U.S. patent application number 12/720765 was filed with the patent office on 2010-06-24 for cleaning process.
Invention is credited to Arnd Kessler, Christian Nitsch, Nadine Warkotsch, JOHANNES ZIPFEL.
Application Number | 20100154832 12/720765 |
Document ID | / |
Family ID | 39672067 |
Filed Date | 2010-06-24 |
United States Patent
Application |
20100154832 |
Kind Code |
A1 |
ZIPFEL; JOHANNES ; et
al. |
June 24, 2010 |
CLEANING PROCESS
Abstract
Process for cleaning dishes in a dishwasher during which the
aqueous washing liquor contained in the interior of the dishwasher
is at least partly removed from the interior of the dishwasher at a
point in time t. The process involves metering a dishwasher
detergent A containing one or more surfactants and one or more
anionic polymers at a time t1<t in an amount m1 and at a time
t2>t in an amount m2 into the interior of the dishwasher. The
process according to the invention differs from conventional
cleaning processes in that formation of deposits is reduced and
drying efficiency improved.
Inventors: |
ZIPFEL; JOHANNES;
(Dusseldorf, DE) ; Warkotsch; Nadine; (Dusseldorf,
DE) ; Kessler; Arnd; (Monheim, DE) ; Nitsch;
Christian; (Dusseldorf, DE) |
Correspondence
Address: |
Henkel Corporation
10 Finderne Avenue
Bridgewater
NJ
08807
US
|
Family ID: |
39672067 |
Appl. No.: |
12/720765 |
Filed: |
March 10, 2010 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
PCT/EP2008/056343 |
May 23, 2008 |
|
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12720765 |
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Current U.S.
Class: |
134/25.2 |
Current CPC
Class: |
C11D 11/0064 20130101;
C11D 3/2086 20130101; A47L 15/0055 20130101; C11D 3/378 20130101;
A47L 15/0057 20130101; C11D 3/06 20130101; C11D 3/3757 20130101;
C11D 11/0023 20130101 |
Class at
Publication: |
134/25.2 |
International
Class: |
A47L 15/44 20060101
A47L015/44 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 10, 2007 |
DE |
10 2007 042 859.8 |
Claims
1. Process for cleaning tableware in an automatic dishwasher
comprising: at least partially removing aqueous cleaning liquor
present in an interior of the automatic dishwasher from the
interior of the automatic dishwasher at a time t, and metering an
automatic dishwashing agent A into the interior of the automatic
dishwasher in a quantity m1 at a time t1<t and in a quantity m2
at a time t2>t, wherein the dishwashing agent A comprises a)
surfactant(s), and b) anionic polymer(s).
2. Process according to claim 1 wherein the surfactant(s) in the
automatic dishwashing agent A is at least a non-ionic surfactant
present in an amount of 0.1 to 30 wt. %, based on total weight of
the automatic dishwashing agent A.
3. Process according to claim 1 wherein the anionic polymer(s) in
the automatic dishwashing agent A is present in an amount of 0.1 to
40 wt. %, based on total weight of the automatic dishwashing agent
A.
4. Process according to claim 1 wherein the anionic polymer(s) is
at least a homopolymer and/or copolymer of acrylic acid or
methacrylic acid.
5. Process according to claim 1 wherein the anionic polymer(s) is
at least a copolymer of i) unsaturated carboxylic acids, ii)
sulfonic acid groups containing monomers, and iii) optionally,
ionic or nonionogenic monomers.
6. Process according to claim 1 wherein the automatic dishwashing
agent A comprises a) 0.5 to 10 wt. % nonionic surfactant(s), b) 0.2
to 20 wt. % sulfonic acid group-containing polymer(s), c) 10 to 40
wt. % phosphate or 10 to 40 wt. % citrate, and d) 0.5 to 5 wt. %
enzyme(s).
7. Process according to claim 1 wherein the dishwashing agent A
further comprises 1 to 20 wt. % sodium percarbonate, based on total
weight of the automatic dishwashing agent A.
8. Process according to claim 1 wherein the dishwashing agent A
further comprises 0.01 to 2 wt. % bleach catalyst, based on total
weight of the automatic dishwashing agent A.
9. Process according to claim 1 wherein the dishwashing agent A is
in liquid form.
10. Process according to claim 1 wherein the weight ratio of the
metered amounts m1 and m2 is from 20:1 to 2:1.
11. Process according to claim 1 wherein the time between times t1
and t2 is from 5 to 50 minutes.
12. Process according to claim 1 wherein the temperature of the
wash liquor at time t1 is from 12 to 45.degree. C.
13. Process according to claim 1 wherein the temperature of the
wash liquor at time t2 is from 30 to 65.degree. C.
14. Process according to claim 1 wherein the process improves
drying in automatic dishwashing.
15. Process according to claim 1 wherein the process reduces
formation of deposits in automatic dishwashing.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation of International
Patent Application No. PCT/EP2008/056343 filed 23 May 2008, which
claims priority to German Patent Application No. 10 2007 042 859.8
filed 10 Sep. 2007, both of which are incorporated herein by
reference.
[0002] The present application relates to a process for cleaning
tableware. In particular, this application relates to a process for
cleaning tableware wherein cleaning agents are metered into the
interior of an automatic dishwasher in a time delay fashion.
[0003] Dishwashing agents are available to the consumer in numerous
presentation forms. In addition to traditional liquid hand
dishwashing detergents, automatic dishwashing agents have become
highly important due to the growing use of automatic dishwashers.
These automatic dishwashing agents are typically offered to the
consumer in solid form, for example, as a powder or as tablets, but
increasingly also in liquid form.
[0004] One of the main aims of automatic cleaning agent
manufacturers is to improve the cleaning performance of these
agents, with greater emphasis focused on cleaning performance in
low temperature cleaning cycles or in cleaning cycles with reduced
water consumption. With this in mind, preferably novel ingredients,
for example, more active surfactants, polymers or bleaching agents,
have been added to the cleaning agents. As these novel ingredients
are available only to a limited extent, and as the added amount of
ingredient per cleaning cycle can not be increased above a certain
amount due to environmental and economic grounds, this approach has
only limited possibilities.
[0005] Another approach for improving the performance profile of
existing washing or cleaning agents involves the development of
novel manufactured forms, for example, by combining solid and
liquid washing or cleaning agent ingredients. Suitable cleaning
agents are combined with one another, for example, in new types of
water-soluble packaging.
[0006] The present application provides an improvement in the known
processes for automatic dishwashing in such a way that these
processes exhibit an improved cleaning performance as well as an
improved drying of the cleaned tableware, without the addition of
further ingredients or increase in the metered quantities, even for
low temperature cleaning cycles or for cleaning cycles with reduced
water consumption.
[0007] This improvement was achieved by a specific dishwashing
process wherein a surfactant- and polymer-containing cleaning agent
is metered into the interior of an automatic dishwasher on a time
delay.
[0008] Accordingly, in one embodiment the present application is a
process for cleaning tableware in an automatic dishwasher.
According to the process, aqueous wash liquor present in the
interior of the automatic dishwasher is at least partially removed
from the interior of the automatic dishwasher at a time t.
Further,
[0009] a) one or more surfactants, and
[0010] b) one or more anionic polymers
are metered into the interior of the automatic dishwasher in a
quantity m1 at a time t1<t and in a quantity m2 at a time
t2>t.
[0011] The inventive process can be carried out in the interior of
a commercial automatic dishwasher, particularly, a commercial
domestic automatic dishwasher.
[0012] The automatic cleaning program for an automatic dishwasher
is generally chosen by the user before the dishwashing process is
carried out from a list of set programs, wherein for this,
particularly temperature of the wash liquor during the cleaning
process, duration of the process or the added cleaning agent and
cleaning agent auxiliaries, are defined (e.g., "2 in 1" and "3 in
1" programs).
[0013] Independent of temperature and cycle length, the automatic
dishwasher process or user-selected cleaning program of the
dishwasher can have at least two washing cycles, such as a pre-wash
cycle, a cleaning cycle and a rinse cycle. These washing cycles
vary, for example, by duration, water consumption and/or
temperature sequence, during which the aqueous cleaning liquor
present in the interior of the automatic dishwasher is at least
partially removed from the interior of the automatic dishwasher
between washing cycles, and optionally replenished with added fresh
water. This exchange of washing liquor is generally accomplished by
a pump system integrated in the dishwasher.
[0014] The partial pumping out of the wash liquor from the interior
of the automatic dishwasher preferably occurs so that at least
about 5 vol. %, preferably about 10 vol. %, particularly preferably
at least about 20 vol. %, quite particularly preferably at least
about 40 vol. % and especially at least about 60 vol. % of the wash
liquor is pumped out of the interior of the dishwasher. In
particularly preferred processes, from about 5 to about 99 vol. %
of the wash liquor, preferably from about 10 to about 90 vol. % of
the wash liquor and particularly preferably from about 20 to about
80 vol. % and especially from about 40 to about 70 vol. % of the
wash liquor is pumped out.
[0015] Accordingly, another embodiment of the present application
is a process for cleaning tableware in an automatic dishwasher.
During the process aqueous wash liquor present in the interior of
the automatic dishwasher is removed from the interior of the
dishwasher at a time t in an amount of from about 5 to about 99
vol. %, preferably from about 10 to about 90 vol. %, and
particularly preferably from about 20 to about 80 vol. % and
especially from about 40 to about 70 vol. % of the wash liquor.
According to the process, an automatic dishwashing agent A
comprising--
[0016] a) one or more nonionic surfactants and
[0017] b) one or more anionic polymers
is metered into the interior of the automatic dishwasher in a
quantity m1 at a time t1<t and in a quantity m2 at a time
t2>t.
[0018] The wash liquor can be completely pumped out; however,
complete removal of the wash liquor from the interior of the
dishwasher requires a comparatively long time and energy
expenditure, and is therefore less preferred.
[0019] According to the inventive process, both before and after
the wash liquor has been at least partially pumped out of the
interior of the dishwasher an automatic dishwashing agent
comprising nonionic surfactants and anionic polymers is metered
into the interior of the dishwasher, and thus into the wash liquor
located in the interior. The length of time between metering times
t1 and t2 can vary, wherein the time difference between the times
t1 and t2 can be about 5 to about 50 minutes, preferably about 10
to about 40 minutes and especially about 15 to about 30
minutes.
[0020] Temperature of the wash liquor at time t1 is preferably from
about 12 to about 45.degree. C., particularly from about 15 to
about 40.degree. C., and especially from about 20 to about
35.degree. C., and at time t2 is preferably from about 30 to about
65.degree. C., particularly from about 35 to about 60.degree. C.,
and especially from about 40 to about 55.degree. C. In a
particularly preferred embodiment of the inventive process, the
temperature of the wash liquor at time t2 is above the temperature
of the wash liquor at time t1. A suitable temperature sequence
wherein the temperature of the wash liquor at time t2 is above the
temperature of the wash liquor at time t1, has proven to be
superior in regard to the cleaning and rinsing performance.
[0021] Alternatively, the inventive dishwashing process can also be
carried out so that the temperature of the wash liquor at time t2
is below or identical to the temperature of the wash liquor at time
t1.
[0022] In preferred process variants, the weight ratio of the
metered amounts m1 and m2 is from about 20:1 to about 2:1,
particularly from about 15:1 to about 3:1 and especially from about
12:1 to about 4:1.
[0023] A characteristic of the automatic dishwashing agents
employed in the inventive process is their content of surfactants
and anionic polymers.
[0024] Nonionic surfactants, anionic surfactants, and amphoteric
surfactants have proven to be particularly effective with respect
to cleaning power and drying, wherein from this group of
surfactants, nonionics provided best results, with anionic and
amphoteric surfactants being preferably employed in combination
with defoamers or foam inhibitors.
