPLICATION
[0040] The surfactant blends of formulae (I) and (II) show, alone or preferably in combination
with hydrotropes (d) in rinse aids or in dishwashing detergents during automatic dishwashing,
an improved drying behaviour on porcelain, glass, metal and plastic (e.g. in the case
of Tupperware, SAN (=styreneacrylonitrile), melamine, polypropylene, polyethylene).
The improved drying performance on plastic and metal substrates is particularly well
pronounced. The improved drying behaviour is moreover more pronounced when using low-temperature
programmes or saving or eco programmes with a reduced maximum temperature in the clear-rinse
cycle and/or in the drying step. In one preferred embodiment, the compounds of the
formula (I) are used rinse aids or dishwashing detergents as additives which serve
to improve the drying performance and/or the cleaning performance. The surfactant
blends can be used here either in aqueous compositions, preferably in aqueous rinse
aids, or else in solid compositions. In general, the surfactant blends are suitable
for producing rinse aids or dishwashing detergents.
[0041] The present application therefore further provides a method for rinsing a hard surface
in an automatic dishwashing machine, wherein said surfaces are brought into contact
with the rinse aid composition or the surfactant blend of the invention. More particularly,
the present invention encompasses a method for automatic dishwashing, where the ware
passes through at least one cleaning cycle using a detergent and water, at least one
clear-rinse cycle using a rinse aid and water, and a final drying cycle, where the
temperature in the drying cycle does not exceed 50 °C, where a surfactant blend as
per the above description is used. By using surfactant blend in a rinse aid composition
as defined above, cleaning performance is improved and the drying temperatures can
be reduced from the 70 to 60 °C otherwise customary in such processes to 55 °C or
even lower, e.g. down to 45 or 50 °C.
[0042] Another object of the present invention is related to use of the surfactant blend
as defined above for making liquid rinsing aids. As explained above, the use of the
surfactant blends of the present invention in dishwashing detergents and/or in rinse
aids thus permits both a notable improve in performance and a saving of energy compared
with current dishwashing processes and compositions since, on account of the improved
drying behaviour, a shorter drying time or preferably a lower drying temperature,
preferably less than 60 degrees centigrade and in particular from 40 to 59 °C, very
particularly preferably from 45 to 55 °C, can be used. The washing process according
to the above description is suitable for meeting the requirements placed on drying
performance and energy consumption according to the German standard DIN EN 50242.
[0043] Finally, another object of the present invention is related to the use of the liquid
rinse aids for making solid dishwashing agents, such as for example powders, tablets,
granules and extrudates.
EXAMPLES
Examples 1 and 2, Comparative Examples C1 to C6
[0044] The following Table 1 shows the exceptional performance of the compositions comprising
the surfactant mixture according to the invention on plastic and metal wares. All
the formulations have exactly the same frame formulation with the non-ionic surfactant
active amount (w/w) being 14%. They differ only in non-ionic surfactant types.
[0045] The test method is defined by
wfk institute. Rinse aid performance is tested with an automatic dish washing machine of Miele
G 1222 SC type over 3 rinse cycles, using Universal 55 °C programme with prewash.
Water hardness is 8-10 °d. The test compositions were placed in the dish washer with
50 g soil. 20 g automatic dishwasher cleaner was dosed at the beginning of washing
process and 5 mL of rinse aid is dosed at the beginning of the rinse cycle.
Substrates tested:
[0046] Substrates tested:
- Porcelain plate
- 3 different types of glass: potassic crystal glass, crystalline glass, soda lime glass
- Stainless steel knives
- Plastic bowls made of polypropylene
[0047] A visual assessment described in
Tenside Surf. Det. 28 (1991) 5 is used to determine the performance of all the dishware. The results are shown in
Table 1 and represent median values over 3 trials for plastic and steel respectively.
Table 1
Performance of rinse aid compositions on plastic and steel |
Examples |
1 |
2 |
C1 |
C2 |
C3 |
C4 |
C5 |
C6 |
C9/11+8.5EO+5.5PO |
10.0 |
4.0 |
4.0 |
4.0 |
4.0 |
4.0 |
- |
- |
C10+8.5EO+5.5PO |
4.0 |
10.0 |
- |
- |
- |
- |
4.0 |
4.0 |
C13/15+9EO+1BO |
- |
- |
10.0 |
- |
- |
- |
- |
- |
C12/15+6EO+3PO |
- |
- |
- |
10.0 |
- |
- |
10.0 |
- |
C12/14+4EO+5PO |
- |
- |
- |
- |
10.0 |
- |
- |
- |
C12/15+6EO+4PO |
- |
- |
- |
- |
- |
10.0 |
- |
10.0 |
Polyglycol butylether |
4.0 |
4.0 |
4.0 |
4.0 |
4.0 |
4.0 |
4.0 |
4.0 |
Cumene sulfonate |
4.0 |
4.0 |
4.0 |
4.0 |
4.0 |
4.0 |
4.0 |
4.0 |
Citric acid |
3.0 |
3.0 |
3.0 |
3.0 |
3.0 |
3.0 |
3.0 |
3.0 |
Preservative |
0.5 |
0.5 |
0.5 |
0.5 |
0.5 |
0.5 |
0.5 |
0.5 |
Water |
Ad 100 |
Performance Plastic |
Stripes and spots |
4 |
2 |
1 |
1 |
1 |
1 |
1 |
3 |
Film |
3 |
3 |
3 |
3 |
2 |
2 |
2 |
2 |
Performance Steel |
Stripes and spots |
4 |
4 |
2 |
3 |
2 |
2 |
2 |
4 |
Film |
3 |
2 |
2 |
2 |
1 |
2 |
1 |
3 |
1. A liquid rinse aid composition, comprising a surfactant blend comprising or consisting
of
(e) a first non-ionic surfactant of formula (I)
R1O(EO)n1(PO)p(EO)n2 (I)
in which
R1 stands for a linear alkyl radical having 9 or 11 carbon atoms;
n1 stands for 0 or an integer of from 6 to 10;
n2 stands for 0 or an integer of from 6 to 10;
p stands for an integer of from 4 to 6;
and
(f) a second non-ionic surfactant of formula (II)
R2O(EO)m1(PO)q(EO)m2 (II)
in which
R2 stands for a linear alkyl radical having 10 carbon atoms;
m1 stands for 0 or an integer of from 6 to 10;
m2 stands for 0 or an integer of from 6 to 10;
q stands for 0 or an integer of from 4 to 6;
on condition that both sums (n1+p+n2) and (m1+q+m2) is different from 0.
2. The composition of Claim 1, wherein n1 stands for 8 to 9, p stands for 5 to 6 and
n2 stands for 0.
3. The composition of Claim 1, wherein m1 stands for 8 to 9; q stands for 5 to 6 and
m2 stands for 0.
4. The composition of Claim 1, wherein the components (a) and (b) are present in a ratio
by weight of 5:1 to 1:5.
5. The composition of Claim 1, wherein the components (a) and (b) are present in a ratio
by weight of 2:1 to 3:1.
6. The composition of Claim 1, further comprising co-surfactants different from components
(a) and (b), hydrotropes and/or organic acids.
7. The composition of Claim 6, wherein said co-surfactants (component c) are selected
from the group consisting of non-ionic surfactants.
8. The composition of Claim 6, wherein said hydrotropes (component d) are selected from
the group consisting of cumene sulfonates, xylene sulfonates, propylene glycols and
their mixtures.
9. The composition of Claim 6, wherein said organic acids (component e) are selected
from the group consisting of mandelic acid, lactic acid, hydroxysuccinic acid, citric
acid tartaric acid, and their mixtures.