[0025] All nonionic surfactants known to the person skilled in the
art can be used as the nonionic surfactant(s). Suitable exemplary
nonionic surfactants include alkyl glycosides that satisfy the
general Formula RO(G).sub.x, wherein R is a primary linear or
methyl-branched, particularly 2-methyl-branched, aliphatic group
containing 8 to 22 and preferably 12 to 18 carbon atoms; and G is a
glycose unit containing 5 or 6 carbon atoms, preferably glucose.
The degree of oligomerization x, which defines the distribution of
monoglycosides and oligoglycosides, is any number from 1.0 to 10,
preferably 1.2 to 1.4.
[0026] Nonionic surfactants of the amine oxide type such as
N-cocoalkyl-N,N-dimethylamine oxide and N-tallow
alkyl-N,N-dihydroxyethylamine oxide, as well as fatty acid
alkanolamides may also be suitable. The quantity in which these
nonionic surfactants are used is preferably no more than the
quantity in which the ethoxylated fatty alcohols are used, and
particularly no more than half that quantity.
[0027] Another class of preferred nonionic surfactants which may be
used, either as the sole nonionic surfactant or in combination with
other nonionic surfactants, is alkoxylated, preferably ethoxylated
or ethoxylated and propoxylated fatty acid alkyl esters preferably
containing 1 to 4 carbon atoms in the alkyl chain.
[0028] Preferred surfactants include weakly foaming nonionic
surfactants. Washing or cleaning compositions, particularly
cleaning compositions for automatic dishwashers, are especially
preferred when they comprise nonionic surfactants from the
alkoxylated alcohols. Preferred nonionic surfactants include
alkoxylated, advantageously ethoxylated, particularly primary
alcohols preferably containing 8 to 18 carbon atoms and, on
average, 1 to 12 moles of ethylene oxide (EO) per mole of alcohol,
wherein the alcohol group can be linear or, preferably,
methyl-branched in the 2-position or can contain, for example,
linear and methyl-branched groups in the form of mixtures typically
present in oxo alcohol groups. Particularly preferred are, however,
alcohol ethoxylates with linear groups from alcohols of natural
origin with 12 to 18 carbon atoms (e.g., from coco-, palm-, tallow-
or oleyl alcohol) and an average of 2 to 8 EO per mol alcohol.
Exemplary preferred ethoxylated alcohols include C.sub.12-13
alcohols with 3 EO or 4 EO, C.sub.9-11 alcohols with 7 EO,
C.sub.13-15 alcohols with 3 EO, 5 EO or 7 EO, C.sub.12-18 alcohols
with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of
C.sub.12-14 alcohol with 3 EO and C.sub.12-18 alcohol with 5 EO.
The cited degrees of ethoxylation constitute statistically average
values that can be a whole or a fractional number for a specific
product. Preferred alcohol ethoxylates have a narrowed homolog
distribution (narrow range ethoxylates, NRE). In addition to these
nonionic surfactants, fatty alcohols with more than 12 EO can also
be used. Examples of these are tallow fatty alcohol with 14 EO, 25
EO, 30 EO or 40 EO.
[0029] Accordingly, ethoxylated nonionic surfactant(s) prepared
from C.sub.6-20 monohydroxy alkanols or C.sub.6-20 alkyl phenols or
C.sub.12-20 fatty alcohols and more than 12 mole, preferably more
than 12 mole and especially more than 20 mole ethylene oxide per
mole alcohol, are used with particular preference. A particularly
preferred nonionic surfactant is obtained from a straight-chain
fatty alcohol containing 16 to 20 carbon atoms (C.sub.16-20
alcohol), preferably a C.sub.1-8 alcohol, and at least 12 moles,
preferably at least 15 moles and more preferably at least 20 moles
of ethylene oxide. Of these nonionic surfactants, the so-called
narrow range ethoxylates are particularly preferred. Moreover,
combinations of one or more tallow fat alcohols with 20 to 30 EO
with a silicone defoamer are particularly preferably used.
[0030] Nonionic surfactants having a melting point above room
temperature are used with particular preference. Nonionic
surfactant(s) with a melting point above about 20.degree. C.,
preferably above about 25.degree. C., particularly preferably from
about 25 to about 60.degree. C. and especially from about 26.6 to
about 43.3.degree. C., is/are particularly preferred.
[0031] Suitable nonionic surfactants with a melting and/or
softening point in the cited temperature range include, for
example, weakly foaming nonionic surfactants that can be solid or
highly viscous at room temperature. If nonionic surfactants are
used that are highly viscous at room temperature, then it is
preferred that they have a viscosity greater than about 20 Pa s,
preferably above about 35 Pa s, and especially above about 40 Pa s.
Nonionic surfactants having a waxy consistency at room temperature
are also preferred, depending on application.
[0032] Nonionic surfactants from the alkoxylated alcohols,
particularly preferably from the mixed alkoxylated alcohols, and
especially from the EO-AO-EO-nonionic surfactants are likewise
incorporated with particular preference.
[0033] Preferably, the nonionic surfactant solid at room
temperature additionally has propylene oxide units in the molecule.
These PO units preferably make up as much as about 25% by weight,
more preferably as much as about 20% by weight and, especially up
to about 15% by weight of the total molecular weight of the
nonionic surfactant. Particularly preferred nonionic surfactants
include ethoxylated monohydroxyalkanols or alkylphenols, which have
additional polyoxyethylene-polyoxypropylene block copolymer units.
The alcohol or alkylphenol component of these nonionic surfactant
molecules preferably makes up about 30 wt. % or more, more
preferably about 50 wt. % or more, and most preferably about 70 wt.
% or more of the total molecular weight of these nonionic
surfactants. Preferred compositions comprise ethoxylated and
propoxylated nonionic surfactants in which the propylene oxide
units in the molecule preferably make up as much as about 25% by
weight, more preferably as much as about 20% by weight and,
especially up to about 15% by weight of the total molecular weight
of the nonionic surfactant.
[0034] Preferred surfactants that are solid at room temperature are
used and belong to the groups of the alkoxylated nonionic
surfactants, more particularly the ethoxylated primary alcohols,
and mixtures of these surfactants with structurally more complex
surfactants, such as
polyoxypropylene/polyoxyethylene/polyoxypropylene ((PO/EO/PO)
surfactants). Such (PO/EO/PO)-nonionic surfactants are moreover
characterized as having good foam control.
[0035] Other particularly preferred nonionic surfactants with
melting points above room temperature comprise about 40 to about
70% of a polyoxypropylene/polyoxyethylene/polyoxypropylene block
polymer blend having about 75% by weight of an inverted block
copolymer of polyoxyethylene and polyoxypropylene with 17 moles of
ethylene oxide and 44 moles of propylene oxide and about 25% by
weight of a block copolymer of polyoxyethylene and polyoxypropylene
initiated with trimethylol propane and comprising 24 moles of
ethylene oxide and 99 moles of propylene oxide per mole of
trimethylol propane.
[0036] Particularly preferred nonionic surfactants in the context
of the present invention include weakly foaming nonionic
surfactants having alternating ethylene oxide and alkylene oxide
units. Among these, surfactants with EO-AO-EO-AO blocks are again
preferred, wherein one to ten EO or AO groups respectively are
linked together before a block of the other groups follows. Here,
nonionic surfactants of the general formula--
##STR00001##
are preferred, wherein R.sup.1 is a linear or branched, saturated
or a mono- or polyunsaturated C.sub.6-24-alkyl or alkenyl group;
R.sup.2 and R.sup.3 are independently --CH.sub.3,
--CH.sub.2CH.sub.3, --CH.sub.2CH.sub.2--CH.sub.3,
CH(CH.sub.3).sub.2; and the indices w, x, y, z are independently
whole numbers from 1 to 6.
[0037] The preferred nonionic surfactants of the previous formula
can be manufactured by known methods from the corresponding
alcohols R.sup.1--OH and ethylene- or alkylene oxide. R.sup.1 in
the previous Formula can vary depending on the origin of the
alcohol. When natural sources are used, R.sup.1 has an even number
of carbon atoms and generally is not branched. Linear alcohols of
natural origin with 12 to 18 carbon atoms (e.g., coconut, palm,
tallow or oleyl alcohol) are preferred. Alcohols available from
synthetic sources include, for example, Guerbet alcohols or
mixtures of methyl branched in the 2-position or linear and methyl
branched groups, as are typically present in oxo alcohols.
Independent of the type of alcohol used for the manufacture of
nonionic surfactants present in the compositions, nonionic
surfactants are preferred, wherein R.sup.1 in the previous formula
stands for an alkyl group containing 6 to 24, preferably 8 to 20,
particularly preferably 9 to 15 and particularly 9 to 11 carbon
atoms.
[0038] In addition to propylene oxide, butylene oxide can
especially be the alkylene oxide unit that alternates with the
ethylene oxide unit in the preferred nonionic surfactants. However,
other alkylene oxides are also suitable, wherein R.sup.2 or R.sup.3
independently are --CH.sub.2CH.sub.2--CH.sub.3 or
CH(CH.sub.3).sub.2. Preferably, nonionic surfactants of the
previous formula are used wherein R.sup.2 or R.sup.3 is --CH.sub.3,
w and x independently are values of 3 or 4, and y and z
independently are values of 1 or 2.
[0039] In summary, nonionic surfactants that are especially
preferred have a C.sub.9-15-alkyl group with 1 to 4 ethylene oxide
units, followed by 1 to 4 propylene oxide units, followed by 1 to 4
ethylene oxide units, followed by 1 to 4 propylene oxide units.
These surfactants exhibit the required low viscosity in aqueous
solution and according to the invention are used with particular
preference.
[0040] Surfactants of the general formula
R.sup.1--CH(OH)CH.sub.2O-(AO).sub.w-(A'O).sub.x-(A''O).sub.y-(A''O).sub.z-
--R.sup.2, wherein R.sup.1 and R.sup.2 independently are a linear
or branched, saturated or unsaturated or mono- or polyunsaturated
C.sub.2-40 alkyl or alkenyl group; A, A', A'' and A'''
independently are --CH.sub.2CH.sub.2, --CH.sub.2CH.sub.2--CH.sub.2,
--CH.sub.2--CH(CH.sub.3), --CH.sub.2--CH.sub.2--CH.sub.2--,
--CH.sub.2--CH(CH.sub.3)--CH.sub.2--, or
--CH.sub.2--CH(--CH.sub.2--CH.sub.3); and w, x, y and z are values
from 0.5 to 90, wherein x, y and/or z can also be 0, are
preferred.
[0041] End-capped polyoxyalkylated nonionic surfactants are
particularly preferred that, according to the formula
R.sup.1O[CH.sub.2CH.sub.2O].sub.xCH2CH(OH)R.sup.2, possess, in
addition to an R.sup.1 that is a linear or branched, saturated or
unsaturated, aliphatic or aromatic hydrocarbon groups containing 2
to 30 carbon atoms, preferably containing 4 to 22 carbon atoms,
contains a further linear or branched, saturated or unsaturated,
aliphatic or aromatic hydrocarbon group R.sup.2 containing 1 to 30
carbon atoms, wherein x is a value from 1 to 90, preferably a value
from 30 to 80, and especially a value from 30 to 60.
[0042] Particularly preferred surfactants are those according to
the formula
R.sup.1O[CH.sub.2CH(CH.sub.3)O].sub.x[CH.sub.2CH.sub.2O].sub.yCH.-
sub.2CH(OH)R.sup.2, wherein R.sup.1 is a linear or branched
aliphatic hydrocarbon group containing 4 to 18 carbon atoms or
mixtures thereof; R.sup.2 is a linear or branched hydrocarbon group
containing 2 to 26 carbon atoms or mixtures thereof; x is a value
from 0.5 to 1.5; and y is a value of at least 15.