10. The composition of Claim 1, further comprising non-ionic surfactants different from
components (a) and (b), cumene sulfonate and/or citric acid.
11. The composition of Claim 1, comprising
(a) 5 to 15 % b.w. surfactant of formula (I);
(b) 1 to 5 % b.w. surfactant of formula (II);
(c) 0 or 1 to 5 % b.w. co-surfactants;
(d) 0 or 1 to 15 % b.w. hydrotropes;
(e) 0 or 1 to 5 % b.w. organic acids,
on condition that the amounts add with water and optionally usual auxiliary agents
to 100 % b.w.
12. A surfactant blend consisting of
(a) a first non-ionic surfactant of formula (I)
R1O(EO)n1(PO)p(EO)n2 (I)
in which
R1 stands for a linear alkyl radical having 9 or 11 carbon atoms;
n1 stands for 0 or an integer of from 6 to 10;
n2 stands for 0 or an integer of from 6 to 10;
p stands for 0 or an integer of from 4 to 6;
and
(b) a second non-ionic surfactant of formula (II)
R2O(EO)m1(PO)q(EO)m2 (II)
in which
R2 stands for a linear alkyl radical having 10 carbon atoms;
m1 stands for 0 or an integer of from 6 to 10;
m2 stands for 0 or an integer of from 6 to 10;
q stands for 0 or an integer of from 4 to 6;
on condition that both sums (n1+p+n2) and (m1+q+m2) is different from 0.
13. A method for rinsing a hard surface in an automatic dishwashing machine, wherein said
surfaces are brought into contact with the composition of Claim 1 or the surfactant
blend of Claim 12.
14. The use of the surfactant blend of Claim 12 for making liquid rinsing aids.
15. The use of the liquid rinsing aids of Claim 1 for making solid dishwashing agents.
1. Flüssiges Klarspülmittel, enthaltend eine Tensidmischung enthaltend oder bestehend
aus
(a) einem ersten nichtionischen Tensid der Formel (I)
R1O(OE)n1(OP)p(OE)n2 (I)
In der
R1 für ein lineares Radikal mit 9 oder 11 Kohlenstoffatomen steht;
n1 für 0 oder eine ganze Zahl von 6 bis 10 steht;
n2 für 0 oder eine ganze Zahl von 6 bis 10 steht;
p für eine ganze Zahl von 4 bis 6 steht;
und
(b) einem zweiten nichtionischen Tensid der Formel (II)
R2O(OE)m1(OP)q(OE)m2 (II)
In der
R2 für ein lineares Radikal mit 10 Kohlenstoffatomen ;
m1 für 0 oder eine ganze Zahl von 6 bis 10 steht;
m2 für 0 oder eine ganze Zahl von 6 bis 10 steht;
q für 0 oder eine ganze Zahl von 4 bis 6 steht;
mit der Maßgabe, dass beide Summen (n1+p+n2) und (m1+q+m2) von 0 verschieden sind.
2. Mittel nach Anspruch 1, wobei n1 für 8 bis 9, p für 5 bis 6 und n2 für 0 steht.
3. Mittel nach Anspruch 1, wobei m1 für 8 bis 9, q für 5 bis 6 und m2 für 0 steht.
4. Mittel nach Anspruch 1, wobei die Komponenten (a) und (b) in einem Gewichtsverhältnis
von 5:1 bis 1:5 vorliegen.
5. Mittel nach Anspruch 1, wobei die Komponenten (a) und (b) in einem Gewichtsverhältnis
von 2:1 bis 1:2 vorliegen.
6. Mittel nach Anspruch 1, ferner enthaltend Co-Tenside, die von den Komponenten (a)
und (b) verschieden sind, Hydrotrope und/oder organische Säuren.
7. Mittel nach Anspruch 6, wobei besagte Co-Tenside (Komponente c) ausgewählt sind aus
der Gruppe, die von nichtionischen Tensiden gebildet wird.