[0043] Further particularly preferred are those end-capped
poly(oxyalkylated) nonionic surfactants of the formula
R.sup.1O[CH.sub.2CH.sub.2O].sub.x[CH.sub.2CH(R.sup.3)O].sub.yCH.sub.2CH(O-
H)R.sup.2, wherein R.sup.1 and R.sup.2 independently are linear or
branched, saturated or mono- or polyunsaturated hydrocarbon groups
containing 2 to 26 carbon atoms; R.sup.3 is --CH.sub.3,
--CH.sub.2CH.sub.3, --CH.sub.2CH.sub.2--CH.sub.3, or
--CH(CH.sub.3).sub.2, preferably --CH.sub.3; and x and y
independently of are a value from 1 to 32, wherein surfactants with
R.sup.3=--CH.sub.3, x is a value from 15 to 32, and y is a value
from 0.5 to 1.5 are quite particularly preferred.
[0044] By adding the above-described nonionic surfactants
containing a free hydroxyl group on one or both terminal alkyl
groups, formation of deposits in the automatic dishwashing can be
significantly reduced compared to conventional polyalkoxylated
fatty alcohols without free hydroxyl groups.
[0045] Further preferred suitable nonionic surfactants include
end-blocked poly(oxyalkylated) nonionic surfactants of the formula
R.sup.1O[CH.sub.2CH(R.sup.3)O].sub.x[CH.sub.2].sub.kCH(OH)[CH.sub.2].sub.-
jOR.sup.2, in which R.sup.1 and R.sup.2 stand for linear or
branched, saturated or unsaturated, aliphatic or aromatic
hydrocarbon groups containing 1 to 30 carbon atoms, R.sup.3 stands
for H or for a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl
or 2-methyl-2-butyl group, x for values between 1 and 30, k and j
have values between 1 and 12, preferably between 1 and 5. Each
R.sup.3 in the above formula
R.sup.1O[CH.sub.2CH(R.sup.3)O].sub.x[CH.sub.2].sub.kCH(OH)[CH.sub.2].sub.-
jOR.sup.2 can be different for the case where x.gtoreq.2. R.sup.1
and R.sup.2 are preferably linear or branched, saturated or
unsaturated, aliphatic or aromatic hydrocarbon groups containing 6
to 22 carbon atoms, groups containing 8 to 18 carbon atoms being
particularly preferred. H, --CH.sub.3 or --CH.sub.2CH.sub.3 are
particularly preferred for the group R.sup.3. Particularly
preferred values for x are in the range from 1 to 20 and more
particularly in the range from 6 to 15.
[0046] As described above, each R.sup.3 in the above formula can be
different for the case where x.gtoreq.2. In this manner the
alkylene oxide unit in the straight brackets can be varied. If, for
example, x has a value of 3, then the substituent R.sup.3 can be
selected to form ethylene oxide (R.sup.3.dbd.H) or propylene oxide
(R.sup.3.dbd.CH.sub.3) units which can be joined together in any
order, for example, (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO),
(PO)(EO)(PO), (PO)(PO)(EO) and (PO)(PO)(PO). The value 3 for x was
selected by way of example and may easily be larger, the range of
variation increasing with increasing x-values and including, for
example, a large number of (EO) groups combined with a small number
of (PO) groups or vice versa.
[0047] Particularly preferred end-capped poly(oxyalkylated)
alcohols corresponding to the above formula have values for both k
and j of 1, so that the above formula can be simplified to
R.sup.1O[CH.sub.2CH(R.sup.3)O].sub.xCH.sub.2CH(OH)CH.sub.2OR.sup.2.
In this last formula, R.sup.1, R.sup.2 and R.sup.3 are as defined
above and x stands for numbers from 1 to 30, preferably 1 to 20 and
especially 6 to 18. Surfactants in which the substituents R1 and R2
have 9 to 14 carbon atoms, R.sup.3 stands for H and x assumes
values of 6 to 15 are particularly preferred.
[0048] The cited carbon chain lengths and degrees of ethoxylation
or alkoxylation of the abovementioned nonionic surfactants
constitute statistically average values that can be a whole or a
fractional number for a specific product. Due to the manufacturing
processes, commercial products of the cited formulas do not consist
in the main of one sole representative, but rather are a mixture,
wherein not only the carbon chain lengths but also the degrees of
ethoxylation or alkoxylation can be average values and thus be
fractional numbers.
[0049] Of course, the abovementioned nonionic surfactants can not
only be employed as single substances, but also as surfactant
mixtures of two, three, four or more surfactants. Accordingly,
surfactant mixtures do not refer to mixtures of nonionic
surfactants that as a whole fall under one of the above cited
general formulas, but rather refer to such mixtures that comprise
two, three, four or more nonionic surfactants that can be described
by the different abovementioned general formulas.
[0050] In preferred process variants the automatic dishwashing
agent A comprises nonionic surfactant(s) in quantities of about 0.1
to about 30 wt. %, preferably about 0.2 to about 20 wt. %,
particularly preferably about 0.5 to about 10 wt. % and especially
from about 1 to about 8 wt. %, each based on the total weight of
the automatic dishwashing agent A. Particularly preferred process
variants are those in which the automatic dishwashing agent A
comprises the nonionic surfactant in amounts of about 0.5 to about
5.0 wt. %, based on the total weight of the automatic dishwashing
agent A.
[0051] Accordingly, a preferred subject matter of the present
application is a process for cleaning tableware in an automatic
dishwasher, during which the aqueous cleaning liquor that is
present in the interior of the automatic dishwasher is at least
partially removed from the interior of the automatic dishwasher at
a time t, wherein an automatic dishwashing agent A, comprising,
based on total weight of the automatic dishwashing agent A--
[0052] a) 0.5 to 5 wt. % nonionic surfactant(s), and
[0053] b) anionic polymer(s)
is metered into the interior of the automatic dishwasher in a
quantity m1 at a time t1<t and in a quantity m2 at a time
t2>t.
[0054] Accordingly, a further preferred subject matter of the
present application is a process for cleaning tableware in an
automatic dishwasher, during which aqueous wash liquor present in
the interior of the automatic dishwasher is removed therefrom in an
amount of about 5 to about 99 vol. %, preferably from about 10 to
about 90 vol. %, particularly preferably from about 20 to about 80
vol. % and especially from about 40 to about 70 vol. % at a time t.
Further, an automatic dishwashing agent A comprising, based on
total weight of the automatic dishwashing agent A--
[0055] a) 0.5 to 10 wt. % nonionic surfactant(s), and
[0056] b) anionic polymer(s)
is metered into the interior of the automatic dishwasher in a
quantity m1 at a time t1<t and in a quantity m2 at a time
t2>t.
[0057] Alternatively or in addition to the nonionic surfactants,
anionic or amphoteric surfactants, preferably in combination with
defoamers or foam inhibitors, can also be employed in the inventive
automatic dishwashing process.
[0058] Exemplary suitable anionic surfactants include those of the
sulfonate and sulfate type. Suitable surfactants of the sulfonate
type include, advantageously C.sub.9-13 alkylbenzene sulfonates,
olefin sulfonates (i.e., mixtures of alkene- and hydroxyalkane
sulfonates) and disulfonates, as are obtained, for example, from
C.sub.12-18 monoolefins having a terminal or internal double bond,
by sulfonation with gaseous sulfur trioxide and subsequent alkaline
or acidic hydrolysis of the sulfonation products. Alkane
sulfonates, obtained for example from C.sub.12-18 alkanes by
sulfochlorination or sulfoxidation with subsequent hydrolysis or
neutralization, are also suitable. Esters of .alpha.-sulfofatty
acids (ester sulfonates) (e.g., .alpha.-sulfonated methyl esters of
hydrogenated coco-, palm nut- or tallow fatty acids) are likewise
suitable.
[0059] Further suitable anionic surfactants include sulfated fatty
acid esters of glycerin. They include the mono-, di- and triesters
and also mixtures of them, such as those obtained by esterification
of a monoglycerin with 1 to 3 moles fatty acid, or by
transesterification of triglycerides with 0.3 to 2 moles glycerin.
Preferred sulfated fatty acid esters of glycerin in this case are
the sulfated products of saturated fatty acids containing 6 to 22
carbon atoms (e.g., caproic acid, caprylic acid, capric acid,
myristic acid, lauric acid, palmitic acid, stearic acid or behenic
acid).
[0060] Preferred alk(en)yl sulfates include the alkali metal and
especially sodium salts of the sulfuric acid half-esters derived
from C.sub.12-C.sub.18 fatty alcohols (e.g., from coconut butter
alcohol, tallow alcohol, lauryl, myristyl, cetyl or stearyl
alcohol) or from C.sub.10-C.sub.20 oxo alcohols and those
half-esters of secondary alcohols of these chain lengths.
Additionally preferred are alk(en)yl sulfates of the said chain
lengths containing a synthetic, straight-chained alkyl group
produced on a petrochemical basis and showing similar degradation
behavior to suitable compounds based on fat chemical raw materials.
C.sub.12-C.sub.16 alkyl sulfates and C.sub.12-C.sub.15 alkyl
sulfates and C.sub.14-C.sub.15 alkyl sulfates are preferred because
of their washing performance. 2,3-Alkyl sulfates, which can be
obtained from the Shell Oil Company under the trade name DAN.RTM.,
are also suitable anionic surfactants.
[0061] Sulfuric acid mono-esters derived from straight-chained or
branched C.sub.7-21 alcohols ethoxylated with 1 to 6 moles ethylene
oxide are also suitable, for example, 2-methyl-branched C.sub.9-11
alcohols with an average of 3.5 mole ethylene oxide (EO) or
C.sub.12-18 fatty alcohols with 1 to 4 EO. Due to their high
foaming performance, they are only used in fairly small quantities
in cleaning compositions, for example, in amounts of 1 to 5% by
weight.
[0062] Other suitable anionic surfactants include the salts of
alkylsulfosuccinic acid, also referred to as sulfosuccinates or
esters of sulfosuccinic acid and the monoesters and/or di-esters of
sulfosuccinic acid with alcohols, preferably fatty alcohols and
especially ethoxylated fatty alcohols. Preferred sulfosuccinates
comprise C.sub.8-18 fatty alcohol groups or mixtures of them.
Especially preferred sulfosuccinates contain a fatty alcohol group
derived from the ethoxylated fatty alcohols that are under
consideration as nonionic surfactants. Once again the particularly
preferred sulfosuccinates are those, whose fatty alcohol groups are
derived from ethoxylated fatty alcohols with narrow range homolog
distribution. It is also possible to use alk(en)ylsuccinic acids
with preferably 8 to 18 carbon atoms in the alk(en)yl chain, or
salts thereof.
[0063] Suitable exemplary amphoteric surfactants include betaines
or alkylamido alkylamines.
[0064] Suitable betaines include alkyl betaines, alkylamido
betaines, imidazolium betaines, sulfo betaines (INCI sultaines), as
well as phospho betaines, preferably satisfying the formula
(R.sup.A)(R.sup.B)(R.sup.C))N.sup.+CH.sub.2COO.sup.-, wherein
R.sup.A is an alkyl group with 8 to 25, preferably 10 to 21 carbon
atoms, optionally interrupted by heteroatoms or heteroatomic
groups, and R.sup.B and R.sup.C are the same or different alkyl
groups with 1 to 3 carbon atoms, in particular C.sub.10-C.sub.22
alkyldimethylcarboxymethylbetaine and C.sub.11-C.sub.17 alkylamido
propyldimethylcarboxymethylbetaine, or formula
R.sup.1--[CO--X--(CH.sub.2).sub.n].sub.x--N.sup.+(R.sup.II)(R.sup.III)---
(CH.sub.2).sub.m-[CH(OH)--CH.sub.2].sub.y--Y.sup.-
wherein R.sup.1 is a saturated or unsaturated C.sub.6-22 alkyl
group, preferably C.sub.8-18 alkyl group, more preferably a
saturated C.sub.10-16 alkyl group, for example, a saturated
C.sub.12-14 alkyl group; X is NH, NR.sup.IV with the C.sub.1-4
alkyl group R.sup.IV, O or S; n is a number from 1 to 10,
preferably 2 to 5, particularly 3; x is 0 or 1, preferably 1;
R.sup.II and R.sup.III are independently a C.sub.1-4 alkyl group,
an optionally hydroxy substituted group, such as a hydroxyethyl
group, but especially a methyl group; m is a number from 1 to 4,
particularly 1, 2 or 3; y is 0 or 1; and Y is COO, SO.sub.3,
OPO(OR.sup.V)O or P(O)(OR.sup.V)O, wherein R.sup.V is a hydrogen
atom H or a C.sub.1-4 alkyl group.
[0065] Alkyl betaines and alkylamido betaines corresponding to the
above formula with a carboxylate group (Y.sup.-.dbd.COO.sup.-) are
also known as carbobetaines.
[0066] Preferred amphoteric surfactants include alkyl betaines
corresponding to formula (A1), allylamido betaines corresponding to
formula (A2), sulfo betaines corresponding to formula (A3) and
amido sulfo betaines corresponding to formula (A4) below:
R.sup.1--N.sup.+(CH.sub.3).sub.2--CH.sub.2COO.sup.- (A1)
R.sup.1--CO--NH--(CH.sub.2).sub.3--N.sup.+(CH.sub.3).sub.2--CH.sub.2COO.-
sup.- (A2)
R.sup.1--N.sup.+(CH.sub.3).sub.2--CH.sub.2CH(OH)CH.sub.2SO.sub.3.sup.-
(A3)
R.sup.1--CO--NH--(CH.sub.2).sub.3--N.sup.+(CH.sub.3).sub.2--CH.sub.2CH(O-
H)CH.sub.2SO.sub.3.sup.- (A4)
wherein R.sup.1 has the same meaning as in Formula A.
[0067] Particularly preferred amphoteric surfactants are the
carbobetaines, and more particularly carbobetaines corresponding to
formulae (A1) and (A2), alkylamido betaines corresponding to
formula (A2) being most particularly preferred. Exemplary suitable
betaines and sulfo betaines include the following compounds named
according to INCI: Almondamidopropyl Betaine, Apricotamidopropyl
Betaine, Avocadamidopropyl Betaine, Babassuamidopropyl Betaine,
Behenamidopropyl Betaine, Behenyl Betaine, Betaine,
Canolamidopropyl Betaine, Capryl/Capramidopropyl Betaine,
Carnitine, Cetyl Betaine, Cocamidoethyl Betaine, Cocamidopropyl
Betaine, Cocamidopropyl Hydroxysultaine, Coco-Betaine,
Coco-Hydroxysultaine, Coco/Oleamidopropyl Betaine, Coco-Sultaine,
Decyl Betaine, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy
Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl Tallow
Glycinate, Dimethicone Propyl PG-Betaine, Erucamidopropyl
Hydroxysultaine, Hydrogenated Tallow Betaine, Isostearamidopropyl
Betaine, Lauramido propyl Betaine, Lauryl Betaine, Lauryl
Hydroxysultaine, Lauryl Sultaine, Milkamidopropyl Betaine,
Minkamidopropyl Betaine, Myristamidopropyl Betaine, Myristyl
Betaine, Oleamidopropyl Betaine, Oleamidopropyl Hydroxysultaine,
Oleyl Betaine, Olivamidopropyl Betaine, Palmamidopropyl Betaine,
Palmitamidopropyl Betaine, Palmitoyl Carnitine, Palm
Kernelamidopropyl Betaine, Polytetrafluoroethylene Acetoxypropyl
Betaine, Ricinoleamidopropyl Betaine, Sesamidopropyl Betaine,
Soyamidopropyl Betaine, Stearamidopropyl Betaine, Stearyl Betaine,
Tallowamidopropyl Betaine, Tallowamidopropyl Hydroxysultaine,
Tallow Betaine, Tallow Dihydroxyethyl Betaine, Undecylenamidopropyl
Betaine and Wheat Germamidopropyl Betaine. A preferred
amphosurfactant is cocamidopropyl betaine (Cocoamidopropyl
betaine). A particularly preferred amphoteric surfactant is
capryl/capramidopropyl betaine (CAB) obtainable, for example, under
the trade name Tegotens.RTM. B 810 from Th. Goldschmidt AG.
[0068] Alkylamido alkylamines (INCI Alkylamido Alkylamines) are
amphoteric surfactants of the formula
R.sup.VI--CO--NR.sup.VII--(CH.sub.2).sub.i--N(R.sup.VIII)--(CH.sub.2CH.s-
ub.2O).sub.j--(CH.sub.2).sub.k-[CH(OH)].sub.l--CH.sub.2--Z--OM
wherein R.sup.VI is a saturated or unsaturated C.sub.6-22 alkyl
group, preferably C.sub.8-18 alkyl group, more preferably a
saturated C.sub.10-16 alkyl group, for example; a saturated
C.sub.12-14 alkyl group; R.sup.VII is hydrogen or a C.sub.1-4 alkyl
group, preferably H; i is a number from 1 to 10, preferably 2 to 5,
particularly 2 or 3; R.sup.VIII is hydrogen or CH.sub.2COOM (for M
see below); j is a number from 1 to 4, preferably 1 or 2,
particularly 1; k is a number from 0 to 4, preferably 0 or 1; 1 is
0 or 1, wherein k is 1 if 1 is 1; Z is CO, SO.sub.2, OPO(OR.sup.12)
or P(O)(OR.sup.12), wherein R.sup.12 is a C.sub.1-4 alkyl group or
M (see below); and M is hydrogen, an alkali metal, an alkaline
earth metal or a protonated alkanolamine (e.g., protonated mono-,
di- or triethanolamine).
[0069] Preferred representatives satisfy the formulas B1 to B4
R.sup.VI--CO--NH--(CH.sub.2).sub.2--N(R.sup.VIII)--CH.sub.2CH.sub.2O--CH-
.sub.2--COOM (B1)
R.sup.VI--CO--NH--(CH.sub.2).sub.2--N(R.sup.VIII)--CH.sub.2CH.sub.2O--CH-
.sub.2CH.sub.2--COOM (B2)
R.sup.VI--CO--NH--(CH.sub.2).sub.2--N(R.sup.VIII)--CH.sub.2CH.sub.2O--CH-
.sub.2CH(OH)CH.sub.2--SO.sub.3M (B3)
R.sup.VI--CO--NH--(CH.sub.2).sub.2--N(R.sup.VIII)--CH.sub.2CH.sub.2O--CH-
.sub.2CH(OH)CH.sub.2--OPO.sub.3HM (B4)
wherein R.sup.VI, R.sup.VIII and M have the same meaning as in
Formula B.
[0070] Exemplary alkylamido alkylamines include the following
compounds named according to INCI: Cocoamphodipropionic Acid,
Cocobetainamido Amphopropionate, DEA-Cocoamphodipropionate,
Disodium Caproamphodiacetate, Disodium Caproamphodipropionate,
Disodium Capryloamphodiacetate, Disodium Capryloamphodipropionate,
Disodium Cocoamphocarboxyethylhydroxypropylsulfonate, Disodium
Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium
Isostearoamphodiacetate, Disodium Isostearoamphodipropionate,
Disodium Laureth-5-Carboxyamphodiacetate Carboxyamphodiacetate,
Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate,
Disodium Oleoamphodipropionate, Disodium
PPG-2-Isodeceth-7-Carboxyamphodiacetate Carboxyamphodiacetate,
Disodium Stearoamphodiacetate, Disodium Tallowamphodiacetate,
Disodium Wheatgermamphodiacetate, Lauroamphodipropionic Acid,
Quaternium-85, Sodium Caproamphoacetate, Sodium
Caproamphohydroxypropylsulfonate, Sodium Caproamphopropionate,
Sodium Capryloamphoacetate, Sodium
Capryloamphohydroxypropylsulfonate, Sodium Capryloamphopropionate,
Sodium Cocoamphoacetate, Sodium Cocoamphohydroxypropylsulfonate,
Sodium Cocoamphopropionate, Sodium Cornamphopropionate, Sodium
Isostearoamphoacetate, Sodium Isostearoamphopropionate, Sodium
Lauroamphoacetate, Sodium Lauroamphohydroxypropylsulfonate, Sodium
Lauroampho PG-Acetate Phosphate, Sodium Lauroamphopropionate,
Sodium Myristoamphoacetate, Sodium Oleoamphoacetate, Sodium
Oleoamphohydroxypropylsulfonate, Sodium Oleoamphopropionate, Sodium
Ricinoleoamphoacetate, Sodium Stearoamphoacetate, Sodium
Stearoamphohydroxypropylsulfonate, Sodium Stearoamphopropionate,
Sodium Tallamphopropionate, Sodium Tallowamphoacetate, Sodium
Undecylenoamphoacetate, Sodium Undecylenoamphopropionate, Sodium
Wheat Germamphoacetate and Trisodium Lauroampho PG-Acetate Chloride
Phosphate.
[0071] Soaps, oils, fats, paraffins or silicone oils, optionally
deposited on carrier materials, are examples of foam inhibitors.
Inorganic salts such as carbonates or sulfates, cellulose
derivatives or silicates as well as their mixtures are examples of
suitable carrier materials. In the context of the present
application, preferred compositions comprise paraffins, preferably
unbranched paraffins (n-paraffins) and/or silicones, preferably
linear polymeric silicones having the structure (R.sub.2SiO).sub.x
and which are also called silicone oils.
[0072] Cleaning agents employed in the inventive process include
anionic polymers as a second ingredient. All washing or cleaning
active anionic polymers known to the person skilled in the art can
be employed as the anionic polymers.
[0073] In preferred inventive processes the automatic dishwashing
agent A comprises anionic polymer(s) in amounts of about 0.1 to
about 40 wt. %, preferably about 0.2 to about 20 wt. %,
particularly preferably about 0.5 to about 15 wt. % and especially
from about 1 to about 10 wt. %, each based on total weight of the
automatic dishwashing agent A. Corresponding agents have proved
advantageous in the inventive processes, particularly with respect
to optimal cleaning and rinsing results.
[0074] Accordingly, a particularly preferred subject matter of the
present application is a process for cleaning tableware in an
automatic dishwasher during which aqueous cleaning liquor present
in the interior of the automatic dishwasher is at least partially
removed from the interior of the automatic dishwasher at a time t.
Further, an automatic dishwashing agent A comprising, based on
total weight of the automatic dishwashing agent A--
[0075] a) 0.5 to 10 wt. % nonionic surfactant(s), and
[0076] b) 0.2 to 20 wt. % anionic polymer(s)
is metered into the interior of the automatic dishwasher in a
quantity m1 at a time t1<t and in a quantity m2 at a time
t2>t.