8. Mittel nach Anspruch 6, wobei besagte Hydrotrope (Komponente d) ausgewählt sind aus
der Gruppe, die gebildet wird von Cumolsulfonaten, Xylolsulfonaten, Propylenglykolen
und deren Gemischen.
9. Mittel nach Anspruch 6, wobei besagte organischen Säuren (Komponente e) ausgewählt
sind aus der Gruppe, die gebildet wird von Mandelsäure, Milchsäure, Hydroxybernsteinsäure,
Zitronensäure, Weinsäure und deren Gemischen.
10. Mittel nach Anspruch 1, ferner enthaltend nichtionische Tenside, die von den Komponenten
(a) und (b) verschieden sind, Cumolsulfonat und/oder Zitronensäure.
11. Mittel nach Anspruch 1, enthaltend
(a) 5 bis 15 Gew.-% Tenside der Formel (I);
(b) 1 bis 5 Gew.-% Tenside der Formel (II);
(c) 0 oder 1 bis 5 Gew.-% Co-Tenside;
(d) 0 oder 1 bis 15 Gew.-% Hydrotrope;
(e) 0 oder 1 bis 5 Gew.-% organische Säuren,
mit der Maßgabe, dass sich die Mengen mit Wasser und gegebenenfalls weiteren üblichen
Hilfsstoffen zu 100 Gew.-% ergänzen.
12. Tensidmischung bestehend aus
(a) einem ersten nichtionischen Tensid der Formel (I)
R1O(OE)n1(OP)p(OE)n2 (I)
In der
R1 für ein lineares Radikal mit 9 oder 11 Kohlenstoffatomen steht;
n1 für 0 oder eine ganze Zahl von 6 bis 10 steht;
n2 für 0 oder eine ganze Zahl von 6 bis 10 steht;
p für eine ganze Zahl von 4 bis 6 steht;
und
(b) einem zweiten nichtionischen Tensid der Formel (II)
R2O(OE)m1(OP)q(OE)m2 (II)
In der
R2 für ein lineares Radikal mit 10 Kohlenstoffatomen ;
m1 für 0 oder eine ganze Zahl von 6 bis 10 steht;
m2 für 0 oder eine ganze Zahl von 6 bis 10 steht;
q für 0 oder eine ganze Zahl von 4 bis 6 steht;
mit der Maßgabe, dass beide Summen (n1+p+n2) und (m1+q+m2) von 0 verschieden sind.
13. Verfahren zur Spülung von harten Oberflächen in einer automatischen Spülmaschine,
wobei besagte harte Oberflächen mit einem Mittel nach Anspruch 1 oder einer Tensidmischung
nach Anspruch 12 in Kontakt gebracht werden.
14. Verwendung der Tensidmischung nach Anspruch 12 zur Herstellung eines flüssigen Klarspülmittels.
15. Verwendung des flüssigen Klarspülmittels nach Anspruch 1 zur Herstellung von festen
Geschirrspülmitteln.
1. Composition d'adjuvant de rinçage liquide, comprenant un mélange d'agents tensioactifs
comprenant ou étant constitué
(a) d'un premier agent tensioactif non ionique de formule (I)
R1O(OE)n1(OP)p(OE)n2 (I)
où
R1 représente un radical alkyle linéaire ayant 9 ou 11 atomes de carbone ;
n1 représente 0 ou un nombre entier allant de 6 à 10 ;
n2 représente 0 ou un nombre entier allant de 6 à 10 ;
p représente un nombre entier allant de 4 à 6 ;
et
(b) d'un deuxième agent tensioactif non ionique de formule (II)
R2O(OE)m1(OP)q(OE)m2 (II)
où
R2 représente un radical alkyle linéaire ayant 10 atomes de carbone ;
m1 représente 0 ou un nombre entier allant de 6 à 10 ;
m2 représente 0 ou un nombre entier allant de 6 à 10 ;
q représente 0 ou un nombre entier allant de 4 à 6 ;
à condition que les deux sommes (n1+p+n2) et (m1+q+m2) soient différentes de 0.