[0077] Accordingly, a further preferred subject matter of the
present application is a process for cleaning tableware in an
automatic dishwasher, during which an aqueous wash liquor present
in the interior of the automatic dishwasher is removed from the
interior of the dishwasher in an amount of from about 5 to about 99
vol. %, preferably from about 10 to about 90 vol. %, particularly
preferably from about 20 to about 80 vol. % and especially from
about 40 to about 70 vol. % at a time t, wherein an automatic
dishwashing agent A comprising, based on total weight of the
automatic dishwashing agent A--
[0078] a) 0.5 to 10 wt. % nonionic surfactant(s), and
[0079] b) 0.2 to 20 wt. % anionic polymer(s)
is metered into the interior of the automatic dishwasher in a
quantity m1 at a time t1<t and in a quantity m2 at a time
t2>t.
[0080] Suitable exemplary anionic polymers include polymeric
polycarboxylates, particularly alkali metal salts of polyacrylic or
polymethacrylic acid, for example, those with a relative molecular
weight of 500 to 70,000 g/mol.
[0081] Particularly suitable polymers include polyacrylates,
preferably having a molecular weight of 2,000 to 20,000 g/mol.
Because of their superior solubility, preferred representatives of
this group are again short-chain polyacrylates having molecular
weights of 2,000 to 10,000 g/mol and, more particularly, 3,000 to
5,000 g/mol.
[0082] Further suitable copolymeric polycarboxylates include
particularly those of acrylic acid with methacrylic acid and of
acrylic acid or methacrylic acid with maleic acid. Copolymers of
acrylic acid with maleic acid comprising about 50 to about 90 wt. %
acrylic acid and about 50 to about 10 wt. % maleic acid have proven
to be particularly suitable. Their relative molecular weight, based
on free acids, generally ranges from about 2,000 to about 70,000
g/mol, preferably about 20,000 to about 50,000 g/mol and especially
about 30,000 to about 40,000 g/mol.
[0083] Preferred inventive processes are those wherein the anionic
polymer is a homopolymer and/or copolymer of acrylic acid or
methacrylic acid.
[0084] Alternatively or in addition to the abovementioned
polycarboxylates, anionic polymers employed in the inventive
process can also comprise sulfonic acid groups.
[0085] Preferred inventive processes are those wherein the anionic
polymer is a copolymer of--
[0086] i) unsaturated carboxylic acids,
[0087] ii) sulfonic acid groups containing monomers, or
[0088] iii) optional additional ionic or nonionogenic monomers.
[0089] Preferred monomers ii) containing sulfonic acid groups
correspond to the formula --
R.sup.5(R.sup.6)C.dbd.C(R.sup.7)--X--SO.sub.3H
wherein R.sup.5 to R.sup.7 independently are --H, --CH.sub.3, a
linear or branched, saturated alkyl group containing 2 to 12 carbon
atoms, a linear or branched, mono- or polyunsaturated alkenyl group
containing 2 to 12 carbon atoms, with --NH.sub.2, --OH or --COOH
substituted alkyl or alkenyl groups or --COOH or --COOR.sup.4,
wherein R.sup.4 is a saturated or unsaturated, linear or branched
hydrocarbon group containing 1 to 12 carbon atoms; and X is an
optional spacer group chosen from --(CH.sub.2).sub.n-- with n=0 to
4, --COO--(CH.sub.2).sub.k-- with k=1 to 6,
--C(O)--NH--C(CH.sub.3).sub.2--,
--C(O)--NH--C(CH.sub.3).sub.2CH.sub.2-- and
--C(O)--NH--CH(CH.sub.2CH.sub.3)--.
[0090] Among these monomers those are preferred of the
formulas--
H.sub.2C.dbd.CH--X--SO.sub.3H
H.sub.2C.dbd.C(CH.sub.3)--X--SO.sub.3H
HO.sub.3S --X--(R.sup.6)C.dbd.C(R.sup.7)--X--SO.sub.3H,
wherein R.sup.6 and R.sup.7 independently are --H, --CH.sub.3,
--CH.sub.2CH.sub.3, --CH.sub.2CH.sub.2CH.sub.3, or
--CH(CH.sub.3).sub.2; and X is an optionally present spacer group
chosen from --(CH.sub.2).sub.n-- with n=0 to 4,
--COO--(CH.sub.2).sub.k-- with k=1 to 6,
--C(O)--NH--C(CH.sub.3).sub.2--,
--C(O)--NH--C(CH.sub.3).sub.2CH.sub.2-- and
--C(O)--NH--CH(CH.sub.2CH.sub.3)--.
[0091] Accordingly, particularly preferred sulfonic acid-containing
monomers include 1-acrylamido-1-propane sulfonic acid,
2-acrylamido-2-propane sulfonic acid,
2-acrylamido-2-methyl-1-propane sulfonic acid,
2-methacrylamido-2-methyl-1-propane sulfonic acid,
3-methacrylamido-2-hydroxypropane sulfonic acid, allyl sulfonic
acid, methallyl sulfonic acid, allyloxybenzene sulfonic acid,
methallyloxybenzene sulfonic acid,
2-hydroxy-3-(2-propenyloxy)propane sulfonic acid,
2-methyl-2-propene-1-sulfonic acid, styrene sulfonic acid, vinyl
sulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate,
sulfomethylacrylamide, sulfomethylmethacrylamide and mixtures of
the cited acids or of their water-soluble salts.
[0092] Sulfonic acid groups can be present in the polymers in
completely or partly neutralized form, meaning, the acidic hydrogen
atom of the sulfonic acid groups can be replaced by metal ions,
preferably alkali metal ions and more particularly sodium ions, in
some or all of the sulfonic acid groups. The addition of copolymers
containing partly or fully neutralized sulfonic acid groups is
preferred according to the invention.
[0093] The molecular weight of the inventively preferred
sulfo-copolymers used can be varied to adapt the properties of the
polymer to the desired application requirement. Preferred automatic
dishwashing agents include copolymers having molecular weights from
about 2000 to about 200,000 gmol.sup.1, preferably about 4000 to
about 25,000 gmol.sup.1 and especially about 5000 to about 15,000
gmol.sup.1.
[0094] Further suitable anionic polymers include hydrophobically
modified anionic polymers, for example, anionic polymers such as --
[0095] i) monomers from the group of the mono- or polyunsaturated
carboxylic acids, [0096] ii) monomers of the general formula
R.sup.1(R.sup.2)C.dbd.C(R.sup.3)--X--R.sup.4, wherein R.sup.1 to
R.sup.3 independently are --H, --CH.sub.3 or --C.sub.2H.sub.5; X is
an optional spacer group chosen from --CH.sub.2--, --C(O)O-- and
--C(O)--NH--; and R.sup.4 is a straight chain or branched saturated
alkyl group containing 2 to 22 carbon atoms or for an unsaturated,
preferably aromatic group containing 6 to 22 carbon atoms, and
[0097] iii) optionally, further monomers.
[0098] Particularly preferred monomers i) from the group of the
mono or polyunsaturated carboxylic acids are unsaturated carboxylic
acids of the general formula R.sup.1(R.sup.2)C.dbd.C(R.sup.3)COOH,
in which R.sup.1 to R.sup.3 independently of one another stand for
--H, --CH.sub.3, a linear or branched, saturated alkyl group
containing 2 to 12 carbon atoms, a linear or branched, mono or
polyunsaturated alkenyl group containing 2 to 12 carbon atoms,
alkyl or alkenyl groups substituted by --NH.sub.2, --OH or --COON
as defined above or for --COOH or --COOR.sup.4, wherein R.sup.4 is
a saturated or unsaturated, linear or branched hydrocarbon group
containing 1 to 12 carbon atoms.
[0099] Accordingly, a particularly preferred subject matter of the
present application is a process for cleaning tableware in an
automatic dishwasher, during which aqueous cleaning liquor present
in the interior of the automatic dishwasher is at least partially
removed from the interior of the automatic dishwasher at a time t,
wherein an automatic dishwashing agent A comprising, based on total
weight of the automatic dishwashing agent A--
[0100] a) 0.5 to 10 wt. % nonionic surfactant(s), and
[0101] b) anionic polymer(s) containing [0102] i. monomers from the
group of mono- or polyunsaturated carboxylic acids [0103] ii.
monomers of the general formula
R.sup.1(R.sup.2)C.dbd.C(R.sup.3)--X--R.sup.4, wherein R.sup.1 to
R.sup.3 independently are --H, --CH.sub.3 or --C.sub.2H.sub.5; X is
an optional spacer group chosen from --CH.sub.2--, --C(O)O-- and
--C(O)--NH--; and R.sup.4 is a straight chain or branched saturated
alkyl group containing 2 to 22 carbon atoms or an unsaturated,
preferably aromatic group containing 6 to 22 carbon atoms, and
[0104] iii. optional further monomers is metered into the interior
of the automatic dishwasher in a quantity m1 at a time t1<t and
in a quantity m2 at a time t2>t.
[0105] Accordingly, a further preferred subject matter of the
present application is a process for cleaning tableware in an
automatic dishwasher, during which aqueous wash liquor present in
the interior of the automatic dishwasher is removed from the
interior of the dishwasher at a time t in an amount of from about 5
to about 99 vol. %, preferably from about 10 to about 90 vol. %,
particularly preferably from about 20 to about 80 vol. % and
especially from about 40 to about 70 vol. % of the wash liquor,
wherein an automatic dishwashing agent A comprising, based on total
weight of the automatic dishwashing agent A,--
[0106] a) 0.5 to 10 wt. % nonionic surfactant(s), and
[0107] b) anionic polymer(s) containing [0108] i. monomers from the
group of the mono- or polyunsaturated carboxylic acids [0109] ii.
monomers of the general formula
R.sup.1(R.sup.2)C.dbd.C(R.sup.3)--X--R.sup.4, wherein R.sup.1 to
R.sup.3 independently are --H, --CH.sub.3 or --C.sub.2H.sub.5; X is
an optional spacer group chosen from --CH.sub.2--, --C(O)O-- and
--C(O)--NH--; and R.sup.4 is a straight chain or branched saturated
alkyl group containing 2 to 22 carbon atoms, or an unsaturated,
preferably aromatic group containing 6 to 22 carbon atoms, and
[0110] iii. optional further monomers is metered into the interior
of the automatic dishwasher in a quantity m1 at a time t1<t and
in a quantity m2 at a time t2>t.
[0111] Particularly preferred carboxyl group-containing monomers i)
of the above-mentioned hydrophobically modified anionic polymers
include acrylic acid, methacrylic acid, ethacrylic acid,
.alpha.-chloroacrylic acid, .alpha.-cyanoacrylic acid, crotonic
acid, .alpha.-phenylacrylic acid, maleic acid, maleic anhydride,
fumaric acid, itaconic acid, citraconic acid, methylenemalonic
acid, sorbic acid, cinnamic acid or their mixtures.
[0112] Monomers of the general formula R.sup.1
(R.sup.2)C.dbd.C(R.sup.3)--X--R.sup.4 can be added as the nonionic
monomers ii). Particularly preferred monomers of this type include
butene, isobutene, pentene, 3-methylbutene, 2-methylbutene,
cyclopentene, hexene, 1-hexene,
2-methlypentene-1,3-methlypentene-1, cyclohexene,
methylcyclopentene, cycloheptene, methylcyclohexene,
2,4,4-trimethylpentene-1,2,4,4-trimethylpentene-2,2,3-dimethylhexene-1,2,-
4-dimethylhexene-1,2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4,4-dimethylh-
exene-1, ethylcyclohexyne, 1-octene, .alpha.-olefins containing 10
or more carbon atoms such as for example 1-decene, 1-dodecene,
1-hexadecene, 1-octadecene and C22-.alpha.-olefin, 2-styrene,
.alpha.-methylstyrene, 3-methylstyrene, 4-propylstyrene,
4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene,
1-vinylnaphthalene, 2-vinylnaphthalene, methyl acrylate, ethyl
acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl
acrylate, methyl methacrylate, N-(methyl)acrylamide, 2-ethylhexyl
acrylate, 2-ethylhexyl methacrylate, N-(2-ethylhexyl)acrylamide,
octyl acrylate, octyl methacrylate, N-(octyl)acrylamide, lauryl
acrylate, lauryl methacrylate, N-(lauryl)acrylamide, stearyl
acrylate, stearyl methacrylate, N-(stearyl)acrylamide, behenyl
acrylate, behenyl methacrylate and N-(behenyl)acrylamide or their
mixtures.
[0113] In a particularly preferred embodiment, the copolymer d)
contains, in addition to monomers i) and ii), a third monomer iii)
from sulfonic acid group-containing monomers.
[0114] Preferred monomers containing sulfonic acid groups include
those of the formula --
R.sup.5(R.sup.6)C.dbd.C(R.sup.7)--X--SO.sub.3H
wherein R.sup.5 to R.sup.7 are independently --H, --CH.sub.3, a
linear or branched, saturated alkyl group containing 2 to 12 carbon
atoms, a linear or branched, mono- or polyunsaturated alkenyl group
containing 2 to 12 carbon atoms, alkyl or alkenyl groups
substituted with --NH.sub.2, --OH or --COOH or --COOH or
--COOR.sup.4, wherein R.sup.4 is a saturated or unsaturated, linear
or branched hydrocarbon group containing 1 to 12 carbon atoms; and
X is an optional spacer group chosen from --(CH.sub.2).sub.n-- with
n=0 to 4, --COO--(CH.sub.2).sub.k-- with k=1 to 6,
--C(O)--NH--C(CH.sub.3).sub.2-- and
--C(O)--NH--CH(CH.sub.2CH.sub.3)--.
[0115] Among these monomers, preferred are those of the formulas
--
H.sub.2C.dbd.CH--X--SO.sub.3H
H.sub.2C.dbd.C(CH.sub.3)--X--SO.sub.3H
HO.sub.3S--X--(R.sup.6)C.dbd.C(R.sup.7)--X--SO.sub.3H
wherein R.sup.6 and R.sup.7 are independently --H, --CH.sub.3,
--CH.sub.2CH.sub.3, --CH.sub.2CH.sub.2CH.sub.3 or
--CH(CH.sub.3).sub.2; and X is an optional spacer group chosen from
--(CH.sub.2).sub.n-- with n=0 to 4, --COO--(CH.sub.2).sub.k-- with
k=1 to 6, --C(O)--NH--C(CH.sub.3).sub.2-- and
--C(O)--NH--CH(CH.sub.2CH.sub.3)--.
[0116] Accordingly, particularly preferred sulfonic acid-containing
monomers include 1-acrylamido-1-propane sulfonic acid,
2-acrylamido-2-propane sulfonic acid,
2-acrylamido-2-methyl-1-propane sulfonic acid,
2-methacrylamido-2-methyl-1-propane sulfonic acid,
3-methacrylamido-2-hydroxypropane sulfonic acid, allyl sulfonic
acid, methallyl sulfonic acid, allyloxybenzene sulfonic acid,
methallyloxybenzene sulfonic acid,
2-hydroxy-3-(2-propenyloxy)propane sulfonic acid,
2-methyl-2-propene-1-sulfonic acid, styrene sulfonic acid, vinyl
sulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate,
sulfomethylacrylamide, sulfomethylmethacrylamide and mixtures of
the cited acids or of their water-soluble salts.
[0117] The sulfonic acid groups may be present in the polymers
completely or partly in neutralized form, meaning, the acidic
hydrogen atom of the sulfonic acid groups can be replaced by metal
ions, preferably alkali metal ions and more particularly sodium
ions, in some or all of the sulfonic acid groups. The addition of
copolymers containing partly or fully neutralized sulfonic acid
groups is preferred according to the invention.
[0118] The molecular weight of the inventively preferred
sulfo-copolymers used can be varied to adapt the properties of the
polymer to the desired application requirement. Preferred automatic
dishwashing agents are characterized in that the copolymers have
molecular weights from about 2000 to about 200,000 gmol.sup.-1,
preferably about 4000 to about 25,000 gmol.sup.-1 and especially
about 5000 to about 15,000 gmol.sup.-1.
[0119] Accordingly, a further particularly preferred subject matter
of the present application is a process for cleaning tableware in
an automatic dishwasher during which aqueous cleaning liquor
present in the interior of the automatic dishwasher is at least
partially removed from the interior of the automatic dishwasher at
a time t, wherein an automatic dishwashing agent A, comprising,
based on the total weight of the automatic dishwashing agent
A--
[0120] a) 0.5 to 10 wt. % nonionic surfactant(s), and
[0121] b) anionic polymer(s), containing [0122] i. monomers from
the group of the mono- or polyunsaturated carboxylic acids, [0123]
ii. monomers of the general formula
R.sup.1(R.sup.2)C.dbd.C(R.sup.3)--X--R.sup.4, wherein R.sup.1 to
R.sup.3 independently are --H, --CH.sub.3 or --C.sub.2H.sub.5; X is
an optional spacer group chosen from --CH.sub.2--, --C(O)O-- and
--C(O)--NH--, and R.sup.4 is a straight chain or branched saturated
alkyl group containing 2 to 22 carbon atoms or an unsaturated,
preferably aromatic group containing 6 to 22 carbon atoms, and/or
[0124] iii. sulfonic acid groups containing monomers is metered
into the interior of the automatic dishwasher in a quantity m1 at a
time t1<t and in a quantity m2 at a time t2>t.
[0125] Accordingly, a further preferred subject matter of the
present application is a process for cleaning tableware in an
automatic dishwasher during which aqueous wash liquor present in
the interior of the automatic dishwasher is removed from the
interior of the dishwasher at a time t in an amount of from about 5
to about 99 vol. %, preferably from about 10 to about 90 vol. %,
particularly preferably from about 20 to about 80 vol. % and
especially from about 40 to about 70 vol. % of the wash liquor,
wherein an automatic dishwashing agent A comprising, based on total
weight of the automatic dishwashing agent A--
[0126] a) 0.5 to 10 wt. % nonionic surfactant(s), and
[0127] b) anionic polymer(s), containing [0128] i. monomers from
the group of the mono- or polyunsaturated carboxylic acids [0129]
ii. monomers of the general formula
R.sup.1(R.sup.2)C.dbd.C(R.sup.3)--X--R.sup.4, wherein R.sup.1 to
R.sup.3 independently are --H, --CH.sub.3 or --C.sub.2H.sub.5; X is
an optional spacer group chosen from --CH.sub.2--, --C(O)O-- and
--C(O)--NH--; and R.sup.4 is a straight chain or branched saturated
alkyl group containing 2 to 22 carbon atoms, or an unsaturated,
preferably aromatic group containing 6 to 22 carbon atoms, and/or
[0130] iii. sulfonic acid groups containing monomers is metered
into the interior of the automatic dishwasher in a quantity m1 at a
time t1<t and in a quantity m2 at a time t2>t.
[0131] The automatic dishwashing agent employed in the inventive
process can have one or more builders as additional ingredients.
These builders include silicates, carbonates and organic
co-builders, as well as phosphates.
[0132] Organic co-builders include polycarboxylates/polycarboxylic
acids, polymeric polycarboxylates, aspartic acid, polyacetals,
dextrins, and other organic co-builders. These classes of
substances are described below.
[0133] Useful organic builders are, for example, polycarboxylic
acids that can be used in the form of the free acid and/or their
sodium salts, polycarboxylic acids in this context being understood
to be carboxylic acids that carry more than one acid function.
These include citric acid, adipic acid, succinic acid, glutaric
acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar
acids, amino carboxylic acids, nitrilotriacetic acid (NTA),
providing such use is not ecologically unsafe, and mixtures
thereof. Besides their building effect, the free acids also
typically have the property of an acidifying component and hence
also serve to establish a relatively low and mild pH of laundry
detergents and cleaning compositions. Citric acid, succinic acid,
glutaric acid, adipic acid, gluconic acid and any mixtures thereof
are particularly mentioned in this regard.
[0134] Particularly preferred inventive automatic dishwashing
agents comprise citrate as one of their essential builders.
According to the invention, preferred processes include those in
which the dishwashing agent A comprises, based on total weight of
the automatic dishwashing agent A, about 5 to about 60 wt. %,
preferably about 10 to about 50 wt. % and particularly about 15 to
about 40 wt. % citrate.
[0135] Accordingly, a preferred subject matter of the present
application is a process for cleaning tableware in an automatic
dishwasher during which aqueous cleaning liquor present in the
interior of the automatic dishwasher is at least partially removed
from the interior of the automatic dishwasher at a time t, wherein
an automatic dishwashing agent A, comprising, based on the total
weight of the automatic dishwashing agent A--
[0136] a) 0.5 to 10 wt. % nonionic surfactant(s),
[0137] b) 0.2 to 20 wt. % anionic polymer(s), and
[0138] c) 10 to 50 wt. % citrate
is metered into the interior of the automatic dishwasher in a
quantity m1 at a time t1<t and in a quantity m2 at a time
t2>t.
[0139] Further preferred is a process for cleaning tableware in an
automatic dishwasher during which aqueous wash liquor present in
the interior of the automatic dishwasher is removed from the
interior of the dishwasher at a time t in an amount of from about 5
to about 99 vol. %, preferably from about 10 to about 90 vol. %,
particularly preferably from about 20 to about 80 vol. % and
especially from about 40 to about 70 vol. % of the wash liquor,
wherein an automatic dishwashing agent A comprising, based on total
weight of the automatic dishwashing agent A--
[0140] a) 0.5 to 10 wt. % nonionic surfactant(s),
[0141] b) 0.2 to 20 wt. % anionic polymer(s), and
[0142] c) 10 to 50 wt. % citrate
is metered into the interior of the automatic dishwasher in a
quantity m1 at a time t1<t and in a quantity m2 at a time
t2>t.
[0143] In the washing and cleaning agent industry, among the many
commercially available phosphates, alkali metal phosphates are
important, with pentasodium or pentapotassium triphosphates (sodium
or potassium tripolyphosphate) particularly preferred.
[0144] "Alkali metal phosphates" collectively refers to alkali
metal (more particularly sodium and potassium) salts of the various
phosphoric acids in which metaphosphoric acids (HPO.sub.3).sub.n
and orthophosphoric acid (H.sub.3PO.sub.4) and representatives of
higher molecular weight can be differentiated. The phosphates
combine several inherent advantages: They act as alkalinity
sources, prevent lime deposits on machine parts and lime
incrustations in fabrics and, in addition, contribute towards the
cleansing power.
[0145] Industrially important phosphates include pentasodium
triphosphate, Na.sub.5P.sub.3O.sub.10 (sodium tripolyphosphate) as
well as the corresponding potassium salt pentapotassium
triphosphate K.sub.5P.sub.3O.sub.10 (potassium tripolyphosphate).
According to the invention, sodium potassium tripolyphosphates are
again preferably employed.
[0146] In the context of the present invention, if phosphates are
incorporated as the active washing or cleaning substances in the
automatic dishwashing agent, then preferred compositions comprise
this/these phosphate(s), preferably alkali metal phosphate(s),
particularly preferably pentasodium or pentapotassium triphosphate
(sodium or potassium tripolyphosphate) in amounts of about 5 to
about 60 wt. %, preferably about 10 to about 50 wt. % and
especially about 15 to about 40 wt. %, each based on the weight of
the automatic dishwashing agent.