2. Composition selon la revendication 1, dans laquelle n1 représente 8 à 9, p représente
5 à 6 et n2 représente 0.
3. Composition selon la revendication 1, dans laquelle m1 représente 8 à 9, q représente
5 à 6 et m2 représente 0.
4. Composition selon la revendication 1, dans laquelle les composants (a) et (b) sont
présents selon un rapport pondéral allant de 5:1 à 1:5.
5. Composition selon la revendication 1, dans laquelle les composants (a) et (b) sont
présents selon un rapport pondéral allant de 2:1 à 3:1.
6. Composition selon la revendication 1, comprenant en outre des co-agents tensioactifs
différents des composants (a) et (b), des hydrotropes et/ou des acides organiques.
7. Composition selon la revendication 6, dans laquelle lesdits co-agents tensioactifs
(composant c) sont choisis dans le groupe constitué par les agents tensioactifs non
ioniques.
8. Composition selon la revendication 6, dans laquelle lesdits hydrotropes (composant
d) sont choisis dans le groupe constitué par les sulfonates de cumène, les sulfonates
de xylène, les propylène glycols et leurs mélanges.
9. Composition selon la revendication 6, dans laquelle lesdits acides organiques (composant
e) sont choisis dans le groupe constitué par l'acide mandélique, l'acide lactique,
l'acide hydroxysuccinique, l'acide citrique, l'acide tartrique, et leurs mélanges.
10. Composition selon la revendication 1, comprenant en outre des agents tensioactifs
non ioniques différents des composants (a) et (b), du sulfonate de cumène et/ou de
l'acide citrique.
11. Composition selon la revendication selon la revendication 1, comprenant :
(a) de 5 à 15% en poids d'agent tensioactif de formule (I) ;
(b) de 1 à 5% en poids d'agent tensioactif de formule (II) ;
(c) 0 ou de 1 à 5% en poids de co-agents tensioactifs ;
(d) 0 ou de 1 à 15% en poids d'hydrotropes ;
(e) 0 ou de 1 à 5% en poids d'acides organiques ;
à condition que les quantités totalisent, avec de l'eau et éventuellement des agents
auxiliaires habituels, 100% en poids.
12. Mélange d'agents tensioactifs, constitué
(a) d'un premier agent tensioactif non ionique de formule (I)
R1O(OE)n1(OP)p(OE)n2 (I)
où
R1 représente un radical alkyle linéaire ayant 9 ou 11 atomes de carbone ;
n1 représente 0 ou un nombre entier allant de 6 à 10 ;
n2 représente 0 ou un nombre entier allant de 6 à 10 ;
p représente 0 ou un nombre entier allant de 4 à 6 ;
et
(b) d'un deuxième agent tensioactif non ionique de formule (II)
R2O(OE)m1(OP)q(OE)m2 (II)
où
R2 représente un radical alkyle linéaire ayant 10 atomes de carbone ;
m1 représente 0 ou un nombre entier allant de 6 à 10 ;
m2 représente 0 ou un nombre entier allant de 6 à 10 ;
q représente 0 ou un nombre entier allant de 4 à 6 ;
à condition que les deux sommes (n1+p+n2) et (m1+q+m2) soient différentes de 0.
13. Méthode de rinçage d'une surface dure dans un lave-vaisselle automatique, dans laquelle
lesdites surfaces sont mises en contact avec la composition selon la revendication
1 ou le mélange d'agents tensioactifs selon la revendication 12.
14. Utilisation du mélange d'agents tensioactifs selon la revendication 12, pour la fabrication
d'adjuvants de rinçage liquides.
15. Utilisation des adjuvants de rinçage liquides selon la revendication 1, pour la fabrication
d'agents solides pour le lavage de vaisselle.