[0147] In a preferred process variant, complexants (preferably
phosphonates) are added to complement the combination of active
substances of nonionic surfactant and anionic polymer. Particularly
preferred automatic dishwashing processes are those wherein the
dishwashing agent A comprises a complexant, preferably
1-hydroxyethane-1,1-diphosphonic acid and/or methylglycine diacetic
acid.
[0148] In addition to 1-hydroxyethane-1,1-diphosphonic acid,
phosphonate complexants include a series of different compounds
such as diethylenetriamine penta(methylene phosphonic acid)
(DTPMP). Hydroxyalkane phosphonates or aminoalkane phosphonates are
particularly preferred in this application. Among the hydroxyalkane
phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of
particular importance as the cobuilder. It is normally added as the
sodium salt, the disodium salt reacting neutral and the tetrasodium
salt reacting alkaline (pH 9). Ethylenediamine tetramethylene
phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate
(DTPMP) and their higher homologs are preferably chosen as the
aminoalkane phosphonates. They are preferably added in the form of
the neutral-reacting sodium salts (e.g., as the hexasodium salt of
EDTMP or as the hepta and octasodium salt of DTPMP). Of the class
of phosphonates, HEDP is preferably used as the builder. The
aminoalkane phosphonates additionally possess a pronounced ability
to complex heavy metals. Accordingly, it can be preferred,
particularly where the agents also contain bleach, to use
aminoalkane phosphonates, particularly DTPMP, or mixtures of the
mentioned phosphonates.
[0149] In the context of this application, a preferred automatic
dishwashing agent A comprises one or more phosphonates from the
group-- [0150] a) aminotrimethylene phosphonic acid (ATMP) and/or
its salts; [0151] b) ethylenediamine tetra(methylene phosphonic
acid) (EDTMP) and/or its salts; [0152] c) diethylenetriamine
penta(methylene phosphonic acid) (DTMP) and/or its salts; [0153] d)
1-hydroxyethane-1,1-diphosphonic acid (HEDP) and/or its salts;
[0154] e) 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and/or
its salts; [0155] f) hexamethylenediamine tetra(methylene
phosphonic acid) (HDTMP) and/or its salts; and/or [0156] g) nitrilo
tri(methylene phosphonic acid) (NTMP) and/or its salts.
[0157] Particularly preferred automatic dishwashing agents comprise
1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriamine
penta(methylene phosphonic acid) (DTMP) as the phosphonates.
[0158] Of course the inventive automatic dishwashing agents can
have two or more different phosphonates. Particularly preferred
automatic dishwashing agents A include both
1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriamine
penta(methylene phosphonic acid) (DTMP) as the phosphonates,
wherein the weight ratio of HEDP to DTPMP is from 20:1 to 1:20,
preferably from 15:1 to 1:15 and especially from 10:1 to 1:10.
[0159] In a preferred embodiment of the present invention, the
weight fraction of phosphonate(s) to total weight of the automatic
dishwashing agent is less than the weight fraction of the
polymer(s) b). In other words, those agents are particularly
preferred in which the ratio of the weight fraction of polymer b)
to the weight fraction of the phosphonate is 200:1 to 2:1,
preferably 150:1 to 2:1, particularly preferably 100:1 to 2:1,
quite particularly preferably 80:1 to 3:1 and especially 50:1 to
5:1.
[0160] The weight fraction of these complexants, in particular, the
sum of the weight fractions of 1-hydroxyethane-1,1-diphosphonic
acid (HEDP) and methyl glycine diacetic acid (MGDA), is preferably
about 0.5 to about 14 wt. %, preferably about 1 to about 12 wt. %
and especially about 2 to about 8 wt. %.
[0161] A further preferred subject matter of the present
application is a process for cleaning tableware in an automatic
dishwasher during which aqueous cleaning liquor present in the
interior of the automatic dishwasher is at least partially removed
from the interior of the automatic dishwasher at a time t, wherein
an automatic dishwashing agent A comprising, based on total weight
of the automatic dishwashing agent A--
[0162] a) 0.5 to 10 wt. % nonionic surfactant(s),
[0163] b) 0.2 to 20 wt. % anionic polymer(s),
[0164] c) 15 to 40 wt. % phosphate or 15 to 40 wt. % citrate,
and
[0165] d) 0.5 to 8 wt. % phosphonate(s),
is metered into the interior of the automatic dishwasher in a
quantity m1 at a time t1<t and in a quantity m2 at a time
t2>t.
[0166] Further preferred is a process for cleaning tableware in an
automatic dishwasher during which aqueous wash liquor present in
the interior of the automatic dishwasher is removed from the
interior of the dishwasher at a time t in an amount of from about 5
to about 99 vol. %, preferably from about 10 to about 90 vol. %,
particularly preferably from about 20 to about 80 vol. % and
especially from about 40 to about 70 vol. % of the wash liquor,
wherein an automatic dishwashing agent A comprising, based on total
weight of the automatic dishwashing agent A--
[0167] a) 0.5 to 10 wt. % nonionic surfactant(s),
[0168] b) 0.2 to 20 wt. % anionic polymer(s),
[0169] c) 15 to 40 wt. % phosphate or 15 to 40 wt. % citrate,
[0170] d) 0.5 to 8 wt. % phosphonate(s),
is metered into the interior of the automatic dishwasher in a
quantity m1 at a time t1<t and in a quantity m2 at a time
t2>t.
[0171] Enzymes can also be incorporated in the inventive process in
order to boost cleaning power. These particularly include
proteases, amylases, lipases, hemicellulases, cellulases or
oxidoreductases, as well as preferably their mixtures. In
principle, these enzymes are of natural origin; improved variants
based on the natural molecules are available for use in laundry
detergents or cleaning compositions and accordingly are preferred.
The detergents or cleaning compositions preferably comprise enzymes
in total quantities of about 1.times.10.sup.-6 to about 5 weight
percent based on active protein. Protein concentration can be
determined using known methods (e.g., the BCA Process or the biuret
process).
[0172] Preferred proteases are those of the subtilisin type.
Examples include the subtilisins BPN' and Carlsberg as well as
their further developed forms, the protease PB92, the subtilisins
147 and 309, the alkaline protease from Bacillus lentus, subtilisin
DY and those enzymes of the subtilases no longer classified in the
stricter sense as subtilisins: thermitase, proteinase K and the
proteases TW3 und TW7.
[0173] Examples of further useable amylases according to the
invention include .alpha.-amylases from Bacillus licheniformis,
from B. amyloliquefaciens, from B. stearothermophilus, from
Aspergillus niger and A. oryzae, as well as their improved further
developments for use in washing and cleaning agents. Moreover, for
these purposes, attention should be drawn to the .alpha.-amylase
from Bacillus sp. A 7-7 (DSM 12368) and the
cyclodextrin-glucanotransferase (CGTase) from B. agaradherens (DSM
9948).
[0174] According to the invention, lipases or cutinases can also be
incorporated, particularly due to their triglyceride cleaving
activities, but also in order to produce in situ peracids from
suitable preliminary steps. These include the available or further
developed lipases originating from Humicola lanuginosa (Thermomyces
lanuginosus), particularly those with the amino acid substitution
D96L. Moreover, suitable cutinases include those originally
isolated from Fusarium solani pisi and Humicola insolens. Further
suitable are lipases or cutinases whose starting enzymes were
originally isolated from Pseudomonas mendocina and Fusarium
solanii.
[0175] In addition, enzymes summarized under the term
hemicellulases can be added. These include mannanases,
xanthanlyases, pectinlyases (=pectinases), pectinesterases,
pectatlyases, xyloglucanases (=xylanases), pullulanases und
.beta.-glucanases.
[0176] To increase the bleaching action, oxidoreductases, for
example, oxidases, oxygenases, katalases, peroxidases like halo-,
chloro-, bromo-, lignin-, glucose- or manganese-peroxidases,
dioxygenases or laccases (phenoloxidases, polyphenoloxidases) can
be incorporated according to the invention. Advantageously,
additional, preferably organic, particularly preferably aromatic
compounds are added that interact with the enzymes to enhance the
activity of the relative oxidoreductases or to facilitate the
electron flow (mediators) between the oxidizing enzymes and the
stains over strongly different redox potentials.
[0177] Enzymes can be added in forms established according to the
prior art. Included here, for example, are solid preparations
obtained by granulation, extrusion or lyophilization, or
particularly liquid compositions or compositions in the form of
gels, enzyme solutions, advantageously highly concentrated, of low
moisture content and/or mixed with stabilizers.
[0178] As an alternative application form, the enzymes can also be
encapsulated, for example, by spray drying or extrusion of the
enzyme solution together with a preferably natural polymer or in
the form of capsules, for example those in which the enzyme is
embedded in a solidified gel, or in those of the core-shell type,
in which an enzyme-containing core is covered with a water-, air-
and/or chemical-impervious protective layer. Further active
principles, for example stabilizers, emulsifiers, pigments,
bleaches or colorants can be applied in additional layers. Such
capsules are made using known methods, for example by vibratory
granulation or roll compaction or by fluidized bed processes.
Advantageously, these types of granulates, for example with an
applied polymeric film former are dust-free and as a result of the
coating are storage stable.
[0179] In addition, it is possible to formulate two or more enzymes
together so that a single granulate exhibits a plurality of
enzymatic activities.
[0180] A protein and/or enzyme can be protected, particularly in
storage, against deterioration such as inactivation, denaturation
or decomposition, for example, through physical influences,
oxidation or proteolytic cleavage. Inhibition of the proteolysis is
particularly preferred during microbial preparation of proteins
and/or enzymes, particularly when the compositions also contain
proteases. For this use, washing or cleaning agents can comprise
stabilizers. The provision of these types of agents represents a
preferred embodiment of the present invention.
[0181] Preferred automatic dishwashing processes are those in which
the dishwashing agent A comprises, based on total weight of the
automatic dishwashing agent A, about 0.2 to about 5 wt. %,
preferably about 0.5 to about 5 wt. % and particularly about 1 to
about 4 wt. % enzyme(s).
[0182] A further preferred subject matter of the present
application is a process for cleaning tableware in an automatic
dishwasher during which aqueous cleaning liquor present in the
interior of the automatic dishwasher is at least partially removed
from the interior of the automatic dishwasher at a time t, wherein
an automatic dishwashing agent A comprising, based on total weight
of the automatic dishwashing agent A--
[0183] a) 0.5 to 10 wt. % nonionic surfactant(s),
[0184] b) 0.2 to 20 wt. % anionic polymer(s), preferably sulfonic
acid group-containing polymer(s),
[0185] c) 15 to 40 wt. % phosphate or 15 to 40 wt. % citrate,
and
[0186] d) 0.5 to 5 wt. % enzyme(s),
is metered into the interior of the automatic dishwasher in a
quantity m1 at a time t1<t and in a quantity m2 at a time
t2>t.
[0187] Further preferred is a process for cleaning tableware in an
automatic dishwasher during which aqueous wash liquor present in
the interior of the automatic dishwasher is removed from the
interior of the dishwasher at a time t in an amount of from about 5
to about 99 vol. %, preferably from about 10 to about 90 vol. %,
particularly preferably from about 20 to about 80 vol. % and
especially from about 40 to about 70 vol. % of the wash liquor,
wherein an automatic dishwashing agent A comprising, based on total
weight of the automatic dishwashing agent A--
[0188] a) 0.5 to 10 wt. % nonionic surfactant(s),
[0189] b) 0.2 to 20 wt. % anionic polymer(s), preferably sulfonic
acid group-containing polymer(s),
[0190] c) 15 to 40 wt. % phosphate or 15 to 40 wt. % citrate,
and
[0191] d) 0.5 to 5 wt. % enzyme(s),
is metered into the interior of the automatic dishwasher in a
quantity m1 at a time t1<t and in a quantity m2 at a time
t2>t.
[0192] Preferred automatic dishwashing agents A additionally
comprise one or more bleaching agents. Among the compounds which
serve as bleaching agents and liberate H.sub.2O.sub.2 in water,
sodium percarbonate, sodium perborate tetrahydrate and sodium
perborate monohydrate are of particular use. Examples of further
bleaching agents that may be used are peroxypyrophosphates, citrate
perhydrates and H.sub.2O.sub.2-liberating peracidic salts or
peracids, such as perbenzoates, peroxyphthalates, diperoxyazelaic
acids, phthaloimino peracids or diperoxydodecanedioic acids.
Moreover, bleaching agents from the group of the organic bleaching
agents can also be used. Typical organic bleaching agents include
diacyl peroxides such as dibenzoyl peroxide. Further typical
organic bleaching agents include peroxy acids, wherein the
alkylperoxy acids and the arylperoxy acids may be named as
examples.
[0193] According to the invention, preferred processes include
those wherein the dishwashing agent A comprises, based on total
weight of the automatic dishwashing agent A, about 1 to about 20
wt. %, preferably about 2 to about 15 wt. % and particularly about
4 to about 12 wt. % sodium percarbonate.
[0194] Chlorine- or bromine-releasing substances can also be
incorporated as bleaching agents. Suitable chlorine- or
bromine-releasing materials include, for example, heterocyclic
N-bromamides and N-chloramides, for example trichloroisocyanuric
acid, tribromoisocyanuric acid, dibromoisocyanuric acid and/or
dichloroisocyanuric acid (DICA) and/or salts thereof with cations
such as potassium and sodium. Hydantoin compounds, such as
1,3-dichloro-5,5-dimethyl hydantoin, are also suitable.
[0195] In order to achieve an improved bleaching action for
cleaning at temperatures of about 60.degree. C. and below, the
inventively employed automatic dishwashing agents can additionally
comprise bleach activators. Bleach activators which can be used are
compounds which, under perhydrolysis conditions, yield aliphatic
peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in
particular 2 to 4 carbon atoms, and/or optionally substituted
perbenzoic acid. Substances, which carry O-acyl and/or N-acyl
groups of said number of carbon atoms and/or optionally substituted
benzoyl groups, are suitable. Polyacylated alkylenediamines are
preferred, tetraacetyl ethylenediamine (TAED) having proven to be
particularly suitable.
[0196] These bleach activators, especially TAED, are preferably
employed in amounts of up to about 10 wt. %, particularly about 0.1
to about 8 wt. %, especially about 2 to about 8 wt. % and
particularly preferably about 2 to about 6 wt. %, each based on the
total weight of the bleach activator-containing composition.
[0197] In addition to, or instead of conventional bleach
activators, so-called bleach catalysts may also be incorporated.
These substances include bleach-boosting transition metal salts or
transition metal complexes such as manganese-, iron-, cobalt-,
ruthenium- or molybdenum-salen or -carbonyl complexes. Manganese,
iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper
complexes with nitrogen-containing tripod ligands, as well as
cobalt-, iron-, copper- and ruthenium-amine complexes may also be
employed as the bleach catalysts.
[0198] Complexes of manganese in the valence state II, III, IV or V
which preferably comprise one or a plurality of macrocyclic ligands
with the donor functions N, NR, PR, O and/or S are particularly
preferably included. Ligands having nitrogen donor functions are
preferably employed. In this regard, it is particularly preferred
to incorporate bleach catalyst(s) into compositions according to
the invention which comprise
1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN),
1,4,7-triazacyclononane (TACN),
1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD),
2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me/Me-TACN)
and/or 2-methyl-1,4,7-triazacyclononane (Me/TACN) as the
macromolecular ligands. Suitable manganese complexes are for
example
[Mn.sup.III.sub.2(.mu.-O).sub.1(.mu.-OAc).sub.2(TACN).sub.2](CIO.sub.4).s-
ub.2,
[Mn.sup.IIIMn.sup.IV(.mu.-O).sub.2(.mu.-OAc).sub.1(TACN).sub.2](BPh.-
sub.4).sub.2,
[Mn.sup.IV.sub.4(.mu.-O).sub.6(TACN).sub.4](CIO.sub.4).sub.4,
[Mn.sup.III.sub.2(.mu.-O).sub.1(.mu.-OAc).sub.2(Me-TACN).sub.2](CIO.sub.4-
).sub.2,
[Mn.sup.IIIMn.sup.IV(.mu.-O).sub.1(.mu.-OAc).sub.2(Me-TACN).sub.2-
](CIO.sub.4)S,
[Mn.sup.IV.sub.2(.mu.-O).sub.3(Me-TACN).sub.2](PF.sub.6).sub.2 and
[Mn.sup.IV.sub.2(.mu.-O).sub.3(Me/Me-TACN).sub.2](PF.sub.6).sub.2(OAc.dbd-
.OC(O)CH.sub.3).
[0199] Inventively preferred automatic dishwashing agents
additionally comprise a bleach catalyst chosen from bleach boosting
transition metal salts and transition metal complexes, preferably
from complexes of manganese with
1,4,7-trimethyl-1,4,7-triazacyclononane (Me.sub.3-TACN) or
1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me.sub.4-TACN), as
these bleach catalysts particularly contribute to an significantly
improved cleaning result.
[0200] The abovementioned bleach boosting transition metal
complexes, especially those with the central atoms Mn and Co, are
added in usual amounts, preferably in an amount of up to about 5
wt. %, particularly from about 0.01 wt. % to about 2 wt. % and
particularly preferably about 0.05 to about 0.8 wt. %, each based
on the total weight of the automatic dishwashing agent A.
[0201] In addition to active substances present in the automatic
dishwashing agent, pH of the added automatic dishwashing agent has
proven relevant for cleaning, rinsing and drying results of the
inventive process. Therefore, particularly good results are
attained with automatic dishwashing agents, whose 1% conc. aqueous
solution (20.degree. C.) exhibits a pH above about 7, preferably
from about 7 to about 12 and particularly preferably from about 9
to about 11. Accordingly, corresponding processes wherein the
automatic dishwashing agent A exhibits a pH (1% conc. aqueous
solution at 20.degree. C.) above about 7, preferably from about 7
to about 12 and particularly preferably from about 9 to about 11,
are likewise inventively preferred.
[0202] The surprising advantages of the inventive process become
evident particularly in those automatic dishwashing processes in
which the wash water has not been softened. ("Wash water" is the
water used for washing). Accordingly, the wash water used for
carrying out the inventive process preferably exhibits a hardness
above about 5.degree. dH, preferably above about 10.degree. dH,
particularly preferably above about 15.degree. dH and in particular
above about 20.degree. dH.
[0203] The inventively employed automatic dishwashing agent A can
be manufactured in solid or liquid form, but can also exist as a
combination of solid and liquid product formats.
[0204] Powders, granulates, extrudates or compactates, especially
tablets, are suitable solid product formats. Liquid product
formats, preferably based on water and/or organic solvents, can be
thickened, for example, in the form of gels.
[0205] The inventively employed automatic dishwashing agents A can
be manufactured as a single phase or multi phase product. Automatic
dishwashing agents with one, two, three or four phases are
especially preferred. Automatic dishwashing agents in the form of a
prefabricated unit dose with two or more phases are particularly
preferred.
[0206] Individual phases of a multi-phase agent can have the same
or different aggregation states. Automatic dishwashing agents
having at least two different solid phases and/or at least two
liquid phases and/or at least one solid and at least one liquid
phase are particularly preferred. Inventive processes wherein the
automatic dishwashing agent A is in solid form are preferred,
however, due to improved cleaning, rinsing and drying results.
[0207] The automatic dishwashing agents A are preferably
prefabricated as unit doses. These unit doses preferably contain
the necessary quantity of washing or cleaning active substances for
one cleaning cycle. Preferred unit doses weigh from about 12 to
about 30 g, preferably from about 14 to about 26 g and especially
from about 15 to about 22 g.
[0208] Volumes of the abovementioned unit doses and their
three-dimensional shape are particularly preferably chosen such
that the prefabricated units can be dosed by being placed in the
dosing chamber of a dishwasher. Consequently, the volume of the
unit dose is preferably from about 10 to about 35 ml, preferably
from about 12 to about 30 ml and especially from about 15 to about
25 ml.
[0209] Automatic dishwashing agents according to the invention, in
particular, prefabricated unit doses, preferably have a
water-soluble coating.
[0210] In an alternative product format the automatic dishwashing
agent A used in the inventive process is metered into the interior
of the dishwasher by a water-insoluble storage reservoir. This
storage reservoir preferably has two or more chambers in which the
automatic dishwashing agent A is present, for example, in the form
of partial formulations that are separated from each other. The
water-insoluble storage reservoir can be integrated into the
dishwasher, but can also be in the form of a two or multi-chamber
bottle.
[0211] As described in the introduction, the inventive cleaning
processes compared to conventional processes exhibit an improved
cleaning and rinsing action, as well as an improved drying of the
cleaned tableware. Use of an inventive automatic dishwashing
process for reducing the formation of deposits in automatic
dishwashing or for improving the drying in automatic dishwashing
are further subject matters of this application.
EXAMPLES
[0212] Drying, deposition and cleaning performance of an automatic
dishwashing process was determined as a function of the type of
metering of the added automatic dishwashing agent.
[0213] For this, tableware was cleaned with 33 ml (16.5 ml F1 and
16.5 ml F2) of an automatic dishwashing agent at a water hardness
of 21.degree. dH in an automatic dishwasher (Miele 1730; Program
55.degree. Normal 3 in 1 Extra Drying).
[0214] The composition of the added dishwashing agents F1 and F2
can be seen in the following Table:
TABLE-US-00001 Raw material F1 [wt. %] F2 [wt. %] KTTP 17.5 10.0
nonionic surfactant 4.0 -- protease 2.0 -- amylase 1.0 --
phosphonate 3.0 5.0 thickener 4.0 -- organic solvent 3.0 3.0
anionic polymer -- 8.6 soda -- 7.0 water, misc. add 100 add 100
[0215] The following three experiments were carried out:
Experiment V1--16.5 ml of each of the compositions F1 and F2 were
simultaneously metered into the interior of the machine in the main
wash cycle of the dishwashing process. Experiment V2--12.5 ml of
composition F1 and 16.5 ml of composition F2 were metered into the
interior of the machine in the main wash cycle of the dishwashing
process; in addition in the following rinse cycle (after a partial
exchange of wash water) 4 ml of composition F1 were metered into
the interior of the machine. Experiment E1--14.5 ml of composition
F1 and F2 ml of composition F2 were simultaneously metered into the
interior of the machine in the main wash cycle of the dishwashing
process; in addition in the following rinse cycle (after a partial
exchange of wash water) 2 ml of each of the compositions F1 and F2
were metered into the interior of the machine.
[0216] In regard to the cleaning performance (determined according
to IKW), no significant differences were observed between both
process variants.
[0217] Drying index was determined according to the EN
specification. The results are presented in the following Table
(the reported values are the mean of 3 experiments):
TABLE-US-00002 V1 V2 E1 Drying index 0.60 0.85 0.80 Deposit
formation No deposits Deposit formation No deposits
[0218] Based on results in experiment V1, the drying index could
consequently be improved in experiment V2 due to the subsequent
metering of a surfactant-containing cleaning agent; however, the
formation of deposits on the surface of the dishes was observed in
both cases. Only by subsequent metering of surfactant and anionic
polymer in experiment E1 could both good drying and deposition
results be obtained.
* * * * *